KR20150054652A - Liquid crystal aligning agent, liquid crystal alignment film, manufacturing method for liquid crystal alignment film, liquid crystal display device, and manufacturing method for liquid crystal display device - Google Patents

Abstract

Provided are a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal orientation and orientation stability. A polymer component and a compound (D) represented by the following chemical formula (1) are contained in the liquid crystal alignment agent. In the chemical formula, A^1 is a group including a polymerized unsaturated bond, A^2 is a functional group capable of reacting with an epoxy group, R^1 is an organic group of (m+n), m is an integer from 2 to 18, and n is an integer from 1 to 18, wherein (m+n)<=20 is satisfied.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal display device, and a liquid crystal display device. FOR LIQUID CRYSTAL DISPLAY DEVICE}

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a process for producing a liquid crystal alignment film, a liquid crystal display device and a process for producing a liquid crystal display device.

Conventionally, various driving methods have been developed as liquid crystal display devices, which have different electrode structures and physical properties of liquid crystal molecules to be used. For example, TN type, STN type, VA type, MVA type, IPS type, FFS type Various liquid crystal display devices are known. These liquid crystal display devices have a liquid crystal alignment film for aligning liquid crystal molecules. As a material of the liquid crystal alignment film, polyamic acid and polyimide are generally used in view of good heat resistance, mechanical strength, and various properties such as affinity with liquid crystal. It has also been proposed to use, as a polymer component of a liquid crystal aligning agent, a polyorganosiloxane in which a group capable of exhibiting a desired function is introduced into a side chain (see, for example, Patent Document 1). Patent Document 1 discloses that a hydrolyzable silane compound containing a silane compound having a chain alkyl group is reacted in the presence of oxalic acid and an alcohol and the polyorganosiloxane obtained by the reaction is used as a polymer component of a liquid crystal aligning agent Lt; / RTI &gt;

Recently, a polymer sustained alignment (PSA) technique has been proposed as a new technique for developing pretilt angle characteristics. In the PSA technique, a liquid crystal cell in which a photopolymerizable compound is incorporated in a liquid crystal layer is constructed, and after the liquid crystal cell is constructed, a voltage is applied to the liquid crystal layer to irradiate light in a state in which the liquid crystal molecules are obliquely aligned, Thereby controlling the molecular orientation of the liquid crystal (see, for example, Patent Document 2). According to this PSA technique, there is an advantage that the viewing angle can be enlarged and a high-speed response can be achieved.

The present applicant has also found that a coating film is formed on a pair of substrates using a liquid crystal aligning agent containing a polyorganosiloxane having a (meth) acryloyl group, and a liquid crystal cell And then irradiating light to the liquid crystal cell in a state in which a voltage is applied between the conductive films of the pair of substrates (see, for example, Patent Document 3).

As a technique for imparting a liquid crystal aligning ability to a polymer thin film formed using a liquid crystal aligning agent, a photo alignment method using photoisomerization, optical dimerization, photolysis, or the like has recently been proposed as a technique to replace the rubbing method. This photo alignment method is a method of applying anisotropy to a film of a radiation-sensitive organic thin film formed on a substrate by irradiating polarized or unpolarized radiation, thereby controlling the orientation of the liquid crystal molecules. According to this method, generation of dust and static electricity in the process can be suppressed as compared with the conventional rubbing method, so that it is possible to suppress the occurrence of defective display caused by dust or the like and lowering of the yield. There is also an advantage that the liquid crystal aligning ability can be uniformly imparted to the coating film formed on the substrate.

Japanese Patent Application Laid-Open No. 9-281502 Japanese Patent Application Laid-Open No. 2003-149647 Japanese Laid-Open Patent Publication No. 2011-118358

In the case of the photo alignment method in which a chemical change is caused by irradiation of ultraviolet rays or the like, the liquid crystal alignment film tends to be inferior to the liquid crystal alignment film in the conventional rubbing process in terms of alignment control force of the liquid crystal. In consideration of this point, in the case of using the photo alignment method, the PSA treatment may be performed for the purpose of increasing the alignment restraining force of the liquid crystal. However, even when the PSA treatment is performed, the alignment restraining force of the liquid crystal molecules can not be sufficiently increased, and in particular, in the liquid crystal display device of the transverse electric field system, the display quality is lowered or burn-in occurs after continuous driving for a long time May occur. Further, in the production of a vertical alignment type liquid crystal display element, the formed liquid crystal cell may be subjected to light irradiation treatment to increase the alignment restraining force of the liquid crystal. However, when the same process is performed, the voltage holding ratio due to continuous driving for a long time tends to decrease, and reliability tends to be poor.

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems and has as its main object to provide a liquid crystal aligning agent capable of obtaining a liquid crystal alignment film having good liquid crystal alignability and orientation stability. Another object of the present invention is to provide a liquid crystal display element having various characteristics such as voltage holding ratio and burn-in characteristics.

DISCLOSURE OF THE INVENTION The present inventors have intensively studied in order to achieve the above-described problems of the prior art, and as a result, they found that the aforementioned problems can be solved by containing a compound specific to a liquid crystal aligning agent, and have completed the present invention. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal alignment film production method, liquid crystal display element and liquid crystal display element production method.

In one aspect, the present invention provides a liquid crystal aligning agent containing a polymer component and a compound (D) represented by the following formula (1):

(In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, R ¹ is an organic group of (m + n) N is an integer of 1 to 18, with the proviso that (m + n)? 20 is satisfied.

In one aspect, the present invention provides a process for producing a liquid crystal alignment film comprising a step of applying a liquid crystal aligning agent on a substrate to form a coating film, and a step of irradiating the coating film with light. A step of applying a liquid crystal aligning agent on each surface of a pair of substrates respectively and then heating the liquid crystal aligning agent to form a coating film; and a step of forming a pair of substrates on which the coating film is formed, A step of arranging the liquid crystal cell so as to oppose the coating film so as to face each other, and a step of irradiating light from the outside of the liquid crystal cell.

According to the liquid crystal aligning agent of the present invention, it is possible to obtain a liquid crystal alignment film having good liquid crystal alignability and orientation stability. In addition, the liquid crystal display device comprising the liquid crystal alignment film produced using the liquid crystal aligning agent has various characteristics such as voltage holding ratio and burn-in characteristics.

1 is a view showing a pattern of a transparent electrode patterned in a comb shape.
2 is a view showing a pattern of a transparent electrode patterned in a slit shape.

(Mode for carrying out the invention)

The liquid crystal aligning agent of the present invention contains a polymer component and a specific compound (D) which is multifunctional. Hereinafter, each component contained in the liquid crystal aligning agent of the present invention and other components arbitrarily blended as required will be described.

&Quot; Polymer component &

The polymer component in the present invention is not particularly limited and examples thereof include polyamic acid, polyamic acid ester, polyimide, polyorganosiloxane, poly (meth) acrylate, polyester, polyamide, cellulose derivative, , Polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and the like. Among them, the liquid crystal aligning agent of the present invention is preferably at least one polymer selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane (hereinafter also referred to as &quot; specific polymer &quot;), .

<Polyamic acid>

The polyamic acid in the present invention can be synthesized by, for example, reacting a tetracarboxylic acid dianhydride with a diamine.

[Tetracarboxylic acid dianhydride]

Examples of the tetracarboxylic acid dianhydride used in the synthesis of the polyamic acid in the present invention include aliphatic tetracarboxylic acid dianhydride, alicyclic tetracarboxylic acid dianhydride, and aromatic tetracarboxylic dianhydride. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a, 4, 5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] furan-1,3-dione, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ (Tetrahydrofuran-2 ', 5'-dione), 5- (2,5-dioxotetrahydro-3 ' 3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane 2: 3,5: 6-2 anhydride, 2 , 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4,6,8-2 anhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane- 5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like;

Tetracarboxylic acid dianhydride described in JP-A-2010-97188, and the like can be used. The tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

[Diamine]

Examples of the diamine used in the synthesis of the polyamic acid in the present invention include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoorganosiloxanes, and the like. Specific examples thereof include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine and the like; As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

As the aromatic diamine, there may be mentioned, for example, dodecanoxydiaminobenzene, tetradecanoxydiaminobenzene, pentadecanoxydiaminobenzene, hexadecanoxydiaminobenzene, octadecanoxydiaminobenzene, cholestanyloxydiaminobenzene, (4-aminobenzoyloxy) cholestane, 3,6-bis (4-aminobenzoyloxy) cholestane, diaminobenzoic acid cholestearyl, diaminobenzoic acid lanostanyl, Bis (4 - ((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1- Heptylcyclohexane, 1,1-bis (4 - ((aminophenyl) methyl) phenyl) -4- ( (4-heptylcyclohexyl) cyclohexane, N- (2,4-diaminophenyl) -4-

^Wherein X ¹ and X ² each independently represent a single bond, -O-, -COO- or -OCO-, R ¹ and R ² each independently represent a single bond, A is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and d is 0 or 1, provided that a and b are simultaneously 0 No)

A diamine containing a liquid crystal aligning group such as a compound represented by the formula

p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 4-aminophenyl-4'-aminobenzoate, 1,5-diaminonaphthalene, 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-bis (trifluoromethyl) -4,4'- diaminobiphenyl, 2,7-diaminofluorene, Bis (4-aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 '- (p- phenylenediisopropylidene) bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 2,6-diamino Pyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminoacrylidine, 3,6-diaminocarbazole, N-methyl- N-ethyl-3,6-diaminocarbazole, N- (4-aminophenyl) -N, N'-dimethylbenzidine, 1,4-bis (4-aminophenyl) -Bis- (4-aminophenyl) -piperazine, and other diamines such as 3,5-diaminobenzoic acid;

As the diaminoorganosiloxane, for example, 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like; The diamine described in JP-A-2010-97188 can be used. These diamines can be used singly or in combination of two or more.

Examples of the divalent group represented by "-X ^I - (R ^I -X ^II ) _d -" in the above formula (a-1) include an alkanediyl group having 1 to 3 carbon atoms, * -O-, Or * -OC ₂ H ₄ -O- (provided that a bonding hand having "*" attached thereto is bonded to a diaminophenyl group). Specific examples of the group "-C _c H _{2c +1} " include a methyl group, an ethyl group, an n-propyl group, an n-butyl group, an n-pentyl group, n-heptadecyl, n-heptadecyl, n-octadecyl, n-hexadecyl, n-hexadecyl, n-nonadecyl group, and n-eicosyl 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 each of the following formulas (a-1-1) to (a-1-3).

<Synthesis of polyamic acid>

The polyamic acid can be obtained by reacting the tetracarboxylic acid dianhydride and the diamine as described above together with a terminal endblocking agent, if necessary. The proportion 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, 1.2 equivalent ratio is more preferable.

Examples of the terminal sealing agent include acid anhydrides such as maleic anhydride, phthalic anhydride and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine and n-butylamine, monoamine compounds such as phenylisocyanate and naphthylisocyanate, Isocyanate compounds and the like. The amount of the end-capping agent used is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, based on 100 parts by weight of the total amount of tetracarboxylic acid dianhydride and diamine to be used.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 캜 to 150 캜, more preferably 0 to 100 캜. The reaction time is preferably 0.1 to 24 hours, more preferably 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include non-protic polar solvents, phenol solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons. Among these organic solvents, at least one kind selected from the group consisting of an aprotic polar solvent and a phenol type solvent (first group of organic solvents), or at least one kind selected from an organic solvent of the first group, It is preferable to use a mixture of at least one member selected from the group consisting of ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents of the second group). 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, relative to the total amount of the organic solvent of the first group and the organic solvent of the second group By weight, and more preferably 30% by weight or less.

