KR20140093162A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display device, and reaction product - Google Patents

Abstract

Provided is a liquid crystal alignment agent in which a low voltage maintenance ratio is degraded by light (ultraviolet light). The present invention relates to the liquid crystal alignment agent comprising (A) a polymer and (B) one or more compounds. The polymer comprises one or more polymers selected from a group comprising polyamic acid, an amide polymer, a polyamic acid ester, and polyorganosiloxane. One or more compounds are selected from a group comprising compounds of a lower formula (1) and a lower formula (2).

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal display element, and a reaction product, and a liquid crystal display device,

The present invention relates to a liquid crystal aligning agent. More specifically, the present invention relates to a liquid crystal aligning agent capable of forming a liquid crystal alignment film with little decrease in voltage-holding ratio due to light.

The liquid crystal display element may be of a twisted nematic (TN) type, a super twisted nematic (STN) type, a VA (vertical alignment) type, a MVA (multidomain vertical alignment) In-Plane Switching (IPS) type, FFS (Fringe Field Switching) type, and the like.

As a material of the liquid crystal alignment film in these various liquid crystal display devices, resin materials such as polyamic acid, polyimide, polyamide, and polyester are known. Particularly, a liquid crystal alignment film made of polyamic acid or polyimide has heat resistance, And is used in many liquid crystal display devices because of its excellent affinity with liquid crystals (Patent Document 1).

In liquid crystal aligning agents, performance that does not cause a decrease in function (in particular, electric characteristics typified by voltage holding ratio) by light irradiation has been demanded more than ever before. The situation is as follows.

In the process of manufacturing a liquid crystal display device, a liquid dropping method, that is, an ODF (One Drop Fill) method, has begun to be widely used from the viewpoint of shortening the process time and improving the yield. The ODF method is a method of applying an ultraviolet curable sealant to a predetermined portion of a substrate on which a liquid crystal alignment film is applied, dropping liquid crystal to a predetermined number of places on the same substrate, The liquid crystal is spread over the entire surface of the substrate, and further the ultraviolet light is irradiated to cure the sealant, thereby manufacturing a liquid crystal cell. The ultraviolet light irradiated at this time is usually stronger than a few tens of Joules per square centimeter. That is, in the liquid crystal display element manufacturing process, the liquid crystal alignment layer is exposed to the strong ultraviolet light together with the liquid crystal.

When the user turns his or her eyes to a change in the application of the liquid crystal display device, the liquid crystal television has been widely used in addition to the notebook PC and the monitor display, which are the main applications of the conventional liquid crystal display device. In addition to the growing demand for liquid crystal projectors for applications, liquid crystal display devices intended for outdoor use such as mobile type and vehicle mounted type have been popular for a long time.

The liquid crystal television is required to have a long replacement cycle and a long life, and thus is exposed to backlight irradiation for a long period of time. As a liquid crystal display element for a liquid crystal projector, a light source having a very high irradiation intensity such as a metal halide lamp is used. BACKGROUND ART Liquid crystal display devices for mobile devices such as mobile phones and car navigation devices for vehicles are also used for sunlight containing strong ultraviolet rays. In order to improve visibility, it is necessary to increase the brightness of the backlight .

As described above, in the liquid crystal display element, with the improvement of the manufacturing process and the diversification of applications, exposure to harsh environments such as high-intensity light irradiation, long-time driving, and the like has been hitherto unthinkable. Liquid crystal alignment films during that time lacked resistance to such harsh environments.

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

SUMMARY OF THE INVENTION 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 having a reduced degree of voltage holding ratio due to light (particularly ultraviolet light).

The above and other objects,

(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) 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 represents a single bond, a carbonyl group or * -CONH- (provided that a bonded ring having "*" is bonded to a heterocyclic ring containing a nitrogen atom)

R ^Ⅱ ~R ^Ⅴ are, each independently, an aryl group, the alkyl group having 1 to 6 carbon atoms, 6 to 12 carbon atoms, a formyl aralkyl group, having a carbon number of 7-13 having a carbon number of 7-13 or aryl group having a carbon number of 8-14 formate Or a C7-C16 alkoxyaryl group having an alkoxy group having from 1 to 4 carbon atoms,

X ^{2 to} X ⁵ each represents a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH) - Combined with a summation)

X ⁶ is a divalent organic group,

W ¹ is n1 + m1-valent organic group,

Z ¹ is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond;

In the formula (2)

n2 is 1 or 2,

m2 is 1 or 2,

R ^VI is an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,

R ^VII is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,

X < ⁷ > is a divalent organic group,

W ² is an organic group of n ² + m ² , and

Z ² is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond).

The liquid crystal aligning agent of the present invention is preferably

Is a liquid crystal aligning agent containing the polymer (A) and the compound (B), or a liquid crystal aligning agent containing the reaction product of the polymer (A) and the compound (B). A liquid crystal aligning agent containing all of the reaction product of the (A) polymer and the (B) compound, and (A) the polymer and the (B) compound.

The liquid crystal aligning agent of the present invention is excellent in liquid crystal alignability and gives a liquid crystal alignment film with a small degree of reduction in voltage holding ratio in accordance with light (particularly ultraviolet light). Therefore, the liquid crystal display element having the liquid crystal alignment film formed of 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, a vehicle-mounted display, and the like.

(Mode for carrying out the invention)

Hereinafter, the present invention will be described in detail.

The liquid crystal aligning agent of the present invention is prepared using the (A) polymer and the (B) compound.

<(A) Polymer>

The polymer (A) in the present invention contains at least one polymer selected from the group consisting of polyamic acid, imidized polymer, polyamic acid ester and polyorganosiloxane. The polymer (A) may contain a polymer other than these. Examples of other polymers usable herein include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, polyvinyl alcohol derivatives and the like .

(A) the polymer is at least one polymer selected from the group consisting of polyamic acid, an imidized polymer thereof, a polyamic acid ester and a polyorganosiloxane in an amount of 30% by weight or more based on the total amount of the polymer (A) , More preferably at least 50 wt%, and more preferably all of the polymer (A) is selected from the group consisting of polyamic acid, imidized polymer, polyamic acid ester and polyorganosiloxane.

The polymer (A) preferably contains at least one polymer selected from the group consisting of polyamic acid, an imidized polymer thereof, and a polyorganosiloxane, and these polymers are preferably used in a proportion of (A) By weight, more preferably 30% by weight or more, further preferably 50% by weight or more, and still more preferably all of the polymer (A) is selected from these polymers. The polymer (A) is particularly preferably a polymer containing at least one member selected from the group consisting of a polyamic acid and an imidization polymer thereof, particularly preferably a polymer containing 30% (A) is 50% by weight or more based on the total amount of the polymer.

[Polyamic acid and its imidized polymer]

The polyamic acid as the polymer (A) in the present invention can be obtained by reacting a tetracarboxylic acid dianhydride with a diamine. The imidized polymer of polyamic acid can be obtained by imidizing the polyamic acid by dehydration ring-closure.

- tetracarboxylic dianhydride -

As the tetracarboxylic acid dianhydride used for synthesizing the polyamic acid, known tetracarboxylic dianhydrides which are used for synthesizing the polyamic acid or the imidized polymer thereof can be used without particular limitation. Examples of such tetracarboxylic acid dianhydrides include tetracarboxylic dianhydrides described in Patent Document 2 (Japanese Unexamined Patent Application Publication No. 2010-97188). Preferred tetracarboxylic acid dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4,5,9b- (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 [ 3.2.1] octane-2,4-dione-6-spiro-3 '- (tetrahydrofuran-2', 5'- dione), 5- (2,5- dioxotetrahydro- 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxynorbornane-2: 3,5: 6-2 anhydride, Oxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraon, bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride and pyromellitic acid Acetic acid dianhydride, and acetic acid dianhydride.

More preferably 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6: 8-2 anhydride, Cyclobutanetetracarboxylic acid dianhydride, and 2,3,4-cyclobutanetetracarboxylic acid dianhydride;

Particularly preferably, these are contained in an amount of 30 mol% or more based on the total amount of the tetracarboxylic acid dianhydride;

Particularly, it is preferable to contain them in an amount of 50 mol% or more based on the total amount of the tetracarboxylic acid dianhydride.

- diamine -

Examples of diamines used for synthesizing polyamic acid include diamines having a pretilt angular expression group and diamines having no pretilt angular expression group.

As the diamine having a pretilt angular expression group, it is preferably an aromatic diamine having a pretilt angular expression group, and specific examples thereof include dodecaneoxy-2,4-diaminobenzene, tetradecanoxy- 4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecaneoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecaneoxy- Diaminobenzene, tetradecanoxy-2,5-diaminobenzene, pentadecanoxy-2,5-diaminobenzene, hexadecaneoxy-2,5-diaminobenzene, octadecanoxy-2,5-diamino Benzene, cholestanyloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholesteryloxy- Diaminobenzoic acid cholesteryl, 3,5-diaminobenzoic acid lanostanyl, 3,6-bis (4-aminobenzoyloxy) cholesteryl, 3,5-diaminobenzoic acid cholestanol, Stannane, 3,6-bis (4-amino Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- ( 4-heptylcyclohexyl) cyclohexane, the following formula (A-1):

(A-1), ^XI and ^XII each represent a single bond, * -O-, * -COO-, or * -OOC- I toward the left direction)

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, with the proviso that a and b are not simultaneously 0;

and c is an integer of 1 to 20).

Examples of the divalent group represented by X ^I -R ^I -X ^II - in the above formula (A-1) include a methylene group, an alkylene group having 2 or 3 carbon atoms, * -O-, * -COO- or * -O- CH ₂ CH ₂ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group). In the group -C _c H _{2c + 1} , when c is 3 or more, this group is preferably a linear group. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or the 3,5-position with respect to the other groups. Specific examples of the compound represented by the formula (A-1) include compounds represented by the following formulas (A-1-1-1), (A-1-1-2)

(In the above formula, &quot; n- &quot; represents a linear chain, respectively).

