TW201434974A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device - Google Patents

Abstract

A liquid crystal alignment agent is provided, which is a solution obtained by containing a polyamic acid or derivatives thereof, obtained by reacting a tetracarboxylic dianhydride with a diamine, and a solvent, wherein the solvent contains at least one compound represented by the following formula (A). The liquid crystal alignment agent, in which change of viscosity at room temperature does not easily happened, does not generate cissing when coating the alignment agent or whitening of a formed alignment film. In addition, the alignment stability of a liquid crystal molecule in the liquid crystal alignment film formed by using the liquid crystal alignment agent is good. Furthermore, a liquid crystal display device having the liquid crystal alignment film has excellent image sticking property. In the formula, R1 and R2 are each independently an alkyl group having 1 to 3 carbons.

Description

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

The present invention relates to a liquid crystal alignment agent and a liquid crystal display element for forming a liquid crystal alignment film of a liquid crystal display element. More specifically, the present invention relates to a liquid crystal alignment agent which is less likely to cause a change in viscosity at room temperature and which does not cause cissing when applying an alignment agent or whitening of an alignment film formed by a film, and is provided with the liquid crystal. A liquid crystal display element of a liquid crystal alignment film obtained by an alignment agent.

In the liquid crystal display device, a liquid crystal alignment film containing a polyacrylic acid, a polyimide, or the like is formed on the surface of a substrate on which a transparent electrode or a metal electrode is provided, as a substrate for a liquid crystal display element, and two liquid crystal display element substrates are aligned. A liquid crystal layer is formed in the gap to form a unit of a sandwich structure. Usually, the surface of the polyimide film formed on the electrode is subjected to a so-called "friction treatment" to produce the liquid crystal alignment film. Further, a vertical alignment film that does not rub, a light alignment film that emits polarized ultraviolet rays (UV), and the like are also used.

Usually, the alignment film is formed by a printing method or an inkjet method, but with the recent The high quality of the liquid crystal display device and the unevenness in printing when the alignment film is formed have an influence on the display characteristics, and it is more important to ensure good film formation properties (see Patent Document 1, etc.).

One of the causes of the film formation failure observed in the formation of the alignment film is a decrease in the viscosity of the alignment agent at room temperature. Since the printing of the liquid crystal alignment agent is performed at room temperature, uneven film thickness due to a decrease in viscosity is becoming a problem. Further, when a coating agent is applied, a phenomenon of pinholes or the like is likely to occur, or a phenomenon in which the alignment agent absorbs moisture and the alignment agent itself or the alignment film is whitened is also problematic. Further, it is known that the film thickness unevenness, the pinhole, and the whitening phenomenon of the liquid crystal alignment film are related to the misalignment of the liquid crystal panel and the afterimage characteristics (see Patent Document 2 and Patent Document 3).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open No. 2009-37222

[Patent Document 2] Japanese Patent Laid-Open No. 10-274772

[Patent Document 3] International Publication No. 2009/148100

An object of the present invention is to provide a liquid crystal alignment agent which is less likely to cause a change in viscosity at room temperature and which does not cause whitening of a depression or a film-forming alignment film when an alignment agent is applied. Further, an object of the present invention is to provide a liquid crystal display element which has a liquid crystal alignment film obtained from the alignment agent and which is excellent in afterimage characteristics and has good alignment stability.

The present invention includes the following constitutions.

[1] A liquid crystal alignment agent containing a polyglycine or a derivative thereof obtained by reacting tetracarboxylic dianhydride with a diamine, and a solvent, and the solvent contains the following formula At least one of the compounds represented by (A): In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms.

[2] The liquid crystal alignment agent according to the above [1], wherein the compound represented by the formula (A) is selected from the group consisting of the following formulas (A-1) to (A-6). At least one of the groups of compounds.

[3] The liquid crystal alignment agent according to [2], wherein the compound represented by the formula (A) is selected from the group consisting of the formula (A-1), the formula (A-4), and the formula (A-). 6) at least one of the group of compounds represented.

[4] The liquid crystal alignment agent according to any one of [1] to [3] wherein the solvent contains at least one selected from the group of poor solvents, the defect The solvent comprises: ethylene glycol carbonate, 1,2-propylene glycol carbonate, 1,3-propanediol carbonate, 2-methyl-1,3-propanediol carbonate, ethylene glycol monobutyl ether (butyl cellosolve), Ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol phenyl ether acetate, ethylene glycol methyl Phenyl ether, ethylene glycol ethyl phenyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl benzene Ether, diethylene glycol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether Acid ester, diethylene glycol monopropyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monododecyl ether, triethylene glycol dimethyl ether , triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol methyl phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate Ester, propylene glycol monophenyl ether, propylene glycol Propyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, n-propyl acetate, butyl acetate, amyl acetate, n-hexyl acetate, cyclohexyl acetate, acetic acid 2 -methylcyclohexyl ester, n-butyl propionate, methyl 2-hydroxy-isobutyrate, 2-methylpentanone-2,4-diol, tert-butanol, triethylmethanol, third pentane Alcohol, 1-methylcyclohexanol, 2,5-dimethylhexane-2,5-diol, n-butanol, bis(3-methylbutyl)ether, di-n-pentyl ether (dipentyl ether) ), 4-heptanone, 5-fluorenone, 2,6-dimethyl-4-heptanone, 4-methyl-2-pentyl acetate, butyl lactate, isoamyl lactate, n-butyl lactate, Dipropylene glycol methyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, benzyl alcohol , phenylethyl alcohol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethyl acetate, 2,4-pentanedione, ethyl-3- Ethoxypropionate, decyl alcohol, tetrahydrofurfuryl alcohol, 3-methyl-3-methoxybutanol, 1,3-dioxolane, isoamyl propionate, isoamyl isobutyrate, diiso) Pentyl ether, butyl benzene, and diisobutyl ketone.

[5] The liquid crystal alignment agent according to any one of [1] to [4] wherein the solvent contains a group selected from the group consisting of N-alkyl-2-pyrrolidone, N-cyclohexyl-2- At least one of the group of good solvents of pyrrolidone, lactone, and 1,3-dialkyl-2-imidazolidinone.

[6] The liquid crystal alignment agent according to [5], wherein the good solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-cyclohexyl-2- At least one of pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidinone.

[7] The liquid crystal alignment agent according to any one of [1] to [6] wherein the tetracarboxylic dianhydride which is reacted with the diamine is selected from the group consisting of the following formula (AN-I) (AN-VII) and at least one of the group of tetracarboxylic dianhydride represented by the formula (PAN-1) to (PAN-8): In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -; in the formula (AN-II), G is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; (AN-II)~ In AN-IV), Y is independently one selected from the group consisting of trivalent groups, and a bond is bonded to any carbon, and at least one hydrogen of the group may be methyl, ethyl or benzene. Base substitution In the formula (AN-III) to the formula (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, and at least the group One hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bond bond attached to the ring may be bonded to any carbon constituting the ring, and two bond bonds may be bonded to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group; in the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-, and r is independent. Is 0 or 1.

[8] The liquid crystal alignment agent according to [7], wherein the tetracarboxylic dianhydride which is reacted with the diamine is selected from the group consisting of the following formula (AN-1-1), and the formula (AN-1-13) ), Formula (AN-2-1), Formula (AN-2-2), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-1), Formula (AN) -4-5), formula (AN-4-6), formula (AN-4-17), formula (AN-4-21), formula (AN-4-26), formula (AN-4-30) At least one of the group consisting of: (AN-9-1), (AN-13-1), (AN-16-1), and (PAN-1):

In the formula (AN-4-17), m is an integer of 1 to 12; in the formula (AN-13-1), Ph represents a phenyl group.

The liquid crystal alignment agent according to any one of the above [1], wherein the diamine reacted with the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DI-1). (DI-16), formula (DIH-1)~ (DIH-3), formula (DI-31)~ (DI-35) and formula (PDI-1)~ (PDI-12) At least one of the groups: In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH- or -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. Can be substituted by -OH; in formula (DI-3) and formula (DI-5)~ (DI-7), G ^{21 is} independently a single bond, -NH-, -NCH ₃ -, -O-, -S -, -SS-, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH _{2 m'} -, -O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m' -O- , -O-CH ₂ -C(CF ₃ ) ₂ -CH ₂ -O-, -O-CO-(CH ₂ ) _m' -CO-O-, -CO-O-(CH ₂ ) _m' -O -CO-, -(CH ₂ ) _m' -NH-(CH ₂ ) _m' -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _{m' k} -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12, k is an integer of 1 to 5, n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; a cyclohexane ring in the formula (DI-2) to (DI-7) And at least one hydrogen of the benzene ring may be -F, -Cl, an alkylene group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substitution, in addition, in the formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring may be represented by the following formula (D) I-4-a)~(DI-4-e) substitution; the bond position is not fixed at the carbon atom constituting the ring, and the bond position on the ring is arbitrary, and -NH _{2 is} in cyclohexane. The bonding position on the ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² ; In the formulae (DI-4-a) and (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; In the formula (DI-11), r is 0 or 1; in the formula (DI-8) to the formula (DI-11), the bonding position of -NH ₂ bonded to the ring is an arbitrary position; In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl is extended, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, and p is independently 0. An integer of ~3, q is an integer from 0 to 4; in the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, -B, carbon number 1 to 6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4; in the formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1; the bonding position is not fixed to the carbon atom constituting the ring; The upper base indicates that the bonding position on the ring is arbitrary; in the formula (DI-13) to the formula (DI-16), the bonding position of the -NH ₂ bonded to the ring is an arbitrary position; In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; in the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, a carbon number of 1 ~20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; formula (DIH-2) and formula In (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position; In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ - or -(CH ₂ ) _m' -, m' is an integer of 1 to 12, and R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or the following a group represented by the formula (DI-31-a) wherein at least one hydrogen of the alkyl group may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡ C-substituted, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF _2, -OCF _3, an alkyl group having 3 to 30 carbon atoms, or a carbon number of 3 to 30 The alkoxy group is substituted, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more alkylene groups. -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- In the diyl, naphthalene-2,7-diyl or inden-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , s, t, and u are independent integers of 0 to 2, and their total is 1 to 5. When s, t, or u is 2, the two bonding groups in each parenthesis may be the same or different, and The two rings may be the same or different, and R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be divalent represented by the following formula (DI-31-b) Substitution, In the formula (DI-31-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6; In formula (DI-32) and formula (DI-33), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, and carbon number is 1~ An alkyl group of 20 or an alkenyl group having 2 to 20 carbon atoms; one hydrogen of the benzene ring in the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the bonding position is not fixed. The group on any one of the carbon atoms represents any bonding position on the ring; in the formula (DI-32) and the formula (DI-33), -NH ₂ bonded to the benzene ring is represented in The bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms, R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-, and R ³² is a carbon number of 6~ An alkyl group of 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group, and r is 0 or 1; -NH ₂ on the benzene ring means that the bonding position on the ring is arbitrary;

In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , b is independently an integer of 0 to 2; in the formula (PDI-12), R ⁴³ is a carbon number From 1 to 10 alkyl groups or alkoxy groups, at least one hydrogen may be substituted by fluorine.

[10] The liquid crystal alignment agent according to [9], wherein the diamine reacted with the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DI-1-3), and the formula (DI-2-1) ), formula (DI-4-1), formula (DI-4-5), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI -5-30), formula (DI-5-37), formula (DI-7-3), formula (DI-8-2), formula (DI-12-1), formula (DI-13-1) , formula (DI-14-8), formula (DIH-2-1), formula (DI-31-2), formula (DI-31-5), formula (DI-31-47), formula (DI- At least one of a group consisting of 34-2), a formula (DI-34-4), a formula (DI-34-7), a formula (PDI-6-1), and a formula (PDI-7-1) :

In the formula (DI-5-1), the formula (DI-5-37), and the formula (DI-7-3), m is an integer from 1 to 12; in the formula (DI-5-30), k is 1~ An integer of 5; in the formula (DI-7-3), n is 1 or 2; in the formula (DI-31-2), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. In the formula (DI-31-5), R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; in the formula (DI-34-2), R ⁴⁰ is hydrogen or carbon. In the formula (DI-34-4) and the formula (DI-34-7), R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

[11] The liquid crystal alignment agent according to any one of [1] to [10] wherein, further comprising a radically polymerizable unsaturated double bond selected from the group consisting of an alkenyl-substituted nadicilide compound Compound, oxazine compound, oxazoline compound, and ring At least one of the group of compounds of the oxygen compound.

[12] The liquid crystal alignment agent according to [11], wherein the alkenyl-substituted nadicilide compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Group of compounds of dicarboxy quinone imine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) At least one of them.

[13] The liquid crystal alignment agent according to [11], wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-extended ethyl bis acrylamide, N, N'-(1,2-dihydroxyethylidene)bisacrylamide, ethylidene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethyl acrylate) At least one of the groups of compounds.

[14] The liquid crystal alignment agent according to [11], wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1, 3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2 -[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) Ethyl]phenyl]propane, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-A At least one of the group consisting of a glycidyl acrylate copolymer and a compound of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

[15] A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of [1] to [14].

[16] A liquid crystal display element comprising the liquid crystal alignment film according to [15].

The present invention can provide a liquid crystal alignment agent which is less likely to cause a change in viscosity at room temperature and which does not cause whitening of a depression or a film-forming alignment film when an alignment agent is applied. In addition, the liquid crystal display element including the liquid crystal alignment film obtained from the liquid crystal alignment agent can provide a liquid crystal display element having excellent afterimage characteristics and excellent alignment stability.

