TW201500462A - Polymer, liquid crystal orientation treating agent, liquid crystal orientation film and liquid crystal display element - Google Patents

Abstract

The present invention is related to a liquid crystal alignment treating agent, which containing the following polymer, which is selected from at least one kind of below-mentioned polyimide. The polyimide is obtained by imidization of a polyimide precursor obtained by carrying out the reaction of a tetracarboxylic acid component containing tetracarboxylic dianhydride expressed by formula [1] and the diamine component of a diamine compound containing the side chain expressed by formula [2]. (in formula [2], Y<1> represents a single bond, -(CH2)a- (a is an integer of 1-15), -O-, -CH2O-, -COO-, or –OCO-, Y<2> represents a single bond, or -(CH2)b- (b is an integer of 1-15), Y<3> represents a single bond, -(CH2)c- (c is an integer of 1-15), -O-, -CH2O-, -COO-, or –OCO-, Y<4> represents a divalent cyclic group of a benzene ring, a cyclohexane ring, or a heterocyclic ring, or a divalent organic group with a carbon number of 17-51 and containing a steroid backbone, an arbitrary hydrogen atom on the aforementioned cyclic group can be replaced by an alkyl group with a carbon number of 1-3, an alkoxyl group with a carbon number of 1-3, an fluorine-containing alkyl group with a carbon number of 1-3, a fluorine-containing alkoxyl group with a carbon number of 1-3, or the fluorine atom, Y<5> represents the divalent cyclic group of a benzene ring, a cyclohexane ring, or a heterocyclic ring, an arbitrary hydrogen atom on the cyclic group can be replaced by an alkyl group with a carbon number of 1-3, an alkoxyl group with a carbon number of 1-3,a fluorine-containing alkyl group with a carbon number of 1-3, a fluorine-containing alkoxyl group with a carbon number of 1-3, or a fluorine atom, n represents an integer of 0-4, Y<6> represents an alkyl group with carbon number 1-18, fluorine-containing alkyl group with a carbon number of 1-18, alkoxyl group with a carbon number of 1-18, or fluorine-containing alkoxyl group with a carbon number of 1-18).

Description

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

The present invention relates to a polymer, a liquid crystal alignment treatment agent used in 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.

As a liquid crystal display element having excellent viewing angle characteristics as compared with a conventional TN (Twisted Nematic) mode liquid crystal display element, a MVA (Multi-domain Vertical Alignment) mode obtained from a wide viewing angle is known. In the MVA mode, a liquid crystal having a negative dielectric anisotropy, a liquid crystal alignment film in which the liquid crystal is vertically aligned, and a structure for controlling the alignment of the liquid crystal alignment direction are used. When the voltage is input, the liquid crystal is tilted in the vertical direction along the alignment control structure. However, in the MVA mode, since the structure protrusion for alignment control is formed in the pixel, the aperture ratio is lower than that in the TN mode or the like, and the light transmittance from the backlight is lowered.

In order to further accelerate the liquid crystal response speed under high light transmittance, a method of controlling the liquid crystal alignment direction during driving using a polymer has been proposed (for example, see Patent Document 1). In the method, A liquid crystal material of a polymerizable compound (also referred to as a monomer) polymerized by heat or ultraviolet irradiation is used in the liquid crystal. In this method, when a voltage is applied between the substrates to cause the liquid crystal molecules to be tilted, the polymer is polymerized by heat or ultraviolet irradiation to form a polymer (the above method is also referred to as PSA treatment). Thereby, even if there is no input voltage, a liquid crystal layer having a predetermined tilt angle can be obtained, and the response speed of the liquid crystal at a high light transmittance can be further accelerated.

[prior technical literature] [Patent Document]

[Patent Document 1] JP-A-2003-149647

In the production of a liquid crystal display element, a step of filling a liquid crystal between two substrates (formation cell gap) in which a liquid crystal alignment film is formed is necessary. Up to now, in the filling of liquid crystals, a vacuum injection method in which liquid crystal is filled between two substrates is a general method using a pressure difference between atmospheric pressure and vacuum. However, in order to improve production efficiency, a liquid crystal dropping method (ODF (One Drop Fill) method) is used as a filling method of liquid crystal.

In the ODF method, in order to directly drop the liquid crystal on the liquid crystal alignment film, it is necessary to apply physical pressure to the liquid crystal alignment film when the liquid crystal is dropped, or to fill the liquid crystal in the entire area of the panel, so it is necessary to increase the liquid crystal dropping point. Therefore, at the droplet contact portion adjacent to the droplet of the liquid crystal drop or the liquid crystal When the liquid crystal display element is used as a liquid crystal display element, display unevenness due to misalignment of the alignment occurs.

Further, when the liquid crystal display element is heated by the irradiation of the backlight constituting the liquid crystal display element, there is a problem that the pretilt angle changes and display failure occurs. Therefore, high stability to heat is required.

The present invention has an object of providing a polymer, a liquid crystal alignment treatment agent, a liquid crystal alignment film, and a liquid crystal display element which are capable of improving the alignment unevenness of the liquid crystal alignment film and having excellent pretilt heat resistance.

As a result of detailed investigation, the present inventors have found that a polyphthalocyanine obtained by reacting a tetracarboxylic acid component having a tetracarboxylic dianhydride having a specific structure with a diamine component having a diamine compound having a specific structure is obtained. The liquid crystal alignment treatment agent of at least one polymer of the polyimide precursor obtained by the ruthenium imidization of the amine precursor and the polyimide precursor is extremely effective in achieving the above object, and the present invention has been completed.

That is, the present invention has the following gist.

(1) A liquid crystal alignment treatment agent comprising at least one polymer selected from the group consisting of polyimine which contains a tetracarboxylic dianhydride represented by the following formula [1] The polyiminoimine precursor obtained by reacting a tetracarboxylic acid component with a diamine component containing a diamine compound represented by the following formula [2] and the polyimine precursor are obtained by imidization By;

(In the formula [2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² Represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a steroid number of 17 to 51 carbon atoms; Any hydrogen atom on the above cyclic group 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 having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, and Y ⁶ The alkyl group having 1 to 18 carbon atoms, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms or the fluorine-containing alkoxy group having 1 to 18 carbon atoms).

(2) The tetracarboxylic acid component contains the following formula [3] The liquid crystal alignment treatment agent according to the above (1), which is characterized by the tetracarboxylic anhydride.

(In the formula [3], Z ¹ is at least one tetravalent group selected from the following formulas [3a] to [3j]).

(In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. Each can be the same or different).

(3) As a solvent in the liquid crystal alignment treatment agent, it is characterized by containing N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. The liquid crystal alignment treatment agent according to the above (1) or (2) above.

(4) The solvent in the liquid crystal alignment agent containing any solvent (1) to (3) selected from the solvents of the formula [D-1] to the formula [D-3] Liquid crystal alignment treatment agent.

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

(5) A liquid crystal alignment film which is characterized by using the liquid crystal alignment treatment agent according to the above (1) to (4).

(6) A liquid crystal alignment film characterized by an inkjet method using the liquid crystal alignment treatment agent according to the above (1) to (4).

(7) A liquid crystal display element characterized by having the liquid crystal alignment film according to (5) or (6) above.

(8) The liquid crystal alignment film according to the above (5) or (6), which is used for a liquid crystal display element, which is formed by a liquid crystal layer between a pair of substrates including electrodes. 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 a step of polymerizing the polymerizable compound is performed while a voltage is input between the electrodes.

(9) A liquid crystal display element comprising the liquid crystal alignment film according to (8) above.

(10) The liquid crystal alignment film according to the above (5) or (6), which is used in a liquid crystal display device which has a liquid crystal layer formed between a pair of substrates having electrodes. A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the pair of substrates, and a step of polymerizing the polymerizable group is performed while a voltage is input between the electrodes.

(11) A liquid crystal display element comprising the liquid crystal alignment film according to (10) above.

(12) A polymer characterized by being at least one selected from the group consisting of polyimines which are tetracarboxylic acids which will contain a tetracarboxylic dianhydride represented by the following formula [1] a polyimine precursor obtained by reacting a component with a diamine component having a diamine compound having a side chain represented by the following formula [2], and a polyimine precursor obtained by hydrazine imidization;

(In the formula [2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² Represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, Any hydrogen atom on the above cyclic group 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 having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group 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, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, and Y ⁶ The alkyl group having 1 to 18 carbon atoms, the fluorine-containing alkyl group having 1 to 18 carbon atoms, the alkoxy group having 1 to 18 carbon atoms or the fluorine-containing alkoxy group having 1 to 18 carbon atoms).

According to the present invention, a polyfluorene imine obtained by reacting a diamine component containing a tetracarboxylic acid component containing a tetracarboxylic dianhydride having a specific structure with a diamine compound having a side chain having a specific structure is used. When the precursor and the polyimine precursor are subjected to a liquid crystal alignment treatment agent of at least one polymer of the polyimine obtained by imidization, the alignment of the liquid crystal display element produced by the ODF method can be improved. Evenly. When the PSA mode is used in particular, the fraction of the polymerizable compound contained in the liquid crystal display element can be made. Uniform dispersion can further improve the uneven alignment. Moreover, by using the liquid crystal alignment treatment agent of the present invention, it is possible to make it excellent in heat resistance at a pretilt angle. Therefore, the liquid crystal display element having the liquid crystal alignment film of the present invention does not have an alignment defect due to uneven alignment, and is excellent in heat resistance, so that it can be a highly reliable liquid crystal display element.

[Formation of the Invention]

The liquid crystal alignment treatment agent of the present invention is at least one polymer (also referred to as a specific polymer) containing a polyimine obtained by the following mercapto imidization, which will contain the following formula [ 1) a tetracarboxylic acid component of a tetracarboxylic dianhydride (also referred to as a specific tetracarboxylic dianhydride) and a diamine compound (also referred to as a specific side chain) having a side chain represented by the following formula [2]; The polyimine precursor obtained by reacting the diamine component of the type diamine compound and the polyimine precursor are obtained by imidization.

Among them, the polyimine precursor is polyamide acid or polyalkyl amide. The polyimine precursor is composed of a tetracarboxylic acid component (for example, a tetracarboxylic acid compound, a tetracarboxylic dianhydride, a dicarboxylic acid dihalide compound, a dicarboxylic acid dialkyl ester compound, a dialkyl ester dihalide compound). a reaction with a diamine component of a diamine compound having two primary or secondary amine groups in the molecule, which can be subjected to dehydration ring closure (deuteration) or by borrowing It is obtained by heating and blocking a polyalkyl amide alkyl ester. These polyamines, polyalkyl amides and polyimines are all used as specific polymers contained in the liquid crystal alignment agent of the present invention.

<Specific tetracarboxylic dianhydride>

The specific tetracarboxylic dianhydride of the tetracarboxylic acid component of the raw material of the polymer contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic dianhydride represented by the following formula [1].

The tetracarboxylic dianhydride represented by the formula [1] is preferably 20 mol% to 100 mol% of the tetracarboxylic acid component. It is also preferably 30% to 70% by mole. Particularly good is 30% by mole to 50% by mole.

<Other tetracarboxylic acid compounds>

In the present invention, other tetracarboxylic acid compounds (also referred to as other tetracarboxylic acid compounds) other than the specific tetracarboxylic dianhydride may be used in combination as a tetracarboxylic acid component insofar as the effects of the present invention are not impaired.

Further, it is preferred to use a tetracarboxylic dianhydride represented by the following formula [3] or a tetracarboxylic acid compound and a dicarboxylic acid dihalide compound (all collectively referred to as other tetracarboxylic acid compounds) of the tetracarboxylic acid derivative.

(In the formula [3], Z ¹ is a group selected from the structures of the following formulas [3a] to [3j]).

In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different.

In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group, and each may be the same or different.

In the structure represented by the formula [3], Z ^{1 is} represented by the formula [3a], the formula [3c], the formula [3d], the formula [3e], and the easiness of the synthesis or the ease of polymerization in the production of the polymer. The structure represented by the formula [3f] or the formula [3g] is preferred. The structure represented by the formula [3a], the formula [3e], the formula [3f] or the formula [3g] is preferably a formula [3e], a formula [3f] or a formula [3g].