Examples of the diamine not having a pretilt angular expression group include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes and the like which do not have a pretilt angular expression group.

Of the diamines having no pretilt angular expression group, examples of the aliphatic diamines include 1,1-meta-xylylenediamine, 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 the aromatic diamine having no pretilt angular expression group include aromatic diamines such as o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane , 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino- Bis (4-aminophenoxy) phenyl] propane, 2,2-bis [4- Bis (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoro Propane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 4,4' - (m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-di Diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6- (4-aminophenyl) -N, N'-dimethylbenzidine, N, N'-bis 4- (4'-trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoromethylbenzoyloxy) Diaminobenzoate, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3- aminobenzylamine, 1- (2,4- diaminophenyl) (4- (aminophenyl) piperidinyl) propane, a-amino-benzene-1,3-diamine, ? -aminophenyl alkylene and the like;

Examples of the diaminoorganosiloxane having no pretilt angular expression group include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like.

As the diamine, in addition to the above, a diamine described in Patent Document 2 (Japanese Patent Application 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 horizontal alignment type liquid crystal display devices such as TN type, STN type, IPS type, FFS type and the like, It is preferable to control the use ratio of the diamine having a pretilt angular expression group so as not to excessively increase the pretilt angle. In this case, the diamine having a pretilt angular expression group is preferably 20 mol% or less, more preferably 10 mol% or less, particularly preferably 5 mol% or less, based on the total amount of diamine . On the other hand, when the liquid crystal aligning agent of the present invention is used to form a liquid crystal alignment film for liquid crystal display devices of vertical alignment type such as VA type and MVA type, the diamine having a pretilt angular expression group is used more than a certain ratio , Thereby obtaining a high pretilt angle. In this case, the diamine having a pretilt angular expression group is preferably in a proportion of 0.1 mol% or more, more preferably 0.5 to 80 mol%, particularly preferably 1 to 50 mol%, based on the total amount of the diamine %.

The diamine used for synthesizing the polyamic acid in the present invention preferably does not contain any of the compound represented by the formula (1) wherein n1 is 2 and the compound represented by the formula (2) wherein n2 is 2 .

- molecular weight modifier -

In the synthesis of the polyamic acid, a polyamic acid having a controlled molecular weight (and an imidized polymer thereof) may be synthesized by allowing a suitable molecular weight regulator to coexist with the tetracarboxylic dianhydride and the diamine as described above.

Examples of the molecular weight modifier that can be used herein include a carbonic acid monoanhydride, a monoamine, and a monoisocyanate compound.

Examples of the carboxylic anhydride include maleic anhydride, phthalic anhydride, itaconic anhydride and the like;

Examples of the monoamine include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine and the like;

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 aforementioned tetracarboxylic acid dianhydride and diamine (and optionally, a molecular weight modifier).

The ratio of the tetracarboxylic acid dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is from 0.2 to 2 equivalents based on 1 equivalent of the amino group of the diamine, Preferably 0.3 to 1.2 equivalents. When a molecular weight modifier is used, the use ratio thereof is preferably 20 parts by weight or less based on 100 parts by weight of the total amount of the tetracarboxylic acid dianhydride and the diamine.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent under the temperature condition of preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C, preferably 0.1 to 24 hours, Is performed for 0.5 to 12 hours.

Examples of the organic solvent that can be used in the synthesis of the polyamic acid include non-protic polar solvents, phenol and derivatives thereof, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Examples of the aprotic polar solvent include N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, , Hexamethylphosphoric triamide and the like;

Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;

Examples of the alcohols include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether and the like;

Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and the like;

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- Ethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetraethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monomethyl ether acetate, Hydrofuran and the like;

Examples of the halogenated hydrocarbons include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene and the like;

Examples of the hydrocarbons include hexane, heptane, octane, benzene, toluene, xylene, isoamyl propionate, isoamyl isobutyrate, and diisopentyl ether.

Among these organic solvents, at least one selected from an aprotic polar solvent and a group consisting of phenol and its derivatives (first group of organic solvents) is used, or at least one selected from organic solvents of the first group And at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (second group of organic solvents) is preferably used. In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, more preferably 40% by weight or less based on the total amount of the organic solvent of the first group and the organic solvent of the second group And more preferably 30% by weight or less.

The amount of the organic solvent used (a) is preferably such that the ratio (b / (a + b)) of the total amount (b) of the tetracarboxylic acid dianhydride and diamine (and the molecular weight modifier, if present) By weight, preferably 0.1 to 50% by weight.

- Synthesis of imidized polymer of polyamic acid -

The imidized polymer of the polyamic acid as the polymer (A) in the present invention can be obtained by dehydrating and ring closure of the obtained polyamic acid to imidize it. Here, the imidization ratio of the imidized polymer is preferably 30% or more, and more preferably 40 to 95%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of the amic acid structure and the number of the imide ring structure in the imidized polymer of the polyamic acid. The imidization rate can be measured, for example, by ¹ H-NMR.

The dehydration ring closure of the polyamic acid is preferably carried out by (i) heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, . &Lt; / RTI &gt;

The reaction temperature in the method of heating the polyamic acid of (i) above is preferably 50 to 200 캜, more preferably 60 to 170 캜. If the reaction temperature is less than 50 ° C, the dehydration ring-closure reaction does not proceed sufficiently, and if the reaction temperature exceeds 200 ° C, the molecular weight of the resulting imidized polymer may be lowered. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, in the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the polyamic acid solution of the above (ii), an acid anhydride such as acetic anhydride, anhydrous propionic acid or trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid, although it depends on the desired imidization rate. As the dehydration cyclization catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. The imidization rate can be increased as the amount of the dehydrating agent and the dehydration ring-closing catalyst is increased. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 캜, more preferably 10 to 150 캜. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

- polyamic ester -

The polyamic ester as the polymer (A) in the present invention can be synthesized, for example, by the following method.

(1) a method of reacting a compound selected from a compound having a polyamic acid and a hydroxyl group, a compound having a halogenide and an oxiranyl group, or

(2) A method of reacting a tetracarboxylic acid diester or a tetracarboxylic acid diester dihalide with a diamine.

The polyamic acid used in the above method (1) is the same as the polyamic acid as the (A) polymer in the present invention.

Examples of the compound having a hydroxyl group used in the method (1) include an alcohol and a phenol compound. Specific examples thereof include alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, sec-butanol, isobutanol, t-butanol and the like;

Examples of the phenol compound include phenol, cresol, and the like.

Examples of the halide include methyl bromide, ethyl bromide, n-propyl bromide, isopropyl bromide, n-butyl bromide, isobutyl bromide, sec-butyl bromide, t- butyl bromide, stearyl bromide, Ethyl, n-propyl chloride, isopropyl chloride, n-butyl chloride, isobutyl chloride, sec-butyl chloride, t-butyl chloride, stearyl chloride, 1,1,1-trifluoro-2- of;

Examples of the compound having an oxiranyl group include propylene oxide and the like.

The reaction of a polyamic acid with a compound selected from a compound having a hydroxyl group, a compound having a halogenide and an oxiranyl group can be carried out in accordance with a known method.

The tetracarboxylic acid diester used in the above method (2) can be obtained, for example, by ring opening of the tetracarboxylic dianhydride exemplified above for use in the synthesis of polyamic acid by alcohol. The alcohol used here is the same as the alcohol as the hydroxyl group-containing compound used in the above method (1). The tetracarboxylic acid diester dihalide can be obtained by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent. Examples of the chlorinating agent include thionyl chloride and the like. The tetracarboxylic acid 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 the tetracarboxylic acid diester or the tetracarboxylic acid diester dihalide with the diamine can be carried out in accordance with a known method.

The polyamic acid ester as the polymer (A) in the present invention may have only an amide ester structure, or may be a partial esterified product in which the amide structure and the amide ester structure coexist.

- polyorganosiloxane-

As the polyorganosiloxane as the polymer (A) in the present invention, a known polyorganosiloxane can be suitably used without particular limitation,

The hydrolysis / condensation product of the hydrolyzable silane compound (polyorganosiloxane 1),

A hydrolysis-condensation product of a hydrolyzable silane compound (polyorganosiloxane 2) containing a hydrolyzable silane compound having an epoxy group,

A hydrolysis-condensation product (polyorganosiloxane 3) of a hydrolysable silane compound containing a hydrolyzable silane compound having a Si-H bond, or

It is preferable to use the reaction product (polyorganosiloxane 4) between the polyorganosiloxane 2 and the carboxylic acid.

Here, as the hydrolyzable silane compound,

Examples of the hydrolyzable silane compound having an epoxy group include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- Glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 3- , 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like; As the hydrolyzable silane compound having Si-H bond, for example, methoxydimethylsilane, ethoxydimethylsilane and the like;

Examples of the other hydrolyzable silane compounds include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- ) Acrylates such as acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyl Trimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane, or dimethyldiethoxysilane, etc. In addition to these, A hydrolyzable silane compound described in Document 3 (International Publication No. 2009/096598) can be used.

When the polyorganosiloxane 4 is used as the polyorganosiloxane in the present invention, the use of the respective hydrolyzable silane compounds such that the epoxy equivalent of the polyorganosiloxane 2 used as the precursor is 100 to 1,000 g / It is desirable to adjust the ratio. 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 Si-H bonds in the polyorganosiloxane 3 are arbitrary, but the ratio of (A) the poly The use ratio of the hydrolyzable silane compound used for synthesizing the reaction product of the organosiloxane and the compound (B) will be described later.

