TWI477554B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Description

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

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film formed from the liquid crystal alignment agent, and a liquid crystal display element comprising the same, wherein the liquid crystal alignment agent is selected from the group consisting of oxetane and thiopyran ( a heterocyclic compound having one or more heterocyclic structures of a group of thiirane), aziridine, and oxazoline, and a polyamic acid selected from the group consisting of polyamic acid and polypyridyl acid At least one of the amine acid derivatives is dissolved in a solvent.

The liquid crystal display element is used for various liquid crystal displays such as a viewfinder and a projection display of a video camera represented by a notebook personal computer or a desktop personal computer. The device has recently been used in television sets. In addition, it can also be used as a photoelectron related component such as a printer head, a Fourier transform element, and a light valve.

The liquid crystal display device usually includes: 1) a pair of substrates disposed opposite to each other, 2) electrodes formed on one surface or both surfaces of the pair of substrates, and 3) liquid crystals formed on opposite surfaces of the pair of substrates An alignment film and 4) a liquid crystal layer formed between the pair of substrates.

Conventional liquid crystal display elements, the mainstream of which is a display element using a nematic liquid crystal, 1) TN (Twisted Nematic) type liquid crystal display element which is twisted by 90 degrees, 2) usually twisted or more A 180 degree STN (Super Twisted Nematic) liquid crystal display device and 3) a TFT (Thin Film Transistor) liquid crystal display device using a thin film transistor are being put into practical use. These liquid crystal display elements have a drawback in that the angle of view of the image can be normally visually narrowed, and when viewed from an oblique direction, the brightness or contrast is lowered and the brightness of the halftone is reversed.

In recent years, the problem of the above-mentioned viewing angle has been improved by the following techniques of liquid crystal display elements: 1) a TN-TFT type liquid crystal display element using an optical compensation film, 2) a vertical alignment and an optical compensation film VA (Vertical Alignment, Vertical alignment type liquid crystal display element, 3) MVA (Multi-Horizon Vertical Alignment) type liquid crystal display element using vertical alignment and protrusion structure technology, or 4) transverse electric field mode IPS (In-Plane Switching) , planar switching) liquid crystal display device, 5) ECB (Electrically Controlled Birefringence) liquid crystal display device, 6) Optically Compensated Bend or Optically Self-Compensated Birefringence (OCB) type liquid crystal display device, etc. The improved technology is being put into practical use or research.

The development of the technology of liquid crystal display elements is achieved not only by improving the driving method or the element structure of these liquid crystal display elements, but also by improving the constituent materials used for the liquid crystal display elements. Among the constituent materials used for the liquid crystal display device, the liquid crystal alignment film is one of the important elements related to the display quality of the liquid crystal display device. With the improvement in the quality of the liquid crystal display device, the role of the liquid crystal alignment film has become important year by year.

The liquid crystal alignment film can be prepared from a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution obtained by dissolving polyacrylic acid or soluble polyimine in an organic solvent. After applying such a solution onto a substrate, film formation is carried out by heating or the like to form a polyimide film. Various liquid crystal alignment agents other than polyglycolic acid have been studied, but in terms of heat resistance, chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment, electrical properties, optical properties, display properties, and the like, Almost unutilized.

In order to improve the display quality of the liquid crystal display element, important characteristics required for the liquid crystal alignment film include a voltage holding ratio. If the voltage holding ratio is low, there is a case where the voltage applied to the liquid crystal is lowered in the frame time, and as a result, the brightness is lowered, and the normal gray scale display is broken. Further, for example, the problem is that even if the initial voltage holding ratio is high, the voltage holding ratio (long-term reliability) after the high-temperature acceleration test is also lowered.

In an attempt to solve the above problems, several methods have recently been proposed.

1) A polyamic acid composition for forming a liquid crystal alignment film and combining two or more kinds of polyamic acid having different physical properties (for example, refer to Japanese Patent Laid-Open No. Hei 11-193345 and Japanese Patent Laid-Open Bulletin No. 11-193347).

2) A varnish composition containing a polymer component containing a poly-proline and a polyamine (for example, see International Publication No. 00/61684) is known.

3) A varnish composition containing two or more kinds of polyamic acids and polyamines having different physical properties and a solvent is known (for example, refer to International Publication No. 01/000733 pamphlet).

4) A varnish composition containing a polymer material containing a polyamine acid or the like synthesized using a diamine compound having a specific structure (for example, refer to JP-A-2002-162630).

5) A technique of adding a low molecular weight epoxy resin to a polyimide and a polyamidonic acid varnish is known (for example, refer to Japanese Laid-Open Patent Publication No. 2005-189270).

However, among these conventional techniques, there is still room for research on the problems of voltage holding ratio and long-term reliability.

In addition, a liquid crystal alignment agent containing a poly-proline and a hardening accelerator having an oxazoline structure is known (for example, refer to Japanese Laid-Open Patent Publication No. Hei 9-302225). However, this hardening accelerator evaporates, sublimes, and decomposes during the hydrazine imidation in the production of a liquid crystal alignment film, and the liquid crystal alignment film is used in the liquid crystal alignment film produced by using such a liquid crystal alignment film. The effects of the characteristics have not been studied.

In view of the above circumstances, it is desired to develop a liquid crystal alignment agent for a liquid crystal display element which improves the voltage holding ratio and long-term reliability, a liquid crystal alignment film formed therewith, and a liquid crystal display element having the same.

The inventors of the present invention have made an effort to solve the above problems.

As a result, it has been found that a liquid crystal display element having a liquid crystal alignment film which is produced by using a liquid crystal alignment agent containing oxetane and thiophene can be provided with good voltage retention and long-term reliability. a compound of one or two or more kinds of heterocyclic structures of sulphur, aziridine, and oxazoline, and one or more kinds of polylysine obtained by reacting a tetracarboxylic dianhydride with a diamine or a derivative thereof The invention thus completes the invention.

Further, it has been found that a liquid crystal alignment film produced by using the above liquid crystal alignment agent can be suitably applied to liquid crystal display elements of various display driving methods by appropriately selecting the above polyamic acid.

The present invention includes the following constitutions.

[1] A liquid crystal alignment agent containing a heterocyclic compound having one or two or more kinds of heterocyclic structures selected from the group consisting of oxetane, thiopyran, aziridine, and oxazoline, and One or two or more polymers selected from the group consisting of polyamic acid and derivatives thereof, which contain 0.1 to 50% by weight of the above heterocyclic compound with respect to the above polymer.

[2] The liquid crystal alignment agent according to the above [1], wherein the heterocyclic compound is a compound having two or more of the above heterocyclic structures.

[3] The liquid crystal alignment agent according to the above [1], wherein the heterocyclic compound is a polymer having the above heterocyclic structure in a side chain.

[4] The liquid crystal alignment agent according to [3] above, wherein the above polymer is a copolymer.

[5] The liquid crystal alignment agent according to any one of the above [1], wherein the polyamic acid is reacted with a tetracarboxylic dianhydride as an acid component and a diamine as an amine component. The resulting reaction product.

[6] The liquid crystal alignment agent according to the above [5], wherein the acid component contains the A component and the B component, the acid component A uses an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is selected from the group consisting of The compounds in the group consisting of the following structural formulae (1), (2), (5) to (7), and (14).

[7] The liquid crystal alignment agent according to the above [6], wherein the aromatic tetracarboxylic dianhydride is a compound of the above structural formula (1).

[8] The liquid crystal alignment agent according to [6] or [7], wherein the acid B component is either or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride.

[9] The liquid crystal alignment agent according to the above [8], wherein the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formulas (19), (23), and (25). And compounds in the group consisting of (35)~(37), (39), (44), and (49).

[10] The liquid crystal alignment agent according to the above [9], wherein the alicyclic tetracarboxylic dianhydride is a compound selected from the group consisting of the above structural formulas (19), (23) and (49).

[11] The liquid crystal alignment agent according to any one of the above [5], wherein the amine component contains the A component and the B component, and the amine component A is selected from the following formula (I). (VII) A diamine represented by the formula in the group of constituents.

[Chemical 3] H ₂ N-A ¹ -NH ₂ (I) (In the formula (I), A ¹ represents -(CH ₂ ) _m -. Here, m represents an integer of 1 to 12. Further, in the general formulae (III), (V), (VII), A ¹ Independently represents a single bond, -O-, -S-, -S-S-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF _{3 2} -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, or -S-(CH ₂ ) _m -S-. Here, m represents an integer of 1 to 12. Further, In the formula (VI), A ² independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or a carbon number of 1~ And an alkyl group bonded to the cyclohexane ring or the benzene ring in the formula (II) to (VII), which may be independently -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl substituted).

[12] The liquid crystal alignment agent according to the above [11], wherein the diamine of the above component A is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-). 16), a compound of the group consisting of (V-1) to (V-12), (V-33), (VII-1) and (VII-2).

[13] The liquid crystal alignment agent according to [11] or [12], wherein the component B of the amine is used in a group selected from the group consisting of the following general formulae (VIII) and (IX) to (XII) The diamine represented by the formula.

In the formula (VIII), R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or -(CH ₂ ) _e -, e is an integer of 1 to 6; R ² is a group having a steroid skeleton, a group represented by the formula (XIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group; When the carbon number is 2-6, any -CH ₂ - may be independently substituted by -O- (in which discontinuity), -CH=CH- or -C≡C-, and the hydrogen of the phenyl group may be independently Fluorine, methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy substituted.

In the formula (IX), R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -.

In the formula (X), R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen or an alkyl group having 1 to 30 carbon atoms; and R ^{5 is} independently a single bond, -CO- or -CH ₂ -; R ⁶ and R ^{7 are} independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group.

In the formula (XI), R ⁸ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be independently -O- (in which discontinuity), -CH=CH- or -C≡C-substituted; R ^{9 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; a is 0 or 1 ;b is 0, 1, or 2; and, c is independently 0 or 1.

In the formula (XII), R ¹⁰ is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms; R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or carbon The number is 1 to 30 fluorinated alkyl groups; R ^{12 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; and d is independently 0 or 1.

In the formula (XIII), R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and a carbon number. Is an oxyalkylene group of 1 to 3, or an alkyleneoxy group having a carbon number of 1 to 3 (wherein oxygen is discontinuously bonded); R ¹⁶ and R ^{17 are} independently hydrogen, fluorine or methyl; R ¹⁸ is Hydrogen, fluorine, chlorine, cyano group, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkoxyalkyl group having 2 to 30 carbon atoms, monofluoromethyl group, difluoro methyl, trifluoromethyl, a fluoromethoxy, difluoromethoxy or trifluoromethoxy group, the alkyl, alkoxy and alkoxyalkyl groups in any of the -CH ₂ - can be difluoromethyl Methylene group or substituted with a group represented by the formula (XIV); ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; f, g and h are independently an integer of 0-4 ;i, j, and k are independently integers from 0 to 3, and the sum of these is greater than or equal to 1; l and m are independently 1 or 2.

In the formula (XIV), R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are each} independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is an integer of 1 to 100.

[14] The liquid crystal alignment agent according to the above [13], wherein the diamine of the component B is selected from the following general formulae (VIII-2), (VIII-4), (VIII-5), (VIII- 6), a diamine represented by the formula in the group consisting of (XI-1), (XI-2), and (XI-6).