The liquid crystal alignment agent of the present invention contains polyamic acid or a derivative thereof as a reaction product of a tetracarboxylic dianhydride and a diamine. Examples of the tetracarboxylic dianhydride include photosensitive tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. Examples of the diamine include a photosensitive diamine, a non-side chain type diamine, a side chain type diamine, and an anthracene. The poly-proline or a derivative thereof is a component which is dissolved in a solvent when it is prepared as a liquid crystal alignment agent to be described later, and is a liquid crystal alignment film which will be described later. A component of a liquid crystal alignment film containing polybenrene as a main component is formed. Examples of such a derivative of polyglycine include soluble polyimine, polyphthalate, polydecanoic acid, polyamidamine, and polydecanoic acid-proline, and the like. Specific examples include: 1) polyimine which is obtained by dehydration ring-closure reaction of all amine groups of polyproline and carboxyl groups, and 2) partial polyimine which is partially subjected to dehydration ring closure reaction, 3) a polyphthalamide obtained by converting a carboxyl group of a poly-proline to an ester, and 4) a part obtained by substituting a part of an acid dianhydride contained in a tetracarboxylic dianhydride compound into an organic dicarboxylic acid and reacting the same The polyaminic acid-polyamide copolymer and 5) a polyamidoximine which is obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyaminic acid polymer and the polyimine polymer may be one type of compound or two or more types.

The terms used in the present invention will be described. The "arbitrary" used in defining the chemical structural formula means that the position is arbitrary and the number is arbitrary. In the chemical structural formula, a group enclosing a character (for example, A) in a hexagonal shape means a group (ring A) of a ring structure.

The tetracarboxylic dianhydride used to produce the polyaminic acid polymer and the polyimine polymer of the present invention will be described. Hereinafter, the description of "tetracarboxylic dianhydride" means not only the case where tetracarboxylic dianhydride is used alone, but also the case where a plurality of tetracarboxylic dianhydrides are used in the form of a mixture.

If necessary, an anisotropic property may be imparted to the alignment film formed of the liquid crystal alignment agent of the present invention by rubbing treatment or light irradiation.

When the anisotropic property is imparted by light irradiation, the liquid crystal alignment agent of the present invention is applied onto a substrate, dried by preheating, and linearly polarized light that is irradiated with ultraviolet rays via a polarizing plate is substantially parallel to the polarizing direction. The photosensitive base derived from the photosensitive diamine of the polymer backbone generates photoisomerization. Since the main chain of the polymer substantially parallel to the polarizing direction is selectively photoisomerized or photodimerized, the direction of the polarizing direction with respect to the ultraviolet ray to be irradiated is substantially perpendicular to the main chain of the polymer forming the film. The ingredients dominate. Therefore, the substrate is heated to dehydrate the polylysine. After the polyimine film is formed in a closed loop, the liquid crystal molecules of the liquid crystal composition injected in the unit assembled using the substrate have the long axes aligned in a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. Perform alignment. Film The step of irradiating the ultraviolet light in a linearly polarized light may be performed before the heating step for polyimidization or after the polyimidization by heating.

The tetracarboxylic dianhydride used to produce the poly-proline or its derivative of the present invention will be described.

The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. The tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic system in which a dicarboxylic acid anhydride is not directly bonded to an aromatic ring (including Tetracarboxylic dianhydride in the group of any of the heterocyclic system and the photosensitive tetracarboxylic dianhydride.

A suitable example of such a tetracarboxylic dianhydride is a formula (AN-I) to a formula (E-I) to the viewpoint of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film. AN-VII) and a tetracarboxylic dianhydride represented by the formula (PAN-1) to (PAN-8).

In the formula (AN-I), the formula (AN-IV), and the formula (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or - C(CF ₃ ) ₂ -. In the formula (AN-II) to the formula (AN-IV), Y is independently one selected from the group consisting of trivalent groups described below, and a bond is bonded to an arbitrary carbon, and at least one hydrogen of the group is present. It may be substituted by a methyl group, an ethyl group or a phenyl group.

In the formula (AN-III) to the formula (AN-V), the ring A is a group of a monocyclic hydrocarbon having 3 to 10 carbon atoms or a group of a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms, and at least 1 of the group The hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bonding bond attached to the ring may be bonded to any carbon constituting the ring, and the two bonding bonds may be bonded to the same carbon, in the formula (AN-VI), X ¹⁰ It is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group. Further, in the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

More specifically, tetracarboxylic dianhydride represented by the following formula (AN-1) to formula (AN-16-14) can be mentioned.

In the formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group or a 1,4-cyclohexylene group. X ^{11 is} independently a single bond or -CH ₂ -. G ^{12 is} independently any of the following trivalent groups.

When G ¹² is >CH-, the hydrogen of CH can be substituted by -CH ₃ . When G ¹² is >N-, G ^{11 is} not a single bond and -CH ₂ -, and X ^{11 is} not a single bond. Moreover, R ¹¹ is hydrogen or -CH ₃ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas.

In the formula (AN-1-2) and the formula (AN-1-14), m is an integer of 1 to 12.

In the formula (AN-2), R ^{12 is} independently hydrogen, -CH ₃ , -CH ₂ CH ₃ or a phenyl group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulas.

In the formula (AN-3), the ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

In the formula (AN-4), the ring A ¹¹ is a cyclohexane ring or a benzene ring. G ¹³ is a single bond, -(CH ₂ ) _m -, -O-, -S-, -C(CH ₃ ) ₂ -, -SO ₂ -, -CO-, -C(CF ₃ ) ₂ -, or The divalent group represented by the following formula (G13-1), m is an integer of 1-12.

In the formula (G13-1), G ^13a and G ^13b are each independently a single bond, -O- or a divalent group represented by -NHCO-. The phenyl group is preferably a 1,4-phenylene group and a 1,3-phenylene group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas.

In the formula (AN-4-17), m is an integer of 1 to 12.

In the formula (AN-5), R ¹¹ is hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom constituting the benzene ring indicates that the bonding position in the benzene ring is arbitrary. Examples of the tetracarboxylic dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

In the formula (AN-6), X ^{11 is} independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH=CH-. n is 1 or 2. Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas.

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas.

In the formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ or a phenyl group, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-8) include compounds represented by the following formulas.

In the formula (AN-9), r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulas.

The formula (AN-10) is the following tetracarboxylic dianhydride.

In the formula (AN-11), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formulas.

In the formula (AN-12), the ring A ^{11 is} independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formulas.

In the formula (AN-13), X ¹³ is an alkylene group having 2 to 6 carbon atoms, and Ph represents a phenyl group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formulas.

In the formula (AN-14), G ^{14 is} independently -O-, -COO- or -OCO-, and r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formulas.

In the formula (AN-15), w is an integer of 1 to 10. Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas.

Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

In the present invention, examples of the photosensitive tetracarboxylic dianhydride include the following formula (PAN-1) to formula (PAN-8).

When it is important to improve the alignment of the liquid crystal display element, among the acid dianhydrides, the formula (AN-1-13), the formula (AN-2-1), and the formula (AN-2-2) are particularly preferable. A compound represented by the formula (AN-4-17) and the formula (PAN-1).

When it is important to increase the transmittance of the liquid crystal display device, among the acid dianhydrides, the formula (AN-1-1), the formula (AN-1-13), and the formula (AN-2-1) are particularly preferable. , (AN-2-2), (AN-3-1), (AN-4-1), (AN-4-30), (AN-9-1), (AN- 13-1), and a compound represented by the formula (AN-16-1).

In the case of paying attention to improving the electrical characteristics of the liquid crystal display element, the acid two Among the anhydrides, it is particularly preferred from the formula (AN-3-2), the formula (AN-4-5), the formula (AN-4-6), the formula (AN-4-21), and the formula (AN-4-26). And a compound represented by the formula (AN-13-1).

The diamines and dioximes used to produce the poly-proline and its derivatives of the present invention will be described. When the polyglycine or its derivative of the present invention is produced, it can be selected from known diamines and dioxins without limitation.

Diamines can be classified into two according to their structures. That is, a diamine having a side chain group and a diamine having no side chain group, the side chain group being a group branched from the main chain when the skeleton linking the two amine groups is regarded as a main chain. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect is required to have a carbon number of 3 or more. Specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and an alkoxyalkyl group having 3 or more carbon atoms. a base, and a group having a steroid skeleton. A group having one or more rings and having a ring having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent It has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. Further, a diamine having no such a side chain group is sometimes referred to as a non-side chain type diamine.

By suitably separating the non-side chain type diamine from the side chain type diamine, it is possible to correspond to the respective pretilt angles required. The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. Further, it is preferable to use a side chain type diamine and a non-side chain type diamine for the purpose of improving the vertical alignment property, the voltage holding ratio, the afterimage characteristics, and the alignment property of the liquid crystal.

The non-side chain type diamine is described. Examples of the known diamine having no side chain include diamines of the following formula (DI-1) to formula (DI-16).

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH- or -O-, m is an integer of 1 to 12, and at least 1 of an alkyl group One hydrogen can be replaced by -OH. In the formula (DI-3) and the formula (DI-5) to the formula (DI-7), G ^{21 is} independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS-, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _m' -, - O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m' -O-, -O-CH ₂ -C(CF ₃ ) ₂ -CH ₂ -O-, -O-CO-(CH ₂ ) _m' -CO-O-, -CO-O-(CH ₂ ) _m' -O-CO-, -( CH ₂ ) _m' -NH-(CH ₂ ) _m' -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _m' ) _k -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12, and k is from 1 to 5. Integer, n is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkyl group having a carbon number of 1 to 10. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH , -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substitution, and further, in the formula (DI-4), the following formula (DI-4-a) can be used. Formula (DI-4-e) substituted. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. Further, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² .

In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ .

In the formula (DI-11), r is 0 or 1. In the formula (DI-8) to the formula (DI-11), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl is extended, and w is an integer from 1 to 10. In the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4. . In the formula (DI-14), the ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, -B, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, or a vinyl group. , alkynyl, q is independently an integer from 0 to 4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. Further, the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. In the formula (DI-13) to the formula (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

As the diamine having no side chain of the formula (DI-1) to formula (DI-16), Specific examples of the following formula (DI-1-1) to formula (DI-16-1) can be cited.

An example of the diamine represented by the formula (DI-1) is shown below.

In the formula (DI-1-7) and the formula (DI-1-8), k is independently an integer of 1 to 3.

Examples of the diamine represented by the formula (DI-2) to the formula (DI-3) are shown below.

An example of the diamine represented by the formula (DI-4) is shown below.

An example of the diamine represented by the formula (DI-5) is shown below.

In the formula (DI-5-1), m is an integer of 1 to 12.

In the formula (DI-5-12) and the formula (DI-5-13), m is an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In the formula (DI-5-35)~(DI-5-37) and (DI-5-39), m is an integer from 1 to 12, and the formula (DI-5-38) and formula (DI- In 5-39), k is an integer of 1 to 5, and in (DI-5-40), n is an integer of 1 or 2.

An example of the diamine represented by the formula (DI-6) is shown below.

An example of the diamine represented by the formula (DI-7) is shown below.

In the formula (DI-7-3) and the formula (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

An example of the diamine represented by the formula (DI-8) is shown below.

An example of the diamine represented by the formula (DI-9) is shown below.

An example of the diamine represented by the formula (DI-10) is shown below.

An example of the diamine represented by the formula (DI-11) is shown below.

An example of the diamine represented by the formula (DI-12) is shown below.

An example of the diamine represented by the formula (DI-13) is shown below.

An example of the diamine represented by the formula (DI-14) is shown below.

An example of the diamine represented by the formula (DI-15) is shown below.

An example of the diamine represented by the formula (DI-16) is shown below.

Explain the second. Examples of known diterpenes having no side chain include dioxins of the following formula (DIH-1) to formula (DIH-3).

In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -.

In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted with a methyl group, an ethyl group or a phenyl group.

In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, and the carbon number is 1 ~20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -.

In the formula (DIH-2) and the formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position.

An example of a dich represented by the formula (DIH-1) to the formula (DIH-3) is shown below.

In the formula (DIH-1-2), m is an integer of 1 to 12.

The side chain type diamine is described. Examples of the side chain group of the side chain type diamine include the following groups.

The side chain group may, first, be an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, or the like. Alkenylcarbonyl, alkenylcarbonyloxy, alkenoxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having 3 or more carbon atoms. However, in the alkoxyalkyl group, the carbon number of the entire group may be 3 or more. These groups may be linear or branched.

Next, the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and examples thereof include a phenyl group and a phenylalkyl group. , phenylalkoxy, phenoxy, phenylcarbonyl, phenylcarbonyloxy, phenoxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkane having 3 or more carbon atoms , cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkane , bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, and cyclohexylbis(phenyl)oxycarbonyl The base of the isocyclic structure.

Further, examples of the ring group include a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings of a benzene ring and a cyclohexane ring. And the bonding group is independently a single bond, -O-, -COO-, -OCO-, -CONH- or an alkylene group having 1 to 3 carbon atoms, and the terminal ring has an alkyl group having 1 or more carbon atoms and a carbon number A fluorine-substituted alkyl group having 1 or more, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. A group having a steroid skeleton is also effective as a side chain group.

The diamine having a side chain includes a compound represented by the following formula (DI-31) to formula (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ - or -(CH ₂ ) _m' -, m' is an integer from 1 to 12. Preferable examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and an alkylene group having 1 to 3 carbon atoms, and a particularly preferred example is a single bond, -O- , -COO-, -OCO-, -CH ₂ O-, -CH ₂ -, and -CH ₂ CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen may be substituted by -F, and at least one -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen of the phenyl group may be substituted by -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF _2, -OCF _{3 ,} an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. The hydrogen of the cyclohexyl group may be substituted by an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, and the bonding position is preferably a meta or para position. That is, when the bonding position of the radical "R ²⁵ -G ²⁶ -" is set to 1 position, the two bonding positions are preferably 3 bits and 5 bits, or 2 bits and 5 bits.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more of the alkyl groups are - CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-. Ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine- 2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or fluoren-9,10-diyl, ring B ²¹ , ring B ²² In the ring B ²³ and the ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , and s, t and u are independently an integer of 0 to 2, and their total is 1 to 5, when s, t or u When it is 2, the two bonding groups in each parenthesis may be the same or different, and the two rings may be the same or different. R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted 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 , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

In the formula (DI-31-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

In formula (DI-32) and formula (DI-33), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, and carbon number is 1~ An alkyl group of 20 or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position in the ring is arbitrary. Preferably, one of the two groups "-phenyl-G ³⁰ -O-" in the formula (DI-32) is bonded to the 3-position of the steroid nucleus and the other is bonded to the 6-position of the steroid nucleus. The bonding position of the two groups "-phenyl-G ³⁰ -O-" in the formula (DI-33) on the benzene ring is preferably meta or para to the bonding position of the steroid nucleus, respectively. In the formula (DI-32) and the formula (DI-33), -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary.

