JP6048117B2 - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and method for manufacturing liquid crystal display element - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal aligning film, a liquid crystal display element, and a method for manufacturing a liquid crystal display element, and more particularly to a liquid crystal aligning agent that can be suitably used for manufacturing a vertical alignment type liquid crystal display element.

  Conventionally, as a liquid crystal display element, various drive systems having different electrode structures and physical properties of liquid crystal molecules to be used have been developed. For example, TN type, STN type, VA type, in-plane switching type (IPS type), etc. Various liquid crystal display elements are known. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. As materials for the liquid crystal alignment film, for example, polyamic acid, polyimide, polyester, polyorganosiloxane, and the like are known.

  In recent years, PSA (Polymer Sustained Alignment) technology, photo-alignment technology, and the like have been proposed as new technologies for imparting pretilt angle characteristics to a coating film formed using a liquid crystal aligning agent (for example, (See Patent Document 1 and Patent Document 2). In the PSA technology, a polymerizable component that is polymerized by light irradiation is mixed in the liquid crystal layer of the liquid crystal cell, and the liquid crystal cell is tilted by application of voltage, and the liquid crystal cell is irradiated with light to thereby irradiate the polymerizable component. This is a technique for controlling the molecular orientation of liquid crystal molecules by polymerization. The photo-alignment technique is a technique for causing a film to exhibit pretilt angle characteristics by irradiating light onto a polymer thin film having a photofunctional group such as a cinnamoyl group.

  When the PSA technique is used, it is necessary to perform light irradiation with a relatively high dose in order to develop a desired pretilt angle characteristic in the coating film. In addition, when the light irradiation amount is increased, there is a concern that the display unevenness of the liquid crystal display element may be generated or the long-term reliability of the panel may be inferior due to the degradation of the liquid crystal molecules and the performance of the liquid crystal alignment film. On the other hand, when the amount of light irradiation is reduced, there arises a problem that the response speed of the liquid crystal molecules to the voltage change becomes slow in the formed liquid crystal display element. In view of the above, in recent years, a desired pretilt angle characteristic can be imparted to a coating film formed using a liquid crystal aligning agent with as little light irradiation dose as possible, and the response speed of liquid crystal molecules to a voltage change is sufficiently high. A technique for obtaining a fast liquid crystal display element has been proposed (see, for example, Patent Document 3). In Patent Document 3, a coating film is formed on a substrate using a liquid crystal aligning agent containing a polyorganosiloxane having a (meth) acryloyl group as a polymer component and a polyamic acid or polyimide, and the substrate is It is disclosed that a liquid crystal display element is manufactured by forming a liquid crystal cell and irradiating the liquid crystal cell with light while a voltage is applied between the substrates.

JP 2003-149647 A JP 2009-36966 A JP 2011-118358 A

  In recent years, liquid crystal display elements are used not only for display terminals such as personal computers as in the past, but also for various applications such as liquid crystal televisions, car navigation systems, mobile phones, smartphones, and information displays. . With such versatility, the liquid crystal display element may be used under conditions that are severer than conventional ones. For example, the liquid crystal display element may be driven for a long time or used in a high temperature environment. In recent years, demands for higher performance of liquid crystal display elements have further increased, and liquid crystal display elements are required to maintain a good display quality even under such severe conditions.

  The present invention has been made in view of the above problems, and can provide a desired pretilt angle characteristic to a coating film with a relatively small amount of light irradiation, and has excellent heat resistance (particularly long-term heat resistance). It is a main object to provide a liquid crystal aligning agent capable of obtaining the above.

  As a result of intensive studies to achieve the above-described problems of the prior art, the present inventors have found that the above-described problems can be solved by including a specific compound in the liquid crystal aligning agent, and the present invention has been completed. It came to do. Specifically, the present invention provides the following liquid crystal aligning agent, liquid crystal alignment film, liquid crystal display element, and liquid crystal display element manufacturing method.

  In one aspect, the present invention includes a compound [E] having an epoxy group and a polymerizable unsaturated bond, and having a molecular weight of 2,000 or less, and a compound [D] having two or more polymerizable unsaturated bonds. (However, excluding those corresponding to the compound [E]).

  According to the liquid crystal aligning agent of the present invention, by including the compound [D] and the compound [E] as a constituent component of the liquid crystal aligning agent, a desired pretilt angle with respect to the coating film even with a relatively small amount of light irradiation. Since the characteristics can be imparted, it is possible to minimize performance degradation due to light irradiation. Further, even when exposed to a high temperature environment for a long time, a good voltage holding characteristic can be maintained, and a liquid crystal display element excellent in heat resistance, particularly in long-term heat resistance can be manufactured.

In addition, the compound [E] preferably has a group represented by the following formula (2) as a group having the polymerizable unsaturated bond, and the compound [D] The group having a saturated bond preferably has two or more groups represented by the following formula (3).
(In Formula (2), R ² is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom. “*” Represents a bond.)
(In Formula (3), R ³ is a hydrogen atom or a methyl group, Y ³ and Y ⁴ are each independently an oxygen atom or a sulfur atom. “*” Represents a bond.)

  The liquid crystal aligning agent of the present invention preferably further contains at least one polymer [A] selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane. By containing the polymer [A], various properties such as liquid crystal orientation, voltage holding ratio, heat resistance, and mechanical strength of the formed coating film can be improved.

  According to another aspect of the present invention, in the first step, the liquid crystal aligning agent described above is applied to each of the conductive films of a pair of substrates having a conductive film, and then heated to form a coating film. A second step of constructing a liquid crystal cell by arranging the pair of substrates on which the coating film is formed so as to face each other through the liquid crystal molecule layer, and the conductive film of the pair of substrates. And a third step of irradiating light to a liquid crystal cell with a voltage applied between them.

  When a liquid crystal display element is produced using the liquid crystal aligning agent of the present invention, by adopting the above method, a desired pretilt angle characteristic can be imparted to the coating film even with a relatively small amount of light irradiation, and heat resistance In particular, the effect of producing a liquid crystal display element excellent in long-term heat resistance can be suitably obtained.

  In one aspect, the present invention provides a liquid crystal alignment film formed using the liquid crystal aligning agent described above. Furthermore, this invention provides the liquid crystal display element which comprises the said liquid crystal aligning film in another one side surface.

The top view which shows the pattern of the transparent electrode patterned by slit shape.

  Below, the liquid crystal aligning agent of this invention is demonstrated in detail. The liquid crystal aligning agent of this invention contains two compounds [D] and a compound [E] which have a polymerizable unsaturated bond. Moreover, the liquid crystal aligning agent of this invention contains a polymer component. The polymer component includes a compound [D] as a polymer, at least one polymer [A] selected from the group consisting of polyamic acid, polyamic acid ester, polyimide and polyorganosiloxane, or both. It is preferable to include. The polymer [A] is a polymer different from the compound [D] and does not have a polymerizable unsaturated bond or has one polymerizable unsaturated bond. Hereinafter, each component contained in the liquid crystal aligning agent of this invention and the other component arbitrarily mix | blended as needed are demonstrated.

≪Polymer [A] ≫
<Polyamic acid>
The polyamic acid as the polymer [A] in the present invention can be synthesized, for example, by reacting a tetracarboxylic dianhydride and a diamine. By including a polyamic acid in the liquid crystal aligning agent, various properties such as liquid crystal alignment properties, voltage holding properties, heat resistance, and mechanical strength can be improved.

[Tetracarboxylic dianhydride]
Examples of the tetracarboxylic dianhydride used for synthesizing the polyamic acid in the present invention include an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, and the like. Can be mentioned. Specific examples of these are:
Examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride;
Examples of the alicyclic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4, 5,9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane -2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene- No 1,2-dicarboxylic acid 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 2,4,6,8-tetracarboxybicyclo [3.3.0] octane-2 : 4,6: 8-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, cyclohexanetetracarboxylic dianhydride Etc .;
Examples of aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride;
In addition to the above, tetracarboxylic dianhydrides described in JP 2010-97188 A can be used. In addition, the said tetracarboxylic dianhydride can be used individually by 1 type or in combination of 2 or more types.

  As tetracarboxylic dianhydride used to synthesize polyamic acid, only alicyclic tetracarboxylic dianhydride is used, or alicyclic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride. It is preferable to use a mixture thereof. In the latter case, the alicyclic tetracarboxylic dianhydride is preferably contained in an amount of 20 mol% or more, more preferably 40 mol% or more based on the total amount of tetracarboxylic dianhydride used in the synthesis. More preferred.

[Diamine]
Examples of the diamine used for synthesizing the polyamic acid in the present invention include aliphatic diamine, alicyclic diamine, aromatic diamine, and diaminoorganosiloxane. Specific examples of these include aliphatic diamines such as metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and the like;
Examples of alicyclic diamines include 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane and the like;

Examples of aromatic diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, 2,2′-dimethyl-4,4′-diaminobiphenyl, 2,2′-bis (trifluoromethyl) -4,4′-diaminobiphenyl, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl ] Propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-(m-phenylenediisopropylene Riden) bisaniline, 1,4-bis (4-aminophenoxy) benzene, 4,4′-bis (4-aminophenoxy) biphenyl, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diamino Pyrimidine, 3,6-diaminoacridine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, N , N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethylbenzidine, 1,4-bis- (4-aminophenyl) -piperazine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-5-amine, 1- (4-aminophen 2) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6-amine, 3,5-diaminobenzoic acid, cholestanyloxy-3,5-diaminobenzene, cholestenyloxy-3, 5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 3,5-diamino Lanostanyl benzoate, 3,6-bis (4-aminobenzoyloxy) cholestane, 3- (3,5-diaminobenzoyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4′- Trifluoromethoxybenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 4- (4'-trifluoro) Olomethylbenzoyloxy) cyclohexyl-3,5-diaminobenzoate, 1,1-bis (4-((aminophenyl) methyl) phenyl) -4-butylcyclohexane, 1,1-bis (4-((aminophenyl) ) Methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenyl) methyl) phenyl ) -4- (4-Heptylcyclohexyl) cyclohexane, 2,4-diamino-N, N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, and the following formula (A-1)
(Wherein, X ^I and X ^II are each independently a single bond, —O—, —COO—, or —OCO—, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1. However, a and b are not 0 at the same time.)
A compound represented by:
Examples of diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane;
In addition to these, diamines described in JP 2010-97188 A can be used. As other diamine, these can be used individually by 1 type or in combination of 2 or more types.