Particularly preferable examples include N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, Amide, m-cresol, xylenol and halogenated phenol is used as a solvent, or a mixture of at least one of them with another organic solvent is used in the above ratio range desirable.

The amount (a) of the organic solvent used is preferably such that the total amount (b) of the tetracarboxylic acid dianhydride and the diamine is 0.1 to 50 wt% with respect to the total amount (a + b) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution may be directly supplied to the preparation of the liquid crystal aligning agent. Alternatively, the polyamic acid contained in the reaction solution may be isolated and then supplied to the preparation of the liquid crystal aligning agent, or after the isolated polyamic acid is purified, . The polyamic acid can be isolated and purified by a known method.

<Polyamic acid ester>

Examples of the polyamic acid ester in the present invention include: [I] a method of synthesizing a polyamic acid obtained by the above-mentioned synthetic reaction by reacting a hydroxyl group-containing compound, a halide and an epoxy group-containing compound; [II] A method of reacting an acid diester with a diamine, a method of reacting a [III] tetracarboxylic acid diester dihalide with a diamine, and the like.

Examples of the hydroxyl group-containing compound used in the method [I] include alcohols such as methanol, ethanol and propanol; Phenols such as phenol and cresol, and the like. Examples of the halide include methyl bromide, ethyl bromide, stearyl bromide, methyl chloride, stearyl chloride, 1,1,1-trifluoro-2-iodoethane and the like, and the epoxy group-containing compound For example, propylene oxide.

The tetracarboxylic acid diester used in the method [II] can be obtained, for example, by ring opening the tetracarboxylic acid dianhydride exemplified in the synthesis of the above polyamic acid by using the above-mentioned alcohols. The reaction of the method [II] is preferably carried out in the presence of a suitable dehydration catalyst. As the dehydration catalyst, for example, 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) -4-methylmorpholinium halide, carbonylimidazole, . The tetracarboxylic acid diester dihalide used in the method [III] can be obtained, for example, by reacting the tetracarboxylic acid diester obtained as described above with a suitable chlorinating agent such as thionyl chloride.

Examples of diamines used in the method [II] and the method [III] include the diamines exemplified for the synthesis of polyamic acid. In addition, the polyamic acid ester may have only an acid ester structure, or may be a partial ester ester in which an acid structure and an acid ester structure coexist.

<Polyimide>

The polyimide contained in the liquid crystal aligning agent of the present invention can be obtained, for example, by imidizing the polyamic acid synthesized as described above by dehydration ring closure.

The polyimide may be a complete imide cargo which is dehydrated and ring-closed with all of the arboric acid structure possessed by the polyamic acid which is the precursor thereof. The polyimide may be dehydrated and ring-closed only a part of the arboric acid structure to form a partial imide cargo . The polyimide in the present invention preferably has an imidization rate of 30% or more, more preferably 50 to 99%, and further preferably 65 to 99% from the viewpoint of electrical characteristics. The imidization rate is a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by a method of heating a polyamic acid or a method of dissolving a polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, All. Of these, the latter method is preferable.

In the method of adding the dehydrating agent and the dehydrating ring-closing catalyst to the solution of the polyamic acid, an acid anhydride such as acetic anhydride, propionic anhydride, 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. As the dehydration ring-closing 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. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents used for 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.

In this way, a reaction solution containing polyimide is obtained. This reaction solution may be provided as it is in the preparation of a liquid crystal aligning agent, or may be supplied to the preparation of a liquid crystal aligning agent after removing the dehydrating agent and the dehydration ring-closing catalyst from the reaction solution. Alternatively, after the polyimide is isolated, Or may be added to the preparation of a liquid crystal aligning agent after purification of the isolated polyimide. These purification operations can be carried out by a known method.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s and a solution of 15 to 500 mPa · s It is more preferable to have a viscosity. The solution viscosity (mPa 占 퐏) of the polymer is preferably 10 weight% or less by weight, which is prepared by using a good solvent of the polymer (for example,? -Butyrolactone, N-methyl- % Of the polymer solution at 25 占 폚 using an E-type rotational viscometer. The weight average molecular weight of the polyamic acid, the polyamic acid ester and the polyimide in terms of polystyrene measured by gel permeation chromatography is preferably 1,000 to 500,000, more preferably 2,000 to 300,000.

&Lt; Polyorganosiloxane >

The polyorganosiloxane contained in the liquid crystal aligning agent of the present invention may be any as long as it has a siloxane skeleton, and the structure of the side chain portion is not particularly limited. (Hereinafter also referred to as an &quot; epoxy group-containing polyorganosiloxane &quot;) having an epoxy group from the viewpoint of reacting with the group &quot; A ² &quot; of the compound (D) to improve liquid crystal alignability and liquid crystal stability Do. Specific examples of the epoxy group-containing polyorganosiloxane include, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-1), a condensate of the hydrolyzate or a hydrolyzate thereof, and the like:

(In the formula (S-1), X ¹ is a monovalent organic group having an epoxy group and Y ¹ is a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxyl group having 1 to 10 carbon atoms, or an aryl group having 6 to 20 carbon atoms And X ¹ and Y ¹ in the molecule may be the same or different from each other).

The remaining structure of X ¹ in the formula (S-1) is not particularly limited as long as it has an epoxy group, and for example, a group in which an epoxy group is bonded to a chain hydrocarbon, an alicyclic hydrocarbon group or an aromatic hydrocarbon group And the like. Specific preferred examples of X &lt; ¹ &gt; include, for example, groups represented by each of the following formulas (X1-1) to (X1-3)

(Wherein &quot; * &quot; represents a bonding bond with a silicon atom).

In the present specification, the term "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain but consist only of a chain structure. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it need not be composed of only the structure of an alicyclic hydrocarbon, and a part thereof may also have a chain structure. The term &quot; aromatic hydrocarbon group &quot; means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it is not necessarily composed of only an aromatic ring structure, and a part thereof may contain a chain structure or a structure of alicyclic hydrocarbon.

Examples of the alkyl group having 1 to 10 carbon atoms for Y ^{1 in} the formula (S-1) include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, These may be linear or branched. Examples of the alkoxyl group having 1 to 10 carbon atoms for Y ¹ include a group formed by bonding the alkyl group and the oxygen atom, and specific examples thereof include a methoxy group and an ethoxy group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a benzyl group and a tolyl group.

The epoxy equivalent of the epoxy group-containing polyorganosiloxane is preferably 100 to 10,000 g / mole, more preferably 150 to 1,000 g / mole.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the epoxy group-containing polyorganosiloxane is preferably 500 to 100,000, more preferably 1,000 to 10,000, still more preferably 1,000 to 5,000.

<Synthesis of polyorganosiloxane>

The epoxy group-containing polyorganosiloxane as described above can be obtained, for example, by mixing a hydrolyzable silane compound having an epoxy group (an epoxy group-containing silane compound) or a mixture of the silane compound containing the epoxy group and another silane compound, , In the presence of water and a catalyst, by hydrolysis and condensation.

Examples of the epoxy group-containing silane compound include 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3- 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2 - (3,4-epoxycyclohexyl) ethyltriethoxysilane, and the like. The epoxy group-containing silane compounds may be used singly or in combination of two or more.

The other silane compound is not particularly limited as long as it is hydrolyzable and includes, for example, methyltrichlorosilane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrichlorosilane, phenyltrimethoxysilane, methyldichlorosilane, methyl Dimethyldimethoxysilane, dimethyldiethoxysilane, diphenyldichlorosilane, diphenyldimethoxysilane, methoxydimethylsilane, ethoxydimethylsilane, chlorotrimethylsilane, bromotrimethylsilane, iodohexyldimethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, Trimethylsilane, trimethylsilane, methoxytrimethylsilane, ethoxytrimethylsilane, tetramethoxysilane, tetraethoxysilane, octadecyltrichlorosilane, octadecyltrimethoxysilane, vinyltrichlorosilane, vinyltrimethoxysilane, vinyltriethoxysilane, Ethoxysilane, allyltrimethoxysilane, allyltriethoxysilane;

Acrylates such as 3- (meth) acryloxypropyltrichlorosilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 2- Acrylates such as 2- (meth) acryloxyethyltrimethoxysilane, 2- (meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltrichlorosilane, 4- (meth) acryloxybutyltrimethoxysilane (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxybutyltriethoxysilane, 3- (meth) acryloxybutyltrimethoxysilane, 3- (Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxyoxytetramethoxysilane, 3- (meth) acryloxyoxytitrimethoxysilane, 3- (Meth) acryloxydecyltrimethoxysilane, 3- (meth) acryloxydodecyltrimethoxysilane, and the like. have. The other silane compounds may be used singly or in combination of two or more kinds. In addition, "(meth) acryloxy" is meant to include "acryloxy" and "methacryloxy".

In the synthesis of the epoxy group-containing polyorganosiloxane, it is preferable to adjust the ratio of the epoxy group-containing silane compound to the other silane compound so that the epoxy equivalence of the resulting polyorganosiloxane is within the above preferable range.

Examples of the organic solvent which can be used in the synthesis of the polyorganosiloxane include hydrocarbons, ketones, esters, ethers, and alcohols. Examples of the hydrocarbons include toluene, xylene, and the like; Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, cyclohexanone and the like; Examples of the ester include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, ethyl lactate and the like; Examples of the ether include ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like; Examples of the alcohols include 1-hexanol, 4-methyl-2-pentanol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n- , Propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono-n-propyl ether and the like. Of these, it is preferable to use a water-insoluble organic solvent. These organic solvents may be used singly or in combination of two or more.

 The amount of the organic solvent used when synthesizing the polyorganosiloxane is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, based on 100 parts by weight of the total silane compound used in the synthesis. The amount of water used when synthesizing the polyorganosiloxane is preferably 0.5 to 100 times by mole, more preferably 1 to 30 times by mole based on the total amount of the silane compound used in the synthesis.

Examples of the catalyst that can be used in the synthesis of the polyorganosiloxane include an acid, an alkali metal compound, an organic base, a titanium compound, and a zirconium compound. Examples of the acid include hydrochloric acid, sulfuric acid, nitric acid, formic acid, oxalic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid and the like; Examples of the alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like; Examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole, triethylamine, tri-n-propylamine, tri- Tertiary organic amines such as butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene, quaternary organic amines such as tetramethylammonium hydroxide, and the like; Respectively.

As the catalyst, an organic base is particularly preferable. The amount of the organic base to be used differs depending on the kind of the organic base, the reaction conditions such as the temperature and the like, and should be appropriately set. For example, the amount is preferably 0.01 to 3 times by mol, more preferably 0.05 It is ~ 1x mall.

The hydrolysis-condensation reaction in the synthesis of the polyorganosiloxane can be carried out by dissolving one or more kinds of hydrolyzable silane compounds in an organic solvent, mixing the resulting solution with an organic base and water, It is preferable to carry out heating by an oil bath or the like.