In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or An alkyl group having 1 to 20 carbon atoms.

[15] The liquid crystal alignment agent according to any one of [1] to [14] which contains two or more of the above polymers.

[16] The liquid crystal alignment agent according to any one of [1] to [15] further comprising an oxirane compound.

[17] A liquid crystal alignment agent comprising a heterocyclic compound having one or two or more kinds of heterocyclic structures of thiopyran and oxazoline, and polyglycine or a derivative thereof, characterized in that: The proline or a derivative thereof contains 1 to 40% by weight of the above heterocyclic compound, and the polylysine or a derivative thereof reacts a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. In the obtained reaction product, the tetracarboxylic dianhydride is either or both of the acid component A and the acid component B, and the acid component A is selected from the following structural formulae (1), (2), ( 5) One or more of the compounds in the group consisting of ~(7) and (14), and the B component of the acid is selected from the following structural formulas (19), (23), (25), (35)~ One or more of the compounds in the group consisting of (37), (39), (44), and (49), wherein the diamine is one or both of the A component of the amine and the B component of the amine, and the amine The component A is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), (V-33). a compound of the group consisting of (VII-1) and (VII-2) Or two or more kinds, the component B of the amine is selected from the following general formulae (VIII-2), (VIII-4), (VIII-5), (VIII-6), (XI-1), (XI-2) And one or more of the compounds represented by the formula in the group consisting of (XI-6).

[化12]

In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen or An alkyl group having 1 to 20 carbon atoms.

The liquid crystal alignment agent according to the above [17], wherein the tetracarboxylic dianhydride is either or both of the A component of the acid and the B component of the acid, and the A component of the acid is the above structure. The compound of the formula (1) wherein the component B of the acid is a compound selected from the group consisting of the above formulas (19), (23) and (49), wherein the diamine is the component A of the amine and the component B of the amine In either or both, the component A of the above amine is one of the compounds selected from the group consisting of the above structural formulas (IV-16), (V-1), (V-7) and (VII-2) or Two or more kinds of the above heterocyclic compounds are selected from the group consisting of N, N, N', N', - tetrathiopyranylmethyl-4,4'-diaminodiphenylethane, styrene-2-isopropene One or two or more kinds of compounds in the group consisting of the oxazoline copolymer and the 1,3-bis(4,5-dihydro-2-oxazolyl)benzene.

[19] The liquid crystal alignment agent according to the above [18], wherein the component B of the above amine is selected from the above formula (VIII-2), (VIII-5), (XI-1), (XI-2) And one or more of the compounds represented by the formula in the group consisting of (XI-6).

[20] The liquid crystal alignment agent according to any one of [17] to [19] further comprising an oxirane compound.

[21] The liquid crystal alignment agent according to the above [20], wherein the oxirane compound is a phenol-dicyclopentadiene resin type epoxy resin, and 2-(3,4-epoxycyclohexyl) Either or both of trimethoxy decane.

[22] A liquid crystal alignment film obtained by calcining a liquid crystal alignment agent according to any one of [1] to [21] to form a film state.

[23] A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one surface or both surfaces of the pair of substrates, and a liquid crystal alignment film formed on a surface of each of the pair of substrates The liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is the liquid crystal alignment film according to [22] above.

According to the present invention, it is possible to provide a liquid crystal display element of various driving methods, which has a high voltage holding ratio and good long-term reliability.

The liquid crystal alignment agent of the present invention is a composition containing a heterocyclic compound having one or more kinds of polylysine and a derivative thereof, and the above heterocyclic compound has a selected from the group consisting of oxetane, thiopyran and nitrogen propylene. One or two or more kinds of heterocyclic structures in the group consisting of pyridine and oxazoline.

<1. Heterocyclic Compound of the Present Invention>

The heterocyclic compound used in the present invention has one or two or more kinds of heterocyclic structures selected from the group consisting of oxetane, thiopyran, aziridine, and oxazoline. The above heterocyclic compound may have only one heterocyclic structure in one compound, or may have two or more heterocyclic structures. Further, the above heterocyclic compound may have one of the above heterocyclic structures in one compound, and preferably has two or more heterocyclic structures. Further, the heterocyclic compound may be a polymer having a heterocyclic structure in a side chain, or may be a copolymer. The polymer having a heterocyclic structure in a side chain may be a homopolymer of a monomer having a heterocyclic structure in a side chain, or a monomer having a heterocyclic structure in a side chain and having no heterocyclic structure. a copolymer of monomers. The copolymer having a heterocyclic structure in a side chain may be a copolymer of two or more kinds of monomers having a heterocyclic structure in a side chain, or may be a mixture of two or more kinds having a heterocyclic structure in a side chain. a copolymer of a body and a monomer having no heterocyclic structure.

The above specific heterocyclic structure has a hetero atom. The reason why the liquid crystal alignment agent having the specific heterocyclic compound has excellent voltage holding ratio and long-term stability is not clear, but it is considered to be in the hetero atom of the specific heterocyclic structure and polylysine in the specific heterocyclic compound. The carbonyl group is involved in the reaction. Therefore, it is preferred that the above specific heterocyclic ring structure is a structure which is present in a specific heterocyclic compound in such a manner that a hetero atom in a specific heterocyclic structure can react with a carbonyl group of polyphthalic acid.

a heterocyclic compound having an oxetane as a main heterocyclic structure (hereinafter also referred to as "oxetane compound") and a heterocyclic compound having a thiopyran as a main heterocyclic structure (hereinafter also referred to as " a thiopyran compound, a heterocyclic compound having an aziridine as a main heterocyclic structure (hereinafter also referred to as "aziridine compound"), and a heterocyclic compound having an oxazoline as a main heterocyclic structure (hereinafter also referred to as As the "oxazoline compound", a solvent which is soluble in polylysine and a derivative thereof is preferred.

Examples of the oxetane compound include EPICLON (trade name, manufactured by Dainippon Ink Chemical Industry Co., Ltd.), bis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and bis[ (3-ethyl-3-oxetanylmethoxy)methyl-phenyl]methane, bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]ether, bis[ (3-ethyl-3-oxetanylmethoxy)methyl-phenyl]propane, bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]indole, bis[ (3-ethyl-3-oxetanylmethoxy)methyl-phenyl]one, bis[(3-ethyl-3-oxetanylmethoxy)methyl-phenyl]hexafluoropropane, Tris[(3-ethyl-3-oxetanylmethoxy)methyl]benzene, and tetrakis[(3-ethyl-3-oxetanylmethoxy)methyl]benzene. Besides, an oligomer or a polymer having an oxetanyl group can also be mentioned.

The thiopyran compound may be exemplified by a method in which a glycidyl group in the following compound is substituted with sulfur according to a method disclosed in, for example, J. Org. Chem., 28, 229 (1963), to convert the following glycidyl group into a ring. Ethylene sulfide based; these glycidyl-based compounds are: phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl Propylene oxide, styrene oxide, Hexafluoropropylene oxide, cyclohexene oxide, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3 -[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, ethyleneglycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, Tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl , neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo neopentyl glycol diglycidyl ether, and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N' -tetraglycidyl-m-xylene, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4, 4'-Diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

The aziridine compound may, for example, be 2,4,6-tris(1'-aziridine)-1,3,5-triazine or ω-aziridinepropionic acid-2,2-dihydroxyl -butanol triesters, 2,4,6-tris(2-methyl-1-aziridine)-1,3,5-triazine, 2,4,6-tris(2-ethyl- 1-aziridinyl)-1,3,5-triazine, 4,4'-bis(ethylidenecarbonylamino)diphenylmethane, bis(2-ethyl-1-aziridine) Benzene-1,3-dimethylguanamine, tris(2-ethyl-1-aziridine)benzene-1,3,5-trimethylamine, bis(2-ethyl-1-nitrogen propylene) Pyridyl) indoleamine, 1,6-bis(ethylidenecarbonylamino)hexane, 2,4-diethylureate toluene, 1,1'-carbonyl- Bis-ethylimine, polymethylene-bis-ethylurea (C2~C4), and N,N'-bis(4,6-secondary ethylenediamine-1,3, 5-Triazin-2-yl)-1,6-hexanediamine. Besides, an oligomer or polymer having an aziridine group can also be mentioned.

The oxazoline compound may, for example, be 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, 4-furan-2-yl Methylene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis(4,5-di Hydrogen-2-oxazolyl)benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxo Oxazoline, 2,6-bis(isopropyl-2-oxazolin-2-yl)pyridine, 2,2'-isopropylidene bis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2, 2'-methylenebis(4-phenyl-2-oxazoline). In addition, a polymer or oligomer having an oxazolyl group such as EPOCROS (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned.

<2. Polymer of the present invention>

The above polymer in the present invention is one or two or more polymers selected from the group consisting of polylysine and derivatives thereof. Polylysine is a reaction product obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. In the present invention, such a polyaminic acid can be used.

Further, the polyproline in the present invention may contain a derivative thereof. The above-mentioned polyamine derivative is a form which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent to be described later, and when the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, polypyrmine may be formed as a main component. The composition of the liquid crystal alignment film. Examples of such derivatives of the polyproline include soluble polyimine, polyphthalamide, and polyamidamine, and more specifically, 1) all amine groups of polyamine Polyimine which is obtained by dehydration and ring-forming reaction with a carboxyl group, 2) partial polyimine which is partially dehydrated to form a cyclic reaction, and 3) polyperurate which is converted into an ester by a carboxyl group of poly-proline And 4) partially replacing one of the acid dianhydrides contained in the tetracarboxylic dianhydride compound with a poly-proline copolymer obtained by reacting an organic dicarboxylic acid, and 5) making the poly-proline- A polyamidoquinone imine obtained by partially or completely dehydrating a polyamine copolymer.

The above polylysine and its derivative can be obtained by a reaction of a tetracarboxylic dianhydride with a diamine. The tetracarboxylic dianhydride in the present invention is one or two or more kinds of tetracarboxylic dianhydrides, and one of the tetracarboxylic dianhydrides may be substituted with a dicarboxylic acid. Here, the ratio of the dicarboxylic acid to the tetracarboxylic dianhydride is preferably 10 mol% or less.

The diamine in the present invention is one or two or more kinds of diamines, and one part of the diamine may be substituted with a monoamine. Here, the ratio of the monoamine to the diamine is preferably 10 mol% or less.

The above tetracarboxylic dianhydride can be arbitrarily selected, and for example, 1) an aromatic tetracarboxylic dianhydride used as an A component of an acid, and 2) an aliphatic tetracarboxylic acid II used as an acid component B can be preferably used. Any one or two or more of an anhydride and an alicyclic tetracarboxylic dianhydride.

Further, in order to use the polyglycolic acid of the present invention as a component of the liquid crystal alignment agent, it is preferred to obtain a form soluble in a solvent. In order to prepare the polylysine of the present invention in the soluble form, it is preferred to appropriately select the tetracarboxylic dianhydride used as the acid component.

Here, as the specific example of the aromatic tetracarboxylic dianhydride which is used as the component A of the acid, the acid dianhydride represented by the following structural formulas (1) to (18) is exemplified. Among the following aromatic tetracarboxylic dianhydrides, acid dianhydrides represented by structural formulas (1), (2), (5), (6), (7), and (14) are more preferable. Most preferably, pyromellitic dianhydride represented by the structural formula (1) can be cited.