The tetracarboxylic acid component other than the tetracarboxylic acid component in the specific polymer contained in the liquid crystal alignment agent of the present invention can be used without using the specific tetracarboxylic dianhydride and other tetracarboxylic acid compounds. Compound.

Specific examples of the tetracarboxylic dianhydride, the tetracarboxylic acid compound or the dicarboxylic acid dihalide compound shown below are mentioned below.

Examples thereof include 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-nonanetetracarboxylic 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.

The other tetracarboxylic acid compound and the tetracarboxylic acid compound are the solubility of a specific polymer of the present invention with respect to a solvent or a coating property of a liquid crystal alignment treatment agent, the alignment property of a liquid crystal when a liquid crystal alignment film is used, a voltage retention ratio, and an accumulated charge. Other characteristics can be used in one type or in a mixture of two or more types.

<Specific side chain diamine compound>

The specific side chain diamine compound contained in the diamine component of the raw material of the polymer contained in the liquid crystal alignment agent of the present invention is a diamine compound having a side chain represented by the following formula [2]. Further, in the present specification, the side chain of the diamine compound means a structure branched from a structure in which two amine groups are bonded.

The diamine compound having a side chain represented by the formula [2] is preferably 20 mol% to 70 mol% of the total diamine component. Among them, 20% to 50% of the total is also preferred. Very good is 20% to 40% by mole.

In the formula [2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, in terms of ease of obtaining raw materials or ease of synthesis, a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is good. It is preferably a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2], Y ² represents a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 15). Among them, a single bond or -(CH ₂ ) _b - (b is an integer of 1 to 10) is preferred.

In the formula [2], Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-. Among them, in terms of ease of synthesis, a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 15), -O-, -CH ₂ O- or -COO- is preferred. It is preferably a single bond, -(CH ₂ ) _c - (c is an integer of 1 to 10), -O-, -CH ₂ O- or -COO-.

In the formula [2], Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number. The alkoxy group of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Further, Y ⁴ may be a divalent organic group selected from an organic group having a carbon number of 17 to 51 having a steroid skeleton. Among them, in view of ease of synthesis, an organic group having a benzene ring, a cyclohexane ring or a carbon number of 17 to 51 having a steroid skeleton is preferred.

In the formula [2], Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, and any hydrogen atom on the cyclic group may be an alkyl group having 1 to 3 carbon atoms and a carbon number. The alkoxy group of 1 to 3, the fluorine-containing alkyl group having 1 to 3 carbon atoms, the fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom is substituted. Among them, a benzene ring or a cyclohexane ring is preferred.

In the formula [2], n represents an integer of 0 to 4. Among them, in view of ease of obtaining raw materials or ease of synthesis, it is preferable to use 0 to 3. It is preferably 0 to 2.

In the formula [2], Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkane having 1 to 18 carbon atoms. Oxygen. Among them, an alkyl group having 1 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 fluorine-containing alkoxy group having 1 to 10 carbon atoms is preferred. It is preferably an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. Particularly preferred is an alkyl group having 1 to 9 carbon atoms or an alkoxy group having 1 to 9 carbon atoms.

A preferred combination of Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ and n in the formula [2] is shown in Tables 13 to 34 of International Publication WO2011/132751. 6~ The same combination of (2-1)~(2-629) disclosed in Table 47. Further, in the tables of the International Publications, Y ¹ to Y ⁶ in the present invention are represented by Y1 to Y6, and thus Y1 to Y6 are read as Y ¹ to Y ⁶ . Further, the organic group having a carbon number of 12 to 25 having a steroid skeleton is read with an organic group having a steroid number of 17 to 51 carbon atoms.

Specific examples of the diamine compound having a side chain represented by the formula [2] include a diamine compound represented by the following formula [2b-1] to the formula [2b-31].

(In the formula [2b-1] to the formula [2b-3], R ¹ represents -O-, -OCH ₂ -, -CH ₂ O-, -COOCH ₂ - or CH ₂ OCO-, and R ² represents a carbon number of 1 ~22 alkyl, alkoxy, fluoroalkyl or fluoroalkoxy).

(In the formula [2b-4] to the formula [2b-6], R ³ represents -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ - or - CH ₂ -, R ⁴ represents an alkyl group having 1 to 22 carbon atoms, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group).

(In the formula [2b-7] and the formula [2b-8], R ⁵ is -COO-, -OCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, - CH ₂ - or -O-, R ⁶ is a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group).

(In the formula [2b-9] and the formula [2b-10], R ⁷ represents an alkyl group having 3 to 12 carbon atoms; and the cis-trans isomerism of the 1,4-cyclohexyl group is each trans isomerism. Better).

(In the formula [2b-11] and the formula [2b-12], R ⁸ represents an alkyl group having 3 to 12 carbon atoms; and the cis-trans isomerism of the 1,4-cyclohexyl group is each trans isomerism. Better).

(In the formula [2b-13], B ⁴ represents an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, B ³ represents a 1,4-cyclohexyl group or a 1,4-phenylene group, and B ² represents an oxygen atom. or -COO - * (However, identification "*" of the bond binding to B ^3), B ¹ represents an oxygen atom or -COO - * (However, identification bond "*" in combination with the (CH ^₂₎ a ₂₎ Further, a ¹ represents an integer of 0 or 1, a ² represents an integer of 2 to 10, and a ³ represents an integer of 0 or 1.

A liquid using a diamine compound having a side chain represented by the formula [2] When the crystal is formed into a liquid crystal alignment film to the treatment agent, the pretilt angle of the liquid crystal can be increased. In this case, for the purpose of improving the effects, the diamine compound represented by the formula [2b-1] to the formula [2b-13] or the formula [2b-22] to [2b-31] is also used in the above diamine compound. It is better. The diamine compound represented by the formula [2b-1] to the formula [2b-12] or the formula [2b-22] to the formula [2b-29] is preferred. Moreover, in order to further improve these effects, it is preferable that these diamine compounds are 5 mol% or more and 80 mol% or less of the whole diamine component. The diamine compound is preferably 5 mol% or more and 60 mol% or less of the entire diamine component, in view of the coatability of the liquid crystal alignment agent or the electrical properties of the liquid crystal alignment film.

The diamine compound having the side chain represented by the above formula [2] is suitable for the solubility of a specific polymer in a solvent or the coating property of a liquid crystal alignment treatment agent, liquid crystal alignment property, a voltage retention ratio, a cumulative charge, etc. when used as a liquid crystal alignment film. The characteristics can be used in one type or in a mixture of two or more types.

<Other diamine components>

As the diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention, a known diamine compound may be used in addition to the diamine compound having a side chain represented by the formula [2].

Among them, a diamine compound having a structure represented by the following formula [4a] is also preferred.

[化27]-(CH ₂ ) _a -COOH [4a]

In the formula [4a], a represents an integer of 0 to 4. In view of the ease of obtaining raw materials or the ease of synthesis, the integer of 0 or 1 is good.

Specific examples of the diamine compound having a structure represented by the formula [4a] include a diamine compound represented by the following formula [4a-1].

In the formula [4a-1], a represents an integer of 0-4. Among them, 0 or 1 is preferable in terms of ease of obtaining raw materials or ease of synthesis.

In the formula [4a-1], n represents an integer of 1 to 4. Among them, it is preferable to use 1 in terms of ease of synthesis.

The method for producing the diamine compound represented by the above formula [4a] is not particularly limited, and preferred examples thereof include the following. As an example, the diamine compound represented by the formula [4a-1] is obtained by synthesizing a dinitro compound represented by the following formula [4a-A], and then converting the nitro group to an amine group.

(In the formula [4a-A], a represents an integer of 0 to 4, and n represents an integer of 1 to 4).

The method for reducing the dinitro group of the dinitro compound represented by the formula [4a-A] is not particularly limited, and is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina or sulphide platinum carbon is used as a catalyst, and the reaction is carried out under hydrogen, hydrazine or hydrogen chloride.

Further, as the diamine compound represented by the above formula [4a], a diamine compound represented by the following formula [4a-2] to formula [4a-5] can be further mentioned.

In the formula [4a-2], A ¹ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, in terms of ease of synthesis, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -N(CH ₃ )-, -CONH -, -NHCO-, -COO- or -OCO- is preferred. Preferred is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH- or -N(CH ₃ )-.

In the formula [4a-2], m ¹ and m ² each represent an integer of 0 to 4, and m ¹ + m ² represents an integer of 1 to 4. It is also preferable that m ¹ + m ² is 1 or 2.

In the formula [4a-3], m ³ and m ⁴ each represent an integer of 1 to 5. Among them, 1 or 2 is preferable in terms of ease of synthesis.

In the formula [4a-4], A ² represents a linear or branched alkyl group having 1 to 5 carbon atoms. Among them, a linear alkyl group having 1 to 3 carbon atoms is preferred.

In the formula [4a-4], m ⁵ represents an integer of 1 to 5. It is also preferably 1 or 2.

In the formula [4a-5], A ³ represents a single bond, -CH ₂ -, -C ₂ H ₄ -, -C(CH ₃ ) ₂ -, -CF ₂ -, -C(CF ₃ ) ₂ -, - O-, -CO-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO-, -OCO-, -CON(CH ₃ )- or -N(CH ₃ )CO-. Among them, a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ - , -COO- or -OCO- is preferred. Preferred are -O-, -CO-, -NH-, -CONH-, -NHCO-, -CH ₂ O-, -OCH ₂ -, -COO- or -OCO-.

In the formula [4a-5], m ⁶ represents an integer of 1 to 4. Among them, in terms of ease of synthesis, 1 is preferred.

The diamine compound represented by the above formula [4a-1] to formula [4a-5] is preferably 30 mol% to 80 mol% of the total diamine component, preferably 50 mol% to 80 mol%. %By.

The diamine compound represented by the above formula [4a-1] to formula [4a-5] is suitable for the solubility of a specific polymer in a solvent or the coating property of a liquid crystal alignment treatment agent, and the alignment property and voltage of a liquid crystal when used as a liquid crystal alignment film. The characteristics such as the retention ratio and the accumulated electric charge can be used in one type or in a mixture of two or more types.

The diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention is preferably a diamine compound represented by the following formula [4b].

In the formula [4b], Y represents at least one monovalent group selected from the following formula [4b-1], formula [4b-2], formula [4b-3], or formula [4b-4], and m represents An integer of 0 to 4, -(Y) _m indicates that there are m substituents Y.

In the formula [4b-1], a represents an integer of 0-4. In view of the ease of obtaining raw materials or the ease of synthesis, the integer of 0 or 1 is good.

In the formula [4b-2], Y ⁷ represents an alkyl group having 8 to 22 carbon atoms.

In the formula [4b-3], Y ⁸ and Y ⁹ each independently represent a hydrocarbon group having 1 to 12 carbon atoms.

In the formula [4b-4], Y ¹⁰ represents an alkyl group having 1 to 8 carbon atoms.

The method for producing the diamine compound represented by the above formula [4b] is not particularly limited, and preferred examples thereof include the following.

As an example, the diamine compound represented by the formula [4b] is obtained by synthesizing a dinitro compound represented by the following formula [4b-A], and then converting the nitro group to an amine group.

(In the formula [4b-A], Y represents a substituent selected from at least one of the above formula [4b-1], formula [4b-2], formula [4b-3] or formula [4b-4], m represents an integer from 0 to 4.)

The method for reducing the dinitro group of the dinitro compound represented by the formula [4b-A] is not particularly limited, and is usually a solvent such as ethyl acetate, toluene, tetrahydrofuran, dioxane or an alcohol solvent. A method in which carbon, platinum oxide, Raney nickel, platinum black, ruthenium-alumina or sulphide platinum carbon is used as a catalyst, and the reaction is carried out under hydrogen, hydrazine or hydrogen chloride.

The following is a formula for the diamine compound represented by the above formula [4b]. The body structure is not limited to these examples.

That is, examples of the diamine compound represented by the formula [4b] include m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2,6-diaminotoluene, and 2 , 4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4,6-diaminoisophthalic acid In addition to the diphenol, a diamine compound having the structure represented by the following formula [4b-6] to [4b-15] can also be mentioned.