In the hydrolysis and condensation reaction, the heating temperature is preferably 130 DEG C or lower, more preferably 40 DEG C to 100 DEG C, preferably 0.5 to 12 hours, and more preferably 1 to 8 hours. During the heating, the mixed solution may be stirred or refluxed.

After completion of the reaction, it is preferable to wash the organic solvent layer collected from the reaction solution with water. At the time of this washing, it is preferable that the cleaning is performed by using water containing a small amount of salt, for example, an aqueous solution of ammonium nitrate of about 0.2 wt%, from the viewpoint of facilitating the cleaning operation. The washing is carried out until the water layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate and molecular sieves, if necessary, and then the solvent is removed to obtain the objective polyorganosiloxane . A commercially available product may also be used as the epoxy group-containing polyorganosiloxane. Examples of such commercially available products include DMS-E01, DMS-E12, DMS-E21 and EMS-32 (manufactured by Chisso Corporation).

As the polyorganosiloxane contained in the liquid crystal aligning agent of the present invention, a compound having a group capable of imparting liquid crystal aligning ability to the coating film (hereinafter also referred to as &quot; liquid crystal aligning group &quot;) can be preferably used. The polyorganosiloxane having a liquid crystal aligning group (hereinafter also referred to as the &quot; aligning group-containing polyorganosiloxane &quot;) may be in a form contained separately from the epoxy group-containing polyorganosiloxane, or may be an epoxy group- Group may be contained in the polyorganosiloxane. Preferably the latter. As specific preferred examples of the polyorganosiloxane containing an oriented group, there may be mentioned, for example, a polyorganosiloxane having a repeating unit represented by the following formula (S-2):

(In the formula (S-2), X ² is a monovalent organic group having a liquid crystal aligning group; Y ¹ has the same meaning as in the formula (S-1)).

The remaining structure of X ² in the formula (S-2) is not particularly limited if it has a liquid crystal aligning group. Specific preferred examples of X &lt; ² &gt; include, for example, groups represented by each of the following formulas (X2-1A) to (X2-3B)

(Wherein R ³ is a liquid crystal aligning group and "*" indicates a bonding bond with a silicon atom).

Examples of the liquid crystal aligning group (R ³ ) include groups capable of imparting pretilt angle characteristics to a coating film (hereinafter also referred to as a &quot; liquid crystal aligning group &quot;) capable of imparting photo- Quot; pretilt angle portion excitation &quot;) and the like.

When the treatment for imparting liquid crystal alignment ability to the coating film is rinsed by the photo alignment method, it is preferable that the coating film contains a polyorganosiloxane having a photo-aligning group. As the photo-alignment group, groups derived from various compounds which exhibit orientation by optical isomerization, photo-dimerization, photodegradation or the like can be adopted, and examples thereof include an azobenzene-containing group containing azobenzene or a derivative thereof as a basic skeleton, Containing group as a basic skeleton, a chalcone-containing group containing a derivative thereof as a basic skeleton, a chalcone-containing group containing a chalcone or a derivative thereof as a basic skeleton, a benzophenone-containing group, coumarin or a derivative thereof A coumarin-containing group contained as a basic skeleton, and the like. Among them, a group having a cinnamic acid structure is preferable in that the photo-alignment property is good and the introduction into a polymer is easy.

The polyorganosiloxane in which R ^{3 in} the formula (S-2) is a photo-orientable group can be obtained, for example, by reacting the epoxy group-containing polyorganosiloxane obtained above with a carbonic acid (C-1) having a photo- have. Preferable examples of the carbonic acid (C-1) include, for example, compounds represented by the following formulas (C1-1) to (C1-3)

(Wherein, R ⁸ and R ¹¹ are, each independently, is a group substituted with at least one hydrogen atom is a fluorine atom or a cyano group in the alkyl group or such a hydrogen atom, an alkyl group having a carbon number of 1~20; R ^6, R ⁷ and R ⁹ are each independently a 1,4-cyclohexylene group or a 1,4-phenylene group, R ¹⁰ is an alkanediyl group having 2 to ¹⁰ carbon atoms, Z ¹ , Z ² , Z ³ , Z ⁴ and Z ⁵ are each independently a single bond, an ether group, a thioether group, an ester group or a thioester group; s, t and u are each independently 0 or 1).

The alkyl group having 1 to 20 carbon atoms represented by R ⁸ and R ¹¹ may be linear or branched, but is preferably straight-chain. Specific preferred examples of the formula (C1-1) include, for example, compounds represented by each of the following formulas (c1-1-1) to (c1-1-10); Specific preferred examples of the formula (C1-2) include, for example, a compound represented by the following formula (c1-2-1); Specific preferred examples of the formula (C1-3) include, for example, compounds represented by the following formula (c1-3-1) and the like:

(Wherein R ⁸ , R ¹⁰ and R ¹¹ have the same meanings as in the formulas (C1-1) to (C1-3)).

Examples of the pretilt angle portion include an alkyl group having 4 to 40 carbon atoms, a fluoroalkyl group having 4 to 40 carbon atoms, an alkoxy group having 4 to 40 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, And the like.

The polyorganosiloxane in which R ^{3 in} the formula (S-2) is a pretilt angle imparting group can be prepared by, for example, reacting the epoxy group-containing polyorganosiloxane obtained above with a carboxylic acid (C-2) having a pretilt angle- . Preferable examples of the carbonic acid (C-2) include, for example, compounds represented by the following formulas (C2-1) to (C2-5)

(Wherein R ²² is an alkyl or fluoroalkyl group having 4 to 20 carbon atoms, R ¹² is a hydrogen atom or an alkyl or fluoroalkyl group having 1 to 20 carbon atoms, R ¹³ and R ¹⁵ are each, independently, Cyclohexylene group or 1,4-phenylene group, R ¹⁴ is a hydrogen atom or a methyl group, R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ each independently represent a hydrogen atom, Z ⁶ , Z ⁷ , Z ⁸ , Z ⁹ , Z ¹⁰ , Z ¹¹ , Z ¹² , Z ¹³ and Z ¹⁴ each independently represent a single bond, an ether group, a thioether An ester group or a thioester group, p is an integer of 0 to 3, q is an integer of 0 to 2, and r is 0 or 1.

The alkyl group of R ²² and R ¹² may be linear or branched, but is preferably straight-chain. Specific preferred examples of the formula (C2-1) include compounds represented by each of the following formulas (c2-1-1) to (c2-1-9); Preferable specific examples of the formula (C2-2) include, for example, compounds represented by each of the following formulas (c2-2-1) to (c2-2-7); Preferable specific examples of the formula (C2-3) include, for example, a compound represented by the following formula (c2-3-1); Preferable specific examples of the formula (C2-4) include, for example, a compound represented by the following formula (c2-4-1); Specific preferred examples of the formula (C2-5) include, for example, compounds represented by the following formula (c2-5-1) and the like:

(Wherein R ²² , R ¹² , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ¹⁹ , R ²⁰ and R ²¹ have the same meanings as in the formulas (C 2-1) to (C 2-5)).

When a vertically aligned liquid crystal display element is produced, it is preferable that the polymer component includes a polyorganosiloxane having a pretilt angle-imparting group. The method for synthesizing the polyorganosiloxane having a pretilt angle-imparting group is not limited to the above. For example, the hydrolytic silane compound having a pretilt angle-imparting group may be synthesized by polymerization including the monomer composition.

As the polyorganosiloxane to be contained in the liquid crystal aligning agent of the present invention, a polyorganosiloxane having a polymerizable unsaturated group may be used. When such a polyorganosiloxane is used, the alignment regulating force of the liquid crystal molecules can be enhanced by the light irradiation treatment after the construction of the liquid crystal cell. Examples of the polymerizable unsaturated group include (meth) acryloyl groups, vinyl groups, and groups having a styryl group. From the viewpoint of good sensitivity to light, among them, a (meth) acryloyl group is preferable . Such a polyorganosiloxane can be obtained, for example, by reacting at least one kind of carboxylic acid represented by each of the above formulas (C2-2) and (C2-5) with an epoxy group-containing polyorganosiloxane.

[Reaction between an epoxy group-containing polyorganosiloxane and a carboxylic acid]

The reaction between an epoxy group-containing polyorganosiloxane and a carboxylic acid having a liquid crystal aligning group (hereinafter also referred to as "carbonic acid (C)") can be preferably carried out in the presence of a catalyst and an organic solvent.

As the carbonic acid to be reacted with the epoxy group-containing polyorganosiloxane, the carbonic acid (C) may be used alone or in combination with other carbonic acid. As the other carbonic acid, for example, a carbonic acid (F) represented by the following formula (f) may be used together with the carbonic acid (C) for the purpose of crosslinking an epoxy group-containing polyorganosiloxane:

(In the formula (f), R ²³ is a tertiary hydrocarbon group having 4 to ²⁰ carbon atoms).

R ²³ in the formula (f) is preferably a group having a tertiary alkyl group or cycloalkane skeleton. Specific examples of R ²³ include groups represented by the following formulas (t-1) and (t-2), respectively:

(T-1), R ⁴¹ , R ⁴² and R ⁴³ are each independently an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms; ⁴⁴ is an alkyl group having 1 to 4 carbon atoms or an alicyclic hydrocarbon group having 4 to 20 carbon atoms of the monovalent, M is ^1, 2, which together with the carbon atom to which the R ⁴⁴ combine to form an alicyclic hydrocarbon having 4 to 20 carbon atoms And &quot; * &quot; represents a bonding hand bonding to an oxygen atom).

The bonding position of the carboxyl group in the formula (f) is preferably a para position.

Specific preferred examples of the carboxylic acid (F) include compounds represented by the following formulas (f-1) and (f-2), respectively. The carbonic acid (F) may be used singly or in combination of two or more.

The proportion of the carboxylic acid (total amount) to be reacted with the epoxy group-containing polyorganosiloxane is preferably 0.001 to 10 moles, more preferably 0.01 to 5 moles, per mole of the epoxy group of the epoxy group-containing polyorganosiloxane More preferably from 0.05 to 2 mol, and particularly preferably from 0.05 to 0.8 mol. In addition, a polyorganosiloxane having a liquid crystal aligning group and an epoxy group can be obtained by lowering the use ratio of the carboxylic acid to that of the epoxy group-containing polyorganosiloxane.

In the case of synthesizing a polyorganosiloxane having a polymerizable unsaturated group, the use ratio (total amount) of the carboxylic acid represented by each of the above formulas (C2-2) and (C2-5) Is preferably from 0.001 to 5 mol, more preferably from 0.01 to 1 mol, and still more preferably from 0.03 to 0.6 mol, per mol of the epoxy group.

When the above-mentioned carbonic acid (F) is used, the use ratio thereof is preferably 0.01 to 1 mol based on 1 mol of the epoxy group. More preferably 0.02 to 0.3 mol, and still more preferably 0.04 to 0.2 mol.

As the catalyst to be used in the reaction, for example, known compounds such as so-called curing accelerators for promoting the reaction of organic bases and epoxy compounds can be used. Examples of the organic base include primary and secondary organic amines such as ethylamine, piperazine and piperidine; Tertiary organic amines such as triethylamine and pyridine; Quaternary organic amines such as tetramethylammonium hydroxide; And the like. As the organic base, a tertiary organic amine or a quaternary organic amine is preferable.

