JP6288412B2 - Liquid crystal alignment agent - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent that can form a liquid crystal alignment film with little decrease in voltage holding ratio due to light.

The liquid crystal display element has a TN (Twisted Nematic) type, a STN (Super Twisted Nematic) type, a VA (Vertical Alignment) type, an MVA (Multidomain VerticalA type), depending on the electrode structure, physical properties of liquid crystal molecules used, the electrode structure, and the like. It can be classified into various modes such as an IPS (In-Plane Switching) type and an FFS (Fringe Field Switching) type.
As materials for the liquid crystal alignment film in these various liquid crystal display elements, resin materials such as polyamic acid, polyimide, polyamide, and polyester are known. In particular, a liquid crystal alignment film made of polyamic acid or polyimide has heat resistance and mechanical strength. Because of its excellent affinity with liquid crystals, it is used in many liquid crystal display elements (Patent Document 1).
In recent years, liquid crystal aligning agents have been increasingly required to have a performance that does not cause a decrease in function (especially electrical characteristics represented by voltage holding ratio) by light irradiation. The circumstances are as follows.
In the manufacturing process of a liquid crystal display element, a liquid crystal dropping method, that is, an ODF (One Drop Fill) method has started to spread from the viewpoint of process shortening and yield improvement. In the ODF method, an ultraviolet light curable sealant is applied to a predetermined location on one of the substrates on which a liquid crystal alignment film is applied, and then the liquid crystal is dropped on a predetermined number of locations on the same substrate. Is used to spread the liquid crystal over the entire surface of the substrate, and further irradiate ultraviolet light to cure the sealing agent to produce a liquid crystal cell. The ultraviolet light irradiated at this time is usually strong at several joules per square centimeter. That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment film is exposed to this intense ultraviolet light together with the liquid crystal.

Turning to changes in the use of liquid crystal display elements, in addition to notebook PCs and monitor displays, which were the main uses of conventional liquid crystal display elements, liquid crystal televisions are becoming increasingly popular, and other than conventional business uses In addition, the demand for liquid crystal projectors for home theater use is increasing, and liquid crystal display devices intended for outdoor use such as mobile type and in-vehicle use have been popular for a long time.
Liquid crystal televisions are required to have a long replacement cycle and a long life, and thus are exposed to backlight irradiation for a long period of time. A liquid crystal display element for a liquid crystal projector uses a light source having a very high irradiation intensity such as a metal halide lamp. Liquid crystal display elements for mobile devices such as mobile phones and in-car car navigation systems are assumed to be used even in sunlight containing strong ultraviolet rays, and it is necessary to increase the brightness of the backlight to improve visibility. .
In this way, liquid crystal display elements are exposed to harsh environments that could not be considered in the past, such as high-intensity light irradiation and long-time driving, due to improvements in the manufacturing process and diversification of applications. It has become. The old liquid crystal alignment film has insufficient resistance to such a harsh environment.

Japanese Patent Laid-Open No. 62-165628 JP 2010-97188 A International Publication No. 2009/096598

  The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal aligning agent with a small degree of voltage holding ratio reduction by light (particularly ultraviolet light).

The above objects and advantages of the present invention are as follows:
(A) a polymer containing at least one polymer selected from the group consisting of polyamic acid, imidized polymer thereof, polyamic acid ester and polyorganosiloxane, and (B) the following formulas (1) and (2) It is achieved by a liquid crystal aligning agent characterized by being prepared using at least one compound selected from the group consisting of compounds represented by

(In the formula (1), n1 is 1 or 2,
m1 is 1 or 2,
n is an integer of 1 to 4,
R ^I is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group,
X ¹ is a single bond, a carbonyl group or ^* -CONH- (wherein a bond marked with “*” is bonded to a heterocyclic ring containing a nitrogen atom);
R ^{II to} R ^V are each independently an alkyl group having 1 to 6 carbon atoms,
X ² to X ⁵ are each a single binding,
X ⁶ is a divalent organic group,
W ¹ is an n1 + m1 valent organic group,
Z ¹ is an amino group, a cyclic ether structure or a group having a polymerizable unsaturated bond;
In formula (2), n2 is 1 or 2,
m2 is 1 or 2,
R ^VI is an alkyl group having a carbon number of 4 to 16,
R ^VII is an alkyl group having a carbon number of 1 to 16,
X ⁷ is a divalent organic group,
W ² is an n2 + m2-valent organic group, and Z ² is an amino group, a cyclic ether structure, or a group having a polymerizable unsaturated bond. )

The liquid crystal aligning agent of the present invention is preferably a liquid crystal aligning agent containing the (A) polymer and the (B) compound, or a reaction product of the (A) polymer and the (B) compound. It is a liquid crystal aligning agent containing. It may be a liquid crystal aligning agent containing all of (A) the polymer and the (B) compound, and the reaction product of the (A) polymer and the (B) compound.

  The liquid crystal aligning agent of this invention is excellent in liquid crystal aligning property, and gives the liquid crystal aligning film with few degrees that a voltage holding rate falls by light (especially ultraviolet light). Therefore, a liquid crystal display element having a liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be suitably applied to a liquid crystal television, a liquid crystal projector, a mobile device, an in-vehicle display, and the like.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of this invention is prepared using (A) polymer and (B) compound.
<(A) Polymer>
The polymer (A) in the present invention contains at least one polymer selected from the group consisting of polyamic acid, its imidized polymer, polyamic acid ester, and polyorganosiloxane. (A) The polymer may contain a polymer other than these. Examples of other polymers that can be used here include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and polyvinyl alcohol derivatives. it can.
(A) The polymer is at least one polymer selected from the group consisting of a polyamic acid, an imidized polymer thereof, a polyamic acid ester, and a polyorganosiloxane. It is preferable to contain at least 50% by weight, more preferably at least 50% by weight. (A) All the polymers are selected from the group consisting of polyamic acid, its imidized polymer, polyamic acid ester and polyorganosiloxane. More preferably.
The polymer (A) preferably contains at least one polymer selected from the group consisting of a polyamic acid, an imidized polymer thereof, and a polyorganosiloxane. A) More preferably 30% by weight or more, more preferably 50% by weight or more based on the total amount of the polymer, and (A) all of the polymers are selected from these polymers. More preferably it is. (A) The polymer is particularly preferably a case containing at least one selected from the group consisting of a polyamic acid and an imidized polymer thereof, and the content ratio is particularly preferably (A) based on the total amount of the polymer. On the other hand, it is a case of 30% by weight or more, and in particular, a case where the content ratio thereof is 50% by weight or more with respect to the total amount of the polymer (A).

[Polyamic acid and imidized polymer thereof]
The polyamic acid as the polymer (A) in the present invention can be obtained by reacting tetracarboxylic dianhydride with diamine. The imidized polymer of polyamic acid can be obtained by dehydrating and cyclizing the polyamic acid to imidize it.

-Tetracarboxylic dianhydride-
As a tetracarboxylic dianhydride used for synthesizing a polyamic acid, a tetracarboxylic dianhydride known to be used for synthesizing a polyamic acid or an imidized polymer thereof is used without particular limitation. be able to. Examples of such tetracarboxylic dianhydrides include tetracarboxylic dianhydrides described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188). Preferred tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5,9b. -Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -Methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2, 4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2 -Dicarboxylic anhydride, 3 5,6 tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane-3,5, It is at least one selected from the group consisting of 8,10-tetraone, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic dianhydride.
More preferably 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride and 1 , 2,3,4-cyclobutanetetracarboxylic dianhydride containing at least one selected from the group consisting of;
Particularly preferably, these are contained in an amount of 30 mol% or more based on the total amount of tetracarboxylic dianhydride;
In particular, it is preferable to contain 50 mol% or more of these with respect to the total amount of tetracarboxylic dianhydride.

-Diamine-
Examples of the diamine used for synthesizing the polyamic acid include a diamine having a pretilt angle developing group and a diamine having no pretilt angle developing group.
The diamine having a pretilt angle developing group is preferably an aromatic diamine having a pretilt angle developing group. Specific examples thereof include dodecanoxy-2,4-diaminobenzene, tetradecanoxy-2,4-diaminobenzene, and the like. Pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2, 5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesta Ruoxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanostannyl 3,5-diaminobenzoate, 3,6- Bis (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4- ((Aminophenyl) methyl) phenyl) -4- (4-heptylcyclohexyl) cyclohexane, Serial formula (A-1)

(In the formula (A-1), X ^I and X ^II are each a single bond, ^* —O—, ^* —COO— or ^* —OOC— (where the bond with “*” represents the formula (A -I) facing left));
R ^I is a single bond, a methylene group or an alkylene group having 2 or 3 carbon atoms;
a is 0 or 1, b is an integer of 0 to 2, provided that a and b are not 0 at the same time;
c is an integer of 1-20. )
The compound etc. which are represented by these can be mentioned.
The formula ^{(A-1) X I -R} I -X II in - a divalent methylene group as a group, an alkylene group having 2 or 3 carbon atoms ^represented, * ^-O-, * -COO- or ^* It is preferably —O—CH ₂ CH ₂ —O— (wherein a bond marked with “*” is bonded to a diaminophenyl group). When c is 3 or more in the group —C _c H _{2c + 1} , this group is preferably linear. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to the other groups. Specific examples of the compound represented by the formula (A-1) include, for example, the following formulas (A-1-1-1), (A-1-1-2), and (A-1-2).

(In the above formula, “n-” represents that each is linear.)
It is preferable that it is a compound represented by each of these.
Examples of the diamine having no pretilt angle-expressing group include aliphatic diamines, alicyclic diamines, aromatic diamines, and diaminoorganosiloxanes that do not have a pretilt angle-expressing group.

Among the diamines having no pretilt angle-expressing group, examples of the aliphatic diamine include 1,1-metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;
Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, and the like;

Examples of aromatic diamines having no pretilt angle-expressing group include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-. Diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 2,7- Diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-Aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) Xafluoropropane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4 '-Bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl- 3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-Aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -pipe Gin, 3,5-diaminobenzoic acid, 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) cyclohexyl-3,5 -Diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1- (2,4-diaminophenyl) piperazine-4-carboxylic acid, 4- (morpholine) -4-yl) benzene-1,3-diamine, 1,3-bis (N- (4-aminophenyl) piperidinyl) propane, α-amino-ω-aminophenylalkylene and the like;

Examples of the diaminoorganosiloxane having no pretilt angle-expressing group include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane.
As the diamine, in addition to the above, a diamine described in Patent Document 2 (Japanese Patent Laid-Open No. 2010-97188) may be used.

