KR102159410B1 - Liquid crystal aligning agents and liquid crystal display devices - Google Patents

Abstract

식 중, R¹ 및 R² 는 각각 독립적으로 탄소수 1 ∼ 3 의 알킬.The present invention is a solution comprising a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride and a diamine, and a solvent, wherein the solvent is a liquid crystal orientation containing at least one compound represented by the following formula (A) It's J. The liquid crystal aligning agent of the present invention does not easily cause a change in viscosity at room temperature, and does not cause cratering at the time of application of the aligning agent or whitening of the film-formed alignment film. Moreover, the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention has good orientation stability of liquid crystal molecules. Further, the liquid crystal display device having the liquid crystal alignment film is excellent in afterimage characteristics.

In the formula, R ¹ and R ² are each independently C1-C3 alkyl.

Description

A liquid crystal aligning agent and a liquid crystal display element TECHNICAL FIELD

The present invention relates to a liquid crystal aligning agent and a liquid crystal display element used to form a liquid crystal aligning film of a liquid crystal display element.

More specifically, it relates to a liquid crystal aligning agent that does not cause a change in viscosity at room temperature and does not cause cratering or whitening of a film-produced alignment film when the alignment agent is applied, and a liquid crystal display device including the obtained liquid crystal alignment film. .

In a liquid crystal display element, a liquid crystal alignment film made of polyamic acid, polyimide, etc. is formed on the surface of a substrate on which a transparent electrode or a metal electrode is formed to form a substrate for a liquid crystal display element, and the two sheets are disposed opposite to each other to form a liquid crystal layer in the gap. Formed into a sandwich structure cell. In general, this liquid crystal aligning film is produced by performing a so-called "rubbing treatment" on the surface of the polyimide film formed on the electrode. Moreover, a vertical alignment film that has not been rubbed, a photoalignment film that irradiates polarized UV light, and the like are also used.

Usually, the printing method or the inkjet method is used to form the alignment layer, but with the recent high quality of the liquid crystal display device, the printing unevenness at the time of forming the alignment layer affects the display characteristics, making it more important to secure good film composition. Became (refer to Patent Document 1, etc.).

One of the causes of poor film production that can be seen during the production of the alignment film film is a decrease in the viscosity of the alignment agent at room temperature. Since printing of the liquid crystal aligning agent is performed at room temperature, film thickness non-uniformity due to a decrease in viscosity has become a problem. Further, a phenomenon in which a pinhole or the like is easily generated due to cratering occurs when the alignment agent is applied, or a phenomenon in which the alignment agent itself or the alignment film is whitened due to moisture absorption of the alignment agent is also a problem. In addition, it is known that the film thickness non-uniformity, pinholes, and whitening of these liquid crystal alignment films lead to problems of alignment properties and afterimage characteristics of a liquid crystal panel (refer to Patent Documents 2 and 3, etc.).

Japanese Laid-Open Patent Publication 2009-37222 Japanese Patent Laid-Open Publication No. Hei 10-274772 International Publication No. 2009/148100

It is an object of the present invention to provide a liquid crystal aligning agent which does not cause a change in viscosity at room temperature and does not cause cratering or whitening of an alignment film produced when an alignment agent is applied. Moreover, it is excellent in the afterimage characteristic which has a liquid crystal aligning film obtained from this aligning agent, and it aims at providing the liquid crystal display element which is favorable in orientation stability.

The present invention has the following configuration.

[1] A solution comprising a polyamic acid or a derivative thereof obtained by reacting a tetracarboxylic dianhydride and a diamine, and a solvent, wherein the solvent contains at least one compound represented by the following formula (A). My :

In the formula, R ¹ and R ² are each independently alkyl having 1 to 3 carbon atoms.

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

[3] At least one compound represented by formula (A) is selected from the group of compounds represented by formulas (A-1), (A-4) and (A-6), the liquid crystal alignment according to item [2]. My.

[4] Ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 2-methyl-1,3-propylene 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 phenyl 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 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 diacetate, 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, acetic acid Pentyl, n-hexyl acetate, cyclohexyl acetate, 2-methylcyclohexyl acetate, n-butyl propionate, 2-hydroxy-methyl isobutyrate, 2-methylpentanone-2,4-diol, t-butyl alcohol, tri Ethylcarbinol, t-amyl alcohol, 1-methylcyclohexanol, 2,5-dimethylhexane-2,5-diol, n-butyl alcohol, bis(3-methylbutyl) ether, di-n-pentyl ether ( Diamyl ether), 4-heptanone, 5-nonanone, 2,6-dimethyl-4-heptanone, 4-methyl-2-pentyl acetate, butyl lactate, isoamyl lactate, n-butyl lactate Stere, dipropylene glycol methyl ether, 4-hydroxy-4-methyl-2-pentanone (diacetone alcohol), methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, benzyl alcohol , Phenethyl alcohol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethyl cetate, 2,4-pentanedione, ethyl-3-ethoxypropio Nate, furfuryl alcohol, tetrahydrofurfuryl alcohol, 3-methyl-3-methoxybutanol, 1,3-dioxolane, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, butyrophenone and di A liquid crystal aligning agent containing at least one selected from the group of poor solvents consisting of isobutyl ketone.

[5] A positive solvent comprising N-alkyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, lactones and 1,3-dialkyl-2-imidazolidinones (F) The liquid crystal aligning agent in any one of said [1]-[4] containing at least 1 selected from the group of.

[6] Good solvents are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, γ-butyrolactone and 1,3-dimethyl-2- The liquid crystal aligning agent according to [5], at least one member selected from imidazolidinone.

[7] A group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII) and (PAN-1) to (PAN-8) with diamine and tetracarboxylic dianhydride reacted At least one member selected from, the liquid crystal aligning agent according to any one of the above [1] to [6]:

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;

In the formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C (CF ₃ ) ₂ -;

In formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups, and the bond hand is connected to an arbitrary carbon, and at least one hydrogen of this group May be substituted with methyl, ethyl or phenyl,

In formulas (AN-III) to (AN-V), 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 one hydrogen of this group is It may be substituted with methyl, ethyl or phenyl, the bond hand hanging on the ring is linked to any carbon constituting the ring, and the two bond hands may be linked to the same carbon;

In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl;

In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

[8] Diamine and tetracarboxylic dianhydride reacted with the following formulas (AN-1-1), (AN-1-13), (AN-2-1), (AN-2-2), (AN -3-1), (AN-3-2), (AN-4-1), (AN-4-5), (AN-4-6), (AN-4-17), (AN-4 -21), (AN-4-26), (AN-4-30), (AN-9-1), (AN-13-1), (AN-16-1) and (PAN-1) At least one member selected from the group consisting of, the liquid crystal aligning agent according to [7] above:

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

[9] Tetracarboxylic dianhydride and diamine reacted are the following formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), (DI-31) to (DI-) At least one member selected from the group consisting of 35) and (PDI-1) to (PDI-12), the liquid crystal aligning agent according to any one of the above [1] to [8]:

In formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ -may be substituted with -NH-, -O-, m is an integer of 1 to 12, and alkylene At least one hydrogen may be substituted with -OH;

In formulas (DI-3) and (DI-5) to (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 'is} -S-, m' are independently an integer of 1 ~ 12, k is 1, It is an integer of -5, and n is 1 or 2;

In formula (DI-4), s is independently an integer of 0-2;

Hydrogen having at least one cyclohexane ring and a benzene ring in formulas (DI-2) to (DI-7) is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ It may be substituted with F ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl, and in the formula (DI-4), the following formulas (DI-4-a) to (DI- You may be substituted with 4-e);

The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ²² Is any position excluding the bonding position of;

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;

In formula (DI-11), r is 0 or 1;

In formulas (DI-8) to (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 alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;

In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego ;

In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, -F, -Cl, -B, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, q is independently an integer of 0-4;

In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group;

In formula (DI-16), G ²⁴ is a single bond, C2-C6 alkylene, or 1,4-phenylene, and r is 0 or 1;

The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;

In formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position;

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

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

In formula (DIH-3), ring E is each independently a cyclohexane ring or a benzene ring, at least one hydrogen of this group may be substituted with methyl, ethyl or phenyl, and Y is a single bond, 1 to C 1 20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -;

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

In 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 '-} and, m' is an integer of 1 ~ 12, R ²⁵ is a group of the formula, or to having a alkyl, phenyl, a steroid skeleton having a carbon number of 3 to 30 ( DI-31-a), in this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ -is -O-, -CH=CH- or -C optionally substituted by a ≡C- is a hydrogen of the phenyl is a _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms It may be substituted with alkoxy, and the bonding position of -NH ₂ bonded to the benzene ring represents an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ -of this alkylene is- O-, -COO-, -OCO-, -CONH-, -CH=CH- may be substituted, and 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, pyridin-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2 ,7-diyl or anthracene-9,10-diyl, in Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , and s , t and u are independently integers of 0 to 2, the sum of which is 1 to 5, and when s, t or u are 2, the two linking groups in each parenthesis may be the same or different, and 2 Ring may be the same or different, R ²⁶ is -F, -OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF _3, and -CH ₂ -having at least one alkyl 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 alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , and R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms;

One hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms, and the group in which the bonding position is not fixed to any one carbon atom constituting the ring, It shows that the bonding position in the ring is arbitrary;

In formulas (DI-32) and (DI-33), -NH ₂ bonded to a benzene ring represents that the bonding position in the ring is arbitrary;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O- or C1-C6 alkylene, G ³² is a single bond or C1-C3 alkylene, R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, -CH ₂ -having at least one alkyl may be substituted with -O-, -CH=CH- or -C≡C-, and R ³² is 6 to carbon atoms 22 alkyl, R ³³ is hydrogen or C1-C22 alkyl, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1; And -NH ₂ bonded to a benzene ring represents that the bonding position in the ring is arbitrary;

In 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;

In formula (PDI-12), R ⁴³ is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine.

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

In formulas (DI-5-1), (DI-5-37) and (DI-7-3), m is an integer of 1 to 12;

In formula (DI-5-30), k is an integer of 1-5;

In formula (DI-7-3), n is 1 or 2;

In the formula (DI-31-2), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms;

In the formula (DI-31-5), R ³⁵ is C1-C30 alkyl or C1-C30 alkoxy;

In formula (DI-34-2), R ⁴⁰ is hydrogen or C1-C20 alkyl;

In formulas (DI-34-4) and (DI-34-7), R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms.

[11] The above [1] further containing at least one selected from the group consisting of an alkenyl substituted nadamide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound and an epoxy compound ] The liquid crystal aligning agent in any one of [10].

[12] Alkenyl substituted nadamide compound is bis(4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl)methane, N,N'-m-xyl Rylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene The liquid crystal aligning agent according to [11], at least one member selected from the group of compounds consisting of -2,3-dicarboxyimide).

[13] Compounds having a radically polymerizable unsaturated double bond include N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, ethylenebisacrylate and 4, At least one member selected from the group of compounds consisting of 4'-methylenebis (N,N-dihydroxyethylene acrylate aniline), the liquid crystal aligning agent according to [11].

[14] The epoxy compound is N,N,N',N'-tetraglycidyl-m-xylenediamine, 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-phenyl At least one member selected from the group of compounds consisting of maleimide-glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, the liquid crystal aligning agent according to [11] above. .

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

[16] A liquid crystal display device comprising the liquid crystal aligning film according to [15].

The present invention can provide a liquid crystal aligning agent which does not easily cause a change in viscosity at room temperature and does not cause cratering or whitening of an alignment film produced when the alignment agent is applied. Moreover, the liquid crystal display element provided with the liquid crystal aligning film obtained by it is excellent in the afterimage characteristic, and can provide a liquid crystal display element which is favorable in orientation stability.

The liquid crystal aligning agent of this invention contains polyamic acid which is a reaction product of tetracarboxylic dianhydride and diamine, or its derivative. As said tetracarboxylic dianhydride, photosensitive tetracarboxylic dianhydride, aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, aromatic tetracarboxylic dianhydride, etc. are mentioned, for example. . Examples of the diamine include photosensitive diamine, non-side-chain diamine, side-chain diamine, and hydrazide. The polyamic acid or its derivative is a component that dissolves in a solvent when the liquid crystal aligning agent described later containing a solvent is used, and when the liquid crystal aligning agent is a liquid crystal aligning film described later, a liquid crystal alignment film containing polyimide as a main component can be formed. It is an ingredient. Examples of such polyamic acid derivatives include soluble polyimide, polyamic acid ester, polyhydrazide acid, polyamic acid amide and polyhydrazide-amic acid, and more specifically 1) Polyimide in which all amino and carboxyls of polyamic acid are dehydrated and cyclized, 2) partial polyimide, which is partially dehydrated and cyclized, 3) polyamic acid ester in which carboxyl of polyamic acid is converted into ester, 4) tetracarboxylic dianhydride A polyamic acid-polyamide copolymer obtained by substituting a part of an acid dianhydride contained in a compound with an organic dicarboxylic acid to react, and 5) a polyamic acid-polyamide copolymer obtained by dehydration and ring closure reaction. Amidimide and the like. The polyamic acid polymer and the polyimide polymer may be one type of compound or two or more types.

The terms used in the present invention will be described. "Arbitrary" used when defining a chemical structural formula indicates that not only the position but also the number is arbitrary. In the chemical structural formula, a group surrounding a letter (eg A) in a hexagon means that it is a group of a ring structure (ring A).

The tetracarboxylic dianhydride used to prepare the polyamic acid polymer and polyimide polymer of the present invention will be described. Hereinafter, the description of "tetracarboxylic dianhydride" not only indicates a case where tetracarboxylic dianhydride is used alone, but also indicates a case where a plurality of tetracarboxylic dianhydrides are used as a mixture.