Examples of the curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol; Imidazole compounds such as 2-methylimidazole and 2-n-heptylimidazole; Organic phosphorus compounds such as diphenylphosphine; Quaternary phosphonium salts such as benzyltriphenylphosphonium chloride; Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and its organic acid salts; Organometallic compounds such as zinc octylate, tin octylate and aluminum acetyl acetone complex; Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride and tetra-n-butylammonium chloride; Boron compounds such as boron trifluoride, triphenyl borate; Metal halide compounds such as zinc chloride and stannic chloride; And the like. Of these, quaternary ammonium salts are preferred.

The catalyst is 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 epoxy group-containing polyorganosiloxane.

Examples of the organic solvent that can be used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. Of these, ether compounds, ester compounds and ketone compounds are preferable from the viewpoints of solubility of raw materials and products and ease of purification of the product. Particularly preferred specific examples of the solvent include 2-butanone, 2-hexanone, Butyl ketone, cyclopentanone, cyclohexanone, and butyl acetate. The organic solvent is preferably used in such a ratio that the solid concentration (the ratio of the total weight of the components other than the solvent in the reaction solution to the total weight of the solution) becomes 0.1 wt% or more, preferably 5 to 50 wt% By weight. The reaction temperature is preferably 0 to 200 캜, more preferably 50 to 150 캜. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

The method for synthesizing the orienting polyorganosiloxane is a method for introducing a liquid crystal aligning group by the ring-opening portion of epoxy contained in the epoxy group-containing polyorganosiloxane. This method of synthesis is convenient in that it is simple, and further, the introduction rate of the liquid crystal aligning group can be increased.

The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography of the polyorganosiloxane containing an oriented group is preferably 1,000 to 200,000, more preferably 2,000 to 50,000, and still more preferably 3,000 to 20,000.

&Quot; Compound (D) &quot;

The compound (D) is represented by the following formula (1)

(In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, R ¹ is an organic group of (m + n) N is an integer of 1 to 18, with the proviso that (m + n)? 20 is satisfied.

In the above formula (1), A ¹ is preferably at least one member selected from the group consisting of a (meth) acryloyloxy group, a vinyl group and a styryl group in view of high reactivity with light, More preferably an acryloyloxy group. The (meth) acryloyloxy group is meant to include an acryloyloxy group and a methacryloyloxy group.

Examples of the functional group (A ² ) capable of reacting with the epoxy group include a carboxyl group, a thiol group, a primary amino group, and an epoxy group. Among them, a carboxyl group is preferable in view of high reactivity with an epoxy group.

Examples of the (m + n) organic group represented by R ¹ include a hydrocarbon group such as a chain hydrocarbon group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group, a methylene group in the hydrocarbon group, an ether group, a thioether group, An ester group or a thioester group. The number of carbon atoms of R ¹ is preferably from 1 to 30, more preferably from 3 to 20.

m is preferably from 2 to 10, more preferably from 2 to 8. n is preferably 2 to 18, more preferably 2 to 10, and even more preferably 2 to 8. (m + n) is preferably 4 to 12, more preferably 4 to 10.

The compound represented by the above formula (1) is preferably a compound represented by the following formula (1-1) (hereinafter also referred to as &quot; carbonic acid-containing polyvalent (meth) acrylate &quot;):

(In the formula (1-1), R ² is a hydrogen atom or a methyl group; R ¹ , m and n are the same as in the formula (1)).

Specific examples of the carboxylic acid-containing polyvalent (meth) acrylate include compounds represented by the following formulas (1-1-1) to (1-1-3), and the like:

(In the formulas (1-1-1) to (1-1-3), R ⁴ is a group represented by the following formula (p-1), formula (p-2) or formula (p-3) a plurality of R ⁴ may, be the same or may be different from each other in inside; of the stage, a plurality of R ^4, a group represented by at least one of the expression (p-1), also at least one is a type (p-2) (P-3), and j is an integer of 1 to 10);

(In the formulas (p-1) to (p-3), R ² is a hydrogen atom or a methyl group, and R ³⁰ is an alkanediyl group having 1 to 6 carbon atoms or a phenylene group).

In the above formulas (1-1-1) to (1-1-3), the number of groups (x) represented by the formula (p-1), the group represented by the formula (p- and the number of groups represented by the formula (p-3) (total number y) can be appropriately adjusted in accordance with the type and blending amount of the polymer and additives used. In the case of a liquid crystal display element of the transverse electric field system, x is preferably larger than y in view of the reduction of the burn-in, and in the case of the vertical alignment type liquid crystal display element, the response speed of the liquid crystal molecules is increased.

As the compound (D), a commercially available product may be used, or a compound obtained by synthesis may be used. Examples of commercially available products of the compound (D) include trade names "TO-2349" and "TO-1382" manufactured by Toagosei Co.,

When the compound (D) is synthesized, the synthesis method thereof is not particularly limited, and the organic chemistry can be appropriately combined. Examples of the carboxylic acid-containing polyfunctional (meth) acrylate represented by the formula (1-1) include [1] a polyfunctional (meth) acrylate compound having a hydroxyl group and an acid such as succinic anhydride A method of reacting an anhydride (corresponding to the following reaction formula (I)); (2) A method of reacting a polyfunctional (meth) acrylate compound with a carbonic acid having a thiol group (Michael addition) (corresponding to the following reaction formula (II)):

(Wherein R ¹ , R ² , m and n are as defined in the above formula (1-1), and R ³⁰ is an alkanediyl group having 1 to 6 carbon atoms or a phenylene group).

The compounding ratio of the compound (D) is preferably 1 to 30 parts by weight based on 100 parts by weight of the entire polymer component in the liquid crystal aligning agent. When the amount is 1 part by weight or more, the effect of improving the liquid crystal alignability and orientation stability can be sufficiently obtained. When the amount is 30 parts by weight or less, defective alignment of the liquid crystal alignment can be suppressed. More preferably 3 to 25 parts by weight, and still more preferably 5 to 20 parts by weight. The compound (D) may be used singly or in combination of two or more.

«Other ingredients»

The liquid crystal aligning agent of the present invention may contain other components as required. Specific examples of such other components include, for example, a compound having two or more epoxy groups in the molecule as a compound not corresponding to the compound (D) (hereinafter also referred to as an &quot; epoxy group-containing compound &quot;), (Hereinafter also referred to as &quot; polyvalent carboxylic acid &quot;), and the like.

<Epoxy group-containing compound>

The epoxy group-containing compound can be used for the purpose of improving the adhesion of the liquid crystal alignment film to the substrate surface. Specific examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl Diethyl ether, trimethylol propane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N N, N ', N'-tetramethyldiphenylmethane, N, N', N'-tetraglycidyl-p-phenylenediamine, , N'-tetraglycidyl-4,4'-diaminodiphenyl ether, N, N, N ', N'-tetraglycidyl-2,2'-dimethyl-4,4'- Phenyl, trimethylolpropane triglycidyl ether, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane , N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N, N-diglycidyl- N, N, N ', N'-tetraglycidyl-1,4-diaminocyclohexane, bis (N, N-dimethylaminocyclohexane) (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N, N-diglycidylaminomethyl) cyclohexane, Benzene, 1,3,5-tris (N, N-diglycidylaminomethyl) cyclohexane, the following formulas (e-1) to (e-3)

And the like. In addition, an epoxy group-containing polyorganosiloxane described in WO 2009/096598 can also be used.

When the epoxy group-containing compound is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent.

<Polyvalent Carbonic Acid>

The polyvalent carboxylic acid can be used for the purpose of improving the liquid crystal alignment property of the liquid crystal alignment film. Specific examples of the polyvalent carboxylic acid include dicarboxylic acids such as fumaric acid, malonic acid, adipic acid, terephthalic acid, isophthalic acid, sebacic acid, diphenyl ether-4,4'-dicarboxylic acid and pyridine- Native mountain; Tricarboxylic acids such as 1,2,4-butanetricarboxylic acid, 1,2,3-cyclohexanetricarboxylic acid, trimellitic acid and 1,2,4-naphthalenetricarboxylic acid; Tetracarboxylic acids such as 1,2,3,4-cyclobutane tetracarboxylic acid, 2,3,5-tricarboxycyclopentylacetic acid, cyclopentanetetracarboxylic acid, cyclohexanetetracarboxylic acid, and pyromellitic acid. have.

When the polybasic carboxylic acid is added to the liquid crystal aligning agent, the blending ratio thereof is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight per 100 parts by weight of the total amount of the polymers contained in the liquid crystal aligning agent.

As the other components, for example, a compound having a functional silane compound, a compound having one epoxy group in the molecule, a compound having at least one oxetanyl group in the molecule, a bismaleimide compound, an antioxidant, a photosensitizer, etc. . The blending amount of these other components can be appropriately adjusted within a range not to impair the effect of the present invention.

As a preferred form of the liquid crystal aligning agent of the present invention,

(I) an embodiment comprising only one kind selected from the group consisting of polyamic acid, polyamic acid ester and polyimide;

(II) a mode comprising a polyorganosiloxane and one kind selected from the group consisting of polyamic acid, polyamic acid ester and polyimide;

(III) a mode comprising only a polyorganosiloxane;

And the like.

Of these, the above-mentioned (II) is preferred, and in the above (II), the polyorganosiloxane is more preferably an epoxy group-containing polyorganosiloxane. The mixing ratio of the polyorganosiloxane in the above (II) is preferably 1 to 30 parts by weight, more preferably 5 to 20 parts by weight per 100 parts by weight of the total of polyamic acid, polyamic acid ester and polyimide .

When a liquid crystal display device is produced by introducing a polymerizable component into an alignment film and irradiating light to the liquid crystal cell after the formation of the liquid crystal cell, at least a part of the polymer component of the liquid crystal aligning agent is polymerized Group in the side chain is preferably blended. The polymer having a polymerizable unsaturated group in the side chain is preferably at least one member selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, more preferably polyorganosiloxane. Particularly, in the aspect of the above (II), the polyorganosiloxane having a polymerizable unsaturated group is suitable because it can obtain an effect of improving the liquid crystal alignability with a small light irradiation dose.

«Solvent»

The liquid crystal aligning agent of the present invention is constituted by dissolving the polymer component, the compound (D) and optionally other components optionally mixed in an organic solvent.

Examples of the solvent used in the preparation of the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, Propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol diisopropyl ether, diethylene glycol diisopropyl ether, Ethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether Tate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di-isopentyl 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 is heated to form a coating film which becomes a liquid crystal alignment film or a liquid crystal alignment film. When the solid concentration is less than 1 wt% , The film thickness of this coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by weight, the film thickness of the coating film becomes excessively large, so that a good liquid crystal alignment film can not be obtained and the viscosity of the liquid crystal aligning agent is increased and the coating property is 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 wt%. In the case of the printing method, it is particularly preferable that the solid concentration is in the range of 3 to 9 wt%, and the solution viscosity is in the range of 12 to 50 mPa · s accordingly. 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 accordingly, the solution viscosity is in the range of 3 to 15 mPa · s. The temperature for preparing the liquid crystal aligning agent is preferably 10 to 50 캜, more preferably 20 to 30 캜.