When the liquid crystal aligning agent of the present invention is used for forming a liquid crystal alignment film for a horizontal alignment type liquid crystal display element such as a TN type, STN type, IPS type, or FFS type, a polyamic acid is synthesized. It is preferable to control the pretilt angle so as not to become excessively high by limiting the proportion of the diamine having a pretilt angle-expressing group in the diamine used in the above. In this case, the diamine having a pretilt angle-expressing group is preferably 20 mol% or less, more preferably 10 mol% or less, and particularly preferably 5 mol% or less, based on the total amount of diamine. It is preferable that On the other hand, when the liquid crystal aligning agent of the present invention is used to form a liquid crystal alignment film for a vertical alignment type liquid crystal display element such as VA type or MVA type, a diamine having a pretilt angle developing group is used. It is preferable to use more than the above ratio to obtain a high pretilt angle. In this case, the diamine having a pretilt angle-expressing group is preferably in a proportion of 0.1 mol% or more, more preferably in a proportion of 0.5 to 80 mol%, based on the total amount of diamine. In particular, the ratio is preferably 1 to 50 mol%.
The diamine used for synthesizing the polyamic acid in the present invention does not include any of the compound in which n1 is 2 in the above formula (1) and the compound in which n2 is 2 in the above formula (2). It is preferable.

-Molecular weight regulator-
When synthesizing a polyamic acid, an appropriate molecular weight regulator is coexisted with the tetracarboxylic dianhydride and diamine as described above to synthesize a polyamic acid (and its imidized polymer) with a regulated molecular weight. Also good.
Examples of molecular weight regulators that can be used here include carboxylic acid monoanhydrides, monoamines, and monoisocyanate compounds.
Examples of the carboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride;
Examples of the monoamine include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine;
Examples of the isocyanate compound include phenyl isocyanate and naphthyl isocyanate.

-Synthesis of polyamic acid-
The polyamic acid in the present invention can be obtained by reacting the above tetracarboxylic dianhydride and diamine (and optionally a molecular weight regulator).
The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction is 0.2 to 2 for the tetracarboxylic dianhydride acid anhydride group to 1 equivalent of the amino group of the diamine. The ratio which becomes an equivalent is preferable, More preferably, it is the ratio which becomes 0.3-1.2 equivalent. When using a molecular weight regulator, it is preferable that the use ratio shall be 20 weight or less with respect to a total of 100 weight part of tetracarboxylic dianhydride and diamine.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 ° C. to 150 ° C., more preferably 0 to 100 ° C., and preferably 0.1 to 24 hours, more preferably 0.00. 5 to 12 hours.

Examples of the organic solvent that can be used in the synthesis of the polyamic acid include an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, and hydrocarbon. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like. ;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate;
Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether. Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc .;
Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;
Examples of the hydrocarbon include hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, and diisopentyl ether.

Among these organic solvents, one or more selected from the group consisting of aprotic polar solvents and phenols and derivatives thereof (first group organic solvents) are used, or selected from the first group of organic solvents It is preferable to use a mixture of at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group organic solvent). . In the latter case, the use ratio of the second group of organic solvents is preferably 50% by weight or less, more preferably 40% by weight or less, with respect to the total of the first group of organic solvents and the second group of organic solvents. Furthermore, it is preferable that it is 30 weight% or less.
The amount of organic solvent used (a) is the ratio of the total amount (b) of tetracarboxylic dianhydride and diamine (and molecular weight modifier, if present) to the total amount (a + b) of the polymerization reaction solution (b / (A + b)) is preferably in an amount of 0.1 to 50% by weight.

-Synthesis of imidized polymer of polyamic acid-
The imidized polymer of polyamic acid as the polymer (A) in the present invention can be obtained by dehydrating and ring-closing imidized polyamic acid obtained as described above. Here, the imidation rate of the imidized polymer is preferably 30% or more, and more preferably 40 to 95%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of amic acid structures and the number of imide ring structures in the imidized polymer of polyamic acid, expressed as a percentage. The imidization rate can be measured, for example, by ¹ H-NMR.
The dehydration ring closure of the polyamic acid is preferably performed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to this solution as necessary. This is done by heating.
The reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the imidized polymer obtained may decrease. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

  On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. Although the usage-amount of a dehydrating agent is based on the imidation ratio desired, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

-Polyamic acid ester-
The polyamic acid ester as the polymer (A) in the present invention can be synthesized, for example, by the following method.
(1) A method of reacting a polyamic acid with a compound having a hydroxyl group, a halide and a compound having an oxiranyl group, or (2) reacting a tetracarboxylic acid diester or tetracarboxylic acid diester dihalide with a diamine. How to make.

The polyamic acid used in the method (1) is the same as the polyamic acid as the polymer (A) in the present invention.
Examples of the compound having a hydroxyl group used in the method (1) include alcohols and phenol compounds. Specific examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, t-butanol and the like;
Examples of phenol compounds include phenol and cresol.
Each can be mentioned.
Examples of the halide include, for example, methyl bromide, ethyl bromide, n-propyl bromide, isopropyl bromide, n-butyl bromide, isobutyl bromide, sec-butyl bromide, t-butyl bromide, stearyl bromide. Methyl chloride, ethyl chloride, n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, secbutyl chloride, t-butyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like;
Examples of the compound having an oxiranyl group include propylene oxide.
Each can be mentioned.
The reaction between the polyamic acid and a compound selected from a compound having a hydroxyl group, a halide and a compound having an oxiranyl group can be carried out according to a known method.

The tetracarboxylic acid diester used in the above method (2) can be obtained, for example, by opening the tetracarboxylic dianhydride exemplified above as used in the synthesis of polyamic acid with an alcohol. . The alcohol used here is the same as the alcohol as the compound having a hydroxyl group used in the method (1). The tetracarboxylic acid diester dihalide can be obtained by reacting the tetracarboxylic acid diester obtained as described above with an appropriate chlorinating agent. Examples of the chlorinating agent include thionyl chloride. The tetracarboxylic dianhydride used as a raw material for these compounds is the same as the tetracarboxylic dianhydride for synthesizing the polyamic acid as the polymer (A) in the present invention.
The diamine used in the method (2) is the same as the diamine for synthesizing the polyamic acid as the polymer (A) in the present invention.
The reaction of tetracarboxylic acid diester or tetracarboxylic acid diester dihalide and diamine can be carried out according to a known method.
The polyamic acid ester as the polymer (A) in the present invention may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

-Polyorganosiloxane-
As the polyorganosiloxane which is the polymer (A) in the present invention, known polyorganosiloxane can be suitably used without any particular limitation,
Hydrolysis / condensation product of hydrolyzable silane compound (polyorganosiloxane 1),
Hydrolyzable silane compound hydrolyzate / condensate (polyorganosiloxane 2), including a hydrolyzable silane compound having an epoxy group,
Hydrolyzate / condensation product (polyorganosiloxane 3) of a hydrolyzable silane compound containing a hydrolyzable silane compound having a Si—H bond, or a reaction product of the polyorganosiloxane 2 and a carboxylic acid (polyorganosiloxane) 4)
Is preferably used.

Here, as the hydrolyzable silane compound,
Examples of hydrolyzable silane compounds having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, and 3-glycidyloxypropylmethyldisilane. Ethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltri Ethoxysilane etc .;
Examples of hydrolyzable silane compounds having a Si—H bond include methoxydimethylsilane and ethoxydimethylsilane;
Examples of other hydrolyzable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth) acryloxypropyltriethoxy. Silane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyl In addition to trimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, and the like, Patent Document 3 ( It may be used hydrolyzable silane compounds described in Publication No. 2009/096598) when.

When polyorganosiloxane 4 is used as the polyorganosiloxane in the present invention, each hydrolyzable silane compound is used so that the epoxy equivalent in polyorganosiloxane 2 used as a precursor is 100 to 1,000 g / mol. It is preferable to adjust the ratio. Although the use ratio of the hydrolyzable silane compound having an epoxy group in the polyorganosiloxane 2 and the use ratio of the hydrolyzable silane compound having an Si—H bond in the polyorganosiloxane 3 are arbitrary, (A) as a polymer The use ratio of the hydrolyzable silane compound used for synthesizing the reaction product of the polyorganosiloxane and the compound (B) will be described later.
The hydrolysis / condensation reaction of the hydrolyzable silane compound can be carried out according to a known method. For example, it is preferably carried out with respect to the total amount of the hydrolyzable silane compound in an appropriate organic solvent, preferably in the presence of an appropriate catalyst. Can be carried out by adding 1 to 30 moles of water. The reaction temperature is preferably 40 to 100 ° C., and the reaction time is preferably 1 to 8 hours.

In the case of using polyorganosiloxane 4 as the polyorganosiloxane, examples of the carboxylic acid used for the reaction with the reactive polyorganosiloxane include 4-n-hexyloxybenzoic acid, 4-cyclohexyloxybenzoic acid, 4- ( n-octyloxy) benzoic acid, 4- (2-ethylhexyloxy) benzoic acid, 4- (n-undecyloxy) benzoic acid, 4- (n-dodecyloxy) benzoic acid, 4- (n-heptadecyloxy) ) Benzoic acid, 4- (3-cholestanyloxy) benzoic acid, 4- (3-cholestenyloxy) benzoic acid, 4- (4,4,5,5,5-pentafluoropentyloxy) benzoic acid, 4 -(4- (4-pentylcyclohexyl) cyclohexyl) phenyloxybenzoic acid, etc. Document 3 can be used a compound corresponding to the carboxylic acids of the "reactive compound" described in (WO 2009/096598). Such a carboxylic acid is preferably used in an amount of 0.05 to 0.9 mol based on 1 mol of the epoxy group of the reactive polyorganosiloxane.
The reaction between the reactive polyorganosiloxane and the carboxylic acid is carried out, for example, in a suitable organic solvent, preferably in the presence of a suitable catalyst, preferably at a temperature of 50 to 150 ° C., preferably 0.5 to 20 hours. The reaction time of
Regarding the hydrolysis / condensation reaction of the hydrolyzable silane compound and the reaction between the reactive polyorganosiloxane and the carboxylic acid, all matters other than those described above are described in Patent Document 3 (International Publication No. 2009/096598). It can be easily carried out as it is or under conditions obtained by making appropriate changes by those skilled in the art.