The hydrolysis-condensation reaction of the hydrolyzable silane compound can be carried out by a known method. For example, the hydrolysis-condensation reaction of the hydrolyzable silane compound in a suitable organic solvent, preferably in the presence of a suitable catalyst, And adding 1 to 30 times the molar amount of water. The reaction temperature is preferably 40 to 100 DEG C, and the reaction time is preferably 1 to 8 hours.

In the case of using the polyorganosiloxane 4 as the polyorganosiloxane, examples of the carbonic acid to be provided for the reaction with the reactive polyorganosiloxane include 4-n-hexyloxybenzoic acid, 4-cyclohexyloxybenzoic acid Benzoic acid, 4- (n-octyloxy) benzoic acid, 4- (n-octyloxy) benzoic acid, 4- (3-cholestanyloxy) benzoic acid, 4- (4,4,5,5,5-pentafluoropentyloxy) benzoic acid, 4- Benzoic acid, 4- (4- (4-pentylcyclohexyl) cyclohexyl) phenyloxybenzoic acid and the like can be mentioned. In addition to the carboxylic acid in the "reactive compound" described in Patent Document 3 (International Publication No. 2009/096598) Corresponding compounds can be used. 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 캜, preferably 0.5 to 20 hours Time.

As to the hydrolysis / condensation reaction of the hydrolyzable silane compound and the reaction between the reactive polyorganosiloxane and the carboxylic acid, all the matters other than the above are disclosed in Patent Document 3 (International Publication No. 2009/096598) , Or a condition added to this by an appropriate change by a person skilled in the art.

<(B) Compound>

The compound (B) in the present invention is a compound represented by the formula (1) (hereinafter also referred to as "compound (1)") and a compound represented by the formula (2) (Hereinafter referred to as &quot; compound &quot;). (B) compound has a specific hindered amine structure or hindered phenol structure in the molecule, as apparent from the above formulas (1) and (2).

[Compound (1)]

As the alkyl group having a carbon number of 1 to 6 in the ^Ⅰ R in the above formula (1), for example, methyl, ethyl, n- propyl, i- propyl, n- butyl, 2-butyl, i- butyl , t-butyl group and the like.

Examples of the aromatic group having 6 to 20 carbon atoms for R ^I include an aryl group having 6 to 12 carbon atoms and other aromatic groups. Examples of the aryl group having 6 to 12 carbon atoms include phenyl, 3-fluorophenyl, 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 a 4-pyridinyl group, a 2-phenyl-4-quinolinyl group, a 2- (4'-t-butylphenyl) Thiophenyl) -4-quinolinyl group, and the like.

Examples of the aralkyl group having 7 to 13 carbon atoms for R ^I include a benzyl group and the like.

Examples of the combination of R ^I and X ¹ in the above formula (1) include a group R ^I -X ¹ - bonded to ^{each other} , and examples thereof include a methyl group, ethyl group, n-propyl group, i- Phenyl group, a benzyl group, a 1,3-dioxobutyl group, a 4-pyridinylcarbonyl group, a benzoyl group, a 2-phenyl- (2'-thiophenyl) -4-quinolinyl group, a group -CONH-Ph (where Ph is a hydrogen atom, A group represented by a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 4-i-propylphenyl group, a 4-n-butylphenyl group or a 3-chloro-4-methylphenyl group. The group R ^I -X ¹ - is preferably a methyl group.

As the alkyl group having a carbon number of 1 to 6 ^{Ⅴ Ⅱ} ~R R in the formula (1), for example, methyl, ethyl, n- propyl, i- propyl, n- butyl, 2-butyl group, an i Butyl group, t-butyl group and the like;

Examples of the aryl group having 6 to 12 carbon atoms include a phenyl group, a 3-fluorophenyl group, a 3-chlorophenyl group, a 4-chlorophenyl group, a 4-i-propylphenyl group, Methylphenyl group and the like;

Examples of the aralkyl group having 7 to 13 carbon atoms include a benzyl group and the like.

7-13 carbon atoms in the aryl groups of R formyl ^{Ⅴ Ⅱ} ~R is a number including carbon of a formyl group. Examples of the formylaryl group include a 3-formylphenyl group and a 4-formylphenyl group.

The 8 to 14 carbon atoms in the formylaralkyl group of R &lt; ^II &gt; to R &lt; ^V &gt; The formylaryl group includes, for example, 3-formylbenzyl group, 4-formylbenzyl group and the like.

7 to 16 carbon atoms in an alkoxy aryl group of R ^Ⅱ ~R ^Ⅴ is, the number of alkoxy groups containing 1 to 4 carbon atoms. Examples of the alkoxyaryl group include a 3-methoxyphenyl group, a 4-methoxyphenyl group, a 3-ethoxyphenyl group, and a 4-ethoxyphenyl group.

As 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 formula (1), they may be bonded to each other through a group R ^II -X ² -, R ^III -X ³ -, R ^IV -X ⁴ - or R ^V -X ⁵ -, respectively, for example, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a benzyl group, a 4-pyridinylcarbonyl group, a benzoyl group, a 2-phenyl-4-quinolinyl group, a 2- (4 (2'-thiophenyl) -4-quinolinyl group, a group -CONH-Ph (wherein Ph represents a phenyl group, a 3-fluorophenyl group, Chlorophenyl group, 4-i-propylphenyl group, 4-n-butylphenyl group or 3-chloro-4-methylphenyl group). Group ^{R Ⅱ -X 2 -, R Ⅲ} -X 3 -, R Ⅳ -X 4 - , and R ^Ⅴ -X ⁵ -, it is preferred that all of these methyl group.

Examples of X ⁶ in the formula (1) include 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- in or _{* -COO-CH 2 -C ::: C-} ( just above, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, "::: Quot; represents a triple bond, and a bonding hand having &quot; * &quot; bonds with a heterocyclic ring containing a nitrogen atom). Examples of the alkylene group having 2 to ⁶ carbon atoms for X ⁶ include a 1,3-propylene group, a 1,6-hexylene group, and the like. This X ⁶ has merely a function of binding a heterocyclic ring having a nitrogen atom to a benzene ring having a group Z ¹ , and the effect of the present invention can be attenuated even if the kind thereof is selected. However, in order to maximize the effect of the present invention, it is preferable to limit the total number of carbon atoms and hetero atoms in X ⁶ to 12 or less. As X ⁶ , from the viewpoints of availability of raw materials and easiness of synthesis, it is preferable to use * -OOC-, * -NHCO- or * -O-CH ₂ -C- C- (where ":::" And the bonding hands to which &quot; * &quot; is bonded are combined with 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, an aminoethyl group and the like;

As the group having a cyclic ether structure, a group having an oxiranyl group is preferable, and examples thereof include an N, N-diglycidylamino group, an epoxycyclohexyl group, a glycidyloxy group and the like;

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 formula (1) is n1 + m1-valent organic group. Examples of W ¹ include a group obtained by removing n1 + m1 hydrogen from an aromatic compound having 6 to 14 carbon atoms and a group obtained by removing n1 + m1 hydrogen from an aliphatic hydrocarbon compound having 1 to 12 carbon atoms. Here, the aromatic compound and the aliphatic hydrocarbon compound may be substituted with a halogen atom, a cyano group, or an alkoxy group, respectively. Examples of the aromatic compound before removing the n1 + m1 hydrogen atoms include benzene, naphthalene, and anthracene. As the aliphatic hydrocarbon compound before n1 + m1 hydrogen is removed, an alkane having 1 to 8 carbon atoms or a cycloalkane having 3 to 8 carbon atoms is preferable, and specific examples thereof include methane, ethane, n-propane, , n-hexane, cyclopentane, cyclohexane, and the like.

W ¹ in the 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.

It is preferable that the position at which X ⁶ in the formula (1) binds to a heterocycle containing a nitrogen atom is in the following position with respect to the nitrogen atom, depending on the value of n.

When n is 1: 3-position

when n is 2 or 3: 3-position or 4-position, particularly preferably 4-position

when n is 4: 4-position or 5-position, particularly preferably 5-position

It is preferable that n in the formula (1) is 2.

If the formula (1) W group ¹ is obtained by removing the n1 + m1 of hydrogen from the benzene in the position of Z ¹ is, according to the values of n1, it is preferable that the following positions relative to X ^6.

When n1 is 1: 3-position or 4-position

When n1 is 2: 2,4-position or 3,5-position

It is preferable that n1 in the formula (1) is 1.

As the compound (1), a compound represented by each of the following formulas (B1-1) to (B1-3) is preferable:

(Wherein (R ^Ⅰ, X ⁶ and Z ¹ in B1-1) ~ (B1-3) are, respectively, the same as defined as in the formula (1)).

Specific examples of such compound (1) include compounds represented by each of the following formulas (1-1) to (1-8).

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

(Formula (B1 ') of n1, n, R ^Ⅰ ~R ^Ⅴ, X ¹ ~X ⁶ and Z ¹ are each, the same as defined as in the formula (1)).

Accordingly, the compound (1) in the present invention is most preferably at least one selected from the group consisting of the compounds represented by the above formulas (B1-1) to (B1-6).

Such a compound (1) can be easily synthesized by appropriately combining the stereochemistry of organic chemistry with the knowledge that a person skilled in the art can have in general.

For example, the compound represented by the above formula (B1-1) is a compound wherein Y ¹ is -OH or -NH ₂ in the following formula (1a) is a hindered amine-type antioxidant, Therefore, the desired compound (1) can be obtained by directly reacting the compound with a desired group Z ¹ and a benzene derivative having a suitable reactive group directly or via other compounds. At this time, if necessary, protecting the group Z ¹ with an appropriate protecting group, performing the above-mentioned reaction, then deprotecting to give a group Z ¹ , or using a compound having the precursor group instead of the group Z ¹ as a raw material, , And after the reaction, the precursor group may be converted into the group Z ¹ :

^(Ⅴ, R ^Ⅰ ~R the formula (1a), X ¹ ~X ⁵ and n are, respectively, the same meaning as in the formula ^(1), Y 1 is -OH or -NH ₂ Im).