Examples of the divalent group represented by “—X ^I — (R ^I —X ^II ) _n —” in the formula (A-1) include alkanediyl groups having 1 to 3 carbon atoms, * —O—, * —COO— or * —O—C ₂ H ₄ —O— (however, a bond marked with “*” is bonded to a diaminophenyl group) is preferred. Specific examples of the group “—C _c H _{2c + 1} ” include, for example, methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, and n-octyl group. N-nonyl group, n-decyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group , N-eicosyl group and the like. The two amino groups in the diaminophenyl group are preferably in the 2,4-position or 3,5-position with respect to other groups.

Specific examples of the compound represented by the formula (A-1) include compounds represented by the following formulas (A-1-1) to (A-1-3).

[Molecular weight regulator]
When synthesizing the polyamic acid, a terminal-modified polymer may be synthesized using an appropriate molecular weight regulator together with the tetracarboxylic dianhydride and diamine as described above. By using such a terminal-modified polymer, the applicability (printability) of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention.

Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like. Specific examples thereof include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic. Acid anhydride, n-hexadecyl succinic acid anhydride, etc .;
Examples of monoamine compounds include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, and n-octylamine;
Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate;
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

<Synthesis of polyamic acid>
The ratio of the tetracarboxylic dianhydride and the diamine used in the polyamic acid synthesis reaction in the present invention is such that the acid anhydride group of the tetracarboxylic dianhydride is 0. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, more preferably 0 to 100 ° C. The reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Here, examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon.
Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, N-ethyl-2-pyrrolidone, N, N as the aprotic polar solvent. -Dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide and the like; as the phenol solvent, for example, phenol, m-cresol, xylenol, halogenated phenol, etc. ;
Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, and the like. Examples of the ketone include acetone, Examples of the ester include, for example, ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and malon Diethyl acid, isoamyl propionate, isoamyl isobutyrate and the like;
Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether. Acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, diisopentyl ether and the like;
Examples of the halogenated hydrocarbon include dichloromethane, 1,2-dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, and the like. Examples of the hydrocarbon include hexane, heptane, octane, Benzene, toluene, xylene, etc. can be mentioned respectively.

  Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenolic solvent (first group of organic solvents), or one or more selected from the first group of organic solvents It is preferable to use a mixture with one or more selected from the group consisting of alcohol, ketone, ester, ether, halogenated hydrocarbon and hydrocarbon (second group organic solvent). In the latter case, the proportion of the second group organic solvent used is preferably 50% by weight or less, more preferably 40% by weight, based on the total amount of the first group organic solvent and the second group organic solvent. Or less, more preferably 30% by weight or less. The amount of organic solvent used (a) is such that the total amount (b) of tetracarboxylic dianhydride and diamine is 0.1 to 50% by weight based on the total amount (a + b) of the reaction solution. It is preferable.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. When polyamic acid is dehydrated and cyclized into a polyimide, the above reaction solution may be directly subjected to dehydration and cyclization reaction, or may be subjected to dehydration and cyclization reaction after isolating the polyamic acid contained in the reaction solution. Alternatively, the isolated polyamic acid may be purified and then subjected to a dehydration ring closure reaction. Isolation and purification of the polyamic acid can be performed according to known methods.

<Polyamic acid ester>
The polyamic acid ester as the polymer [A] contained in the liquid crystal aligning agent of the present invention is, for example, [I] esterifying the polyamic acid obtained by the above synthesis reaction using a hydroxyl group-containing compound or an ether compound. And [II] a method of reacting a tetracarboxylic acid diester compound and a diamine. Here, the tetracarboxylic acid diester compound in the method [II] includes a tetracarboxylic acid diester compound which is a precursor of the tetracarboxylic dianhydride, specifically, for example, tetracarboxylic acid diester dichloride, Examples thereof include tetracarboxylic acid diester having two carboxyl groups. Examples of the diamine used in the method [II] include the diamines exemplified in the description of the synthesis of the polyamic acid. In addition, the polyamic acid ester as the polymer [A] may have only an amic acid ester structure, or may be a partially esterified product in which an amic acid structure and an amic acid ester structure coexist.

<Synthesis of polyimide and polyimide>
The polyimide contained in the liquid crystal aligning agent of the present invention can be obtained, for example, by dehydrating and ring-closing and imidizing the polyamic acid synthesized as described above. By including polyimide in the liquid crystal aligning agent, various characteristics such as liquid crystal alignment, voltage holding characteristics, heat resistance, and mechanical strength can be improved.

  The polyimide may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid that is the precursor, and only a part of the amic acid structure is dehydrated and cyclized, It may be a partially imidized product in which an imide ring structure coexists. The polyimide in the present invention preferably has an imidation ratio of 30% or more, more preferably 50 to 99%, and still more preferably 60 to 99%. This imidation ratio represents the ratio of the number of imide ring structures to the total of the number of polyimide amic acid structures and the number of imide ring structures in percentage. Here, a part of the imide ring may be an isoimide ring.

  The polyamic acid is preferably dehydrated and closed by heating the polyamic acid, or by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the solution as necessary. . Of these, the latter method is preferred.

  In the method of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, for example, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride can be used as the dehydrating agent. It is preferable that the usage-amount of a dehydrating agent shall be 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. As the dehydration ring closure catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, triethylamine and the like can be used. It is preferable that the usage-amount of a dehydration ring-closing catalyst shall be 0.01-10 mol with respect to 1 mol of dehydrating agents to be used. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.

  In this way, a reaction solution containing polyimide is obtained. This reaction solution may be used for the preparation of the liquid crystal aligning agent as it is, may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, and the liquid crystal after isolating the polyimide. You may use for preparation of an aligning agent, or you may use for preparation of a liquid crystal aligning agent, after purifying the isolated polyimide. These purification operations can be performed according to known methods.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s, when this is made into a solution having a concentration of 10% by weight, and 15 to 500 mPa · s. More preferably, it has a solution viscosity of s. In addition, the solution viscosity (mPa · s) of the above polymer is based on a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (eg, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). The value measured at 25 ° C. using an E-type rotational viscometer.
Regarding the polyamic acid, polyamic acid ester, and polyimide, the polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography is preferably 1,000 to 500,000, and preferably 2,000 to 300,000. More preferred.

<Polyorganosiloxane>
The polyorganosiloxane as the polymer [A] contained in the liquid crystal aligning agent of the present invention is, for example, one or more hydrolyzable silane compounds, preferably hydrolyzed in the presence of an organic solvent and a catalyst. It can be obtained by a method of decomposing and condensing. Examples of the silane compound used for the synthesis include the silane compound (si-3) shown below. The explanation of the hydrolytic condensation reaction of the silane compound described in the compound [D] can be applied to the organic solvent, catalyst, reaction conditions and the like used for the synthesis.
With respect to the polyorganosiloxane, the polystyrene-reduced weight average molecular weight measured by gel permeation chromatography is preferably 500 to 100,000, more preferably 1,000 to 50,000, and 1,000. More preferably, it is ˜30,000.

As the polymer [A], the liquid crystal aligning agent of the present invention is a polymer selected from the group consisting of the above polyamic acid, polyamic acid ester, polyimide, and polyorganosiloxane, alone or in combination of two or more. May be contained. In the liquid crystal aligning agent of the present invention, the content ratio of each polymer with respect to the total amount of the polymer [A] can be appropriately selected depending on the use and environment to be used. From the viewpoint of strength, liquid crystal orientation, and the like, the polymer [A] preferably contains at least one selected from the group consisting of polyamic acid, polyamic acid ester and polyimide, and is selected from the group consisting of polyamic acid and polyimide. More preferably, the polymer [A] is at least one selected from the group consisting of polyamic acid and polyimide.
When the polymer [A] includes at least one of polyamic acid and polyimide, the total content is 1 to 100% by weight with respect to the total amount of the polymer [A] contained in the liquid crystal aligning agent. It is preferable that it is 5 to 100% by weight. In addition, as a polymer [A], 1 type of the polymer shown above may be used independently, and may be used in combination of 2 or more type. When two or more types are used in combination, a combination of polymers having the same main skeleton may be used, or a combination of polymers having different main skeletons may be used.

<< Compound [D] >>
The compound [D] used in the present invention has two or more polymerizable unsaturated bonds in the molecule. In addition, compound [D] means what does not correspond to compound [E] explained in full detail among the compounds which have a 2 or more polymerizable unsaturated bond. Although the structure in the polymerizable unsaturated bond part of the said compound [D] is not specifically limited, As group which has a polymerizable unsaturated bond, it is the group (henceforth a specific group (g1) represented by following formula (3). .), And preferably two or more.
(In Formula (3), R ³ is a hydrogen atom or a methyl group, Y ³ and Y ⁴ are each independently an oxygen atom or a sulfur atom. “*” Represents a bond.)

Y ³ and Y ⁴ in the above formula (3) are each preferably an oxygen atom from the viewpoint of expressing desired pretilt angle characteristics with a smaller amount of light irradiation.

  Compound [D] may be a monomer or a polymer. Specific examples thereof include, as a monomer, for example, two or more polymerizable unsaturated bonds, a benzene ring and a cyclohexane ring. A compound having at least one ring structure (hereinafter also referred to as “specific monomer”), etc .; as a polymer, polyorganosiloxane, polyester, polyamic acid, polyimide, etc. as the main skeleton, and in the side chain Examples thereof include compounds having two or more polymerizable unsaturated bonds;

<Specific monomer>
The specific monomer is not particularly limited as long as it has two or more polymerizable unsaturated bonds and has at least one of a benzene ring and a cyclohexane ring. Specific examples of the specific monomer include a compound having two or more polymerizable unsaturated bonds and a group represented by the following formula (4).
(In the formula (4), Ac ¹ and Ac ² are independently a benzene ring or a cyclohexane ring, it may .X ^a may have a substituent is a single bond, 1 to 4 carbon atoms A divalent hydrocarbon group, an oxygen atom, a sulfur atom, or —COO—, where “*” represents a bond.)