(In the formula [4b-6] to the formula [4b-9], A ¹ represents an alkyl group having 1 to 22 carbon atoms or a fluorine-containing alkyl group).

The diamine component of the specific polymer contained in the liquid crystal alignment agent of the present invention may be a diamine compound represented by the formula [4a-1] to the formula [4a-5] and a diamine compound represented by the formula [4b]. A diamine compound other than the other (also referred to as another diamine compound) is used as the diamine component. The specific examples are given below, but are not limited to these examples.

For example, 4,4'-diaminobiphenyl, 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'-diaminobiphenyl, 3,3'-trifluoromethyl-4,4'-diaminobiphenyl, 3,4'-diamine linkage Phenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenyl Methane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodi Phenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2,2'-diamine Diphenyl 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'-thio Diphenylamine, 3,3'-thiodiphenylamine, 4,4'- Amino diphenylamine, 3,3'-diamine Diphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 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'-diaminodiphenyl)amine, 4,4'-diaminodiphenyl Methyl ketone, 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-diaminonaphthalene, 1,2-bis(4-aminophenyl)B Alkane, 1,2-bis(3-aminophenyl)ethane, 1,3-bis(4-aminophenyl)propane, 1,3-bis(3-aminophenyl)propane, 1, 4-bis(4-aminophenyl)butane, 1,4-bis(3-aminophenyl)butane, bis(3,5-diethyl-4-aminophenyl)methane, 1 , 4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenyl)benzene, 1,3- Bis(4-aminophenyl)benzene, 1, 4-bis(4-aminobenzyl)benzene, 1,3-bis(4-aminophenoxy)benzene, 4,4'-[1,4-phenylene bis(methyl) Diphenylamine, 4,4'-[1,3-phenylenebis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3 , 4'-[1,3-phenylenebis(methyl)diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'- [1,3-phenylene bis(methyl))diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3) -aminophenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylene bis[(3-aminophenyl)methanone 〕, 1,4-phenylene bis(4-aminobenzoate), 1,4- Phenyl bis(3-aminobenzoate), 1,3-phenylene bis(4-aminobenzoate), 1,3-phenylene bis(3-aminobenzoic acid) Ester), bis(4-aminophenyl)terephthalate, bis(3-aminophenyl)terephthalate, bis(4-aminophenyl)isophthalic acid , bis(3-aminophenyl)isophthalic acid, N,N'-(1,4-phenylene)bis(4-aminobenzamide), N,N'-(1,3 -phenyl)bis(4-aminobenzamide), N,N'-(1,4-phenylene)bis(3-aminobenzamide), N,N'-(1 , 3-phenylene) bis(3-aminobenzamide), N,N'-bis(4-aminophenyl)terephthalamide, N,N'-bis(3-amine Phenyl phenyl phthalamide, N, N'-bis(4-aminophenyl) m-xylyleneamine, N,N'-bis(3-aminophenyl) meta-xylene Indoleamine, 9,10-bis(4-aminophenyl)anthracene, 4,4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4- Aminophenoxy)phenyl]propane, 2,2'-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2'-bis(4-aminophenyl) Hexafluoropropane, 2,2'-bis(3-aminophenyl)hexafluoropropane, 2,2'-bis(3-amino-4-methylphenyl)hexafluoropropane, 2,2'- double( 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 -(3-Aminophenoxy)heptane, 1,8-bis(4-aminophenoxy)octane, 1,8-bis(3-aminophenoxy)octane, 1,9 - bis(4-aminophenoxy)decane, 1,9-double (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)undecane, 1,12-bis(4-aminophenoxy)dodecane, 1,12-bis(3-aminophenoxy)dodecane, bis(4-aminocyclohexyl)methane, bis(4-amino-3-methylcyclohexyl)methane, 1,3-two Aminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diamine Alkyl octane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

Further, as the other diamine compound, an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring or a heterocyclic ring may be used for the side chain of the diamine, and a large cyclic substituent having such a group may be further used. It is used without limitation to the effects of the present invention. Specific examples thereof include diamine compounds represented by the following formulas [DA1] to [DA13].

(In the formula [DA1]~Form [DA6], A ¹ represents -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO- or -NH-, A ² It is a linear or branched alkyl group having 1 to 22 carbon atoms or a linear or branched fluorine-containing alkyl group having 1 to 22 carbon atoms.

(In the formula [DA7], p represents an integer of 1 to 10).

(In the formula [DA10], m represents an integer of 0 to 3, and in the formula [DA13], n represents an integer of 1 to 5).

The diamine compound represented by the following formula [DA14] can also be used without departing from the effects of the present invention.

(In the formula [DA14], A ¹ is selected from the group consisting of -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -CH ₂ O-, -OCO-, -CON(CH) ₃ )- or -N(CH ₃ )CO-divalent organic group, A ² is a single bond, an aliphatic hydrocarbon group having 1 to 20 carbon atoms, a non-aromatic cyclic hydrocarbon group or an aromatic hydrocarbon group, and A ³ is selected from the group consisting of Single bond, -O-, -NH-, -N(CH ₃ )-, -CONH-, -NHCO-, -COO-, -OCO-, -CON(CH ₃ )-, -N(CH ₃ )CO -or-O(CH ₂ ) _m - (m is an integer of 1 to 5), A ⁴ is an aromatic heterocyclic ring containing nitrogen, and n is an integer of 1 to 4).

Further, as the other diamine compound, a diamine compound represented by the following formula [DA15] and formula [DA16] can be used.

As the other diamine compound, a diamine compound represented by the following formula [DA17] can be used.

(In the formula [DA17], X ₁ and X ₂ each independently represent a H atom, a methyl group or an ethyl group, and m represents an integer of 1 to 3).

The specific structure of the diamine compound represented by the formula [DA17] is shown below, but is not limited to these examples.

In other words, the diamine compound represented by the formula [DA17] may, for example, be a diamine compound having the structure represented by the following formula [DA17-1] to [DA17-6].

The other diamine compound may be used in combination with the solubility of a specific polymer of the present invention, the solubility of a liquid crystal alignment agent, the alignment property of a liquid crystal when a liquid crystal alignment film, a voltage retention ratio, and an accumulated charge. It can be used in two types or more.

<specific polymer>

The specific polymer contained in the liquid crystal alignment agent of the present invention is selected from the group consisting of the tetracarboxylic acid component containing the tetracarboxylic dianhydride represented by the above formula [1] and containing the side represented by the above formula [2]. The polyimine precursor obtained by the above diamine component of the chain diamine compound and at least one polymer of the polyimine obtained by imidization of the polyimine precursor.

The polyimine precursor obtained by reacting the tetracarboxylic acid component of the tetracarboxylic dianhydride represented by the above formula [1] with the aforementioned diamine component of the diamine compound having the side chain represented by the above formula [2] For example, it is a structure represented by the following formula [A].

(In the formula [A], R ¹ is a tetravalent organic group derived from a tetracarboxylic acid component, R ² is a divalent organic group derived from a diamine component, and A ¹ and A ² represent a hydrogen atom or an alkane having 1 to 8 carbon atoms. The groups may be the same or different, and A ³ and A ⁴ represent a hydrogen atom, an alkyl group having 1 to 5 carbon atoms or an ethyl fluorenyl group, each of which may be the same or different, and n represents a positive integer).

The specific polymer contained in the liquid crystal alignment agent of the present invention is a tetracarboxylic acid component represented by the following formula [B] and represented by the following formula [C]. Since the diamine compound is used as a raw material, it can be obtained relatively easily. From this reason, it is known that the polyaminic acid or the polyamic acid formed by the structural formula of the repeating unit represented by the following formula [D] is ruthenium imidized. Polyimine is preferred.

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

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

Further, in the general synthetic method, 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. An alkyl group or an ethylidene group having 1 to 5 carbon atoms of A ³ and A ^{4 is} shown.

<Method of Manufacturing Specific Polymer>

In the present invention, the specific polymer is such that the above diamine component and the above tetracarboxylic acid The acid component is obtained by a reaction. Specifically, a method of polycondensing a tetracarboxylic dianhydride with a diamine component to obtain a poly-proline, a method of dehydrating polycondensation of a tetracarboxylic acid and a diamine component to obtain a poly-proline, or a dicarboxylic acid can be used. A method in which an acid dihalide and a diamine component are polycondensed to obtain a polyamic acid.

In order to obtain a polyalkyl phthalate, a method of polycondensing a tetracarboxylic acid of a carboxylic acid group and a diamine component, and a polycondensation of a dialkyl ester of a carboxylic acid group by a polycondensation may be used. A method of converting an acid dihalide with a diamine component or a method of converting a carboxyl group of a polylysine to an ester.

To obtain a polyimine, a method of subjecting the aforementioned polyamic acid or polyalkyl amide to ring closure to obtain a polyimine can be used.

The reaction of the diamine component and the tetracarboxylic acid component is generally carried out by using a diamine component and a tetracarboxylic acid component in an organic solvent. The organic solvent used at this time is not particularly limited as long as it can dissolve only the produced polyimide precursor. Specific examples of the organic solvent used in the reaction are listed below, but are not limited thereto.

For example, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylacetamide, Dimethyl sulfonium, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone, 4-hydroxy-4-methyl-2-pentanone or the following formula [ D-1]~ a solvent represented by the formula [D-3].

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

These can be used alone or in combination. Further, even if it is a solvent which does not dissolve the polyimide precursor, it can be used in the above solvent in the range in which only the produced polyimide intermediate precursor is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and further causes the polyimine precursor formed by the hydrolysis, it is preferred to use an organic solvent to be dried by dehydration.

When the diamine component and the tetracarboxylic acid component are reacted in an organic solvent, a solution in which a diamine component is dissolved or dissolved in an organic solvent is added, and a tetracarboxylic acid component is directly added or dispersed or dissolved in an organic solvent. A method of adding, a method of adding a diamine component to a solution in which a tetracarboxylic acid component is dispersed or dissolved in an organic solvent, or a method of adding a diamine component and a tetracarboxylic acid component in an interactive manner, etc., can be used. A method. Further, when a plurality of kinds of diamine components or tetracarboxylic acid components are used for the reaction, the reaction may be carried out in a mixed state in advance, or the reaction may be carried out in a separate order, and the low-molecular weight bodies of the respective reactions may be further mixed and reacted. polymer. The polymerization temperature at this time is any temperature selected from the range of -20 ° C to 150 ° C, preferably in the range of -5 ° C to 100 ° C. Also, the reaction can be carried out at any concentration. If the concentration is too low, it becomes difficult to obtain a polymer having a high molecular weight. If the concentration is too high, the viscosity of the reaction liquid is too high and it is difficult to uniformly stir. Therefore, it is preferably from 1 to 50% by mass, more preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

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. Similarly to the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the resulting polyimide precursor.

The polyimine of the present invention is a polyimine obtained by subjecting the polyimine precursor to ring closure, and a ring closure ratio (also referred to as a ruthenium imidation ratio) of the amidino group for the polyimide. It does not need to be 100%, and can be adjusted to suit the purpose or purpose.

As a method for carrying out the ruthenium imidization of the polyimide precursor, the hot hydrazide of the solution of the directly heated polyimide precursor or the catalyst added to the solution of the polyimide precursor may be added. The catalyst is imidized.

The temperature at which the polyimide precursor is thermally imidated in a solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the ruthenium imidization reaction is excluded. It is better to perform it outside the system.

The ruthenium imide of the polyimide precursor is imidized into a solution of the polyimide precursor, and the basic catalyst and the acid anhydride are added at -20 to 250 ° C, preferably at 0 to 180 ° C. Stir. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, of the prolyl group. The amount is 1 to 50 moles, preferably 3 to 30 moles, of the prolyl group. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is also preferred because it has moderate alkalinity in the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. When acetic anhydride is used, purification after completion of the reaction can be easily carried out, which is preferable. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyimine precursor or polyimine is recovered from the reaction solution of the polyimine precursor or the polyimine, only the reaction solution may be placed in a solvent to precipitate. Examples of the solvent used for the precipitation include methanol, ethanol, isopropyl alcohol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, toluene, benzene, water, and the like. . After the polymer precipitated by the solvent is filtered and recovered, it can be dried at normal temperature or under reduced pressure under normal pressure or reduced pressure. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times to reduce impurities (impurities) in the polymer. Examples of the solvent in this case include alcohols, ketones, and hydrocarbons. When three or more types of solvents selected from the group are used, the purification efficiency can be further improved, which is preferable.