<(B) Compound>
The compound (B) in the present invention is a compound represented by the above formula (1) (hereinafter also referred to as “compound (1)”) and a compound represented by the above formula (2) (hereinafter referred to as “compound (2)”. Or at least one compound selected from the group consisting of: The compound (B) has a specific hindered amine structure or hindered phenol structure in the molecule, as is apparent from the above formulas (1) and (2).

[Compound (1)]
The alkyl group having 1 to 6 carbon atoms ^{R I} in formula (1), for example a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl, 2-butyl, i- butyl Group, t-butyl group and the like.
The aromatic group having 6 to 20 carbon atoms R ^I, can be mentioned aryl group and other aromatic group having 6 to 12 carbon atoms, wherein the aryl group having 6 to 12 carbon atoms, such as phenyl group 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group, 3-chloro-4-methylphenyl group and the like;
Examples of the other aromatic groups include 4-pyridinyl group, 2-phenyl-4-quinolinyl group, 2- (4′-t-butylphenyl) -4-quinolinyl group, and 2- (2′-thiophenyl)-. 4-quinolinyl group etc. can be mentioned, respectively.
The aralkyl group having 7 to 13 carbon atoms R ^I, such as a benzyl group may be mentioned.

As a combination of R ^I and X ¹ in the above formula (1), as a group R ^I —X ¹ — in which these are combined, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl Group, 2-butyl group, i-butyl group, t-butyl group, formyl group, acetyl group, phenyl group, benzyl group, 1,3-dioxobutyl group, 4-pyridinylcarbonyl group, benzoyl group, 2-phenyl -4-quinolinyl group, 2- (4'-t-butylphenyl) -4-quinolinyl group, 2- (2'-thiophenyl) -4-quinolinyl group, group -CONH-Ph (where Ph is a phenyl group, 3-fluorophenyl group, 3-chlorophenyl group, 4-chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group or 3-chloro-4-methylphenyl group. , And the like group represented by the. The group R ^I —X ¹ — is preferably a methyl group.
Examples of the alkyl group having 1 to 6 carbon atoms of R ^{II to} R ^V in the above formula (1) include a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a 2-butyl group, i- butyl group, and a t- butyl group can ani gel.

Examples of the combination of R ^II and X ² , R ^III and X ³ , R ^IV and X ⁴ and R ^V and X ⁵ in the above formula (1) include groups R ^II -X ^2- , R ^III- X ^3- , R ^IV -X ⁴ -or R ^V -X ^5- may be, for example, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-butyl group, i- etc. butyl group, t- butyl group can be mentioned. The groups R ^II -X ^2- , R ^III -X ^3- , R ^IV -X ⁴ -and R ^V -X ⁵ -are all preferably methyl groups.

X ⁶ in Formula (1) is, for example, a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, an oxygen atom, ^* -OOC-, ^* -CO-, ^* -COO-, ^* -CONH-, ^* —NHCO—, ^* —NH—, ^* —N (CH ₃ ) —, ^* —N (C ₂ H ₅ ) —, ^* —CR ₂ CR ₂ OOC—, ^* —COO—CR ₂ CR ₂ —OOC— , ^* —O—CH ₂ —C ::: C— or ^* —COO—CH ₂ —C ::: C— (in the above, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ::: ”represents a triple bond, and a bond marked with“ * ”is bonded to a heterocyclic ring having a nitrogen atom. Examples of the alkylene group having 2 to ⁶ carbon atoms of X ⁶ include a 1,3-propylene group and a 1,6-hexylene group. This X ⁶ only needs to have a function of bonding a heterocyclic ring having a nitrogen atom and a benzene ring having a group Z ^1, and the effect of the present invention is reduced no matter how the type is selected. Not. However, in order to maximize the effects of the present invention, it is preferable to keep the total number of carbon atoms and hetero atoms in X ⁶ to 12 or less. X ⁶ represents ^* —OOC—, ^* —NHCO— or ^* —O—CH ₂ —C ::: C— (where “:::” is It represents a triple bond, and a bond marked with “*” is preferably bonded to a heterocyclic ring containing a nitrogen atom.
Examples of the group having an amino group of Z ¹ in the above formula (1) include an amino group, an aminomethyl group, and an aminoethyl group;
The group having a cyclic ether structure is preferably a group having an oxiranyl group, such as an N, N-diglycidylamino group, an epoxycyclohexyl group, a glycidyloxy group, etc .;
Examples of the group having a polymerizable unsaturated bond include a (meth) acryloyloxy group, a vinyl group, a vinyloxy group, and an allyl group.

W ¹ in the above formula (1) is an n1 + m1 valent organic group. The W ¹ is obtained, for example, by removing n1 + m1 hydrogen from an aromatic compound having 6 to 14 carbon atoms, or by removing n1 + m1 hydrogen from an aliphatic hydrocarbon compound having 1 to 12 carbon atoms. The group etc. which can be mentioned can be mentioned. Here, the aromatic compound and the aliphatic hydrocarbon compound may each be substituted with a halogen atom, a cyano group, or an alkoxy group. Examples of the aromatic compound before removing n1 + m1 hydrogens include benzene, naphthalene, and anthracene. The aliphatic hydrocarbon compound before removing n1 + m1 hydrogen is preferably an alkane having 1 to 8 carbons or a cycloalkane having 3 to 8 carbons, and specifically, for example, methane, ethane, n-propane, n- Examples include butane, n-pentane, n-hexane, cyclopentane, and cyclohexane.
W ¹ in the above formula (1) is preferably a group obtained by removing n1 + m1 hydrogen from benzene or a group obtained by removing n1 + m1 hydrogen from ethane.

The position at which X ⁶ in Formula (1) is bonded to the heterocyclic ring containing a nitrogen atom is preferably in the following position relative to the nitrogen atom, depending on the value of n.
When n is 1: 3rd position When n is 2 or 3: 3rd or 4th position, particularly preferably 4th position When n is 4: 4th or 5th position, particularly preferably 5th position In the above formula (1) n is preferably 2.
When W ¹ in the above formula (1) is a group obtained by removing n1 + m1 hydrogens from benzene, the position of Z ¹ is the following position with respect to X ⁶ according to the value of n1 Is preferred.
When n1 is 1: 3rd or 4th position When n1 is 2: 2nd, 4th or 3rd, 5th Preferably n1 in the above formula (1) is 1.
As the compound (1), compounds represented by the following formulas (B1-1) to (B1-3) are preferable.

(R ^I , X ⁶ and Z ¹ in the formulas (B1-1) to (B1-3) have the same meanings as in the above formula (1).)
Specific examples of such compound (1) include compounds represented by the following formulas (1-1) to (1-8), for example.

  The compound (1) in the present invention is preferably a compound represented by the following formula (B1 ′), and more preferably a compound represented by the above formula (B1-1).

(In the formula (B1 ′), n1, n, R ^{I to} R ^V , X ^{1 to} X ⁶ and Z ¹ have the same meanings as in the above formula (B1).)
Therefore, the compound (1) in the present invention is most preferably at least one selected from the group consisting of compounds represented by the formulas (B1-1) to (B1-6).
Such a compound (1) can be easily synthesized by demonstrating the knowledge that those skilled in the art normally have and combining organic chemistry methods appropriately.
For example, the compound represented by the above formula (B1-1) is a compound in which Y ¹ is —OH or —NH ₂ in the following formula (1a), and a commercially available product can be easily obtained as a hindered amine anti-aging agent. Therefore, the desired compound (1) can be obtained by reacting the compound with a benzene derivative having the desired group Z ¹ and an appropriate reactive group directly or indirectly through another compound. Can do. At this time, if necessary, the group Z ¹ is protected with an appropriate protecting group and then the above reaction is carried out, followed by deprotection to form the group Z ¹ , or the precursor group is substituted in place of the group Z ^1. It is also possible to carry out the above reaction using as a starting material a compound having the compound, and to convert the precursor group to the group Z ¹ after the reaction.

(In the formula (1a), R ^{I to} R ^V , X ^{1 to} X ⁵ and n each have the same meaning as in the above formula (1), and Y ¹ is —OH or —NH _2. )
For example equation (1) ^{X 6} in the ^* -OOC- (where "*" bond marked with are combined with heterocycles containing a nitrogen atom.), Compound, in formula (1a) ^{Y 1} is - Can be obtained by esterification reaction of a compound that is OH with a desired group Z ¹ and a benzene derivative having —COOH or —COOX (X is a halogen atom) as a reactive group;
In the formula (1), a compound in which X ⁶ is ^* —NHCO— (wherein a bond marked with “*” is bonded to a heterocyclic ring containing a nitrogen atom) is represented by the formula (1a) wherein Y ¹ is − Can be obtained by amidation reaction of a compound that is NH ₂ with a desired group Z ¹ and a benzene derivative having —COOH or —COOX (X is a halogen atom) as a reactive group;
In the formula (1), X ⁶ is ^* —O—CH ₂ —C ::: C— (where “:::” represents a triple bond, and the bond marked with “*” contains a nitrogen atom. The compound which is bound to the ring) is
An intermediate having a triple bond at the terminal, obtained by reacting a compound in which Y ¹ is —OH in formula (1a) with 3-halogenated-1-propyne,
It can be obtained by adding a desired group Z ¹ and a benzene derivative having a halogen atom as a reactive group. In the above, when the groups ^{Z 1} is -NH ₂ may perform the above reaction in terms of protected the -NH _2, or to reproduce the -NH ₂ is deprotected to subsequent, or instead of -NH ₂ It is preferable to perform the above reaction using a compound having —NO ₂ as a raw material, and to convert —NO ₂ to —NH ₂ after the reaction.