In the above formula (4), Ac ¹ and Ac ² may be the same or different, but each is preferably a benzene ring. In addition, each ring of Ac ¹ and Ac ² may have a substituent. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, an alkyl group having 1 to 4 carbon atoms, a fluoroalkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms. , Hydroxyl group, cyano group and the like.
Divalent hydrocarbon group having 1 to 4 carbon atoms in X ^a may be saturated or unsaturated, or may be branched be linear. Specific examples of the hydrocarbon group include methylene group, ethylene group, propane-1,1-diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2- Examples thereof include a diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a butane-2,3-diyl group, and a vinylene group.
Specific examples of the group represented by the above formula (4) include groups represented by the following formulas (4-1) to (4-6).
(In the formula, “*” indicates a bond.)

The specific monomer is preferably a di (meth) acrylate having two acryloyl groups or methacryloyl groups as a polymerizable unsaturated bond, and among them, a compound represented by the following formula (D-1). It is preferable.
(In Formula (D-1), R ² is each independently a hydrogen atom or a methyl group, r 1 and r 2 are each independently 1 or 2, and s 1 and s 2 are each independently 0-4. (Ac ¹ , Ac ² and X ^a are each synonymous with the above formula (4).)

Specific examples of the di (meth) acrylate represented by the above formula (D-1) include di (meth) acrylate having a biphenyl structure (a group represented by the above formula (4-1)), for example, 4 ′ -(Meth) acryloyloxy-biphenyl-4-yl- (meth) acrylate, 2- [4 '-(2- (meth) acryloyloxy-ethoxy) -biphenyl-4-iroxy] -ethyl (meth) acrylate, bishydroxyethoxy Biphenyl di (meth) acrylate, 2- (2- {4 ′-[2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -biphenyl-4-yloxy} -ethoxy) -ethyl (meth) acrylate, 2 -(4'-acryloyloxy-biphenyl-4-yloxy) -ethyl (meth) acrylate and the like;
Examples of the di (meth) acrylate having a phenyl-cyclohexyl structure (group represented by the above formula (4-2)) include 4- (4- (meth) acryloyloxy-phenyl) -cyclohexyl (meth) acrylate, 2- { 4- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -cyclohexyloxy} -ethyl (meth) acrylate, 2- [2- (4- {4- [2- (2- (meth) acryloyloxy) -Ethoxy) -ethoxy] -phenyl} -cyclohexyloxy) -ethoxy] -ethyl (meth) acrylate and the like;

As a di (meth) acrylate having a 2,2-diphenylpropane structure (group represented by the above formula (4-3)), for example, 4- [1- (4- (meth) acryloyloxy-phenyl) -1-methyl -Ethyl] -phenyl (meth) acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-ethoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -ethyl (meth) acrylate Bishydroxyethoxy-bisphenol A di (meth) acrylate, 2- {2- [4- (1- {4- [2- (2- (meth) acryloyloxy-ethoxy) -ethoxy] -phenyl} -1-methyl -Ethyl) -phenoxy] -ethoxy} -ethyl (meth) acrylate, 2- (4- {1- [4- (2- (meth) acryloyloxy-propoxy) -fur Nyl] -1-methyl-ethyl} -phenoxy) -1-methyl-ethyl (meth) acrylate, 2- {2- [4- (1- {4- [2- (2- (meth) acryloyloxy-propoxy)] -Propoxy] -phenyl} -1-methyl-1-ethyl) -phenoxy] -1-methyl-ethoxy} -1-methyl-ethyl (meth) acrylate, 3- {4- [1- (3- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethylphenoxy-2-hydroxy-propyl (meth) acrylate, 3- (4- {1- [4- (3- (Meth) acryloyloxy-2-hydroxy-propoxy) -3-cyclohexyl-phenyl] -1-methyl-ethyl} -2-cyclohexyl Ru-phenoxy) -2-hydroxy-2-propyl (meth) acrylate, 3- (5- {1- [6- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -biphenyl-3-yl]- 1-methyl-ethyl} -biphenyl-2-yloxy) -2-hydroxy-propyl (meth) acrylate, 3- {4- [1- (4- {1- [4- (3- (meth) acryloyloxy-2] -Hydroxy-propoxy) -3-methyl-phenyl] -1-methyl-ethyl} -phenyl) -1-methyl-ethyl] -2-methyl-phenoxy} -2-hydroxy-propyl (meth) acrylate, 3- ( 4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy -Propyl (meth) acrylate, 3- [4- (1- {4- [3- (4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1- Methyl-ethyl} -phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propyl (meth) acrylate, 3- {4- [1- (4- { 3- [4- (1- {4- [3- (4- {1- [4- (3- (meth) acryloyloxy-2-hydroxy-propoxy) -phenyl] -1-methyl-ethyl} -phenoxy) -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy] -2-hydroxy-propoxy] -phenyl} -1-methyl-ethyl) -phenoxy} -2-hydroxy-propyl Pyr (meth) acrylate, 1- (2- {4- [1- (4- {2- [2-hydroxy-3- (1-methylene-allyloxy) -propoxy] -propoxy} -phenyl) -1-methyl -Ethyl] -xy} -1-methyl-ethoxy) -3- (1-methylene-allyloxy) -propan-2-ol and the like;
Examples of di (meth) acrylate having a diphenylmethane structure (group represented by the above formula (4-4)) include 4- (4- (meth) acryloyloxy-benzyl) -phenyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-ethoxy) -benzyl] -phenyl} -ethyl (meth) acrylate, 2- [2- (4- {4- [2- (2- (meth) acryloyloxy-ethoxy) -Ethoxy] -benzyl} -phenoxy) -ethoxy] -ethyl (meth) acrylate, 2- {4- [4- (2- (meth) acryloyloxy-propoxy) -benzyl-phenoxy} -1-methyl-ethyl (meth) ) Acrylate, 2- [2- (4- {4- [2- (2- (meth) acryloyloxy-propoxy) -propoxy] -benzyl} -fe Carboxymethyl) -1-methyl - ethoxy] -1-methyl - Echiruechiru (meth) acrylate, the following formula (D-1-1) or formula (D-1-2)
(In the formula, each R ² independently represents a hydrogen atom or a methyl group.)
A compound represented by each of the above;

As a di (meth) acrylate having a diphenylthioether structure (group represented by the above formula (4-5)), for example, 4- (4-thio (meth) acryloylsulfanyl-phenylsulfanyl) -phenyldithio (meth) Acrylate, bis (4-methacryloylthiophenyl) sulfide, etc .;
Other di (meth) acrylates include, for example, 2,5-bis {4- (3-acryloyloxy-propoxy) -benzoic acid} toluene; In the present specification, “(meth) acrylate” means “acrylate” and “methacrylate”, and “(meth) acryloyloxy” means “acryloyloxy” and “methacryloyloxy”.
The di (meth) acrylate can be synthesized by combining organic chemistry methods as appropriate, and can also be obtained as a commercial product. As di (meth) acrylate, the above-mentioned ones can be used alone or in combination of two or more.

On the other hand, when the compound (D) is a polymer, a compound having a polyorganosiloxane as a main skeleton (hereinafter also referred to as “specific polyorganosiloxane”) can be preferably used.
<Specific polyorganosiloxane>
The specific polyorganosiloxane as the compound [D] in the present invention has two or more groups having a polymerizable unsaturated bond in the side chain of the polyorganosiloxane skeleton. The group having a polymerizable unsaturated bond is preferably a group represented by the above formula (3), and particularly preferably an acryloyl group or a methacryloyl group.
The specific polyorganosiloxane preferably has a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of 500 to 100,000, more preferably 1,000 to 50,000, More preferably, it is 1,000 to 10,000.

The specific polyorganosiloxane is, for example,
(1a) a method of hydrolytic condensation of a hydrolyzable silane compound (si-1) having a polymerizable unsaturated bond, or a mixture of the silane compound (si-1) and another silane compound;
(2a) Polymer (epoxy group) obtained by hydrolytic condensation of a hydrolyzable silane compound (si-2) containing an epoxy group or a mixture of the silane compound (si-2) and another silane compound Containing polyorganosiloxane) and a carboxylic acid (C-1) having a polymerizable unsaturated bond;

[Silane Compound (si-1)]
The silane compound (si-1) only needs to have at least one polymerizable unsaturated bond, and examples thereof include a compound represented by the following formula (s-1).
(In formula (s-1), each X is independently a halogen atom, an alkoxy group having 1 to 4 carbon atoms or an alkyl group having 1 to 4 carbon atoms, provided that three X's present in the molecule among more than one X is a halogen atom or an alkoxy group having 1 to 4 carbon atoms .n is an integer from 1 to 6 ^.R 3, ^{Y 3} and ^{Y 4,} synonymous respectively the equation (3) .)

In the above formula (s-1), the divalent group “—C _n H _2n —” may be linear or branched. For example, a methylene group, ethylene group, propane-1,1- Diyl group, propane-1,2-diyl group, propane-1,3-diyl group, propane-2,2-diyl group, butane-1,3-diyl group, butane-1,4-diyl group, butane- Examples include 2,3-diyl group, pentane-1,5-diyl group, pentane-2,4-diyl group, heptane-1,6-diyl group and the like. Among these, those in which n is an integer of 1 to 5 are preferable, and linear ones such as an ethylene group, a propane-1,3-diyl group, and a butane-1,4-diyl group are more preferable.
X is a halogen atom, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc .; a C 1-4 alkoxy group, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc .; Examples of the alkyl group of 1 to 4 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, and an isobutyl group;
X may be a halogen atom or an alkoxy group having 1 to 4 carbon atoms, but two or more of the three existing in the molecule may be a halogen atom or an alkoxy group having 1 to 4 carbon atoms. Is preferred. The three Xs present in the molecule may be the same or different.