<< Liquid Crystal Alignment Film and Liquid Crystal Display Device >>

The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Further, the liquid crystal display element of the present invention comprises a liquid crystal alignment film formed using the liquid crystal aligning agent. The operation mode to which the liquid crystal display element of the present invention is applied is not particularly limited and can be applied to various operation modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type and the like. The liquid crystal display element of the present invention can be produced, for example, by a method including the following steps (1) to (3).

[Process (1): Formation of coating film]

First, a liquid crystal aligning agent is applied to each surface of a pair of substrates, followed by heating to form a coating film.

(1-1) In the case of producing a liquid crystal display device of TN type, STN type, VA type or MVA type, two substrates on which a patterned transparent conductive film is formed are paired, The liquid crystal aligning agent of the present invention is preferably applied on the film formation side by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method, respectively. 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, and poly (alicyclic olefin) can be used. As the transparent conductive film to be formed on one surface of the substrate, an ITO film made of NESA film (a registered trademark of PPG Corporation of the US) or indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) made of tin oxide (SnO ₂ ) . In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photoetching after forming a patternless transparent conductive film, a method of using a mask having a desired pattern in forming a transparent conductive film, and the like . In the application of the liquid crystal aligning agent, a functional silane compound, a functional titanium compound or the like is added to the surface of the substrate surface on which the coating film is to be formed in advance in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film It is also possible to carry out the pre-treatment for applying the coating.

(1-2) In the case of manufacturing an IPS or FFS type liquid crystal display element, the electrode formation surface of the substrate on which the electrode made of the transparent conductive film or the metal film patterned in the comb shape is formed, The liquid crystal aligning agent of the present invention is applied to one side of the substrate, and then each coated side is heated to form a coated film. The preferable thicknesses of the coating film to be formed and the material of the substrate, the material of the transparent conductive film, the coating method, the heating conditions after coating, the method of patterning the transparent conductive film or metal film, the pretreatment of the substrate, same. As the metal film, for example, a film made of a metal such as chromium can be used.

In any of the cases (1-1) and (1-2), a coating film serving as a liquid crystal alignment film or a liquid crystal alignment film is formed by applying a liquid crystal aligning agent on a substrate and then removing the organic solvent. The removal of the solvent is preferably performed by heat treatment. Concretely, after application of the liquid crystal aligning agent, preheating (prebaking) is preferably carried out for the purpose of preventing liquid leakage of the applied alignment agent. The prebaking temperature is preferably 30 to 200 캜, more preferably 40 to 150 캜, particularly preferably 40 to 100 캜. The prebaking time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, for the purpose of completely removing the solvent, a firing (post-baking) step is carried out for the purpose of thermally modifying the acid structure present in the polymer, if necessary. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 占 폚, more preferably 120 to 250 占 폚. The post baking time is preferably 5 to 200 minutes, and more preferably 10 to 100 minutes. In this way, the film thickness of the film to be formed is preferably 0.001 to 1 占 퐉, and more preferably 0.005 to 0.5 占 퐉.

When the polymer contained in the liquid crystal aligning agent of the present invention is a polyamic acid, a polyamic acid ester, or an imidized polymer having an imidazole ring structure and an arboric acid structure, the dehydration ring-closure reaction is advanced by further heating after formation of the coating film , Or a more imaged coating film may be used.

[Orientation-imparting treatment]

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, a treatment for imparting a liquid crystal aligning ability to a coating film formed in the above step (1) is usually carried out. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the treatment for imparting the orientation function include a rubbing treatment in which the coating film is rubbed in a predetermined direction by a roll formed of fibers such as nylon, rayon, and cotton, and a treatment by a photo alignment method. Of these, it is preferable to use the photo alignment method in that it is possible to suppress the occurrence of defective display and lowering the yield due to dust and static electricity, and that the liquid crystal aligning ability can be uniformly imparted to the coating film. On the other hand, in the case of producing a VA type liquid crystal display device, the coating film formed in the above step (1) can be directly used as a liquid crystal alignment film, but the coating film may be subjected to the above treatment.

In addition, it is also possible to apply a treatment for changing the pretilt angle of a part of the liquid crystal alignment film by irradiating a part of the liquid crystal alignment film to the rubbed liquid crystal alignment film, or a process for forming a resist film on a part of the surface of the liquid crystal alignment film, After the rubbing treatment is performed in a direction different from the rubbing treatment, a treatment for removing the resist film may be performed so that the liquid crystal alignment film has a liquid crystal aligning ability different for each region. In this case, it is possible to improve the visual field characteristic of the obtained liquid crystal display element.

In the photo alignment method, a coating film formed on a substrate is irradiated with polarized light or non-polarized radiation to impart a liquid crystal alignment capability to the coating film. As the radiation, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. When the radiation to be used is linearly polarized light or partial polarized light, the irradiation may be performed in a direction perpendicular to the substrate surface, in an oblique direction, or in combination thereof. In the case of irradiating non-polarized radiation, the irradiation direction is set to an oblique direction.

As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. The ultraviolet ray in the preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter, a diffraction grating, or the like.

The light irradiation is carried out by a method of irradiating a coating film after the post-baking step, a method of irradiating the coating film before the post-baking step after the pre-baking step, a method of irradiating the coating film during heating of the coating film in at least one of the pre- And the like. The irradiation amount of light is preferably 100 to 50,000 J / m 2, and more preferably 300 to 20,000 J / m 2. The light irradiation to the coating film may be performed while heating the coating film to enhance the reactivity. The temperature at the time of heating is usually 30 to 250 占 폚, preferably 40 to 200 占 폚, and more preferably 50 to 150 占 폚. By this light irradiation treatment, a liquid crystal alignment film is formed on the substrate.

[Process (2): Construction of cell]

(2-1) Two substrates (one pair) on which a liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is prepared in which the pair of substrates are arranged so that the liquid crystal alignment film faces the liquid crystal. To produce a liquid crystal cell, for example, the following two methods can be used. First, the first method is a conventionally known method. In this method, two substrates are opposed to each other via a gap (cell gap) so that each liquid crystal alignment film is opposed to each other, and the peripheral portions of the two substrates are bonded to each other using a sealant, Liquid crystal is injected and filled in the cell gap defined by the liquid crystal cell, and then the injection port is sealed to manufacture a liquid crystal cell. The second method is a so-called ODF (One Drop Fill) method. In this method, for example, an ultraviolet curable sealant is applied to a predetermined place on one of the two substrates on which the liquid crystal alignment film is formed, and further liquid crystal is dropped to a predetermined number of places on the liquid crystal alignment film surface Then, the other substrate is bonded so that the liquid crystal alignment film faces the other substrate. Then, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. In either case, it is preferable that the liquid crystal cell manufactured as described above is further heated to a temperature at which the liquid crystal used is isotropic, and then gradually cooled to room temperature to remove the flow alignment at the time of filling the liquid crystal . As the sealing agent, for example, an epoxy resin containing a curing agent and an aluminum oxide spheres as a spacer can be used. The thickness of the liquid crystal layer is preferably 1 to 5 mu m.

 (2-2) In the case of producing a liquid crystal display element of the PSA system, a liquid crystal cell is constructed in the same manner as in the above (2-1) except that a photopolymerizable compound is injected or dropped together with a liquid crystal.

[Process (3): light irradiation on liquid crystal cell]

After the formation of the liquid crystal cell, the liquid crystal cell is irradiated with light from the outside. It is possible to stabilize the liquid crystal alignment by storing the direction in which the liquid crystal molecules are tilted by this light irradiation. In the light irradiation for the liquid crystal cell, in the liquid crystal display device of the past system, in a state in which voltage is applied between the conductive films of the pair of substrates, in the liquid crystal display device of the transverse electric field system, I do. The voltage to be applied here may be DC or AC of 5 to 50 V, for example. As the light to be irradiated, for example, ultraviolet rays and visible rays including light having a wavelength of 150 to 800 nm can be used, but ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. As the light source of the irradiation light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. The ultraviolet ray in the above-mentioned preferable wavelength range can be obtained by a means for using the light source together with, for example, a filter diffraction grating or the like. The irradiation dose of light is preferably 1,000 J / m 2 or more and less than 200,000 J / m 2, and more preferably 1,000 to 100,000 J / m 2.

The liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called an "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate comprising a H film itself have. When the coating film is subjected to the rubbing treatment, the two substrates are opposed to each other such that the rubbing directions of the coating films are at a predetermined angle, for example, orthogonal or anti-parallel to each other.

The liquid crystal display device of the present invention can be effectively applied to various devices and can be applied to various devices such as a clock, a portable game, a word processor, a notebook computer, a car navigation system, a camcorder, a PDA, Phones, various monitors, liquid crystal televisions, information displays, and the like.

(Example)

Hereinafter, the present invention will be described more specifically by way of examples, but the present invention is not limited to these examples.

The solution viscosity, the imidization rate of the polyimide, the weight average molecular weight of the polymer and the epoxy equivalent of each polymer solution in the synthesis examples were measured by the following methods.

[Solution viscosity of polymer solution]

The solution viscosity [mPa 占 퐏] of the polymer solution was measured at 25 占 폚 using an E-type rotational viscometer for a solution prepared by using a predetermined solvent at a polymer concentration of 10% by weight.

[Imidization Rate of Polyimide]

The polyimide solution was poured into pure water, and the obtained precipitate was sufficiently dried under reduced pressure at room temperature, then dissolved in deuterated dimethyl sulfoxide, and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was obtained from the formula shown in the following formula (1): &lt; EMI ID =

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

(In the formula (1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and? Is the peak area derived from the proton The ratio of the number of other protons to one proton in the NH group).

[Weight average molecular weight of polymer]

The weight average molecular weight Mw of the polymer is a polystyrene reduced value measured by gel permeation chromatography under the following conditions.

Column: TSKgelGRCXLII manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Epoxy equivalent]

The epoxy equivalent is a value measured in accordance with the "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

The following synthesis examples were repeated with the following synthesis scales, if necessary, to obtain the necessary amounts of products used in the following Synthesis Examples, Examples and Comparative Examples.

&Lt; Synthesis of Compound (D) >

[Synthesis Example 1: Synthesis of compound (1-2-1)] [

Compound (1-2-1) was synthesized according to Reaction Scheme 1 below.

To a 100 mL three-necked flask equipped with a thermometer, reflux tube and dropping funnel were added 6.24 g of the compound (1-2 A), 8.64 g of acetonitrile, 6 mg of 2,6-di-t-butyl-4-methoxyphenol, 2.40 g of captoppropionic acid was added and heated to 50 캜. Subsequently, 6.07 g of triethylamine was added dropwise over 1 hour, and the mixture was allowed to react at 50 DEG C for 1 hour. After completion of the reaction, 100 mL of ethyl acetate was added, and the mixture was washed once with 100 mL of 1M oxalic acid water and 5 times with water, and then subjected to solvent substitution twice with butyl cellosolve to obtain a compound having a solid concentration of 20 wt% -1) of butyl cellosolve solution.

[Synthesis Example 2: Synthesis of compound (1-3-1)] [

Compound (1-3-1) was synthesized according to Reaction Scheme 2 below.