The molecular weight of the specific polymer contained in the liquid crystal alignment agent of the present invention is determined by GPC (Gel Permeation Chromatography) in consideration of the strength of the obtained liquid crystal alignment film, workability at the time of formation of the liquid crystal alignment film, and coating property. The weight average molecular weight measured is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

<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, and contains a polymer component and a solvent, and is used for forming a coating solution of a polymer film.

As described above, in the liquid crystal alignment treatment agent of the present invention, as the polymer component, the specific polymer, that is, the polymer having the following polymer, is selected from the group consisting of the tetracarboxylic acid represented by the above formula [1]. Polyimide component obtained from a tetracarboxylic acid component of an anhydride and a diamine component having a diamine component containing a side chain compound represented by the above formula [2], and a polyimidine precursor obtained by the ruthenium imidization At least one of the quinone imines has a structure in which the physical pressure of the liquid crystal alignment film can be reduced when the liquid crystal is dropped, and has a structure having a high hydrophobicity. Therefore, as described in the following examples, the present invention can be provided. The alignment unevenness of the liquid crystal display element of the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent is improved, and the heat resistance of the excellent pretilt angle is improved.

In detail, the alignment unevenness of the liquid crystal display element is such that when the liquid crystal by the ODF method is dropped, physical pressure is applied to the liquid crystal alignment film, so that the vertical alignment of the liquid crystal may be lowered. Further, the adsorbed water or the impurities adhering to the surface of the liquid crystal alignment film may be removed by dropping the liquid crystal in the ODF step, which may be caused by the amount of adsorbed water or impurities in the liquid crystal dropping portion or the liquid crystal droplets contacting each other. The difference is produced. Here, the ODF method is a liquid crystal alignment film formed by directly dropping liquid crystal on a substrate.

The above specific content contained in the liquid crystal alignment treatment agent of the present invention Since the polymer has a methyl group derived from the tetracarboxylic dianhydride represented by the formula [1] in the main chain, it is flexible (soft), and when a liquid crystal alignment treatment agent is applied to a substrate, the specific polymer is easily moved to The surface layer of the coating film (finally the liquid crystal alignment film) (ie, the opposite side to the substrate). Further, since the specific polymer has a side chain represented by the formula [2] on the diamine compound having a side chain represented by the formula [2], the side chain represented by the formula [2] on the surface layer of the coating film or the liquid crystal alignment film is used. The density becomes higher. By shifting the specific polymer to the surface layer as described above, and the density of the side chain represented by the formula [2] in the surface layer is increased, the physical pressure on the liquid crystal alignment film at the time of liquid crystal dropping can be reduced.

On the other hand, when the specific polymer migrates to the surface layer and the density of the side chain represented by the formula [2] in the surface layer becomes high, the hydrophobicity of the liquid crystal alignment film becomes high. Further, by using the tetracarboxylic dianhydride represented by the formula [1], the liquid crystal alignment treatment agent is applied to the substrate, and the heat-induced imidization of the liquid crystal alignment treatment is easily performed, and the hydrophobicity of the liquid crystal alignment film is also changed. high. Thus, since it is a highly hydrophobic one, the amount of adsorbed water or impurities which are liquid crystal dropping parts etc. can be made uniform.

This result is presumed to be an improvement in alignment unevenness which is caused by the ODF method.

Especially for the PSA mode, when the liquid crystal containing a monomer (polymerizable compound) is dropped on the liquid crystal alignment film by the ODF method, when the liquid crystal is wet-diffused, the separation phenomenon of the monomer (also referred to as chromatographic imaging) is caused. When the PSA treatment is performed in this state, a region in which the pretilt angles of the liquid crystals are different is generated, and alignment unevenness is likely to occur. Among them, the PSA is a liquid crystal display element in which a liquid crystal molecule whose substrate is vertically aligned is subjected to an electric field and is responsive (vertical alignment mode), in advance of the liquid crystal group. A polymerizable compound is added to the product. Further, the polymerizable compound is a compound which is polymerized by at least one of an active energy ray and heat.

In the case of the PSA mode, the liquid crystal alignment treatment agent of the present invention has a higher hydrophobicity and can make the dispersion of the monomer uniform, thereby suppressing variations in the pretilt angle and improving alignment unevenness.

Further, it is presumed that when the specific polymer migrates on the surface layer and the density of the side chain represented by the formula [2] in the surface layer becomes high, the side chain represented by the formula [2] can be stabilized, and the heat resistance of the pretilt angle can be changed. Good.

On the other hand, the liquid crystal alignment treatment agent of the present invention has excellent printability, and a uniform coating film having no eye hole or uneven film thickness can be obtained.

The liquid crystal display element having the liquid crystal alignment film produced by using the liquid crystal alignment treatment agent of the present invention has no alignment defect due to misalignment, and has excellent thermal stability due to the pretilt angle, so that it has excellent reliability in display quality. Liquid crystal display element.

All of the polymer components in the liquid crystal alignment agent of the present invention may be specific polymers or may be mixed with other polymers. In this case, the content of the other polymer other than the above is 0.5% by mass to 15% by mass of the specific polymer, preferably 1% by mass to 10% by mass. The polymer other than this may, for example, be a polyimine imine or a polyimine which does not use the tetracarboxylic dianhydride represented by the above formula [1]. Further, examples thereof include an acrylic polymer, a methacrylic polymer, polystyrene, polyamine or polyoxyalkylene.

The solid content concentration in the liquid crystal alignment treatment agent of the present invention can be appropriately changed by setting the thickness of the liquid crystal alignment film formed, It is preferably 0.5 to 10% by mass, preferably 1 to 8% by mass. When the solid content concentration is less than 0.5% by mass, it is difficult to form a coating film which is uniform and free from defects, and if it is more than 10% by mass, the storage stability of the solution may be deteriorated. The solid component is a component which removes a solvent from a liquid crystal alignment treatment agent, and shows the above-mentioned specific polymer or other polymer other than this, and various additives mentioned later.

The organic solvent in the liquid crystal alignment treatment agent of the present invention is preferably from 70 to 99.9% by mass in terms of the content of the organic solvent from the viewpoint of forming a uniform liquid crystal alignment film by coating. The content can be appropriately changed by the thickness of the intended liquid crystal alignment film.

The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve only the organic solvent (also referred to as a good solvent) of the specific polymer. Specific examples of the good solvent are exemplified below, but are not limited thereto.

For example, N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, dimethyl fluorene, Γ-butyrolactone, 1,3-dimethyl-imidazolidinone, methyl ethyl ketone, cyclohexanone, cyclopentanone or 4-hydroxy-4-methyl-2-pentanone. Further, examples thereof include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and a solvent represented by the above formula [D-1] to formula [D-3]. These can be used alone or in combination.

Among them, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and γ-butyrolactone are preferably used. When the solubility of a specific polymer in a solvent is high, it is preferred to use a solvent represented by the above formula [D-1] to formula [D-3].

The good solvent in the liquid crystal alignment agent of the present invention is preferably 10 to 100% by mass based on the total amount of the solvent contained in the liquid crystal alignment treatment agent. Among them, 20 to 90% by mass is preferred. It is preferably 30 to 80% by mass.

In the liquid crystal alignment treatment agent of the present invention, an organic solvent (also referred to as a weak 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. Specific examples of the weak solvent are exemplified below, but are not limited to these examples.

For example, ethanol, isopropyl alcohol, 1-butanol, 2-butanol, isobutyl alcohol, tert-butyl alcohol, 1-pentanol, 2-pentanol, 3-pentanol, 2-methyl 1-butanol, isoamyl alcohol, tert-pentyl alcohol, 3-methyl-2-butanol, neopentyl alcohol, 1-hexanol, 2-methyl-1-pentanol, 2- Methyl-2-pentanol, 2-ethyl-1-butanol, 1-heptanol, 2-heptanol, 3-heptanol, 1-octanol, 2-octanol, 2-ethyl-1- Hexanol, cyclohexanol, 1-methylcyclohexanol, 2-methylcyclohexanol, 3-methylcyclohexanol, 1,2-ethanediol, 1,2-propanediol, 1, 3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3-butanediol, 1,5-pentanediol, 2-methyl Base-2,4-pentanediol, 2-ethyl-1,3-hexanediol, dipropyl ether, dibutyl ether, dihexyl ether, dioxane, ethylene glycol dimethyl ether , ethylene glycol diethyl ether, ethylene glycol dibutyl ether, 1,2-butoxyethane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol Ethyl ethyl 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, propyl carbonate, ethyl carbonate, 2-(A Oxymethoxy)ethanol, ethylene glycol monobutyl ether, ethylene glycol Monoisoamyl ether, ethylene glycol monohexyl ether, 2-(hexyloxy)ethanol, mercapto alcohol, diethylene glycol, propylene glycol, propylene glycol monobutyl ether, 1-(butoxyethoxy)propyl Alcohol, propylene glycol monomethyl ether acetate, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, tripropylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol single Ethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monoacetate, ethylene glycol diacetate, diethylene glycol monoethyl ether acetate, diethylene glycol Monobutyl ether acetate, 2-(2-ethoxyethoxy)ethyl acetate, diethylene glycol acetate, triethylene glycol, triethylene glycol monomethyl ether, triethyl Glycol monoethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropane Acid propyl, butyl 3-methoxypropionate, methyl lactate, ethyl lactate, milk n- propyl, n- butyl lactate, isopentyl lactate or the above formula [D-1] to Formula [D-3] FIG solvent.

Wherein 1-hexanol, cyclohexanol, 1,2-ethanediol, 1,2-propanediol, propylene glycol monobutyl ether or ethylene glycol monobutyl ether, or the above formula [D] The solvent represented by the formula [1-3] is preferably a solvent represented by the formula [D-3].

These weak solvents are preferably from 1 to 70% by mass based on the total of the organic solvent contained in the liquid crystal alignment agent. Among them, 1 to 60% by mass is preferred. More preferably, it is 5 to 60% by mass.

The liquid crystal alignment treatment agent of the present invention may contain an epoxy group, an isocyanate group or an oxetane in order not to impair the effects of the present invention. a crosslinkable compound of an alkyl group or a cyclic carbonate group, a crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group, a hydroxyalkyl group and a lower alkoxyalkyl group, or a polymerizable unsaturated bond a crosslinkable compound. These substituents or polymerizable unsaturated bonds must have two or more of the crosslinkable compounds.

Examples of the crosslinkable compound having an epoxy group or an isocyanate group include bisphenol acetone glycidyl ether, phenol varnish epoxy resin, cresol epoxide epoxy resin, triglycidyl isocyanurate, and tetraglycidyl alcohol. Aminodiphenyl, tetraglycidyl-m-xylenediamine, tetraglycidyl-1,3-bis(aminoethyl)cyclohexane, tetraphenylglycidyl ether, triphenyl shrinkage Glycerol ether, bisphenol hexafluoroacetic acid diglycidyl ether, 1,3-bis(1-(2,3-epoxypropoxy)-1-trifluoromethyl-2,2,2-three Fluoromethyl)benzene, 4,4-bis(2,3-epoxypropoxy)octafluorobiphenyl, triglycidyl-p-aminophenol, tetraglycidyl p-xylenediamine, 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-epoxy)) Propoxy)phenyl)-1-methylethyl)phenyl)ethyl)phenoxy)-2-propanol and the like.

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

Specifically, a crosslinkable compound represented by the formula [4a] to the formula [4k] disclosed on pages 58 to 59 of International Publication WO2011/132751 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 [5].

Specifically, a crosslinkable compound represented by the formula [5-1] to the formula [5-42] disclosed on pages 76 to 82 of International Publication WO2011/132751 can be mentioned.