Preferable specific examples of the silane compound (si-1) include, for example, 3- (meth) acryloxypropyltrimethoxysilane, 1- (meth) acryloxymethyltrimethoxysilane, 2- (meth) acryloxyethyltrimethoxysilane. 4- (meth) acryloxybutyltrimethoxysilane, 5- (meth) acryloxypentyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 1- (meth) acryloxymethyltriethoxysilane, 2 -(Meth) acryloxyethyltriethoxysilane, 4- (meth) acryloxybutyltriethoxysilane, 5- (meth) acryloxypentyltriethoxysilane, (meth) acrylic acid-2-hydroxy-5- (trimethoxy Silanyl) -pentyl ester, (meth) acrylic acid 1-hydroxy-4- (trimethoxysilane sulfonyl) - and butyl esters.
Among these, 3-methacryloxypropyltrimethoxysilane and 3-acryloxypropyltrimethoxysilane can be preferably used in the synthesis of the specific polyorganosiloxane. In addition, as a silane compound (si-1), it can be used individually by 1 type or in combination of 2 or more types among the above.
In the above, “(meth) acryloxy” includes both “acryloxy” and “methacryloxy”.

[Silane compound (si-2)]
The structure of the silane compound (si-2) is not particularly limited as long as it has an epoxy group, but preferably has a group represented by the following formula (ep-1) or formula (ep-2). The group represented by the above formula (ep-1) or formula (ep-2) is particularly 3-epoxypropyl group, 3-glycidyloxypropyl group, 2- (3,4-epoxycyclohexyl) ethyl. Groups are preferred.
(In formula (ep-1), A is a single bond or an oxygen atom, h is an integer of 1 to 3, and i is an integer of 0 to 6. However, when i is 0, (A is a single bond. In formula (ep-2), j is an integer of 1 to 6. "*" indicates a bond with a silicon atom.)

  Preferable specific examples of the silane compound (si-2) include, for example, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxy Propylmethyldiethoxysilane, 3-glycidyloxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ) Ethyltriethoxysilane and the like. Among these, at least one of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane and 3-glycidyloxypropyltrimethoxysilane can be particularly preferably used. In addition, as a silane compound (si-2), it can be used individually by 1 type or in combination of 2 or more types among the above.

[Other silane compounds (si-3)]
In the synthesis of the specific polyorganosiloxane, a silane compound other than the above (other silane compound (si-3)) can also be used. The other silane compound (si-3) may be any hydrolyzable silane compound having no polymerizable unsaturated bond and no epoxy group. Specific examples thereof include tetramethoxysilane and tetraethoxy. Silane, methyltrimethoxysilane, methyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, Examples thereof include dimethyldimethoxysilane and dimethyldiethoxysilane. These can be used individually by 1 type or in combination of 2 or more types.

[Hydrolysis condensation reaction of silane compounds]
The hydrolytic condensation reaction of the silane compound in the present invention can be carried out by reacting one or more of the above silane compounds with water, preferably in the presence of an appropriate catalyst and an organic solvent.

When synthesizing a specific polyorganosiloxane by the above method (1a), the compound (si-1) may be used alone as the silane compound used for the synthesis, or together with the compound (si-1), other silanes As the compound, at least one of a silane compound (si-2) and another silane compound (si-3) may be used in combination. The use ratio of the silane compound (si-1) is preferably 5 mol% or more, more preferably 10 to 70 mol%, with respect to the total amount of the silane compound used in the reaction, and 20 to 50. More preferably, it is mol%.
When synthesizing a specific polyorganosiloxane by the above method (2a), the compound (si-2) may be used alone as the silane compound used for the synthesis, or together with the compound (si-2), other silanes As the compound, at least one of a silane compound (si-1) and another silane compound (si-3) may be used in combination. The use ratio of the silane compound (si-2) is preferably 70 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more with respect to the total amount of the silane compound used in the reaction. More preferably.

The ratio of water used in the hydrolysis condensation reaction is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, relative to a total of 1 mol of the silane compound.
As said catalyst, an acid, an alkali metal compound, an organic base, a titanium compound, a zirconium compound etc. can be mentioned, for example. Specific examples of these catalysts include acids such as hydrochloric acid, sulfuric acid, nitric acid, formic acid, succinic acid, acetic acid, trifluoroacetic acid, trifluoromethanesulfonic acid, phosphoric acid, acidic ion exchange resins, and various Lewis acids;
Examples of alkali metal compounds include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like;
Examples of organic bases include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine and pyrrole:
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene:
And quaternary organic amines such as tetramethylammonium hydroxide; Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
As the catalyst, alkali metal compounds or organic compounds can be used from the viewpoints of suppressing side reactions such as ring opening of epoxy groups, increasing the rate of hydrolysis and condensation, and excellent storage stability. A base is preferred, and an organic base is particularly preferred.
The amount of the organic base used varies depending on the reaction conditions such as the type of organic base and temperature, and should be set as appropriate. More preferably, it is 0.05-1 times mole.

Examples of the organic solvent that can be used in the hydrolysis condensation reaction include hydrocarbons, ketones, esters, ethers, alcohols, and the like.
Specific examples thereof include hydrocarbons such as toluene and xylene;
Examples of ketones include methyl ethyl ketone, methyl isobutyl ketone, methyl n-amyl ketone, diethyl ketone, and cyclohexanone;
Examples of esters include ethyl acetate, n-butyl acetate, i-amyl acetate, propylene glycol monomethyl ether acetate, 3-methoxybutyl acetate, and ethyl lactate;
Ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, dioxane and the like;
Examples of the alcohol 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-butyl ether, propylene glycol monomethyl ether, And propylene glycol monoethyl ether and propylene glycol mono-n-propyl ether; respectively. Of these, it is preferable to use a water-insoluble organic solvent. In addition, these organic solvents can be used individually by 1 type or in mixture of 2 or more types.
The ratio of the organic solvent used in the hydrolysis condensation reaction is preferably 10 to 10,000 parts by weight, more preferably 50 to 1,000 parts by weight, with respect to 100 parts by weight of the total silane compounds.

The hydrolysis condensation reaction is preferably carried out by dissolving the silane compound as described above in an organic solvent, mixing this solution with an organic base and water, and heating the solution with, for example, an oil bath.
During the hydrolysis condensation reaction, the heating temperature is preferably 130 ° C. or lower, more preferably 40 to 100 ° C., and preferably 0.5 to 12 hours, more preferably 1 to 8 hours. During heating, the mixture may be stirred or placed under reflux.
After completion of the reaction, the organic solvent layer separated from the reaction solution is preferably washed with water. In this washing, washing with water containing a small amount of salt, for example, an aqueous ammonium nitrate solution of about 0.2% by weight is preferable because the washing operation is facilitated. Washing is performed until the aqueous layer after washing becomes neutral, and then the organic solvent layer is dried with a desiccant such as anhydrous calcium sulfate or molecular sieves as necessary, and then the solvent is removed to remove the solvent. The polyorganosiloxane (specific polyorganosiloxane in the case of method (1a) and epoxy group-containing polyorganosiloxane in the case of method (2a)) can be obtained.

[Carboxylic acid (C-1)]
When the compound [D] in the present invention is obtained by the above method (2a), the carboxylic acid (C-1) used for the reaction with the epoxy group-containing polyorganosiloxane has its structure as long as it has a polymerizable unsaturated bond. Is not particularly limited. Preferable specific examples of such carboxylic acid (C-1) include, for example, acrylic acid, methacrylic acid, 2-acryloxyethyl-2-hydroxyethyl-phthalic acid, 2- (meth) acryloyloxyethyl hexahydrophthal Examples include acids and compounds represented by the following formulas (c-1) to (c-20). These can be used individually by 1 type or in combination of 2 or more types.

[Reaction of epoxy group-containing polyorganosiloxane and carboxylic acid (C-1)]
The reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid (C-1) can be preferably carried out in the presence of a catalyst and an organic solvent.

As the carboxylic acid used for the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid (C-1), the carboxylic acid (C-1) can be used alone or in combination with other carboxylic acids. Examples of other carboxylic acids that can be used here include formic acid, acetic acid, propionic acid, benzoic acid, and methylbenzoic acid.
The proportion of carboxylic acid (C-1) used is preferably 30 mol% or more, more preferably 35 mol% or more, based on the total amount of carboxylic acid used in the reaction.
The proportion of carboxylic acid (total amount) used is preferably 5 mol% or more, more preferably 10 to 80 mol%, and still more preferably based on the epoxy group of the epoxy group-containing polyorganosiloxane. It is 15-60 mol%, Most preferably, it is 20-40 mol%.
In addition, compound [D] can be made into the polyorganosiloxane which further has an epoxy group by making the usage-amount of carboxylic acid less than the epoxy group which an epoxy-group-containing polyorganosiloxane has.