If necessary, the alignment film formed from the liquid crystal aligning agent of the present invention may be provided with anisotropy by rubbing treatment or light irradiation.

When imparting anisotropy by light irradiation, the liquid crystal aligning agent of the present invention is applied to a substrate, dried by preheating, and then linearly polarized light of ultraviolet rays is irradiated through a polarizing plate. A photosensitive group derived from a chain, photosensitive diamine causes photoisomerization. As the main chain of the polymer substantially parallel to the polarization direction is selectively photo-isomerized or light dimerized, the main chain of the polymer forming the film is dominated by a component that is substantially perpendicular to the polarization direction of the irradiated ultraviolet rays. Therefore, after heating the substrate to dehydrate and ring the polyamic acid to form a polyimide film, the liquid crystal molecules of the liquid crystal composition injected into the cells assembled using the substrate are in a direction perpendicular to the polarization direction of the irradiated ultraviolet rays. Align and orient. The step of irradiating the film with linearly polarized light of ultraviolet rays may be before the heating step for polyimideization, or after heating and polyimideization.

Tetracarboxylic dianhydride used to prepare the polyamic acid and its derivatives of the present invention will be described.

The tetracarboxylic dianhydride used in the present invention is not limited and can be selected from known tetracarboxylic dianhydrides. Such tetracarboxylic dianhydride is an aromatic system in which a dicarboxylic anhydride is directly bonded to an aromatic ring (including a heteroaromatic ring system) and an aliphatic system in which a dicarboxylic acid anhydride is not directly bonded to an aromatic ring It may belong to any group of (including a heterocyclic system) and photosensitive tetracarboxylic dianhydride.

Preferred examples of such tetracarboxylic dianhydride include formulas (AN-I) to (AN-VII) and formulas (PAN-1) from the viewpoint of easiness of obtaining raw materials, ease of polymer polymerization, and electrical properties of the film. Tetracarboxylic dianhydride represented by-(PAN-8) is mentioned.

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C (CF ₃ ) ₂ -. In the formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups, the bond hand is connected to an arbitrary carbon, and at least one of these groups Hydrogen may be substituted with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), 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 one hydrogen of these groups is It may be substituted with methyl, ethyl, or phenyl, and the bond hand hanging on the ring is linked to any carbon constituting the ring, and the two bond hands may be linked to the same carbon, in formula (AN-VI) , X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl. And, in the formula (AN-VII), G ¹⁰ is independently -O-, -COO-, or -OCO-, and r is independently 0 or 1.

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

In formula (AN-1), G ¹¹ is a single bond, C1-C12 alkylene, 1,4-phenylene, or 1,4-cyclohexylene. 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-, hydrogen of CH may be substituted with -CH ₃ .

When G ¹² is >N-, there is no case where G ¹¹ is a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And R ¹¹ is hydrogen or -CH ₃ . As an example of the tetracarboxylic dianhydride represented by formula (AN-1), a compound represented by the following formula is mentioned.

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

In formula (AN-2), R ¹² is independently hydrogen, -CH ₃ , -CH ₂ CH ₃ or phenyl. As an example of the tetracarboxylic dianhydride represented by formula (AN-2), the compound represented by the following formula is mentioned.

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring. As an example of the tetracarboxylic dianhydride represented by formula (AN-3), the compound represented by the following formula is mentioned.

In formula (AN-4), 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 following It is a divalent group represented by the formula (G13-1) of, and m is an integer of 1 to 12.

In formula (G13-1), G ^13a and G ^13b are each independently a single bond, a divalent group represented by -O- or -NHCO-. Phenylene is preferably 1,4-phenylene and 1,3-phenylene. As an example of the tetracarboxylic dianhydride represented by formula (AN-4), a compound represented by the following formula is mentioned.

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

In 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. As an example of the tetracarboxylic dianhydride represented by formula (AN-5), the compound represented by the following formula is mentioned.

In 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. As an example of the tetracarboxylic dianhydride represented by formula (AN-6), a compound represented by the following formula is mentioned.

In formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. As an example of the tetracarboxylic dianhydride represented by formula (AN-7), the compound represented by the following formula is mentioned.

In formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring. As an example of the tetracarboxylic dianhydride represented by formula (AN-8), the compound represented by the following formula is mentioned.

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

Formula (AN-10) is the following tetracarboxylic dianhydride.

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring. As an example of the tetracarboxylic dianhydride represented by formula (AN-11), the compound represented by the following formula is mentioned.

In formula (AN-12), each of ring A ¹¹ is independently a cyclohexane ring or a benzene ring. As an example of the tetracarboxylic dianhydride represented by Formula (AN-12), the compound represented by the following formula is mentioned.

In formula (AN-13), X ¹³ is alkylene having 2 to 6 carbon atoms, and Ph represents phenyl. As an example of the tetracarboxylic dianhydride represented by formula (AN-13), the compound represented by the following formula is mentioned.

In formula (AN-14), G ¹⁴ is independently -O-, -COO-, or -OCO-, and r is independently 0 or 1. As an example of the tetracarboxylic dianhydride represented by formula (AN-14), the compound represented by the following formula is mentioned.

In formula (AN-15), w is an integer of 1-10. As an example of the tetracarboxylic dianhydride represented by formula (AN-15), a compound represented by the following formula is mentioned.

The following compounds are mentioned as tetracarboxylic dianhydride other than the above.

In the present invention, the following formulas (PAN-1) to (PAN-8) can be mentioned as the photosensitive tetracarboxylic dianhydride.

In the case of focusing on improving the orientation of the liquid crystal display element, among the above acid dianhydrides, formulas (AN-1-13), (AN-2-1), (AN-2-2), and (AN-4 The compounds represented by -17) and (PAN-1) are particularly preferred.

In the case of focusing on improving the transmittance of the liquid crystal display element, among the above acid dianhydrides, formulas (AN-1-1), (AN-1-13), (AN-2-1), and (AN-2 -2), (AN-3-1), (AN-4-1), (AN-4-30), (AN-9-1), (AN-13-1) and (AN-16-1 A compound represented by) is particularly preferred.

In the case of focusing on improving the electrical properties of a liquid crystal display device, among the above acid dianhydrides, formulas (AN-3-2), (AN-4-5), (AN-4-6), and (AN- The compounds represented by 4-21), (AN-4-26) and (AN-13-1) are particularly preferred.

The diamine and dihydrazide used to prepare the polyamic acid and its derivatives of the present invention will be described. In producing the polyamic acid of the present invention or a derivative thereof, it can be selected from known diamines and dihydrazides without limitation.

Diamines can be divided into two types according to their structure. That is, when the skeleton connecting two amino groups is viewed as a main chain, it is a group branching from the main chain, that is, a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms, and specific examples include a group having 3 or more carbon atoms, alkyl of 3 or more carbon atoms, alkoxyalkyl of 3 or more carbon atoms, and a steroid skeleton. As a group having one or more rings, the ring at the terminal has an effect as a side chain group having any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, and alkoxyalkyl having 2 or more carbon atoms as a substituent. In the following description, the diamine having such a side chain group is sometimes referred to as a side chain diamine. And the diamine which does not have such a side chain group may be called a non-side chain type diamine.

By appropriately using the non-side chain type diamine and the side chain type diamine separately, it is possible to respond to the pretilt angle required for each. It is preferable to use side chain type diamine together so that it does not impair the characteristic of this invention. In addition, it is preferable to select and use the side-chain type diamine and the non-side-chain type diamine for the purpose of improving vertical alignment, voltage retention, afterimage characteristics, and alignment with respect to liquid crystal.

The non-side chain type diamine will be described. The diamine of the following formulas (DI-1) to (DI-16) is mentioned as a diamine which does not have a known side chain.

In the above formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ -may be substituted with -NH-, -O-, m is an integer of 1 to 12, and alkyl At least one hydrogen of ene may be substituted with -OH. In formulas (DI-3) and (DI-5) to (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 'is} -S-, m' are independently an integer of 1 ~ 12, k is 1, It is an integer of -5, and n is 1 or 2. In formula (DI-4), s is an integer of 0-2 independently. In formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) _{It is 2} -or C1-C10 alkylene. At least one hydrogen of the cyclohexane ring and the benzene ring in formulas (DI-2) to (DI-7) is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and in the formula (DI-4), the following formulas (DI-4-a) to (DI-4-e) ) May be substituted. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In addition, the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is an arbitrary position except for the bonding position of G ²¹ or G ²² .

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

In formula (DI-11), r is 0 or 1. In formulas (DI-8) to (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 alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1-10. In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 to be. In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, -F, -Cl, -B, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, q is independently an integer of 0-4. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In formula (DI-16), G ²⁴ is a single bond, C2-C6 alkylene, or 1,4-phenylene, and r is 0 or 1. And, the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) are exemplified as diamines having no side chains of the formulas (DI-1) to (DI-16).

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

In formulas (DI-1-7) and (DI-1-8), k is an integer of 1-3 each independently.

Examples of diamines represented by formulas (DI-2) to (DI-3) are shown below.

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

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

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

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

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

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

In formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is an integer of 1 to 12, and formulas (DI-5-38) and (DI-5- In 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 formula (DI-6) is shown below.

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

In formulas (DI-7-3) and (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 formula (DI-8) is shown below.

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

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

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

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

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

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

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

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

Explain about dihydrazide. As the dihydrazide which does not have a known side chain, the dihydrazide of the following formula (DIH-1)-(DIH-3) is mentioned.

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

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

In formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen of these groups may be substituted with methyl, ethyl or phenyl, and Y is a single bond, 1 to 20 carbon atoms. Of alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -.

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

Examples of dihydrazide represented by formulas (DIH-1) to (DIH-3) are shown below.

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

The side chain type diamine will be described. The following groups are mentioned as a side chain group of a side chain type diamine.

As a side chain group, first, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy , Alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. Alkyl, alkenyl, and alkynyl in these groups are all groups having 3 or more carbon atoms. However, in the alkyloxyalkyl, it is sufficient to have 3 or more carbon atoms as a whole group. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy, provided that the terminal ring has an alkyl of 1 or more carbon atoms as a substituent, alkoxy of 1 or more carbon atoms, or alkoxyalkyl of 2 or more carbon atoms. , Phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexyl Phenyloxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl And groups having a cyclic structure such as cyclohexylbis(phenyl)oxycarbonyl.

In addition, as a group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings consisting of a benzene ring and a cyclohexane ring, the bonding group is independently a single bond, -O-, -COO- , -OCO-, -CONH-, or alkylene having 1 to 3 carbon atoms, and the terminal ring is a substituent having 1 or more carbon atoms, fluorine-substituted alkyl having 1 or more carbon atoms, alkoxy of 1 or more carbon atoms, or alkoxyalkyl of 2 or more carbon atoms Can be raised. It is effective as an airway side chain group having a steroid skeleton.

Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).

In 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 '-} and, m' is an integer of 1-12. Preferred examples of G ²⁶ are single bonds, -O-, -COO-, -OCO-, -CH ₂ O- and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are single bonds, -O-, -COO- , -OCO-, -CH ₂ O-, -CH ₂ -and -CH ₂ CH ₂ -. R ²⁵ is a group having a C3-C30 alkyl, phenyl, or steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ -may be substituted with -O-, -CH=CH- or -C≡C-. Hydrogen of the phenyl is _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, and may be substituted by alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms, a cycloalkyl Hydrogen of hexyl may be substituted with C3-C30 alkyl or C3-C30 alkoxy. The bonding position of -NH ₂ bonded to the benzene ring represents an arbitrary position in the ring, and the bonding position is preferably meta or para. That is, when the bonding position of the group "R ²⁵ -G ²⁶ -" is set to the 1 position, it is preferable that the two bonding positions are the 3 position and the 5 position or the 2 position and the 5 position.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ -of this alkylene is- You may be substituted with 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, pyridin-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and In ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , s, t and u are independently integers of 0 to 2, the sum of which is 1 to 5, s, t or When u is 2, the two linking 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 having 1 to 30 carbon atoms, a fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon _{atoms, -CN, -OCH 2 F, -OCHF} 2 or -OCF of the _three, are At least one -CH ₂ -of alkyl 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 alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferred examples of R ²⁶ are alkyl having 1 to 30 carbon atoms and alkoxy having 1 to 30 carbon atoms.

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , and R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms. In addition, a group in which the bonding position is not fixed to any one carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. It is preferable that one of the two groups "-phenylene-G ³⁰ -O-" in 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 positions of the two groups "-phenylene-G ³⁰ -O-" in the formula (DI-33) to the benzene ring are preferably meta-positions or para-positions with respect to the bonding positions of the steroid nuclei. . In formulas (DI-32) and (DI-33), -NH ₂ bonded to a benzene ring Represents that the bonding position in the ring is arbitrary.

In formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbons, and G ³² is a single bond or alkylene having 1 to 3 carbons. R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ -of this alkyl may be substituted with -O-, -CH=CH- or -C≡C-. R ³² is C6-C22 alkyl, and R ³³ is hydrogen or C1-C22 alkyl. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferable that it is independently a meta position or a para position with respect to the bonding position of G ³¹ .

The specific example of the side chain type diamine is illustrated below. As the diamine having a side chain of the formulas (DI-31) to (DI-35), compounds represented by the following formulas (DI-31-1) to (DI-35-3) can be mentioned.

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

In the formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms or 5 to carbon atoms 25 alkoxy. R ³⁵ is C1-C30 alkyl or C1-C30 alkoxy, Preferably it is C3-C25 alkyl or C3-C25 alkoxy.