12.2 g of the compound (1-3 A), 15.8 g of acetonitrile, 12 mg of 2,6-di-t-butyl-4-methoxyphenol and 12.2 g of mercuric acid were added to a 100 mL three-necked flask equipped with a thermometer, 3.61 g of mercaptopropionic acid was added and heated to 50 占 폚. Subsequently, 6.07 g of triethylamine was added dropwise over 1 hour, and the mixture was allowed to react at 50 DEG C for 1 hour. After completion of the reaction, 100 mL of ethyl acetate was added, washed once with 100 mL of 1M oxalic acid water and 5 times with water, and then subjected to solvent substitution twice with butyl cellosolve to obtain a compound having a solid content concentration of 20 wt% -1) of butyl cellosolve solution.

<Synthesis of polyorganosiloxane>

Synthesis Example 3: Synthesis of epoxy group-containing polyorganosiloxane (EPS-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 mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with an aqueous 0.2 wt% ammonium nitrate solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain a polyorganosiloxane (EPS-1) As a viscous transparent liquid.

As a result of ¹ H-NMR analysis of the polyorganosiloxane (EPS-1), a peak based on an oxiranyl group was obtained in the vicinity of a chemical shift (?) = 3.2 ppm as a theoretical intensity, (Secondary) reaction was not taking place. The polyorganosiloxane (EPS-1) had an Mw of 2,200 and an epoxy equivalent of 186 g / mol.

[Synthesis Example 4: Synthesis of epoxy group-containing polyorganosiloxane (EPS-2)] [

To a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel and a reflux condenser, 458.7 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 162.8 g of 3-methacryloxypropyltrimethoxysilane, 3108 g of isobutyl ketone, and 62.2 g of triethylamine were placed and mixed at room temperature. Subsequently, 621.5 g of deionized water was added dropwise from the dropping funnel over 30 minutes, and the mixture was reacted at 80 DEG C for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out, washed with a 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 polyorganosiloxane (EPS-2) As a viscous transparent liquid. The weight average molecular weight Mw of this polyorganosiloxane (EPS-2) was 2,900.

[Synthesis Example 5: Synthesis of carbonic acid (3-6-1) containing liquid crystal aligning group]

Carbonic acid (3-6-1) was synthesized according to Reaction Scheme 3 below.

Synthesis of compound (3-6-1A)

24.4 g (0.2 mol) of p-hydroxybenzaldehyde, 138.2 g (1.0 mol) of potassium carbonate and 600 mL (MS dried) of acetone were placed in a 2 L eggplant-shaped flask equipped with a reflux condenser, 32.6 g (0.22 mol) of bromobutyronitrile was added and the mixture was refluxed for 3 hours. After completion of the reaction, 1 L of ethyl acetate was added, and the mixture was washed with 1 L of water, then washed twice with 200 mL of saturated sodium carbonate aqueous solution, and further washed with 300 mL of water three times. Next, after the organic layer was dried with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain 35.5 g of a yellow transparent liquid of the compound (3-6-1A).

Synthesis of compound (3-6-1)

35.5 g (0.188 mol) of the compound (3-6-1A), 224 mL of pyridine and 39.13 g (0.376 mol) of malonic acid were dissolved in a 1000 mL three-necked flask equipped with a reflux condenser, a thermometer and a nitrogen inlet tube. Next, 16.0 g (0.188 mol) of piperidine was added and refluxed for 3 hours. After completion of the reaction, 800 mL of ethyl acetate and 800 mL of THF were added, and the mixture was washed once with 1 L of 2N hydrochloric acid and twice with 1N hydrochloric acid, and then 1.5 L of saturated sodium carbonate was added and washed twice with 400 mL of ethyl acetate . Next, 400 mL of ethyl acetate and 800 mL of THF were added, acidified with 8N hydrochloric acid water (500 mL), washed with 400 mL of water three times, dried with magnesium sulfate, concentrated and precipitated to give carbonic acid (3-6-1 ) Of white crystals (25.2 g).

[Synthesis Example 6: Synthesis of carbonic acid (3-9-1) containing liquid crystal aligning group]

20 g of 4-bromodiphenyl ether, 0.18 g of palladium acetate, 0.98 g of tris (2-tolyl) phosphine, 32.4 g of triethylamine and 135 mL of dimethylacetamide were added to a 500 mL three-necked flask equipped with a cooling tube, , As a solution. Next, 7 g of acrylic acid was added to the solution using a syringe and stirred, followed by reaction at 120 ° C for 3 hours under stirring. After completion of the reaction was confirmed by thin layer chromatography (TLC), the reaction solution was cooled to room temperature. The insoluble matter was separated by filtration, and the filtrate was poured into 300 mL of 1N hydrochloric acid to recover the precipitate. This precipitate was recrystallized from a mixed solvent of ethyl acetate and hexane (ethyl acetate: hexane = 1: 1 (volume ratio)) to obtain the compound represented by the following formula (3-9-1) ).

[Synthesis Example 6-1: Synthesis of carbonic acid (F-2)] [

Carbonic acid (F-2) was synthesized according to the following reaction formula.

· Synthesis of Compound (F-2D)

21.6 g of monomethyl terephthalate, 88 mL of thionyl chloride and 5 drops of N, N-dimethylformamide were added to a 200 mL eggplant-shaped flask equipped with a stirrer, a reflux condenser and a nitrogen inlet tube, and refluxed at 80 ° C for 1 hour. After completion of the reaction, thionyl chloride was distilled off under reduced pressure in an aspirator to obtain a pale yellow solid of the compound (F-2B). 50 mL of tetrahydrofuran was added to the solid to obtain Solution A. On the other hand, 13.7 g of 1-ethylcyclopentanol was added to a 500-mL three-necked flask equipped with a thermometer, a nitrogen inlet tube, and a dropping funnel. Subsequently, 90 mL of 1.6 M n-butyllithium hexane solution was added dropwise over 30 minutes. Then, the solution A was added dropwise over 30 minutes, and the mixture was stirred under ice-cooling, and after 2 hours, 100 mL of water was added to stop the reaction. Next, 400 mL of ethyl acetate was added and the mixture was washed with 400 mL of water four times, and then concentrated to dryness to obtain 32.8 g of an orange liquid of the compound (F-2D).

Synthesis of Compound (F-2)

32.8 g of the compound (F-2D), 150 mL of methanol, 50 mL of water and 9.95 g of lithium hydroxide monohydrate were placed in a 1 L eggplant-shaped flask and reacted at room temperature for 1 hour. After completion of the reaction, 250 mL of tetrahydrofuran and 300 mL of ethyl acetate were added, and the mixture was washed once with 400 mL of diluted hydrochloric acid and three times with 300 mL of water. Dried over magnesium sulfate, concentrated, and hexane was added to precipitate crystals. The precipitated crystals were collected by filtration and dried to obtain 14.1 g of yellow needle-like crystals of the compound (F-2).

[Synthesis Example 7: Synthesis of polyorganosiloxane (S-2-1) containing an oriented group]

3.5 g of the polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 24 g of methyl isobutyl ketone, 2.42 g of carbonic acid (3-6-1) (polyorganosiloxane ( (Equivalent to 50 mol% based on the silicon atoms of the epoxy resin (EPS-1)) and 0.35 g of trade name "UCAT 18X" (curing accelerator of epoxy compound manufactured by SANA PROS Co., Ltd.) were charged and refluxed for 5 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the resulting solution was dissolved in ethyl acetate. The resulting solution was washed three times with water and then the solvent was distilled off to obtain a polyorganosiloxane (S-2-1 ) Of white powder. The weight average molecular weight of the polyorganosiloxane (S-2-1) was 9,200.

[Synthesis Examples 8 to 10 and 10A: Synthesis of polyorganosiloxane containing an oriented group]

(S-2-2) to (S-2-4), (S-2-2) to (S-2-4) were obtained in the same manner as in Synthesis Example 7, except that the kinds and amounts of the compounds used were changed as shown in Table 1 below. S-2-10) was synthesized.

In Table 1, the numerical value of the amount of the carbonic acid to be added represents the amount [mol%] of the epoxy group-containing polyorganosiloxane to the silicon atom.

[Synthesis Example 11: Synthesis of polyamic acid (PA-1)] [

5.55 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 9.45 g of a diamine compound represented by the following formula (3-7DA) were dissolved in 85 g of N-methyl-2-pyrrolidone (NMP) The reaction was carried out for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 10 g of polyamic acid (PA-1).

Synthesis Example 12: Synthesis of polyamic acid (PA-2)

19.61 g (0.1 mole) of cyclobutanetetracarboxylic dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'-dimethylbiphenyl were added to 367.6 g of N-methyl- And the reaction was carried out at room temperature for 6 hours. The reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 35 g of polyamic acid (PA-2).

[Example 1]

(1) Preparation of liquid crystal aligning agent

100 parts by weight of polyorganosiloxane (S-2-1) and 1,000 parts by weight of polyamic acid (PA-2) as a polymer component, TO- (NMP) and butyl cellosolve (BC) as a solvent were added to 100 parts by weight of a solvent A solution having a composition of NMP: BC = 50: 50 (weight ratio) and a solid content concentration of 3.0 wt%. This solution was filtered with a filter having a pore diameter of 0.2 탆 to prepare a liquid crystal aligning agent (A-1).

(2) Production of transverse electric field type liquid crystal display device

A glass substrate having two systems of metal electrodes of chromium patterned in a comb shape and having one side and a counter glass substrate on which no electrode is formed are made to be a pair and a side having an electrode of the glass substrate and a side , The liquid crystal aligning agent (A-1) prepared above was coated with a spinner, prebaked on a hot plate at 80 DEG C for 1 minute, and then heated in an oven where the inside of the tube was replaced with nitrogen at 200 DEG C for 1 hour Post baking) to form a coating film having a thickness of 0.1 mu m. Fig. 1 shows a schematic diagram showing the electrode pattern configuration on the glass substrate. Two metal electrodes (conductive film patterns) of the transverse electric field type liquid crystal display element are hereinafter referred to as electrode 11 and electrode 12, respectively.

Subsequently, polarizing ultraviolet rays of 300 J / m &lt; 2 &gt; including a bright line of 313 nm were irradiated from the normal direction of the substrate using a Hg-Xe lamp and a Glane Taylor prism on the surface of these coating films to obtain a pair of substrates having a liquid crystal alignment film. A bead spacer was sprayed on one surface of the substrate having the liquid crystal alignment film, and an epoxy resin adhesive containing an aluminum oxide sphere having a diameter of 5.5 mu m was further coated on the outer periphery by screen printing. Thereafter, the surfaces of the liquid crystal alignment layers on the respective substrates of the pair of substrates were opposed to each other so that the directions of the substrates when the polarized ultraviolet rays were irradiated were opposite to each other and pressed, and the adhesive was heated at 150 DEG C for 1 hour Cured.

Subsequently, a liquid crystal mixture obtained by adding 0.3 wt% of a polymerizable liquid crystal represented by the following formula (L-1) to a liquid crystal "MLC-7028" manufactured by Merck Ltd. was charged in the gap between the substrates from the liquid crystal injection port, The injection port was sealed. Thereafter, in order to remove the flow orientation at the time of liquid crystal injection, it was heated at 150 占 폚 and gradually cooled to room temperature. Further, UV light irradiation (irradiation amount: 2,000 mJ / cm2 (? = 365 nm) ). Next, a polarizing plate was bonded to both outer sides of the substrate so that the polarizing directions thereof were orthogonal to each other and the optical axis of the polarized ultraviolet ray of the liquid crystal alignment film was orthogonal to the projection direction to the substrate surface.