As the catalyst used in the reaction, for example, a compound known as a so-called curing accelerator that accelerates the reaction of an organic base or an epoxy compound can be used.
Here, examples of the organic base include primary and secondary organic amines such as ethylamine, diethylamine, piperazine, piperidine, pyrrolidine, and pyrrole;
Tertiary organic amines such as triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine, diazabicycloundecene;
And quaternary organic amines such as tetramethylammonium hydroxide. Of these, tertiary organic amines or quaternary organic amines are preferred as the organic base.
Examples of the curing accelerator include tertiary amines such as benzyldimethylamine and 2,4,6-tris (dimethylaminomethyl) phenol;
Imidazole compounds such as 2-methylimidazole, 2-n-heptylimidazole, 2-n-undecylimidazole, 2-phenylimidazole;
Organophosphorus compounds such as diphenylphosphine and triphenylphosphine;
Quaternary phosphonium salts such as benzyltriphenylphosphonium chloride, tetra-n-butylphosphonium bromide, methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide;
Diazabicycloalkenes such as 1,8-diazabicyclo [5.4.0] undecene-7 and organic acid salts thereof; organometallic compounds such as zinc octylate, tin octylate and aluminum acetylacetone complex;
Quaternary ammonium salts such as tetraethylammonium bromide, tetra-n-butylammonium bromide, tetraethylammonium chloride, tetra-n-butylammonium chloride;
Boron compounds such as boron trifluoride and triphenyl borate;
Metal halides such as zinc chloride and stannic chloride;
High melting point dispersion type latent curing accelerators such as amine addition type accelerators such as dicyandiamide and adducts of amine and epoxy resin; curing accelerators such as the above imidazole compounds, organophosphorus compounds and quaternary phosphonium salts Microcapsule type latent curing accelerator coated with polymer on surface; amine salt type latent curing accelerator; high temperature dissociation type thermal cationic polymerization type latent curing accelerator such as Lewis acid salt and Bronsted acid salt Curable curing accelerator; 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 with respect to 100 parts by weight of the epoxy group-containing polyorganosiloxane. The

Examples of the organic solvent that can be used in the reaction between the epoxy group-containing polyorganosiloxane and the carboxylic acid (C-1) include hydrocarbon compounds, ether compounds, ester compounds, ketone compounds, amide compounds, and alcohol compounds. be able to. Of these, ether compounds, ester compounds, and ketone compounds are preferred from the viewpoints of solubility of raw materials and products, and ease of purification of the products, and specific examples of particularly preferred solvents include 2-butanone and 2-hexanone. And methyl isobutyl ketone and butyl acetate.
The organic solvent is preferably used at a solid content concentration (ratio in which the total weight of components other than the solvent in the reaction solution occupies the total weight of the solution) is 0.1% by weight or more, and 5 to 50% by weight. It is more preferable to use at a ratio of%.
The reaction temperature is preferably 0 to 200 ° C, more preferably 50 to 150 ° C. The reaction time is preferably 0.1 to 50 hours, more preferably 0.5 to 20 hours.

[Vertical orientation group]
When the liquid crystal aligning agent of the present invention is applied to a vertical alignment type liquid crystal display element, the specific polyorganosiloxane as the compound [D] is a vertical alignment group for imparting good vertical alignment to the coating film. You may have. Examples of such vertical alignment groups include alkyl groups having 4 to 40 carbon atoms, fluoroalkyl groups having 4 to 40 carbon atoms, alkoxy groups having 4 to 40 carbon atoms, groups having a steroid skeleton having 17 to 51 carbon atoms, and many And a group having a ring structure.
Here, examples of the alkyl group include an n-butyl group, an n-pentyl group, an n-hexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-hexadecyl group, and an n-octadecyl group. ;
Examples of the fluoroalkyl group include trifluoromethylpropyl group, trifluoromethylbutyl group, trifluoromethylhexyl group, trifluoromethyldecyl group, pentafluoroethylpropyl group, pentafluoroethylbutyl group, pentafluoroethyloctyl group and the like. ;
Examples of the alkoxy group include a butoxy group, a pentyloxy group, a hexyloxy group, a hexyloxy group, and an octyloxy group;
Examples of the group having a steroid skeleton include a cholestanyl group, a cholestenyl group, and a lanostannyl group;
Examples of the group having a polycyclic structure include 4,4′-biphenylene group, 4,4′-bicyclohexylene group, and the following formula:
A group having at least one selected from the group consisting of;

As a method for introducing a vertical alignment group into a specific polyorganosiloxane, for example,
(1b) A method in which a polyorganosiloxane having a polymerizable unsaturated bond and an epoxy group is reacted with the carboxylic acid (C-2) having the vertical alignment group;
(2b) a method of reacting the epoxy group-containing polyorganosiloxane with the carboxylic acid (C-1) and the carboxylic acid (C-2);
(3b) at least one nucleophilic compound selected from the group consisting of a polyorganosiloxane having a polymerizable unsaturated bond, the thiol compound having the vertical alignment group, and the amine compound having the vertical alignment group ( a method of reacting r1) with;
Etc.

[Carboxylic acid (C-2)]
When the vertical alignment group is introduced into the specific polyorganosiloxane by the method (1b) or the method (2b), the carboxylic acid (C-2) reacted with the epoxy group of the polyorganosiloxane is the liquid crystal alignment property. As long as it has a group, its structure is not particularly limited. As a preferable specific example of such carboxylic acid (C-2), for example,
Long chain fatty acids such as caproic acid, n-octanoic acid, n-decanoic acid, n-dodecanoic acid, n-hexadecanoic acid, stearic acid;
Long-chain alkyl such as 4-n-hexylbenzoic acid, 4-n-octylbenzoic acid, 4-n-decylbenzoic acid, 4-n-dodecylbenzoic acid, 4-n-hexadecylbenzoic acid, 4-stearylbenzoic acid A benzoic acid having a group;
Long such as 4-n-hexyloxybenzoic acid, 4-n-octyloxybenzoic acid, 4-n-decyloxybenzoic acid, 4-n-dodecyloxybenzoic acid, 4-n-hexadecyloxybenzoic acid, 4-stearyloxybenzoic acid Benzoic acid having a chain alkoxy group;
Cholestanyloxybenzoic acid, cholestenyloxybenzoic acid, lanostannyloxybenzoic acid, cholestanyloxycarbonylbenzoic acid, cholestenyloxycarbonylbenzoic acid, lanostanyloxycarbonylbenzoic acid, succinic acid-5ξ-cholestan-3-yl, Benzoic acid having a steroid skeleton such as succinic acid-5ξ-cholesten-3-yl, succinic acid-5ξ-lanostane-3-yl;
4- (4-pentyl-cyclohexyl) benzoic acid, 4- (4-hexyl-cyclohexyl) benzoic acid, 4- (4-heptyl-cyclohexyl) benzoic acid, 4′-pentyl-bicyclohexyl-4-carboxylic acid, 4 '-Hexyl-bicyclohexyl-4-carboxylic acid, 4'-heptyl-bicyclohexyl-4-carboxylic acid, 4'-pentyl-biphenyl-4-carboxylic acid, 4'-hexyl-biphenyl-4-carboxylic acid, 4 '-Heptyl-biphenyl-4-carboxylic acid, 4- (4-pentyl-bicyclohexyl-4-yl) benzoic acid, 4- (4-hexyl-bicyclohexyl-4-yl) benzoic acid, 4- (4- Heptyl-bicyclohexyl-4-yl) benzoic acid, 6- (4′-cyanobiphenyl-4-yloxy) hexanoic acid and the like Benzoic acid;
And fluoroalkyl group-containing carboxylic acids such as 6,6,6-trifluorohexanoic acid and 4- (4,4,4-trifluorobutyl) benzoic acid; These can be used individually by 1 type or in combination of 2 or more types.
In addition, when introducing a vertical alignment group by the method (2b), the carboxylic acid (C-2) is included in the “other carboxylic acid” in the method (2a).

In the case of using the method (1b) in the reaction between the epoxy group of the polyorganosiloxane and the carboxylic acid (C-2), the proportion of the carboxylic acid (C-2) used is based on the total amount of the carboxylic acid used in the reaction. Thus, it is preferably 75 mol% or more, and more preferably 90 mol% or more.
On the other hand, when the method (2b) is used, the proportion of the carboxylic acid (C-2) used is preferably 40 to 70 mol%, preferably 50 to 65 mol%, based on the total amount of carboxylic acid used in the reaction. More preferably.
In addition, each conditions, such as a catalyst and organic solvent which can be used for reaction, reaction temperature, and reaction time, are the catalyst and organic solvent which were demonstrated in reaction of the said epoxy group containing polyorganosiloxane and carboxylic acid (C-1). The description of each condition such as reaction temperature and reaction time can be applied.

[Nucleophilic compound (r1)]
On the other hand, when the vertical alignment group is introduced into the specific polyorganosiloxane by the method (3b), the nucleophilic compound (r1) may be a mercapto group or -NHR (where R is a hydrogen atom or As long as it has a C1-C6 alkyl group and the said vertical alignment group, the structure is not limited. As such a nucleophilic compound (r1),
Examples of amine compounds include pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine , Primary amines such as nonadecylamine, 4- (4-pentylcyclohexyl) -phenylamine, 4-octyloxyphenylamine;
For example, dibutylamine, dipentylamine, dihexylamine, diheptylamine, dioctylamine, dinonylamine, didecylamine, diundecylamine, didodecylamine, ditridecylamine, ditetradecylamine, dipentadecylamine, dihexadecylamine, dihepta Secondary amines such as decylamine, dioctadecylamine, dinonadecylamine; and the like.
Examples of thiol compounds include butanethiol, pentanethiol, hexanethiol, heptanethiol, octanethiol, nonanethiol, decanethiol, undecanethiol, dodecanethiol, tridecanethiol, tetradecanethiol, pentadecanethiol, hexadecanethiol, heptadecanethiol. , Octadecanethiol, nonadecanethiol, 4-butylbenzenethiol, 4-pentylbenzenethiol, 4-hexylbenzenethiol, 4-heptylbenzenethiol, 4-octylbenzenethiol, 4-decylbenzenethiol, 4-dodecylbenzenethiol, 4-tetradecylbenzenethiol, 4-hexadecylbenzenethiol, 4-butoxybenzenethiol, 4-hexyloxybe Zenchioru, 4-octyloxy benzenethiol, 4-dodecyloxy benzenethiol, 4- (4'-butylcyclohexyl) benzenethiol, 4- (4'-hexylcyclohexyl) benzenethiol, etc.; can be exemplified.

[Reaction of polyorganosiloxane having polymerizable unsaturated bond and nucleophilic compound (r1)]
The reaction between the polyorganosiloxane having a polymerizable unsaturated bond and the nucleophilic compound (r1) can be preferably carried out in the presence of a catalyst and an organic solvent.

When the vertically aligning group is introduced into the specific polyorganosiloxane by the method (3b), the nucleophilic compound (r1) may be used alone as the amino compound or thiol compound used in the reaction. Along with the compound (r1), at least one of other amino compounds and other thiol compounds may be used in combination. Specifically, as other amino compounds, for example, amino acid derivatives such as glycine and alanine, 4-aminobenzoic acid, sarcosine and the like; as other thiol compounds, for example, thioglycolic acid, mercaptopropionic acid, mercaptobutanoic acid, 4 -Mercaptobenzoic acid, N-acetylcysteine and the like;
The proportion of the nucleophilic compound (r1) used in the above reaction is preferably 1 mol% or more and 3 to 50 mol% or more with respect to the polymerizable unsaturated bonding group of the specific polyorganosiloxane. Is more preferable, and it is still more preferable that it is 5-30 mol%.