In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-. R ³² is an alkyl group having 6 to 22 carbon atoms, and R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. Moreover, -NH ₂ bonded to the benzene ring means that the bonding position on the ring is arbitrary, but is preferably independent and the bonding position with respect to G ³¹ is meta or para.

Specific examples of the side chain type diamine are exemplified below. The diamine having a side chain of the formula (DI-31) to the formula (DI-35) is represented by the following formula (DI-31-1) to formula (DI-35-3). Compound.

An example of the compound represented by the formula (DI-31) is shown below.

In the formula (DI-31-1) to (DI-31-11), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably an alkyl group having 5 to 25 carbon atoms or Alkoxy group having 5 to 25 carbon atoms. R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In the formula (DI-31-12) to the formula (DI-31-17), R ³⁶ is an alkyl group having 4 to 30 carbon atoms, and preferably an alkyl group having 6 to 25 carbon atoms. R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and preferably an alkyl group having 8 to 25 carbon atoms.

In the formula (DI-31-18) to the formula (DI-31-43), R ³⁸ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, preferably an alkyl group having 3 to 20 carbon atoms. Or an alkoxy group having a carbon number of 3 to 20. R ³⁹ is hydrogen, -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 , preferably having a carbon number of 3 to 25. An alkyl group or an alkoxy group having a carbon number of 3 to 25. Further, G ³³ is an alkylene group having 1 to 20 carbon atoms.

An example of the compound represented by the formula (DI-32) is shown below.

An example of the compound represented by the formula (DI-33) is shown below.

An example of the compound represented by the formula (DI-34) is shown below.

In the formula (DI-34-1) to the formula (DI-34-12), R ⁴⁰ is hydrogen or an alkyl group having 1 to 20 carbon atoms, preferably hydrogen or an alkyl group having 1 to 10 carbon atoms, and R ⁴¹ is Hydrogen or an alkyl group having 1 to 12 carbon atoms.

An example of the compound represented by the formula (DI-35) is shown below.

In the formula (DI-35-1) to the formula (DI-35-3), R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

As the diamine in the present invention, a diamine other than the diamine represented by the formula (DI-1-1) to the formula (DI-35-3) can also be used. Examples of such a diamine include compounds represented by the following formula (DI-36-1) to formula (DI-36-8).

In the formula (DI-36-1) to the formula (DI-36-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

The photosensitive diamine will be described. In the present invention, it can be selected from known photosensitive diamines without limitation. For example, examples of such a photosensitive diamine compound include the following formula (PDI-1) to formula (PDI-12).

In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , and b is an integer of 0-2. In the formula (PDI-12), R ⁴³ is an alkyl group or alkoxy group having 1 to 10 carbon atoms, and at least one hydrogen may be substituted by fluorine.

In each of the diamines, a part of the diamine may be substituted with a monoamine in a range of 40 mol% or less based on the monoamine of the diamine. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the obtained polymer can be easily controlled (polymerized The molecular weight of the proline or its derivative can improve the coating properties of the liquid crystal alignment agent, for example, without impairing the effects of the present invention. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and positive ten Monoamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-dodecylamine.

The polyaminic acid or a derivative thereof may further contain a monoisocyanate compound in its monomer. By containing a monoisocyanate compound in the monomer, the terminal of the obtained polyaminic acid or its derivative is modified, and the molecular weight is adjusted. By using the terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From this point of view, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

Among the photosensitive diamines, from the viewpoint of photosensitivity, the following formula (PDI-6-1) or formula (PDI-7-1) is more preferable.

Among the specific examples of the diamine, in the case where it is important to further improve the alignment of the liquid crystal, the diamine is preferably represented by the formula (DI-1-3), the formula (DI-4-5), and the formula (DI-5-). 1), formula (DI-5-37), formula (DI-7-3), formula (DI-31-2), formula (DI-31-5), formula (DI-31-47), formula ( DI-34-2), formula (DI-34-4) or formula (DI-34-7) The diamine shown.

Among the specific examples of the diamine, in the case where the transmittance is further increased, the diamine is preferably represented by the formula (DI-1-3), the formula (DI-2-1), and the formula (DI-12-1). And a diamine represented by the formula (DIH-2-1).

Among the specific examples of the diamine, in the case where it is emphasized that the electrical properties are further improved, the diamine is preferably represented by the formula (DI-4-1), the formula (DI-4-5), and the formula (DI-5-1). , formula (DI-5-5), formula (DI-5-9), formula (DI-5-30), formula (DI-5-37), formula (DI-8-2), formula (DI- 13-1), a diamine represented by the formula (DI-14-8) or the formula (DIH-2-1).

The polyphthalic acid polymer and the polyimine polymer used in the present invention can be obtained by reacting an acid dianhydride with a diamine component in a solvent. In the synthesis reaction, conditions other than the usual polyamine synthesis can be directly applied, except for the selection of the raw materials, without special conditions. The solvent to be used will be described later.

The liquid crystal alignment agent may be a so-called blend type, or may further contain polyamic acid or a derivative thereof, or may further contain other components than polyamine or a derivative thereof. The other components may be one type or two or more types.

Further, for example, the liquid crystal alignment agent may further contain an acrylic polymer, an acrylate, within a range not detracting from the effects of the present invention, preferably within 20% by weight of the polyaminic acid or a derivative thereof. A polymer, a tetracarboxylic dianhydride, or other polymer component such as a polyamidoximine which is a reaction product of a dicarboxylic acid or a derivative thereof and a diamine.

The polyaminic acid or a derivative thereof can be produced in the same manner as the known polyglycine or a derivative thereof for forming a film of polyimine. The total addition amount of the tetracarboxylic dianhydride is preferably set to be approximately equal to the total number of moles of the diamine (the molar ratio is about 0.9 to 1.1).

The molecular weight of the polyaminic acid or its derivative is preferably 10,000 to 500,000, more preferably 20,000 to 200,000, in terms of polystyrene-equivalent weight average molecular weight (Mw). The molecular weight of the polyaminic acid or its derivative can be determined by measurement by a gel permeation chromatography (GPC) method.

The polyaminic acid or a derivative thereof can be confirmed by the presence of an infrared (Infrared, IR), nuclear magnetic resonance (NMR) pair to make the poly-proline or its derivative The solid component obtained by precipitation in a large amount of poor solvent was analyzed. In addition, the monomer to be used can be confirmed by gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography mass spectrometry (Gas Chromatography-Mass). Spectrometry, GC-MS) Decomposes the poly-proline or a derivative thereof using an aqueous solution of a strong base such as KOH or NaOH, and then extracts the extract extracted from the decomposition product using an organic solvent.

<Alkenyl substituted nadic ylidene compound>

For example, for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadic quinone imine compound. The alkenyl substituted nadic ylidene imine compound may be used alone or in combination of two or more. For the purpose, the content of the alkenyl-substituted nadic ylidene compound is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, still more preferably 1% by weight, relative to the polyamic acid or a derivative thereof. 50wt%.

The Nadik imine compound is specifically described below.

The alkenyl-substituted nadicylimine compound is preferably a compound which is soluble in a solvent which dissolves the poly-proline or a derivative thereof used in the present invention. This alkenyl substituted Nadick Examples of the quinone imine compound include compounds represented by the following formula (NA).

In the formula (NA), L ¹ and L ^{2 are} independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an aryl group or a benzyl group, n It is 1 or 2.

In the formula (NA), when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and an aryl group having 6 to 12 carbon atoms. , benzyl, from -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (here, Z ¹ , Z ² and Z ^{3 are} independently an alkylene group having 2 to 6 carbon atoms, r The base represented by 0 or 1, and k is an integer from 1 to 30, consists of -(Z ⁴ ) _r -BZ ⁵ -H (here, Z ⁴ and Z ⁵ independently represent a carbon number of 1 to 4). An alkyl group or a cycloalkyl group having 5 to 8 carbon atoms, B is a phenyl group, and r is a group represented by 0 or 1), and is represented by -BTBH (wherein B is a stretching phenyl group, and T is a group represented by -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S- or -SO ₂ -), or 1 hydrogen to 3 hydrogens of these groups via -OH Substituted base.

In this case, preferred W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, a cyclohexyl group, a phenyl group, a benzyl group, or a poly(ethyleneoxy)ethyl group having 4 to 10 carbon atoms. A phenoxyphenyl group, a phenylmethylphenyl group, a phenyl isopropylidenephenyl group, and a group in which one hydrogen or two hydrogens of these groups are substituted with -OH.

In the formula (NA), when n=2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, and -Z ¹ - a group represented by O-(Z ² O) _k -Z ³ - (here, Z ¹ -Z ³ , and k have the meanings as described above), consisting of -Z ⁴ -BZ ⁵ - (here, Z ⁴ , The meaning of Z ⁵ and B is as defined above. The group represented by -B-(OB) _r -T-(BO) _r -B- (here, B is a phenyl group and T is a carbon number of 1-3). The alkyl group, -O- or -SO ₂ -, r has the meaning indicated above, or a group in which one hydrogen to three hydrogens of these groups are substituted by -OH.

In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenyl group, a phenylene group, a benzene dimethyl group, and a -C ₃ H ₆ -O-(Z ² -O) group. a group represented by _n -OC ₃ H ₆ - (here, Z ² is an alkylene group having 2 to 6 carbon atoms, and n is 1 or 2), and is represented by -BTB- (wherein B is a stretching phenyl group, Further, T is a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (here, B is a stretching phenyl group), and these groups One hydrogen or two hydrogen-substituted groups.

Such an alkenyl-substituted nadicylimine compound can be maintained at a temperature of from 80 ° C to 220 ° C by using an alkenyl-substituted nadic anhydride anhydride derivative and a diamine as described in, for example, Japanese Patent No. 2729565. A compound obtained by synthesis or a commercially available compound in an hour to 20 hours. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-A Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-allyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -Isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-isopropenyl- Methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl bicyclo [2.2.1] hept-5-ene-2,3 -Dicarboxy quinone imine, N-cyclohexyl-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-phenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindole Imine, N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allyl bicyclo [2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -benzyl-methallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine, N-(2-hydroxyethyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2,2-di Methyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-(2,2-dimethyl-3-hydroxypropane Allyl group Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyanthracene Imine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-hydroxycyclohexyl) -allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-(4-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine, N-(4-hydroxyphenyl) -methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyfluorene Imine, N-(3-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(p-hydroxybenzyl) -allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl Yttrium, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyanthracene Imine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methylallylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)phenyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-{4-(4-hydroxyphenylisopropylidene)phenyl }-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)phenyl} -Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, and oligomers thereof, N,N'-extended ethyl-bis(allyl bicyclol [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene-bis(ene) Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-dodecamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine), N, N'-docamethylene-bis(allylmethyl bicyclic [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), 1, 2-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)propoxy}ethane, 1,2-double {3'-( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, 1,2-bis{3'-(methylallylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, bis[2'-{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine) propoxy}ethyl]ether, 1,4-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine) propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)propoxy }Butane, N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Amine), N,N'-interphenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-phenylene - bis (allylmethyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-{(1-methyl)-2,4-phenylene }--bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-p-xylylene-bis (allyl bicyclo [2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), 2,2-bis[4-{ 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(ene Propylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine) phenoxy} phenyl] propane, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) benzene Methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)phenyl}methane, double {4-(methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine) phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline)phenyl} Ether, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(methylallylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} fluorene, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline)phenyl} fluorene, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}indole, 1,6-bis(allylbicyclo[2.2.1] Geng-5- Alkene-2,3-dicarboxy quinone imine)-3-hydroxy-hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine)-3,6-dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)-5-hydroxyl -cyclohexane, 1,5-bis{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}-3-hydroxy-pentyl Alkane, 1,4-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-2-hydroxy-benzene, 1,4-bis(allylyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)benzenedimethyl-double (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylmethyl) Ring [2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine), N, N'- (2-hydroxy)benzenedimethyl-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-pair (2,3 -dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(ene Propylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[ 2.2.1]hept-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1]hept-5-ene- 2,3-Dicarboxy quinone imine)-4-hydroxy-phenyl}ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine)-5-hydroxy-phenyl}indole, 1,1,1-tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) }Phenoxymethylpropane, N,N',N"-tris(ethylethylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine) Polycyanates, oligomers thereof, and the like.

Further, the alkenyl-substituted nadicylimine compound used in the present invention may be an asymmetric alkyl group. A compound represented by the following formula which is a phenyl group.

Preferred compounds among the alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'- Phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-meta-phenyl-bis(allylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-m-xylylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl] Propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, double { 4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) phenyl}methane.

Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}methane, bis{4-(methylallylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} ether, bis {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine) phenyl} hydrazine, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole.

More preferred alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinazoline) .

N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- P-Benzyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene-bis(ene) Propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine).

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-dual [ 4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, double {4-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane , bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane.

Further, as a particularly preferred alkenyl-substituted nadicylimine compound, a bis{4-(allylbicyclo[2.2.1]hept-5-ene represented by the following formula (NA-1) is exemplified. -2,3-dicarboxy quinazoline)phenyl}methane, N,N'- represented by formula (NA-2) Meta-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine), and N,N'- represented by formula (NA-3) Hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine).

<Compound having a radical polymerizable unsaturated double bond>

For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound or two or more types of compounds. Further, an alkenyl-substituted nadic quinone imine compound is not contained in the compound having a radical polymerizable unsaturated double bond. For the purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, still more preferably 1% by weight with respect to the polyaminic acid or a derivative thereof. %~50wt%.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl substituted imidide compound is reduced in order to reduce the ion density of the liquid crystal display element, suppress the increase in the ion density over time, and further suppress Production of afterimage The compound/alkenyl-substituted nadic ylidene compound having a radical polymerizable unsaturated double bond is preferably 0.1 to 10, more preferably 0.5 to 5 by weight.

The compound having a radical polymerizable unsaturated double bond will be specifically described below. Examples of the compound having a radical polymerizable unsaturated double bond include a (meth) acrylate, a (meth)acrylic acid derivative such as (meth) acrylamide, and a bismaleimide. The compound having a radical polymerizable unsaturated double bond is more preferably a (meth)acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl methacrylate.