The crosslinkable compound having at least one substituent selected from the group consisting of a hydroxyl group and an alkoxy group may, for example, be an amine-based resin having a hydroxyl group or an alkoxy group, and examples thereof include a melamine resin, a urea resin, and a hydrazine. Amine resin, glycoluril-formaldehyde resin, amber mercaptophthalamide-formaldehyde resin or ethylene urea-formaldehyde resin. Specifically, a hydrogen atom of an amine group may be used, which is a methylol or alkoxymethyl group or a melamine derivative, a benzoguanamine derivative, or a glycoluril. The melamine derivative or the benzoguanamine derivative may be present in two or three doses. These are preferably one or more than 6 or less methylol groups or alkoxymethyl groups per one triazine ring.

As such a melamine derivative or a benzoguanamine derivative As an example, each of the triazine rings of the sold product, MX-750 substituted by an average of 3.7 methoxymethyl groups, and each triazine ring is substituted by an average of 5.8 methoxymethyl groups. MW-30 (above is manufactured by Sanwa Chemical Co., Ltd.) or Cymel300, 301, 303, 350, 370, 771, 325, 327, 703, 712, etc. methoxymethylated melamine, Cymel 235, 236, 238, 212, 253, 254 and other methoxymethylated butoxymethylated melamine, Cymel 506, 508 and other butoxymethylated melamine, such as Cymel1141 containing carboxyl group methoxymethylated isobutoxymethylated melamine a methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1123, a methoxymethylated butoxymethylated benzoguanamine such as Cymel 1123-10, a butoxy group such as Cymel 1128 Benzobenzamide, a carboxyl group-containing methoxymethylated ethoxymethylated benzoguanamine such as Cymel 1125-80 (manufactured by Mitsui Cyanamide Co., Ltd.). Further, examples of the glycoluril include butoxymethylated glycoluril such as Cymel 1170, methylolated glycoluril such as Cymel 1172, and methoxymethylolated glycoluril such as Powder Link 1174.

Examples of the benzene or phenolic compound having a hydroxyl group or an alkoxy group include 1,3,5-glycol(methoxymethyl)benzene and 1,2,4-cis (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 on pages 62 to 66 of International Publication WO2011/132751 can be mentioned.

Examples of the crosslinkable compound having a polymerizable unsaturated bond include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, and three. a crosslinkable compound having three polymerizable unsaturated groups in a molecule such as (meth)acryloxyethoxy trimethylolpropane or glycerol polyglycidyl ether poly(meth)acrylate, and further examples thereof Ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, tetraethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol II Methyl) acrylate, polypropylene glycol di(meth) acrylate, butane diol di(meth) acrylate, neopentyl glycol di(meth) acrylate, ethylene oxide bisphenol A type II (A) Acrylate, propylene oxide bisphenol type di(meth) acrylate, 1,6-hexanediol di(meth) acrylate, glycerol di(meth) acrylate, pentaerythritol di(methyl) Acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, diethylene glycol diglycidyl ether di(meth)acrylate, o-benzene a crosslinkable compound having two polymerizable unsaturated groups in a molecule such as diglycidyl dicarboxylate di(meth)acrylate or hydroxypivalic acid neopentyl glycol di(meth)acrylate, and may also be mentioned 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 2-phenoxy-2-hydroxypropyl (methyl) Acrylate, 2-(methyl)propenyloxy-2-hydroxypropyl phthalate, 3-chloro-2-hydroxypropyl (meth) acrylate, glycerol mono(meth)acrylic acid A crosslinkable compound having one polymerizable unsaturated group in the molecule such as an ester, 2-(meth)acryloyloxyethyl phosphate or N-methylol (meth)acrylic acid decylamine.

Further, a compound represented by the following formula [7] can also be used.

(In the formula [7], E ₁ represents a group selected from the group consisting of a cyclohexane ring, a bicyclohexane ring, a benzene ring, a biphenyl ring, a terphenyl ring, a naphthalene ring, an anthracene ring, an anthracene ring or a phenanthrene ring. The group, E ₂ represents a group selected from the following formula [7a] or formula [7b], and n represents an integer of 1 to 4).

The above compound is an example of a crosslinkable compound, but is not limited thereto. In addition, the crosslinkable compound to be used in the liquid crystal alignment agent of the present invention may be one type or two or more types.

The content of the crosslinkable compound in the liquid crystal alignment agent of the present invention is preferably 0.1 to 150 parts by mass based on 100 parts by mass of all the polymer components. When the crosslinking reaction is carried out and the intended effect is exhibited, it is preferably 0.1 to 100 parts by mass, and particularly preferably 1 to 50 parts by mass, based on 100 parts by mass of all the polymer components.

When the liquid crystal alignment treatment agent of the present invention is used as a liquid crystal alignment film, the charge movement in the liquid crystal alignment film is promoted, and the compound which promotes discharge of the liquid crystal cell using the liquid crystal alignment film is added to the international public. It is preferred that the nitrogen represented by the formula [M1] to the formula [M156] disclosed on pages 69 to 73 of WO2011/132751 contains a heterocyclic amine compound. The amine compound may be directly added to the composition, or may be dissolved in a suitable solvent to a concentration of 0.1% by mass to 10% by mass, preferably 1% by mass to 7% by mass, and then preferably added. The solvent is not particularly limited as long as it can dissolve only the organic solvent of the specific polymer.

In the liquid crystal alignment treatment agent of the present invention, a compound which improves the film thickness uniformity 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. Further, a compound or the like which improves 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 rhodium-based surfactant, and a separator-based surfactant.

More specifically, for example, Eftop EF 301, EF 303, EF 352 (above, Tohkem Products Co., Ltd.), MEGAFACF 171, F173, R-30 (above, manufactured by Dainippon Ink Co., Ltd.), Florad FC430, FC431 (above, Sumitomo 3M Co., Ltd.), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (above, manufactured by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of all the polymer components contained in the liquid crystal alignment treatment agent.

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

Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymethane alkyl propyl triethylamine, N-trimethoxymethyl propyl propyl triethylamine, 10-trimethoxy carboxyalkyl -1,4,7-triazadecane, 10-triethoxycarbamido-1,4,7-triazadecane, 9-trimethoxycarbamido-3,6-diaza Heteroalkyl acetate, 9-triethoxycarbamido-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzene Methyl-3-aminopropyltriethoxydecane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxydecane, N- Bis(oxyethylene)-3-aminopropyltrimethoxyfluorene , N-bis(oxyethylene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-double (N , N-diglycidylaminomethyl)cyclohexane or N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and the like.

When the compound is adhered to the substrate, it is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, based on 100 parts by mass of all the polymer components contained in the liquid crystal alignment agent. When the amount is less than 0.1 part by mass, the adhesion improving effect cannot be expected. When the amount is more than 30 parts by mass, the storage stability of the liquid crystal alignment agent may be deteriorated.

In the liquid crystal alignment treatment agent of the present invention, the weak solvent, the crosslinkable compound, the compound which improves the film thickness uniformity or the surface smoothness of the liquid crystal alignment film, and the compound which adheres to the substrate can be added without damaging the present invention. Within the scope of the effects of the invention, a dielectric or a conductive material for the purpose of changing electrical characteristics such as dielectric constant or conductivity of the liquid crystal alignment film may be added.

<Liquid alignment film ‧ Liquid crystal display element>

The liquid crystal alignment treatment agent of the present invention is applied to a substrate and fired, and then subjected to alignment treatment by rubbing treatment or light irradiation, and can be used as a liquid crystal alignment film. Moreover, when it is a vertical alignment use etc., it can use as a liquid-crystal alignment film without the alignment process. The substrate to be used in this case is not particularly limited as long as it has a high transparency, and a plastic substrate such as an acrylic substrate or a polycarbonate substrate other than the glass substrate can be used. From the viewpoint of simplification of the steps, it is preferred to use a substrate such as an ITO electrode to be driven by liquid crystal. Further, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the single-sided substrate, and a material that reflects light such as aluminum can be used as the electrode at this time.

The coating method of the liquid crystal alignment treatment agent is not particularly limited. Screen printing, offset printing, flexographic printing or ink jet methods are generally carried out in the industry. Examples of the other coating method include a dipping method, a roll coating method, a slit coater method, a spinning method, and a spray method, and the like can be used for the purpose.

After the liquid crystal alignment agent is applied onto the substrate, it is preferably used in a solvent of a liquid crystal alignment treatment agent by a heating means such as a hot plate, a heat cycle type oven or an IR (infrared) type oven, at 30 to 300 ° C, preferably The solvent was evaporated at a temperature of 30 to 250 ° C to form a liquid crystal alignment film. When the thickness of the liquid crystal alignment film after firing is too thick, it is disadvantageous in the power consumption level of the liquid crystal display element. If it is too thin, the reliability of the liquid crystal display element may be lowered. Therefore, it is preferably 5 to 300 nm. More preferably, it is 10~100nm. When the liquid crystal is horizontally aligned or obliquely aligned, the liquid crystal alignment film after firing is treated by rubbing or polarized ultraviolet irradiation or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a liquid crystal cell is produced as a liquid crystal display element by a known method. To be exemplified, the liquid crystal layer disposed between the substrates and the liquid crystal layer disposed between the substrates and the liquid crystal alignment layer formed by the liquid crystal alignment treatment agent of the present invention disposed between the substrate and the liquid crystal layer A liquid crystal display element of a liquid crystal cell of a film. Examples of the liquid crystal display device of the present invention include a vertical alignment (VA) method, an IPS (In-Plane Switching) method, a twisted nematic (TN: Twisted Nematic) method, and an OCB alignment (OCB). :Optically Compensated Bend), etc., or PSA (Polymer Sustained Alignment). And LCD with The film may be provided on at least one of the two substrates.

As a method of producing a liquid crystal cell, a pair of substrates formed by preparing a liquid crystal alignment film can be exemplified, and a spacer is spread on a liquid crystal alignment film of a single substrate, and the other substrate is bonded so that the liquid crystal alignment film surface becomes inside, and the liquid crystal is decompressed. A method of injecting and sealing the film, or a method of laminating a liquid crystal on a liquid crystal alignment film surface of a spacer, and bonding the substrate to seal it. In the ODF method, the alignment unevenness is likely to occur. However, by using the liquid crystal alignment treatment agent of the present invention, even if the ODF method is used, the occurrence of alignment unevenness can be suppressed.

When a PSA type liquid crystal display element is produced, it has a step of irradiating ultraviolet rays while applying a voltage to a liquid crystal alignment film or a liquid crystal layer of a liquid crystal cell. Further, the liquid crystal display device of the PSA type is a liquid crystal material (liquid crystal composition) for polymerizing a polymerizable compound which is polymerized by at least one of an active energy ray and heat, and is applied to a liquid crystal cell. Those who are exposed to ultraviolet rays.

The polymerizable compound is a polymerizable compound having a photopolymerizable group at each of two terminals, and a group having a photopolymerization group represented by the following formula (IV), as shown by the following formula (III). A polymerizable compound having a terminal having a terminal to be photocrosslinked or a polymerizable compound having a photocrosslinking group at each of two terminals represented by the following formula (V). Further, in the following formulae (III) to (V), R ¹² is H or an alkyl group having 1 to 4 carbon atoms, and Z ¹ represents an alkyl group having 1 to 12 carbon atoms or an alkoxy group having 1 to 12 carbon atoms. a divalent aromatic ring or a heterocyclic ring substituted, Z ² represents a monovalent aromatic ring or a heterocyclic ring, and the monovalent aromatic ring or heterocyclic ring may be selected from an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms. Substituted by one or more substituents of the group, Q ¹ is a divalent organic group. Q ¹ represents a ring structure having a stretching phenyl group (-C ₆ H ₄ -), a stretching phenyl group (-C ₆ H ₄ -C ₆ H ₄ -) or a cyclohexyl group (-C ₆ H ₁₀ -). good. This is because the interaction with the liquid crystal is likely to become large.

Specific examples of the polymerizable compound represented by the formula (III) include the following polymerizable compounds. Wherein V is a single bond or -R ¹⁹ O-, and R ¹⁹ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R ¹⁹ O-, and R ¹⁹ is a linear chain. Or a branched alkyl group having 2 to 6 carbon atoms. Further, W is a single bond or -OR ²⁰ -, and R ²⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -OR ²⁰ -, and R ²⁰ is linear or branched. Alkyl groups having a carbon number of 2 to 6. Further, V and W may have the same structure or may be different, and if they are the same, they are easily synthesized.