For example, the X ⁶ in the formula (1) * -OOC- (so long as those hands coupled tagged "*" in combination with a heterocyclic ring containing the nitrogen atom) of compounds, Y ¹ in the formula (1a) Is obtained by an esterification reaction of a compound of formula (II) 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 A compound * -NHCO- (so long as those hands coupled tagged "*" in combination with a heterocyclic ring having a nitrogen atom) is the Y ¹ in the formula (1a) - NH ₂ with a benzene derivative having a desired group Z ¹ and a reactive group of -COOH or -COOX (wherein X is a halogen atom);

In the formula (1), X ⁶ is * -O-CH ₂ -C :: C- (wherein ":::" represents a triple bond, and the bonded hands marked with "*"Lt; RTI ID = 0.0 &gt;

To an intermediate having a triple bond at the terminal, which is obtained by the reaction of a compound represented by the formula (1a) wherein Y ¹ is -OH with 3-halogenated-

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 group Z ¹ is -NH _2, then protect the art -NH ₂ subjected to the reaction, playing a -NH ₂ by deprotection after, or a -NO ₂ instead of the -NH ₂ Is used as a raw material to carry out the above-mentioned reaction, and it is preferable to convert -NO ₂ to -NH ₂ after the reaction.

[Compound (2)]

Examples of the alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the middle of R ^{VI in} the above formula (2) include a carbon number which may be interrupted by the sulfur atom Is preferably an alkyl group having 4 to 16 carbon atoms, and examples thereof include a t-butyl group, a 1-methylpentadecyl group, and an octylthiomethyl group. Of these, a t-butyl group is particularly preferable.

Examples of the alkyl group having 1 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond in the course of R ^VII include a methyl group, ethyl group, n-propyl group, i- Butyl group, a t-butyl group, an n-pentyl group, and an n-octyl group. Of these, a methyl group or a t-butyl group is preferable. The position on the benzene ring of R ^VII is preferably the 5-position or the 6-position and more preferably the 6-position when the hydroxyl group is 1-position and R ^VI is 2-position.

Examples of X ⁷ in the formula (2) include 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- in or _{* -COO-CH 2 -C ::: C-} ( just above, R is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, "::: Quot; represents a triple bond, and a bonding hand to which &quot; * &quot; is bonded is bonded to a benzene ring having a hydroxyl group). This X ⁷ has merely a function of binding a benzene ring having a hydroxyl group to a benzene ring having a group Z ² , and the effect of the present invention can be attenuated even if the kind thereof is selected. However, in order to maximize the effect of the present invention, it is preferable to limit the total number of carbon atoms and hetero atoms in X ⁷ to 12 or less. X ^{7 is preferably} -COO-CH ₂ CH ₂ -OOC-, -COO-CH ₂ -C-, or -CH ₂ CH ₂ -OOC- or -CH ₂ CH ₂ -COO- in view of the availability of raw materials and ease of synthesis. - (wherein &quot; ::: &quot; represents a triple bond, and a bonding hand to which &quot; * &quot; is bonded to a heterocyclic ring containing a nitrogen atom).

In the formula (2), W ² is an organic group of n ² + m ² . This W ² can be understood to be the same as W ¹ after n 1 and m ¹ in the above description of W ¹ are read in place of n 2 and m 2, respectively.

A preferable group for Z ² is the same as that for Z ¹ .

In the above formula (2), n2 is preferably 1.

As the compound (2), a compound represented by each of the following formulas (B2-1) to (B2-3) is preferable:

(Formula (B2-1) ~ (B2-3) of X ⁷ and Z ² are, respectively, the same as defined as in the formula (2)).

Specific examples of such compound (2) include compounds represented by the following formulas (2-1) to (2-8), and the like.

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

(Formula (B2 ') of n2, R ^{Ⅵ, Ⅶ} R and X ⁷ are, respectively, the same as defined as in the formula (2)).

Therefore, the compound (2) in the present invention is most preferably at least one selected from the group consisting of the compounds represented by the above formulas (B2-1) to (B2-6).

Such a compound (2) can be easily synthesized by appropriately combining the stereochemistry of organic chemistry with the knowledge that a person skilled in the art can have in general.

For example, a compound represented by the above formula (B2-1) can be easily obtained as a hindered phenol-based antioxidant in a compound wherein Y ² is -COOH in the following formula (2a). Therefore, And the benzene derivative having a desired group Z ² and an appropriate reactive group are directly or indirectly reacted via other compounds to obtain the desired compound (2). At this time, if necessary, protecting the group Z ² with an appropriate protecting group, carrying out the above reaction, then deprotecting to give a group Z ² , or using a compound having the precursor group in place of the group Z ² as a raw material, , And after the reaction, the precursor group may be converted into the group Z ² :

(In the formula (2a), R ^VI and R ^VII each have the same meaning as in the formula (2), and Y ² is -COOH).

For example, in the formula (2), the compound in which X ⁷ is * -COO-CH ₂ CH ₂ -OOC- (provided that the bonded hands marked with "*" are bonded to a benzene ring containing a hydroxyl group)

An intermediate having an -OH at the terminal obtained by the reaction of a compound in which Y &lt; ¹ &gt; is -COOH and ethylene glycol in the formula (2a)

Can be obtained by an esterification reaction 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 (2), X ⁷ is * -COO-CH ₂ -C :: C- (wherein ":::" represents a triple bond, and "*" A compound having a triple bond at the terminal, which is obtained by an ester reaction between a compound in which Y ² is -COOH in formula (2a) and 3-hydroxy-1-propyne,

By adding a desired group Z ² and a benzene derivative having a halogen atom as a reactive group. In the above, in the case of group Z ² is -NH _2, then protect the art -NH ₂ subjected to the reaction, playing a -NH ₂ by deprotection after, or a -NO ₂ instead of the -NH ₂ Is used as a raw material to carry out the above-mentioned reaction, and it is preferable to convert -NO ₂ to -NH ₂ after the reaction.

&Lt; Preferred combination of (A) polymer and (B)

When the liquid crystal aligning agent of the present invention contains the reaction product of the (A) polymer and the compound (B), the reaction product is obtained by reacting (A) the polymer and (B) B) compound is added to the reaction product. On the other hand, when the liquid crystal aligning agent of the present invention contains the polymer (A) and the compound (B) as separate and independent components, it is preferable that the liquid crystal alignment film From the viewpoint of maximizing the effect. By taking such a state, the hindered amine structure derived from the compound (B) or the hindered phenol structure is bonded to the polymer chain through the flexible bonding unit in the liquid crystal alignment film to be formed. Therefore, the hindered amine structure or the hindered phenol structure can move relatively freely in the liquid crystal layer while being restrained by the polymer chain, so that the impurity trap function and the like of the structure can be effectively expressed, It can be considered that the electric characteristics are improved.

In the case where the liquid crystal aligning agent of the present invention contains the reaction product of the (A) polymer and the compound (B), and the case where the polymer (A) and the compound (B) are contained as separate and independent components, The polymer (A) and the compound (B) are preferably selected according to the following guidelines.

When the (A) polymer is a polyamic acid, the site of reaction with the compound (B) in the polymer (A) is preferably a carboxy group having an acidic structure. Therefore, Z ¹ or Z ² of the compound (B) is preferably a group having an amino group and a cyclic ether structure, respectively. Examples of the compound (B) to be used in this case include compounds represented by the formulas (1-1) to (1-3), (1-5) to (1-8), (2-1) 2), (2-4), (2-5), (2-7) and (2-8).

Next, when the polymer (A) is an imidized polymer of a polyamic acid, since the reaction site with the compound (B) in the polymer (A) is preferably a carboxy group having an acidic structure, It is preferable that the carboxy group remains in a significant ratio. From this viewpoint, the imidization 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 compound (B) used in this case is the same as in the case where the (A) polymer is a polyamic acid.

When the polymer (A) is a polyorganosiloxane, the reaction between the polymer (A) and the compound (B)

(A) the polymer is a polyorganosiloxane having an epoxy group (polyorganosiloxane 2), (B) the compound is a group having a polymerizable unsaturated bond, or

(A) the polymer is a polyorganosiloxane having a Si-H bond (polyorganosiloxane 3), and (B) the compound is a group having a polymerizable unsaturated bond. Examples of the compound (B) to be used in this case include compounds represented by the above formulas (1-4), (2-3) and (2-6), respectively.

&Lt; Use ratio of (B) compound >

When the liquid crystal aligning agent of the present invention contains the reaction product of the (A) polymer and the (B) compound, the proportion of the compound (B) in the liquid crystal aligning agent of the present invention is in the range of (A) (B) is contained as an independent and independent component, it is preferably 0.1 to 30 parts by weight, more preferably 0.5 to 20 parts by weight, per 100 parts by weight of the polymer (A) , Particularly preferably 1 to 15 parts by weight.

By setting the ratio to be used in this range, it is possible to obtain a liquid crystal alignment film in which a decrease in voltage holding ratio due to light (particularly ultraviolet light) is suppressed.

&Lt; Reaction product of (A) polymer with (B) compound >

Next, a method of synthesizing the reaction product in the case where 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 polymer (A), which is a polyamic acid or an imidized polymer thereof, and the compound (B) having a polymerizable unsaturated bond can be carried out preferably by mixing them in an appropriate solvent and reacting them. At this time, a catalyst may be used, but it may be a no catalyst. As the solvent, the same solvent as that used for polymerizing polyamic acid can be used. The reaction temperature is preferably 40 to 80 占 폚, more preferably 50 to 70 占 폚;

The reaction time is preferably 15 minutes to 4 hours, more preferably 30 minutes to 2 hours.