Specific examples of the difunctional (meth) acrylate include, for example, exoethyl diacrylate, Aronix M-210, Aronix M-240, and Aronix M-6200, which are products of the East Asian synthetic chemical industry. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604, and KAYARAD R-684, which are products of Nippon Kayaku (shares), V260, V312, and V335HP, which are products of Osaka Organic Chemical Industry Co., Ltd., and Co., Ltd. Light Acrylate BA-4EA, Light Acrylate BP-4PA and Light Acrylate BP-2PA for the products of the Grease Chemical Industry (stock).

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4′-methylenebis(N,N-dihydroxyethyl acrylate), which is a synthetic chemical industry in East Asia. (shares) products of Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, which are products of Osaka Organic Chemical Industry Co., Ltd., are products of Nippon Chemical Co., Ltd.

Specific examples of the (meth) acrylamide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, and N-positive Propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylate Amine, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-di Ethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-propylene hydrazinopyridine, N-propenylpyrrolidine, N,N'-methylenebispropene decylamine, N,N'-extended ethyl bis acrylamide, N,N'-dihydroxyethylidene bis decylamine, N-(4-hydroxyphenyl) Methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N- Dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-( Methoxymethyl)methacrylamide, N-(hydroxyl Yl) -2-methyl-acrylamide, N- benzyl-2-methyl acrylamide, and N, N'- methylene bis methyl acrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bispropenylamine, ethylidene diacrylate, And 4,4'-methylenebis(N,N-dihydroxyethyl acrylate).

For example, BMI-70 and BMI-80 which are products of KI Chemicals Co., Ltd., and BMI-1000, BMI-3000, BMI- which are products of Daiwa Kasei Industrial Co., Ltd. 4000, BMI-5000 and BMI-7000.

<oxazine compound>

For example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose described, the content of the oxazine compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, still more preferably from 1% by weight to 20% by weight, based on the polyaminic acid or a derivative thereof.

The oxazine compound will be specifically described below.

The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves poly-proline or a derivative thereof and has ring-opening polymerizability.

Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

The structure of the oxazine is known in various structures. In the present invention, the structure of the oxazine is not particularly limited, and examples of the oxazine structure in the oxazine compound include an aldehyde having a condensed polycyclic aromatic group such as benzoxazine or naphthoxazine. The structure of the azine.

Examples of the oxazine compound include compounds represented by the following formula (OX-1) to formula (OX-6). Further, in the following formula, a bond represented toward the center of the ring means that the bond is bonded to any one of the carbons constituting the ring and the bondable substituent.

In the formula (OX-1)~(OX-3), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, and in the formula (OX-1) to (OX-6), L ⁵ to L ⁸ It is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ is a single bond, -O-, -S-, -SS- , -SO ₂ -, -CO-, -CONH-, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _v -, -O-(CH _{2 v} -O-, -S-(CH ₂ ) _v -S-, where v is an integer from 1 to 6, in the formula (OX-5) and the formula (OX-6), Q ^{2 is} independently a single bond , -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having 1 to 3 carbon atoms, a benzene ring and a naphthalene ring in Q ² The hydrogen bonded thereto is independently and may be substituted by -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

Further, the oxazine compound includes an oligomer or polymer having an oxazine structure in a side chain, and an oligomer or polymer having an oxazine structure in the main chain.

Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.

In the formula (OX-1-2), L ³ is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably an alkyl group having 1 to 30 carbon atoms, more preferably an alkyl group having 1 to 20 carbon atoms.

The oxazine compound represented by the formula (OX-3) includes an oxazine compound represented by the following formula (OX-3-I).

In the formula (OX-3-I), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and Q ¹ is a single bond, -CH ₂ -, -C(CH ₃ ) ₂ -, -CO-, -O-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

In the formula, L ³ and L ^{4 are} preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Among these, more preferably, it is exemplified by the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the formula (OX-3). -7), formula (OX-3-9), formula (OX-4-1)~form (OX-4-6), formula (OX-5-3), formula (OX-5-4), and An oxazine compound represented by the formula (OX-6-2) to (OX-6-4).

The oxazine compound can be produced by the same method as the method described in International Publication No. 2004/009708, Japanese Patent Laid-Open No. Hei 11-12258, and Japanese Patent Laid-Open No. 2004-352670.

The oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound with a primary amine and an aldehyde (refer to International Publication No. 2004/009708).

The oxazine compound represented by the formula (OX-2) can be obtained by reacting a compound having a naphthol-based hydroxyl group by a method in which a primary amine is slowly added to formaldehyde, and reacting (refer to International Publication 2004/ 009708).

The oxazine compound represented by the formula (OX-3) can be obtained by subjecting the phenol compound to 1 mol in the presence of a secondary aliphatic amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound. The aldehyde having at least 2 mols or more of the phenolic hydroxyl group of the phenol compound and the 1 mol of the primary amine are reacted in an organic solvent (refer to International Publication No. 2004/009708 and Japanese Patent Laid-Open No. Hei 11-12258).

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) can be obtained by having 4,4'-diaminodiphenylmethane or the like at a temperature of 90 ° C or higher. A benzene ring and an organic group-containing diamine bonded to these benzene rings, an aldehyde such as formaldehyde, and a phenol are subjected to a dehydration condensation reaction in n-butanol (refer to Japanese Patent Laid-Open No. 2004-352670).

<oxazoline compound>

For example, in order to stabilize the electrical characteristics of the liquid crystal display element for a long period of time, the present invention The liquid crystal alignment agent may further contain an oxazoline compound. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the purpose, the content of the oxazoline compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20% by weight, based on the polyphthalic acid or a derivative thereof. Alternatively, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1% by weight based on the purpose of the polyaminic acid or its derivative. 40wt%.

The oxazoline compound will be specifically described below.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more kinds. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. Further, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in a side chain, or two or more kinds of monomers having an oxazoline structure in a side chain. Copolymer with a monomer having no oxazoline structure.

The oxazoline structure is preferably a structure which exists in the oxazoline compound in such a manner that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyphthalic acid.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2. - benzylidene-2-phenyl-4H-oxazol-5-one, 1,4-bis(4,5-dihydro-2-oxazolyl)benzene, 1,3-bis (4,5 -dihydro-2-oxazolyl) Benzene, 2,3-bis(4-isopropenyl-2-oxazolin-2-yl)butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-double (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 to these oxazoline compounds, a polymer or oligomer having an oxazolyl group such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.) may be mentioned. Among these oxazoline compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable.

<epoxy compound>

For example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The epoxy compound may be one compound or two or more compounds. For the purpose, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20% by weight, based on the polyaminic acid or a derivative thereof.

The epoxy compound will be specifically described below.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, and hexafluoroepoxy. Propane, epoxycyclohexane, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidylphthalate Yttrium, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3-[2-( Perfluorohexyl)ethoxy]-1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, and propylene glycol diglycidyl glycol. Ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromo new Pentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl) Aminopropyltrimethoxydecane.

Examples of the compound having three epoxy rings in the molecule include 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4] -([2,3-Epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Techmore VG3101L", manufactured by Mitsui Chemicals, Inc.).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl. Base-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4' -Diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

In addition to the above, an oligomer having an epoxy ring or a polymer may be exemplified as a compound having an epoxy ring in the molecule. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-ethyl-3-oxetanyl) Methyl ester, N-cyclohexylmaleimide and N-phenylmaleimide.

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexyl horse.醯imino-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxy methacrylate Ethyl ester-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate Ester copolymer.

Among these, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is particularly preferred. , N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl- 3',4'-Epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxycyclohexyl)B Trimethoxy decane.

More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, and isocyanuric glycidyl glycol. A chain aliphatic epoxy compound and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl glycol, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, glycidyl isocyanurate, and chain aliphatic. An epoxy compound and a cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A epoxy compound. Hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, Phenolic novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, containing naphthalene Skeleton epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type diglycidyl ether A compound and a biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin.

Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxiranyl group.

Examples of the glycidyl decylamine include a glycidyl guanamine type epoxy compound.

Examples of the chain aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of an olefin compound.

Examples of the cyclic aliphatic epoxy compound include an epoxy group-containing compound obtained by oxidizing a carbon-carbon double bond of a cycloolefin compound.

Examples of the bisphenol A type epoxy compound include jER828. jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all manufactured by Mitsubishi Chemical Corporation), Epotohto YD-128 (manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332, DER-324 Manufactured by The Dow Chemical Company, Epiclon 840, Epiclon 850, Epiclon 1050 (both manufactured by Di Ai Sheng (DIC)), Epomik R-140, Epomik R-301, and Epomik R-304 (all Mitsui Chemical (company) manufacturing).

Examples of the bisphenol F-type epoxy compound include jER806, jER807, and jER4004P (all manufactured by Mitsubishi Chemical Corporation), Epotohto YDF-170, Epotohto YDF-175S, and Epotohto YDF-2001 (all of which are Dongdu Huacheng (shares) ) Manufacturing), DER-354 (manufactured by The Dow Chemical Company), Epiclon 830, and Epiclon 835 (all manufactured by Di Ai Sheng (share)).

Examples of the bisphenol type epoxy compound include an epoxide of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include Suntohto ST-3000 (manufactured by Tohto Kasei Co., Ltd.), Rikaresin HBE-100 (manufactured by Shin-Nihon Chemical Co., Ltd.), and Denacol EX-252 (long 濑) Nagase chemteX (manufacturing).

Examples of the hydrogenated bisphenol type epoxy compound include an epoxide of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane.

Examples of the brominated bisphenol-A type epoxy compound include jER5050 and jER5051 (all manufactured by Mitsubishi Chemical Corporation), Epotohto YDB-360, and Epotohto YDB-400 (all manufactured by Toho Chemical Co., Ltd.). DER-530, DER-538 (all manufactured by The Dow Chemical Company), Epiclon 152, and Epiclon 153 (all manufactured by Di Ai Sheng (share)).

Examples of the phenol novolac type epoxy compound include jER152 and jER154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (manufactured by Tohto Kasei Co., Ltd.), DEN431 and DEN438 (all manufactured by Dow Chemical Co., Ltd.). Epiclon N-770 (made by Di Ai Sheng (share)), EPPN-201, and EPPN-202 (both manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Dongdu Chemical Co., Ltd.), Epiclon N-665, and Epiclon N-695 ( All are manufactured by Di Ai Sheng (share), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the bisphenol A novolac type epoxy compound include jER157S70 (manufactured by Mitsubishi Chemical Corporation) and Epiclon N-880 (manufactured by Di Aisheng (stock)).

Examples of the epoxy compound containing a naphthalene skeleton include Epiclon HP-4032, Epiclon HP-4700, and Epiclon HP-4770 (all manufactured by Di Aisin Co., Ltd.), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (formula: EP-1), catechol diglycidyl ether (formula: EP-2), and resorcinol. Diglycidyl ether (formula EP-3), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([ 2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (formula EP-4), tris(4-glycidoxyphenyl)methane (formula EP-5 below) ), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (manufactured by The Dow Chemical Company), Denacol EX-201 (长濑化成(股) (manufacturing), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmore VG3101L (manufactured by Mitsui Chemicals Co., Ltd.), represented by the following formula EP-6 a compound and a compound represented by the following formula EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (manufactured by The Dow Chemical Company) and Epiclon HP-7200 (manufactured by Di Aisheng (stock)).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Rikaresin DME-100 (manufactured by Shin Nippon Chemical and Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (hereinafter, EP-8), diethylene glycol diglycidyl ether (hereinafter, EP-9), and polyethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether (formula EP-10), tripropylene glycol diglycidyl ether (formula EP-11 below), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether ( Formula EP-12), 1,4-butanediol diglycidyl ether (formula EP-13 below), 1,6-hexanediol diglycidyl ether (formula EP-14 below), dibromo Neopentyl glycol diglycidyl ether (formula EP-15 below), Denacol EX-810, Denacol EX-851, Denacol EX-8301, Denacol EX-911, Denacol EX-920, Denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 Manufactured by the company), DD-503 (made by ADEKA), Rikaresin W-100 (manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2, 4-hexanediol (formula EP-16), glycerol polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX -611, Denacol EX-321, and Denacol EX-411 (all manufactured by Changchun Huacheng (share)).

As the polysulfide type diglycidyl ether compound, for example, FLDP-50, and FLDP-60 (both manufactured by Toray Thiokol (share)).

Examples of the biphenol-type epoxy compound include YX-4000 and YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all manufactured by Nippon Kayaku Co., Ltd.).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (formula: EP-17), diglycidyl phthalate (formula: EP-18), and phthalic acid (2-methyloxiranylmethyl) ester (Equation EP-19), hexahydrophthalic acid diglycidyl ester (Equation EP-20), and the following formula EP-21 The compound represented by the formula, the compound represented by the following formula EP-22, and the compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871. jER872 (all manufactured by Mitsubishi Chemical Co., Ltd.), Epiclon 200, Epiclon 400 (all manufactured by Di Aisheng (share)), Denacol EX-711, and Denacol EX-721 (all manufactured by Changchun Huacheng (share)).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (Equation EP-24), N,N-diglycidyl-o-toluidine (Equation EP-25), N,N-diglycidyl-m-toluidine (formula EP-26), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27), 3- (N,N-diglycidyl)aminopropyltrimethoxydecane (formula EP-28), N,N,O-triglycidyl-p-aminophenol (formula EP-29) , N, N, O-triglycidyl-m-aminophenol (formula EP-30), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl Methane (formula EP-31), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP- 32), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33), 1, 4 - bis(N,N-diglycidylaminomethyl)cyclohexane (formula EP-34 below), 1,3-bis(N,N-diglycidylamino)cyclohexane (bottom Illustrative formula EP-35), 1,4-bis(N,N-diglycidylamino)cyclohexane (formula EP-36 below), 1,3-bis(N,N-diglycidyl) Amine Benzene (formula EP-37 below), 1,4-bis(N,N-diglycidylamino)benzene (formula EP-38 below), 2,6-bis (N,N-diverted water) Glycerylaminomethyl)bicyclo[2.2.1]heptane (formula EP-39 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexyl Methane (formula EP-40), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (the following formula) EP-41), N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (formula EP-42), 1,3,5-tri (4- (N,N-diglycidyl)aminophenoxy)benzene (formula EP-43 below), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether ( The following formula EP-44), three (4-(N, N-) Diglycidyl)aminophenyl)methane (formula EP-45 below), 3,4,3',4'-tetrakis (N,N-diglycidylamino)biphenyl (formula EP below) -46), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (formula: EP-47), a compound represented by the following formula EP-48 And a compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having an oxiranyl group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxiranyl group include N-phenylmaleimide-glycidyl methacrylate copolymer and N-cyclohexylmaleimide-methacrylic acid. Glycidylglyceride copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate Ester copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having an oxiranyl group include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidol (meth)acrylate. ester.

Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the monomer having an oxiranyl group include (meth)acrylic acid, methyl (meth)acrylate, and (a) Ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-Ethyl-3-oxetanyl)methyl ester, N-cyclohexylmaleimide, and N-phenylmaleimide.

As the glycidyl iso-glycidyl cyanide, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (EP-50 of the following formula), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following formula EP-51) and an isomeric isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolead PB3600 (manufactured by Daicel).

Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Celloxide 2021 (Dai Sai (share) ))), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (formula: EP-52) Formula EP-53), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (Equation EP-54), ε-caprolactone modified 3, 4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-diethoxylated limonene (Celloxide 3000 (manufactured by Daicel) The following formula EP-55) is a compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all manufactured by The Ciba-Geigy Chemical Corp.). (available from Huntsman. Japan (shares)), EHPD-3150 (manufactured by Daicel), and a cyclic aliphatic epoxy resin.

The epoxy compound is preferably a polyglycidylamine compound, a bisphenol A novolac More than one type of epoxy compound, cresol novolak type epoxy compound, and cyclic aliphatic type epoxy compound, more preferably N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane , trade name "Techmore VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexene carboxylate, N-phenylmaleimide-methyl One or more of glycidyl acrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type epoxy compound, and cresol novolak type epoxy compound.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to each purpose.

For example, examples of the polymer compound include polymer compounds which are soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, anthrone modified polyurethane, and anthrone modified polyester.

Further, as the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be cited when it is desired to raise the antistatic property, and 3) when it is desired to lift the substrate. In the case of adhesion, a decane coupling agent or a titanium-based coupling agent may be mentioned, and 4) a ruthenium imidization catalyst may be mentioned when ruthenium imidization is carried out at a low temperature.

As the decane coupling agent, for example, vinyl trimethoxy decane, vinyl triethoxy decane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy oxime Alkane, N-(2-aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-amino Phenyltrimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethyl Oxydecane, 3-glycidoxypropylmethyldimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropene oxime Propyltrimethoxydecane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylidene)-3-(triethoxydecyl)-1-propylamine, and N, N'-bis[3-(trimethoxydecyl)propyl]ethylenediamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane.

Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy substitution Cyclic amines such as isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. Or two or more.

The amount of the decane coupling agent to be added is usually from 0% by weight to 20% by weight, preferably from 0.1% by weight to 10% by weight based on the total mass of the polyaminic acid or its derivative.

The amount of the ruthenium imidization catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, based on the carbon group of the polyamic acid or a derivative thereof.

The amount of the other additives to be added varies depending on the use thereof, but is usually 0% by weight to 100% by weight, preferably 0.1% by weight to 50% by weight based on the total weight of the polyaminic acid or its derivative.

Further, the liquid crystal alignment agent of the present invention may further contain an acrylic polymer, an acrylate polymer, for example, in a range not detracting from the effects of the present invention (preferably within 20% by weight of the polyaminic acid or a derivative thereof). And a tetracarboxylic dianhydride, another polymer component such as a polyamidoximine which is a reaction product of a dicarboxylic acid or a derivative thereof and a diamine.

Further, the liquid crystal alignment agent may further contain a solvent, for example, from the viewpoint of applicability of the liquid crystal alignment agent or adjustment of the concentration of the polyamic acid or a derivative thereof. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is generally used for a production step or a use of a polymer component such as polyacrylic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types.

The concentration of the poly-proline in the alignment agent is preferably from 0.1% by weight to 40% by weight. When the alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polyamic acid with a solvent in advance.

The solid content concentration in the alignment agent is not particularly limited, and may be selected in accordance with various coating methods described below. In general, in order to suppress unevenness at the time of coating, pinholes, and the like, it is preferably 0.1% by weight to 30% by weight, and more preferably 1% by weight to 10% by weight based on the weight of the varnish.

The solvent used in the liquid crystal alignment agent of the present invention is a solution containing a compound represented by the above formula (A) as a solvent component. Specific examples of the formula (A) include a solvent represented by the above formula (A-1) to formula (A-6). From the viewpoint of solubility of polyproline, (A-1), (A-4) and (A-6) are preferred.

The ratio of the solvent represented by the formula (A) in the alignment agent is excellent It is selected from 0.1% by weight to 90% by weight, more preferably from 10% by weight to 85% by weight.

The solvent component in the liquid crystal alignment agent of the present invention may be only the solvent represented by the above formula (A), but in order to control the coating property to the substrate or to ensure the solubility of the resin component, it is preferred to The second solvent and/or the third solvent described below are contained in addition to the first solvent represented by (A).

In order to control the coating property to the substrate, as the second solvent, an alcohol, a ketone, an ester, or a solvent which is a poor solvent can be used in a range in which the produced polyaminic acid polymer or the polyimide polymer is not precipitated. Ethers, halogenated hydrocarbons, hydrocarbons, and the like. Examples of such a solvent include ethylene glycol carbonate, 1,2-propylene glycol carbonate, 1,3-propanediol carbonate, pentanediol carbonate, hexanediol carbonate, and 2-methyl-1. 3-propanediol carbonate, 2,2-dimethyl-1,3-propanediol carbonate, 2-hydroxy-2-methyl-1,3-propanediol carbonate, 2-ethoxycarbonyl-2-methyl -1,3-propanediol carbonate, ethylene glycol methyl ether, ethylene glycol dimethyl ether, ethylene glycol ether, ethylene glycol propyl ether, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl Ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol phenyl ether acetate, ethylene glycol methyl phenyl ether, ethylene Alcohol ethyl phenyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl phenyl ether, diethylene Alcohol monoethyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether acetate, two Glycol monopropyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol single Dodecyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl ether, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether Acetate, propylene glycol methyl phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether, propylene glycol monopropyl ether, dipropylene glycol, Dipropylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monopropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, n-propyl acetate, butyl acetate, amyl acetate, n-hexyl acetate , cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 3-methoxybutyl acetate, 2-methylcyclohexyl acetate, n-butyl propionate, 2-hydroxy- Methyl isobutyrate, butyl butyrate, amyl butyrate, isoamyl butyrate, 2-methylpentanone-2,4-diol, tert-butanol, triethylmethanol, third pentanol , 1-methylcyclohexanol, 2,5-dimethylhexane-2,5-diol, n-butanol, bis(3-methylbutyl)ether, di-n-pentyl ether (dipentyl ether) , 2-pentanone, 3-pentanone, 2-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-octanone, 2-nonanone, 5-nonanone, 2,6- Dimethyl-4-heptanone, 4-methyl-2-pentyl acetate, butyl lactate, isoamyl lactate, lactic acid isoamyl ester, methyl lactate, lactate B Ester, n-propyl lactate, n-butyl lactate, dipropylene glycol methyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl-3-methyl Propionate, ethyl-3-ethoxypropionate, benzyl alcohol, 1-phenoxy-2-propanol, phenylethyl alcohol, 1-methoxy-2-propanol, 1-ethoxyl 2-propanol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethyl acetate, 2-hydroxypropyl acetate, 3-hydroxyacetic acid Propyl ester, 2-hydroxybutyl acetate, 3-hydroxybutyl acetate, 4-hydroxybutyl acetate, 2-hydroxyethyl propionate, 2-hydroxypropyl propionate, 3-hydroxypropyl propionate, lactic acid 2 -hydroxyethyl ester, 2-hydroxypropyl lactate, 3-hydroxypropyl lactate, 2,4-pentanedione, ethyl-3-ethoxypropionate, decyl alcohol, tetrahydrofurfuryl alcohol, 3-methyl- 3-methoxybutanol, 1,3-dioxolane, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, butyl benzene, methyl isobutyl ketone, cyclohexanone, Or diisobutyl ketone and the like.

In order to secure solubility in the polyamic acid polymer or the polyimine polymer, a good solvent may be used in combination as the third solvent (good solvent). Examples of such a solvent include N-alkyl-2-pyrrolidones, lactones, and 1,3-dialkyl-2-imidazolidinone. Examples thereof include γ-butyrolactone, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, dimethyl hydrazine, dimethyl hydrazine, and the like. Hexamethylarylene, N-methyl caprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, Hexamethylphosphonium triamine, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, diethylacetamide, 3- Methoxy-N,N-dimethylpropanamide, 3-butoxy-N-methylpropionamide, N,N-dimethylpropanamide, 3-hexyloxy-N,N- Dimethyl propyl amide, m-cresol, xylenol, phenol, halogenated phenol, and the like.

Among these solvents, the third solvent is particularly preferably N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, γ-butyrolactone, and 1,3-dimethyl-2-imidazolidinone.

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of performing heat drying, and a step of heating and calcining. In the liquid crystal alignment film of the present invention, if necessary, the film obtained by the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment to impart anisotropy. Alternatively, if necessary, the light may be irradiated after the coating step, the heat drying step, or the light may be irradiated after the heating calcination step to impart anisotropy. Further, it can also be used as a liquid crystal alignment film for vertical alignment (VA) which is not subjected to rubbing treatment.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid crystal display element, similarly to the production of a normal liquid crystal alignment film. The substrate may be an electrode or color in which an indium tin oxide (ITO), an indium zinc oxide (In ₂ O ₃ -ZnO, IZO), an indium gallium zinc oxide (In-Ga-ZnO ₄ , IGZO) electrode, or the like may be provided. A glass substrate such as a filter.

As a method of applying a liquid crystal alignment agent onto a substrate, a rotator method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known. These methods can also be equally applied to the present invention.

The heating and drying step is generally 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. The heat drying step is preferably carried out at a temperature within a range in which the solvent can be evaporated, more preferably at a relatively low temperature with respect to the temperature in the heating calcination step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heating calcination step may dehydrate the polylysine or its derivative. The conditions required for the ring closure reaction are carried out. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. These methods can also be equally applied to the present invention. It is usually preferably carried out at a temperature of from about 100 ° C to about 300 ° C for from 1 minute to 3 hours, more preferably from 120 ° C to 280 ° C, still more preferably from 150 to 250 ° C.

In the method for forming a liquid crystal alignment film of the present invention, in order to align the liquid crystal in one direction with respect to the horizontal direction and/or the vertical direction, a known formation method such as a rubbing method or a photo-alignment method can be suitably used as the alignment film. A method of imparting anisotropy. The photoalignment method can be used particularly suitably.

The liquid crystal alignment film of the present invention using a rubbing method can be formed by the steps of applying the liquid crystal alignment agent of the present invention onto a substrate, heating and drying the substrate coated with the alignment agent, and heating the film. The step of simmering and the step of rubbing the film.

The rubbing treatment can be carried out in the same manner as the rubbing treatment for the alignment treatment of the liquid crystal alignment film, as long as it is a condition that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. Preferred conditions are a hair injection amount of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a roll rotation speed of 500 rpm to 2,000 rpm.

A method of forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention by the photo-alignment method can be formed by heating and drying the coating film, irradiating the linearly polarized light or the non-polarized light of the radiation, thereby imparting anisotropy to the coating film, and then heating the film. Simmered. Alternatively, it may be formed by heating and drying the coating film, heating and simmering, and then irradiating the linearly polarized light or the non-polarized light of the radiation. From the viewpoint of the alignment, the irradiation step of the radiation is preferably performed before the heating calcination step.

Further, in order to improve the liquid crystal alignment performance of the liquid crystal alignment film, it is also possible to face the linearly polarized light or the non-polarized light which is irradiated with radiation while being heated by the coating film. The irradiation of the radiation may be carried out in the step of heating and drying the coating film or in the step of heating and calcining, or may be carried out between the heating and drying step and the heating and calcining step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Further, the heating calcination temperature in this step is preferably in the range of 30 ° C to 300 ° C, and more preferably in the range of 50 ° C to 250 ° C.

As the radiation, for example, ultraviolet light or visible light containing light having a wavelength of 150 nm to 800 nm can be used, and ultraviolet light containing light of 300 nm to 400 nm is preferable. In addition, linear or unpolarized light can be used. The light is not particularly limited as long as it imparts liquid crystal alignment performance to the coating film. However, when it is desired to exhibit a strong alignment regulating force to the liquid crystal, linear polarization is preferable.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment properties even with low-energy light irradiation. The irradiation step is preferably linearly polarized irradiation ^{0.05J / cm 2 ~ 20J / cm} 2, more preferably ^{0.5J / cm 2 ~ 10J / cm} 2. Further, the wavelength of the linearly polarized light is preferably 200 nm to 400 nm, and more preferably 300 nm to 400 nm. The angle of irradiation of the film surface by the linearly polarized light is not particularly limited. When a strong alignment regulating force for the liquid crystal is to be exhibited, it is preferable to be as perpendicular as possible to the film surface from the viewpoint of shortening the alignment treatment time. Further, by irradiating the linearly polarized light, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light.

When the pretilt angle is to be made to appear, the light irradiated to the film may be the same linearly polarized light as described, or may be unpolarized. When the pretilt angle purports to show, the film is irradiated with a light irradiation amount is preferably ^{0.05J / cm 2 ~ 20J / cm} 2, particularly preferably ^{0.5J / cm 2 ~ 10J / cm} 2, its wavelength is preferably 250nm ~ 400nm, It is particularly preferably 300 nm to 380 nm. When the pretilt angle is to be expressed, the irradiation angle of the light irradiated to the film on the surface of the film is not particularly limited, but from the viewpoint of shortening the alignment treatment time, it is preferably 30 to 60 degrees.