Moreover, as another specific example of the polymerizable compound represented by the formula (III), a polymerizable compound of the following formula may be mentioned.

(wherein, V is a single bond or -R ¹⁹ O-, and R ¹⁹ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably -R ¹⁹ O-, and R ¹⁹ is straight a chain or a branched carbon group having 2 to 6 carbon atoms. Further, W is a single bond or -OR ²⁰ -, and R ²⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms, preferably - As shown by OR ²⁰ -, R ²⁰ is a linear or branched alkyl group having 2 to 6 carbon atoms. V and W may be the same or different structures, and are easily synthesized at the same time. Further, R ¹² is H or carbon number 1 ~4 alkyl)

The method for producing the polymerizable compound is not particularly limited. For example, the polymerizable compound represented by the following formula (1) can be synthesized by a combination of methods in organic synthetic chemistry. For example, 2-(bromomethyl) can be used using SnCl ₂ by the method proposed by Talaga et al., P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis, 530 (1990), as shown in the following reaction formula. Acrylic (2-(bromomethyl)propenoic acid) is synthesized after reaction with an aldehyde or a ketone. Amberlyst 15 is a strong acid ion exchange resin manufactured by Rohm and Haas Company.

(wherein R' represents a monovalent organic group)

Further, 2-(bromomethyl)acrylic acid can be represented by the following reaction formula by Ramarajan et al., K. Ramarajan, K. Kamalingam, DJO' Donnell and KDBerlin, Organic Synthesis, vol. 61, 56-59 (1983). The method is synthesized.

As a specific synthesis example, when a polymerizable compound represented by the above formula (1) wherein R is -R ¹ O- and W is -OR ² - and R ¹ and R ² are the same, the following reaction formula is shown. 2 methods.

Further, when the polymerizable compound represented by the above formula (1) is synthesized in which R ¹⁹ and R ²⁰ are different, a method represented by the following reaction formula can be mentioned.

When the polymerizable compound represented by the above formula (1) in which V and W are a single bond is synthesized, the method represented by the following reaction formula can be mentioned.

In the step of applying a voltage to the liquid crystal alignment film or the liquid crystal layer to produce a liquid crystal cell by irradiation with ultraviolet rays, for example, a liquid crystal alignment film and a liquid crystal layer are applied by applying a voltage between electrodes provided on the substrate. A method of applying an electric field and maintaining the electric field to irradiate ultraviolet rays. The voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The amount of ultraviolet light to be irradiated is, for example, 1 to 60 J, preferably 40 J or less, and when the amount of ultraviolet irradiation is small, the liquid crystal display can be suppressed. It is preferable that the reliability of the destruction of the member of the display element is lowered, and the manufacturing efficiency is improved by reducing the ultraviolet irradiation time. Further, the wavelength of the ultraviolet ray to be irradiated is, for example, 200 nm to 400 nm.

When the ultraviolet ray is irradiated to the liquid crystal alignment film or the liquid crystal layer, the polymerizable compound can be reacted to form a polymer, and the polymer can memorize the tilt direction of the liquid crystal molecules, thereby accelerating the obtained polymer. The response speed of the liquid crystal display element.

In the PSA mode, the monomer is contained by the ODF method. When the liquid crystal of the (polymerizable compound) is dropped on the liquid crystal alignment film, the separation phenomenon of the monomer is caused when the liquid crystal is wet-expanded, and when the PSA treatment is performed in this state, a region different from the pretilt angle of the liquid crystal is generated. In the liquid crystal display device of the present invention, the liquid crystal alignment treatment agent of the present invention can be used to suppress uneven alignment.

In the above-described PSA liquid crystal display device which is produced by containing a polymerizable compound in a liquid crystal forming a liquid crystal alignment film, the liquid crystal display device of the present invention may be such that the liquid crystal alignment agent is contained in the liquid crystal alignment agent. The component of the polymerizable group in which at least one of the wire and the heat is polymerized is contained in the producer (SC-PVA method). The component containing a polymerizable group polymerized by at least one of an active energy ray and heat includes a polymerizable compound which is the same as the PSA method described above, or a polymerizable property which is polymerized by at least one of an active energy ray and heat. Base polymer. In the case of the SC-PVA method, in the same manner as the above-described PSA method, there is a step of irradiating ultraviolet rays while applying a voltage to the liquid crystal alignment film or the liquid crystal layer of the liquid crystal cell. So on the liquid crystal alignment film or liquid When the ultraviolet layer is irradiated with ultraviolet light, the polymerizable compound or the polymer containing the polymerizable group reacts to form a polymer, whereby the tilt direction of the liquid crystal molecules can be memorized, so that the obtained liquid crystal display element can be accelerated. The speed of response.

A liquid crystal display element having a liquid crystal alignment film produced by using the liquid crystal alignment agent of the present invention has excellent misalignment thermal stability without uneven alignment unevenness, and thus has high reliability in display quality. Liquid crystal display element. It is especially useful for large-screen and high-definition LCD TVs.

[Examples]

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

The abbreviations used in the synthesis examples, Examples 1 to 15 and Comparative Examples 1 to 5 are as follows.

<tetracarboxylic acid component> (specific tetracarboxylic dianhydride)

A1: tetracarboxylic dianhydride represented by the following formula [A1]

(other tetracarboxylic dianhydride)

A2: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A2])

A3: bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride (tetracarboxylic dianhydride represented by the following formula [A3])

A4: tetracarboxylic dianhydride represented by the following formula [A4]

A5: tetracarboxylic dianhydride represented by the following formula [A5]

<Diamine component> (side chain diamine compound)

B1: 1,3-diamino-4-[4-(trans-4-n-heptylcyclohexyl)phenoxy Benzobenzene (diamine compound represented by the following formula [B1])

B2: 1,3-diamino-5-[4-(trans-4-n-heptylcyclohexyl)phenoxymethyl]benzene (diamine compound represented by the following formula [B2])

B3: 1,3-diamino-4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (shown in the following formula [B3]) Amine compound)

B4: 1,3-diamino-5-{4-[4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxymethyl}benzene (shown by the following formula [B4] Amine compound)

B5: specific side chain type diamine compound represented by the following formula [B5]

(other diamine compounds)

C1: m-phenylenediamine (diamine compound represented by the following formula [C1])

C2: p-phenylenediamine (diamine compound represented by the following formula [C2])

C3: 3,5-diamino benzoic acid (diamine compound represented by the following formula [C3])

C4: a diamine compound represented by the following formula [C4]

C5: a diamine compound represented by the following formula [C5]

C6: 1,3-diamino-4-octadecylbenzene (diamine compound represented by the following formula [C6])

<Crosslinking compound>

D1: YH-434L (made by Toki Chemical Co., Ltd.) (epoxy-based cross-linking compound)

D2: OXT-221 (made by East Asia Synthetic) (oxetane-based cross-linking compound)

D3: a crosslinkable compound represented by the following formula (hydroxylated phenol-based crosslinkable compound)

<organic solvent> (polar solvent)

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

G-BL: γ-butyrolactone

(other organic solvents)

BCS: 2-butoxyethanol

PB: propylene glycol monobutyl ether

<Measurement of molecular weight of polyimine precursor and polyimine]

The molecular weight of the polyimine precursor and the polyimine in the synthesis example is a room temperature gel permeation chromatography (GPC) device (GPC-101) (manufactured by Showa Denko Co., Ltd.), and a column (KD-803, KD). -805) (manufactured by Shodex Co., Ltd.), and the measurement was carried out as follows.

Column temperature: 50 ° C

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

Flow rate: 1.0ml/min

The calibration curve was prepared using standard samples: 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 ruthenium rate of polyimine]

The oxime imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR (nuclear magnetic resonance) sample tube (NMR sampling standard tube, 5 (manufactured by Kusano Scientific Co., Ltd.), a solution of dimethyl hydrazine (DMSO-d6, 0.05% by mass of TMS (tetramethyl decane)) (0.53 ml) was added thereto, and ultrasonic waves were applied to completely dissolve them. This solution was measured for 500 MHz proton NMR by an NMR measuring machine (JNW-ECA500) (manufactured by JEOL Ltd.). The ruthenium imidization rate is determined by using a proton from a structure which does not change before and after imidization as a reference proton, and the peak value of the proton is used and the NH group derived from proline which is present in the vicinity of 9.5 ppm to 10.0 ppm. The proton peak product value is obtained by the following formula.

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

In the above formula, x is the proton peak product value derived from the NH group of proline, y is the peak integrated value of the reference proton, and α is one for the case of polyproline (the imidization ratio is 0%). The ratio of the number of reference protons of the NH proton of proline.

The polylysine and the polyimide of Synthesis Examples 1 to 15 are shown in Table 1.

<Synthesis Example 1>

A1 (3.44 g, 16.2 mmol), B1 (3.70 g, 9.73 mmol), C1 (2.45 g, 22.7 mmol) were mixed in NMP (28.1 g), and after reacting at 40 ° C for 5 hours, A2 (3.18 g) was added. 16.2 mmol) and NMP (23.0 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (A) having a solid concentration of 20.0% by mass. The polyamine has a number average molecular weight of 11,500 and a weight average molecular weight of 38,600.

<Synthesis Example 2>

NMP was added to the polyamic acid solution (A) (15.0 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1, and after diluting to 6 mass%, acetic anhydride (2.33) was added as a ruthenium catalyst. g), pyridine (1.21 g), and reacted at 40 ° C for 3 hours. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (B). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 10,980, and a weight average molecular weight of 33,200.

<Synthesis Example 3>

A1 (3.31 g, 15.6 mmol), B1 (3.56 g, 9.36 mmol), C4 (2.67 g, 21.8 mmol) were mixed in NMP (27.7 g), and after reacting at 40 ° C for 5 hours, A2 (3.06 g) was added. 15.6 mmol) and NMP (22.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

NMP was added to the obtained polyamic acid solution (20.5 g), and after diluting to 6% by mass, acetic anhydride (2.32 g) and pyridine (1.21 g) were added as a ruthenium catalyzed catalyst, and the mixture was carried out at 40 ° C for 3 hours. reaction. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (C). The polyimine had a hydrazine imidation ratio of 72%, a number average molecular weight of 11,800, and a weight average molecular weight of 32,400.

<Synthesis Example 4>

A1 (2.59 g, 12.2 mmol), B3 (3.70 g, 8.56 mmol), C2 (1.72 g, 15.9 mmol) were mixed in NMP (24.4 g), and after reacting at 40 ° C for 5 hours, A3 (3.06 g) was added. 12.2 mmol) and NMP (19.9 g) were reacted at 50 ° C for 5 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.03 g) and pyridine (1.04 g) as a ruthenium hydride catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (D). The polyimine had a hydrazine imidation ratio of 51%, a number average molecular weight of 12,100, and a weight average molecular weight of 35,200.

<Synthesis Example 5>

A1 (1.98 g, 9.35 mmol), B2 (4.61 g, 9.35 mmol), C3 (2.13 g, 14.0 mmol) were mixed in NMP (25.2 g), and after reacting at 40 ° C for 5 hours, A2 (2.75 g) was added. 14.0 mmol) and NMP (20.7 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass% in the obtained polyamic acid solution (15.1 g), acetic anhydride was added as a ruthenium amide catalyst. (2.04 g) and pyridine (1.05 g) were reacted at 40 ° C for 3 hours. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (E). The polyimine had a hydrazine imidation ratio of 70%, a number average molecular weight of 13,000, and a weight average molecular weight of 34,200.

<Synthesis Example 6>

A1 (1.34 g, 6.29 mmol), B4 (2.81 g, 6.29 mmol), C4 (1.79 g, 14.7 mmol) were mixed in NMP (19.4 g), and after reacting at 40 ° C for 5 hours, A2 (2.88 g) was added. 14.7 mmol) was reacted with NMP (15.9 g) at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (1.01 g) and pyridine (0.79 g) as a ruthenium catalyst, and 1.5 at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (F). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 14,200, and a weight average molecular weight of 35,100.