In addition, as the above-mentioned 2) aliphatic tetracarboxylic dianhydride or alicyclic tetracarboxylic dianhydride which is used as the component B of the acid, for example, acid dianhydride represented by the following structural formulas (19) to (67) is specifically exemplified.

The tetracarboxylic dianhydride is preferably an acid dianhydride represented by the structural formulas (19) to (39), (44), and (49), and more preferably a structural formula (19). The acid dianhydride represented by (23), (25), (35), (36), (37), (39), (44), and (49) is particularly preferably a structural formula (19). The acid dianhydride represented by (23) and (49) is particularly preferably 1,2,3,4-cyclobutanetetracarboxylic dianhydride represented by the structural formula (19).

Further, in order to prepare the polylysine in the present invention into a solvent-soluble polyimine, it is preferred to use structural formulas (24), (35) to (44), (49), (50). Acid anhydrides represented by (53) and (60).

In the tetracarboxylic dianhydride of the present invention, one of the tetracarboxylic dianhydrides represented by the structural formulae (1) to (67) may be used alone, or two or more of them may be used in combination. A liquid crystal alignment film formed by using a liquid crystal alignment agent containing polyamic acid to impart a particularly good voltage holding ratio to a liquid crystal display element containing the same, wherein the polyamic acid is an aromatic tetracarboxylic dianhydride, and An aliphatic tetracarboxylic dianhydride or an alicyclic tetracarboxylic dianhydride (particularly preferred is pyromellitic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride), which is Synthesis of tetracarboxylic dianhydride.

Further, in the tetracarboxylic dianhydride of the present invention, other tetracarboxylic dianhydrides other than the tetracarboxylic dianhydride represented by the structural formulae (1) to (67) may be used. The other tetracarboxylic dianhydride is arbitrary, and for example, a tetracarboxylic dianhydride having a side chain structure may also be mentioned. By using a liquid crystal alignment film formed of a liquid crystal alignment agent containing poly-proline, the pretilt angle of the liquid crystal display element containing the same can be increased, and the polyamic acid is a tetracarboxylic acid having a side chain structure. Anhydride is synthesized from the tetracarboxylic dianhydride in the present invention.

The tetracarboxylic dianhydride having a side chain structure is not particularly limited, and those having a steroid skeleton represented by the following structural formulae (68) and (69) can be preferably used in the present invention.

Further, the above-mentioned other tetracarboxylic dianhydride which can be used in the tetracarboxylic dianhydride of the present invention is not limited to the above tetracarboxylic dianhydride, and within the scope of achieving the object of the present invention, of course, various forms of tetracarboxylic acid exist. Acid dianhydride. Further, other tetracarboxylic dianhydrides may be used singly or in combination of two or more.

Further, a part of the tetracarboxylic dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with a carboxylic anhydride. The polymerization can be terminated by partially substituting one of the tetracarboxylic dianhydrides with the carboxylic acid anhydride, and the progress of the previous reaction can be suppressed, so that the molecular weight of the obtained polymer (polyglycine) can be easily controlled. The ratio of the carboxylic anhydride to the tetracarboxylic dianhydride is not particularly limited as long as the effect of the present invention is not impaired, and it is preferably 10 mol% or less of the target total amine amount.

As described above, the polyphthalic acid contained in the liquid crystal alignment agent of the present invention is obtained by reacting tetracarboxylic dianhydride with a diamine.

The above diamine can be arbitrarily selected, and a diamine represented by the general formulae (I) to (VII) is preferred.

H ₂ N-A ¹ -NH ₂ (I)

In the formula (I), A ¹ represents -(CH ₂ ) _m -. Here, m represents an integer from 1 to 12. Further, in the general formulae (III), (V), (VII), A ¹ independently represents a single bond, -O-, -S-, -S-S-, -SO ₂ -, -CO-, -CONH. -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, or -S-(CH ₂ ) _m -S-. Here, m represents an integer from 1 to 12. Further, in the formula (VI), A ² independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or the carbon number is 1 to 6 alkylene groups. Further, the hydrogen bonded to the cyclohexane ring or the benzene ring in the general formulae (II) to (VII) may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, - PO ₃ H ₂ , benzyl or 4-hydroxybenzyl.

Examples of the diamine represented by the formula (I) include diamines represented by the structural formulae (I-1) to (I-4).

Examples of the diamine represented by the formula (II) include diamines represented by the structural formulae (II-1) and (II-2).

Examples of the diamine represented by the formula (III) include diamines represented by the structural formulae (III-1) to (III-3).

Examples of the diamine represented by the formula (IV) include diamines represented by the structural formulae (IV-1) to (IV-16).

Examples of the diamine represented by the formula (V) include diamines represented by the structural formulae (V-1) to (V-33).

Examples of the diamine represented by the formula (VI) include diamines represented by the structural formulae (VI-1) to (VI-6).

The diamine represented by the formula (VII) may, for example, be a diamine represented by the structural formulae (VII-1) to (VII-16).

Among these, structural formulas (IV-1) to (IV-5), (IV-15), (IV-16), (V-1) to (V-12), and (V-) are more preferable. 26), (V-27), (V-31), (V-33), (VI-1), (VI-2), (VI-6), (VII-1) to (VII-5) The diamines represented by the formulae (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), Diamines represented by V-33), (VII-1), and (VII-2).

The diamine of the above formula (I) to (VII) may be used singly as the diamine of the present invention, and two or more kinds thereof may be used. In the diamine of the present invention, the molar ratio of the diamine represented by the above formulas (I) to (VII) is based on the structure of the diamine represented by the selected general formulae (I) to (VII), and The desired voltage holding ratio can be adjusted, preferably from 1 to 100%, more preferably from 5 to 80%.

As described above, the diamine of the present invention is preferably one or two or more kinds of diamines, particularly in applications requiring a large pretilt angle such as a VA type liquid crystal display element, an OCB type liquid crystal display element, or an STN type liquid crystal display element. A diamine having a side chain structure is used.

In the present specification, the term "diamine having a side chain structure" means a substituent having a branch of an autonomous chain and having a desired pretilt angle (side chain) when a substituent linking two amine groups is a main chain. Diamine. That is, a diamine having a side chain structure can be provided by reacting with a tetracarboxylic dianhydride to provide a polylysine or a polyimine having a side chain group with respect to a polymer main chain (branched polyamine) Or branch polyimine). The liquid crystal alignment film formed of a liquid crystal alignment agent containing a polyamic acid or a polyimine having a side chain group with respect to such a polymer main chain can increase the pretilt angle of the liquid crystal display element. The above-mentioned contents are disclosed, for example, in the above-mentioned Patent Document 1 (Japanese Patent Laid-Open No. Hei 11-193345).

Therefore, the side chain of the diamine having a side chain structure can be appropriately selected depending on the required pretilt angle. For example, the side chain is preferably a group having a carbon number of 3 or more. Specifically, 1) a phenyl group which may have a substituent, a cyclohexyl phenylene group which may have a substituent, a bis(cyclohexyl) phenylene group which may have a substituent, or an alkyl group having a carbon number of 3 or more a base, an alkenyl group, or an alkynyl group, 2) a phenoxy group which may have a substituent, a cyclohexyloxy group which may have a substituent, a bis(cyclohexyl)oxy group which may have a substituent, a phenylcyclohexyloxy group having a substituent, a cyclohexylphenoxy group which may have a substituent, or an alkoxy group, an alkenyloxy group or an alkynyloxy group having a carbon number of 3 or more, 3) a phenylcarbonyl group, or a carbon An alkylcarbonyl group, an alkenylcarbonyl group or an alkynylcarbonyl group having a number of 3 or more, 4) a phenylcarbonyloxy group, or an alkylcarbonyloxy group, an alkenylcarbonyloxy group or an alkynylcarbonyloxy group having a carbon number of 3 or more a group, 5) a phenoxycarbonyl group which may have a substituent, a cyclohexyloxycarbonyl group which may have a substituent, a bis(cyclohexyl)oxycarbonyl group which may have a substituent, and a bis(cyclohexyl)benzene which may have a substituent An oxycarbonyl group, a cyclohexyl bis(phenyl)oxycarbonyl group which may have a substituent, or an alkoxycarbonyl group, an alkenyloxycarbonyl group or an alkyne having a carbon number of 3 or more An oxycarbonyl group, 6) a phenylaminocarbonyl group, or an alkylaminocarbonyl group having a carbon number of 3 or more, an alkenylaminocarbonyl group, or an alkynylaminocarbonyl group, 7) a cyclic alkylene group having a carbon number of 3 or more a group, 8) a cyclohexylalkylene group which may have a substituent, a phenylalkylene group which may have a substituent, a bis(cyclohexyl)alkylene group which may have a substituent, a cyclohexylphenyl group which may have a substituent An alkyl group, a bis(cyclohexyl)phenylalkylene group which may have a substituent, a phenylalkoxy group which may have a substituent, an alkylphenoxycarbonyl group, or an alkylbiphenyloxycarbonyl group, 9) a phenyl or cyclohexyl group substituted with a fluorine-substituted alkyl group or an alkoxy group, and 10) two or more benzene rings or cyclohexane rings bonded by a single bond, or via -O-, -COO- , -OCO-, -CONH- or a cyclic polymer group bonded by an alkyl group, a fluorine-substituted alkyl group, or an alkoxy group bonded to an alkylene group having 1 to 3 carbon atoms, or a group having a steroid skeleton Etc., but not limited to this.

Here, examples of the "substituent group" include an alkyl group, an alkoxy group, or an alkoxyalkyl group.

Further, bis(cyclohexyl) or bis(phenyl) may be bonded through an alkylene group.

Further, in the present specification, when it is called "alkyl group", "alkenyl group" or "alkynyl group", it may be linear or branched.

Specific examples of the diamine having a side chain structure which can be used in the present invention include diamines represented by the formulae (VIII) and (IX) to (XII).

[Chem. 24]

Here, in the formula (XIII), R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or - (CH ₂ ) _e -, e is an integer of 1 to 6, and R ² is a group having a steroid skeleton, a group represented by the formula (VIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group. When the carbon number of the group is 2 to 6, any -CH ₂ - may be independently substituted by -O- (in which discontinuity), -CH=CH- or -C≡C-, and the hydrogen of the phenyl group may be independently Substituted by fluorine, methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy.

In the formula (IX), R ^{3 is} independently hydrogen or a methyl group, R ⁴ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ^{5 is} independently a single bond, -CO- or -CH ₂ -. Further, in the formula (X), R ^{3 is} independently hydrogen or a methyl group, R ⁴ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ^{5 is} independently a single bond, -CO- or -CH ₂ -, Further, R ⁶ and R ^{7 are} independently hydrogen, an alkyl group having 1 to 30 carbon atoms, or a phenyl group.

In the formula (XI), R ⁸ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be independently -O- (in which discontinuity), -CH=CH- or -C≡C-substituted, R ^{9 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, ring A is 1,4-phenylene or 1,4-cyclohexylene, a is 0 or 1 , b is 0, 1, or 2, and c is independently 0 or 1.

In the formula (XII), R ¹⁰ is an alkyl group having 3 to 30 carbon atoms or a fluorinated alkyl group having 3 to 30 carbon atoms, R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or The fluorinated alkyl group having a carbon number of 1 to 30, R ^{12 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and d is independently 0 or 1.