The light source used in the step of illuminating the linearly polarized or non-polarized light of the radiation can use an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep ultraviolet (Deep Ultraviolet, Deep UV) lamp, a halogen lamp, a metal halide lamp, and a high light source without limitation. Power metal halide lamps, xenon lamps, mercury xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, Light Emitting Diode (LED) lamps, sodium lamps, microwave-excited electrodeless lamps, and the like.

The liquid crystal alignment film of the present invention can be suitably obtained by a method including further steps other than the above steps. For example, the liquid crystal alignment film of the present invention is The step of washing the film after the simmering or radiation irradiation with the cleaning liquid is not an essential step, but the cleaning step may be provided according to the other steps.

Examples of the cleaning method using the cleaning liquid include brushing, spraying, steam cleaning, or ultrasonic cleaning. These methods can be performed separately or in combination. As the cleaning liquid, pure alcohol or various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, acetone, and methyl ethyl ketone can be used. Ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently refined and has less impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

In order to improve the liquid crystal alignment performance of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be applied before and after the heating calcination step, before and after the rubbing step, or before or after the polarized or unpolarized radiation irradiation. In the annealing treatment, the annealing temperature is 30 ° C to 180 ° C, preferably 50 ° C to 150 ° C, and the time is preferably 1 minute to 2 hours. Further, examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, an LED lamp, and the like. Light exposure preferably 0.3J ^{/ cm 2 ~ 10J / cm 2} .

The film thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 nm to 300 nm, and more preferably 30 nm to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring device such as a profiler or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized in that the anisotropy of the alignment is particularly large. The size of such anisotropy can be evaluated by a method using polarized light described in JP-A-2005-275364 or the like. Further, as shown in the following examples, it can also be evaluated by a method using ellipsometry. When the alignment film of the present invention is used as an alignment film for a liquid crystal composition, it can be considered to have a larger The anisotropic material of the film has a large alignment limiting force for the liquid crystal composition.

In addition to the alignment use of the liquid crystal composition for liquid crystal displays, the liquid crystal alignment film of the present invention can be used for alignment control of optical compensation materials or all other liquid crystal materials. Further, the alignment film of the present invention can be used alone for optical compensation materials because of its large anisotropy.

The present invention provides a liquid crystal display element including a pair of substrates disposed oppositely, electrodes formed on one or both of opposite surfaces of the pair of substrates, and pairs formed on the pair of substrates a liquid crystal alignment film on the surface and a liquid crystal layer formed between the pair of substrates, and the liquid crystal alignment film is an alignment film of the present invention.

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 a vapor deposited film of ITO or metal. Further, the electrode may be formed on the entire surface of one face of the substrate, or may be formed, for example, in a patterned desired shape. The desired shape of the electrode may be, for example, a comb type or a sawtooth structure. The electrodes may be formed on one of the pair of substrates or may be formed on the two substrates. The form of formation of the electrode differs depending on the type of the liquid crystal display element. For example, in the case of an In-Plane Switching (IPS) type liquid crystal display element or a Fringe Field Switching (FFS) type liquid crystal display element, The electrode is disposed on one of the pair of substrates, and in the case of other liquid crystal display elements, the electrode is disposed on both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in a form of sandwiching a liquid crystal composition by the pair of substrates facing each other in which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a microparticle or a resin sheet or the like may be used between the pair of substrates as needed. Spacers in appropriate spacing.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. A preferred liquid crystal composition having positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Laid-Open No. Hei 8-157826, and Japanese Patent Laid-Open No. Hei 8- 231960, Japanese Patent Laid-Open No. Hei 9-241644 (EP 885272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1), 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), 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 No. 2000-087040, Japanese Patent No. A liquid crystal composition disclosed in Unexamined-Japanese-Patent--------------------------------------------------------------------------------------------------------------------- .

As a preferable example of the liquid crystal composition having the negative dielectric anisotropy, Japanese Patent Laid-Open No. Sho 57-114532, Japanese Patent Laid-Open No. Hei 2-4725, Japanese Patent Laid-Open No. Hei 4-224885, and Japanese Patent No. Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Laid-Open No. Hei 10-168453, Japanese Patent Laid-Open No. Hei 10-236989, Japanese Patent Laid-Open No. Hei 10-236990, Japanese Patent Laid-Open 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 Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. 10- 237035, Japanese patent special Kaiping 10-237075, Japanese Patent Laid-Open No. Hei 10-237076, Japanese Patent Laid-Open No. Hei 10-237448 (EP967261A1), Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-291945, Japanese Patent No. Kaiping 11-029581, Japanese Patent Laid-Open No. Hei 11-080049, Japanese Patent Laid-Open No. 2000-256307, Japanese Patent Laid-Open No. 2001-019965, Japanese Patent Laid-Open No. 2001-072626, Japanese Patent Laid-Open No. 2001-192657, Japanese Patent Laid-Open No. 2010 A liquid crystal composition disclosed in -037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Patent Laid-Open No. 2010-537010, Japanese Patent Laid-Open No. Hei No. Hei.

Further, for example, from the viewpoint of improving the alignment property, the liquid crystal composition used in the element of the present invention may be further added with an additive, for example. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

[Examples]

Hereinafter, the present invention will be described by way of examples, but the invention is not limited to these examples. The evaluation method in the examples is as follows.

<weight average molecular weight (Mw)>

The weight average molecular weight of polylysine is determined by using a 2695 separation module. A 2414 differential refractometer (manufactured by Waters) was measured by a GPC method and then converted to polystyrene. The obtained polylysine was subjected to a mixed solution of phosphoric acid-dimethylformamide (DMF) (phosphoric acid/DMF=0.6/100: weight ratio) in such a manner that the polyglycine concentration became about 2% by weight. dilution. The column was HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing agent at a column temperature of 50 ° C and a flow rate of 0.40 mL / min. The measurement was carried out under the conditions. Standard polystyrene uses TSK standard polystyrene manufactured by Tosoh.

<Viscometry>

The viscosity of polylysine was measured using a TVE-25L-shaped viscometer manufactured by Toki Sangyo Co., Ltd.

<Evaluation of printability (depression)>

On the thoroughly cleaned glass substrate, a few drops of the sample solution of the synthesized polylysine were added dropwise, rotated by a spinner at a rotation speed of 3000 rpm for 10 seconds, and then left at room temperature, and the alignment was visually evaluated. The depression of the agent. The humidity in the room where the evaluation of the depression was performed was about 50%.

<Alternating Current (AC) afterimage (luminance change rate)>

The luminance-voltage characteristics (B-V characteristics) of the liquid crystal display element described later were measured. This is taken as the luminance-voltage characteristic before stress is applied: B (front). Then, after applying an alternating current of 4.5 V and 60 Hz to the element for 20 minutes, the short circuit was performed for 1 second, and then the luminance-voltage characteristic (B-V characteristic) was measured again. This was taken as the luminance-voltage characteristic after stress application: B (post). Based on these values, the luminance change rate ΔB (%) was estimated using the following formula.

ΔB (%) = [B (post) - B (pre)] / B (pre) (Formula 1) These measurements were carried out in accordance with International Publication No. 2000/43833. It can be said that the smaller the value of ΔB (%) in the voltage of 0.75 V, the more the generation of the AC afterimage can be prevented.

<Alignment stability (liquid crystal alignment axis stability)>

The rate of change of the liquid crystal alignment axis on the electrode side of the liquid crystal display element to be described later was obtained. Determination The liquid crystal alignment angle φ (front) on the electrode side before the stress was applied, and then a rectangular wave of 4.5 V and 60 Hz was applied to the device for 20 minutes, and then short-circuited for 1 second, and the electrode side was measured again after 1 second and 5 minutes. The liquid crystal alignment angle φ (back). Based on these values, the change of the liquid crystal alignment angle Δφ (deg.) after 1 second and 5 minutes was estimated using the following formula. △ φ (deg.) = φ (post) - φ (pre) (Formula 2) These measurements are referred to J. Hilfiker, B. Johs, C. Herzinger, JF Elman, E. Montbach, D. Bryant, and PJ Bos "Thin Solid Films", 455-456, (2004) 596-600. It can be said that Δφ is small, the rate of change of the liquid crystal alignment axis is small, and the stability of the liquid crystal alignment axis is good.

The solvent, the additive, and the liquid crystal composition used in the examples are as follows.

<solvent>

DMIB: N, N, 2-trimethylpropanamide

DEIB: N,N-diethyl-2-methylpropanamide

NMP: N-methyl-2-pyrrolidone

NEP: N-ethyl-2-pyrrolidone

GBL: γ-butyrolactone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

BL: n-butyl lactate

MMB: 3-methoxy-3-methylbutanol

DPM: Dipropylene glycol methyl ether

PGB: propylene glycol monobutyl ether

<additive>

Ad1: bis[4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl]methane

Ad2: N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Ad3: 3-aminopropyltriethoxysilane

Ad4: 1,3-bis(4,5-dihydro-2-oxazolyl)benzene

Ad5: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane

<Liquid crystal composition>

Positive liquid crystal composition:

Physical property values: NI 100.1 ° C; △ ε 5.1; Δn 0.093; η 25.6 mPa. s.

Negative liquid crystal composition:

Physical property values: NI 75.7 ° C; Δ ε -4.1; Δn 0.101; η 14.5 mPa. s.

<1. Synthesis of polyaminic acid>

[Synthesis Example 1]

Diamine (DI-5-1, m=2) 1.4291 g and dehydrated DMIB 18.5 g were placed in a 50 mL brown four-necked flask equipped with a thermometer, a stirrer, a raw material input port, and a nitrogen inlet, and dried under a nitrogen gas stream. Stir and dissolve. Then, 0.6899 g of acid dianhydride (AN-1-13), 0.8810 g of acid dianhydride (AN-3-2), and 18.5 g of dehydrated DMIB were added, and stirring was continued for 24 hours at room temperature. BC 10.0g was added to the reaction solution, A polyamic acid solution having a polymer solid content concentration of 6 wt% was obtained. The polyaminic acid solution was set to PA1. The polyamine acid contained in PA1 has a weight average molecular weight of 84,000.

[Synthesis Example 2 to Synthesis Example 22]

A polyamic acid solution (PA2)-polyglycine solution having a polymer solid concentration of 6 wt% was prepared according to Synthesis Example 1, except that the solvent composition, the tetracarboxylic dianhydride, and the diamine were changed as shown in Table 1. PA22). The results of Synthesis Example 1 were included, and the results of measurement of the weight average molecular weight of the obtained polyamic acid were summarized in Table 1.

[Comparative Synthesis Example 1 to Comparative Synthesis Example 5]

A polyamic acid solution (PA23)-polyglycine solution having a polymer solid concentration of 6 wt% was prepared according to Synthesis Example 1, except that the solvent composition, the tetracarboxylic dianhydride, and the diamine were changed as shown in Table 2. PA27). The measurement results of the weight average molecular weight of the obtained polyamic acid are summarized in Table 2.

<2. Storage stability and printability (depression) of polyproline

[Example 1]

The polyamic acid solution (PA1) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 1 was measured for viscosity immediately after the synthesis, and the result was 39.3 Pa. s (initial viscosity). Further, the viscosity of the varnish after storage for 30 days at room temperature was measured, and it was 38.0 Pa. s. The printability (depression) was visually confirmed by the above method, and as a result, no depression of the alignment agent was observed.

[Example 2 to Example 22]

The polyamic acid solution (PA2)-polyglycine solution (PA22) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 2 to Synthesis Example 22 was also measured for initial viscosity in the same manner as in Example 1. Viscosity after 30 days. The results of Example 1 were included, and the results of the viscosity measurement of the obtained polylysine and the results of the printability were summarized in the table. 3 in.

[Comparative Example 1 to Comparative Example 5]

The polyamic acid solution (PA23)-polyglycine solution (PA27) having a polymer solid content concentration of 6 wt% prepared in Comparative Synthesis Example 1 to Comparative Synthesis Example 5 was measured in the same manner as in Example 1. Viscosity and viscosity after 30 days. The results of the viscosity measurement of the obtained polylysine and the results of the printability are summarized in Table 4.

According to comparison between Example 1 to Example 22 and Comparative Example 1 to Comparative Example 5, it is understood that the liquid crystal alignment agent of the present invention has a small decrease in viscosity at room temperature, and liquid crystal The storage stability of the alignment agent is high. Further, it is understood that the liquid crystal alignment agent of the present invention has no depression after being applied onto a substrate, and has high printability.

<3. Blending of polylysine>

The poly-proline acid PA1 synthesized in Synthesis Example 1 as the polymer [A] and the poly-proline acid PA4 synthesized in Synthesis Example 4 as the polymer [B] were [A]/[B]= The weight ratio of 1.0/9.0 was mixed to make PA28.

A polyglycine having a polymer solid content concentration of 6 wt% was prepared according to PA28, except that the kind of the poly (A) component polyamine and the [B] component polyamic acid and the [A]/[B] mixing ratio were changed. Solution (PA29) ~ polyaminic acid solution (PA40). In the case of PA28, the kind of the poly [A] component of the [A] component and the polyamine derivative of the [B] component and the [A]/[B] mixing ratio are summarized in Table 5.

In the polyglycine solution (PA5) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 5, the additive (Ad1) was added in a ratio of 5 wt% based on the weight of the polymer. The obtained polyaminic acid solution was designated as PA41.

In addition to changing the type of polylysine and the type and amount of the additive, a polyaminic acid solution (PA42) to a polyaminic acid solution (PA45) was prepared by adding an additive according to PA41. PA41 was contained, and the kind of the polyamic acid, the kind and amount of the additive were summarized in Table 6.

<4. Method of Manufacturing Liquid Crystal Display Element>

<<4-1. IPS type liquid crystal display element>>

[Example 23]

A mixed solvent of DMIB/BC=70/30 (weight ratio) was added to the polyamic acid solution (PA1) having a polymer solid content concentration of 6 wt% prepared in Synthesis Example 1, and diluted to a polymer solid content concentration. A liquid crystal alignment agent was prepared at 4 wt%. The liquid crystal alignment agent was coated on the glass substrate by a spinner. In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was dried by heating at 70 ° C for 80 seconds, and then heat-treated at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The whitening of the formed alignment film was visually confirmed, but no whitening was observed.