(3) Evaluation of liquid crystal orientation

With respect to the liquid crystal display device manufactured as described above, the presence or absence of an abnormal domain in a change of light and dark when a voltage of 5 V was turned on / off (applied / released) was observed by an optical microscope. In this case, the case where no abnormal domains were observed was evaluated as &quot; excellent &quot; in the liquid crystal orientation, the case where the abnormal domains were observed slightly and the case where the abnormal domains were observed at a plurality of locations were evaluated as & . As a result, in Example 1, the liquid crystal alignment property was &quot; positive &quot;.

(4) Evaluation of burn-in characteristics

The transverse electric field type liquid crystal display device manufactured as described above was placed under an environment of 25 占 폚 and 1 atmospheric pressure and a voltage of 3.5 V AC and 5 V DC voltage was applied to the electrode 11 for 2 hours " Immediately thereafter, a voltage of 4 V of alternating current was applied to both the electrode 11 and the electrode 12. The time from when the application of the voltage of 4 V of alternating current to both the electrodes to when the difference in light transmittance between the electrode 11 and the electrode 12 becomes impossible to visually confirm was measured. The burn-in characteristic is &quot; acceptable &quot; when the burn-in characteristic is &quot; excellent &quot;, the burn-in characteristic is &quot; good &quot; Sec, the burn-in property was evaluated as &quot; defective &quot;. As a result, in Example 1, the burn-in property was &quot; good &quot;.

[Examples 2 to 20, Comparative Examples 1 and 2]

The liquid crystal aligning agents (A-2) to (A-20) and (A-20) were obtained in the same manner as in Example 1 except that the types and amounts of the polymer, the compound R-1) and (R-2) were prepared. Using the obtained liquid crystal aligning agents (A-2) to (A-20), (R-1) and (R-2), liquid crystal display devices were produced in the same manner as in Example 1, And burn-in characteristics were evaluated. The results are shown in Table 3 below.

In Table 2, numerical values in parentheses indicate compounding ratio (parts by weight) of each compound. Carboxylic acid-containing polyfunctional acrylates (trade names: TO-1382 and TO-2349) of Compound (D) were obtained from Toagosei Co., The abbreviations of the compounds (D) and other components in Table 2 are as follows.

(Compound (D))

D-1: Compound represented by the formula (1-2-1)

D-2: The compound represented by the above formula (1-3-1)

(Other additives)

EP-1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

As shown in Table 3, all of the liquid crystal display devices of Examples 1 to 20 were evaluated as "excellent" or "good" in liquid crystal alignability and burn-in characteristics. In contrast, in Comparative Examples 1 and 2 in which the compound (D) was not contained in the liquid crystal aligning agent, the liquid crystal alignability was evaluated as "poor" and the burn-in characteristics were evaluated as "possible".

[Synthesis Example 13: Synthesis of carbonic acid (7-3-1) containing liquid crystal aligning group]

Carbonic acid (7-3-1) was synthesized according to Reaction Scheme 4 below.

Synthesis of compound (7-3-1A)

(36.22 mmol) of hydroxybenzoic acid, 150 mL of tetrahydrofuran, 100 mL of t-butanol, and 0.177 g (1.45 g) of N, N-dimethylaminopyridine were placed in a 1 L three-necked flask equipped with a thermometer, lt; / RTI &gt; Next, 8.22 g (39.84 mmol) of dicyclohexylcarbodiimide was dissolved in 50 mL of tetrahydrofuran and added dropwise over 30 minutes to the dropping funnel, and the mixture was allowed to react for 15 hours. After completion of the reaction, the filtrate was subjected to Celite filtration. The resulting filtrate was concentrated, and 300 mL of ethyl acetate was added. The mixture was washed with an aqueous solution of sodium hydrogencarbonate twice and three times with water, followed by concentration and vacuum drying to obtain an isochromic viscous liquid . This viscous liquid was purified by silica column purification (developing solvent: hexane / ethyl acetate = 80/20) to obtain 3.6 g of a white crystal of the compound (7-3-1A).

Synthesis of compound (7-3-1B)

12.5 g (63.1 mmol) of the compound (7-3-1A), 16.64 g (66.2 mmol) of 11-bromododecanol and 16.64 g (66.2 mmol) of N, N-dimethylacetamide were placed in a 500 mL three-necked flask equipped with a thermometer and a nitrogen- Acetamide, 9.58 g (69.4 mmol) of potassium carbonate and 2.09 g (12.6 mmol) of potassium iodide were added, and the mixture was reacted at 100 DEG C for 2 hours. After completion of the reaction, 500 mL of ethyl acetate was added, and the mixture was washed once with diluted hydrochloric acid and three times with water, dried with magnesium sulfate, concentrated and dried to obtain 21.3 g of a white solid of the compound (7-3-1B).

Synthesis of compound (7-3-1D)

16.48 g (58.4 mmol) of the compound (7-3-1C), 21.3 g (58.4 mmol) of the compound (7-3-1B) and 440 mL (methylene chloride) were added to a 1 L three- Was added, suspended, and ice-cooled. Next, 13.47 g (70.3 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride and 1.43 g (11.7 mmol) of N, N-dimethylaminopyridine were added and stirred for 2 hours under ice- Thereafter, the mixture was returned to room temperature and allowed to react for 16 hours. After completion of the reaction, 2 L of ethyl acetate was added, and the mixture was washed three times with water, followed by drying with magnesium sulfate. Next, the white precipitate formed by concentration was filtrated and dried to obtain 26.0 g of white crystals of the compound (7-3-1D).

· Synthesis of carbonic acid (7-3-1)

26.0 g (41.3 mmol) of the compound (7-3-1D), 55 mL of trifluoroacetic acid and 110 mL of methylene chloride were added to a 500 mL eggplant-shaped flask, and the mixture was reacted at room temperature for 5 hours. After the completion of the reaction, the solvent was removed by an aspirator, 2 L of ethyl acetate and 2 L of tetrahydrofuran were added, washed three times with water, and then dried with magnesium sulfate. Next, the precipitate formed by concentration was filtered and dried to obtain 20.64 g of a white crystal of carbonic acid (7-3-1).

[Synthesis Example 14: Synthesis of carbonic acid (8-1-1) containing liquid crystal aligning group]

Carbonic acid (8-1-1) was synthesized according to Reaction Scheme 5 below.

Synthesis of compound (8-1-1A)

15.0 g of the compound (6-6-1), 16.6 g of the compound (7-3-1B) and 270 mL of methylene chloride were added to a 1 L three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, . Then, 10.47 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 1.11 g of N, N-dimethylaminopyridine were added and reacted at 5 ° C or lower for 24 hours. After completion of the reaction, 500 mL of ethyl acetate and 250 mL of THF were added, and the mixture was washed once with diluted hydrochloric acid and three times with water, dried with magnesium sulfate, and then concentrated and crystallized to obtain white crystals of the compound (8-1-1A) (Purity 100%).

· Synthesis of carbonic acid (8-1-1)

18.4 g of the compound (8-1-1A), 90 mL of methylene chloride and 45 mL of trifluoroacetic acid were added to a 500 mL eggplant-shaped flask equipped with a nitrogen inlet tube, and the reaction was carried out at room temperature for 4 hours. After completion of the reaction, trifluoroacetic acid was removed from the aspirator, dissolved in 600 mL of ethyl acetate and 300 mL of THF, and washed three times with water. Next, after drying with magnesium sulfate, concentration and crystallization were carried out to obtain 12.8 g (purity: 99.9%) of white crystals of the carbonic acid (8-1-1).

[Synthesis Example 15: Synthesis of carbonic acid (9-1-1) containing liquid crystal aligning group]

(9-1-1) was synthesized according to Reaction Scheme 6 below.

Synthesis of compound (9-1-1A)

Compound (9-1-1A) was synthesized by the same method as Compound (8-1-1).

Synthesis of compound (9-1-1B)

Compound (9-1-1B) was synthesized by the same method as compound (7-3-1B).

Synthesis of compound (9-1-1C)

3.4 g of the compound (9-1-1A), 2.2 g of the compound (9-1-1B) and 30 mL of methylene chloride were added to a 100 mL three-necked flask equipped with a stirrer, a thermometer and a nitrogen inlet tube, . Next, 1.7 g of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.18 g of N, N-dimethylaminopyridine were added and reacted at 5 ° C or lower for 24 hours. After completion of the reaction, 300 mL of ethyl acetate was added, and the mixture was washed with water three times with water, dried with magnesium sulfate, concentrated and then precipitated to obtain 2.4 g of white crystals of the compound (9-1-1C).

· Synthesis of carbonic acid (9-1-1)

2.4 g of the compound (9-1-1C), 4 mL of trifluoroacetic acid and 8 mL of methylene chloride were added to a 100 mL eggplant-shaped flask, and the reaction was allowed to proceed at room temperature for 2 hours. After completion of the reaction, the solvent was removed by an aspirator, and then 50 mL of ethyl acetate and 50 mL of tetrahydrofuran were added, washed three times with water, and then dried with magnesium sulfate. Next, the precipitate formed by concentration was filtered and dried to obtain 1.7 g of a white crystal of carbonic acid (9-1-1).

[Synthesis Example 16: Synthesis of carbonic acid (10-1-1) containing liquid crystal aligning group]

Carbonic acid (10-1-1) was synthesized according to the following Reaction Scheme 7.

Synthesis of compound (10-1-1A)

Compound (10-1-1A) was synthesized in the same manner as compound (7-3-1).

Synthesis of compound (10-1-1B)

(20 mmol) of the compound (10-1-1A), 5.89 g (20 mmol) of the compound (9-1-1B) and 80 mL of methylene chloride were added to a 300 mL three-necked flask equipped with a thermometer and a nitrogen- Then, it was ice-cooled. Subsequently, 4.60 (24 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.489 g (4.0 mmol) of N, N-dimethylaminopyridine were added and stirred for 4 hours , And returned to room temperature and allowed to react overnight. After completion of the reaction, 1000 mL of ethyl acetate was added, and the mixture was washed with 300 mL of water four times, followed by drying with magnesium sulfate. Next, the precipitate was concentrated to about 100 mL, and the resulting white precipitate was filtered and dried to obtain 7.93 g (purity 94.4%, yield: 53.8%) of a white crystal of the compound (10-1-1B).

· Synthesis of carbonic acid (10-1-1)

4.72 g (6.41 mmol) of the compound (10-1-1B), 7 mL of trifluoroacetic acid and 14 mL of methylene chloride were added to a 100 mL eggplant-shaped flask, and the mixture was reacted at room temperature for 1 hour. After completion of the reaction, the solvent was removed by an aspirator, and then 100 mL of ethyl acetate and 100 mL of THF (including a stabilizer) were added, washed with 100 mL of water three times, and then dried with magnesium sulfate. Next, several milligrams of a polymerization inhibitor were added and the mixture was concentrated to about 80 mL. The resultant precipitate was filtered and dried to obtain 2.59 g (purity 97.2%, yield: 59.4%) of white crystals of the carboxylic acid (10-1-1).