In the formula (XIII), R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and a carbon number. Is an oxyalkylene group of 1 to 3, or an alkyleneoxy group having a carbon number of 1 to 3 (wherein oxygen is discontinuously bonded); R ¹⁶ and R ^{17 are} independently hydrogen, fluorine or methyl; R ¹⁸ is Hydrogen, fluorine, chlorine, cyano group, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkoxyalkyl group having 2 to 30 carbon atoms, monofluoromethyl group, difluoro methyl, trifluoromethyl, a fluoromethoxy, difluoromethoxy or trifluoromethoxy group, the alkyl, alkoxy and alkoxyalkyl groups in any of the -CH ₂ - can be difluoromethyl Methylene group or substituted with a group represented by the formula (XIV); ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; f, g and h are independently an integer of 0-4 ;i, j, and k are independently integers from 0 to 3, and the sum of these is greater than or equal to 1; 1 and m are independently 1 or 2.

Here, in the general formula ^{(XIV), R 19, R} 20, R 21 and R ²² independently is an alkyl group having a carbon number of 1 to 10, or a phenyl group, and n is an integer of from 1 to 100.

The diamine represented by the formula (VIII) may, for example, be a diamine represented by the following formula or a structural formula (VIII-1) to (VIII-43).

In the formulae (VIII-1) to (VIII-11), R ^{23 is} preferably an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, more preferably a carbon number of An alkyl group of 5 to 25 or an alkoxy group having a carbon number of 5 to 25. Further, R ^{24 is} preferably an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, more preferably an alkyl group having 3 to 25 carbon atoms or a carbon number of 3 to 25 Alkoxy.

In the formulae (VIII-12) to (VIII-15), R ^{25 is} preferably an alkyl group having 4 to 30 carbon atoms, more preferably an alkyl group having 6 to 25 carbon atoms. In the general formulae (VIII-16) and (VIII-17), R ^{26 is} preferably an alkyl group having 6 to 30 carbon atoms, more preferably an alkyl group having 8 to 25 carbon atoms.

In the formulae (VIII-18) to (VIII-37), R ^{27 is} preferably an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, more preferably a carbon number of An alkyl group of 3 to 25 or an alkoxy group having a carbon number of 3 to 25. R ^{28 is} preferably -H, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , more Preferably, it is an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

Among these, a diamine represented by the general formula (VIII-1) to (VIII-11) is preferred. More preferably, the diamines represented by the general formulae (VIII-2), (VIII-4), (VIII-5), and (VIII-6) can be mentioned.

In the above formula (IX), it is preferred that one of the two "NH ₂ -Ph-R ⁵ -O-" is bonded to the 3-position of the steroid core and the other is bonded to the 6-position. Further, the two amine groups are bonded to the carbon of the phenyl ring, respectively, preferably to the meta or para position relative to the bonding position of R ⁵ .

Examples of the diamine represented by the formula (IX) include diamines represented by the structural formulae (IX-1) to (IX-4).

In the formula (X), two "NH ₂ -(R ⁷ -)Ph-R ⁵ -O-" are bonded to the carbon of the phenyl ring, respectively, preferably bonded to the steroid nucleus. Carbon, and bonded to the meta or para carbon. Further, the two amine groups are bonded to the carbon of the phenyl ring, respectively, preferably to the carbon of the meta or para position relative to R ⁵ .

Examples of the diamine represented by the formula (X) include diamines represented by the structural formulae (X-1) to (X-8).

[化34]

In the above formula (XI), the two amine groups are bonded to the carbon of the phenyl ring, respectively, preferably to the carbon of the meta or para position relative to R ⁹ .

The diamine represented by the formula (XI) may, for example, be a diamine represented by the formulae (XI-1) to (XI-8).

In the general formulae (XI-1) to (XI-3), R ^{29 is} preferably -H, an alkyl group having 1 to 30 carbon atoms, and is in the formula (XI-4) to (XI-8). R ^{30 is} preferably -H and an alkyl group having 1 to 20 carbon atoms.

In the above formula (XII), the two amine groups are bonded to the carbon of the phenyl ring, respectively, and are preferably bonded to the meta or para carbon with respect to R ¹² .

The diamine represented by the formula (XII) may, for example, be a diamine represented by the formula (XII-1) to (XII-3).

In the formula (XII-1) to (XII-3), R ^{31 is} preferably an alkyl group having 6 to 20 carbon atoms, and R ^{32 is} preferably an alkyl group having -H and a carbon number of 1 to 10 carbon atoms. .

In the diamine of the present invention, a diamine represented by the above formula (VIII) to (XII) may be used alone, or two or more kinds thereof may be used. The molar ratio of the diamine having a side chain structure in the diamine of the present invention can be adjusted according to the structure of the selected diamine having a side chain structure and the desired pretilt angle, preferably from 1 to 100%. The better is 10~100%.

Further, in the diamine of the present invention, a diamine represented by the general formulae (I) to (VII) and a diamine having a side chain structure represented by the general formulae (VIII) to (XII) may be used. amine. The other diamine is arbitrary, and examples thereof include a naphthalene-based diamine having a naphthalene structure, an fluorene-based diamine having a fluorene structure, or a decane-based siloxane having a siloxane bond. A diamine or a diamine having a side chain structure other than the general formulae (VIII) to (XII).

The oxirane-based diamine is not particularly limited, and those represented by the following formula (XV) can be preferably used in the present invention.

[化37]

In the formula (XV), R ³³ and R ^{34 each} independently represent an alkyl group having 1 to 3 carbon atoms or a phenyl group, and A ³ independently represents a methylene group, a phenylene group or a phenylene group substituted with an alkyl group. 1 represents an integer from 1 to 6, and m represents an integer from 1 to 10.

Further, the other diamine is not particularly limited, and in the present invention, for example, those represented by the following general formulae (1') to (8') can be preferably used.

In the general formulae (1') to (8'), R ³⁵ and R ³⁶ independently represent an alkyl group having 3 to 30 carbon atoms.

Further, the other diamines other than the general formulae (I) to (XII) used in the diamine of the present invention are not limited to the above diamines, and of course, various forms are possible within the scope of achieving the object of the present invention. Diamine. Further, the above other diamines may be used alone or in combination of two or more.

The diamine in the present invention can impart a good pretilt angle to the liquid crystal alignment film formed by using the liquid crystal alignment agent of the present invention by appropriately selecting the kind of the diamine and the combination thereof.

In many cases, in the case of a VA type liquid crystal display element, a large pretilt angle of about 80 to 90 degrees is required, and in the case of an OCB type liquid crystal display element, a pretilt angle of about 7 to 20 degrees is required, and a TN type is required. In the case of a liquid crystal display element or an STN type liquid crystal display element, a pretilt angle of about 3 to 10 degrees is required, and in the case of an IPS type liquid crystal display element, a small pretilt angle of about 0 to 3 degrees is required. Therefore, the liquid crystal alignment agent of the present invention which can appropriately adjust the pretilt angle by using a diamine having a side chain structure can be applied to any type of liquid crystal display element.

As described above, a part of the diamine used in the diamine of the present invention may be substituted with a monoamine. The polymerization can be terminated by partially replacing one of the diamines with a monoamine, and the progress of the previous reaction can be suppressed. Therefore, the molecular weight of the obtained polymer (polyglycine) can be easily controlled. The ratio of the monoamine to the diamine is not particularly limited as long as the effect of the present invention is not impaired, and it is preferably set to 10 mol% or less of the target total amine amount.

Further, the liquid crystal alignment agent of the present invention further contains an oxirane compound, and is preferable from the viewpoint of suppressing deterioration of storage characteristics of the liquid crystal display device of the present invention. The above oxirane compound is a compound having one or two or more oxiranyl groups. The oxirane compound can be a polymer. In the case of a polymer, the oxirane compound may be a homopolymer or a copolymer.

Examples of the oxirane compound include an ether type oxirane compound, a cyclic aliphatic oxirane compound, an ester type oxirane compound, an amine type oxirane compound, and a heterocyclic epoxy group. An alkyl compound, a decane type oxirane compound, an oxirane group-containing acrylic compound, or the like. As the oxirane compound, one type or two or more types of these oxirane compounds can be used.

Commercially available examples of the ether-type oxirane compound include Epikote 1001, Epikote 1002, Epikote 1003, Epikote 1004, Epikote 1007, Epikote 1009, Epikote 1010 (manufactured by Yuka Shell Epoxy Co., Ltd.), and Epikote 807 (Yuka Shell). Epoxy (manufactured by Epoxy Co., Ltd.), EPICLON HP-7200HH, EPICLON EXA-7260HH (manufactured by Dainippon Ink Co., Ltd.); commercially available cyclic aliphatic oxirane compounds, for example, CY-175, CY177, CY179 (manufactured by CIBA-GEIGY Co., Ltd.), ERL-4234, ERL-4299, ERL-4221, ERL-4206 (manufactured by UCC); commercially available ester-type oxirane compounds, for example, Shodyne 508 (Showa Electric ( (manufacturing)), Araldite CY-182, Araldite CY-192, Araldite CY-184 (manufactured by CIBA-GEIGY), Epikote 871, Epikote 872 (manufactured by Yuka Shell Epoxy), ED-5661, ED-5662 ( Celanese Coating (manufactured by Celanese Coating); an amine-type oxirane compound, for example, tetraglycidyldiaminediphenylmethane, triglycidyl-aminophenol, triglycidyl-aminophenol, Diglycidyl aniline, diglycidyl toluene Amine, tetraglycidyl meta-xylylenediamine, diglycidyltribromoaniline, tetraglycidyl bisaminomethylcyclohexane; a commercial product of a heterocyclic oxirane compound, for example, : Araldite PT810 (manufactured by CIBA-GEIGY Co., Ltd.), Epikote RXE-15 (manufactured by Yuka Shell Epoxy Co., Ltd.), EPITEC (manufactured by Nissan Chemical Co., Ltd.); decane-type oxirane compound, for example, (3- Glycidoxypropyl)trimethoxydecane, (3-glycidoxypropyl)methyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 5 6-epoxyhexyltriethoxydecane, (3-glycidoxypropyl)dimethylethoxydecane, (3-glycidoxypropyl)methyldiethoxydecane, and the like.

Examples of the other oxirane compound include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, and epoxy. Cyclohexane, N-glycidyl phthalimide, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N, N- Diglycidyl aniline, and 3-[2-(perfluorohexyl)ethoxy]-1,2-epoxypropane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol dihydrate Glycerol 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, and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N, N, N', N'-tetraglycidyl meta-xylene, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N '-tetraglycidyl-4,4'-diaminodiphenylmethane And 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

The polyproline and its derivatives of the present invention may have any weight average molecular weight. The weight average molecular weight of the above polyamic acid and its derivative is not particularly limited, and in the case of being used as a component of a liquid crystal alignment agent, it is preferably 5 × 10 ³ or more, more preferably 1 × 10 ^{4 or more.} . Polyamic acid having a weight average molecular weight of 5 × 10 ³ or more and a derivative thereof do not evaporate in the step of calcining the liquid crystal alignment film, and have better physical properties as a component of the liquid crystal alignment agent.