Then, using a friction processing device manufactured by Iinuma Gauge Co., Ltd., the amount of hair intrusion in the rubbing cloth (hair length: 1.8 mm: rayon) was 0.20 mm, and the moving speed of the platform was 60 mm/sec. The obtained liquid crystal alignment film was subjected to a rubbing treatment under the conditions of a roll rotation speed of 1,000 rpm.

Two sheets of the alignment film formed on the substrate are formed with the alignment film facing directions, and the rubbing directions of the respective alignment films are made parallel, thereby forming a liquid crystal composition for injecting the opposing alignment films. The voids are then laminated to assemble into an empty IPS unit having a cell thickness of 4 μm. Further, an injection port for injecting liquid crystal into the empty IPS unit is provided at a position where the flow direction of the liquid crystal is substantially parallel to the rubbing direction of the alignment film, for example, at the time of injection. The positive liquid crystal composition was vacuum-injected into the produced empty IPS unit to fabricate a liquid crystal display element. The flow alignment of the produced liquid crystal display element was visually confirmed, but no flow alignment was observed.

The AC residual image (luminance change rate) ΔB (%) was measured by the method described above using the IPS liquid crystal display device produced as described above, and found to be 4.9%.

Using the IPS liquid crystal display device produced as described above, the liquid crystal alignment axis stability Δφ (deg) was measured by the above-described method, and the initial value was 0.025 deg, and the value after 5 minutes was 0.015 deg.

[Examples 24 to 34]

Polymeric acid solution PA1 with polymer solid content concentration of 6wt%, polyglycine solution PA2~polyglycine solution PA8, polyaminic acid solution PA28, polyamidic acid solution PA29, polyaminic acid solution A solvent similar to the solvent composition of polylysine was added to PA41 and polyamine acid solution PA45, and diluted to a polymer solid content concentration of 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, an IPS liquid crystal display element was produced in accordance with the method of Example 23, and a positive type liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained IPS liquid crystal display device were measured. The results obtained are summarized in Table 7 together with the results of Example 23.

[Comparative Example 6]

Adding a mixed solvent of NMP/BC=70/30 (weight ratio) to a polyamic acid solution PA23 having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent . Using the obtained liquid crystal alignment agent, an IPS liquid crystal display element was produced in accordance with the method of Example 23, and a positive type liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained IPS liquid crystal display device were measured. The results obtained are shown in Table 7 together with the results of the examples.

<<4-2.TN type liquid crystal display element>>

[Example 35]

A mixed solvent of DMIB/BC=70/30 (weight ratio) was added to a polyamic acid solution (PA9) having a polymer solid content concentration of 1 wt% prepared in Synthesis Example 1, and diluted to a polymer solid concentration. A liquid crystal alignment agent was prepared at 4 wt%. The liquid crystal alignment agent was coated on the glass substrate by a spinner. Further, in addition to the subsequent examples and comparative examples, the rotational speed of the rotator is adjusted corresponding to the viscosity of the liquid crystal alignment agent. The alignment film was changed to the following film thickness. After coating, the film was dried by heating at 70 ° C for 80 seconds, and then heat-treated at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The whitening of the formed alignment film was visually confirmed, but no whitening was observed. Then, using the rubbing treatment device manufactured by Iidas Co., Ltd., the frictional cloth (hair length of 1.8 mm: rayon) was 0.30 mm, the platform moving speed was 60 mm/sec, and the roller rotation speed was The obtained liquid crystal alignment film was subjected to rubbing treatment at 1,000 rpm.

Two sheets of the substrate on which the alignment film is formed on the substrate are faced with the alignment film, and the rubbing direction of the respective alignment films is made vertical, thereby forming a liquid crystal composition for injecting the opposing alignment films. The voids are then laminated to assemble into an empty TN unit having a cell thickness of 4 μm. Further, an injection port for injecting liquid crystal into the empty TN unit is provided at a position where the flow direction of the liquid crystal is substantially parallel to the rubbing direction of the alignment film, for example, at the time of injection. The positive liquid crystal composition was vacuum-injected into the produced empty TN unit to fabricate a liquid crystal display element. The flow alignment of the produced liquid crystal display element was visually confirmed, but no flow alignment was observed.

The AC afterimage (luminance change rate) ΔB (%) was measured by the method described above using the TN liquid crystal display device produced as described above, and found to be 5.8%.

Using the TN liquid crystal display element produced as described above, the liquid crystal alignment axis stability Δφ (deg) was measured by the above-described method, and the initial value was 0.036 deg, and the value after 5 minutes was 0.020 deg.

[Example 36 to Example 41]

Adding polypyridic acid solution PA10~polyglycine solution PA11, polylysine solution PA30~polyglycine solution PA32 and polylysine solution PA42 to the polymer solid concentration of 6wt% The solvent of the amine acid consists of the same solvent and is diluted The polymer solid content concentration was 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a TN liquid crystal display element was produced in accordance with the method of Example 35, and a positive type liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained TN liquid crystal display element were measured. The results obtained are summarized in Table 8 together with the results of Example 35.

[Comparative Example 7]

Adding a mixed solvent of NMP/BC=70/30 (weight ratio) to a polyamic acid solution PA24 having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent . Using the obtained liquid crystal alignment agent, a TN liquid crystal display element was produced in accordance with the method of Example 35, and a positive type liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained TN liquid crystal display element were measured. The results obtained are shown in Table 8 together with the results of the examples.

<<4-3. VA type liquid crystal display element>>

[Example 42]

A mixed solvent of DMIB/BC=70/30 (weight ratio) was added to a polyglycine solution (PA12) having a polymer solid concentration of 6 wt% prepared in Synthesis Example 12, and diluted to a polymer solid concentration. A liquid crystal alignment agent was prepared at 4 wt%. The liquid crystal alignment agent was coated on the glass substrate by a spinner. In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was dried by heating at 70 ° C for 80 seconds, and then heat-treated at 230 ° C for 15 minutes to form an alignment film having a film thickness of 100 ± 10 nm. The whitening of the formed alignment film was visually confirmed, but no whitening was observed.

Two sheets of the substrate on which the alignment film is formed on the substrate are faced with the alignment film, and a space for injecting the liquid crystal composition between the opposing alignment films is formed, and then bonded to each other to be assembled into a cell thickness of 4 μm. Empty VA unit. Further, an injection port for injecting liquid crystal into the empty VA unit is provided at a position where the flow direction of the liquid crystal at the time of injection is substantially parallel to the rubbing direction of the alignment film. The negative liquid crystal composition was vacuum-injected into the produced empty VA unit to fabricate a liquid crystal display element. The flow alignment of the produced liquid crystal display element was visually confirmed, but no flow alignment was observed.

The AC afterimage (luminance change rate) ΔB (%) was measured by the method described above using the VA liquid crystal display device produced as described above, and found to be 6.3%.

Using the VA liquid crystal display device produced as described above, the liquid crystal alignment axis stability Δφ (deg) was measured by the above-described method, and the initial value was 0.047 deg, and the value after 5 minutes was 0.022 deg.

[Examples 43 to 47]

Adding polypyridic acid solution PA13~polyglycine solution PA14, polylysine solution PA33, polylysine solution PA34 and polyglycine solution PA43 to the polymer solid concentration of 6wt% The solvent of the amine acid consists of the same solvent and is diluted The polymer solid content concentration was 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a VA liquid crystal display element was produced in accordance with the method of Example 42, and a negative liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained VA liquid crystal display device were measured. The results obtained are summarized in Table 9 together with the results of Example 42.

[Comparative Example 8]

Adding a mixed solvent of NMP/BC=70/30 (weight ratio) to a polyamic acid solution PA25 having a polymer solid content concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent . Using the obtained liquid crystal alignment agent, a VA liquid crystal display element was produced in accordance with the method of Example 43, and a positive type liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the obtained VA liquid crystal display device were measured. The results obtained are shown in Table 9 together with the results of the examples.

<<4-4. Transverse electric field photoisomerization type liquid crystal display element>>

[Example 48]

Adding a mixed solvent of DMIB/BC=70/30 (weight ratio) to a polyglycine solution (PA15) having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal An aligning agent. The liquid crystal alignment agent was applied to each of the glass substrate with the column spacer and the glass substrate with the ITO electrode by a spinner. In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was dried by heating at 70 ° C for 80 seconds. Then, Multi Light ML-501C/B manufactured by Ushio Electric Co., Ltd. was used to irradiate the substrate with ultraviolet light linearly polarized from the vertical right to the polarizing plate. The exposure energy at this time is measured by using an ultraviolet ray cumulative photometer UIT-150 (light receiver UVD-S365) manufactured by Oxtail Motor Co., Ltd., and is adjusted so as to become 2.0±0.1 J/cm ² at a wavelength of 365 nm. Exposure time. Then, the crucible was heated at 230 ° C for 15 minutes, and finally thermally annealed at 100 ° C for 30 minutes on a hot plate. The film thickness of the formed alignment film was 100 ± 10 nm. The whitening of the formed alignment film was visually confirmed, but no whitening was observed.

Two sheets of the alignment film formed on the substrate are faced with the alignment film, and the polarization directions of the ultraviolet rays irradiated to the respective alignment films are parallel, thereby forming an alignment film for facing the opposite direction. The voids of the liquid crystal composition were injected and bonded, and assembled into an empty FFS unit having a cell thickness of 4 μm. Further, an injection port for injecting liquid crystal into the empty FFS unit is provided at a position where the flow direction of the liquid crystal at the time of injection is substantially parallel to the polarization direction of the ultraviolet ray irradiated to the alignment film. The positive liquid crystal composition was vacuum-injected into the produced empty FFS unit to produce a transverse electric field photoisomerization type liquid crystal display element. The flow alignment of the produced liquid crystal display element was visually confirmed, but no flow alignment was observed.

Using a transverse electric field photoisomerization type liquid crystal display fabricated in the manner described The element was measured for the AC afterimage (luminance change rate) ΔB (%) by the method described above, and found to be 2.8%.

Using the transverse electric field photoisomerization type liquid crystal display device produced as described above, the liquid crystal alignment axis stability Δφ (deg) was measured by the above-described method, and the initial value was 0.021 deg, and the value after 5 minutes was obtained. 0.012deg.

[Example 49 to Example 53]

A solvent having the same solvent composition as that of polylysine was added to the polypergic acid solution PA16-polyglycine solution PA20 having a polymer solid concentration of 6 wt%, and diluted to a polymer solid concentration of 4 wt%. A liquid crystal alignment agent is prepared. Using the obtained liquid crystal alignment agent, a transverse electric field photoisomerization type liquid crystal display element was produced in accordance with the method of Example 48, and a positive liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the transverse electric field photoisomerization type liquid crystal display device obtained were measured. The results obtained are summarized in Table 10 together with the results of Example 48.

[Examples 54 to 58]

Adding a solvent having the same solvent composition as that of polylysine to polyphosphoric acid solution PA35~polyglycine solution PA38 and polylysine solution PA44 having a polymer solid concentration of 6 wt%, and diluting into a polymer The solid content concentration was 4% by weight to prepare a liquid crystal alignment agent. A transverse electric field was produced in accordance with the method of Example 48 except that the lamp of the light source was changed from Multi Light ML-501C/B manufactured by Oxtail Motor Co., Ltd. to a metal halide lamp UVL-1500M2-N1 manufactured by Oxtail Motor Co., Ltd. A photoisomerization type liquid crystal display element is injected into a positive type liquid crystal composition. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the transverse electric field photoisomerization type liquid crystal display device obtained were measured. The results obtained are summarized in Table 10 together with the results of Examples 48 to 53.

[Comparative Example 9]

Adding a mixed solvent of NMP/BC=70/30 (weight ratio) to a polyamic acid solution PA26 having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent . Using the obtained liquid crystal alignment agent, a transverse electric field photoisomerization type liquid crystal display element was produced in accordance with the method of Example 48, and a positive liquid crystal composition was injected. The alignment film whitening, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) of the transverse electric field photoisomerization type liquid crystal display device obtained were measured. The results obtained are shown in Table 10 together with the results of the examples.

<<4-5. Transverse electric field photodecomposition type liquid crystal display element>>

[Example 59]

Adding a mixed solvent of DMIB/BC=70/30 (weight ratio) to a polyglycine solution (PA21) having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal An aligning agent. The liquid crystal alignment agent was applied to each of the glass substrate with the column spacer and the glass substrate with the ITO electrode by a spinner. In addition, in the following examples and comparative examples, the rotational speed of the rotator was adjusted in accordance with the viscosity of the liquid crystal alignment agent, and the alignment film was changed to the following film thickness. After coating, the film was dried by heating at 70 ° C for 80 seconds, and then heated and calcined at 230 ° C for 30 minutes to form an alignment film having a film thickness of 100 ± 10 nm. Then, the Multi Light ML-501C/B manufactured by Oxtail Motor Co., Ltd. was used to irradiate the substrate with ultraviolet light linearly polarized from the vertical right to the polarizing plate. The exposure energy at this time is measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceiver UVD-S365) manufactured by Oxtail Motor Co., Ltd., and is adjusted so as to become 2.0±0.1 J/cm ² at a wavelength of 254 nm. Exposure time. The whitening of the formed alignment film was visually confirmed, but no whitening was observed.

Two sheets of the alignment film formed on the substrate are faced with the alignment film, and the polarization directions of the ultraviolet rays irradiated to the respective alignment films are parallel, thereby forming an alignment film for facing the opposite direction. The voids of the liquid crystal composition were injected and bonded, and assembled into an empty FFS unit having a cell thickness of 4 μm. Further, an injection port for injecting liquid crystal into the empty FFS unit is provided at a position where the flow direction of the liquid crystal at the time of injection is substantially parallel to the polarization direction of the ultraviolet ray irradiated to the alignment film. The positive liquid crystal composition was vacuum-injected into the produced empty FFS unit to produce a lateral electric field photodegradable liquid crystal display element. The flow alignment of the produced liquid crystal display element was visually confirmed, but no flow alignment was observed.