The reaction of the polyorganosiloxane 2 with the compound (B) having a polymerizable unsaturated bond is preferably carried out preferably in the presence of an appropriate organic solvent, preferably in the presence of a catalyst. Examples of the organic solvent usable herein include organic solvents usually used in the synthesis reaction of the polyorganosiloxane. As the catalyst, known compounds can be used, for example, as an organic base or a so-called curing accelerator for promoting the reaction between an oxiranyl compound and an acid anhydride.

Examples of the organic base include triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, tetramethylammonium hydroxide and the like;

Examples of the curing accelerator include tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride and the like.

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, based on 100 parts by weight of the polyorganosiloxane 2.

The reaction temperature is preferably 40 to 200 占 폚, more preferably 50 to 150 占 폚. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The reaction of the polyorganosiloxane 3 with the compound (B) having a polymerizable unsaturated bond is preferably a hydrosilylation reaction in the presence of a catalyst, preferably in an organic solvent.

As the catalyst, known catalysts for hydrosilylation reaction can be used, and for example, compounds or complexes containing platinum, rhodium or palladium can be used. Among them, compounds or complexes containing platinum are preferable, and specific examples thereof include hexachloroplatinic acid (IV) acid hexahydrate, platinum-carbonylvinylmethyl complex, platinum-divinyltetramethyldisiloxane complex, platinum-cyclovinylmethylsiloxane Complex, platinum-octylaldehyde / octanol complex, and the like. The above platinum compound or complex may be carried on a suitable carrier such as activated carbon. The amount of the catalyst to be used is preferably from 0.01 to 10,000 ppm, more preferably from 0.1 to 100 ppm, based on the weight of the compound (B) to be used, as the amount of metal atoms contained in the compound or complex.

As the organic solvent that can be used for the hydrosilylation reaction, an aromatic hydrocarbon or an ether is preferable, and specific examples thereof include toluene, xylene, mesitylene, diethylbenzene, tetrahydrofuran, diethylether, 1,4 -Dioxane, diphenyl ether, and the like. The solvent is used in such a ratio that the solid concentration (the ratio of the weight of the components other than the solvent in the reaction solution to the total weight of the solution) is preferably 0.1 wt% or more, and more preferably 5 to 50 wt%.

The reaction temperature is preferably 40 to 250 占 폚, more preferably 50 to 180 占 폚. The reaction time is preferably 0.1 to 120 hours, more preferably 1 to 10 hours.

<Other additives>

The liquid crystal aligning agent of the present invention contains the above-mentioned polymer (A) and the compound (B) as essential components, and is preferably constituted as a solution composition dissolved in a solvent to be described later. However, May be further contained.

Such other additives include, for example, a compound having at least one epoxy group in the molecule (hereinafter referred to as an &quot; epoxy compound &quot;), and a functional silane compound.

[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, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl N, N, N ', N'-bis (N, N-diglycidylaminomethyl) cyclohexane, N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl-benzylamine, N, N-diglycidylaminomethylcyclohexane, N, Glycidyl-cyclohexylamine, and the like.

The mixing ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight, based on 100 parts by weight of the total amount of the polymers. However, (B) to a compound, Z ¹ is the case resulting from the compound (1) or Z ² having a cyclic ether structure is used the resulting compound (2) having a cyclic ether structure, excess of the epoxy compound as the other additives If used heavily, the advantageous effects of the present invention may be impaired. Therefore, when the compound (B) in which Z ¹ or Z ² is a group having a cyclic ether structure is used, the use ratio of the epoxy compound as the other additive is preferably 200 parts by weight or less based on 100 parts by weight of the compound (B) And is more preferably limited to 100 parts by weight or less.

[Functional silane compound]

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-ureidopropyltriethoxy Silane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N- Trimethoxysilyl-1,4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3 , 6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazononanoate, Benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl- N-phenyl-3-aminopropyltriethoxysilane, and the like.

The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, and more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total amount of the polymers.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention is preferably a liquid crystal aligning agent which is obtained by the reaction product of the polymer (A) and the compound (B), the polymer (A) and the compound (B), and other additives optionally blended Is dissolved and contained in a solvent.

As the solvent usable in the liquid crystal aligning agent of the present invention, it is preferable to use an organic solvent, and examples thereof include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxypropyl acetate, ethyl lactate, N-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethyleneglycol-ethyl 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, diethyl Ethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration of 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, etc., Is in the range of 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the surface of the substrate as described later, and preferably, it is heated to form a coating film which becomes a liquid crystal alignment film. When the solid concentration is less than 1% by weight, On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large and a good liquid crystal alignment film can not be obtained. In addition, the viscosity of the liquid crystal aligning agent increases, The characteristic becomes poor.

A particularly preferable range of the solid concentration is different depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, in the case of the spinner method, 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 to set the solid content concentration in the range of 3 to 9 wt% and accordingly the solution viscosity in the range of 12 to 50 mPa · s. In the case of the ink-jet method, it is particularly preferable that the solid concentration is in the range of 1 to 5 wt%, and the solution viscosity is therefore in the range of 3 to 15 mPa · s.

The temperature for preparing the liquid crystal aligning agent of the present invention is preferably 10 to 45 占 폚, and more preferably 20 to 30 占 폚. When the liquid crystal aligning agent of the present invention is stored, it is preferable to store the liquid crystal aligning agent at 45 DEG C or lower in order to avoid the reaction of the (B) compound with the (A) polymer during storage.

&Lt; Method of 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 for forming the liquid crystal alignment film are different depending on the display mode of the liquid crystal display device to which they are applied.

Formation of the liquid crystal alignment film can be performed, for example, in accordance with a method of (1) a coating film forming process and (2) a rubbing process in this order. (2) The rubbing process is arbitrary. When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display device of vertical alignment type such as a VA type or MVA type, (2) the rubbing step may not be performed.

Each of the steps for forming a liquid crystal alignment film will be described below.

(1) Coating film formation process

When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display device of a longitudinal electric field system such as a TN type, an STN type, a VA type, an MVA type and the like, two substrates on which a patterned transparent conductive film is formed, , And the liquid crystal aligning agent of the present invention is coated on each of the transparent conductive film formation surfaces to form a coating film. On the other hand, when the liquid crystal aligning agent of the present invention is applied to a liquid crystal display device of a horizontal electric field system such as an IPS or FFS type, a pair of electrodes And a counter substrate on which electrodes are not formed are formed as a pair and a liquid crystal aligning agent of the present invention is applied to the surface of the comb-shaped electrode and the surface of the counter substrate to form a coating film.

In any of the above cases, examples of the substrate include glass such as float glass and soda glass;

A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, or the like can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ -SnO ₂ , a NESA (registered trademark) film made of SnO ₂ , or the like can be used. As the metal film, for example, a film made of a metal such as chromium can be used. The patterning of the transparent conductive film and the metal film includes, 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, a method of forming a transparent conductive film by using a mask having a desired pattern Method and the like.

In order to make the adhesion between the substrate and the electrode and the coating film better at the time of applying the liquid crystal aligning agent onto the substrate, a functional silane compound, a titanate compound and the like are previously coated on the substrate and the electrode The pre-treatment for heating may be performed.

The application of the liquid crystal aligning agent onto the substrate can be preferably carried out by an appropriate application method such as an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. After the application, the coated surface can be formed by preheating (prebaking) the coating surface and then baking (postbaking). The prebaking condition is, for example, a heating time of 0.1 to 5 minutes at a heating temperature of 40 to 120 캜, and a post baking condition is, for example, a heating temperature of 120 to 300 캜, preferably 150 to 250 캜 For example 5 to 200 minutes, preferably 10 to 100 minutes. The film thickness of the coated film after post-baking is preferably 0.001 to 1 mu m, more preferably 0.005 to 0.5 mu m.

When the liquid crystal aligning agent of the present invention is applied to a vertical alignment type liquid crystal display device such as VA type or MVA type, the coating film formed as described above can be used as it is as a liquid crystal alignment film. In this case, however, the following (2) rubbing step may be optionally performed.

(2) Rubbing process

When the liquid crystal aligning agent of the present invention is applied to a horizontally aligned liquid crystal display device such as a TN type, an STN type, an IPS type or an FFS type, the rubbing treatment is performed after the above-mentioned (1) .

The rubbing treatment can be carried out by rubbing the surface of the coating film formed on the substrate in a predetermined direction with a roll of cloth made of, for example, nylon, rayon, cotton or the like.

<Liquid crystal display element>

Using the substrate having the liquid crystal alignment film formed as described above, a liquid crystal display device can be manufactured as follows.

A pair of substrates on which a liquid crystal alignment film is formed as described above is prepared, and a liquid crystal cell having a configuration in which liquid crystal is sandwiched between the pair of substrates is manufactured. To produce a liquid crystal cell, for example, the following two methods can be used.

As a first method, a pair of substrates are disposed opposite to each other with a gap (cell gap) interposed therebetween so that the liquid crystal alignment films face each other, and peripheral portions of the pair of substrates are bonded using a sealant, A liquid crystal is injected and filled in a cell gap defined by the liquid crystal cell, and then the liquid crystal cell is manufactured by sealing the injection port.

As a second method, for example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which a liquid crystal alignment film is formed, and liquid crystal is dropped to a predetermined number of places on the liquid crystal alignment film surface A method of manufacturing a liquid crystal cell by bonding the other substrate so that the liquid crystal alignment film is opposed to the substrate and spreading the liquid crystal widely over the entire surface of the substrate and then curing the sealing agent by irradiating ultraviolet light to the entire surface of the substrate ODF (One Drop Fill) method).

In any of the above methods, it is preferable that the liquid crystal cell using the liquid crystal cell is heated to a temperature at which the liquid crystal using isotropic phase is gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal.

Then, the liquid crystal display element of the present invention can be obtained by bonding the polarizing plate to the outer surface of the liquid crystal cell in a predetermined direction.