Here, the weight average molecular weight of polylysine and its derivative is measured by a gel permeation chromatography (GPC) method. For example, the obtained polyglycine and its derivative are diluted with dimethyl formamide (DMF) to have a polyglycine concentration of about 1 wt%, using Chromatopac C-R7A (Shimadzu Corporation) Manufactured by DMC as a developing solvent by a gel permeation chromatography (GPC) method and converted to polystyrene. Further, in order to carry out GPC measurement of polyacrylic acid or polyacrylic acid with good precision, a developing solvent is prepared, which is a mineral acid such as phosphoric acid, hydrochloric acid, nitric acid or sulfuric acid, or lithium bromide or chlorinated. An inorganic salt such as lithium is dissolved in a DMF solvent.

The polyaminic acid of the present invention and derivatives thereof can be produced by a known method. For example, one or two or more kinds of diamines represented by the general formulae (I) to (XII) are introduced into a reaction container having a raw material inlet, a nitrogen gas inlet, a thermometer, a stirrer, and a condenser, and are optionally selected from the group consisting of One or two or more kinds of diamines of other diamines, and further, a required amount of a monoamine may be added as needed.

Next, one or two or more kinds of a solvent (for example, N-methyl-2-pyrrolidone or dimethylformamide as a guanamine-based polar solvent) and a tetracarboxylic dianhydride are added, and further, if necessary The carboxylic anhydride is charged. In this case, the total amount of the tetracarboxylic dianhydride to be added is preferably about the same as the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The polylysine solution can be obtained by reacting for 1 to 48 hours at a temperature of 0 to 70 ° C under stirring. Further, it is also possible to increase the reaction temperature (for example, 50 to 80 ° C) by heating to obtain a polyglycine having a small molecular weight.

The polylysine of the present invention precipitates in a large amount of poor solvents, and completely separates the solid component and the solvent by filtration, etc., by infrared method (InfraRed, IR), nuclear magnetic resonance (NMR) Analyzed and identified. Further, after decomposing the solid polyamic acid in a strong alkaline aqueous solution such as KOH or NaOH, it is extracted with an organic solvent, and is subjected to gas chromatography (GC) and high performance liquid chromatography (high performance liquid chromatography). HPLC- or gas chromatograph-mass spectrometry (GC-MS) analysis can be used to identify the monomers used.

The obtained polyamic acid solution can be used after being diluted with a solvent in order to adjust to a desired viscosity.

Further, when the polyglycine of the present invention is made into a soluble polyimine which is a polyglycine derivative, it can be used as a dehydrating agent such as acetic anhydride, propionic anhydride, trifluoroacetic anhydride or the like. An acid anhydride, and a tertiary amine such as triethylamine, pyridine or collidine which are dehydrated to form a ring catalyst, and a polyamidic acid solution is subjected to hydrazine imidization at a temperature of 20 to 150 ° C. .

Alternatively, a large amount of a poor solvent (an alcohol solvent such as methanol, ethanol or isopropyl alcohol or a glycol solvent) may be used to precipitate the polyamic acid from the polyaminic acid solution, and to a solvent such as toluene or xylene. In the same manner, the dehydrating agent and the dehydration to a ring catalyst are used, and the precipitated polyaminic acid is subjected to a hydrazine imidization reaction at a temperature of 20 to 150 °C.

In the above hydrazine imidization reaction, the ratio of the dehydrating agent to the dehydration to the ring catalyst is preferably 0.1 to 10 (mole ratio). The total amount of the two is preferably 1.5 to 10 moles per mole of the total amount of the dianhydride contained in the tetracarboxylic dianhydride to be used. The degree of ruthenium imidization can be controlled by adjusting the chemical hydrazide dehydrating agent, the amount of the catalyst, the reaction temperature and the reaction time to obtain a partial polyimine.

The obtained polyimine may be separated from the solvent, and then redissolved in the solvent described later together with the above heterocyclic compound to be used as a liquid crystal alignment agent, or may be separated from the solvent, and the above heterocyclic compound may be added and used as a solvent. Liquid crystal alignment agent.

Further, as described above, a part of the acid dianhydride used in the tetracarboxylic dianhydride of the present invention may be substituted with an organic dicarboxylic acid. When the polydiamine acid of the present invention is produced using an organic dicarboxylic acid and a tetracarboxylic dianhydride, a poly-proline-polyamine copolymer can be obtained. Here, the ratio of the organic dicarboxylic acid to the tetracarboxylic dianhydride is not particularly limited as long as the effect of the present invention is not impaired, and the standard is preferably 10 mol% or less.

Further, the polyamidoquinone imine can be produced by chemically imidating the polyamine-polyamine copolymer.

<3. Liquid crystal alignment agent of the present invention>

The liquid crystal alignment agent of the present invention contains the above heterocyclic compound, the above polyamic acid of the present invention and a derivative thereof. The liquid crystal alignment agent of the present invention may further contain a solvent in view of adjustment of physical properties such as viscosity, ease of handling, and simplification of steps, and may further contain various additives contained in a usual liquid crystal alignment agent.

The content of the above-mentioned heterocyclic compound in the liquid crystal alignment agent is based on the weight of the polyglycine and its derivative in the liquid crystal alignment agent from the viewpoint of long-term stability of electrical properties when used in a liquid crystal display device. Preferably, it is 0.1 to 50 wt% of the total amount, more preferably 1 to 40 wt%, and particularly preferably 1 to 20 wt%.

The content of the above heterocyclic ring structure in the above heterocyclic compound in the liquid crystal alignment agent varies depending on the type of the heterocyclic ring structure. The content of the oxetane compound in the liquid crystal alignment agent is preferably such that when the oxetane structure in the oxetane compound is converted to oxetane, Its derivative is 0.1 to 40 wt%. Further, the content of the thiopyran compound in the liquid crystal alignment agent is preferably from 0.1 to 40% by weight based on the polypyridic acid and its derivative when the thiopyran structure in the thiopyran compound is converted to thiopyran. . Further, the content of the aziridine compound in the liquid crystal alignment agent is preferably 0.1 when the aziridine structure in the aziridine compound is converted to aziridine, and the polyproline and its derivative are 0.1. ~40 wt%. Further, the content of the oxazoline compound in the liquid crystal alignment agent is preferably 0.1 in terms of conversion of the oxazoline structure in the oxazoline compound to oxazoline, relative to polylysine and its derivative. ~40 wt%.

Further, when the heterocyclic compound contains two or more kinds of heterocyclic structures, the content of the heterocyclic ring structure in the liquid crystal alignment agent can be determined from the ratio of each heterocyclic ring structure in the heterocyclic compound.

The content of the oxirane compound in the liquid crystal alignment agent of the present invention is preferably in terms of ethylene oxide based on the viewpoint of suppressing deterioration of the storage characteristics of the liquid crystal display device of the present invention. The amine acid and its derivative are 1 to 20 wt%.

As the poly-proline and its derivative in the present invention, the above polylysine and its derivative can be used. For example, in the case of polylysine, a polyamic acid obtained by reacting the A component or the B component of the above acid with the A component or the B component of the above-mentioned amine, and the A component and the B component of the acid are Polylysine obtained by reacting the A component or the B component of the amine, polyamine acid obtained by reacting the A component or the B component of the acid with the A component and the B component of the amine, and the acid Polyamide or the like obtained by reacting the component A and the component B with the component A and the component B of the above amine.

The content of the polyamic acid and the derivative thereof in the liquid crystal alignment agent of the present invention can be appropriately selected depending on the method of applying the liquid crystal alignment agent onto the substrate. For example, a printing machine used in a manufacturing process of a liquid crystal display element (including an offset printing machine or an ink jet printer. Hereinafter, simply referred to as a "printing machine") is used. The content of the poly-proline and its derivative in the alignment agent is preferably from 0.5 to 30% by weight, more preferably from 1 to 15% by weight, based on the viscosity with the liquid crystal alignment agent (described later) The relationship is appropriately adjusted.

The solvent used in the present invention includes a solvent which is usually used in the production steps or uses of a polymer component such as polyaminic acid, soluble polyimine, and polyamidoximine, and can be used depending on the purpose of use. Make the appropriate choices. The solvent is preferably a mixed solvent containing the solvents of the following 1) and 2), wherein 1) is a readily soluble aprotic polar organic solvent for polyglycine or soluble polyimine, 2) is a change The surface tension is a solvent for the purpose of improving coatability and the like.

If these solvents are exemplified, they are as follows.

1) an aprotic polar organic solvent (hereinafter, an aprotic polar organic solvent) which is a good solvent for polyglycine or soluble polyimine: for example, N-methyl-2-pyrrolidone, dimethylimidazole Dimethyl imidazolidinone, methyl caprolactam, N-methylpropionamide, N,N-dimethylacetamide, dimethyl sulfoxide, N N-dimethylformamide, N,N-diethylformamide, diethylacetamide, γ-butyrolactone, valerolactone. Among these, N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, γ-valerolactone, and the like are more preferably exemplified.

2) A solvent (hereinafter, other solvent) for changing the surface tension to improve coating properties, etc.: for example, alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, or different Ethylene glycol monoalkyl ether such as isophorone or ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetate or B Dipropylene glycol monoalkane ether such as diol monophenyl ether acetate, triethylene glycol monoalkyl ether or propylene glycol monobutyl ether; dipropylene glycol dialkylate such as diethyl malonate; dipropylene glycol monomethyl ether An ester compound such as a monoalkyl ether or an acetate. Among these, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, and the like are more preferably exemplified.

The type and ratio of the aprotic polar solvent and the other solvent can be appropriately set in consideration of the printability, coatability, solubility, and storage stability of the liquid crystal alignment agent. The aprotic polar solvent is superior in solubility and storage stability to other solvents, and other solvents tend to be excellent in printability and coatability.

As described above, the liquid crystal alignment agent of the present invention may contain various additives. As the various additives, a polymer compound other than polyamine or a derivative thereof or a low molecular compound can be selected depending on the purpose.

For example, in the organic solvent, a soluble polymer compound can be used as an additive, and by adding these soluble polymer compounds, the electrical properties or alignment of the formed liquid crystal alignment film can be controlled. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, polyoxymethylene modified polyurethane, and polyoxygen modified Polyester, etc.

Further, an additive of a low molecular compound, for example, 1) may use a surfactant according to the purpose when it is desired to improve coatability, 2) an antistatic agent may be used when antistatic is necessary, and 3) a substrate is desired to be improved. A silane coupling agent or a titanium-based coupling agent can be used for the adhesion or rubbing resistance, and 4) a ruthenium-imiding catalyst can be used in the case of ruthenium imidization at a low temperature.

Examples of the above decane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxy. Baseline, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-amino Phenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, 3-chloropropylmethyldimethoxydecane , 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylene)-3 - (triethoxydecyl)-1-propylamine, N,N'-bis[3-(trimethoxydecyl)propyl]ethylenediamine, and the like.

For the above-mentioned quinone imidization catalyst, it is preferred to add an aliphatic amine such as trimethylamine, triethylamine, tripropylamine or tributylamine; N,N-dimethylaniline, N,N-diethyl Aromatic amines such as aniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, A catalyst such as a cyclic substituted amine such as an isoquinoline, a hydroxy-substituted isoquinoline, an imidazole, a methyl-substituted imidazole or a hydroxy-substituted imidazole. In particular, N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, isoquinoline and the like can be mentioned.

The amount of the decane coupling agent to be added is usually from 0 to 10% by weight, preferably from 0.1 to 3% by weight based on the total weight of the polymer.