<Synthesis Example 7>

A1 (1.40 g, 6.60 mmol), B5 (3.79 g, 7.70 mmol), C3 (1.84 g, 12.1 mmol) were mixed in NMP (22.1 g) at 40 ° C After reacting for 5 hours, A2 (3.02 g, 15.4 mmol) and NMP (18.1 g) were added, and the reaction was carried out at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained polyamic acid solution (15.0 g) was added to acetic anhydride (2.01 g) and pyridine (1.04 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (G). The polyimine had a hydrazine imidation ratio of 53%, a number average molecular weight of 10,800, and a weight average molecular weight of 31,100.

<Synthesis Example 8>

A1 (2.54 g, 12.0 mmol), B1 (4.56 g, 12.0 mmol), C2 (1.94 g, 18.0 mmol) were mixed in NMP (28.7 g), and after reacting at 40 ° C for 5 hours, A4 (4.03 g) was added. 18.0 mmol) and NMP (28.7 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution (H) having a solid concentration of 20.0% by mass. The polyamine has a number average molecular weight of 12,900 and a weight average molecular weight of 36,300.

<Synthesis Example 9>

A1 (3.22 g, 15.2 mmol), B5 (4.99 g, 10.1 mmol), C5 (5.51 g, 40.5 mmol) were mixed in NMP (40.0 g), and reacted at 40 ° C for 5 hours, then A4 (7.94 g) was added. , 35.4mmol) with NMP (32.7 g), the reaction was carried out at 40 ° C for an hour to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline acid solution (15.0 g) was added to acetic anhydride (2.15 g) and pyridine (1.11 g) as a ruthenium amide catalyst, and 1.5 at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (I). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 12,200, and a weight average molecular weight of 33,700.

<Synthesis Example 10>

A1 (2.98 g, 14.1 mmol), B3 (6.08 g, 14.1 mmol), C4 (4.00 g, 32.8 mmol) were mixed in NMP (50.4 g), and reacted at 40 ° C for 5 hours, then A5 (9.84 g) was added. 32.8 mmol) and NMP (41.2 g) were reacted at 40 ° C for 8 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline acid solution (15.0 g) was added to acetic anhydride (1.88 g) and pyridine (1.00 g) as a ruthenium amide catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (J). The polyimine had a ruthenium iodide ratio of 74%, a number average molecular weight of 11,500, and a weight average molecular weight of 35,600.

<Synthesis Example 11>

A1 (3.40 g, 16.0 mmol), C6 (3.62 g, 9.61 mmol), C1 (2.42 g, 22.4 mmol) were mixed in NMP (19.8 g), and reacted at 40 ° C for 5 hours, then A2 (3.14 g) was added. 16.0 mmol) and NMP (16.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution (K) having a solid concentration of 20.0% by mass. The polyamic acid had a number average molecular weight of 12,100 and a weight average molecular weight of 32,000.

<Synthesis Example 12>

A1 (3.30 g, 15.6 mmol), C6 (3.51 g, 9.33 mmol), C4 (2.66 g, 21.8 mmol) were mixed in NMP (19.8 g), and after reacting at 40 ° C for 5 hours, A2 (3.05 g) was added. 15.6 mmol) and NMP (16.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.28 g) and pyridine (1.17 g) as a ruthenium hydride catalyst, and it was carried out at 40 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (L). The polyimine had a ruthenium iodide ratio of 73%, a number average molecular weight of 12,000, and a weight average molecular weight of 29,100.

<Synthesis Example 13>

A2 (3.53 g, 18.0 mmol), B1 (2.05 g, 5.40 mmol), C1 (1.36 g, 12.6 mmol) were mixed in NMP (30.1 g), and the reaction was carried out at 40 ° C for 8 hours to obtain a solid concentration of 20.0. Mass% polyamine solution.

After adding NMP and diluting to 6 mass%, the obtained polyamic acid solution (15.0 g) was added to acetic anhydride (1.59 g) and pyridine (0.74 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to give a polyimine powder (M). The polyimine had a hydrazine imidation ratio of 50%, a number average molecular weight of 14,700, and a weight average molecular weight of 40,100.

<Synthesis Example 14>

A3 (1.51 g, 6.05 mmol), B4 (2.70 g, 6.05 mmol), C4 (1.73 g, 14.1 mmol) were mixed in NMP (19.2 g), and after reacting at 80 ° C for 5 hours, A2 (2.77 g) was added. 14.1 mmol) and NMP (19.2 g) were reacted at 40 ° C for 6 hours to obtain a polyamic acid solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (2.15 g) and pyridine (1.11 g) as a ruthenium catalyzed catalyst, and it was carried out at 40 ° C at 2.5 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol and dried under reduced pressure at 60 ° C. To polyimine powder (N). The polyimine had a hydrazine imidization ratio of 53%, a number average molecular weight of 13,800, and a weight average molecular weight of 37,700.

<Synthesis Example 15>

A3 (3.43 g, 13.7 mmol), B3 (4.15 g, 9.60 mmol), C2 (1.93 g, 17.8 mmol) were mixed in NMP (26.8 g), and reacted at 80 ° C for 5 hours, then A2 (2.69 g) was added. 13.7 mmol) and NMP (22.0 g) were reacted at 40 ° C for 6 hours to obtain a polyglycine solution having a solid concentration of 20.0% by mass.

After adding NMP and diluting to 6 mass%, the obtained poly-proline solution (15.0 g) was added to acetic anhydride (3.57 g) and pyridine (1.66 g) as a ruthenium catalyzed catalyst, and it was carried out at 50 ° C. Hour response. The reaction solution was poured into methanol (350 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 60 ° C to obtain a polyimine powder (O). The polyimine had a ruthenium iodide ratio of 52%, a number average molecular weight of 15,600, and a weight average molecular weight of 32,700.

<Example 1>

Polylysine solution (A) (9.03 g), NMP (8.91 g), and BCS (12.0 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 1 were mixed at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment. Agent (1). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 2>

The polyimine powder (B) (1.80 g) obtained in Synthesis Example 2, NMP (2.72 g), NEP (9.03 g), and BCS (16.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (2). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 3>

The polyimine powder (C) (1.80 g), NEP (13.2 g), BCS (7.50 g) and PB (7.53 g) obtained in Synthesis Example 3 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (3). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 4>

The polyimine powder (D) (1.81 g) obtained in Synthesis Example 4, NMP (7.41 g), NEP (9.10 g), BCS (6.00 g), and PB (6.04 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (4) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 5>

The polyimine powder (E) (1.79 g) obtained in Synthesis Example 5, NMP (4.20 g), NEP (11.9 g), and PB (11.9 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (5). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 6>

The polyimine powder (F) (1.80 g), NEP (7.20 g), G-BL (9.06 g) and BCS (12.0 g) obtained in Synthesis Example 6 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment. Treatment agent (6). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 7>

The polyimine powder (G) (1.80 g), NEP (13.2 g), G-BL (6.02 g), BCS (6.01 g), and PB (3.00 g) obtained in Synthesis Example 7 were subjected to 8 at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (7). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 8>

Polylysine solution (H) (9.00 g), G-BL (9.00 g), BCS (6.04 g), and PB (6.00 g) having a solid content concentration of 20.0% by mass obtained in Synthesis Example 8 were carried out at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (8). No turbidity or precipitates were observed in the liquid crystal alignment agent The abnormal image is confirmed to be a homogeneous solution.

<Example 9>

The polyimine powder (I) (1.80 g), NMP (14.7 g) and BCS (13.5 g) obtained in Synthesis Example 9 were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (9). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 10>

The polyimine powder (J) (1.80 g) obtained in Synthesis Example 10, NMP (1.22 g), NEP (12.0 g), BCS (9.01 g), and PB (6.00 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (10) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 11>

The polyimine powder (B) (1.80 g), NMP (1.23 g), NEP (12.0 g), BCS (9.02 g), PB (6.03 g) and D1 (0.05 g) obtained in Synthesis Example 2 were in 25 The mixture was mixed for 8 hours at ° C to obtain a liquid crystal alignment treatment agent (11). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 12>

The polyimine powder (C) (1.80 g) obtained in Synthesis Example 3, G- BL (19.2 g), BCS (9.01 g), and D2 (0.05 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (12). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 13>

Polyimine powder (C) (1.80 g) obtained in Synthesis Example 3, NMP (8.70 g), G-BL (9.00 g), BCS (9.01 g), PB (9.00 g), and D3 (0.05 g) The mixture was mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent (13). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 14>

The polyimine powder (B) (1.05 g), NMP (2.00 g), G-BL (9.02 g), BCS (9.02 g), and PB (9.02 g) obtained in Synthesis Example 2 were subjected to 8 at 25 ° C. The mixture was mixed in an hour to obtain a liquid crystal alignment treatment agent (14). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Example 15>

The polyimine powder (C) (1.06 g) obtained in Synthesis Example 3, NMP (5.01 g), NEP (9.10 g), BCS (7.60 g), and PB (7.60 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (15) was obtained. No turbidity, precipitates, etc. were observed in the liquid crystal alignment agent An abnormal image was confirmed as a homogeneous solution.

<Comparative Example 1>

Polylysine solution (K) (9.03 g), NMP (9.30 g), and BCS (12.2 g) having a solid content concentration of 19.9% by mass obtained in Synthesis Example 11 were mixed at 25 ° C for 6 hours to obtain a liquid crystal alignment treatment agent. (16). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Comparative Example 2>

The polyimine powder (L) (1.80 g) obtained in Synthesis Example 12, NEP (13.2 g), BCS (7.52 g), and PB (7.50 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent. (17). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Comparative Example 3>

The polyimine powder (M) (1.80 g) obtained in Synthesis Example 13 and NMP (2.71 g) NEP (9.00 g) and BCS (16.5 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment treatment agent ( 18). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Comparative Example 4>

The polyimine powder (N) (1.80 g) obtained in Synthesis Example 14, NEP (7.25 g), G-BL (9.06 g), and BCS (12.0 g) were mixed at 25 ° C for 8 hours to obtain a liquid crystal alignment. Treatment agent (19). No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

<Comparative Example 5>

The polyimine powder (O) (1.80 g) obtained in Synthesis Example 15, NMP (7.19 g), NEP (9.00 g), BCS (6.00 g), and PB (5.99 g) were mixed at 25 ° C for 8 hours. A liquid crystal alignment treatment agent (20) was obtained. No abnormality such as turbidity or precipitates was observed in the liquid crystal alignment agent, and it was confirmed to be a homogeneous solution.

Using the liquid crystal alignment treatment agents obtained in Examples 1 to 15 and Comparative Examples 1 to 5, "production of liquid crystal cells (general liquid crystal cell)", "evaluation of heat resistance of pretilt angle (general liquid crystal cell)", and "electrical characteristics" were performed. (Evaluation of voltage holding ratio) (general liquid crystal cell), "production of liquid crystal cell, and evaluation of dispersibility of monomer (PSA cell)". This condition is as follows.

<Evaluation of heat resistance of liquid crystal cell production and pretilt angle (vertical alignment) (general liquid crystal cell)>

The liquid crystal alignment treatment agents obtained in Examples 1 to 15 and Comparative Examples 1 to 5 were spin-coated on an ITO surface of a substrate having a 30×40 mm ITO electrode, and heat-treated at 80° C. for 5 minutes on a hot plate to form a heat cycle type. Heat treatment at 230 ° C for 30 minutes in a dust-free oven to obtain a film thickness A substrate of 100 nm with a liquid crystal alignment film (polyimine film).

The obtained polyimide film surface was rubbed with a man-made fiber cloth using a friction device having a roll diameter of 120 mm at a roller rotation speed of 300 rpm, a roll speed of 20 mm/sec, and a pushing amount of 0.2 mm. The substrate of the liquid crystal alignment film.

Two sheets of the liquid crystal alignment film with the rubbed treatment were prepared, and the liquid crystal alignment film surface was placed inside, and a spacer of 40 μm was interposed, and the rubbing direction was combined in the opposite direction, and the cells were formed by adhering the sealant around the inside. In the empty cell, a liquid crystal MLC-2003 (manufactured by Merck Japan Co., Ltd.) was injected by a vacuum injection method, and an antiparallel alignment nematic liquid crystal cell was obtained by sealing the injection port.