As the liquid crystal, for example, a nematic liquid crystal, a smectic liquid crystal or the like can be used.

In the case of producing a horizontally oriented liquid crystal display element, nematic liquid crystals having positive dielectric anisotropy are preferable, and examples thereof include biphenyl-based liquid crystals, phenylcyclohexane-based liquid crystals, ester-based liquid crystals, , Biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, quartz-based liquid crystal and the like. A cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal or the like may be added to these liquid crystals and used.

On the other hand, when a vertical alignment type liquid crystal display element is manufactured, a nematic liquid crystal having a negative dielectric anisotropy is preferable. For example, a dicyanobenzene liquid crystal, a pyridazine liquid crystal, A biphenyl-based liquid crystal, a phenylcyclohexane-based liquid crystal, and the like can be used.

As the polarizing plate used for the outside of the liquid crystal cell, a polarizing plate in which a polarizing film called &quot; H film &quot; in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched orientation is sandwiched by a cellulose acetate protective film or a polarizing plate made of H film itself have.

(Example)

&Lt; Synthesis of Compound (B) >

[Synthesis of Compound (1)

Synthesis Example 1-1

(Compound (1-1)) represented by the above formula (1-1) was synthesized according to Reaction Scheme 1 below.

17 g (0.10 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 100 mL of tetrahydrofuran (THF) and 17 mL (0.12 mol) of triethylamine were added to the reaction vessel and mixed . This was cooled with 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 the temperature at 5 ° C. After completion of dropwise addition, the reaction was carried out with stirring at 25 DEG C for 3 hours. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the mixture was sequentially extracted and washed three times with 150 mL of a 1 mol / L aqueous sodium hydroxide solution and 150 mL of distilled water. Subsequently, the solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 150 mL of ethanol to obtain 28 g (0.087 mol, yield 87%) of a pale yellow compound (1-1a).

Subsequently, 28 g (0.087 mol) of the compound (1-1a), 2.8 g of palladium carbon (5.0 wt% of palladium loading), 200 mL of tetrahydrofuran and 200 mL of ethanol were added to a separate reaction vessel and mixed with 28 mL of hydrazine monohydrate The system was heated to 70 캜 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 carbon, 300 mL of ethyl acetate was added to the filtrate, and extracted and washed five times with 200 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from ethyl acetate (25 mL) and hexane (80 mL) to obtain 20 g (0.070 mol, yield 81%) of a pale brown compound (1-1).

Synthesis Example 1-2

(Compound (1-2)) represented by the above formula (1-2) was synthesized according to Reaction Scheme 2 below.

17 g (0.10 mol) of 1,2,2,6,6-pentamethyl-4-aminopiperidine, 100 mL of tetrahydrofuran, and 17 mL (0.12 mol) of triethylamine were added to the reaction vessel and mixed. This was cooled with 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 the temperature at 5 DEG C, and the reaction was carried out at 25 DEG C for 3 hours with stirring. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the mixture was sequentially extracted and washed three times with 150 mL of a 1 mol / L aqueous sodium hydroxide solution and 150 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the obtained solid was recrystallized from 100 mL of ethanol to obtain 29 g (0.091 mol, yield: 91%) of a pale yellow compound (1-2a).

Subsequently, 28 g (0.091 mol) of the compound (1-2a), 2.8 g of palladium carbon (palladium loading amount 5.0 wt%), 200 mL of tetrahydrofuran and 200 mL of ethanol were added to a separate reaction vessel and mixed. 28 mL of hydrazine monohydrate was slowly dropped thereinto, and then the system was heated to 70 DEG C and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the reaction mixture was filtered through Celite to remove palladium 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 solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from ethyl acetate (20 mL) and hexane (80 mL) to obtain 19 g (0.064 mol, yield 70%) of a pale brown compound (1-2).

Synthesis Example 1-3

(Compound (1-3)) represented by the above formula (1-3) was synthesized according to the following Reaction Schemes 3a to 3c.

(Synthesis of compound (1-3a)

17 g (0.10 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 12 g (0.10 mol) of 3-bromo-1-propyne and 17 g Mol) and 100 mL of N, N-dimethylformamide (DMF) were mixed, and the reaction was carried out with stirring at room temperature for 5 hours. After the completion of the reaction, 400 mL of ethyl acetate was added to the reaction mixture, followed by extraction and washing four times with 200 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure to obtain a solid. Recrystallization was performed using 50 mL of ethanol to obtain 19 g (0.090 mole, yield 90%) of a white compound (1-3a).

(Synthesis of compound (1-3b)

44 g (0.20 mol) of 4-iodoaniline, 185 g (2.0 mol) of epichlorohydrin and 350 mL of toluene were mixed and stirred at 80 DEG C for 5 hours. Then, a sodium hydroxide aqueous solution having a concentration of 3 mol / Was added dropwise, and the reaction was carried out at 80 DEG C under stirring for further 2 hours. After the completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, followed by extraction and washing with 250 mL of distilled water four times. The solvent was removed from the recovered organic layer under reduced pressure to obtain 50 g (0.15 mol, yield 75%) of a pale brown compound (1-3b).

(Synthesis of compound (1-3)) [

(0.90 mmol) of dichlorobis (triphenylphosphine) palladium (II), 0.17 g (0.90 mmol) of copper (I) iodide in acetonitrile (0.26 mol) of triethylamine were added and mixed. A solution prepared by dissolving 19 g (0.090 mole) of the compound (1-3a) in 50 ml of acetonitrile was added dropwise thereto, and the reaction was carried out at 40 ° C for 4 hours with stirring. After the completion of the reaction, the catalyst was removed from the reaction mixture by Celite filtration. Then, 400 mL of ethyl acetate was added to the filtrate, and extracted and washed three times with 250 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 60 mL of ethanol to obtain 27 g (0.066 mol, yield: 73%) of a pale yellow compound (1-3).

Synthesis Example 1-4

(Compound (1-4)) represented by the above formula (1-4) was synthesized according to the following Reaction Schemes 4a and 4b.

(Synthesis of compound (1-4a)

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 added to the reaction vessel and mixed. This was cooled with an ice bath, and a solution prepared by dissolving 13 g (0.12 mol) of methacryloyl chloride in 150 mL of dichloromethane was dropped thereinto while maintaining the temperature at 5 ° C., and the reaction was carried out at 25 ° C. for 3 hours with stirring. After the completion of the reaction, 500 mL of ethyl acetate and 500 mL of tetrahydrofuran were added to the reaction mixture. The reaction mixture was washed once with 500 mL of hydrochloric acid at a concentration of 1 mol / L and three times with 250 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure to obtain 16 g (0.077 mole, yield: 77%) of a white compound (1-4a).

(Synthesis of Compound (1-4)) [

16 g (0.077 mol) of the compound (1-4a), 13 g (0.077 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine and 300 mL of tetrahydrofuran were added to the reaction vessel and mixed did. This was cooled with an ice bath, and 18 g (0.092 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) -4-aminopyridine (DMAP) (1.15 g, 0.015 mol) was added, and the reaction was carried out at 25 DEG C for 2 hours with stirring. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and then extracted and washed three times with 200 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 50 mL of ethanol to obtain 23 g (0.065 mol, yield 85%) of a white compound (1-4).

Synthesis Example 1-5

(Compound (1-5)) represented by the above formula (1-5) was synthesized according to Reaction Scheme 5 below.

17 g (0.10 mol) of 4-hydroxy-1,2,2,6,6-pentamethylpiperidine, 100 mL of tetrahydrofuran, and 17 mL (0.12 mol) of triethylamine were added to the reaction vessel and mixed. This was cooled with an ice bath, and a solution prepared by dissolving 23 g (0.10 mol) of 3,5-dinitrobenzoyl chloride in 100 mL of tetrahydrofuran was added dropwise thereto while maintaining the temperature at 5 ° C., followed by stirring at 25 ° C. for 3 hours The reaction was carried out. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and the mixture was sequentially extracted and washed three times with 150 mL of a 1 mol / L aqueous sodium hydroxide solution and 150 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 150 mL of ethanol to obtain 29 g (0.080 mole, yield 80%) of a pale yellow compound (1-5a).

29 g (0.080 mol) of the compound (1-5), 2.9 g of palladium carbon (5.0% by weight of palladium), 200 mL of tetrahydrofuran and 200 mL of ethanol were added to a separate reaction vessel and mixed with 29 mL of hydrazine monohydrate Slowly dropped. Thereafter, the temperature of the system was raised to 70 占 폚, and the reaction was carried out with stirring for 2 hours. After completion of the reaction, the reaction mixture was filtered through Celite to remove palladium carbon. To the obtained filtrate, 300 mL of ethyl acetate was added, followed by extraction and washing with 200 mL of distilled water five times. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 30 mL of ethyl acetate and 90 mL of hexane to obtain 18 g (0.058 mole, yield: 73%) of a pale brown compound (1-5).

Synthesis Example 2-1

(Compound (2-1)) represented by the above formula (2-1) was synthesized according to the following Reaction Schemes 6a to 6c.

(Synthesis of compound (2-1a)) [

25 g (0.10 mol) of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 40 mL (0.55 mol) of thionyl chloride and 1 mL of N, N-dimethylformamide were added to the reaction vessel, The reaction was carried out with stirring for 1 hour. After completion of the reaction, thionyl chloride was removed from the reaction mixture using an aspirator to obtain a pale yellow acid chloride compound.

62 g (1.0 mol) of ethylene glycol, 11 g (0.11 mol) of triethylamine and 100 mL of tetrahydrofuran were added to a separate reaction vessel and mixed. This was cooled with an ice bath, and a solution prepared by dissolving the above acid chloride compound in 50 mL of tetrahydrofuran was added dropwise thereto while maintaining the temperature at 5 DEG C, and the reaction was carried out at 25 DEG C for 3 hours with stirring. After the completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, followed by extraction and washing three times with 300 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure to obtain 21 g (0.070 mole, 70% yield) of a white compound (2-1a).