The amount of the ruthenium-imidation catalyst added is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, per mole of the carbonyl group of the poly-proline and its derivative.

The amount of other additives to be added varies depending on the use thereof, and is usually from 0 to 30% by weight, preferably from 0.1 to 10% by weight based on the total weight of the polyamidamine and its derivative.

The viscosity of the liquid crystal alignment agent of the present invention varies depending on the method of application, the concentration of polyglycine and its derivatives, the type of polyphthalic acid and its derivatives used, and the type and ratio of the solvent. For example, in the case of coating with a printing machine, it is preferably 5 to 100 mPa. s (better 10~80 mPa.s). If less than 5 mPa. s, it is difficult to obtain a sufficient film thickness; if more than 100 mPa. s, the printing unevenness becomes larger. In the case of coating by spin coating, it is preferably 5 to 200 mPa. s (better 10~100 mPa.s).

The viscosity of the liquid crystal alignment agent is measured by a rotational viscosity measurement method, and can be measured, for example, using a rotary viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature: 25 ° C).

Another preferred embodiment of the liquid crystal alignment agent of the present invention is a composition containing two or more kinds of polyaminic acid and derivatives thereof. For example, the liquid crystal alignment agent contains two kinds of polyaminic acid; the polyamic acid obtained by reacting the tetracarboxylic dianhydride with the diamine having no side chain structure or a derivative thereof is made into polyamic acid I, When the polyamic acid obtained by reacting a tetracarboxylic dianhydride with a diamine having a diamine having a side chain structure or a derivative thereof is a polyamic acid II, the poly-proline I and the poly-proline II The composition can be prepared by mixing the above polyamic acid I with polyamic acid II. By using a liquid crystal alignment film formed of a liquid crystal alignment agent containing polyaminic acid I, a good voltage holding ratio can be imparted to a liquid crystal display element containing the same. By using a liquid crystal alignment film formed of a liquid crystal alignment agent containing polyphthalic acid II, a suitable pretilt angle can be imparted to a liquid crystal display element containing the same.

The weight ratio of the mixed polyaminic acid I to the polyamic acid II is preferably I/II = 99/1 to 50/50, more preferably I/II = 95/5 to 80/20. The weight ratio can be appropriately adjusted, for example, based on the obtained pretilt angle, and if the ratio of polyamine acid II is increased, the pretilt angle can be increased. As described above, in the present invention, even if two or more kinds of the above polymers (blend) are contained, it is possible to impart better characteristics as the liquid crystal alignment agent of the present invention.

<4. Liquid crystal alignment film of the present invention>

The liquid crystal alignment film of the present invention is obtained by calcining the polyamic acid in the liquid crystal alignment agent of the present invention to form a film of the liquid crystal alignment agent of the present invention.

In the liquid crystal alignment film, the liquid crystal alignment agent of the present invention can be applied, for example, to a substrate for a liquid crystal display element or a substrate for measurement such as calcium fluoride or barium, and the film of the liquid crystal alignment agent is heated to, for example, 150. It is formed at ~400 ° C, more preferably 180 to 280 ° C. Here, the film thickness of the liquid crystal alignment film is preferably from 10 to 300 nm, more preferably from 30 to 100 nm. Further, the liquid crystal alignment film is preferably subjected to rubbing treatment.

The film thickness of the liquid crystal alignment film can be adjusted by the viscosity of the liquid crystal alignment agent or the coating method of the liquid crystal alignment agent. Further, the film thickness of the liquid crystal alignment film can be measured by a well-known film thickness measuring device such as a profilometer or an ellipsometer. Further, the components in the liquid crystal alignment film may be subjected to hydrolysis or the like as necessary, and analyzed by a usual analysis means such as IR or MS.

<5. Liquid crystal display element of the present invention>

The liquid crystal display device of the present invention includes: 1) a pair of substrates disposed opposite to each other, 2) a liquid crystal alignment film of the present invention formed on a surface of the pair of substrates, and 3) sandwiched between the pair of substrates The liquid crystal layer.

The pair of electrode-attached substrates disposed opposite each other is preferably a transparent substrate (for example, a glass substrate).

Electrodes may be provided on the surface of at least one or both of the pair of substrates in accordance with the form of the liquid crystal display element. The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include indium tin oxide (ITO) or a vapor deposited film of a metal. The electrodes may be formed on the entirety of the surface of the substrate, for example, may be formed into a patterned specific shape. The liquid crystal alignment film of the present invention can be formed on the surface of the substrate on which the electrode is not provided, and the liquid crystal alignment film of the present invention can be formed on the electrode of the substrate on which the electrode is provided. The formation of the liquid crystal alignment film of the present invention is as described above.

The liquid crystal layer sandwiched between the pair of substrates contains a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and a liquid crystal composition having a positive dielectric anisotropy and a dielectric composition having a negative dielectric anisotropy may be used depending on the driving mode. Any composition.

An example of a preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (EP 885 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), and Japanese Patent Laid-Open No. Hei 8-199168 Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 (EP885271A1), and Japanese Patent Laid-Open No. Hei 10-204016 (EP844229A1) Japanese Patent Laid-Open No. Hei 10-204436, Japanese Patent Laid-Open No. Hei 10-231482, Japanese Patent Laid-Open Publication No. 2000-087040, and Japanese Patent Laid-Open No. 2001-48822.

A liquid crystal composition which can be used for a VA type liquid crystal display element can be made into various liquid crystal compositions which have a negative dielectric anisotropy. An example of a preferred liquid crystal composition is disclosed in Japanese Laid-Open Patent Publication No. Sho 57-114532, Japanese Patent Laid-Open No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, and Japanese Patent Laid-Open No. Hei 8-40953 Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei 10- No. Hei No. Hei No. Hei. Japanese Laid-Open Patent Publication No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei 10--237000, Japanese Patent Laid-Open No. Hei 10-237004 Japanese Laid-Open Patent Publication No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Laid-Open No. Hei 10-237076, Japanese Patent Laid-Open No. Hei 10-237448 Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10- Japanese Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Japanese Patent Laid-Open Publication No. 2001-192657, and the like.

One or more optically active compounds may be added to the liquid crystal composition having positive or negative dielectric anisotropy.

The liquid crystal display element of the present invention may of course contain other components.

For example, in a TFT liquid crystal element using a color display of a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, and the like are formed on the first transparent substrate, and the second transparent substrate may have A black matrix, a color filter, a planarization film, a pixel electrode, and the like that shield light other than the pixel region.

Further, in the VA liquid crystal display device, particularly the MVA liquid crystal display device, minute projections called domains are formed on the first transparent substrate. In addition, a spacer may be formed to adjust the cell gap between the substrates.

The liquid crystal display device of the present invention can be produced by any method, for example, by a method comprising the steps of: 1) applying a liquid crystal alignment agent to the above two transparent substrates, and 2) drying the applied liquid crystal alignment agent. Step, 3) in order to dehydrate the dried liquid crystal alignment agent. a step of performing a necessary heat treatment by a ring-forming reaction, 4) a step of aligning the obtained alignment film, 5) a step of laminating the two substrates, and sealing the liquid crystal between the substrates, or on a substrate After the liquid crystal is dropped, it is bonded to another substrate.

The coating method of the step of applying the liquid crystal alignment agent is known as a spin coating method, a printing method, a dipping method, a dropping method, an inkjet method, or the like. These methods are also applicable to the present invention.

Further, the drying step and the method of performing the necessary heat treatment step in the dehydration reaction are known as a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. . These methods are also applicable to the present invention. The drying step is preferably carried out at a lower temperature (50 to 140 ° C) in the range in which the solvent can be evaporated. The step of heat treatment is preferably carried out at a temperature of usually about 150 to 300 °C.

The alignment treatment of the liquid crystal alignment film is usually performed by rubbing treatment on an IPS type liquid crystal display element, an OCB type liquid crystal display element, a TN type liquid crystal display element, or an STN type liquid crystal display element. In the VA type liquid crystal display element, many of them are not subjected to rubbing treatment.

Next, an adhesive is applied to one of the substrates to be bonded, and liquid crystal is injected into the vacuum. In the case of the drop dropping method, the liquid crystal is dropped onto the substrate before bonding, and then bonded to the other substrate. The liquid crystal display element of the present invention is produced by curing with a bonding agent by heat or ultraviolet rays.

In the liquid crystal display device of the present invention, a polarizing plate (polarizing film), a wavelength plate, a light scattering film, a driving circuit, or the like can be mounted.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to the examples. Further, the names of the tetracarboxylic dianhydride, the diamine and the solvent used in the examples are represented by the following abbreviations.

[tetracarboxylic dianhydride] pyromellitic dianhydride {(1)}: PMDA 1,2,3,4-cyclobutane tetracarboxylic dianhydride {(19)}: CBDA butane tetracarboxylic dianhydride {(23)}: BDA 2,3,5-tricarboxycyclopentyl acetic acid dianhydride {(49)}: TCMP

[Diamine] 4,4'-diaminodiphenylmethane {Formula (V-1)}: DDM 4,4'-Diaminodiphenylethane {Formula (V-7)}: DET 4 , 4'-[1,3-propanebis(4,1-phenylenemethylene)]bis[aniline]{form(VII-2)}:BABZP3 2-(phenylmethyl)-1,4 -diaminobenzene {Formula (IV-16)}: PhPDA 5-[[4-(4'-pentyl[1,1'-bicyclohexyl]-4-yl)phenyl]methyl]-1 , 3-diaminobenzene {Formula (VIII-5) / R ²³ = C ₅ H ₁₁ }: 5ChCh 1,1-bis(4-((4-aminophenoxy)phenyl))-4- n-Pentylcyclohexane {Formula (XI-1) / R ²⁹ = C ₅ H ₁₁ }: 5HBA 1,1-bis(4-((4-aminophenyl)methyl)phenyl)-4- n-Heptylcyclohexane {Formula (XI-2) / R ²⁹ = C ₇ H ₁₅ }: 7HBZ 1,1-bis[(4-((4-aminophenoxy)phenyl))-4- n-Heptylcyclohexylethyl]cyclohexane {Formula (XI-6)/R ³⁰ =C ₇ H ₁₅ }:7H2HBA

[thiopyran]N,N,N',N'-tetrathiopyranylmethyl-4,4'-diaminodiphenylmethane: TMAP

[oxazoline compound] styrene-2-isopropenyl-oxazoline copolymer (manufactured by Nippon Shokubai Co., Ltd.: EPOCROS RPS-1005): PSO 1,3-bis(4,5-dihydro-2 -oxazolyl)benzene: BHO

[Ethylene oxide compound] Phenol-dicyclopentadiene (DCPD) resin type epoxy resin (manufactured by Dainippon Ink (E): EPICLON HP-7200HH): EPO 2-(3,4-epoxycyclohexyl Ethyltrimethoxydecane: EES

[Solvent] N-methyl-2-pyrrolidone: NMP butyl siroli (ethylene glycol monobutyl ether): BC γ-butyrolactone: GBL

<1. Synthesis of polyaminic acid>

[Synthesis of Polyamide] Synthesis Example 1 In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 1.676 g of 5ChCh, 1.792 g of PhPDA, and 58 g of dehydrated NMP were placed. The mixture was stirred and dissolved under a dry nitrogen stream. Then, 2.532 g of CBDA was added, and the reaction was carried out for 30 hours at room temperature. In the reaction, when the reaction temperature is raised, the reaction temperature is suppressed to about 70 ° C or lower to cause a reaction. To the obtained solution, 36 g of BC was added to synthesize a polyglycine solution (PA1) having a concentration of 6 wt%. The obtained PA1 had a weight average molecular weight of 37,000.