[Synthesis Example 17: Synthesis of polyorganosiloxane (S-2-5) having an oriented group]

Into a 100 mL three-necked flask were introduced 8.7 g of the polyorganosiloxane (EPS-1) synthesized in Synthesis Example 3, 114 g of methyl isobutyl ketone, 2.7 g of the compound (6-6-1) (polyorganosiloxane (Equivalent to 20 mol% based on the silicon atom of EPS-1), 8.5 g of compound (7-3-1) (corresponding to 30 mol% based on the silicon atom of polyorganosiloxane EPS- 0.89 g of tetrabutylammonium bromide was added, and the mixture was reacted at 90 DEG C for 30 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. The resulting precipitate was dissolved in ethyl acetate and the resulting solution was washed three times with water. The solvent was distilled off to obtain a polyorganosiloxane (S-2-5 ) Of white powder. The weight average molecular weight of the polyorganosiloxane (S-2-5) was 9,500.

[Synthesis Examples 18 to 21, 21A: Synthesis of polyorganosiloxane containing an oriented group]

(S-2-6) to (S-2-9), (S-2-9) and (S-2-9) were prepared in the same manner as in Synthesis Example 17, except that the kinds and amounts of the compounds used were changed as shown in Table 4 below. S-2-11) was synthesized.

In Table 4, the numerical value of the amount of the carbonic acid to be added represents the input amount (mol%) of the epoxy group-containing polyorganosiloxane to the silicon atom.

[Synthesis Example 22: Synthesis of polyimide (PI-1)] [

19.1 g of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride as a tetracarboxylic acid dianhydride and 18.1 g of cholestanyloxy-2,4-diaminobenzene (compound represented by the following formula (DA-1) And 7.42 g of p-phenylenediamine were dissolved in 140 g of NMP, and the reaction was carried out at 60 DEG C for 4 hours. A small amount of the resulting polyamic acid solution was collected, and NMP was added thereto. The viscosity of the solution was measured with a solution having a solid concentration of 10%. As a result, the solution viscosity was 100 mPa · s. To the obtained polyamic acid solution, 325 g of NMP, 6.74 g of pyridine and 8.69 g of acetic anhydride were added, followed by dehydration cyclization at 110 DEG C for 4 hours. After the imidization reaction, the solvent in the system was replaced with a solvent by fresh NMP (in this operation, pyridine and acetic anhydride used in the imidization reaction were removed out of the system), and a polyimide (PI-1) having an imidization rate of about 50% To obtain a solution containing about 15% by weight.

[Example 21]

(1) Preparation of liquid crystal aligning agent

200 parts by weight of a polyorganosiloxane (S-2-5) containing a scavenger and 1,000 parts by weight of polyimide (PI-1) as the polymer component and the compound (1-2-1) as the compound (D) And NMP and butyl cellosolve (BC) as solvents were added thereto to prepare a solution having a solvent composition of NMP: BC = 50: 50 (weight ratio) and a solid concentration of 3.0% by weight. This solution was filtered with a filter having a pore size of 0.2 탆 to prepare a liquid crystal aligning agent (A-21).

(2) Fabrication of liquid crystal display element having transparent electrode without pattern

Using the liquid crystal aligning agent (A-21) prepared above, a liquid crystal display element having a pattern-free transparent electrode was produced. First, a liquid crystal aligning agent (A-21) was applied on a transparent electrode surface of a glass substrate having a transparent electrode (no pattern) made of an ITO film by using a liquid crystal alignment film printing machine (manufactured by Nippon Sha Shingen Co., Ltd.) . Subsequently, the substrate was heated (prebaked) on a hot plate at 80 DEG C for 1 minute to remove the solvent, and then heated on a hot plate at 150 DEG C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 ANGSTROM.

The coating film was rubbed with a rubbing machine having a roll covered with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair pressing indentation length of 0.1 mm. Thereafter, ultrasonic cleaning was performed for 1 minute in ultrapure water, and then the substrate was dried in a 100 占 폚 clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair of substrates (two substrates) each having a liquid crystal alignment film.

Next, an epoxy resin adhesive containing an aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the outer edges of each of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces were laminated so as to face each other and pressed to cure the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection hole was sealed with an acrylic photo-curable adhesive to produce a liquid crystal display device.

The above operation was repeated to produce three liquid crystal display elements each having a pattern-free transparent electrode. One of them was provided for evaluation of the orientation as described later. The remaining two liquid crystal display elements were irradiated with light in a state in which a voltage was applied between the conductive films by the following method (light irradiation step), and then provided for the evaluation of the orientation property and the voltage holding ratio.

(Light irradiation step)

Two of the three liquid crystal display elements obtained above were applied with an alternating current of 10 V at a frequency of 60 Hz between the electrodes, and ultraviolet light was irradiated to the light source with a metal halide lamp using a metal halide lamp And irradiated from the outside of the liquid crystal display element at an irradiation dose of 100,000 J / m &lt; 2 &gt;. This irradiation dose is a value measured using a photometer which is measured based on a wavelength of 365 nm.

(3) Evaluation of orientation

With respect to the three liquid crystal display devices manufactured as described above, the presence or absence of light leakage and orientation confusion in a voltage unapplied state was visually observed under backlight irradiation. In the evaluation, the case where there is no light leakage and orientation disorder is referred to as "good" and the case where light leakage and orientation disorder is present is defined as "poor" in orientation. As a result, all of the liquid crystal display elements of Example 21 were excellent in orientation.

(4) Evaluation of Voltage Conservation Rate

Of the liquid crystal display devices manufactured above, a voltage of 5 V was applied to the liquid crystal display device at an irradiation dose of 100,000 J / m &lt; 2 &gt; at an application time of 60 microseconds and a span of 167 milliseconds, and then a voltage of 167 milliseconds The conservation rate [%] was measured. As the measuring device, VHR-1 manufactured by Toyotecnica Co., Ltd. was used. As a result, the voltage holding ratio was 98%.

(5) Fabrication of liquid crystal display element having patterned transparent electrode

Using the liquid crystal aligning agent (A-21) prepared above, a liquid crystal display element having a patterned transparent electrode was produced. First, on each electrode surface of a pair of glass substrates (substrates A and B) each having ITO electrodes partitioned into a plurality of regions as shown in Fig. 2, a liquid crystal alignment film printing machine Liquid crystal aligning agent (A-21) was applied by using a liquid crystal aligning agent (trade name: A-21). Subsequently, the substrate was heated (prebaked) on a hot plate at 80 DEG C for 1 minute to remove the solvent, and then heated on a hot plate at 150 DEG C for 10 minutes (post baking) to form a coating film having an average film thickness of 600 ANGSTROM. This coating film was ultrasonically cleaned in ultrapure water for 1 minute, and then dried in a 100 ° C clean oven for 10 minutes to obtain a pair of substrates having a liquid crystal alignment film (two pieces).

Subsequently, an epoxy resin adhesive containing an aluminum oxide spheres having a diameter of 5.5 mu m was applied to the outer edges of each of the pair of substrates having the liquid crystal alignment film, and then the liquid crystal alignment film faces were laminated so as to face each other and pressed to cure the adhesive. Subsequently, a nematic liquid crystal (MLC-6608, manufactured by Merck Ltd.) was filled between a pair of substrates from a liquid crystal injection port, and then a liquid crystal injection port was sealed with an acrylic photo-curable adhesive to produce a liquid crystal display device.

The above operation was repeated to produce three liquid crystal display elements each having a patterned transparent electrode. With respect to these three liquid crystal display elements, ultraviolet rays were irradiated at an irradiation dose of 100,000 J / m &lt; 2 &gt; under a voltage applied between the conductive films in the same manner as in the case of the liquid crystal cell having the patternless transparent electrode, , And the response speed was evaluated. The electrode pattern used here is a pattern similar to the electrode pattern of the PSA mode.

(6) Evaluation of response speed

For each of the above-prepared three liquid crystal display elements, a visible light lamp was irradiated without applying a voltage first, and the luminance of light transmitted through the liquid crystal display element was measured by a photomulti meter. The measured value at this time was regarded as a relative transmittance of 0%. Next, the transmittance (luminance of light transmitted through the liquid crystal display element) when an AC voltage of 60 V was applied for 5 seconds between the electrodes of the liquid crystal display element was measured in the same manner as described above, and this value was regarded as a relative transmittance of 100%. Then, when the alternating current of 60 V was applied to each liquid crystal display element, the time from the relative transmittance to the transition from 10% to 90% was measured, and this time was defined as the response speed [msec]. The response speed was evaluated by an average value of three cells. As a result, the response speed of the liquid crystal display element of Example 21 was 10 msec.

[Examples 22 to 26, Comparative Example 3]

The liquid crystal aligning agents (A-22) to (A-26) and (R-26) were obtained in the same manner as in Example 21 except that the kind and amount of the polymer (P) -3) was prepared. Using the obtained liquid crystal aligning agents (A-22) to (A-26) and (R-3), liquid crystal display devices having patternless transparent electrodes and liquid crystal display devices having patterned transparent electrodes And various evaluations were carried out as described above. The results are shown in Table 6 below.

In Table 5, the numerical values in parentheses of each compound represent the compounding ratio (parts by weight) of each compound. The abbreviations of compound (D) are the same as in Table 2.

[Table 6]

As shown in Table 6, all of the liquid crystal display elements of Examples 21 to 26 were evaluated as &quot; good &quot; In addition, the voltage maintenance rate was as high as 98% or more, and the response speed was also fast. On the other hand, in Comparative Example 3, although the liquid crystal alignability and the response speed were equal to those in Examples, the voltage holding ratio was as low as 95%.

11, 12: electrode

Claims (9)

A liquid crystal aligning agent containing a polymer component and a compound (D) represented by the following formula (1)

(In the formula (1), A ¹ is a group containing a polymerizable unsaturated bond, A ² is a functional group capable of reacting with an epoxy group, R ¹ is an organic group of (m + n) N is an integer of 1 to 18, with the proviso that (m + n)? 20 is satisfied. The method according to claim 1,
And n is an integer of 2 to 18. The method according to claim 1,
A ¹ is at least one member selected from the group consisting of a (meth) acryloyloxy group, a vinyl group and a styryl group. The method according to claim 1,
As the polymer component, a liquid crystal aligning agent comprising at least one member selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane. The method according to claim 1,
As the polymer component, a liquid crystal aligning agent comprising an epoxy group-containing polyorganosiloxane. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1 to 5. A method for manufacturing a liquid crystal display device, comprising the steps of: applying a liquid crystal aligning agent according to any one of claims 1 to 5 on a substrate to form a coated film;
And irradiating the coating film with light. A liquid crystal display element comprising the liquid crystal alignment film according to claim 6 or the liquid crystal alignment film obtained by the manufacturing method according to claim 7. A step of applying a liquid crystal aligning agent according to any one of claims 1 to 5 on each surface of a pair of substrates and then heating the same to form a coated film,
A step of arranging a pair of substrates on which the coating film is formed so as to face each other with the liquid crystal molecules interposed therebetween so as to face each other to construct a liquid crystal cell;
A step of irradiating light from the outside of the liquid crystal cell
Wherein the liquid crystal display element is a liquid crystal display element.

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