[Compound (2)]
The formula in ^(2), the alkyl group having a carbon number of 4 to 16 of ^{R VI,} example if t- butyl group, etc. 1-methyl pentadecyl group can be exemplified, these out t- butyl group Particularly preferred.
As the alkyl group having a carbon number of 1 to 16 R ^VII, for example a methyl group, an ethyl group, n- propyl group, i- propyl, n- butyl group, i- butyl, t- butyl group, n- pentyl group , N-octyl group and the like, among which a methyl group or a t-butyl group is preferable. Position on the benzene ring of R ^VII is a hydroxyl group the ^1-position, when the 2-position of the ^{R VI,} Ru Oh at 6-position.

X ⁷ in the formula (2) is, for example, a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, an oxygen atom, ^* -OOC-, ^* -CO-, ^* -COO-, ^* -CONH-, ^* —NHCO—, ^* —NH—, ^* —N (CH ₃ ) —, ^* —N (C ₂ H ₅ ) —, ^* —CR ₂ CR ₂ OOC—, ^* —COO—CR ₂ CR ₂ —OOC— , ^* —O—CH ₂ —C ::: C— or ^* —COO—CH ₂ —C ::: C— (in the above, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms; ::: ”represents a triple bond, and a bond marked with“ * ”is bonded to a benzene ring having a hydroxyl group. This X ⁷ only needs to have a function of binding a benzene ring having a hydroxyl group and a benzene ring having a group Z ^2, and the effect of the present invention is not diminished no matter how the type is selected. . However, in order to maximize the effects of the present invention, it is preferable to keep the total number of carbon atoms and heteroatoms in X ⁷ to 12 or less. As X ⁷ , from the viewpoint of availability of raw materials and ease of synthesis, ^* —COO—CH ₂ CH ₂ —OOC—, ^* —COO—CH ₂ —C ::: C— or ^* —CH ₂ CH ₂ -OOC- (where ":::" represents a triple bond, and a bond marked with "*" is bonded to a heterocyclic ring containing a nitrogen atom) is preferred.

W ² in the above formula (2) is an n2 + m2-valent organic group. W ² can be understood in the same manner as W ¹ after replacing n 1 and m ^{1 in} the description of W ¹ with n 2 and m 2, respectively.
Preferred groups for Z ^{2 are the same} as those for Z ¹ .
In the above formula (2), n2 is preferably 1.
As the compound (2), compounds represented by the following formulas (B2-1) to (B2-3) are preferable.

(X ⁷ and Z ² in the formulas (B2-1) to (B2-3) have the same meanings as in the above formula (2).)
Specific examples of such a compound (2) include compounds represented by the following formulas (2-1) to (2-8).

  The compound (2) in the present invention is preferably a compound represented by the following formula (B2 ′), and more preferably a compound represented by the above formula (B2-1).

(In the formula (B2 ′), n2, R ^VI , R ^VII and X ⁷ have the same meanings as in the above formula (B2).)
Therefore, the compound (2) in the present invention is most preferably at least one selected from the group consisting of compounds represented by the formulas (B2-1) to (B2-6).
Such a compound (2) can be easily synthesized by demonstrating the knowledge that a person skilled in the art normally has and appropriately combining organic chemistry methods.
For example, since the compound represented by the above formula (B2-1) is a compound in which Y ² is —COOH in the following formula (2a), a commercially available product can be easily obtained as a hindered phenol-based antioxidant. The desired compound (2) can be obtained by reacting the compound with a benzene derivative having the desired group Z ² and an appropriate reactive group directly or indirectly through another compound. . At this time, if necessary, the group Z ² is protected with an appropriate protecting group and then the above reaction is performed, and then the group Z ² is generated by deprotecting the group Z ² or the precursor group is replaced with the group Z ^2. the compound having performed the reaction as a raw material, may be converted after the reaction the front Kamoto based Z ^2.

(In Formula (2a), R ^VI and R ^VII have the same meanings as in Formula (2) above, and Y ² is —COOH.)
For example, in the formula (2), a compound in which X ⁷ is ^* —COO—CH ₂ CH ₂ —OCC— (where a bond marked with “*” is bonded to a benzene ring containing a hydroxyl group)
A compound in which Y ¹ is —COOH in formula (2a) and an intermediate having —OH at the terminal obtained by the reaction of ethylene glycol;
A benzene derivative having the desired group Z ¹ and the reactive group —COOH or —COOX (where X is a halogen atom);
Can be obtained by an esterification reaction of
In Formula (2), X ⁷ is ^* —COO—CH ₂ —C ::: C— (where “:::” represents a triple bond, and the bond marked with “*” represents a benzene ring containing a hydroxyl group; The compound that binds)
An intermediate having a triple bond at the terminal, obtained by an ester reaction between a compound in which Y ² is —COOH in formula (2a) and 3-hydroxy-1-propoate,
It can be obtained by adding a desired group Z ² and a benzene derivative having a halogen atom as a reactive group. In the above, when the base ^{Z 2} is -NH ₂ may perform the above reaction in terms of protected the -NH _2, or to reproduce the -NH ₂ is deprotected to subsequent, or instead of -NH ₂ It is preferable to perform the above reaction using a compound having —NO ₂ as a raw material, and to convert —NO ₂ to —NH ₂ after the reaction.

<Preferred combination of (A) polymer and (B) compound>
When the liquid crystal aligning agent of this invention contains the reaction product of (A) polymer and (B) compound, this reaction product is that (A) polymer and (B) compound react. Thus, a reaction product obtained by adding the (B) compound to the (A) polymer is preferable. On the other hand, when the liquid crystal aligning agent of the present invention contains the (A) polymer and the (B) compound as independent components, they react with each other in the liquid crystal alignment film to be bonded. The formation is preferable from the viewpoint of maximizing the effects of the present invention. By taking such an aspect, in the liquid crystal aligning film formed, the hindered amine structure or the hindered phenol structure derived from the compound (B) is bonded to the polymer chain via a flexible bonding group. Therefore, the hindered amine structure or the hindered phenol structure can move relatively freely in the liquid crystal layer while being constrained by the polymer chain, and thus, for example, the impurity trapping function of the structure is effectively expressed. This is considered to improve the electrical characteristics of the liquid crystal display element.
When the liquid crystal aligning agent of this invention contains the reaction product of (A) polymer and (B) compound, and the case where (A) polymer and (B) compound are each contained as an independent separate component In any case, the (A) polymer and the (B) compound are preferably selected according to the following guidelines.

First, when the polymer (A) is a polyamic acid, the reaction site with the compound (B) in the polymer (A) is preferably a carboxy group having an amic acid structure. Therefore, it is preferable that Z ¹ or Z ² of the compound (B) is a group having an amino group and a cyclic ether structure, respectively. Therefore, as the compound (B) used in this case, for example, the above formulas (1-1) to (1-3), (1-5) to (1-8), (2-1), (2- 2), (2-4), (2-5), (2-7) and the compound represented by each of (2-8) can be illustrated.
Next, when the polymer (A) is an imidized polymer of polyamic acid, the reaction site with the compound (B) in the polymer (A) is preferably a carboxy group having an amic acid structure. It is preferable that a significant proportion of carboxy groups remain in the imidized polymer. From such a viewpoint, the imidation ratio of the imidized polymer in this case is preferably 99% or less, more preferably 30 to 90%, and particularly preferably 40 to 85%. Therefore, the (B) compound used in this case is the same as in the case where the (A) polymer is a polyamic acid.
Furthermore, when (A) the polymer is a polyorganosiloxane, the reaction between (A) the polymer and (B) compound is as follows:
When (A) the polymer is a polyorganosiloxane having an epoxy group (polyorganosiloxane 2) and (B) the compound is a group having a polymerizable unsaturated bond, or (A) the polymer is a Si-H bond. It is preferable that the compound (B) is a group having a polymerizable unsaturated bond. Examples of the compound (B) used in this case include compounds represented by the above formulas (1-4), (2-3) and (2-6).

<Use ratio of (B) compound>
The ratio of the compound (B) used in the liquid crystal aligning agent of the present invention is such that the liquid crystal aligning agent of the present invention contains a reaction product of the (A) polymer and the (B) compound, and (A) In any case where the polymer and the compound (B) are contained as independent separate components, it is preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the (A) polymer. 0.5 to 20 parts by weight, more preferably 1 to 15 parts by weight.
By setting the use ratio in this range, a liquid crystal alignment film in which a decrease in voltage holding ratio due to light (particularly ultraviolet light) is suppressed can be obtained.

<Reaction product of (A) polymer and (B) compound>
Next, a method for synthesizing the reaction product when the liquid crystal aligning agent of the present invention contains a reaction product of the (A) polymer and the (B) compound will be described.
The reaction between the polyamic acid or its imidized polymer (A) polymer and the compound (B) having a polymerizable unsaturated bond is preferably carried out by mixing and reacting them in an appropriate solvent. be able to. At this time, a catalyst may be used, but no catalyst is sufficient. Here, as the solvent, the same solvent as that used when polymerizing the polyamic acid can be used. The reaction temperature is preferably 40-80 ° C, more preferably 50-70 ° C;
The reaction time is preferably 15 minutes to 4 hours, more preferably 30 minutes to 2 hours.