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

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, preferably alkyl having 3 to 20 carbon atoms or 3 to carbon atoms It is an alkoxy of 20. R ³⁹ is hydrogen, -F, alkoxy of 1 to 30 carbon atoms alkyl having 1 to 30 carbon atoms of, -CN, and -OCH ₂ F, -OCHF ₂ or -OCF _3, preferably alkyl having a carbon number of 3 to 25 carbon atoms or It is 3-25 alkoxy. And G ³³ is C1-C20 alkylene.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

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

In formulas (DI-34-1) to (DI-34-12), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbons, preferably hydrogen or alkyl having 1 to 10 carbons, and R ⁴¹ is hydrogen or It is a C1-C12 alkyl.

Examples of the compound represented by the formula (DI-35) are shown below.

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

As the diamine in the present invention, diamines other than the diamines represented by formulas (DI-1-1) to (DI-35-3) can also be used. As such diamine, the compound represented by following formula (DI-36-1)-(DI-36-8) is mentioned, for example.

In formulas (DI-36-1) to (DI-36-8), each of R ⁴² 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, as such a photosensitive diamine compound, the following formula (PDI-1)-(PDI-12) is mentioned.

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 formula (PDI-12), R ⁴³ is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine.

In each diamine, a part of the diamine may be substituted with a monoamine in the range where the ratio of the monoamine to the diamine is 40 mol% or less. Such substitution can cause termination of the polymerization reaction when generating the polyamic acid, and can suppress further progress of the polymerization reaction. For this reason, by such substitution, the molecular weight of the obtained polymer (polyamic acid or its derivative) can be easily controlled, and, for example, the effect of the present invention is not impaired and the coating properties of the liquid crystal aligning agent can be improved. . The diamine substituted with a monoamine may be one or two or more, as long as the effect of the present invention is not impaired. As the monoamine, for example, aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine , n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n- Octadecylamine and n-eicosylamine.

The polyamic acid or its derivative may further contain a monoisocyanate compound in the monomer. By containing the monoisocyanate compound in the monomer, the terminal of the obtained polyamic acid or its derivative is modified, and the molecular weight is adjusted. By using this terminal-modified polyamic acid or a derivative thereof, for example, the effect of the present invention is not impaired and the coating properties of the liquid crystal aligning agent can be improved. From the above viewpoint, the content of the monoisocyanate compound in the monomer is preferably 1 to 10 mol% with respect to the total amount of diamine and tetracarboxylic dianhydride in the monomer. As said monoisocyanate compound, phenyl isocyanate and naphthyl isocyanate are mentioned, for example.

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

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

Among the specific examples of the diamine, when it is important to further improve the transmittance, the diamine is represented by formulas (DI-1-3), (DI-2-1), (DI-12-1), and (DIH-2- The diamine represented by 1) is preferable.

Among the specific examples of the diamine, in the case where it is important to further improve the electrical properties, the diamine is represented by formulas (DI-4-1), (DI-4-5), (DI-5-1), and (DI-5). -5), (DI-5-9), (DI-5-30), (DI-5-37), (DI-8-2), (DI-13-1), (DI-14-8 ) Or a diamine represented by (DIH-2-1) is preferable.

The polyamic acid polymer and polyimide polymer used in the present invention are obtained by reacting an acid dianhydride and a diamine component in a solvent. In this synthesis reaction, special conditions other than the selection of raw materials are not required, and the conditions for conventional polyamic acid synthesis can be applied as they are. The solvent to be used will be described later.

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

Further, for example, the liquid crystal aligning agent is an acrylic acid polymer, an acrylate polymer, and a tetracarboxyl in a range in which the effect of the present invention is not impaired (preferably within 20% by weight of the polyamic acid or its derivative). Other polymer components, such as polyamideimide, which is a reaction product of acid dianhydride, dicarboxylic acid, or a derivative thereof and diamine, may be further contained.

The polyamic acid or a derivative thereof can be prepared in the same manner as a known polyamic acid or a derivative thereof used in the formation of a polyimide film. It is preferable that the total amount of tetracarboxylic dianhydride injected is substantially equal to the total number of moles of diamine (about 0.9 to 1.1 in mole ratio).

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

The presence of the polyamic acid or a derivative thereof can be confirmed by analyzing a solid content obtained by precipitation with a large amount of poor solvent by IR and NMR. In addition, by analyzing the extract with an organic solvent of the decomposition product of the polyamic acid or its derivative in a strong alkali aqueous solution such as KOH or NaOH by GC, HPLC or GC-MS, the monomer used can be confirmed.

<Alkenyl substituted nadimide compound>

For example, the liquid crystal aligning agent of the present invention may further contain an alkenyl substituted nadiimide compound for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long term. The alkenyl-substituted nadiimide compounds may be used alone or in combination of two or more. For the above purposes, the content of the alkenyl-substituted nadiimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and still more preferably 1 to 50% by weight based on the polyamic acid or its derivative. Do.

Hereinafter, the nadimide compound will be specifically described.

It is preferable that the alkenyl-substituted nadiimide compound is a compound that can be dissolved in a solvent that dissolves the polyamic acid or its derivative used in the present invention. Examples of such an alkenyl-substituted nadimide compound include a compound represented by the following formula (NA).

In formula (NA), L ¹ and L ² are independently hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl or benzyl, n is 1 or 2 to be.

In formula (NA), when n=1, W is C1-C12 alkyl, C2-C6 alkenyl, C5-C8 cycloalkyl, C6-C12 aryl, benzyl, -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, r is 0 or 1, and k is It is an integer of 1 to 30), -(Z ⁴ ) _r -BZ ⁵ -H (here, Z ⁴ and Z ⁵ are independently alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms) , B is phenylene, and r is 0 or 1), a group represented by -BTBH (wherein B is phenylene, and T is -CH ₂ -, -C(CH ₃ ) ₂ -, -O- , -CO-, -S- or -SO ₂ -), or a group in which 1-3 hydrogens of these groups are substituted with -OH.

In this case, preferred W is alkyl having 1 to 8 carbon atoms, alkenyl having 3 to 4 carbon atoms, cyclohexyl, phenyl, benzyl, poly(ethyleneoxy)ethyl having 4 to 10 carbon atoms, phenyloxyphenyl, phenylmethylphenyl, phenyliso Propylidenephenyl and one or two hydrogens of these groups are substituted with -OH.

In the formula (NA), when n=2, W is a C2-C20 alkylene, a C5-C8 cycloalkylene, a C6-C12 arylene, -Z ¹ -O-(Z ² O ) _k -Z ^3- (here, the meanings of Z ¹ to Z ^{3 and} k are the same as above), -Z ⁴ -BZ ^5- (here, the meanings of Z ⁴ , Z ⁵ and B are as described above ), -B-(OB) _r -T-(BO) _r -B- (wherein B is phenylene, T is alkylene having 1 to 3 carbon atoms, -O- or -SO ₂ -, , the meaning of r is as described above) or a group in which 1-3 hydrogens of these groups are substituted with -OH.

At this time, preferred W is alkylene having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, -C ₃ H ₆ -O-(Z ² -O) _n -OC ₃ H _6- (here , Z ² is an alkylene having 2 to 6 carbon atoms, n is 1 or 2), a group represented by -BTB- (wherein B is phenylene, and T is -CH ₂ -, -O- or -SO ₂ -is), -BOBC ₃ H ₆ -BOB- (here, B is phenylene), and one or two hydrogens of these groups are substituted with -OH.

Such an alkenyl-substituted nadiimide compound is synthesized by holding an alkenyl-substituted nadic anhydride derivative and a diamine at a temperature of 80 to 220°C for 0.5 to 20 hours, as described in Japanese Patent Publication No.2729565. The obtained compound or a commercially available compound can be used. As a specific example of an alkenyl substituted nadiimide compound, the compound shown below is mentioned.

N-methyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-di Carboximide, N-methyl-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-methyl-metalylmethylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide,

N-(2-ethylhexyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-allyl-allylbicyclo[2.2.1]hepto-5- N-2,3-dicarboximide, N-allyl-allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-allyl-metalylbicyclo[2.2.1]hepto -5-ene-2,3-dicarboximide, N-isopropenyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-isopropenyl-allyl (methyl )Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-isopropenyl-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-cyclohexyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-cyclohexyl-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboximide, N-cyclohexyl-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-phenyl-allylbicyclo[2.2.1]hepto-5- N-2,3-dicarboximide,

N-phenyl-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo[2.2.1]hepto-5-ene-2,3 -Dicarboximide, N-benzyl-allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-benzyl-metalylbicyclo[2.2.1]hepto-5-ene- 2,3-dicarboximide, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-hydroxyethyl)- Allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2-hydroxyethyl)-metalylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide,

N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2,2-dimethyl-3-hyde Roxypropyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide, N-(2,3-dihydroxypropyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi Mid, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-hydroxycyclohexyl)-allyl (Methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide,

N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(4-hydroxyphenyl)-allyl(methyl)bicyclo[2.2 .1]Hepto-5-ene-2,3-dicarboximide, N-(4-hydroxyphenyl)-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N -(4-hydroxyphenyl)-metalylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1 ]Hepto-5-ene-2,3-dicarboximide, N-(3-hydroxyphenyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-{2-(2-hydroxyethoxy)ethyl}-allyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboximide,

N-{2-(2-hydroxyethoxy)ethyl}-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-{2-(2-hydride Roxyethoxy)ethyl}-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-{2-(2-hydroxyethoxy)ethyl}-metalylmethylbicyclo [2.2.1]Hepto-5-ene-2,3-dicarboximide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hepto -5-ene-2,3-dicarboximide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl(methyl)bicyclo[2.2.1]hepto-5- N-2,3-dicarboximide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-metalylbicyclo[2.2.1]hepto-5-ene-2,3- Dicarboximide, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-{4-( 4-hydroxyphenylisopropylidene)phenyl}-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide, N-{4-(4-hydroxyphenylisopropyl Liden)phenyl}-metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide and oligomers thereof,

N,N'-ethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Trimethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Dodecamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1] ]Hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide),

1,2-bis{3'-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}ethane, 1,2-bis{3'-(allylmethyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}ethane, 1,2-bis{3'-(metalylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide)propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}ethyl]ether , Bis[2'-{3'-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}ethyl]ether, 1,4-bis{3'- (Allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}butane, 1,4-bis{3'-(allylmethylbicyclo[2.2.1]hepto-5 -Ene-2,3-dicarboxyimide)propoxy}butane,

N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis(allylmethyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3 -Dicarboximide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-{(1 -Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-xylylene-bis(allyl Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m- Xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide),

2,2-bis[4-{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, 2,2-bis[4-{ 4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(metalylbicyclo[2.2) .1]hepto-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide )Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}methane,

Bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(metalylmethylbicyclo[2.2.1]hepto-5- N-2,3-dicarboximide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}ether, bis{4-( Allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl}ether, bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}sulfone, bis{4-(allylmethylbicyclo[2.2] .1]hepto-5-ene-2,3-dicarboximide)phenyl}sulfone,

Bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}sulfone, 1,6-bis(allylbicyclo[2.2.1]hepto-5-ene -2,3-dicarboxyimide)-3-hydroxy-hexane, 1,12-bis(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)-3,6- Dihydroxy-dodecane, 1,3-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)-5-hydroxy-cyclohexane, 1,5-bis{ 3'-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1) ]Hepto-5-ene-2,3-dicarboximide)-2-hydroxy-benzene,

1,4-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)-2,5-dihydroxy-benzene, N,N'-p-(2- Hydroxy)xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-(2-hydroxy)xylylene-bis(allyl Methylcyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis(metalylbicyclo[2.2.1]hepto-5-ene-2,3-di Carboximide), N,N'-p-(2,3-dihydroxy)xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide),

2,2-bis[4-{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)-2-hydroxy-phenoxy}phenyl]propane, bis{4 -(Allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide)-4-hydroxy-phenyl}ether, bis{3-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)- 5-hydroxy-phenyl}sulfone, 1,1,1-tri{4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)}phenoxymethylpropane, N ,N',N"-tri(ethylenemetalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)isocyanurate and oligomers thereof.

In addition, the alkenyl-substituted nadiimide compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene/phenylene group.

Among the alkenyl substituted nadimide compounds, preferred compounds are shown below.

N,N'-ethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Trimethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Dodecamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1] ]Hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide),

N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis(allylmethyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3 -Dicarboximide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-{(1 -Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-xylylene-bis(allyl Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m- Xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hepto -5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3 -Dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenoxy}phenyl ]Propane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide)phenyl}methane.

Bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(metalylmethylbicyclo[2.2.1]hepto-5- N-2,3-dicarboximide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}ether, bis{4-( Allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl}ether, bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}sulfone, bis{4-(allylmethylbicyclo[2.2] .1]Hepto-5-ene-2,3-dicarboximide)phenyl}sulfone, bis{4-(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl} Sulfone.

A more preferable alkenyl substituted nadimide compound is shown below.

N,N'-ethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide), N,N'-ethylene-bis(metalylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Trimethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N '-Dodecamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1] ]Hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide).

N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-phenylene-bis(allylmethyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3 -Dicarboximide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-{(1 -Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide), N,N'-p-xylylene-bis(allyl Bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m- Xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide).

2,2-bis[4-{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenoxy}phenyl]propane, 2,2-bis[4-{ 4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(metalylbicyclo[2.2) .1]hepto-5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide )Phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl}methane, bis{4-(metalylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboximide)phenyl}methane, bis{4-(metalylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl}methane .

And as a particularly preferable alkenyl substituted nadimide compound, the following formula (bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide)phenyl represented by NA-1) Methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide) represented by formula (NA-2) and formula (NA-3 ) Represented by N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide).