The AC afterimage (luminance change rate) ΔB (%) was measured by the above-described method using the transverse electric field photodegradable liquid crystal display device produced as described above, and found to be 7.8%.

Using the transverse electric field photodegradable liquid crystal display device produced as described above, the liquid crystal alignment axis stability Δφ (deg) was measured by the above-described method, and the initial value was 0.062 deg, and the value after 5 minutes was 0.032 deg. .

[Example 60 to Example 62]

Adding a solvent having the same solvent composition as the polylysine to the polyamic acid solution PA22, the polyaminic acid solution PA39, and the polyaminic acid solution PA40 having a polymer solid concentration of 6 wt%, respectively, and diluting into a polymer The solid content concentration was 4% by weight to prepare a liquid crystal alignment agent. Using the obtained liquid crystal alignment agent, a transverse electric field photodegradable liquid crystal display element was produced in accordance with the method of Example 59, and a positive liquid crystal composition was injected. The alignment film whitening and flow distribution of the transverse electric field photodegradable liquid crystal display element obtained were measured Direction, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg). The results obtained are summarized in Table 11 together with the results of Example 59.

[Comparative Example 10]

Adding a mixed solvent of NMP/BC=70/30 (weight ratio) to a polyamic acid solution PA27 having a polymer solid concentration of 6 wt%, and diluting to a polymer solid content concentration of 4 wt% to prepare a liquid crystal alignment agent . Using the obtained liquid crystal alignment agent, a transverse electric field photodegradable liquid crystal display element was produced in accordance with the method of Example 59, and a positive liquid crystal composition was injected. The alignment film whitening, the flow alignment, the AC afterimage (luminance change rate) ΔB (%), and the liquid crystal alignment axis stability Δφ (deg) of the obtained transverse electric field photodegradable liquid crystal display device were measured. The results obtained are shown in Table 11 together with the results of the examples.

According to the comparison of Examples 23 to 62 and Comparative Example 6 to Comparative Example 10, it is understood that the liquid crystal display element produced by using the liquid crystal alignment agent of the present invention lowers the AC afterimage and has high stability of the liquid crystal alignment axis.

[Industrial availability]

By providing the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention, it is possible to produce a liquid crystal display element having excellent afterimage characteristics and excellent alignment stability.

Claims (16)

A liquid crystal alignment agent containing a polyglycine or a derivative thereof obtained by reacting tetracarboxylic dianhydride with a diamine, and a solvent containing a solvent of the following formula (A) At least one of the indicated compounds: In the formula, R ¹ and R ² are each independently an alkyl group having 1 to 3 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein the compound represented by the formula (A) is a compound selected from the group consisting of the compounds represented by the following formulas (A-1) to (A-6). At least one of the groups, The liquid crystal alignment agent according to claim 2, wherein the compound represented by the formula (A) is selected from the group consisting of the formula (A-1), the formula (A-4) and the formula (A-6). At least one of the groups of compounds represented. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the solvent contains at least one selected from the group consisting of a poor solvent, and the poor solvent comprises: ethylene glycol carbonate Ester, 1,2-propylene glycol carbonate, 1,3-propanediol carbonate, 2-methyl-1,3-propanediol carbonate, ethylene glycol monobutyl ether (butyl cellosolve), ethylene glycol monomethyl ether Acid ester, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, ethylene glycol monophenyl ether, ethylene glycol phenyl ether acetate, ethylene glycol methyl phenyl ether, ethylene glycol Phenyl phenyl ether, ethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl phenyl ether, diethylene glycol single Ether, diethylene glycol monoethyl ether acetate, diethylene glycol diethyl ether, diethylene glycol monobutyl ether, diethylene glycol dibutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol Monopropyl ether, diethylene glycol mono-2-ethylhexyl ether, triethylene glycol monomethyl ether, triethylene glycol monododecyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether Tetraethylene glycol dimethyl ether, propylene glycol diacetic acid Ester, propylene glycol monomethyl ether, propylene glycol methyl phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether acetate, propylene glycol monophenyl ether, propylene glycol monopropyl ether, dipropylene glycol dimethyl ether, dipropylene glycol Monopropyl ether, tripropylene glycol dimethyl ether, tripropylene glycol diethyl ether, n-propyl acetate, butyl acetate, amyl acetate, n-hexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, n-butyl propionate Ester, methyl 2-hydroxy-isobutyrate, 2-methylpentanone-2,4-diol, tert-butanol, triethylmethanol, third pentanol, 1-methylcyclohexanol, 2 , 5-dimethylhexane-2,5-diol, n-butanol, bis(3-methylbutyl)ether, di-n-pentyl ether (dipentyl ether), 4-heptanone, 5-fluorenone , 2,6-dimethyl-4-heptanone, 4-methyl-2-pentyl acetate, butyl lactate, isoamyl lactate, n-butyl lactate, dipropylene Glycol methyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, benzyl alcohol , phenylethyl alcohol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethyl acetate, 2,4-pentanedione, ethyl-3- Ethoxypropionate, decyl alcohol, tetrahydrofurfuryl alcohol, 3-methyl-3-methoxybutanol, 1,3-dioxolane, isoamyl propionate, isoamyl isobutyrate, diiso) Pentyl ether, butyl benzene, and diisobutyl ketone. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the solvent contains a group selected from the group consisting of N-alkyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, At least one of the group of good solvents of lactones and 1,3-dialkyl-2-imidazolidinones. The liquid crystal alignment agent according to claim 5, wherein the good solvent is selected from the group consisting of N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-cyclohexyl-2-pyrrolidone. At least one of γ -butyrolactone and 1,3-dimethyl-2-imidazolidinone. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the tetracarboxylic dianhydride which is reacted with the diamine is selected from the group consisting of the following formula (AN-I) (AN-VII) and at least one of the group of tetracarboxylic dianhydride represented by the formula (PAN-1) to (PAN-8): In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -; in the formula (AN-II), G is a single bond, and the carbon number is 1~ 20 alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; (AN-II)~ In AN-IV), Y is independently one selected from the group consisting of trivalent groups, and a bond is bonded to any carbon, and at least one hydrogen of the group may be methyl, ethyl or benzene. Base substitution In the formula (AN-III) to the formula (AN-V), the ring A is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, and at least the group One hydrogen may be substituted by a methyl group, an ethyl group or a phenyl group, and the bond bond attached to the ring may be bonded to any carbon constituting the ring, and two bond bonds may be bonded to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group; in the formula (AN-VII), G ^{10 is} independently -O-, -COO- or -OCO-, and r is independent. Is 0 or 1; The liquid crystal alignment agent according to claim 7, wherein the tetracarboxylic dianhydride which is reacted with the diamine is selected from the group consisting of the following formula (AN-1-1) and the formula (AN-1-13). ), Formula (AN-2-1), Formula (AN-2-2), Formula (AN-3-1), Formula (AN-3-2), Formula (AN-4-1), Formula (AN) -4-5), formula (AN-4-6), formula (AN-4-17), formula (AN-4-21), formula (AN-4-26), formula (AN-4-30) At least one of the group consisting of: (AN-9-1), (AN-13-1), (AN-16-1), and (PAN-1): In the formula (AN-4-17), m is an integer of 1 to 12; in the formula (AN-13-1), Ph represents a phenyl group. The liquid crystal alignment agent according to any one of claims 1 to 3, wherein the diamine reacted with the tetracarboxylic dianhydride is selected from the group consisting of the following formula (DI-1) (DI-16), formula (DIH-1) ~ formula (DIH-3), formula (DI-31) ~ formula (DI-35) and formula (PDI-1) ~ formula (PDI-12) At least one of the groups: In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH- or -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. Can be substituted by -OH; in formula (DI-3) and formula (DI-5)~ (DI-7), G ^{21 is} independently a single bond, -NH-, -NCH ₃ -, -O-, -S -, -SS-, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH _{2 m'} -, -O-(CH ₂ ) _m' -O-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, -(OC ₂ H ₄ ) _m' -O- , -O-CH ₂ -C(CF ₃ ) ₂ -CH ₂ -O-, -O-CO-(CH ₂ ) _m' -CO-O-, -CO-O-(CH ₂ ) _m' -O -CO-, -(CH ₂ ) _m' -NH-(CH ₂ ) _m' -, -CO-(CH ₂ ) _k -NH-(CH ₂ ) _k -, -(NH-(CH ₂ ) _{m' k} -NH-, -CO-C ₃ H ₆ -(NH-C ₃ H ₆ ) _n -CO- or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12, k is an integer from 1 to 5, n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; in the formula (DI-6) and (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or an alkylene group having a carbon number of 1 to 10; formula (DI-2) At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , - CO ₂ H, -C ONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl group, and, in the formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring may be represented by the following formula (DI-4-a) a substituent of the formula (DI-4-e); a group in which the bonding position is not fixed to a carbon atom constituting the ring means that the bonding position on the ring is arbitrary, and -NH _{2 is} on the cyclohexane ring or the benzene ring. The bonding position is any position other than the bonding position of G ²¹ or G ²² ; In the formulae (DI-4-a) and (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; In the formula (DI-11), r is 0 or 1; in the formula (DI-8) to the formula (DI-11), the bonding position of -NH ₂ bonded to the ring is an arbitrary position; In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Phenyl is extended, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, and p is independently 0. An integer of ~3, q is an integer from 0 to 4; in the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, -B, carbon number 1 to 6 alkyl, alkoxy, vinyl, alkynyl, q is independently an integer of 0 to 4; in the formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1; the bonding position is not fixed to the carbon atom constituting the ring; The upper base indicates that the bonding position on the ring is arbitrary; in the formula (DI-13) to the formula (DI-16), the bonding position of the -NH ₂ bonded to the ring is an arbitrary position; In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; in the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; In (DIH-3), ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond and has a carbon number of 1 to 20 carbon atoms. Alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ - or -C(CF ₃ ) ₂ -; formula (DIH-2) and formula (DIH- In 3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position; In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- , -OCF ₂ - or -(CH ₂ ) _m' -, m' is an integer of 1 to 12, and R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or the following a group represented by the formula (DI-31-a) wherein at least one hydrogen of the alkyl group may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡ C-substituted, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF _2, -OCF _3, an alkyl group having 3 to 30 carbon atoms, or a carbon number of 3 to 30 The alkoxy group is substituted, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are independently a single bond or an alkylene group having 1 to 12 carbon atoms, and one or more alkylene groups. -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- In the diyl, naphthalene-2,7-diyl or inden-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , s, t, and u are independent integers of 0 to 2, and their total is 1 to 5. When s, t, or u is 2, the two bonding groups in each parenthesis may be the same or different, and The two rings may be the same or different, and R ²⁶ is -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, or CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be divalent represented by the following formula (DI-31-b) Substitution, In the formula (DI-31-b), R ²⁷ and R ^{28 are} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6; In formula (DI-32) and formula (DI-33), G ^{30 is} independently a single bond, -CO- or -CH ₂ -, R ^{29 is} independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, and carbon number is 1~ An alkyl group of 20 or an alkenyl group having 2 to 20 carbon atoms; one hydrogen of the benzene ring in the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the bonding position is not fixed. The group on any one of the carbon atoms represents any bonding position on the ring; in the formula (DI-32) and the formula (DI-33), -NH ₂ bonded to the benzene ring is represented in The bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms, R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-, and R ³² is a carbon number of 6~ An alkyl group of 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is a 1,4-phenylene group or a 1,4-cyclohexylene group, and r is 0 or 1; -NH ₂ on the benzene ring means that the bonding position on the ring is arbitrary; In the formula (PDI-7), R ^{51 is} independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , and b is independently an integer of 0 to 2. The liquid crystal alignment agent according to claim 9, wherein the diamine reacted with the tetracarboxylic dianhydride is selected from the following formula (DI-1-3), formula (DI-2-1) ), formula (DI-4-1), formula (DI-4-5), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI -5-30), formula (DI-5-37), formula (DI-7-3), formula (DI-8-2), formula (DI-12-1), formula (DI-13-1) , formula (DI-14-8), formula (DIH-2-1), formula (DI-31-2), formula (DI-31-5), formula (DI-31-47), formula (DI- At least one of a group consisting of 34-2), a formula (DI-34-4), a formula (DI-34-7), a formula (PDI-6-1), and a formula (PDI-7-1) : In the formula (DI-5-1), the formula (DI-5-37), and the formula (DI-7-3), m is an integer from 1 to 12; in the formula (DI-5-30), k is 1~ An integer of 5; in the formula (DI-7-3), n is 1 or 2; in the formula (DI-31-2), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms. In the formula (DI-31-5), R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms; in the formula (DI-34-2), R ⁴⁰ is hydrogen or carbon. In the formula (DI-34-4) and the formula (DI-34-7), R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms. The liquid crystal alignment agent according to any one of claims 1 to 3, further comprising a compound selected from the group consisting of an alkenyl-substituted nadic ylidene compound having a radical polymerizable unsaturated double bond. At least one of the group of the compound of the oxazine compound, the oxazoline compound, and the epoxy compound. The liquid crystal alignment agent according to claim 11, wherein the alkenyl-substituted nadicilimine compound is selected from the group consisting of bis{4-(allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinhomine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl In the group of compounds of quinone imine) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine) at least one. The liquid crystal alignment agent according to claim 11, wherein the compound having a radical polymerizable unsaturated double bond is selected from the group consisting of N, N'-extended ethyl bis acrylamide, N, N' a compound of -(1,2-dihydroxyethylidene)bisacrylamide, ethylidene diacrylate, and 4,4'-methylenebis(N,N-dihydroxyethylidene anilide) At least one of the groups. The liquid crystal alignment agent according to claim 11, wherein the epoxy compound is selected from the group consisting of N, N, N', N'-tetraglycidyl-m-xylylenediamine, 1,3- Bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, 2-[ 4-(2,3-epoxypropoxy)benzene 2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)]ethyl]phenyl]propane, 3,4-epoxy ring Hexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer, and 2-(3,4-ring At least one of the group of compounds of oxycyclohexyl)ethyltrimethoxydecane. A liquid crystal alignment film formed of the liquid crystal alignment agent according to any one of claims 1 to 14. A liquid crystal display element comprising the liquid crystal alignment film according to claim 15 of the patent application.