Here, the weight average molecular weight of the polyamic acid is obtained by diluting the obtained polyaminic acid to a polyglycine concentration by a dilution of (phosphoric acid/DMF=0.6/100:weight ratio). In the case of 1 wt%, Chromatopac C-R7A (manufactured by Shimadzu Corporation) was used, and the above diluted solution was used as a developing solvent, and it was measured by a GPC method and converted into polystyrene. Further, the column was measured using GF-7HQ (manufactured by Showa Denko Co., Ltd.) under the conditions of a column temperature of 50 ° C and a flow rate of 0.6 mL/min.

In Synthesis Examples 2 and 3, as shown in Table 1, the composition of the tetracarboxylic dianhydride, the diamine, and the solvent was changed, and in addition, the polyaminic acid solution (PA2, PA3) was synthesized in accordance with Synthesis Example 1. Synthesis Example 1 was included, and the results are summarized in Table 1.

Synthesis Example 4 In a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen inlet, 2.919 g of DDM, 54 g of dehydrated NMP, and 15 g of dehydrated GBL were placed, and the mixture was stirred and dissolved under a dry nitrogen stream. Next, 1.155 g of CBDA and 1.927 g of PMDA were added, and the mixture was reacted at room temperature for 30 hours. In the reaction, when the reaction temperature is raised, the reaction temperature is suppressed to be about 70 ° C or lower to cause a reaction. To the obtained solution, 25 g of BC was added to synthesize a polyglycine solution (PA4) having a concentration of 6 wt%. The obtained PA4 had a weight average molecular weight of 45,000.

Synthesis Examples 5 to 10 The composition of the tetracarboxylic dianhydride, the diamine and the solvent was changed as shown in Table 1, except that the polyaminic acid solution (PA5 to PA10) was synthesized in accordance with Synthesis Example 4. Synthesis Example 4 was included, and the results are summarized in Table 1.

<2. Manufacturing of liquid crystal display element>

[Example 1] A polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, Mix at a weight ratio of 1/9. To the obtained mixture, a thiol compound, i.e., TMAP, which is 5 wt% based on the weight of the polymer, is added. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 2] A polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, Mix at a weight ratio of 1/9. To the obtained mixture, 10 wt% of an oxazoline compound, i.e., PSO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 1] A polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution (PA2) having a concentration of 6 wt% synthesized in Synthesis Example 2, Mix at a weight ratio of 1/9. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and polyglycine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 2] A polyglycine solution (PA1) having a concentration of 6 wt% synthesized in Synthesis Example 1 and a polyglycine solution (PA3) having a concentration of 6 wt% synthesized in Synthesis Example 3, Mix at a weight ratio of 1/9. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and (polyglycine) was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

Method for Producing Liquid Crystal Display Element [Examples 1, 2 and Comparative Examples 1 and 2] A liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spin coater to form a film having a film thickness of 70 nm. . After coating, the film was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 220 ° C for 40 minutes. Then, the obtained polyimide film was subjected to a rubbing treatment to form a liquid crystal alignment film. The rubbing treatment was carried out using a friction treatment device RM02-9 manufactured by Iguchi Gauge Co., Ltd., and the friction amount of the rubbing cloth (hair length 1.9 mm: YA-18R type Rayon manufactured by Yoshikawa Chemical Co., Ltd.) was 0.40 mm. The obtained polyimide film was subjected to a rubbing treatment at a moving speed of 60 mm/sec and a roll rotation speed of 1,000 rpm.

The liquid crystal alignment film formed on the glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes.

Dispersing a gap material of 4 μm on a glass substrate, forming a surface of the liquid crystal alignment film as an inner side surface, and a pair of glass substrates forming a liquid crystal alignment film are arranged opposite each other in a rubbing direction, and then ringing An oxygen hardener seals the periphery of the liquid crystal alignment film to produce an antiparallel element having a gap of 4 μm. The liquid crystal composition I shown below was injected into the above gap of the element, and the injection port for the liquid crystal composition was sealed with a light hardener. Next, heat treatment was performed at 110 ° C for 30 minutes to produce a liquid crystal display element.

[39]

[Example 3] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, Mix at a weight ratio of 2/8. To the obtained mixture, 10% by weight of the oxazoline compound, that is, BHO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 4] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA6) having a concentration of 6 wt% synthesized in Synthesis Example 6, Mix at a weight ratio of 2/8. To the obtained mixture, 10% by weight of the oxazoline compound, that is, BHO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 5] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, Mix at a weight ratio of 2/8. To the obtained mixture, 10% by weight of the oxazoline compound, that is, BHO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 6] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, Mix at a weight ratio of 1/9. To the obtained mixture, 20% by weight of the oxazoline compound, that is, BHO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 7] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, Mix at a weight ratio of 2/8. To the obtained mixture, 10 wt% of an oxazoline compound, i.e., PSO, was added with respect to the weight of the polymer. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 8] In a polyglycine solution (PA8) having a concentration of 6 wt% synthesized in Synthesis Example 8, an oxazoline compound was added in an amount of 10 wt% based on the weight of the polymer. That is BHO. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 9] In a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, an oxazoline compound was added in an amount of 20 wt% based on the weight of the polymer. That is BHO. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 10] In a polyglycine solution (PA10) having a concentration of 6 wt% synthesized in Synthesis Example 10, an oxazoline compound was added in an amount of 10 wt% based on the weight of the polymer. That is BHO. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 11] In a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, an oxazoline compound was added in an amount of 10 wt% based on the weight of the polymer. That is PSO. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 12] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, Mix at a weight ratio of 2/8. In the obtained mixture, 10% by weight of the oxazoline compound, that is, BHO, based on the weight of the polymer, is added, and 10 wt% of the epoxy is added based on the weight of the polymer. The ethane compound is EPO. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Example 13] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, Mix at a weight ratio of 2/8. In the obtained mixture, 10% by weight of the oxazoline compound, that is, BHO, based on the weight of the polymer, is added, and 10 wt% of the epoxy is added based on the weight of the polymer. The ethane compound is EES. Thereafter, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and polylysine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 3] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA5) having a concentration of 6 wt% synthesized in Synthesis Example 5, Mix at a weight ratio of 2/8. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and polyglycine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 4] A polyglycine solution (PA4) having a concentration of 6 wt% synthesized in Synthesis Example 4 and a polyglycine solution (PA7) having a concentration of 6 wt% synthesized in Synthesis Example 7, Mix at a weight ratio of 2/8. A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to the obtained mixture, and polyglycine was diluted to 4 wt% with respect to the whole to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 5] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA9) having a concentration of 6 wt% synthesized in Synthesis Example 9, and polyglycine was added. The liquid crystal alignment agent was prepared by diluting to 4 wt% with respect to the whole. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

[Comparative Example 6] A mixed solvent of NMP/BC = 1/1 (weight ratio) was added to a polyglycine solution (PA10) having a concentration of 6 wt% synthesized in Synthesis Example 10, and polylysine was added. The liquid crystal alignment agent was prepared by diluting to 4 wt% with respect to the whole. Using the obtained liquid crystal alignment agent, a liquid crystal display element was produced as follows.

Method for producing a liquid crystal display device [Examples 3 to 13 and Comparative Examples 3 to 6] A liquid crystal alignment agent was applied onto two glass substrates with an ITO electrode by a spin coater to form a film having a film thickness of 70 nm. . After coating, the film was dried by heating at 80 ° C for about 5 minutes, and then heat-treated at 220 ° C for 20 minutes. Then, the obtained polyimide film was subjected to a rubbing treatment to form a liquid crystal alignment film. The friction treatment was carried out using a friction treatment device RM02-9 manufactured by Iguchi Gauge Co., Ltd., and the amount of hair squeezed in the friction cloth (hair length 1.9 mm: YA-18R Rayon manufactured by Yoshikawa Chemical Co., Ltd.) was 0.40. The obtained polyimide film was subjected to a rubbing treatment at a moving speed of 60 mm/sec and a roll rotation speed of 1,000 rpm.

The liquid crystal alignment film formed on the glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes.

Dispersing a gap material of 7 μm on one glass substrate, forming a surface of the liquid crystal alignment film as an inner side surface, and opposing a pair of glass substrates forming a liquid crystal alignment film in a reverse parallel manner, and then ringing An oxygen hardener seals the periphery of the liquid crystal alignment film to produce an antiparallel element having a gap of 7 μm. The liquid crystal composition II shown below was injected into the above gap of the element, and the injection port for the liquid crystal composition was sealed with a light hardener. Next, heat treatment was performed at 110 ° C for 30 minutes to produce a liquid crystal display element.

<3. Evaluation of electrical characteristics>

[Test Examples 1 to 19] The liquid crystal display elements produced in Examples 1 to 13 and Comparative Examples 1 to 6 were subjected to measurement of voltage holding ratio and long-term reliability.

1) Measurement of Voltage Retention Rate The measurement of the voltage holding ratio was carried out using a liquid crystal physical property evaluation device 6254 manufactured by Toyo Corporation (Toyo Corporation). Measurement conditions: gate width was 60 μs, frequency was 0.3 Hz, wave height was ±5 V, and measurement temperature was set to 60 °C. It is considered that the larger the value, the better the electrical characteristics. The results are shown in Table 2 and Table 3.

2-1) Measurement of long-term reliability [Test Examples 1 to 4] The voltage holding ratio was determined over time with respect to the liquid crystal display element to be produced, and the retention characteristics were evaluated. The test method for maintaining characteristics was to place the liquid crystal display element in an ambient gas having a temperature of 100 ° C for 100 hours, and take it out over time to measure the voltage holding ratio. It is considered that the decrease in the voltage holding ratio is smaller (for example, if the standing time is 100 hours or more under the above conditions, and the rate of reduction of the voltage holding ratio is less than 1%), the long-term reliability is better. The results are shown in Table 2. The reduction rate can be obtained according to the following formula.

Reduction rate (%) = (initial voltage retention rate - final voltage retention rate) / (initial voltage retention rate) × 100

2-2) Measurement of long-term reliability [Test Examples 5 to 19] With respect to the liquid crystal display element to be produced, the voltage holding ratio was determined over time to evaluate the retention characteristics. In the test method for maintaining characteristics, the liquid crystal display element was placed in an ambient gas at a temperature of 60 ° C for 500 hours, and taken out over time to measure the voltage holding ratio. It is considered that the decrease in the voltage holding ratio is smaller (for example, if the standing time is 500 hours or more under the above conditions and the rate of reduction of the voltage holding ratio is less than 2%), the long-term reliability is better. The results are shown in Table 3.

As shown in Tables 2 and 3, in the case of using a liquid crystal display element in which a liquid crystal alignment film of the compound disclosed above was used, deterioration of storage characteristics was remarkably suppressed. As a result, it is considered that the above-mentioned thiopyran compound and the above oxazoline compound have some effects such as a reaction with the above polylysine. Further, in consideration of the reactivity of the heterocyclic structure or the like, the above-described effects similar to those of the thiopyranium compound or the oxazoline compound can be expected even for the oxetane compound or the aziridine compound.