<Compound having a radical polymerizable unsaturated double bond>

For example, the liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electrical properties of the liquid crystal display device for a long time. The compound having a radically polymerizable unsaturated double bond may be one type of compound or two or more types of compounds. In addition, alkenyl-substituted nadimide compounds are not included in the compound having a radically polymerizable unsaturated double bond. For the above purposes, the content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and 1 to 50% by weight based on the polyamic acid or its derivative. It is more preferable.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl substituted nadiimide compound reduces the ion density of the liquid crystal display device, suppresses an increase in ion density over time, and also suppresses the occurrence of afterimages. In order to do this, the compound having a radically polymerizable unsaturated double bond/alkenyl-substituted nadiimide compound is preferably 0.1 to 10 by weight, and more preferably 0.5 to 5.

Hereinafter, a compound having a radically polymerizable unsaturated double bond will be described in detail. Examples of the compound having a radically polymerizable unsaturated double bond include (meth)acrylic acid derivatives such as (meth)acrylic acid ester and (meth)acrylic acid amide, and bismaleimide. The compound having a radically 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)acrylic acid ester include, for example, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, Isoboronyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate.

Specific examples of the bifunctional (meth)acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200, manufactured by Toa Synthetic Chemical Co., Ltd., and Nippon Gaya. KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, which are products of Koo Co., Ltd., V260, V312 and V335HP, which are products of Osaka Organic Chemicals Co., Ltd., and Products light acrylate BA-4EA, light acrylate BP-4PA, and light acrylate BP-2PA are mentioned.

As a specific example of a trifunctional or higher polyfunctional (meth)acrylic acid ester, for example, 4,4'-methylenebis (N,N-dihydroxyethylene acrylate aniline), Aro, a product of Toa Synthetic Chemical Co., Ltd. Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20 manufactured by Nippon Kayaku Co., Ltd. , KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and VGPT, a product of Osaka Organic Chemical Industries, Ltd., are mentioned.

Specific examples of the (meth)acrylic acid amide derivative include, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N-cyclopropylmethacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N-ethyl-N-methylacrylamide, N,N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N- Acryloylpyrrolidine, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-dihydroxyethylenebisacrylamide, N-(4-hydroxyphenyl)methacryl Amide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(iso-butoxymethyl)methacrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N, N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methacrylamide, N-benzyl -2-methacrylamide and N,N'-methylenebismethacrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis(N,N-di Hydroxyethylene acrylate aniline) is particularly preferred.

Examples of bismaleimide include BMI-70 and BMI-80 manufactured by K-I Hwasung Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, and BMI-5000 manufactured by Daiwa Chemical Co., Ltd. And BMI-7000.

<oxazine compound>

For example, the liquid crystal aligning agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical properties in a liquid crystal display device for a long period of time. The oxazine compound may be one type of compound or two or more types of compounds. For the above purposes, the content of the oxazine compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 20% by weight based on the polyamic acid or its derivative.

Hereinafter, the oxazine compound will be described in detail.

The oxazine compound is soluble in a solvent in which the polyamic acid or a derivative thereof is dissolved, and an oxazine compound having ring-opening polymerization property is preferable.

Moreover, the number of oxazine structures in the oxazine compound is not particularly limited.

Various structures are known in the oxazine structure. In the present invention, the structure of the oxazine is not particularly limited, but the oxazine structure in the oxazine compound includes a structure of an oxazine having an aromatic group containing a condensed polycyclic aromatic group such as benzoxazine or naphthooxazine. I can.

As an oxazine compound, the compound represented by following formula (OX-1)-(OX-6) is mentioned, for example. In addition, in the following formula, the bond indicated toward the center of the ring represents that it is bonded to any one carbon that constitutes a ring and allows bonding of a substituent.

In formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ⁵ to L ⁸ Is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in formulas (OX-3), (OX-4) and (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 of 1 to 6, and in formulas (OX-5) and (OX-6), Q ² is Independently, a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or alkylene having 1 to 3 carbon atoms, and benzene in Q ² The hydrogen bonded to the ring and naphthalene ring may be independently substituted with -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 the side chain, and an oligomer or polymer having an oxazine structure in the main chain.

As an oxazine compound represented by formula (OX-1), the following oxazine compounds are mentioned, for example.

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

As an oxazine compound represented by formula (OX-2), the following oxazine compounds are mentioned, for example.

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

Examples of the oxazine compound represented by formula (OX-3) include 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 -. As an oxazine compound represented by formula (OX-3-I), the following oxazine compounds are mentioned, for example.

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

As an oxazine compound represented by formula (OX-4), the following oxazine compounds are mentioned, for example.

As an oxazine compound represented by formula (OX-5), the following oxazine compounds are mentioned, for example.

As an oxazine compound represented by formula (OX-6), the following oxazine compounds are mentioned, for example.

Among these, more preferably, formulas (OX-2-1), (OX-3-1), (OX-3-3), (OX-3-5), (OX-3-7), ( OX-3-9), (OX-4-1) to (OX-4-6), (OX-5-3), (OX-5-4) and (OX-6-2) to (OX- The oxazine compound represented by 6-4) is mentioned.

The oxazine compound can be produced by the same method as described in WO 2004/009708, JP 11-12258, and JP 2004-352670.

The oxazine compound represented by formula (OX-1) is obtained by reacting a phenol compound with a primary amine and an aldehyde (see International Publication 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then reacting by adding a compound having a naphthol-based hydroxyl group (see International Publication 2004/009708. ).

The oxazine compound represented by formula (OX-3) contains 1 mol of a phenol compound, at least 2 mol or more of aldehyde and 1 mol of primary amine per 1 mol of the phenolic hydroxyl group in an organic solvent as a secondary aliphatic amine and a tertiary aliphatic It is obtained by reacting in the presence of an amine or a basic nitrogen-containing heterocyclic compound (see International Publication No. 2004/009708 and Japanese Laid-Open Patent Publication No. Hei 11-12258).

The oxazine compounds represented by formulas (OX-4) to (OX-6) include aldehydes such as diamine and formalin having a plurality of benzene rings such as 4,4'-diaminodiphenylmethane and an organic group bonding them, and It is obtained by subjecting phenol to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90°C or higher (see Japanese Laid-Open Patent Publication No. 2004-352670).

<oxazoline compound>

For example, the liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical properties in a liquid crystal display device for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one type of compound or two or more types of compounds. For the above purposes, the content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and even more preferably 1 to 20% by weight based on the polyamic acid or its derivative. Alternatively, the content of the oxazoline compound is preferably 0.1 to 40% by weight based on the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

Hereinafter, the oxazoline compound will be described in detail.

The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Moreover, although it is sufficient to have one oxazoline structure in one compound, it is preferable to have two or more oxazoline compounds. Moreover, the oxazoline compound may be a polymer having an oxazoline ring structure in a side chain or a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or may be a copolymer of a monomer having an oxazoline structure in the side chain and a monomer not having an oxazoline structure. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more types of monomers having an oxazoline structure in the side chain, or two or more types of monomers having an oxazoline structure in the side chain and a monomer having no oxazoline structure It may be a copolymer with.

The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure and the carbonyl group of the polyamic acid can react.

As an oxazoline compound, for example, 2,2'-bis(2-oxazoline), 1,2,4-tris(2-oxazolinyl-2)-benzene, 4-furan-2-ylmethylene- 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-bis(isopropyl -2-oxazolin-2-yl)pyridine, 2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2- Oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline). In addition, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Catalyst) can also be mentioned. Among these, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable.

<epoxy compound>

For example, the liquid crystal aligning agent of the present invention may further contain an epoxy compound for the purpose of stabilizing electrical properties in a liquid crystal display device for a long period of time. The epoxy compound may be one type of compound or two or more types of compounds. For the above purposes, the content of the epoxy compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and still more preferably 1 to 20% by weight based on the polyamic acid or its derivative.

Hereinafter, the epoxy compound will be described in detail.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of compounds having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide, hexafluoropropylene oxide, and cyclo Hexene oxide, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N-butyl) epoxy Side, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline and 3-[2-(perfluorohexyl)ethoxy]-1,2 -Epoxy propane is mentioned.

As a compound having two epoxy rings in the molecule, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene Glycol diglycidyl ether, neopentyl glycol glycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxysilane.

As a compound having three epoxy rings in the molecule, for example, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2, 3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Tekmore VG3101L", (made by Mitsui Chemical Co., Ltd.)) is mentioned.

As a compound having four epoxy rings in the molecule, for example, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N'-tetraglycidyl- m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl Methane and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. As a monomer having an epoxy ring, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methylglycidyl (meth)acrylate are mentioned, for example.

Other monomers that copolymerize with a monomer having an epoxy ring include, for example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and butyl (meth)acrylic. Rate, iso-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxy Propyl (meth)acrylate, styrene, methylstyrene, chlormethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide. .

Polyglycidyl methacrylate etc. are mentioned as a preferable specific example of the polymer of the monomer which has an epoxy ring. In addition, as a preferred specific example of a copolymer of a monomer having an epoxy ring and another monomer, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer , Benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3- Ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

Among these examples, N,N,N',N'-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N ',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Tecmore VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate , N-phenylmaleimide-glycidylmethacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane are particularly preferred.

More systematically, as the epoxy compound, for example, glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamide, glycidyl isocyanurate, chain aliphatic type And epoxy compounds and cyclic aliphatic epoxy compounds. In addition, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

As the epoxy compound, for example, glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamide, glycidyl isocyanurate, chain aliphatic epoxy compound and cyclic Aliphatic epoxy compounds are mentioned.

As glycidyl ether, for example, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, bisphenol type epoxy compound, hydrogenated bisphenol-A type 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, phenol novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compound , Brominated cresol novolak type epoxy compound, bisphenol A novolak type epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadienephenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic A polyglycidyl ether compound, a polysulfide type diglycidyl ether compound, and a biphenol type epoxy compound.

As glycidyl ester, a diglycidyl ester compound and a glycidyl ester epoxy compound are mentioned, for example.

As glycidylamine, a polyglycidylamine compound and a glycidylamine type epoxy resin are mentioned, for example.

As an epoxy group-containing acrylic compound, the homopolymer and a copolymer of the monomer which has oxiranyl are mentioned, for example.

As glycidylamide, a glycidylamide type epoxy compound is mentioned, for example.

As a chain aliphatic epoxy compound, a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound is mentioned, for example.

As a cyclic aliphatic epoxy compound, a compound containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound is mentioned, for example.

Examples of the bisphenol A epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all manufactured by Mitsubishi Chemical Co., Ltd.), Ephotote YD-128 (manufactured by Toto Chemical Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301 And Epomic R-304 (all manufactured by Mitsui Chemicals Co., Ltd.).

As a bisphenol F type epoxy compound, for example, jER806, jER807, jER4004P (all manufactured by Mitsubishi Chemical Co., Ltd.), Epotot YDF-170, Epotot YDF-175S, Epotot YDF-2001 (all are Toto Chemical Co., Ltd.) (Manufactured by Co., Ltd.), DER-354 (manufactured by Dow Chemical Co., Ltd.), Epiclon 830, and Epiclon 835 (both manufactured by DIC Corporation) are mentioned.

As a bisphenol type epoxy compound, the epoxidation of 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is mentioned, for example.

Examples of the hydrogenated bisphenol-A type epoxy compound include Suntot ST-3000 (manufactured by Toto Chemical Co., Ltd.), Lika Resin HBE-100 (manufactured by Shinnihon Rica Co., Ltd.) and Denacol EX-252 (Nagase Chem. Tex Co., Ltd. product) is mentioned.

As a hydrogenated bisphenol type epoxy compound, the epoxidation product of hydrogenated 2,2-bis(4-hydroxyphenyl)-1,1,1,3,3,3-hexafluoropropane is mentioned, for example.

As a brominated bisphenol-A type epoxy compound, for example, jER5050, jER5051 (all manufactured by Mitsubishi Chemical Co., Ltd.), Ephotote YDB-360, Ephotote YDB-400 (all manufactured by Toto Chemical Co., Ltd.), DER -530, DER-538 (all manufactured by The Dow Chemical Company), Epiclon 152, and Epiclon 153 (all manufactured by DIC Corporation) are mentioned.

As a phenol novolak type epoxy compound, for example, jER152, jER154 (all manufactured by Mitsubishi Chemical Co., Ltd.), YDPN-638 (manufactured by Toto Chemical Corporation), DEN431, DEN438 (all manufactured by The Dow Chemical Company), Epiclon N -770 (manufactured by DIC Corporation), EPPN-201 and EPPN-202 (all manufactured by Nippon Kayaku Corporation) are mentioned.

As a cresol novolak type epoxy compound, for example, jER180S75 (manufactured by Mitsubishi Chemical Co., Ltd.), YDCN-701, YDCN-702 (all manufactured by Toto Chemical Co., Ltd.), Epiclon N-665, and Epiclon N-695 (all DIC (manufactured by Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025 and EOCN-1027 (all manufactured by Nippon Kayaku Co., Ltd.) are mentioned.

As a bisphenol A novolak type epoxy compound, jER157S70 (made by Mitsubishi Chemical Corporation) and Epiclon N-880 (made by DIC Corporation) are mentioned, for example.

Examples of the naphthalene skeleton-containing epoxy compound include Epiclon HP-4032, Epiclon HP-4700, Epiclon HP-4770 (all manufactured by DIC Corporation) and NC-7000 (manufactured by Nippon Kayaku Corporation). .

As an aromatic polyglycidyl ether compound, for example, hydroquinone diglycidyl ether (following formula EP-1), catechol diglycidyl ether (following formula EP-2) resorcinol diglycidyl ether (following Formula EP-3), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl)] Ethyl]phenyl]propane (the following formula EP-4), tris(4-glycidyloxyphenyl)methane (the following formula EP-5), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (The Dow Chemical Company), Denacol EX-201 (manufactured by Nagase Chemtex Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Kayaku Co., Ltd.), Techmoa VG3101L (Mitsui Chemical Co., Ltd.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7 are mentioned.