(Synthesis of compound (2-1b)

15 g (0.10 mol) of 4-aminomethylbenzoic acid, 120 mL of an aqueous solution of sodium hydroxide at a concentration of 1 mol / L and 250 mL of ethanol were placed in a reaction container and mixed. This was cooled with an ice bath, 24 g (0.11 mol) of di-tert-butyl dicarbonate was added little by little while maintaining the temperature at 5 ° C, and the reaction was carried out at 25 ° C for 12 hours with stirring. 500 ml of distilled water and saturated citric acid were added until the liquid became acidic. The precipitated solid was collected by filtration and dried to obtain 23 g (0.092 g) of the white compound (2-1b) Mol, yield: 92%).

(Synthesis of compound (2-1)) [

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 added to the reaction vessel and mixed. This was cooled with an ice bath and 16 g (0.084 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.04 mol of N, N-dimethyl- 1.7 g (0.014 mol) of aminopyridine was added, and the reaction was carried out at 25 DEG C for 2 hours with stirring. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and then extracted and washed three times with 200 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 55 mL of ethanol to obtain 30 g (0.056 mole, yield 80%) of a white compound (2-1c).

Subsequently, 30 g (0.056 mol) of the compound (2-1c), 100 mL of dichloromethane and 30 mL of trifluoroacetic acid were added to a separate reaction vessel, and the reaction was carried out at 25 ° C for 2 hours with stirring. After completion of the reaction, the solvent was removed from the reaction mixture under reduced pressure, and the obtained solid was recrystallized from ethyl acetate (30 mL) and hexane (100 mL) to obtain 20 g (0.046 mol, yield: 82% .

Synthesis Example 2-2

(Compound (2-2)) represented by the above formula (2-2) was synthesized according to the following Reaction Schemes 7a and 7b.

(Synthesis of compound (2-2a)

25 g (0.10 mol) of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 6.2 g (0.11 mol) of propargyl alcohol and 400 mL of tetrahydrofuran were mixed in a reaction container. This was cooled with an ice bath and 23 g (0.12 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.1 g of N, N-dimethyl- 2.4 g (0.020 mol) of aminopyridine was added, and the reaction was carried out at 25 DEG C for 2 hours with stirring. After the completion of the reaction, 400 mL of ethyl acetate was added to the reaction mixture, followed by extraction and washing three times with 250 mL of distilled water. The solvent was removed from the organic layer under reduced pressure to obtain a solid. Recrystallization was performed using 50 mL of ethanol to obtain 25 g (0.088 mole, yield: 88%) of a white compound (2-2a).

(Synthesis of compound (2-2)) [

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 mmol) of dichlorobis (triphenylphosphine) palladium (II) A solution prepared by dissolving 25 g (0.088 mol) of the compound (2-2a) in 50 mL of acetonitrile was added 0.17 g (0.88 mmol) of copper (I), 300 mL of acetonitrile and 27 g And the reaction was carried out with stirring at 40 占 폚 for 4 hours. After the completion of the reaction, the catalyst was removed from the reaction mixture by Celite filtration. Then, 400 mL of ethyl acetate was added, and extracted and washed three times with 250 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 50 mL of ethanol to obtain 34 g (0.069 mol, yield 78%) of a pale yellow compound (2-2).

Synthesis Example 2-3

(Compound (2-3)) represented by the above formula (2-3) was synthesized according to the following Reaction Schemes 8a to 8c.

(Synthesis of compound (2-3a)

25 g (0.10 mol) of 3,5-di-tert-butyl-4-hydroxybenzoic acid, 40 mL (0.55 mol) of thionyl chloride and 1 mL of N, N-dimethylformamide were added to the reaction vessel, The reaction was carried out with stirring for 1 hour. The residual thionyl chloride was removed from the reaction mixture after completion of the reaction using an aspirator to obtain a pale yellow acid chloride compound.

62 g (1.0 mol) of ethylene glycol, 11 g (0.11 mol) of triethylamine and 100 mL of tetrahydrofuran were added to a separate reaction vessel and mixed. This was cooled with an ice bath, and a solution prepared by dissolving the above acid chloride compound in 50 mL of tetrahydrofuran was added dropwise thereto while maintaining the temperature at 5 DEG C, and the reaction was carried out at 25 DEG C for 3 hours with stirring. After the completion of the reaction, 500 mL of ethyl acetate was added to the reaction mixture, followed by extraction and washing three times with 300 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure to obtain 21 g (0.070 mol, 70% yield) of a white compound (2-3a).

(Synthesis of compound (2-3b)

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 added to the reaction vessel and mixed. This was cooled with an ice bath, and a solution prepared by dissolving 13 g (0.12 mol) of methacryloyl chloride in 150 mL of dichloromethane was dropped thereinto while maintaining the temperature at 5 ° C., and the reaction was carried out at 25 ° C. for 3 hours with stirring. After the completion of the reaction, 500 mL of ethyl acetate and 500 mL of tetrahydrofuran were added to the reaction mixture. The reaction mixture was washed once with 500 mL of hydrochloric acid at a concentration of 1 mol / L and three times with 250 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure to obtain 16 g (0.077 mol, 77% yield) of a white compound (2-3b).

(Synthesis of Compound (2-3)) [

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 added to the reaction vessel and mixed. This was cooled with an ice bath and 16 g (0.084 mol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 0.02 mol of N, N-dimethyl- (0.014 mol) was added, and the reaction was carried out with stirring at 25 占 폚 for 2 hours. After the completion of the reaction, 300 mL of ethyl acetate was added to the reaction mixture, and then extracted and washed three times with 200 mL of distilled water. The solvent was removed from the recovered organic layer under reduced pressure, and the resulting solid was recrystallized from 60 mL of ethanol to obtain 25 g (0.052 mol, yield 74%) of a white compound (2-3).

<Synthesis of imidized polymer of polyamic acid>

Synthesis Examples PI-1 to PI-6

N-methyl-2-pyrrolidone (NMP) was added to the reaction vessel so as to have a monomer concentration of 20 wt%, tetracarboxylic dianhydride and diamine of the type and ratio (mol% And the reaction was carried out at 60 DEG C for 6 hours to obtain solutions each containing polyamic acid. In Synthesis Example PI-4, the reaction of the tetracarboxylic dianhydride and the diamine was carried out in the coexistence of the type and the ratio (mol%) of the molecular weight modifier shown in Table 1. The monomer concentration in this Synthesis Example PI-4 is a value including the concentration of the molecular weight modifier in addition to the tetracarboxylic acid dianhydride and the diamine.

NMP was added to each solution of the resulting polyamic acid to dilute the polyamic acid to a concentration of 7% by weight. Then, pyridine and acetic anhydride were added to the solution of the polyamic acid solution in the amount shown in Table 1 And the 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 a fresh NMP solvent to obtain a solution containing 15% by weight of each of the imidized polymers PI-1 to PI-6.

With respect to each of the imidized polymers, the imidization ratios measured by the following methods are shown together in Table 1.

[Measurement of imidization rate of imidized polymer]

The solution containing the imidized polymer was poured into pure water and the resulting precipitate was sufficiently dried under reduced pressure at room temperature and dissolved in deuterated dimethyl sulfoxide. From the ¹ H-NMR spectrum measured at room temperature using tetramethylsilane as a reference material , And the imidization rate was determined by the following formula (1): &lt; EMI ID =

Imidization rate (%) = {(1-A ¹ ) / (A ² × α)} × 100 (1)

(1) wherein A ¹ is an area of a peak derived from a proton of an NH group near 10 ppm of chemical shift, A ² is an area of a peak derived from other protons, and? Is a precursor of an imidized polymer (The ratio of the number of other protons to one proton of the NH group in the polyamic acid).

<Synthesis of polyamic acid>

Synthesis Examples PA-1 and PA-2

Tetracarboxylic acid dianhydride and diamine of the type and ratio (mol%) shown in Table 1 as monomers were added to the reaction vessel, and NMP was added and dissolved so that the monomer concentration was 20% by weight, and the reaction was carried out at 60 DEG C for 6 hours , NMP was added to the obtained solution and diluted to obtain a solution containing 15 wt% each of polyamic acid PA-1 and PA-2.

The abbreviations of the respective monomers and the molecular weight modifiers in Table 1 are as follows.

[Tetracarboxylic acid dianhydride] In Table 1, "acid anhydride" is used.

TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride

BODA: bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic acid dianhydride

CB: 1,2,3,4-cyclobutane tetracarboxylic acid 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

100.0 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were placed in a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, And mixed at room temperature. Subsequently, 100 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the reaction was carried out for 6 hours while stirring at 80 DEG C under reflux. After completion of the reaction, the organic layer taken out from the reaction mixture was repeatedly washed with 0.2 wt% aqueous ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a reactive polyorganosiloxane As a viscous transparent liquid. As a result of ¹ H-NMR analysis of this reactive polyorganosiloxane, it was found that a peak based on the epoxy group was obtained in the vicinity of the chemical shift (?) = 3.2 ppm in accordance with the theoretical strength, and a subsidiary reaction of the epoxy group occurred during the reaction . The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500 and the epoxy equivalent was 180 g / mol.

Then, 10.0 g of the above-mentioned reactive polyorganosiloxane, 30.28 g of methyl isobutyl ketone as a solvent, 3.98 g of 4-dodecyloxybenzoic acid as carbonic acid, and UCAT 18X (trade name: (Manufactured by Nippon Shokubai Co., Ltd.), and the reaction was carried out at 100 ° C for 48 hours with stirring. The solution obtained by adding ethyl acetate to the reaction mixture after completion of the reaction was filtered three times, and the recovered organic layer was dried with magnesium sulfate and then the solvent was distilled off to obtain 9.0 g of polyorganosiloxane PS-1. The weight average molecular weight Mw of the obtained polyorganosiloxane PS-1 was 9,900.