The reaction between the polyorganosiloxane 2 and the compound (B) having a polymerizable unsaturated bond is preferably carried out in the presence of a suitable organic solvent, preferably in the presence of a catalyst. Examples of the organic solvent that can be used here include organic solvents that are usually used in the synthesis reaction of polyorganosiloxane. As said catalyst, a well-known compound can be used as what is called a hardening accelerator which accelerates | stimulates reaction of an organic base or an oxiranyl compound and an acid anhydride, for example.
Examples of the organic base include triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide;
Examples of the curing accelerator include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, and tetra-n-butylammonium chloride.
These catalysts are used in an amount of preferably 100 parts by weight or less, more preferably 0.01 to 100 parts by weight, and still more preferably 0.1 to 20 parts by weight with respect to 100 parts by weight of the polyorganosiloxane 2. The
The reaction temperature is preferably 40 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The reaction between the polyorganosiloxane 3 and the compound (B) having a polymerizable unsaturated bond is preferably a hydrosilylation reaction performed in the presence of a catalyst, preferably in an organic solvent.
As the catalyst, those known as hydrosilylation catalysts can be used, and for example, a compound or complex containing platinum, rhodium or palladium can be used. Of these, compounds or complexes containing platinum are preferred, and specific examples thereof include hexachloroplatinic acid (IV) hexahydrate, platinum carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane complex, platinum- Examples include octyl aldehyde / octanol complex. The platinum compound or complex may be supported on a suitable carrier such as activated carbon. The amount of the catalyst used is preferably 0.01 to 10,000 ppm, more preferably 0.1 based on the weight of the compound (B) used as the amount of metal atoms contained in the compound or complex. ~ 100 ppm.
The organic solvent that can be used in the hydrosilylation reaction is preferably an aromatic hydrocarbon or ether, and specific examples thereof include toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethyl ether, 1,4-dioxane, diphenyl ether, and the like. it can. The solvent is used in such a ratio that the solid content concentration (the ratio of the weight of components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1% by weight or more, more preferably 5 to 50% by weight. The
The reaction temperature is preferably 40 to 250 ° C, more preferably 50 to 180 ° C. The reaction time is preferably 0.1 to 120 hours, more preferably 1 to 10 hours.

<Other ingredients>
Although the liquid crystal aligning agent of this invention contains the above (A) polymer and (B) compound as an essential component, Preferably these are comprised as a solution composition melt | dissolved in the below-mentioned solvent, It may further contain other components as necessary.
Examples of such other components include a compound having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), a functional silane compound, and the like.

[Epoxy compound]
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3 -Bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylme Emissions, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - cyclohexyl amine may be mentioned as preferred.
The blending ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer. However, when the compound (1) in which Z ¹ is a group having a cyclic ether structure or the compound (2) in which Z ² is a group having a cyclic ether structure is used as the (B) compound, If too much epoxy compound is used, the advantageous effects of the present invention may be impaired. Therefore, when using the compound (B) in which Z ¹ or Z ² is a group having a cyclic ether structure, the proportion of the epoxy compound used as the other component is set to 100 parts by weight of the compound (B). It is preferable to keep it at 200 parts by weight or less, and it is more preferred to keep it at 100 parts by weight or less.

[Functional silane compounds]
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9- Triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltri Examples include methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, and N-phenyl-3-aminopropyltriethoxysilane.
The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

<Liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is arbitrarily mix | blended as needed with the above (A) polymer and (B) compound, or the reaction product of (A) polymer and (B) compound, and as needed. The other additives are preferably dissolved and contained in a solvent.
As a solvent that can be used in the liquid crystal aligning agent of the present invention, an organic solvent is preferably used. For example, N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N— Dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, Ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate , Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene A carbonate etc. can be mentioned. These can be used alone or in admixture of two or more.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably, when heated, a coating film that becomes a liquid crystal aligning film is formed, but the solid content concentration is less than 1% by weight. In this case, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive. Thus, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thus the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-45 degreeC, More preferably, it is 20-30 degreeC. When the liquid crystal aligning agent of the present invention is stored, it is preferably stored at 45 ° C. or lower in order to avoid the reaction between the (A) polymer and the (B) compound during storage.

<Method for forming liquid crystal alignment film>
A liquid crystal alignment film can be formed using the liquid crystal aligning agent of the present invention.
The process for forming the liquid crystal alignment film and the electrode configuration on the substrate on which the liquid crystal alignment film is formed differ depending on the display mode of the liquid crystal display element to which these are applied.
The liquid crystal alignment film can be formed by, for example, a method of performing (1) a coating film forming step and (2) a rubbing step in this order. (2) The rubbing process is optional. When the liquid crystal aligning agent of the present invention is applied to a vertical alignment type liquid crystal display element such as a VA type or an MVA type, (2) the rubbing step may not be performed.
Hereinafter, each of the steps for forming the liquid crystal alignment film will be described.

(1) Coating Film Formation Step When the liquid crystal aligning agent of the present invention is applied to a vertical electric field type liquid crystal display element such as a TN type, STN type, VA type, MVA type, etc., a patterned transparent conductive film is provided. As a pair of two substrates, the liquid crystal aligning agent of the present invention is applied to each transparent conductive film forming surface to form a coating film. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a lateral electric field type liquid crystal display element such as an IPS type or FFS type, a pair of electrodes in which a transparent conductive film or a metal film is patterned in a comb shape on one side. A coating film is formed by applying the liquid crystal aligning agent of the present invention to the surface on which the comb-like electrode is formed and one surface of the counter substrate, respectively. .
In any of the above cases, examples of the substrate include glass such as float glass and soda glass;
A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ —SnO _{2 or} a NESA (registered trademark) film made of SnO ₂ can be used. As the metal film, for example, a film made of a metal such as chromium can be used. For patterning the transparent conductive film and the metal film, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a transparent conductive film without a pattern, or having a desired pattern when forming the transparent conductive film For example, a method using a mask can be used.

When applying the liquid crystal aligning agent on the substrate, a functional silane compound, titanate compound or the like was previously applied on the substrate and the electrode in order to further improve the adhesion between the substrate and the electrode and the coating film. You may give the pretreatment heated later.
The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as an offset printing method, a spin coating method, a roll coater method, or an ink jet printing method. After coating, the coated surface can be preheated (prebaked) and then baked (postbaked) to form a coating film. The prebaking condition is, for example, a heating time of 0.1 to 5 minutes at a heating temperature of 40 to 120 ° C., and the postbaking condition is, for example, a heating temperature of 120 to 300 ° C., preferably 150 to 250 ° C. The heating time is 5 to 200 minutes, preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.
When the liquid crystal aligning agent of the present invention is applied to a vertical alignment type liquid crystal display element such as a VA type or an MVA type, the coating film formed as described above can be used as it is as a liquid crystal alignment film. . However, even in this case, the following (2) rubbing step may be optionally performed.

(2) Rubbing step When the liquid crystal aligning agent of the present invention is applied to a horizontal alignment type liquid crystal display element such as a TN type, STN type, IPS type, or FFS type, after the above (1) coating film forming step. (2) A rubbing process is performed.
The rubbing treatment can be performed by rubbing the surface of the coating film formed on the substrate with a roll around which a cloth made of fibers such as nylon, rayon, and cotton is wound.

<Liquid crystal display element>
Using the substrate having the liquid crystal alignment film formed as described above, a liquid crystal display element can be manufactured as follows.
A pair of substrates on which the liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which the liquid crystal is sandwiched between the pair of substrates is manufactured. In order to manufacture a liquid crystal cell, the following two methods can be mentioned, for example.
As a first method, a pair of substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the pair of substrates are bonded together using a sealant, and the substrate surface and A method of manufacturing a liquid crystal cell can be mentioned by injecting and filling liquid crystal into a cell gap partitioned by an appropriate sealing agent, and then sealing the injection hole.
As a second method, for example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and further, a predetermined number of locations on the surface of the liquid crystal alignment film. After the liquid crystal is dropped on the liquid crystal, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate. A method for manufacturing a cell (ODF (One Drop Fill) method) can be given.

In any of the above methods, it is preferable that the liquid crystal cell is then heated to a temperature at which the used liquid crystal takes an isotropic phase, and then slowly cooled to room temperature, thereby removing the flow alignment at the time of filling the liquid crystal.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell in a predetermined direction.
As the liquid crystal, for example, nematic liquid crystal, smectic liquid crystal, or the like can be used.
In the case of producing a horizontal alignment type liquid crystal display element, a nematic liquid crystal having positive dielectric anisotropy is preferable, for example, biphenyl liquid crystal, phenyl cyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, Pyrimidine liquid crystals, dioxane liquid crystals, bicyclooctane liquid crystals, cubane liquid crystals and the like are used. A cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, or the like may be added to these liquid crystals.
On the other hand, when manufacturing a vertical alignment type liquid crystal display element, a nematic liquid crystal having negative dielectric anisotropy is preferable, for example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl type. A liquid crystal, a phenylcyclohexane type liquid crystal, or the like can be used.
The polarizing plate used outside the liquid crystal cell is composed of a polarizing film called “H film” in which polyvinyl alcohol is stretched and oriented while absorbing iodine and sandwiched between cellulose acetate protective films, or the H film itself. A polarizing plate etc. can be mentioned.

<Synthesis of Compound (B)>
[Synthesis of Compound (1)]
Synthesis Example 1-1
The compound represented by the above formula (1-1) (compound (1-1)) was synthesized according to the following scheme 1.

In a reaction vessel, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine 17 g (0.10 mol), tetrahydrofuran (THF) 100 mL and triethylamine 17 mL (0.12 mol) were charged and mixed. This was cooled in an ice bath, and a solution prepared by dissolving 19 g (0.10 mol) of 4-nitrobenzoyl chloride in 100 mL of tetrahydrofuran was added dropwise thereto while maintaining a temperature of 5 ° C. After completion of the dropping, the reaction was carried out at 25 ° C. with stirring for 3 hours. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were sequentially performed once with 150 mL of sodium hydroxide aqueous solution having a concentration of 1 mol / L and three times with 150 mL of distilled water. Thereafter, the solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 150 mL of ethanol to obtain 28 g (0.087 mol, light yellow compound (1-1a)). Rate 87%).
Next, in another reaction vessel, 28 g (0.087 mol) of the above compound (1-1a), 2.8 g of palladium carbon (palladium supported amount of 5.0% by weight), 200 mL of tetrahydrofuran and 200 mL of ethanol were charged and mixed. After 28 mL of hydrazine monohydrate was slowly added dropwise thereto, the system was heated to 70 ° C. and stirred for 2 hours to carry out the reaction. After completion of the reaction, the reaction mixture was filtered through Celite to remove palladium on carbon, 300 mL of ethyl acetate was added to the filtrate, and extraction and washing were performed 5 times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure is recrystallized using 25 mL of ethyl acetate and 80 mL of hexane, thereby obtaining 20 g (0.070) of a light brown compound (1-1). Mol, yield 81%).

Synthesis Example 1-2
According to the following scheme 2, a compound represented by the above formula (1-2) (compound (1-2)) was synthesized.