As a dicyclopentadienephenol type epoxy compound, TACTIX-556 (manufactured by The Dow Chemical Company) and Epiclon HP-7200 (manufactured by DIC Corporation) are mentioned, for example.

Examples of the alicyclic diglycidyl ether compound include a cyclohexanedimethanol diglycidyl ether compound and Likaresin DME-100 (manufactured by Shinnihon Rica Co., Ltd.).

As an aliphatic polyglycidyl ether compound, for example, ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether (following formula EP-10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (Formula EP-12 below), 1,4-butanediol diglycidyl ether (Formula EP-13 below), 1,6-hexanediol diglycidyl ether (Formula EP-14 below), dibromoneopentyl 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 (all manufactured by Nagase Chemtex Co., Ltd.), DD-503 (manufactured by ADEKA Co., Ltd.), Licaregin W-100 (Shinnihon Rica Co., Ltd.) ) Manufacturing), 1,3,5,6-tetraglycidyl-2,4-hexanediol (following formula EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polygly Cidyl ether, pentaerythritol polyglycidyl ether, Denacol EX-313, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all manufactured by Nagase Chemtex Co., Ltd.) are mentioned. .

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toray Thiokol Co., Ltd.).

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

As a diglycidyl ester compound, for example, diglycidyl terephthalate (following formula EP-17), diglycidyl phthalate (following formula EP-18), bis(2-methyloxiranylmethyl)phthalate ( The following formula EP-19), diglycidylhexahydrophthalate (following formula EP-20), the compound represented by the following formula EP-21, the compound represented by the following formula EP-22, and the compound represented by the following formula EP-23 are mentioned. I can.

As glycidyl ester epoxy compounds, for example, jER871, jER872 (all manufactured by Mitsubishi Chemical Corporation), Epiclon 200, Epiclone 400 (all manufactured by DIC Corporation), Denacol EX-711, and Denacol EX -721 (all manufactured by Nagase Chemtex Co., Ltd.) is mentioned.

As the polyglycidylamine compound, for example, N,N-diglycidylaniline (formula EP-24 below), N,N-diglycidyl-o-toluidine (formula EP-25), N ,N-diglycidyl-m-toluidine (formula EP-26 below), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27 below), 3-(N ,N-diglycidyl)aminopropyltrimethoxysilane (formula EP-28 below), N,N,O-triglycidyl-p-aminophenol (formula EP-29 below), N,N,O- Triglycidyl-m-aminophenol (formula EP-30 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (formula EP-31 below), 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 ( The following formula EP-34), 1,3-bis(N,N-diglycidylamino)cyclohexane (the following formula EP-35), 1,4-bis(N,N-diglycidylamino)cyclo Hexane (following formula EP-36), 1,3-bis(N,N-diglycidylamino)benzene (following formula EP-37), 1,4-bis(N,N-diglycidylamino) Benzene (formula EP-38 below), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (formula EP-39 below), N,N,N',N '-Tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula EP-40 below), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)- 4,4'-diaminobiphenyl (formula EP-41 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether (formula EP-42 below), 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (formula EP-43 below), 2,4,4'-tris(N,N-diglycidyl) Amino) diphenyl ether (following formula EP-44), tris(4-(N,N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3',4'-tetra kiss( N,N-diglycidylamino)biphenyl (formula EP-46 below), 3,4,3',4'-tetrakis (N,N-diglycidylamino) diphenyl ether (formula EP below -47), the compound represented by the following formula EP-48, and the compound represented by the following formula EP-49 are mentioned.

As a homopolymer of a monomer having oxiranyl, polyglycidyl methacrylate is mentioned, for example. As a copolymer of a monomer having oxiranyl, for example, N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer Cidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl ) Methyl methacrylate-glycidyl methacrylate copolymer and styrene-glycidyl methacrylate copolymer.

As a monomer having oxiranyl, glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methylglycidyl (meth)acrylate are mentioned, for example.

Examples of other monomers other than the oxiranyl-containing monomer in the copolymer of the oxiranyl-containing monomer include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth) Acrylate, butyl (meth)acrylate, iso-butyl (meth)acrylate, t-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate )Acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chlormethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, N-cyclohexylmaleimide and N -Phenyl maleimide is mentioned.

As glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (the following Formula EP-50), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (the following formula EP-51 ) And glycidyl isocyanurate type epoxy resins.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolide PB3600 (manufactured by Daicel Co., Ltd.).

As a cyclic aliphatic epoxy compound, for example, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Celoxide 2021 (manufactured by Daicel), the following formula EP) -52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (formula EP-53 below), 2,3-epoxycyclopentane- 2',3'-epoxycyclopentane ether (the following formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8 ,9-diepoxylimonene (Celoxide 3000 (manufactured by Daicel), the following formula EP-55), a compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all of The Ciba -Geigy Chemical Corp. make (available from Huntsman Japan Co., Ltd.), EHPD-3150 (made by Daicel Co., Ltd.), and a cyclic aliphatic epoxy resin.

The epoxy compound is preferably at least one of a polyglycidylamine compound, a bisphenol A novolak type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic epoxy compound, and N,N,N',N'-tetra Glycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'- Diaminodiphenylmethane, trade name "Tecmoa VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidylmethacrylate copolymer , N,N,O-triglycidyl-p-aminophenol, bisphenol A novolak type epoxy compound, and cresol novolak type epoxy compound is more preferably at least one.

Moreover, for example, the liquid crystal aligning agent of this invention may contain various additives further. Examples of various additives include high molecular weight compounds and low molecular weight compounds other than polyamic acid and its derivatives, and can be selected and used depending on the respective purpose.

For example, examples of the polymer compound include a polymer compound soluble in an organic solvent. Adding such a high molecular compound to the liquid crystal aligning agent of the present invention is preferable from the viewpoint of controlling the electrical properties and alignment properties of the formed liquid crystal aligning film. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

In addition, as the low-molecular compound, for example, 1) a surfactant for this purpose when trying to improve coating properties, 2) an antistatic agent when trying to improve antistatic properties, and 3) when trying to improve adhesion to a substrate. A silane coupling agent, a titanium-based coupling agent, and 4) an imidization catalyst may be used when imidation is carried out at a low temperature.

Examples of the silane coupling agent include vinyl trimethoxysilane, vinyl triethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-(2-aminoethyl)-3- Aminopropylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propylamine and N,N' -Bis[3-(trimethoxysilyl)propyl]ethylenediamine is mentioned. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of the imidation catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; Aromatic amines such as N,N-dimethylaniline, N,N-diethylaniline, methyl substituted aniline, and hydroxy substituted aniline; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. And cyclic amines of. The imidation catalyst is preferably one or two or more selected from N,N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine and isoquinoline. .

The amount of the silane coupling agent added is usually 0 to 20% by weight, preferably 0.1 to 10% by weight of the total weight of the polyamic acid or its derivative.

The amount of the imidation catalyst added is usually 0.01 to 5 equivalents, and preferably 0.05 to 3 equivalents, based on the carbonyl group of the polyamic acid or its derivative.

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

In addition, for example, the liquid crystal aligning agent of the present invention is an acrylic acid polymer, an acrylate polymer, and a tetracarboxylate within a range that does not impair the effect of the present invention (preferably within 20% by weight of the polyamic acid or derivative thereof). Other polymer components, such as polyamideimide, which is a reaction product of an acid dianhydride, a dicarboxylic acid, or a derivative thereof and a diamine, may be further contained.

Further, for example, the liquid crystal aligning agent may further contain a solvent from the viewpoint of coating properties of the liquid crystal aligning agent and concentration adjustment of the polyamic acid or its derivative. The solvent can be applied without particular limitation as long as it has the ability to dissolve the polymer component. The solvent widely includes a solvent commonly used in the manufacturing process or use of a polymer component such as polyamic acid and soluble polyimide, and may be appropriately selected according to the purpose of use. One type of solvent may be sufficient, and two or more types of mixed solvent may be sufficient as the said solvent.

It is preferable that the concentration of the polyamic acid in the alignment agent is 0.1 to 40% by weight. When this aligning agent is applied to a substrate, an operation of diluting the contained polyamic acid with a solvent in advance for adjustment of the film thickness may be required.

The solid content concentration in the alignment agent is not particularly limited, and an optimum value may be selected according to the following various coating methods. Usually, in order to suppress unevenness at the time of application, pinholes, etc., it is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight, based on the weight of the varnish.

The solvent used for the liquid crystal aligning agent of this invention is a solution containing the compound represented by said formula (A) as a solvent component. As a specific example of the said formula (A), the solvent represented by said formula (A-1)-(A-6) is mentioned, for example. From the viewpoint of the solubility of the polyamic acid, (A-1), (A-4) and (A-6) are preferred.

It is preferable that it is 0.1-90 weight%, and, as for the ratio of the solvent represented by said formula (A) in the said aligning agent, it is more preferable that it is 10-85 weight%.

The solvent component in the liquid crystal aligning agent of the present invention may be only the solvent represented by the formula (A), but in order to control the coating property to the substrate or to secure the solubility of the resin component, the solvent component represented by the formula (A) It is preferable to contain the following 2nd solvent and/or 3rd solvent in addition to a 1st solvent.

In order to control the coating property to the substrate, as the second solvent, a polyamic acid polymer or polyimide polymer that generates alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents, is not deposited. It can be used together within the range that does not exist. As such a solvent, for example, ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, pentylene carbonate, hexylene carbonate, 2-methyl-1,3-propylene carbonate, 2,2-dimethyl -1,3-propylene carbonate, 2-hydroxy-2-methyl-1,3-propylene carbonate, 2-acetoxy-2-methyl-1,3-propylene carbonate, ethylene glycol methyl ether, ethylene glycol dimethyl ether, Ethylene glycol ethyl 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 glycol 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 Glycol monoethyl 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, di Ethylene 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 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 ethyl 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, acetic acid n-propyl, butyl acetate, pentyl acetate, n acetate -Hexyl, cyclohexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, 3-methoxybutyl acetate, 2-methylcyclohexyl acetate, n-butyl propionate, 2-hydroxy-methylisobutyrate, butyl butyrate, Pentyl butyrate, isoamyl butyrate, 2-methylpentanone-2,4-diol, t-butyl alcohol, triethylcarbinol, t-amyl alcohol, 1-methylcyclohexanol, 2,5-dimethylhexane-2 ,5-diol, n-butyl alcohol, bis(3-methylbutyl) ether, di-n-pentyl ether (diamyl 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, lactic acid Isoamyl, lactate isoamyl ester, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, dipropylene glycol methyl ether, 4-hydroxy-4-methyl-2-pentanone ( Diacetone alcohol), methyl-3-methoxypropionate, ethyl-3-ethoxypropionate, benzyl alcohol, 1-phenoxy-2-propanol, phenethyl alcohol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethylacetate, 2-hydroxypropylacetate, 3-hydroxypropylacetate , 2-hydroxybutyl acetate, 3-hydroxybutyl acetate, 4-hydroxybutyl acetate, 2-hydroxyethylpropionate, 2-hydroxypropylpropionate, 3-hydroxypropylpropionate, 2 -Hydroxyethyl lactate, 2-hydroxypropyl lactate, 3-hydroxypropyl lactate, 2,4-pentanedione, ethyl-3-ethoxypropionate, furfuryl alcohol, tetrahydrofurfuryl alcohol, 3-methyl-3-methoxybutanol, 1,3-dioxolane, isoamylpropionate, isoamylisobutylate, diisopentyl ether, butyrophenone, methylisobutylketone, cyclohexanone or diisobutyl Ketones, etc. are mentioned.

In order to ensure the solubility in the polyamic acid polymer or polyimide polymer, a good solvent can be used together as the third solvent (good solvent). Examples of such a solvent include N-alkyl-2-pyrrolidones, lactones, and 1,3-dialkyl-2-imidazolidinones, such as γ-butyrolactone, N-methyl- 2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, dimethylsulfoxide, dimethylsulfone, hexamethylsulfoxide, N-methylcaprolactam, 2-pyrrolidone , N-ethylpyrrolidone, N-vinylpyrrolidone, tetramethylurea, 1,3-dimethyl-2-imidazolidinone, hexamethylphosphoriamide, N,N-dimethylformamide, N,N- Diethylformamide, N,N-dimethylacetamide, diethylacetamide, 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N-methylpropanamide, N,N-dimethylpropanamide, 3-hexyloxy-N,N-dimethylpropanamide, m-cresol, xylenol, phenol, halogenated phenol, etc. are mentioned.

Among these, 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 aligning film of this invention is a film formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal aligning film of this invention can be obtained by the usual method of producing a liquid crystal aligning film from a liquid crystal aligning agent. For example, the liquid crystal aligning film of this invention can be obtained by going through the process of forming the coating film of the liquid crystal aligning agent of this invention, the process of heat drying, and the process of heat-baking. About the liquid crystal aligning film of this invention, you may give anisotropy by rubbing the film|membrane obtained through a heat drying process and a heat baking process as mentioned later as needed. Alternatively, if necessary, light may be irradiated after the coating film step or the heat drying step, or light may be irradiated after the heat firing step to impart anisotropy. Moreover, you may use also as a liquid crystal aligning film for VA which has not been rubbed.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element, similarly to the production of an ordinary liquid crystal aligning film. The substrate includes a glass substrate on which electrodes such as ITO (Indium TinOxide), IZO (In ₂ O ₃ -ZnO), IGZO (In-Ga-ZnO ₄ ) electrodes, color filters, etc. may be formed.

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

As the heat drying step, 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 are generally known. The heat drying step is preferably carried out at a temperature within a range in which evaporation of the solvent is possible, and more preferably carried out at a temperature relatively lower than the temperature in the heat firing step. Specifically, the heat drying temperature is preferably in the range of 30°C to 150°C, and further preferably in the range of 50°C to 120°C.