&Lt; Preparation and evaluation of liquid crystal aligning agent >

Example 1

[Preparation of liquid crystal aligning agent]

NMP and butyl cellosolve (BC) were added to a solution containing the imidized polymer obtained in Synthesis Example PI-1 as a polymer (A), and further, Compound (B) obtained in Synthesis Example 1-1 (1-1) was added to 5 parts by weight of the polymer (A) based on 100 parts by weight of the polymer to prepare a solution having a solvent composition of NMP: BC = 65:35 (weight ratio) and a solid content concentration of 4% And filtered through a filter having a pore diameter of 1 탆 to prepare a liquid crystal aligning agent.

[Production of liquid crystal cell]

The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of ITO using a liquid crystal aligning agent printing machine (manufactured by Nihon Sha Sein Insights Co., Ltd.), and preliminarily dried on a hot plate at 80 캜 for 1 minute Baked, and post baked on a hot plate at 200 DEG C for 10 minutes to form a coating film having an average film thickness of 800 ANGSTROM. This operation was repeated to obtain a pair of substrates having a liquid crystal alignment film on the transparent electrode.

An epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 3.5 mu m was applied to the outer edge of the surface of the one pair of the substrates having the liquid crystal alignment film and then the other substrate was stacked so that the liquid crystal alignment film surface was opposed Squeezed together, and the adhesive was cured. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was injected and filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic light-curable adhesive. Thereafter, in order to remove the flow alignment at the time of injecting the liquid crystal, the liquid crystal cell was heated to 150 DEG C and then slowly cooled to room temperature to produce a vertically aligned liquid crystal cell.

[Evaluation of liquid crystal cell]

(1) Evaluation of liquid crystal alignment property

The liquid crystal cell manufactured as described above was sandwiched between two polarizing plates arranged in crossed nicols and the dark state of the visible light was observed with naked eyes to judge the case where light leakage was not observed as the " The case where light leakage was observed was evaluated as &quot; poor &quot; in the liquid crystal alignment property. As a result, the liquid crystal alignment property of this liquid crystal cell was found to be &quot; good &quot;.

(2) Evaluation of Voltage Conservation Rate

A voltage of 1 V was applied to the liquid crystal cell prepared above at 70 DEG C for 30 seconds and a voltage maintenance ratio (initial voltage maintenance ratio) after the application was canceled was measured under the conditions of an AC voltage of 1 V, a measurement temperature of 70 DEG C and a frame period of 167 milliseconds As a result, the voltage holding ratio of this liquid crystal cell was 98.1%.

(3) Evaluation of light resistance

The liquid crystal cell after the measurement of the initial voltage maintenance rate was placed at a distance of 5 cm from the 100-watt white fluorescent lamp, and the voltage maintenance rate (voltage maintenance rate after light irradiation) was measured in the same manner as above after irradiating light for 500 hours. In this case, 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", the light resistance is 1% to 3%, and the light resistance is 3% Defective &quot;, the light resistance of the liquid crystal cell was evaluated as &quot; good &quot;.

Examples 2 to 10 and Comparative Examples 1 and 2

In the same manner as in Example 1 except that the polymer (A) and the compound (B) of the kind described in Table 2 were used in the amounts described in the same Table in the preparation of the liquid crystal aligning agent of Example 1 , And a liquid crystal aligning agent were prepared, and liquid crystal cells were produced using these liquid crystal aligning agents, and various evaluations were carried out.

In Examples 7 and 8, two kinds of polymers each containing a polymer were used as a polymer (A). In Example 9, the polyorganosiloxane PS-1 obtained in Synthesis Example PS-1 was added to a solution containing the imidized polymer PI-6 obtained in Synthesis Example PI-6 as the polymer (A) at a weight ratio PI-6: PS-1 = 95: 5.

In Comparative Examples 1 and 2, other additives of the kind and amount described in Table 2 were used in place of the compound (B), respectively.

The evaluation results are shown in Table 2.

The abbreviations of the compounds (B) and other additives in Table 2 are as follows.

[(B) compound]

1-1: Compound (1-1) obtained in Synthesis Example 1-1

1-2: Compound (1-2) obtained in Synthesis Example 1-2

1-3: Compound (1-3) obtained in Synthesis Example 1-3

1-4: Compound (1-4) obtained in Synthesis Example 1-4

1-5: Compound (1-5) obtained in Synthesis Example 1-5

2-1: The compound (2-1) obtained in Synthesis Example 2-1

2-2: The compound (2-2) obtained in the above Synthesis Example 2-2

2-3: Compound (2-3) obtained in Synthesis Example 2-3

[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) a liquid crystal aligning agent which is prepared by using 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 represents a single bond, a carbonyl group or * -CONH- (provided that a bonded ring having "*" is bonded to a heterocyclic ring containing a nitrogen atom)
R ^Ⅱ ~R ^Ⅴ are, each independently, an aryl group, the alkyl group having 1 to 6 carbon atoms, 6 to 12 carbon atoms, a formyl aralkyl group, having a carbon number of 7-13 having a carbon number of 7-13 or aryl group having a carbon number of 8-14 formate Or a C7-C16 alkoxyaryl group having an alkoxy group having from 1 to 4 carbon atoms,
X ^{2 to} X ⁵ each represents a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH) - Combined with a summation)
X ⁶ is a divalent organic group,
W ¹ is n1 + m1-valent organic group,
Z ¹ is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond;
In the formula (2)
n2 is 1 or 2,
m2 is 1 or 2,
R ^VI is an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,
R ^VII is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,
X &lt; ⁷ &gt; is a divalent organic group,
W ² is an organic group of n ² + m ² , and
Z ² is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond). The method according to claim 1,
A liquid crystal aligning agent containing (A) a polymer and (B) a compound. The method according to claim 1,
A liquid crystal aligning agent containing a reaction product of (A) a polymer and (B) a compound. The method according to claim 1,
Wherein 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)

(R ¹ , X ⁶ and Z ¹ in the formulas (B1-1) to (B1-3) have the same meanings as in the formula (1), respectively;
X ⁷ and Z ² in the formulas (B2-1) to (B2-3) are the same as those in the formula (2), respectively). The method according to claim 1,
(A) the liquid crystal aligning agent contains at least one polymer selected from the group consisting of polyamic acid and imidized polymer thereof. The method according to claim 1,
Z ¹ in the formula (1) and Z ² in the formula (2) are each independently an amino group, an aminomethyl group, an N, N-diglycidylamino group or a (meth) acryloyloxy group Liquid crystal aligning agent. 5. The method of claim 4,
X ⁶ in the formula (1) and X ⁷ in the formula (2) each independently represent 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-, with the proviso that R Is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, &quot; ::: &quot; represents a triple bond, and in the case of the formula (1) And in the case of the formula (2), a benzene ring having a hydroxyl group is bonded). The method according to claim 1,
Wherein the compound represented by the formula (1) is a compound represented by the following formula (B1 '),
Wherein the compound represented by the formula (2) is a compound represented by the following formula (B2 '):

(Formula (B1 '), and n1, n, R ^Ⅰ ~R ^Ⅴ, X ¹ and Z ¹ ~X ⁶ of, respectively, the same meaning as in the formula (1),
N2, R &lt; ^{vi &} gt ;, R &lt; ^VII &gt; and X &lt; ⁷ &gt; in the formula (B2 ') are the same as those in the formula (2). 3. The method of claim 2,
Wherein the content of the compound (B) in the liquid crystal aligning agent is 0.1 to 30 parts by weight based on 100 parts by weight of the polymer (A) contained in the liquid crystal aligning agent. The method of claim 3,
(B) is 0.1 to 30 parts by weight based on 100 parts by weight of the (A) polymer. 6. The method of claim 5,
(A) the polymer is selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2: From a group consisting of a tetracarboxylic acid dianhydride containing at least one member selected from the group consisting of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and a polyamic acid obtained by reacting a diamine with an imidized polymer A liquid crystal aligning agent containing at least one kind of polymer selected. A liquid crystal alignment film formed from the liquid crystal aligning agent according to any one of claims 1 to 11. A liquid crystal display element 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, imidized polymer thereof, polyamic acid ester and polyorganosiloxane, and
(B) 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 represents a single bond, a carbonyl group or * -CONH- (provided that a bonded ring having "*" is bonded to a heterocyclic ring containing a nitrogen atom)
R ^Ⅱ ~R ^Ⅴ are, each independently, an aryl group, the alkyl group having 1 to 6 carbon atoms, 6 to 12 carbon atoms, a formyl aralkyl group, having a carbon number of 7-13 having a carbon number of 7-13 or aryl group having a carbon number of 8-14 formate Or a C7-C16 alkoxyaryl group having an alkoxy group having from 1 to 4 carbon atoms,
X ^{2 to} X ⁵ each represents a single bond, a carbonyl group, * -CH ₂ -CO- or * -CH ₂ -CH (OH) - Combined with a summation)
X ⁶ is a divalent organic group,
W ¹ is n1 + m1-valent organic group,
Z ¹ is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond;
In the formula (2)
n2 is 1 or 2,
m2 is 1 or 2,
R ^VI is an alkyl group having 4 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,
R ^VII is a hydrogen atom or an alkyl group having 1 to 16 carbon atoms which may be interrupted by an oxygen atom, a sulfur atom, a carbonyl group or an ester bond,
X &lt; ⁷ &gt; is a divalent organic group,
W ² is an organic group of n ² + m ² , and
Z ² is a group having an amino group, a cyclic ether structure or a polymerizable unsaturated bond).