In a reaction vessel, 1,2,2,6,6-pentamethyl-4-aminopiperidine (17 g, 0.10 mol), tetrahydrofuran (100 mL) and triethylamine (17 mL, 0.12 mol) were charged and mixed. This was cooled in an ice bath, and while maintaining the temperature at 5 ° C., a solution of 19 g (0.10 mol) of 4-nitrobenzoyl chloride in 100 mL of tetrahydrofuran was added dropwise thereto, and the mixture was stirred at 25 ° C. for 3 hours. The reaction was performed. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were sequentially performed once with 150 mL of sodium hydroxide aqueous solution having a concentration of 1 mol / L and three times with 150 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 100 mL of ethanol, and 29 g (0.091 mol, yield 91%) of a pale yellow compound (1-2a) was obtained. )Obtained.
Next, in another reaction vessel, 28 g (0.091 mol) of the compound (1-2a), 2.8 g of palladium carbon (palladium supported amount of 5.0% by weight), 200 mL of tetrahydrofuran and 200 mL of ethanol were charged and mixed. Here, 28 mL of hydrazine monohydrate was slowly added dropwise, and then the system was heated to 70 ° C. and reacted with stirring for 2 hours. After completion of the reaction, the reaction mixture was filtered through Celite to remove palladium on carbon, and 300 mL of ethyl acetate was added to the filtrate, followed by extraction and washing with 200 mL of distilled water five times. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 20 mL of ethyl acetate and 80 mL of hexane, whereby 19 g (0.064) of a light brown compound (1-2) was obtained. Mol, yield 70%).

Example 1-3
The compound represented by the above formula (1-3) (compound (1-3)) was synthesized according to the following schemes 3a to 3c.

(Synthesis of Compound (1-3a))
In a reaction vessel, 17 g (0.10 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 12 g (0.10 mol) of 3-bromo-1-propyne, 17 g of potassium carbonate (0 .12 mol) and 100 mL of N, N-dimethylformamide (DMF) were charged and mixed, and the reaction was carried out at room temperature with stirring for 5 hours. After adding 400 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were performed 4 times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 50 mL of ethanol, and 19 g (0.090 mol, yield 90%) of the white compound (1-3a) was obtained. Obtained.

(Synthesis of Compound (1-3b))
In a reaction vessel, 44 g (0.20 mol) of 4-iodoaniline, 185 g (2.0 mol) of epichlorohydrin and 350 mL of toluene were charged and mixed. After stirring at 80 ° C. for 5 hours, a concentration of 3 mol / mol 150 mL of L aqueous sodium hydroxide solution was added dropwise, and the reaction was carried out at 80 ° C. with stirring for another 2 hours. After adding 500 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were performed 4 times with 250 mL of distilled water. The solvent was removed from the collected organic layer under reduced pressure to obtain 50 g (0.15 mol, yield 75%) of a light brown compound (1-3b).

(Synthesis of Compound (1-3))
In a reaction vessel, 30 g (0.090 mol) of the above compound (1-3b), 0.63 g (0.90 mmol) of dichlorobis (triphenylphosphine) palladium (II), 0.17 g of copper (I) iodide ( 0.90 mmol), 300 mL of acetonitrile and 27 g (0.26 mol) of triethylamine were charged and mixed. A solution prepared by dissolving 19 g (0.090 mol) of the above compound (1-3a) in 50 mL of acetonitrile was added dropwise thereto, and then reacted at 40 ° C. with stirring for 4 hours. After removing the catalyst from the reaction mixture after completion of the reaction by Celite filtration, 400 mL of ethyl acetate was added to the filtrate, followed by extraction and washing three times with 250 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 60 mL of ethanol, whereby 27 g (0.066 mol, yield) of a pale yellow compound (1-3) was obtained. 73%).

Synthesis Example 1-4
The compound represented by the above formula (1-4) (compound (1-4)) was synthesized according to the following schemes 4a and 4b.

(Synthesis of Compound (1-4a))
In a reaction vessel, 14 g (0.10 mol) of 4-hydroxybenzoic acid, 8.0 g (0.20 mol) of sodium hydroxide and 500 mL of distilled water were charged and mixed. The solution was cooled in an ice bath and maintained at a temperature of 5 ° C., and a solution of 13 g (0.12 mol) of methacryloyl chloride in 150 mL of dichloromethane was added dropwise thereto, and the reaction was allowed to proceed with stirring at 25 ° C. for 3 hours. went. After completion of the reaction, 500 mL of ethyl acetate and 500 mL of tetrahydrofuran were added to the reaction mixture, followed by extraction and washing sequentially with 500 mL of hydrochloric acid having a concentration of 1 mol / L and 3 times with 250 mL of distilled water. The solvent was removed from the collected organic layer under reduced pressure to obtain 16 g (0.077 mol, yield 77%) of a white compound (1-4a).

(Synthesis of Compound (1-4))
In a reaction vessel, 16 g (0.077 mol) of the above compound (1-4a), 13 g (0.077 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine and 300 mL of tetrahydrofuran were charged. Mixed. This was cooled in an ice bath and maintained at a temperature of 5 ° C., while 18 g (0.092 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and N , N-dimethyl-4-aminopyridine (DMAP) 1.9 g (0.015 mol) was added, and the reaction was carried out at 25 ° C. with stirring for 2 hours. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, it was extracted and washed three times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 50 mL of ethanol to obtain 23 g (0.065 mol, yield 85) of white compound (1-4). %)Obtained.

Synthesis Example 1-5
According to the following scheme 5, the compound represented by the above formula (1-5) (compound (1-5)) was synthesized.

In a reaction vessel, 4-hydroxy-1,2,2,6,6-pentamethylpiperidine (17 g, 0.10 mol), tetrahydrofuran (100 mL) and triethylamine (17 mL, 0.12 mol) were charged and mixed. This was cooled in an ice bath, and while maintaining a temperature of 5 ° C., a solution prepared by dissolving 23 g (0.10 mol) of 3,5-dinitrobenzoyl chloride in 100 mL of tetrahydrofuran was added dropwise thereto, and then 3 ° C. at 25 ° C. The reaction was carried out with stirring for a period of time. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were sequentially performed once with 150 mL of sodium hydroxide aqueous solution having a concentration of 1 mol / L and three times with 150 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 150 mL of ethanol, and 29 g (0.080 mol, yield 80) of pale yellow compound (1-5a) was obtained. %)Obtained.
In a separate reaction vessel, 29 g (0.080 mol) of the above compound (1-5), 2.9 g of palladium on carbon (palladium supported amount of 5.0% by weight), 200 mL of tetrahydrofuran and 200 mL of ethanol were charged and mixed. To the solution, 29 mL of hydrazine monohydrate was slowly added dropwise. Thereafter, the temperature of the system was raised to 70 ° C., and the reaction was carried out with stirring for 2 hours. The reaction mixture after completion of the reaction was filtered through Celite to remove palladium on carbon. After adding 300 mL of ethyl acetate to the obtained filtrate, extraction washing was performed 5 times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 30 mL of ethyl acetate and 90 mL of hexane, whereby 18 g (0.058) of a light brown compound (1-5) was obtained. Mol, yield 73%).

Synthesis Example 2-1
The compound represented by the above formula (2-1) (compound (2-1)) was synthesized according to the following schemes 6a to 6c.

(Synthesis of Compound (2-1a))
In a reaction vessel, 3,5-di-tert-butyl-4-hydroxybenzoic acid 25 g (0.10 mol), thionyl chloride 40 mL (0.55 mol) and N, N-dimethylformamide 1 mL were charged and mixed. The reaction was conducted at 80 ° C. with stirring for 1 hour. After the reaction was completed, residual thionyl chloride was removed from the reaction mixture using an aspirator to obtain a light yellow acid chloride compound.
In a separate reaction vessel, 62 g (1.0 mol) of ethylene glycol, 11 g (0.11 mol) of triethylamine and 100 mL of tetrahydrofuran were charged and mixed. This was cooled in an ice bath, and while maintaining a temperature of 5 ° C., a solution of the above acid chloride compound dissolved in 50 mL of tetrahydrofuran was added dropwise thereto, and the reaction was carried out at 25 ° C. with stirring for 3 hours. After adding 500 mL of ethyl acetate to the reaction mixture after completion of the reaction, it was extracted and washed three times with 300 mL of distilled water. The solvent was removed from the collected organic layer under reduced pressure to obtain 21 g (0.070 mol, yield 70%) of a white compound (2-1a).

(Synthesis of Compound (2-1b))
In a reaction vessel, 15 g (0.10 mol) of 4-aminomethylbenzoic acid, 120 mL of sodium hydroxide aqueous solution having a concentration of 1 mol / L and 250 mL of ethanol were charged and mixed. This was cooled in an ice bath, and while maintaining the temperature at 5 ° C., 24 g (0.11 mol) of di-tert-butyl dicarbonate was added little by little, and the reaction was carried out with stirring at 25 ° C. for 12 hours. It was. After removing ethanol from the reaction mixture after completion of the reaction under reduced pressure, 500 mL of distilled water and saturated citric acid were added until the solution became acidic, and the precipitated solid was filtered and dried to obtain a white compound (2-1b) 23 g (0.092 mol, yield 92%) was obtained.

(Synthesis of Compound (2-1))
In a reaction vessel, 21 g (0.070 mol) of the compound (2-1a), 18 g (0.070 mol) of the compound (2-1b) and 300 mL of tetrahydrofuran were charged and mixed. This was cooled in an ice bath, and while maintaining a temperature of 5 ° C., 16 g (0.084 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N, N— 1.7 g (0.014 mol) of dimethyl-4-aminopyridine was added, and the reaction was carried out at 25 ° C. with stirring for 2 hours. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, it was extracted and washed three times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 55 mL of ethanol to obtain 30 g (0.056 mol, yield 80) of white compound (2-1c). %)Obtained.
Next, in another reaction vessel, 30 g (0.056 mol) of the above compound (2-1c), 100 mL of dichloromethane and 30 mL of trifluoroacetic acid were charged and mixed, and the reaction was performed at 25 ° C. with stirring for 2 hours. After completion of the reaction, the solid obtained by removing the solvent from the reaction mixture under reduced pressure was recrystallized using 30 mL of ethyl acetate and 100 mL of hexane, whereby 20 g (0) of a light brown compound (2-1) was obtained. 0.046 mol, yield 82%).