The heat firing step can be carried out under conditions necessary for the polyamic acid or its derivative to exhibit a dehydration/ring closure reaction. As for the firing of the coating film, 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 are generally known. These methods can be applied equally to the present invention. In general, it is preferable to carry out for 1 minute to 3 hours at a temperature of about 100 to 300°C, more preferably 120 to 280°C, and still more preferably 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 and/or vertical direction, as a means for imparting anisotropy to the alignment film, a known forming method such as a rubbing method or a photo alignment method is preferable. Can be used. In particular, a photoalignment method can be preferably used.

The liquid crystal aligning film of the present invention using the rubbing method includes a step of applying the liquid crystal aligning agent of the present invention to a substrate, a step of heat-drying the substrate coated with the aligning agent, a step of heat-baking the film, and a rubbing treatment of the film. It can be formed through a process.

The rubbing treatment can be performed in the same manner as the rubbing treatment for the alignment treatment of a conventional liquid crystal alignment film, and it is sufficient to be a condition in which sufficient retardation is obtained in the liquid crystal alignment film of the present invention. Preferred conditions are a hair indentation amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm/sec, and a roller rotation speed of 500 to 2,000 rpm.

The method of forming the liquid crystal aligning film of the present invention by the photoalignment method will be described in detail. The liquid crystal aligning film of the present invention using the photo-alignment method can be formed by heat-drying the coating film and then irradiating linearly polarized light or non-polarized light of radiation to impart anisotropy to the coating film and heat-baking the film. Alternatively, it can be formed by heating and drying the coating film and heating and firing, and then irradiating linearly polarized light or non-polarized light of radiation. From the viewpoint of orientation, it is preferable to perform the irradiation step of radiation before the heating and firing step.

Moreover, in order to improve the liquid crystal aligning ability of a liquid crystal aligning film, it is also possible to irradiate linearly polarized light or non-polarized light of radiation while heating a coating film. The irradiation of radiation may be performed in a step of heat-drying the coating film or a step of heat-baking, or may be performed between a heat-drying step and a heat-baking step. The heating drying temperature in the step is preferably in the range of 30°C to 150°C, and further preferably in the range of 50°C to 120°C. Moreover, it is preferable that the heating and firing temperature in the step is in the range of 30°C to 300°C, and further preferably in the range of 50°C to 250°C.

As the radiation, for example, ultraviolet rays or visible light including light of a wavelength of 150 to 800 nm can be used, but ultraviolet rays including light of 300 to 400 nm are preferable. Moreover, linearly polarized light or non-polarized light can be used. These lights are not particularly limited as long as they are light capable of imparting liquid crystal alignment ability to the coating film, but linearly polarized light is preferable when a strong alignment regulating force is expressed for the liquid crystal.

The liquid crystal aligning film of this invention can show high liquid crystal aligning ability even in light irradiation of low energy. The dose of linearly polarized light in the radiation irradiation step is preferably 0.05 to 20 J/cm 2, more preferably 0.5 to 10 J/cm 2. Moreover, it is preferable that it is 200-400 nm, and, as for the wavelength of linearly polarized light, it is more preferable that it is 300-400 nm. The irradiation angle of linearly polarized light with respect to the film surface is not particularly limited, but in the case of attempting to express a strong alignment regulating force with respect to the liquid crystal, it is preferable to be as perpendicular to the film surface as possible from the viewpoint of shortening the alignment treatment time. Moreover, the liquid crystal aligning film of this invention can align a liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

When the pretilt angle is to be expressed, the light irradiated to the film may be linearly polarized or non-polarized as described above. In the case of expressing the pre-tilt angle, the irradiation amount of light irradiated to the film is preferably 0.05 to 20 J/cm 2, particularly preferably 0.5 to 10 J/cm 2, and the wavelength is preferably 250 to 400 nm. And 300 to 380 nm is particularly preferable. When the pretilt angle is to be expressed, the irradiation angle of the light irradiated to the film to the surface of the film is not particularly limited, but it is preferably 30 to 60 degrees from the viewpoint of shortening the alignment treatment time.

Light sources used in the process of irradiating linearly polarized or unpolarized radiation include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, mercury. Xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, LED lamps, sodium lamps, microwave excitation induction lamps, etc. can be used without limitation.

The liquid crystal aligning film of the present invention is preferably obtained by a method further including steps other than the steps described above. For example, the liquid crystal aligning film of the present invention does not necessarily require a process of cleaning the film after firing or irradiation with radiation, but a cleaning process can be formed depending on the situation of other processes.

As a cleaning method with a cleaning liquid, brushing, jet spraying, steam cleaning, or ultrasonic cleaning may be mentioned. These methods may be carried out alone or in combination. As a cleaning solution, pure water or various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen-based solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone can be used. It can be, but is not limited to these. Of course, these cleaning solutions are sufficiently purified and contain less impurities. Such a cleaning method can also be applied to the cleaning process in the formation of the liquid crystal alignment film of the present invention.

In order to increase the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be used before and after the heating and firing process, before and after the rubbing process, or before and after irradiation with polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30 to 180°C, preferably 50 to 150°C, and the time is preferably 1 minute to 2 hours. Moreover, UV lamp, fluorescent lamp, LED lamp, etc. are mentioned as annealing light used for annealing treatment. It is preferable that the irradiation amount of light is from 0.3 to 10 J/cm 2.

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal aligning film of the present invention can be measured by a known film thickness measuring device such as a step meter or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having a particularly large alignment anisotropy. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP 2005-275364 A. Moreover, evaluation can also be carried out by the method using ellipsometry as shown in the following examples. When the alignment film of the present invention is used as an alignment film for a liquid crystal composition, a material having a larger film anisotropy is considered to have a large alignment regulating force with respect to the liquid crystal composition.

The liquid crystal aligning film of this invention can be used for orientation control of an optical compensation material and all other liquid crystal materials other than the orientation use of the liquid crystal composition for liquid crystal displays. Further, since the alignment film of the present invention has a large anisotropy, it can be used alone for an optical compensating material.

The present invention provides a pair of substrates disposed to face each other, an electrode formed on one or both of the facing surfaces of each of the pair of substrates, and a liquid crystal formed on the facing surface of each of the pair of substrates. In a liquid crystal display device having an alignment film and a liquid crystal layer formed between the pair of substrates, there is provided a liquid crystal display device in which 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 ITO and a metal vapor deposition film. Moreover, the electrode may be formed on the entire surface of one surface of the substrate, or may be formed in a desired shape patterned, for example. Examples of the desired shape of the electrode include a comb or zigzag structure. The electrode may be formed on one of a pair of substrates, or may be formed on both substrates. The form of electrode formation differs depending on the type of liquid crystal display device. For example, in the case of an IPS type liquid crystal display device or an FFS type liquid crystal display device, an electrode is disposed on one of the pair of substrates, and other liquid crystal display devices In the case of, electrodes are disposed on both sides of the pair of substrates. The liquid crystal alignment layer is formed on the substrate or electrode.

The liquid crystal layer is formed in a form in which the liquid crystal composition is sandwiched by the pair of substrates on which the surface on which the liquid crystal alignment film is formed is opposed. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, interposed between the pair of substrates and forming an appropriate gap may be used as necessary.

There is no restriction|limiting in particular in a liquid crystal composition, Various liquid crystal compositions whose dielectric anisotropy is positive (positive) or negative (負) can be used. Preferred liquid crystal compositions having a positive dielectric anisotropy include Japanese Patent Publication No. 3086228, Japanese Patent Publication No. 2635435, Japanese Laid-Open Patent Publication No. Hei 5-501735, Japanese Laid-Open Patent Publication No. Hei 8-157826, Japanese Laid-Open Patent Publication No. 8-231960, and Japanese Laid-Open Patent Publication. Patent Publication Hei 9-241644 (EP885272A1), Japanese Patent Application Publication Hei 9-302346 (EP806466A1), Japanese Patent Application Publication Hei 8-199168 (EP722998A1), Japanese Patent Application Publication Hei 9-235552, Japanese Patent Application Publication Hei 9- 255956, Japanese Unexamined Patent Application Publication No. Hei 9-241643 (EP885271A1), Japanese Unexamined Patent Publication No. 10-204016 (EP844229A1), Japanese Unexamined Patent Publication No. Hei 10-204436, Japanese Unexamined Patent Publication No. 10-231482, Japanese Unexamined Patent Publication 2000- 087040, Japanese Unexamined Patent Application Publication No. 2001-48822, International Publication No. 2010/050324, Japanese Unexamined Patent Publication 2011-016986, Japanese Unexamined Patent Publication 2011-506707, International Publication No. 2010/0522891, Japanese Unexamined Patent Publication 2005-239763, etc. There is a liquid crystal composition.

As a preferred example of the liquid crystal composition having the negative dielectric anisotropy, JP-A-57-114532, JP-A-2-4725, JP-A4-224885, JP-A8-40953, JP Unexamined Patent Publication Hei 8-104869, Japanese Unexamined Patent Publication Hei 10-168076, Japanese Unexamined Patent Publication Hei 10-168453, Japanese Unexamined Patent Publication Hei 10-236989, Japanese Unexamined Patent Publication Hei 10-236990, Japanese Unexamined Patent Publication Hei 10 -236992, Japanese Unexamined Patent Publication Hei 10-236993, Japanese Unexamined Patent Publication Hei 10-236994, Japanese Unexamined Patent Publication Hei 10-237000, Japanese Unexamined Patent Publication Hei 10-237004, Japanese Unexamined Patent Publication Hei 10-237024, Japanese Unexamined Patent Publication Patent Publication No. Hei 10-237035, Japanese Patent Application No. Hei 10-237075, Japanese Patent Application No. Hei 10-237076, Japanese Patent Application No. Hei 10-237448 (EP967261A1), Japanese Patent Application No. Hei 10-287874, Japanese Patent Application No. Hei 10-287875, Japanese Unexamined Patent Publication Hei 10-291945, Japanese Unexamined Patent Publication Hei 11-029581, Japanese Unexamined Patent Publication Hei 11-080049, Japanese Unexamined Patent Publication 2000-256307, Japanese Unexamined Patent Publication 2001-019965, Japanese Unexamined Patent Publication Patent Publication 2001-072626, Japanese Unexamined Patent Publication 2001-192657, Japanese Unexamined Patent Publication 2010-037428, International Publication 2011/024666, International Publication 2010/072370, Japanese Unexamined Patent Publication 2010-537010, and Japanese Unexamined Patent Publication 2012-077201 , A liquid crystal composition disclosed in Japanese Unexamined Patent Application Publication No. 2009-084362 or the like.

In addition, for example, the liquid crystal composition used for the device of the present invention may further add an additive from the viewpoint of improving alignment. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoaming agents, polymerization initiators, polymerization inhibitors, and the like.

Example

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

<Weight average molecular weight (Mw)>

The weight average molecular weight of the polyamic acid was measured by the GPC method using a 2695 separation module 2414 differential refractometer (manufactured by Waters), and calculated in terms of polystyrene. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF = 0.6/100: weight ratio) so that the polyamic acid concentration became about 2% by weight. The column was measured using HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing agent under conditions of a column temperature of 50°C and a flow rate of 0.40 ml/min. As the standard polystyrene, TSK standard polystyrene manufactured by Tosoh Corporation was used.

<Viscosity measurement>

The viscosity of the polyamic acid was measured using a TVE-25L type viscometer manufactured by Toki Industries Co., Ltd.

<Evaluation of Printability (Craterability)>

A few drops of the sample solution of the synthesized polyamic acid were added dropwise onto the glass substrate cleaned cleanly, put in a spinner for 10 seconds at a rotation speed of 3000 rpm, and then allowed to stand at room temperature, and the cratering property of the aligning agent was visually evaluated. The humidity in the room where the cratering property was evaluated was about 50%.

<AC afterimage (luminance change rate)>

The luminance-voltage characteristics (B-V characteristics) of the liquid crystal display device described later were measured. Let this be the luminance-voltage characteristic: B (before) before stress application. Next, after applying an AC of 4.5 V and 60 Hz to the device for 20 minutes, it was short-circuited for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This is referred to as luminance-voltage characteristic: B (after) after stress application. Based on these values, the luminance change rate ΔB (%),

ΔB (%) = [B (after)-B (before)]/B (before) (Equation 1)

It was estimated using the equation of These measurements were made with reference to International Publication 2000/43833. It can be said that the smaller the value of ΔB (%) at a voltage of 0.75 V, the more the generation of an AC afterimage can be prevented.

<Orientation stability (liquid crystal orientation axis stability)>

The rate of change of the liquid crystal alignment axis on the electrode side of the liquid crystal display device to be described later was determined. The liquid crystal alignment angle φ (before) on the electrode side before application of the stress was measured, and then, after applying a square wave 4.5 V and 60 Hz to the element for 20 minutes, short-circuited for 1 second, and after 1 second and 5 minutes, the electrode side again The liquid crystal orientation angle φ (after) of was measured. Based on these values, change Δφ (deg.) of the liquid crystal alignment angle after 1 second and after 5 minutes,

Δφ (deg.) = φ (after)-φ (before) (Equation 2)

It was estimated using the equation of These measurements were performed with reference to J. Hilfiker, B. Johs, C. Herzinger, J. F. Elman, E. Montbach, D. Bryant, and P. J. Bos Thin Solid Films, 455-456, (2004) 596-600. It can be said that the smaller Δφ has a smaller rate of change of the liquid crystal alignment axis, and the stability of the liquid crystal alignment axis is good.