As said organic solvent, a polar compound can be used preferably, for example, a nitrile, a sulfoxide, ether, ester etc. can be mentioned. Specific examples of these include nitriles such as acetonitrile; sulfoxides such as dimethyl sulfoxide; ethers such as diethyl ether and dipropyl ether; esters such as ethyl acetate and butyl acetate; Can be mentioned. Moreover, when the nucleophilic compound (r1) is an amine, an alcohol can also be used as the organic solvent. Specific examples of the alcohol include trifluoroethanol and hexafluoroethanol.
From the viewpoint of reaction rate, the solvent is preferably used in such a ratio that the solid content concentration (the ratio of the total weight of components other than the solvent in the reaction solution to the total weight of the solution) is 40% by weight or more. More preferably, it is used at a ratio of ˜90% by weight.

Examples of the catalyst used for the reaction include aluminum chloride and formic acid when the nucleophilic compound (r1) is an amine. When the nucleophilic compound (r1) is a thiol, examples include organic bases, and specifically, tertiary amines such as trimethylamine, diethylmethylamine, ethyldimethylamine, triethylamine, and tripropylamine. Can be preferably used.
The reaction temperature is preferably 10 to 100 ° C, more preferably 40 to 80 ° C. The reaction time is preferably 0.5 to 8 hours, more preferably 1 to 6 hours.

  In addition, when using specific polyorganosiloxane as compound [D], you may use what is marketed as polyorganosiloxane which has a (meth) acryloyl group. Examples of such commercially available products include AC-SQ, MAC-SQ (above, manufactured by Toagosei Co., Ltd.), PSS- (1-propyl methacrylate) -heptaisobutyl substituted product (manufactured by Sigma Aldrich Japan Co., Ltd.) And the like.

  The proportion of the compound [D] used in the liquid crystal aligning agent of the present invention is 1 to 100 weights with respect to 100 parts by weight of the polymer [A] when the polymer [A] is contained in the liquid crystal aligning agent. Part. By setting it to 1 part by weight or more, it is possible to impart a good pretilt angle characteristic to the coating film even with a relatively small light irradiation amount, and to sufficiently increase the response speed of the liquid crystal molecules. Moreover, the content rate of polymer [A] can be increased by setting it as 100 weight part or less, and, thereby, the liquid crystal orientation and electrical property of the coating film formed can be made favorable. As the said usage rate, it is more preferable that it is 1-70 weight part, and it is still more preferable that it is 3-50 weight part.

<< Compound [E] >>
Compound [E] is a compound having an epoxy group and a polymerizable unsaturated bond and having a molecular weight of 2,000 or less, and examples thereof include a compound represented by the following formula (1).
(In Formula (1), Z is an epoxy group, W is a group having a polymerizable unsaturated bond, and R ¹ is an (m + n) -valent organic group. M and n are each independently 1 It is an integer of ~ 8.)

It is not particularly restricted but includes divalent organic group R ¹ in the formula (1), for example, like hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may be a chain hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group. Here, the chain hydrocarbon group means a saturated hydrocarbon group and an unsaturated hydrocarbon group which are composed of only a chain structure without including a cyclic structure in the main chain. However, both linear and branched are included. The alicyclic hydrocarbon group means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it is not necessary to be comprised only by the structure of an alicyclic hydrocarbon, The thing which has a chain structure in the part is also included. An aromatic hydrocarbon means a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it is not necessary to be composed only of an aromatic ring structure, and a part thereof may include a chain structure or an alicyclic hydrocarbon structure. In addition, the divalent organic group of R ¹ has —O—, —COO—, —CO—, —NH—, —NH—CO— or the like between the carbon-carbon bonds in the hydrocarbon group. It may have a substituent such as a halogen atom, an alkoxy group, a hydroxyl group, or a cyano group.
m and n are each preferably an integer of 1 to 5, and more preferably an integer of 1 to 3.
W may be a group having a polymerizable unsaturated bond, and its structure is not particularly limited, but at least one is a group represented by the following formula (2) (hereinafter also referred to as a specific group (g2)). It is preferable that
(In Formula (2), R ² is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom. * Represents a bond.)

Y ³ and Y ⁴ in the formula (2) are each preferably an oxygen atom.
The molecular weight of the compound [E] is 2,000 or less, preferably 1,500 or less, more preferably 1,000 or less, from the viewpoint of uniform dispersibility in the solution.

Compound [E] is, for example,
(1c) By reacting a compound (ex-1) having two or more epoxy groups with a carboxylic acid having a polymerizable unsaturated bond, polymerization is performed on a part of the epoxy groups of the compound (ex-1). A method of introducing a group having a polymerizable unsaturated bond;
(2c) at least one nucleophilic compound selected from the group consisting of a compound (ex-2) having two or more polymerizable unsaturated bonds, an amino compound having an epoxy group, and a thiol compound having an epoxy group (Ex-3) and a method of introducing an epoxy structure into a part of the polymerizable unsaturated bond of the compound (ex-2);
Etc.
In addition, compound [E] can use the compound obtained by the said method (1c) or (2c) individually by 1 type or in combination of 2 or more types.

-About method (1c) [compound (ex-1)]
Although the structure will not be specifically limited if a compound (ex-1) has two or more epoxy groups, For example, the compound represented by a following formula (e1-1) can be used.
(In formula (e1-1), Z is an epoxy group, R ⁵ is an m-valent organic group, and m is an integer of 2 to 6.)

In the formula (e1-1), R ⁵ is an m-valent organic group. A specific example of the organic group can be applied to the description of R ¹ in the formula (1).
m is preferably 2 to 4, and more preferably 2 or 4.

Preferable specific examples of the compound (ex-1) include, for example, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl. Ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N , N ′, N′-tetraglycidyl-p-phenylenediamine, N, N, N ′, N′-tetraglycidyl-m-phenylenediamine, N, N, N ′, N′-tetraglycidyl-4 4′-diaminodiphenylmethane, N, N, N ′, N′-tetraglycidyl-4, 4′-diaminodiphenyl ether, N, N, N ′, N′-tetraglycidyl-2,2′-dimethyl-4,4 '-Diaminobiphenyl, 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-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, N, N, N ′, N′-tetraglycidyl-1,2-diaminocyclohexane, N, N, N ′, N′-tetraglycidyl-1,3- Diaminocyclohexane, N, N, N ′, N′-tetraglycidyl-1,4-diaminocyclohexane, bis (N, N-diglycidyl-4-aminocyclohexyl) methane, bis (N, N-diglycidyl-2-methyl-) 4-aminocyclohexyl) methane, bis (N, N-diglycidyl-3-methyl-4-aminocyclohexyl) methane, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, 1,4-bis (N , N-diglycidylaminomethyl) cyclohexane, 1,3-bis (N, N-diglycidylaminomethyl) benzene, 1,4-bis (N, N-diglycidylaminomethyl) benzene, 1,3,5- Tris (N, N-diglycidylaminomethyl) cyclohexane, 1,3,5-tris (N, N-diglycidylaminomethyl) ) Benzene, the following formula (e1-1-1) ~ (e1-1-3)
And the like, and the like.

[Carboxylic acid having a polymerizable unsaturated bond]
Examples of the carboxylic acid having a polymerizable unsaturated bond that can be used in the method (1c) include those exemplified as specific examples of the carboxylic acid (C-1). In addition, as said carboxylic acid, said thing can be used individually by 1 type or in mixture of 2 or more types.

[Reaction of Compound (ex-1) with Carboxylic Acid]
The reaction of the compound (ex-1) and the carboxylic acid having a polymerizable unsaturated bond can be preferably performed in the presence of a catalyst and an organic solvent.

The ratio of the carboxylic acid having a polymerizable unsaturated bond in the above reaction is 0.01 to 10 equivalents and 0.1 to 3 equivalents with respect to 1 equivalent of the epoxy group of the compound (ex-1). It is preferable that it is 0.2-1 equivalent.
Reaction temperature becomes like this. Preferably it is 10-200 degreeC, More preferably, it is 50-120 degreeC, More preferably, it is 70-110 degreeC. The reaction time is preferably 0.5 to 20 hours, more preferably 1 to 10 hours.

The organic solvent is not particularly limited as long as it can dissolve the compound (ex-1) and a carboxylic acid having a polymerizable unsaturated bond. Preferable specific examples of the organic solvent include N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide and the like.
The organic solvent is preferably used at a solid content concentration (ratio of the total weight of components other than the solvent in the reaction solution in the total weight of the solution) from 1 to 50% by weight from the viewpoint of the reaction rate. More preferably, it is used at ˜40% by weight, more preferably 5˜20% by weight. Examples of the catalyst include the compounds exemplified as the catalyst that can be used for the reaction of the epoxy group-containing polyorganosiloxane and the carboxylic acid (C-1). As the catalyst used for the reaction, a quaternary ammonium salt is particularly preferable.
In the above reaction, for example, a commercially available polymerization inhibitor may be added in order to prevent gelation.

-About method (2c) [compound (ex-2)]
As the compound having a polymerizable unsaturated bond used in the method (2c), for example, a compound having two or more specific groups (g2) can be preferably used. Specific examples thereof include compounds exemplified as specific examples of di (meth) acrylate in the specific monomer. In addition, as a compound (ex-2), the said thing can be used individually by 1 type or in mixture of 2 or more types.