The pretilt angle of the liquid crystal cell produced above was measured. Further, the liquid crystal cell was heated in a heat cycle type oven at 120 ° C for 24 hours, and then the pretilt angle was measured. Further, it was carried out using a tilt measuring device (model PAS-301 manufactured by ELSICON Co., Ltd.). The results are shown in Table 2.

<Production of Liquid Crystal Cell and Evaluation of Electrical Characteristics (General LCD Cell)>

The liquid crystal alignment treatment agents obtained in Examples 1 to 5 and Comparative Examples 3 and 5 were spin-coated on the ITO surface of a substrate having a 30×40 mm ITO electrode, and baked on a hot plate at 80° C. for 5 minutes in a heat cycle type. After heat-treating at 230 ° C for 30 minutes in a dust-free oven, a substrate having a polyimine liquid crystal alignment film having a thickness of 100 nm was obtained.

Prepare two pieces of the obtained substrate with the liquid crystal alignment film, and set the liquid crystal alignment film surface as the inner side, and combine them to sandwich the spacer of 6 μm. The sealant adheres to the surrounding area to create a hollow cell. MLC-6608 (manufactured by Merck Japan) was injected into the cell by a reduced pressure injection method, and a nematic liquid crystal cell was obtained by sealing the injection port.

In the liquid crystal cell produced as described above, a voltage of 1 V was applied at a temperature of 80 ° C for 60 μm, and a voltage after 16.67 ms and after 50 ms was measured, and how much voltage was maintained as a voltage holding ratio (VHR). . Further, the measurement was carried out using a VHR-1 voltage retention ratio measuring device (manufactured by Toyo Technica) at a setting of Voltage: ±1 V, Pulse Width: 60 μs, Flame Period: 16.67 ms, or 50 ms. After the irradiation of the ultraviolet ray of 50 J/cm ² in terms of 365 nm on the liquid crystal cell after the measurement of the voltage holding ratio was completed, the voltage holding ratio was measured under the same conditions as above. Further, ultraviolet irradiation was carried out using a desktop type UV curing device (HCT3B28HEX-1) (manufactured by Sen Light (SEN LIGHT CORPORATION)). The results are shown in Table 3.

<Production of Liquid Crystal Cell and Evaluation of Monomer Dispersibility (PSA Cell)>

The liquid crystal alignment treatment agents obtained in the examples 1 to 8 and the examples 12 to 15 and the comparative examples 1 to 5 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm, and the solution was stored at -15 ° C for 48 hours. Evaluation of monomer dispersion (PSA cells). This solution was spin-coated on a substrate (length 40 mm × width 30 mm, thickness 0.7 mm) and a center of an ITO electrode having a pattern of 20 × 10 mm in a pattern of 10 × 10 mm in a center washed with pure water and isopropyl alcohol (IPA). An ITO surface with a 10×40 mm ITO electrode substrate (40 mm in length × 30 mm in width, 0.7 mm in thickness) is attached to the hot plate. After heat treatment at 100 ° C for 5 minutes, a polyimide film having a film thickness of 100 nm was obtained. The surface of the coating film was washed with pure water, and then heat-treated at 100 ° C for 15 minutes in a heat cycle type dust-free oven to obtain a substrate with a liquid crystal alignment film.

On the liquid crystal alignment film surface of the substrate with the liquid crystal alignment film, a spacer of 4 μm was fixed, and a polymerizable compound represented by the following formula was added to a nematic liquid crystal (MLC-6608) (manufactured by Merck Japan Co., Ltd.). (1) A liquid crystal mixed with a nematic liquid crystal (MLC-6608) is dropped at 1 point, wherein a polymerizable compound (1) is 100% by mass of the nematic liquid crystal (MLC-6608). ) was 0.7% by mass, and the panel was bonded to the liquid crystal cell for evaluation of monomer dispersion after adhering to the surrounding with a sealant.

Where the monomer present in the liquid crystal cell exists due to resistance When it is lowered, when the obtained liquid crystal cell is supplied with a voltage of 5 V, the dispersed region of the monomer in the liquid crystal cell shows black. The dispersibility of the monomer can be evaluated by measuring the size of the circle of the black display produced when the voltage is applied. The results of measuring the diameter of the circle of the black display generated when the voltage was applied are shown in Table 2.

In addition, the liquid crystal alignment treatment agent obtained in each of Examples 9 to 11 was evaluated for the dispersibility of the monomer in the same manner as described above except that the polymerizable compound (2) was used instead of the polymerizable compound (1).

<Evaluation of inkjet coating property of liquid crystal alignment treatment agent>

The liquid crystal alignment treatment agent (14) obtained in Example 14 of the present invention and the liquid crystal alignment treatment agent (15) obtained in Example 15 were subjected to pressure filtration using a membrane filter having a pore diameter of 1 μm to evaluate inkjet coating properties. The inkjet coater was HIS-200 (manufactured by Hitachi Plant Technologies Co., Ltd.). The coating was applied to an ITO (Indium Tin Oxide) vapor-deposited substrate washed with pure water and IPA to have 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. The time of application to the dummy drying was 60 seconds, and the dummy drying was carried out on a hot plate at 70 ° C for 5 minutes. From the results, it was found that all the examples showed that no eye holes or pinholes were observed on the obtained liquid crystal alignment film, and a uniformly coated liquid crystal alignment film was obtained.

As a result of the above, it was found that the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 15 were compared with the liquid crystal alignment films obtained by the liquid crystal alignment treatment agents of Comparative Examples 1 to 5, respectively. It is widely dispersed. Therefore, it was confirmed that the hydrophobicity of Examples 1 to 15 was high and the alignment unevenness was small. Further, in the case of Comparative Example 2 in which Example 3 and Substituting B1 were both C6 and Comparative Example 2 which was the same as Example 3, it was confirmed that Example 3 has a very large monomer dispersibility. Further, in the evaluation of the liquid crystal alignment property, the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Examples 1 to 15 were compared with the liquid crystal alignment films obtained from the liquid crystal alignment treatment agents of Comparative Examples 1 to 5, and The change before and after the heating of the inclination angle is small, and the heat resistance of the pretilt angle is excellent.

In Comparative Example 3 to Comparative Example 5 which did not contain a specific tetracarboxylic dianhydride or Comparative Example 1 and Comparative Example 2 which did not contain a specific side chain type diamine compound, the monomer expansion was narrow, and the heat resistance of the pretilt angle was also inferior.

Further, as is clear from Table 3, the liquid crystal cell obtained from the liquid crystal alignment treatment agent of the example had a small decrease in voltage holding ratio even when exposed to ultraviolet light. Specific examples are the comparison between Example 1 and Comparative Example 3 which is the same as Example 1 except that A1 is not used, or Comparative Example 5 in which Example 4 and Example A are the same as Example 4 except that A1 is used instead of A1. . By using the liquid crystal alignment treatment agent of the present invention, a liquid crystal display element having excellent voltage retention and light resistance can be obtained. It is presumed that the liquid crystal alignment agent of the present invention contains a polymer (polyimine or polyimine precursor) containing the tetracarboxylic dianhydride represented by [1] as a raw material, so that firing is performed when a liquid crystal alignment film is formed. In the case where the structure of the tetracarboxylic dianhydride shown in [1] is crosslinked with a polymer or the like, ruthenium imidation is also caused between the polymer molecules, and the voltage holding ratio is excellent in light resistance.

[Industrial Applicability]

The liquid crystal alignment treatment agent of the present invention can provide a liquid crystal alignment film which is improved in alignment unevenness and excellent in heat resistance at a pretilt angle. Therefore, the liquid crystal display element having the liquid crystal alignment film obtained by the liquid crystal alignment treatment agent of the present invention can be excellent in reliability, and can be suitably used for a liquid crystal television or the like having a high definition in a large screen, and can be used for a TN element or an STN element. , TFT liquid crystal elements, especially for vertical alignment type liquid crystal display elements.

Claims (12)

A liquid crystal alignment treatment agent characterized by containing at least one polymer selected from the group consisting of polyiminoimine which is a tetracarboxylic acid containing a tetracarboxylic dianhydride represented by the following formula [1] a polyimine precursor obtained by reacting an acid component with a diamine component containing a diamine compound having a side chain represented by the following formula [2], and a polyimide obtained by hydrazine imidization; (In the formula [2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² Represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, Any hydrogen atom on the above cyclic group 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 having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms And an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms. The liquid crystal alignment treatment agent of claim 1, wherein the tetracarboxylic acid component is tetracarboxylic acid anhydride represented by the following formula [3]; (In the formula [3], Z ¹ is at least one tetravalent group selected from the following formula [3a] to formula [3j]); (In the formula [3a], Z ² to Z ⁵ represent a hydrogen atom, a methyl group, a chlorine atom or a benzene ring, and each may be the same or different. In the formula [3g], Z ⁶ and Z ⁷ represent a hydrogen atom or a methyl group. Each can be the same or different). The liquid crystal alignment treatment agent of claim 1, wherein the liquid crystal is used as a liquid crystal The solvent in the treating agent contains N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone or γ-butyrolactone. The liquid crystal alignment treatment agent of claim 1, wherein the solvent in the liquid crystal alignment treatment agent contains a solvent selected from the solvents of the following formula [D-1] to formula [D-3]; (In the formula [D-1], D ¹ represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-2], D ² represents an alkyl group having 1 to 3 carbon atoms, and in the formula [D-3], D ³ represents an alkyl group having 1 to 4 carbon atoms. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 1. A liquid crystal alignment film characterized by using the liquid crystal alignment treatment agent of claim 1, which is obtained by an inkjet method. A liquid crystal display element characterized by having a liquid crystal alignment film as claimed in claim 5 or claim 6. The liquid crystal alignment element of the liquid crystal display device of claim 5 or claim 6, wherein the liquid crystal display element is formed by a liquid crystal layer between a pair of substrates having electrodes, and is passed through the pair of substrates A liquid crystal composition containing a polymerizable compound polymerized by at least one of an active energy ray and heat is disposed between the electrodes, and a step of polymerizing the polymerizable compound is carried out while inputting a voltage between the electrodes. A liquid crystal display element characterized by having a liquid crystal alignment film of claim 8. The liquid crystal alignment element of the liquid crystal display element of claim 5 or claim 6, wherein the liquid crystal display element is formed by a liquid crystal layer between a pair of substrates having electrodes, and is passed through the pair of substrates A liquid crystal alignment film containing a polymerizable group polymerized by at least one of an active energy ray and heat is disposed between the electrodes, and a step of polymerizing the polymerizable group is performed while a voltage is input between the electrodes. A liquid crystal display element characterized by having the liquid crystal alignment film of claim 10. A polymer characterized by being at least one selected from the group consisting of polytetraimine which is a tetracarboxylic acid component containing a tetracarboxylic dianhydride represented by the following formula [1] and containing a polyimine precursor obtained by reacting a diamine component of a diamine compound having a side chain represented by the following formula [2], and a polyiminoimine precursor obtained by hydrazine imidization; (In the formula [2], Y ¹ represents a single bond, -(CH ₂ ) _a - (a is an integer of 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ² Represents a single bond or -(CH ₂ ) _b - (b is an integer from 1 to 15), Y ³ represents a single bond, -(CH ₂ ) _c - (c is an integer from 1 to 15), -O-, -CH ₂ O-, -COO- or -OCO-, Y ⁴ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a heterocyclic ring, or a divalent organic group having a carbon number of 17 to 51 having a steroid skeleton, Any hydrogen atom on the above cyclic group 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 having 1 to 3 carbon atoms. Substituted by an alkoxy group or a fluorine atom, Y ⁵ represents a divalent cyclic group selected from a benzene ring, a cyclohexane ring or a hetero ring, and any hydrogen atom on the ring group may be an alkyl group having 1 to 3 carbon atoms And an alkoxy group having 1 to 3 carbon atoms, a fluorine-containing alkyl group having 1 to 3 carbon atoms, a fluorine-containing alkoxy group having 1 to 3 carbon atoms or a fluorine atom, and n is an integer of 0 to 4, Y ⁶ represents an alkyl group having 1 to 18 carbon atoms, a fluorine-containing alkyl group having 1 to 18 carbon atoms, an alkoxy group having 1 to 18 carbon atoms or a fluorine-containing alkoxy group having 1 to 18 carbon atoms.