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

<solvent>

DMIB: N,N,2-trimethylpropionamide

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]hepto-5-ene-2,3-dicarboxyimide)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)ethyltrimethoxysilane

<Liquid Crystal Composition>

Positive liquid crystal composition:

Property value: NI 100.1 °C; Δε 5.1; Δn 0.093; η 25.6 mPa·s.

Negative liquid crystal composition:

Property value: NI 75.7 °C; Δε -4.1; Δn 0.101; η 14.5 mPa·s.

<1. Synthesis of polyamic acid>

[Synthesis Example 1]

1.4291 g of diamine (DI-5-1, m = 2) and 18.5 g of dehydrated DMIB were placed in a 50 ml brown four-necked flask equipped with a thermometer, agitator, a raw material input inlet and a nitrogen gas inlet, and stirred under a dry nitrogen stream. Dissolved. Subsequently, 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 at room temperature for 24 hours. BC 10.0 g was added to this reaction solution to obtain a polyamic acid solution having a polymer solid content concentration of 6% by weight. This polyamic acid solution is referred to as PA1. The weight average molecular weight of the polyamic acid contained in PA1 was 84,000.

[Synthesis Examples 2 to 22]

As shown in Table 1, except having changed the solvent composition, tetracarboxylic dianhydride and diamine, according to Synthesis Example 1, polyamic acid solutions (PA2)-(PA22) having a polymer solid content concentration of 6% by weight were prepared. . Table 1 summarizes the measurement results of the weight average molecular weight of the obtained polyamic acid, including the results of Synthesis Example 1.

[Comparative Synthesis Examples 1 to 5]

As shown in Table 2, except having changed the solvent composition, tetracarboxylic dianhydride, and diamine, according to Synthesis Example 1, polyamic acid solutions (PA23)-(PA27) having a polymer solid content concentration of 6% by weight were prepared. . Table 2 summarizes the measurement results of the weight average molecular weight of the obtained polyamic acid.

<2. Preservation stability and printability of polyamic acid (cratering property)>

[Example 1]

The viscosity immediately after synthesis was measured for the polyamic acid solution (PA1) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 1, and it was 39.3 Pa·s (initial viscosity). Moreover, as a result of measuring the viscosity after storing this varnish at room temperature for 30 days, it was 38.0 Pa*s. As a result of visually checking the printability (cratering property) by the above-described method, no cratering of the alignment agent was observed.

[Examples 2 to 22]

About polyamic acid solutions (PA2)-(PA22) prepared in Synthesis Examples 2 to 22 having a polymer solid content concentration of 6% by weight, the initial viscosity and the viscosity after 30 days were measured in the same manner as in Example 1. Including the results of Example 1, the results of viscosity measurement and printability of the obtained polyamic acid are summarized in Table 3.

[Comparative Examples 1 to 5]

About the polyamic acid solutions (PA23)-(PA27) prepared in Comparative Synthesis Examples 1 to 5 and having a polymer solid content concentration of 6% by weight, the initial viscosity and the viscosity after 30 days were measured in the same manner as in Example 1. Table 4 summarizes the results of viscosity measurement and printability of the obtained polyamic acid.

By comparison between Examples 1-22 and Comparative Examples 1-5, it turns out that the liquid crystal aligning agent of this invention has little fall of the viscosity at room temperature, and the storage stability of a liquid crystal aligning agent is high. Further, it can be seen that the liquid crystal aligning agent of the present invention has no cratering after it is applied to a substrate, and has high printability.

<3. Blend of polyamic acid>

The polyamic acid PA1 synthesized in Synthesis Example 1 as the polymer [A] and the polyamic acid PA4 synthesized in Synthesis Example 4 as the polymer [B] were mixed in a weight ratio of [A]/[B] = 1.0/9.0 to obtain PA28. .

Polyamic acid solution (PA29) to (PA40) having a polymer solid content concentration of 6% by weight in accordance with PA28, except for changing the type of the [A] component and the component [B] polyamic acid and the mixing ratio of [A]/[B] Was prepared. Including PA28, the types of the [A] component and the [B] component polyamic acid, and the mixing ratio [A]/[B] are summarized in Table 5.

The additive (Ad1) was added to the polyamic acid solution (PA5) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 5 at a rate of 5% by weight per polymer weight. The obtained polyamic acid solution is referred to as PA41.

Except having changed the type of the polyamic acid, the type and the amount of the additive, an additive was added in accordance with PA41 to prepare polyamic acid solutions (PA42) to (PA45). Including PA41, the types of polyamic acid, types and amounts of additives are summarized in Table 6.

<4. Liquid crystal display element manufacturing method>

<<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% by weight prepared in Synthesis Example 1, and diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. The liquid crystal aligning agent was applied to the glass substrate with a spinner. In addition, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including Examples and Comparative Examples, so that the alignment film became the following film thickness. After the film was applied, it was heated and dried at 70° C. for 80 seconds, followed by heating at 230° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm. Whitening of the formed alignment film was visually confirmed, but whitening was not observed.

Next, the obtained liquid crystal aligning film was applied using a rubbing treatment apparatus manufactured by Inuma Gauge Co., Ltd., and the amount of hair indentation of a rubbing cloth (1.8 mm of simulation length: rayon) was 0.20 mm, the stage movement speed was 60 mm/sec, and the roller rotation speed was The rubbing treatment was performed under conditions of 1,000 rpm.

Two substrates with an alignment layer formed on the substrate, the surfaces on which the alignment layers are formed are opposed, and a gap for injecting the liquid crystal composition between the facing alignment layers is formed so that the rubbing directions of the alignment layers are parallel. ), an empty IPS cell having a cell thickness of 4 μm was assembled. Further, the injection port for injecting the liquid crystal into this empty IPS cell was formed at a position in which the direction in which the liquid crystal flows during injection was substantially parallel to the rubbing direction of the alignment film. A liquid crystal display device was manufactured by vacuum injecting the positive liquid crystal composition into the prepared empty IPS cell. Although the flow orientation of the manufactured liquid crystal display device was visually confirmed, the flow orientation was not observed.

It was 4.9% as a result of measuring AC afterimage (luminance change rate) ΔB (%) by the method described above using the IPS liquid crystal display device manufactured above.

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

[Examples 24-34]

To each of the polyamic acid solutions PA1 and PA2 to PA8, PA28, PA29, PA41 and PA45 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and then diluted to 4% by weight of the polymer solid content concentration as a liquid crystal aligning agent. I did. Using the obtained liquid crystal aligning agent, an IPS liquid crystal display element was produced by the method according to Example 23, and a positive liquid crystal composition was injected. The alignment film whitening of the obtained IPS liquid crystal display element, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) were measured. The obtained result was put together with the result of Example 23 and summarized in Table 7.

[Comparative Example 6]

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

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

[Example 35]

A mixed solvent of DMIB/BC = 70/30 (weight ratio) was added to the polyamic acid solution (PA9) having a polymer solid content concentration of 1% by weight prepared in Synthesis Example 1, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. The liquid crystal aligning agent was applied to the glass substrate with a spinner. In addition, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including Examples and Comparative Examples, so that the alignment film became the following film thickness. After the film was applied, it was heated and dried at 70° C. for 80 seconds, followed by heating at 230° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm. Whitening of the formed alignment film was visually confirmed, but whitening was not observed.

Next, the obtained liquid crystal aligning film was applied using a rubbing treatment device manufactured by Inuma Gauge Co., Ltd., and the amount of hair indentation of the rubbing cloth (1.8 mm in length: rayon) was 0.30 mm, the stage movement speed was 60 mm/sec, and the roller rotation speed was The rubbing treatment was performed under conditions of 1,000 rpm.

Two substrates with an alignment layer formed on the substrate, the surfaces on which the alignment layers are formed are opposed, and the rubbing direction of each alignment layer is vertical, and a void for injecting the liquid crystal composition between the facing alignment layers is formed and bonded together. An empty TN cell having a thickness of 4 μm was assembled. Further, the injection port for injecting liquid crystal into this empty TN cell was formed at a position in which the direction in which the liquid crystal flows during injection was substantially parallel to the rubbing direction of the alignment film. A liquid crystal display device was manufactured by vacuum injecting the positive liquid crystal composition into the prepared empty TN cell. Although the flow orientation of the manufactured liquid crystal display device was visually confirmed, the flow orientation was not observed.

It was 5.8% as a result of measuring AC afterimage (luminance change rate) ΔB (%) by the method described above using the TN liquid crystal display element manufactured above.

As a result of measuring liquid crystal alignment axis stability Δφ (deg) by the method described above using the TN liquid crystal display device manufactured above, the initial value was 0.036 deg, and the value after 5 minutes was 0.020 deg.

[Examples 36 to 41]

To each of the polyamic acid solutions PA10 to PA11, PA30 to PA32, and PA42 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a TN liquid crystal display element was produced by the method according to Example 35, and a positive liquid crystal composition was injected. The alignment film whitening of the obtained TN liquid crystal display element, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) were measured. The obtained results were put together with the results of Example 35 and summarized in Table 8.

[Comparative Example 7]

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

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

[Example 42]

A mixed solvent of DMIB/BC = 70/30 (weight ratio) was added to the polyamic acid solution (PA12) having a polymer solid content concentration of 6% by weight prepared in Synthesis Example 12, and the mixture was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. The liquid crystal aligning agent was applied to the glass substrate with a spinner. In addition, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including Examples and Comparative Examples, so that the alignment film became the following film thickness. After the film was applied, it was heated and dried at 70° C. for 80 seconds, followed by heating at 230° C. for 15 minutes to form an alignment film having a thickness of 100 ± 10 nm. Whitening of the formed alignment film was visually confirmed, but whitening was not observed.

Two substrates on which the alignment film was formed on the substrate were opposed to each other, and a void for injecting the liquid crystal composition was formed between the opposed alignment films and bonded together to assemble an empty VA cell having a cell thickness of 4 µm. Further, the injection port for injecting the liquid crystal into this empty VA cell was formed at a position in which the direction in which the liquid crystal flows during injection was substantially parallel to the rubbing direction of the alignment film. A liquid crystal display device was manufactured by vacuum injecting the negative liquid crystal composition into the prepared empty VA cell. Although the flow orientation of the manufactured liquid crystal display device was visually confirmed, the flow orientation was not observed.

It was 6.3% as a result of measuring AC afterimage (luminance change rate) ΔB (%) by the method described above using the VA liquid crystal display element manufactured above.

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

[Examples 43 to 47]

To each of the polyamic acid solutions PA13-14, PA33, PA34, and PA43 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a VA liquid crystal display element was produced by the method according to Example 42, and a negative liquid crystal composition was injected. The alignment film whitening of the obtained VA liquid crystal display element, flow alignment, AC afterimage (luminance change rate) ΔB (%), and liquid crystal alignment axis stability Δφ (deg) were measured. The obtained results were put together with the results of Example 42 and summarized in Table 9.

[Comparative Example 8]

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

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

[Example 48]

A mixed solvent of DMIB/BC = 70/30 (weight ratio) was added to the polyamic acid solution (PA15) having a polymer solid content concentration of 6% by weight, and diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. The liquid crystal aligning agent was applied with a spinner to each of the glass substrates with column spacers and one glass substrate with ITO electrodes. In addition, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including Examples and Comparative Examples, so that the alignment film became the following film thickness. After film application, it was heated and dried at 70° C. for 80 seconds. Next, linearly polarized light of ultraviolet rays was irradiated through a polarizing plate from a vertical direction to the substrate using the Ushio Electric Co., Ltd. multi-light ML-501C/B. The exposure energy at this time was measured using a UV-integrating photometer UIT-150 (receiver UVD-S365) manufactured by Ushio Electric Co., Ltd., and exposure time to be 2.0 ± 0.1 J/cm 2 at a wavelength of 365 nm. Was adjusted. Next, heat firing was performed at 230°C for 15 minutes, and finally, thermal annealing was performed at 100°C for 30 minutes on a hot plate. The film thickness of the formed alignment film was 100 ± 10 nm. Whitening of the formed alignment film was visually confirmed, but whitening was not observed.

Two substrates with alignment layers formed on the substrate face each other, so that the polarization directions of the ultraviolet rays irradiated to each alignment layer are parallel, and a void for injecting a liquid crystal composition between the facing alignment layers is formed. By bonding, an empty FFS cell having a cell thickness of 4 µm was assembled. Further, the injection port for injecting the liquid crystal into this empty FFS cell was formed at a position in which the direction in which the liquid crystal flows during injection was substantially parallel to the polarization direction of ultraviolet rays irradiated to the alignment film. The positive liquid crystal composition was vacuum-injected into the prepared empty FFS cell to prepare a transverse electric field photoisomerization liquid crystal display device. Although the flow orientation of the manufactured liquid crystal display device was visually confirmed, the flow orientation was not observed.

It was 2.8% as a result of measuring AC afterimage (luminance change rate) ΔB (%) by the method described above using the transverse electric field photoisomerization type liquid crystal display device manufactured above.

As a result of measuring liquid crystal alignment axis stability Δφ (deg) by the method described above using the transverse electric field photoisomerization type liquid crystal display device prepared above, the initial value was 0.021 deg, and the value after 5 minutes was 0.012 deg.

[Examples 49 to 53]

To each of the polyamic acid solutions PA16 to PA20 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transverse electric field photoisomerization type liquid crystal display element was produced by the method according to Example 48, 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 transverse electric field photoisomerization liquid crystal display device were measured. The obtained result was put together with the result of Example 48 and summarized in Table 10.

[Examples 54 to 58]

To each of the polyamic acid solutions PA35 to PA38 and PA44 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Except for changing the lamp of the light source from Ushio Electric Co., Ltd. multi-light ML-501C/B to Ushio Electric Co., Ltd. metal halide lamp UVL-1500M2-N1, in the same manner as in Example 48 transverse electric field light An isomerization type liquid crystal display device was manufactured, 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 transverse electric field photoisomerization liquid crystal display device were measured. The obtained results were put together with the results of Examples 48 to 53 and summarized in Table 10.