[Nucleophilic compound (ex-3)]
The nucleophilic compound (ex-3) is a compound having a mercapto group or —NHR (where R represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms) and an epoxy group, and the rest The structure is not particularly limited. Preferable specific examples of the nucleophilic compound (ex-3) include, for example, 1,2-epoxyethylamine, 2,3-epoxypropylamine, 3,4-epoxybutylamine, N-methyl as an amino compound having an epoxy group. -1,2-epoxyethylamine, N-ethyl-2,3-epoxypropylamine, N-methyl-2,3-epoxypropylamine, N-ethyl-2,3-epoxypropylamine, etc .; having an epoxy group Examples of the thiol compound include 2,3-epoxypropane-1-mercaptan, 3,4-epoxybutane-1-mercaptan, 4,5-epoxy-n-pentane-1-mercaptan, and 5,6-epoxy-n-hexane. -1-mercaptan and the like;

[Reaction of Compound (ex-2) with Nucleophilic Compound (ex-3)]
The reaction between the compound (ex-2) having two or more polymerizable unsaturated bonds and the nucleophilic compound (ex-3) can be preferably carried out in the presence of a catalyst and an organic solvent.
The proportion of the nucleophilic compound (ex-3) used is 0.01 to 10 equivalents and 0.1 to 3 equivalents relative to 1 equivalent of the polymerizable unsaturated bonding group that the compound (ex-2) has. It is preferable that it is, and it is more preferable that it is 0.2-1 equivalent.
Regarding the conditions such as the catalyst and organic solvent that can be used in the reaction and the reaction temperature, the catalyst and organic solvent described in the reaction of the specific polyorganosiloxane and the nucleophilic compound (r1), the reaction temperature, etc. A description of each condition can be applied.

The proportion of the compound [E] used in the liquid crystal aligning agent of the present invention is 1 to 100 weights with respect to 100 parts by weight of the polymer [A] when the polymer [A] is contained in the liquid crystal aligning agent. Part. By making it 1 part by weight or more, the long-term heat resistance of the liquid crystal alignment film to be formed can be made better, and by making it 100 parts by weight or less, the content ratio of the polymer component can be increased. The mechanical strength, liquid crystal orientation, and electrical characteristics of the coating film can be improved. The use ratio is more preferably 1 to 70 parts by weight, and further preferably 3 to 50 parts by weight.
On the other hand, when the liquid crystal aligning agent contains the specific polyorganosiloxane (compound [D]) without containing the polymer [A] as the polymer component, the liquid crystal aligning agent is used with respect to 100 parts by weight of the specific polyorganosiloxane. The amount is preferably 1 to 100 parts by weight, more preferably 1 to 50 parts by weight, and still more preferably 3 to 20 parts by weight.

As the polymer component in the liquid crystal aligning agent of the present invention, the compound [D], that is, the specific polyorganosiloxane may be contained alone, but the polymer [A] is contained alone or together with the specific polyorganosiloxane. It is preferable. By including the polymer [A] in the liquid crystal aligning agent, various properties such as liquid crystal alignment, voltage holding ratio, heat resistance, and mechanical strength of the formed coating film can be improved.
Here, in the liquid crystal aligning agent containing the polymer [A] and the specific polyorganosiloxane as the polymer component, a desired pretilt angle characteristic can be imparted to the coating film even with a relatively small amount of light irradiation. Unevenness may easily occur. This is presumably due to the low viscosity of the polyorganosiloxane. In this respect, in the mixed system of the polymer [A] and the specific polyorganosiloxane, by including the compound [E] as a constituent component of the liquid crystal aligning agent, coating unevenness is formed in the coating film formed using the liquid crystal aligning agent. Can be suitably suppressed.

≪Other ingredients≫
The liquid crystal aligning agent of this invention may contain the other component as needed. Examples of such other components include compounds other than the polymer [A] and the specific polyorganosiloxane other than the compound [E] and a compound having at least one epoxy group in the molecule (hereinafter referred to as “the polymer [A]”). , “Epoxy group-containing compound”), functional silane compounds, and the like.

<Other polymers>
The above other polymers can be used for improving solution properties and electrical properties. Examples of such other polymers include polyesters, polyamides, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, poly (meth) acrylates, and the like.
When other polymers are added to the liquid crystal aligning agent, the blending ratio is preferably 50% by weight or less, more preferably 0.1 to 40% by weight, more preferably 0.1% by weight to the total amount of the polymer in the composition. 1 to 30% by weight is more preferable.

<Epoxy group-containing compound>
The epoxy group-containing compound can be used to improve the adhesion and electrical properties with the substrate surface in the liquid crystal alignment film. Here, examples of the epoxy group-containing compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1 , 6-hexanediol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodi Enirumetan, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - may be mentioned as being preferred and cyclohexylamine.
In addition, as an example of the epoxy group-containing compound, an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can also be used.
When these epoxy compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal aligning agent. preferable.

<Functional silane compound>
The functional silane compound can be used for the purpose of improving the printability of the liquid crystal aligning agent. Examples of such functional silane compounds include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl). ) -3-Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3- Aminopropyltrimethoxysilane, N-triethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl -3,6- Methyl azananoate, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycid And xylpropyltrimethoxysilane.
When these functional silane compounds are added to the liquid crystal aligning agent, the blending ratio is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight, based on 100 parts by weight of the total polymer.

  As other components, in addition to the above, a compound having at least one oxetanyl group in the molecule, an antioxidant, or the like can be used.

≪Solvent≫
The liquid crystal aligning agent of the present invention is preferably constituted by dissolving the above compound [D] and compound [E], and other components optionally blended as necessary, in an organic solvent.
Here, examples of the solvent used for preparing the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol Dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, dipropylene glycol monomethyl ether (DPM), diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, di Examples include isopentyl ether, ethylene carbonate, and propylene carbonate. These can be used alone or in admixture of two or more.

  The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later and preferably heated to form a liquid crystal alignment film or a liquid crystal alignment film. When the solid content concentration is less than 1% by weight, the film thickness of the coating film is too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive and a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases and the coating characteristics are increased. Is inferior.

The particularly preferable range of the solid content concentration varies depending on the method used when the liquid crystal aligning agent is applied to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10-50 degreeC, More preferably, it is 20-30 degreeC.

≪Liquid crystal alignment film and liquid crystal display element≫
The liquid crystal alignment film of the present invention is formed by the liquid crystal aligning agent prepared as described above. Moreover, the liquid crystal display element of this invention comprises the liquid crystal aligning film formed using the said liquid crystal aligning agent. The operation mode of the liquid crystal display element is not particularly limited, but is preferably a vertical alignment type. Below, while explaining the manufacturing method of the liquid crystal display element of this invention, the manufacturing method of the liquid crystal aligning film of this invention is also demonstrated in the description. Hereinafter, a method for manufacturing a vertical alignment type liquid crystal display element will be described as an example.

[First step: Formation of coating film]
First, the liquid crystal aligning agent of this invention is apply | coated on a board | substrate, Then, a coating film is formed on a board | substrate by heating an application surface.
First, as a pair of two substrates provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention is preferably formed on the surface of the transparent conductive film on the substrate, preferably by an offset printing method or a spin coating method. They are respectively applied by a roll coater method or an ink jet printing method. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As a transparent conductive film provided on one surface of the substrate, an NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. Can be used. In order to obtain a patterned transparent conductive film, for example, after forming a transparent conductive film without a pattern, a method of forming a pattern by photo-etching, a method of using a mask having a desired pattern when forming the transparent conductive film, etc. Can be. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.

  After applying the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied liquid crystal aligning agent. The pre-baking temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, and more preferably 0.5 to 5 minutes. Then, a baking (post-baking) process is implemented for the purpose of removing a solvent completely and heat imidating the amic acid structure which exists in a polymer as needed. The post-bake temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C. The post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the film thickness of the formed film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm.

By removing the organic solvent by heating after applying the liquid crystal aligning agent, a coating film to be an alignment film is formed. At this time, 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 imide ring structure and an amic acid structure, It is good also as a more imidized coating film by advancing the dehydration ring-closing reaction by further heating after the coating film formation.
The coating film formed as described above can be used as it is as a liquid crystal alignment film, but may be rubbed as desired.

[Second step: Construction of liquid crystal cell]
Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and a liquid crystal cell is manufactured by disposing a liquid crystal between the two substrates disposed to face each other. Here, when the rubbing treatment is performed on the coating film, the two substrates are disposed to face each other so that the rubbing directions in the respective coating films are at a predetermined angle, for example, orthogonal or antiparallel.

In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method (vacuum injection method). First, two substrates are arranged opposite to each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the substrate surface and the sealant are bonded. After injecting and filling the liquid crystal into the cell gap partitioned by (1), the liquid crystal cell is manufactured by sealing the injection hole. The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped to predetermined locations on the surface of the liquid crystal alignment film. Thereafter, the other substrate is bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, thereby manufacturing a liquid crystal cell. . Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase and then gradually cooled to room temperature. It is desirable to remove.

As the sealing agent, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
Examples of the liquid crystal include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenylcyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyls. A cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like can be used. Further, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck & Co., Inc.). A ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
The thickness of the liquid crystal molecule layer is preferably 1 to 5 μm.

[Third step: light irradiation step]
After the construction of the liquid crystal cell, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films of the pair of substrates.
The voltage applied here can be, for example, 5 to 50 V direct current or alternating current.
As light to irradiate, for example, ultraviolet light and visible light including light having a wavelength of 150 to 800 nm can be used, but ultraviolet light including light having a wavelength of 300 to 400 nm is preferable. As a light source of 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, or the like can be used. In addition, the ultraviolet rays in the above preferable wavelength region can be obtained by means of using a light source in combination with, for example, a filter or a diffraction grating.

The amount of light irradiation is preferably 1,000 J / m ² or more and less than 100,000 J / m ² , more preferably 1,000 to 50,000 J / m ² . For example, in the production of a conventionally known PSA mode liquid crystal display element, it was necessary to irradiate light of about 100,000 J / m ^{2. In the} method for producing a liquid crystal display element according to the present invention, the amount of irradiation 50,000J / ^{m 2} or less, even when a further 10,000 J / ^{m 2} or less, it is possible to obtain a liquid crystal display device having a desired pretilt angle characteristic, the manufacturing cost of the liquid crystal display device Contributes to reduction. In addition, it is possible to suppress a decrease in electrical characteristics due to intense light irradiation and a decrease in the response of liquid crystal molecules to voltage changes.