Synthesis Example 2-2
A compound represented by the above formula (2-2) (compound (2-2)) was synthesized according to the following schemes 7a and 7b.

(Synthesis of Compound (2-2a))
In a reaction vessel, 3,5-di-tert-butyl-4-hydroxybenzoic acid 25 g (0.10 mol), propargyl alcohol 6.2 g (0.11 mol) and tetrahydrofuran 400 mL were mixed. The mixture was cooled in an ice bath and maintained at a temperature of 5 ° C., while 23 g (0.12 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N, N— Dimethyl-4-aminopyridine (2.4 g, 0.020 mol) was added, and the reaction was performed at 25 ° C. with stirring for 2 hours. After adding 400 mL of ethyl acetate to the reaction mixture after completion of the reaction, extraction and washing were performed 3 times with 250 mL of distilled water. The solid obtained by removing the solvent from the organic layer under reduced pressure was recrystallized using 50 mL of ethanol to obtain 25 g (0.088 mol, yield 88%) of a white compound (2-2a). .

(Synthesis of Compound (2-2))
In a reaction vessel, 29 g (0.088 mol) of the compound (1-3b) obtained in the same manner as in Synthesis Example 1-3, 0.62 g (0.88) of dichlorobis (triphenylphosphine) palladium (II) Mmol), 0.17 g (0.88 mmol) of copper (I) iodide, 300 mL of acetonitrile, and 27 g (0.26 mol) of triethylamine were mixed and mixed with 25 g (0. 088 mol) in 50 mL of acetonitrile was added dropwise, and the reaction was performed at 40 ° C. with stirring for 4 hours. After removing the catalyst from the reaction mixture after completion of the reaction by Celite filtration, 400 mL of ethyl acetate was added, followed by extraction and washing with 250 mL of distilled water three times. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 50 mL of ethanol to obtain 34 g (0.069 mol, yield) of a pale yellow compound (2-2). 78%).

Synthesis Example 2-3
A compound represented by the above formula (2-3) (compound (2-3)) was synthesized according to the following schemes 8a to 8c.

(Synthesis of Compound (2-3a))
In a reaction vessel, 3,5-di-tert-butyl-4-hydroxybenzoic acid 25 g (0.10 mol), thionyl chloride 40 mL (0.55 mol) and N, N-dimethylformamide 1 mL were charged and mixed. The reaction was conducted at 80 ° C. with stirring for 1 hour. Residual thionyl chloride was removed from the reaction mixture after completion of the reaction using an aspirator to obtain a light yellow acid chloride compound.
In another reaction vessel, 62 g (1.0 mol) of ethylene glycol, 11 g (0.11 mol) of triethylamine and 100 mL of tetrahydrofuran were charged and mixed. This was cooled in an ice bath, and while maintaining the temperature at 5 ° C., a solution obtained by dissolving the above acid chloride compound in 50 mL of tetrahydrofuran was added dropwise thereto, and then reacted at 25 ° C. with stirring for 3 hours. . After adding 500 mL of ethyl acetate to the reaction mixture after completion of the reaction, it was extracted and washed three times with 300 mL of distilled water. The solvent was removed from the collected organic layer under reduced pressure to obtain 21 g (0.070 mol, yield 70%) of a white compound (2-3a).

(Synthesis of Compound (2-3b))
In a reaction vessel, 14 g (0.10 mol) of 4-hydroxybenzoic acid, 8.0 g (0.20 mol) of sodium hydroxide and 500 mL of distilled water were charged and mixed. The solution was cooled in an ice bath and a solution of 13 g (0.12 mol) of methacryloyl chloride dissolved in 150 mL of dichloromethane was added dropwise thereto while maintaining the temperature at 5 ° C. Went. After completion of the reaction, 500 mL of ethyl acetate and 500 mL of tetrahydrofuran were added to the reaction mixture, followed by extraction and washing sequentially with 500 mL of hydrochloric acid having a concentration of 1 mol / L and 3 times with 250 mL of distilled water. The solvent was removed from the collected organic layer under reduced pressure to obtain 16 g (0.077 mol, yield 77%) of white compound (2-3b).

(Synthesis of Compound (2-3))
In a reaction vessel, 21 g (0.070 mol) of the above compound (2-3a), 14 g (0.070 mol) of the above (2-3b) and 300 mL of tetrahydrofuran were charged and mixed. This was cooled in an ice bath, and while maintaining a temperature of 5 ° C., 16 g (0.084 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and N, N-dimethyl- 4-aminopyridine 1.7g (0.014mol) was added, and it reacted under stirring at 25 degreeC for 2 hours. After adding 300 mL of ethyl acetate to the reaction mixture after completion of the reaction, it was extracted and washed three times with 200 mL of distilled water. The solid obtained by removing the solvent from the collected organic layer under reduced pressure was recrystallized using 60 mL of ethanol to obtain 25 g (0.052 mol, yield 74) of the white compound (2-3). %)Obtained.

<Synthesis of imidized polymer of polyamic acid>
Synthesis Examples PI-1 to PI-6
In the reaction vessel, tetracarboxylic dianhydride and diamine of the types and proportions (mol%) shown in Table 1 were charged as monomers, and N-methyl-2-pyrrolidone (NMP) was added so that the monomer concentration was 20% by weight. ) Was added and dissolved, and the reaction was carried out at 60 ° C. for 6 hours to obtain solutions containing polyamic acid. In Synthesis Example PI-4, the reaction of the tetracarboxylic dianhydride and diamine was carried out in the presence of a molecular weight regulator of the type and proportion (mol%) shown in Table 1. The monomer concentration in Synthesis Example PI-4 is a value including the concentration of the molecular weight regulator in addition to tetracarboxylic dianhydride and diamine.
After adding NMP to the obtained polyamic acid solution and diluting to a polyamic acid concentration of 7% by weight, each of pyridine and acetic anhydride is listed in Table 1 with respect to 1 mol of the amic acid unit of the polyamic acid. In an amount of (2 moles) and a dehydration ring closure reaction was carried out at 110 ° C. for 4 hours. After completion of the reaction, the solvent in the system was replaced with new NMP to obtain solutions containing 15% by weight of imidized polymers PI-1 to PI-6, respectively.
For each imidized polymer, the imidization ratio measured by the following method is shown in Table 1.

[Measurement of imidization rate of imidized polymer]
It was charged a solution containing imidized polymer in pure water, after which the resulting precipitate was thoroughly dried under reduced pressure at room temperature, dissolved in deuterated dimethyl sulfoxide was measured at room temperature using tetramethylsilane as a reference substance ¹ From the 1 H-NMR spectrum, the imidation ratio was determined by the following formula (1).
Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (1)
(In the above formula (1), A ¹ is the area of the peak derived from the proton of the NH group appearing near the chemical shift of 10 ppm, A ² is the area of the peak derived from the other proton, and α is the imidized weight (This is the ratio of the number of other protons to one proton of the NH group in the precursor of the coalescence (polyamic acid).)

<Synthesis of polyamic acid>
Synthesis Examples PA-1 and PA-2
In the reaction vessel, tetracarboxylic dianhydride and diamine of the types and proportions (mol%) shown in Table 1 were charged as monomers, and NMP was added and dissolved so that the monomer concentration was 20% by weight. Then, NMP was added to the obtained solution and diluted to obtain solutions containing 15% by weight of polyamic acids PA-1 and PA-2, respectively.

Abbreviations of each monomer and molecular weight regulator in Table 1 have the following meanings.
[Tetracarboxylic dianhydride] In Table 1, expressed as "acid anhydride".
TCA: 2,3,5-tricarboxycyclopentylacetic acid dianhydride BODA: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride CB: 1,2,3,4 -Cyclobutanetetracarboxylic dianhydride [diamine]
PDA: p-phenylenediamine HCDA: 3,5-diaminobenzoic acid-3-cholestanyl 35DAB: 3,5-diaminobenzoic acid HCODA: cholestanyloxy-2,4-diaminobenzene LDA: 4- (2- (4 ' -N-pentylbicyclohexyl) ethyl) phenoxy-2,4-diaminobenzene PBCH5DAB: 4- (4'-n-pentylbicyclohexyl) phenoxy-2,4-diaminobenzene [molecular weight regulator]
ANI: Aniline

<Synthesis of polyorganosiloxane>
Synthesis example PS-1
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine at room temperature. Mixed with. Next, 100 g of deionized water was dropped from the dropping funnel over 30 minutes, and then the reaction was performed at 80 ° C. with stirring under reflux for 6 hours. After completion of the reaction, the organic layer taken out from the reaction mixture was repeatedly washed with 0.2 wt% ammonium nitrate aqueous solution until the water after washing became neutral, and then the solvent and water were distilled off under reduced pressure to react. Polyorganosiloxane was obtained as a viscous transparent liquid. As a result of ¹ H-NMR analysis of this reactive polyorganosiloxane, a peak based on the epoxy group was obtained in the vicinity of chemical shift (δ) = 3.2 ppm according to the theoretical intensity, and side reaction of the epoxy group occurred during the reaction. It was confirmed that this was not happening. The obtained reactive polyorganosiloxane had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g / mol.
Next, 10.0 g of the above reactive polyorganosiloxane, 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as a carboxylic acid, and UCAT 18X (trade name, 0.10 g of San Apro Co., Ltd.) was charged, and the reaction was performed at 100 ° C. with stirring for 48 hours. A solution obtained by adding ethyl acetate to the reaction mixture after completion of the reaction was washed three times with water, and the collected organic layer was dried over magnesium sulfate, and then the solvent was distilled off to obtain polyorganosiloxane PS-1 in 9. 0 g was obtained. The resulting polyorganosiloxane PS-1 had a weight average molecular weight Mw of 9,900.