[Comparative Example 9]

A mixed solvent of NMP/BC = 70/30 (weight ratio) was added to the polyamic acid solution PA26 having a polymer solid content concentration of 6% by weight, and diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transverse electric field photoisomerization type liquid crystal display element was produced by the method according to Example 48, 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 transverse electric field photoisomerization liquid crystal display device were measured. The obtained results are listed in Table 10 together with the results of the above examples.

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

[Example 59]

A mixed solvent of DMIB/BC = 70/30 (weight ratio) was added to the polyamic acid solution (PA21) having a polymer solid content concentration of 6% by weight, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. The liquid crystal aligning agent was applied with a spinner to each of the glass substrate with column spacers and one glass substrate with ITO electrodes. In addition, the rotational speed of the spinner was adjusted according to the viscosity of the liquid crystal aligning agent, including the following Examples and Comparative Examples, so that the alignment film became the following film thickness. After the film was applied, it was heated and dried at 70° C. for 80 seconds, and then heated and baked at 230° C. for 30 minutes to form an alignment film having a thickness of 100 ± 10 nm. Next, linearly polarized light of ultraviolet rays was irradiated with the Ushio Electric Co., Ltd. multi-light ML-501C/B through a polarizing plate from a vertical direction to the substrate. The exposure energy at this time was measured by measuring the amount of light using the Ushio Electric Co., Ltd. ultraviolet-integrating photometer UIT-150 (receiver UVD-S254), and the exposure time to be 2.0 ± 0.1 J/cm 2 with a wavelength of 254 nm. Was adjusted. Whitening of the formed alignment film was visually confirmed, but whitening was not observed.

Two substrates with alignment layers formed on the substrate face each other, so that the polarization directions of the ultraviolet rays irradiated to each alignment layer are parallel, and a void for injecting a liquid crystal composition between the facing alignment layers is formed. By bonding, an empty FFS cell having a cell thickness of 4 µm was assembled. Further, the injection port for injecting the liquid crystal into this empty FFS cell was formed at a position in which the direction in which the liquid crystal flows during injection was substantially parallel to the polarization direction of ultraviolet rays irradiated to the alignment film. The positive liquid crystal composition was vacuum-injected into the prepared empty FFS cell to prepare a transverse electric field photodegradable liquid crystal display device. Although the flow orientation of the manufactured liquid crystal display device was visually confirmed, the flow orientation was not observed.

It was 7.8% as a result of measuring AC afterimage (luminance change rate) ΔB (%) by the method described above using the transverse electric field photodecomposition type liquid crystal display device manufactured above.

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

[Examples 60 to 62]

To each of the polyamic acid solutions PA22, PA39, and PA40 having a polymer solid content concentration of 6% by weight, a solvent identical to the solvent composition of the polyamic acid was added, and it was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transverse electric field photodecomposition type liquid crystal display device was produced by the method according to Example 59, 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 transverse electric field photolysis type liquid crystal display device were measured. The obtained results were combined with the results of Example 59 and summarized in Table 11.

[Comparative Example 10]

A mixed solvent of NMP/BC=70/30 (weight ratio) was added to the polyamic acid solution PA27 having a polymer solid content concentration of 6% by weight, and the mixture was diluted to 4% by weight of a polymer solid content concentration to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, a transverse electric field photodecomposition type liquid crystal display device was produced by the method according to Example 59, 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 transverse electric field photolysis type liquid crystal display device were measured. The obtained results are listed in Table 11 together with the results of the above examples.

From the comparison between Examples 23 to 62 and Comparative Examples 6 to 10, it can be seen that the liquid crystal display device manufactured using the liquid crystal aligning agent of the present invention has a high stability of the liquid crystal aligning axis by reducing the AC afterimage.

By providing the liquid crystal aligning film formed using the liquid crystal aligning agent of this invention, a liquid crystal display element excellent in afterimage characteristic and excellent orientation stability can be manufactured.

Claims (16)

A liquid crystal aligning agent comprising a polyamic acid obtained by reacting tetracarboxylic dianhydride and diamine, or a derivative thereof, and a solvent, wherein the solvent contains at least one compound represented by the following formula (A):

In the formula, R ¹ and R ² are each independently alkyl having 1 to 3 carbon atoms. The method of claim 1,
A liquid crystal aligning agent in which the compound represented by formula (A) is at least one member selected from the group of compounds represented by the following formulas (A-1) to (A-6).

The method of claim 2,
A liquid crystal aligning agent in which the compound represented by formula (A) is at least one selected from the group of compounds represented by formulas (A-1), (A-4) and (A-6). The method of claim 1,
Solvent is ethylene carbonate, 1,2-propylene carbonate, 1,3-propylene carbonate, 2-methyl-1,3-propylene 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, di Ethylene glycol dimethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol methyl phenyl 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 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 diacetate, propylene glycol monomethyl ether, propylene glycol methylphenyl 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, pentyl acetate, acetic acid n-hexyl, cyclohexyl acetate, 2-methylcyclohexyl acetate, n-butyl propionate, methyl 2-hydroxy-isobutyrate, 2-methylpentanone-2,4-diol, t-butyl alcohol, triethylcarbinol , t-amyl alcohol, 1-methylcyclohexanol, 2,5-dimethylhexane-2,5-diol, n-butyl alcohol, bis(3-methylbutyl) ether, di-n-pentyl ether (diamyl ether ), 4-heptanone, 5-nonanone, 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, phenethyl Alcohol, 1-butoxy-2-propanol, 2-(2-methoxypropoxy)propanol, 2-hydroxyethyl cetate, 2,4-pentanedione, ethyl-3-ethoxypropionate, fur Furyl alcohol, tetrahydrofurfuryl alcohol, 3-methyl-3-methoxybutanol, 1,3-dioxolane, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, butyrophenone and diisobutyl ketone A liquid crystal aligning agent containing at least one selected from the group of poor solvents consisting of. The method of claim 1,
The solvent is at least selected from the group of good solvents consisting of N-alkyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, lactones, and 1,3-dialkyl-2-imidazolidinones. Liquid crystal aligning agent containing one. The method of claim 5,
Good solvents are N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, γ-butyrolactone and 1,3-dimethyl-2-imidazoli At least one liquid crystal aligning agent selected from dinon. The method of claim 1,
The tetracarboxylic dianhydride to be reacted with the diamine is selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII) and (PAN-1) to (PAN-8) At least one liquid crystal aligning agent:

In formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;
In the formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C (CF ₃ ) ₂ -;
In formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups, and the bond hand is connected to an arbitrary carbon, and at least one hydrogen of this group May be substituted with methyl, ethyl or phenyl;

In formulas (AN-III) to (AN-V), 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 one hydrogen of this group is It may be substituted with methyl, ethyl or phenyl, the bond hand hanging on the ring is linked to any carbon constituting the ring, and the two bond hands may be linked to the same carbon;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl, and Ph represents phenyl;
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

The method of claim 7,
Diamine and tetracarboxylic dianhydride reacted with the following formulas (AN-1-1), (AN-1-13), (AN-2-1), (AN-2-2), (AN-3- 1), (AN-3-2), (AN-4-1), (AN-4-5), (AN-4-6), (AN-4-17), (AN-4-21) , (AN-4-26), (AN-4-30), (AN-9-1), (AN-13-1), (AN-16-1) and (PAN-1) At least one liquid crystal aligning agent selected:

In formula (AN-4-17), m is an integer of 1 to 12; In the formula (AN-13-1), Ph represents phenyl. The method of claim 1,
Tetracarboxylic dianhydride and diamine reacted with the following formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), (DI-31) to (DI-35) and At least one liquid crystal aligning agent selected from the group consisting of (PDI-1) to (PDI-12):

In formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ -may be substituted with -NH-, -O-, m is an integer of 1 to 12, and alkylene At least one hydrogen may be substituted with -OH;
In formulas (DI-3) and (DI-5) to (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 'is} -S-, m' are independently an integer of 1 ~ 12, k is 1, It is an integer of -5, and n is 1 or 2;
In formula (DI-4), s is independently an integer of 0-2;
In formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -or C1-C10 alkylene;
Hydrogen having at least one cyclohexane ring and a benzene ring in formulas (DI-2) to (DI-7) is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl may be substituted, and in the formula (DI-4), the following formulas (DI-4-a) to (DI-4-) may be substituted with e);
The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary, and the bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is G ²¹ or G ²² Is any position excluding the bonding position of;

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;

In formula (DI-11), r is 0 or 1;
In formulas (DI-8) to (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 alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene, phenylene or alkyl substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;
In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbons, alkoxy having 1 to 5 carbons, or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego ;
In formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, -F, -Cl, -B, alkyl having 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, q is independently an integer of 0-4;
In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group;
In formula (DI-16), G ²⁴ is a single bond, C2-C6 alkylene, or 1,4-phenylene, and r is 0 or 1;
The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary;
In formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position;

In the formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or- C(CF ₃ ) ₂ -;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring, or a naphthalene ring, and at least one hydrogen of this group may be substituted with methyl, ethyl or phenyl;
In formula (DIH-3), ring E is each independently a cyclohexane ring or a benzene ring, at least one hydrogen of this group may be substituted with methyl, ethyl or phenyl, and Y is a single bond, 1 to C 1 20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -or -C(CF ₃ ) ₂ -;
In formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position;

In 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 '-} and, m' is an integer of 1 ~ 12, R ²⁵ is a group of the formula, or to having a alkyl, phenyl, a steroid skeleton having a carbon number of 3 to 30 ( DI-31-a), in this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ -is -O-, -CH=CH- or -C optionally substituted by a ≡C- is a hydrogen of the phenyl is a _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms It may be substituted with alkoxy, and the bonding position of -NH ₂ bonded to the benzene ring represents an arbitrary position in the ring,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ -of this alkylene is- O-, -COO-, -OCO-, -CONH-, -CH=CH- may be substituted, and 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, pyridin-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2 ,7-diyl or anthracene-9,10-diyl, in Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , and s , t and u are independently integers of 0 to 2, the sum of which is 1 to 5, and when s, t or u are 2, the two linking groups in each parenthesis may be the same or different, and 2 Ring may be the same or different, R ²⁶ is -F, -OH, alkyl having 1 to 30 carbon atoms, fluorine-substituted alkyl having 1 to 30 carbon atoms, alkoxy having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF _3, and -CH ₂ -having at least one alkyl 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 alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , and R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms or alkenyl having 2 to 20 carbon atoms;
One hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms, and the group in which the bonding position is not fixed to any one carbon atom constituting the ring It shows that the bonding position in the ring is arbitrary;
In formulas (DI-32) and (DI-33), -NH ₂ bonded to a benzene ring represents that the bonding position in the ring is arbitrary;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O- or C1-C6 alkylene, G ³² is a single bond or C1-C3 alkylene, R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, -CH ₂ -having at least one alkyl may be substituted with -O-, -CH=CH- or -C≡C-, and R ³² is 6 to carbon atoms 22 alkyl, R ³³ is hydrogen or C1-C22 alkyl, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1; And -NH ₂ bonded to a benzene ring represents that the bonding position in the ring is arbitrary;

In formula (PDI-7), R ⁵¹ is independently -CH ₃ , -OCH ₃ , -CF ₃ or -COOCH ₃ , and b is an integer of 0-2 independently. The method of claim 9,
Tetracarboxylic dianhydride and diamine reacted with the following formula (DI-1-3), (DI-2-1), (DI-4-1), (DI-4-5), (DI-5) -1), (DI-5-5), (DI-5-9), (DI-5-30), (DI-5-37), (DI-7-3), (DI-8-2 ), (DI-12-1), (DI-13-1), (DI-14-8), (DIH-2-1), (DI-31-2), (DI-31-5), Group consisting of (DI-31-47), (DI-34-2), (DI-34-4), (DI-34-7), (PDI-6-1) and (PDI-7-1) At least one liquid crystal aligning agent selected from:

In formulas (DI-5-1), (DI-5-37) and (DI-7-3), m is an integer of 1 to 12;
In formula (DI-5-30), k is an integer of 1-5;
In formula (DI-7-3), n is 1 or 2;
In the formula (DI-31-2), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms;
In the formula (DI-31-5), R ³⁵ is C1-C30 alkyl or C1-C30 alkoxy;
In formula (DI-34-2), R ⁴⁰ is hydrogen or C1-C20 alkyl;
In formulas (DI-34-4) and (DI-34-7), R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms. The method of claim 1,
A liquid crystal aligning agent further containing at least one selected from the group of compounds consisting of an alkenyl substituted nadamide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound and an epoxy compound. The method of claim 11,
Alkenyl substituted nadamide compound is bis(4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl)methane, N,N'-m-xylylene-bis (Allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboximide) and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2, At least one liquid crystal aligning agent selected from the group of compounds consisting of 3-dicarboxyimide). The method of claim 11,
Compounds having a radically polymerizable unsaturated double bond include N,N'-ethylenebisacrylamide, N,N'-(1,2-dihydroxyethylene)bisacrylamide, ethylenebisacrylate and 4,4'- At least one liquid crystal aligning agent selected from the group of compounds consisting of methylenebis(N,N-dihydroxyethyleneacrylate aniline). The method of claim 11,
Epoxy compound is N,N,N',N'-tetraglycidyl-m-xylenediamine, 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- At least one liquid crystal aligning agent selected from the group of compounds consisting of a glycidyl methacrylate copolymer and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. A liquid crystal aligning film formed by the liquid crystal aligning agent in any one of Claims 1-14. A liquid crystal display device comprising the liquid crystal alignment film according to claim 15.