Further, in the liquid crystal alignment agent, when the oxirane compound is used in combination with the compound disclosed above, the storage characteristics of the obtained liquid crystal display element can be more significantly suppressed as compared with the case of using the compound disclosed above alone. Deterioration.

As described above, the liquid crystal alignment agent containing the polylysine of the present invention and the compound disclosed above has a high voltage holding ratio when the liquid crystal alignment film of the liquid crystal display element is formed, and the deterioration of the storage characteristics can be remarkably suppressed.

Claims (25)

A liquid crystal alignment agent containing a heterocyclic compound having one or two or more kinds of heterocyclic structures selected from the group consisting of oxetane, thiopyran, aziridine, and oxazoline, and a polyvalent compound selected from the group consisting of One or two or more polymers of valine and a derivative thereof are characterized in that they contain 0.1 to 50% by weight of the above heterocyclic compound with respect to the above polymer. The liquid crystal alignment agent according to claim 1, wherein the heterocyclic compound is a compound having two or more of the above heterocyclic structures. The liquid crystal alignment agent according to claim 1, wherein the above heterocyclic compound is a polymer having the above heterocyclic structure in a side chain. The liquid crystal alignment agent according to claim 3, wherein the polymer is a copolymer. The liquid crystal alignment agent according to claim 1, wherein the polyamic acid is a reaction product obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. The liquid crystal alignment agent according to claim 2, wherein the polyamic acid is a reaction product obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. The liquid crystal alignment agent according to claim 5, wherein the acid component contains the A component and the B component, the acid component A uses an aromatic tetracarboxylic dianhydride, and the aromatic tetracarboxylic dianhydride is selected from the group consisting of Compounds of the group consisting of structural formulae (1), (2), (5) to (7), and (14). [Chemical 1] The liquid crystal alignment agent according to claim 7, wherein the aromatic tetracarboxylic dianhydride is a compound of the above structural formula (1). The liquid crystal alignment agent according to claim 7, wherein the acid B component is either or both of an aliphatic tetracarboxylic dianhydride and an alicyclic tetracarboxylic dianhydride. The liquid crystal alignment agent according to claim 9, wherein the aliphatic tetracarboxylic dianhydride and the alicyclic tetracarboxylic dianhydride are selected from the following structural formulas (19), (23), and (25); Compounds in the group consisting of (35)~(37), (39), (44), and (49). The liquid crystal alignment agent according to claim 10, wherein the alicyclic tetracarboxylic dianhydride is a compound selected from the group consisting of the above structural formulas (19), (23) and (49). The liquid crystal alignment agent according to any one of claims 5 to 5, wherein the amine component contains the component A and the component B, and the component A of the amine is selected from the group consisting of the following formulas (I) to (VII). Diamine represented by the formula [Chemical 3]H ₂ N-A ¹ -NH ₂ (I) (In the formula (I), A ¹ represents -(CH ₂ ) _m -; wherein m represents an integer of 1 to 12; and, in the formula (III), (V), (VII), A ¹ Independently represents a single bond, -O-, -S-, -S-S-, -SO ₂ -, -CO-, -CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF _{3 2} -, -(CH ₂ ) _m -, -O-(CH ₂ ) _m -O-, or -S-(CH ₂ ) _m -S-; here, m represents an integer from 1 to 12; In the formula (VI), A ² independently represents a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or a carbon number of 1~ 6 alkylene; in addition, the hydrogen bonded to the cyclohexane ring or the benzene ring in the general formula (II) to (VII) can be independently used as -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ , benzyl or 4-hydroxybenzyl substituted). The liquid crystal alignment agent according to claim 12, wherein the diamine of the above component A is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-16). ), a compound in the group consisting of (V-1)~(V-12), (V-33), (VII-1), and (VII-2). The liquid crystal alignment agent according to claim 12, wherein the B component of the amine is a diamine represented by the general formula selected from the group consisting of the following general formula (VIII) and (IX) to (XII); (In the formula (VIII), R ¹ is a single bond, -O-, -CO-, -COO-, -OCO-, -CONH-, -CH ₂ O-, -CF ₂ O- or -(CH _{2 e} -, e is an integer of 1 to 6; R ² is a group having a steroid skeleton, a group represented by the formula (XIII), an alkyl group having 1 to 30 carbon atoms, or a phenyl group; When the number is 2-6, any of -CH ₂ - may be independently substituted by -O- (in which discontinuity), -CH=CH- or -C≡C-, and the hydrogen of the phenyl group may be independently fluorine. Methyl, methoxy, monofluoromethoxy, difluoromethoxy or trifluoromethoxy; in the general formula (IX), R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen or carbon number Is an alkyl group of 1 to 30; R ^{5 is} independently a single bond, -CO- or -CH ₂ -; in the formula (X), R ^{3 is} independently hydrogen or methyl; R ⁴ is hydrogen or has a carbon number of 1 the ~ 30 alkyl; R ⁵ is independently a single bond, CO- or -CH ₂ -; and, R ⁶ and R ⁷ are independently hydrogen, an alkyl group having a carbon number of 1 to 30, or a phenyl group; in the formula In (XI), R ⁸ is hydrogen or an alkyl group having 1 to 30 carbon atoms, and any -CH ₂ - of the alkyl group may be independently -O- (in which discontinuity), -CH =CH- or -C≡C-substituted; R ^{9 is} independently -O- or an alkylene group having 1 to 6 carbon atoms; ring A is 1,4-phenylene or 1,4-cyclohexylene; Is 0 or 1; b is 0, 1 or 2; and c is independently 0 or 1; in the formula (XII), R ¹⁰ is an alkyl group having 3 to 30 carbon atoms, or a carbon number of 3 to 30. A fluorinated alkyl group; R ¹¹ is hydrogen, an alkyl group having 1 to 30 carbon atoms, or a fluorinated alkyl group having 1 to 30 carbon atoms; and R ^{12 is} independently -O- or an alkylene group having 1 to 6 carbon atoms. Base; and, d is independently 0 or 1); (In the formula (XIII), R ¹³ , R ¹⁴ and R ^{15 are} independently a single bond, -O-, -COO-, -OCO-, -CONH-, an alkylene group having 1 to 4 carbon atoms, and a carbon number. Is an oxyalkylene group of 1 to 3, or an alkyleneoxy group having a carbon number of 1 to 3 (wherein oxygen is discontinuously bonded); R ¹⁶ and R ^{17 are} independently hydrogen, fluorine or methyl; R ¹⁸ is Hydrogen, fluorine, chlorine, cyano group, alkyl group having 1 to 30 carbon atoms, alkoxy group having 1 to 30 carbon atoms, alkoxyalkyl group having 2 to 30 carbon atoms, monofluoromethyl group, difluoro methyl, trifluoromethyl, a fluoromethoxy, difluoromethoxy or trifluoromethoxy group, the alkyl, alkoxy and alkoxyalkyl groups in any of the -CH ₂ - can be difluoromethyl Methylene group or substituted with a group represented by the formula (XIV); ring B and ring C are independently 1,4-phenylene or 1,4-cyclohexylene; f, g and h are independently an integer of 0-4 ;i, j, and k are independently integers from 0 to 3, and the sum of these is greater than or equal to 1; l and m are independently 1 or 2); (In the formula (XIV), R ¹⁹ , R ²⁰ , R ²¹ and R ^{22 are each} independently an alkyl group having 1 to 10 carbon atoms or a phenyl group, and n is an integer of 1 to 100). The liquid crystal alignment agent according to claim 14, wherein the diamine of the component B is selected from the following general formulae (VIII-2), (VIII-4), (VIII-5), (VIII-6). , a diamine represented by the formula in the group consisting of (XI-1), (XI-2), and (XI-6) (In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen. Or an alkyl group having a carbon number of 1 to 20). The liquid crystal alignment agent according to claim 1, which further contains an oxirane compound. The liquid crystal alignment agent according to claim 2, which further contains an oxirane compound. The liquid crystal alignment agent according to any one of claims 1 to 17, which contains two or more of the above polymers. A liquid crystal alignment agent containing a heterocyclic compound having one or two or more kinds of heterocyclic structures of thiopyran and oxazoline, and polyglycine or a derivative thereof, characterized in that: relative to the above polylysine Or a derivative thereof, which contains 1 to 40% by weight of the above heterocyclic compound, and the polylysine or a derivative thereof is a reaction obtained by reacting a tetracarboxylic dianhydride as an acid component with a diamine as an amine component. The product, the tetracarboxylic dianhydride is either or both of the acid component A and the acid component B, and the acid component A is selected from the following structural formulas (1), (2), and (5). (7) and (14) one or more of the compounds in the group of the constituents, and the B component of the acid is selected from the following structural formulas (19), (23), (25), (35) to (37) And one or more of the compounds in the group consisting of (39), (44) and (49), wherein the diamine is one or both of the A component of the amine and the B component of the amine, and the A component of the amine It is selected from the following structural formulae (IV-1), (IV-2), (IV-15), (IV-16), (V-1) to (V-12), (V-33), ( One of the compounds in the group consisting of VII-1) and (VII-2) or More than or equal to the above, the B component of the amine is selected from the following general formulae (VIII-2), (VIII-4), (VIII-5), (VIII-6), (XI-1), (XI-2) and (XI-6) one or more of the compounds represented by the formula in the group consisting of [11] (In the above formula, R ²³ independently represents an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms, R ²⁹ represents hydrogen or an alkyl group having 1 to 30 carbon atoms, and R ³⁰ represents hydrogen. Or an alkyl group having a carbon number of 1 to 20). The liquid crystal alignment agent according to claim 19, wherein the tetracarboxylic dianhydride is either or both of the A component of the acid and the B component of the acid, and the A component of the acid is the structural formula The compound of (1), the component B of the acid is a compound selected from the group consisting of the above formulas (19), (23) and (49), and the diamine is any of the component A of the amine and the component B of the amine. In one or both, the component A of the above amine is one or two of the compounds selected from the group consisting of the above structural formulas (IV-16), (V-1), (V-7) and (VII-2). More than the above, the above heterocyclic compound is selected from the group consisting of N, N, N', N', - tetrathiopyranylmethyl-4,4'-diaminodiphenylethane, styrene-2-isopropenyl One or more of the compounds of the oxazoline copolymer and the group consisting of 1,3-bis(4,5-dihydro-2-oxazolyl)benzene. The liquid crystal alignment agent according to claim 20, wherein the component B of the amine is selected from the group consisting of the above formula (VIII-2), (VIII-5), (XI-1), (XI-2), and One or two or more compounds represented by the formula in the group of (XI-6). The liquid crystal alignment agent according to any one of the items 19 to 21, further comprising an oxirane compound. The liquid crystal alignment agent according to claim 22, wherein the oxirane compound is a phenol-dicyclopentadiene resin type epoxy resin, and 2-(3,4-epoxycyclohexyl)ethyl group. Either or both of trimethoxy decane. A liquid crystal alignment film obtained by calcining a liquid crystal alignment agent according to any one of claims 1 to 23 to form a film state. A liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both surfaces of the pair of substrates facing each other; and a liquid crystal alignment film formed on a surface of the pair of substrates facing each other The liquid crystal layer between the pair of substrates is characterized in that the liquid crystal alignment film is a liquid crystal alignment film according to claim 24 of the patent application.