<Preparation and evaluation of liquid crystal aligning agent>
Example 1
[Preparation of liquid crystal aligning agent]
(A) NMP and butyl cellosolve (BC) are added to the solution containing the imidized polymer obtained in Synthesis Example PI-1 as a polymer, and the compound obtained in Synthesis Example 1-1 as a compound (B) (1-1) is added in an amount of 5 parts by weight based on 100 parts by weight of the polymer (A), and a solution having a solvent composition of NMP: BC = 65: 35 (weight ratio) and a solid content concentration of 4% by weight is obtained. Was filtered through a filter having a pore size of 1 μm to prepare a liquid crystal aligning agent.
[Manufacture of liquid crystal cells]
The liquid crystal aligning agent prepared above was applied on the transparent electrode surface of the glass substrate with a transparent electrode made of ITO using a liquid crystal aligning agent printer (Nissha Printing Co., Ltd.), and on a hot plate at 80 ° C. After pre-baking for 1 minute, a film having an average film thickness of 800 mm was formed by post-baking on a hot plate at 200 ° C. for 10 minutes. This operation was repeated to obtain a pair of substrates having a liquid crystal alignment film on the transparent electrode.
After applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 3.5 μm to the outer edge of the surface having the liquid crystal alignment film of one of the pair of substrates, the other substrate is attached to the liquid crystal alignment film. The adhesive was cured by overlapping and pressing so that the surfaces were opposed. Next, after nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was injected and filled between the pair of substrates from the liquid crystal injection port, the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature to produce a vertical alignment type liquid crystal cell.

[Liquid crystal cell evaluation]
(1) Evaluation of liquid crystal orientation The case where the liquid crystal cell produced above is sandwiched between two polarizing plates arranged in crossed Nicols, and the dark state when no voltage is applied is visually examined, and no light leakage is observed. When the liquid crystal orientation was “good” and the case where light leakage was observed was evaluated as “liquid crystal orientation”, the liquid crystal orientation of this liquid crystal cell was “good”.
(2) Evaluation of voltage holding ratio With respect to the liquid crystal cell manufactured as described above, a voltage of 1 V was applied at 70 ° C. for 30 seconds, and the voltage holding ratio (initial voltage holding ratio) after application release was AC voltage 1 V, measurement temperature 70 When measured under the conditions of ° C. and a frame period of 167 milliseconds, the voltage holding ratio of this liquid crystal cell was 98.1%.
(3) Evaluation of light resistance The liquid crystal cell after the initial voltage holding ratio measurement was placed at a distance of 5 cm from the 100 watt type white fluorescent lamp, irradiated with light for 500 hours, and then the voltage holding ratio ( The voltage retention after light irradiation) was measured. At this time, when the difference between the initial voltage holding ratio and the voltage holding ratio after light irradiation is less than 1% point, the light resistance is “good”, when the difference is 1 to 3% point, the light resistance is “good”, and When the value exceeding 3% point was evaluated as “light”, the light resistance of this liquid crystal cell was “good”.

Examples 2 to 10 and Comparative Examples 1 and 2
In [Preparation of liquid crystal aligning agent] in Example 1 above, the examples shown in Table 2 were used except that the types shown in Table 2 were used as the (A) polymer and (B) compound, respectively. In the same manner as in Example 1, liquid crystal aligning agents were prepared, liquid crystal cells were produced using these, and various evaluations were performed.
In Examples 7 and 8, two kinds of solutions containing the polymer were mixed and used as the (A) polymer. In Example 9, as the polymer (A), the polyorganosiloxane PS-1 obtained in Synthesis Example PS-1 was added to the solution containing the imidized polymer PI-6 obtained in Synthesis Example PI-6. It was used by adding PI-6: PS-1 = 95: 5 by weight ratio.
In Comparative Examples 1 and 2, other additives of the types and amounts described in Table 2 were used in place of the compound (B).
The evaluation results are shown in Table 2.

Abbreviations of the compound (B) and other additives in Table 2 have the following meanings, respectively.
[(B) Compound]
1-1: Compound (1-1) obtained in Synthesis Example 1-1 above
1-2: Compound (1-2) obtained in Synthesis Example 1-2 above
1-3: Compound (1-3) obtained in Synthesis Example 1-3 above
1-4: Compound (1-4) obtained in Synthesis Example 1-4 above
1-5: Compound (1-5) obtained in Synthesis Example 1-5 above
2-1: Compound (2-1) obtained in Synthesis Example 2-1
2-2: Compound (2-2) obtained in Synthesis Example 2-2
2-3: Compound (2-3) obtained in Synthesis Example 2-3 above
[Other additives]
Add-1: Piperidine Add-2: Phenol

Claims (14)

(A) a polymer containing at least one polymer selected from the group consisting of polyamic acid, imidized polymer thereof, polyamic acid ester and polyorganosiloxane, and (B) the following formulas (1) and (2) The liquid crystal aligning agent prepared using the at least 1 sort (s) of compound selected from the group which consists of a compound represented by each of these.

(In the formula (1), n1 is 1 or 2,
m1 is 1 or 2,
n is an integer of 1 to 4,
R ^I is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group,
X ¹ is a single bond, a carbonyl group or ^* -CONH- (wherein a bond marked with “*” is bonded to a heterocyclic ring containing a nitrogen atom);
R ^{II to} R ^V are each independently an alkyl group having 1 to 6 carbon atoms,
X ² to X ⁵ are each a single binding,
X ⁶ is a divalent organic group,
W ¹ is an n1 + m1 valent organic group,
Z ¹ is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated structure;
In formula (2), n2 is 1 or 2,
m2 is 1 or 2,
R ^VI is an alkyl group having a carbon number of 4 to 16,
R ^VII is an alkyl group having a carbon number of 1 to 16,
X ⁷ is a divalent organic group,
W ² is an n2 + m2-valent organic group, and Z ² is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated structure. )   The liquid crystal aligning agent of Claim 1 containing (A) polymer and (B) compound.   The liquid crystal aligning agent of Claim 1 containing the reaction product of (A) polymer and (B) compound. The compound (B) is at least one selected from the group consisting of compounds represented by the following formulas (B1-1) to (B1-3) and (B2-1) to (B2-3). The liquid crystal aligning agent as described in any one of Claims 1-3 which exists.

(R ^I , X ⁶ and Z ¹ in the formulas (B1-1) to (B1-3) each have the same meaning as in the above formula (1);
X ⁷ and Z ^{2 in} formulas (B2-1) to (B2-3) each have the same meaning as in formula (2) above. )   (A) The liquid crystal aligning agent as described in any one of Claims 1-4 in which a polymer contains the at least 1 sort (s) of polymer selected from the group which consists of a polyamic acid and its imidation polymer. Z ¹ in the above formula (1) and Z ² in the above formula (2) are each independently an amino group, an aminomethyl group, an N, N-diglycidylamino group or a (meth) acryloyloxy group. The liquid crystal aligning agent as described in any one of 1-5. X ⁶ in the above formula (B1) and X ⁷ in the above formula (B2) are each independently a single bond, a methylene group, an alkylene group having 2 to 6 carbon atoms, an oxygen atom, ^* -OOC-, ^* -CO- ^* -COO-, ^* -CONH-, ^* -NHCO-, ^* -NH-, ^* -N (CH ₃ )-, ^* -N (C ₂ H ₅ )-, ^* -CR ₂ CR ₂ OOC-, _{^{* -COO-CR 2 CR 2 -OOC-}} , * the _-O-CH 2 -C ::: C-, or _{^{* -COO-CH 2 -C ::: C-}} ( although more, R represents a hydrogen atom or a carbon In the case of the above formula (1), “:::” represents a triple bond, and a bond marked with “*” is bonded to a heterocyclic ring containing a nitrogen atom. In the case of the above formula (2), it is bonded to a benzene ring having a hydroxyl group.) The liquid crystal aligning agent as described in any one of 6. The compound represented by the formula (B1) is a compound represented by the following formula (B1 ′),
The compound represented by the formula (B2) is a compound represented by the following formula (B2 ′).
The liquid crystal aligning agent as described in any one of Claims 1-3.

(In the formula (B1 ′), n1, n, R ^{I to} R ^V , X ^{1 to} X ⁶ and Z ¹ have the same meanings as in the above formula (B1);
N2, R ^VI , R ^VII and X ⁷ in the formula (B2 ′) have the same meanings as in the formula (B2). )   (B) The liquid crystal aligning agent of Claim 2 whose content rate of a compound is 0.1-30 weight part with respect to 100 weight part of polymers contained in a liquid crystal aligning agent.   (B) The liquid crystal aligning agent of Claim 3 whose usage-amount of a compound is 0.1-30 weight part with respect to 100 weight part of (A) polymers. (A) the polymer is
2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-dianhydride and 1,2, A tetracarboxylic dianhydride containing at least one selected from the group consisting of 3,4-cyclobutanetetracarboxylic dianhydride;
The liquid crystal aligning agent of Claim 5 containing the at least 1 sort (s) of polymer selected from the group which consists of the polyamic acid obtained by making diamine react, and its imidized polymer.   The liquid crystal aligning film formed from the liquid crystal aligning agent as described in any one of Claims 1-11.   A liquid crystal display device comprising the liquid crystal alignment film according to claim 12. (A) a polymer containing at least one polymer selected from the group consisting of polyamic acid, its imidized polymer, polyamic acid ester and polyorganosiloxane;
(B) A reaction product with at least one compound selected from the group consisting of compounds represented by the following formulas (1) and (2).

(In the formula (1), n1 is 1 or 2,
m1 is 1 or 2,
n is an integer of 1 to 4,
R ^I is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aromatic group having 6 to 20 carbon atoms, an aralkyl group having 7 to 13 carbon atoms, or a 1,3-dioxobutyl group,
X ¹ is a single bond, a carbonyl group or ^* -CONH- (wherein a bond marked with “*” is bonded to a heterocyclic ring containing a nitrogen atom);
R ^{II to} R ^V are each independently an alkyl group having 1 to 6 carbon atoms,
X ² to X ⁵ are each a single binding,
X ⁶ is a divalent organic group,
W ¹ is an n1 + m1 valent organic group,
Z ¹ is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated structure;
In formula (2), n2 is 1 or 2,
m2 is 1 or 2,
R ^VI is an alkyl group having a carbon number of 4 to 16,
R ^VII is an alkyl group having a carbon number of 1 to 16,
X ⁷ is a divalent organic group,
W ² is an n2 + m2-valent organic group, and Z ² is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated structure. )