And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.
As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film itself in which a polarizing film called an “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films The polarizing plate which consists of can be mentioned.

  The liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, PDAs, digital cameras, mobile phones, smartphones, It can be used for various display devices such as various monitors, liquid crystal televisions, and information displays.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

In the synthesis examples, the solution viscosity of each polymer solution, the imidization ratio of polyimide, and the weight average molecular weight of the polymer were measured by the following methods.
[Solution viscosity of polymer solution]
The solution viscosity [mPa · s] of the polymer solution was measured at 25 ° C. using an E-type rotational viscometer for a solution prepared to a polymer concentration of 10% by weight using a predetermined solvent.
[Imidation rate of polyimide]
The polyimide solution was poured into pure water, and the resulting 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 substance. From the obtained ¹ H-NMR spectrum, the imidization rate [%] was determined by the formula represented by the following formula (1x).
Imidation rate [%] = (1-A ¹ / A ² × α) × 100 (1x)
(In Formula (1x), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polymer precursor (polyamic acid). The number ratio of other protons to one proton of NH group in)
[Weight average molecular weight of polymer]
The weight average molecular weight Mw of the polymer is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions.
Column: Tosoh Co., Ltd., TSKgelGRCXLII
Solvent: Tetrahydrofuran Temperature: 40 ° C
Pressure: 68 kgf / cm ²
The epoxy equivalent is a value measured according to the “hydrochloric acid-methyl ethyl ketone method” of JIS C2105.
The following synthesis examples were repeated at the following synthesis scale as necessary to secure the necessary amount of product to be used in the following synthesis examples, examples and comparative examples.

<Synthesis of Polymer [A]>
[Synthesis Example 1]
110 g (0.50 mol) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride as tetracarboxylic dianhydride, 43 g (0.40 mol) of p-phenylenediamine as diamine and 3- (3,5-diamino) Benzoyloxy) cholestane 52 g (0.10 mol) was dissolved in 830 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours. A small amount of the obtained polyamic acid (PA-1) solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyamic acid concentration of 10% by weight was 60 mPa · s.
Next, 1,900 g of NMP was added to the obtained polyamic acid solution, 40 g of pyridine and 51 g of acetic anhydride were added, and dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with a new NMP (the pyridine and acetic anhydride used in the dehydration cyclization reaction were removed from the system in this operation), so that the imidation ratio was about 50%. A solution containing about 15% by weight of polyimide (PI-1) was obtained. A small amount of the obtained polyimide solution was taken, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 47 mPa · s.

<Synthesis of Compound [D]>
[Synthesis Example 2]
In a reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser, 378 g of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 375 g of 3-methacryloxypropyltrimethoxysilane, 753 g of methyl isobutyl ketone and Triethylamine 75g was charged and mixed at room temperature. Next, 602.3 g of deionized water was dropped from the dropping funnel over 30 minutes, and the mixture was reacted at 60 ° C. for 6 hours while mixing under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2 wt% ammonium nitrate aqueous solution until the washed water became neutral. Thereafter, the solvent and water were distilled off under reduced pressure to obtain polyorganosiloxane (EPS-1) as a viscous transparent liquid. The weight average molecular weight Mw of this polyorganosiloxane (EPS-1) was 2,900.

[Synthesis Example 3]
In a 200 mL three-necked flask, 10.0 g of polyorganosiloxane (EPS-1), 74.10 g of methyl isobutyl ketone, 3.08 g of 4- (trans-4-N-pentylcyclohexyl) benzoic acid (polyorganosiloxane (EPS-1) ) And 0.10 g of a trade name “UCAT 18X” (an epoxy compound curing accelerator, manufactured by San Apro Co., Ltd.), and reacted at 90 ° C. with stirring for 72 hours. Went. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate. A solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was evaporated to remove polyorganosiloxane (D- 7.8 g of 1) white powder was obtained. The weight average molecular weight Mw of the polyorganosiloxane (D-1) was 3,800.

[Synthesis Example 4]
In a 200 mL three-necked flask equipped with a thermometer, 33.0 g of a trade name “AC-SQ TA100” (hydrolysis condensate of 3-acryloxypropyltrimethoxysilane, manufactured by Toagosei Co., Ltd.), 1-octadecanethiol 5 .73 g (corresponding to 10 mol% of AC-SQ TA100 silicon atom), 6.37 g of mercaptopropionic acid (corresponding to 30 mol% of AC-SQ TA100 silicon atom), 45.1 g of acetonitrile and 16.2 g of triethylamine, The reaction was carried out at 50 ° C. for 1 hour. After completion of the reaction, acetonitrile and triethylamine were distilled off under reduced pressure to obtain polyorganosiloxane (D-2). The weight average molecular weight Mw of the polyorganosiloxane (D-2) was 3,300.

<Synthesis of Compound [E]>
[Synthesis Example 5]
In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube and a thermometer, 4.2 g of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 38.5 g of NMP, tetra 0.42 g of butylammonium bromide and 2.58 g of methacrylic acid were added and reacted at 90 ° C. for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed 3 times with 100 mL of water. Next, 68 g of butyl cellosolve was added and concentrated to 45 g, and then 68 g of butyl cellosolve was added and concentrated to 45 g.

[Synthesis Example 6]
In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen introduction tube and a thermometer, 4.2 g of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 33.5 g of NMP, tetra 0.42 g of butylammonium bromide and 1.71 g of methacrylic acid were added and reacted at 90 ° C. for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed 3 times with 100 mL of water. Next, 68 g of butyl cellosolve was added and concentrated to 45 g. Then, 68 g of butyl cellosolve was added and concentrated to 45 g, and butyl cellosolve was added to obtain a solution of compound (E-2) having a solid content concentration of 10%.

[Synthesis Example 7]
N, N, N ′, N′-tetraglycidyl-m-xylylenediamine 4.2 g, NMP 35.2 g, tetrabutylammonium bromide in a 100 mL three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer 0.42 g and methacrylic acid 2.01 g were added and reacted at 90 ° C. for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed 3 times with 100 mL of water. Next, 68 g of butyl cellosolve was added and concentrated to 45 g. Then, 68 g of butyl cellosolve was added and concentrated to 45 g, and butyl cellosolve was added to obtain a solution of the compound (E-3) having a solid content concentration of 10%.

[Synthesis Example 8]
In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer, 4.2 g of N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane, 31.9 g of NMP, tetra 0.42 g of butylammonium bromide and 1.43 g of acrylic acid were added and reacted at 90 ° C. for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed 3 times with 100 mL of water. Next, 68 g of butyl cellosolve was added and concentrated to 45 g. Then, 68 g of butyl cellosolve was added and concentrated to 45 g again, and butyl cellosolve was added to obtain a compound (E-4) solution having a solid content concentration of 10%.

[Synthesis Example 9]
In a 100 mL three-necked flask equipped with a reflux tube, a nitrogen inlet tube and a thermometer, 4.2 g of N, N, N ′, N′-tetraglycidyl-m-xylylenediamine, 33.3 g of NMP, tetrabutylammonium 0.42 g of bromide and 1.68 g of acrylic acid were added and reacted at 90 ° C. for 7 hours. After completion of the reaction, 200 mL of ethyl acetate was added, and liquid separation washing was performed 3 times with 100 mL of water. Next, 68 g of butyl cellosolve was added and concentrated to 45 g. Then, 68 g of butyl cellosolve was added and concentrated to 45 g again, and butyl cellosolve was added to obtain a solution of the compound (E-5) having a solid content concentration of 10%.

<Preparation of liquid crystal aligning agent>
[Example 1]
NMP and butyl cellosolve (BC) are added as an organic solvent to a solution containing polyimide (PI-1) as a polymer, and further compound (E-1) is used as compound [E], and compound (D-1 ) Is added so that the content ratio of polyimide (PI-1), compound (E-1) and compound (D-1) contained in the polymer solution is 100: 10: 10 (weight ratio). A solution having a composition of NMP: BC = 50: 50 (weight ratio) and a solid concentration of 8.0% by weight was obtained. A liquid crystal aligning agent was prepared by filtering this solution using a filter having a pore size of 1 μm.

<Manufacture and evaluation of liquid crystal display elements>
Using the liquid crystal aligning agent prepared above, the pattern of the transparent electrode (2 types) and the amount of ultraviolet irradiation (3 levels) were changed to produce a total of 6 liquid crystal display elements. Further, various characteristics of the manufactured liquid crystal display elements were evaluated.

[Production of liquid crystal cell having transparent electrode without pattern]
The liquid crystal aligning agent prepared above was applied onto the transparent electrode surface of a glass substrate having a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), and a hot plate at 80 ° C. After removing the solvent by heating (prebaking) for 1 minute above, it was heated (postbaked) for 10 minutes on a hot plate at 150 ° C. to form a coating film having an average film thickness of 600 mm.
The coating film was rubbed with a rubbing machine having a roll wrapped with a rayon cloth at a roll rotation speed of 400 rpm, a stage moving speed of 3 cm / sec, and a hair foot indentation length of 0.1 mm. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then drying was performed in a 100 ° C. clean oven for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film.

  Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure bonded. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. .

The above operation was repeated to produce three liquid crystal cells having unpatterned transparent electrodes. One of them was used for evaluation of the pretilt angle described later. The remaining two liquid crystal cells were irradiated with light in a state where a voltage was applied between the conductive films by the following method.
For two of the liquid crystal cells obtained above, an alternating current of 10 Hz is applied between the electrodes, and the liquid crystal is driven, using an ultraviolet irradiation device using a metal halide lamp as a light source, It was irradiated at a dose of 10,000 J / ^{m 2} or 100,000J / ^{m 2.} In addition, this irradiation amount is the value measured using the light meter measured on the basis of wavelength 365nm. The light irradiation amount 100,000 J / m ² is a value usually employed in the PSA mode.

<Evaluation of liquid crystal display element>
[Evaluation of pretilt angle]
About each liquid crystal display element manufactured above, nonpatent literature 1 (TJ Scheffer et.al., J.Appl.Phys.vol.48, p.1783 (1977)) and nonpatent literature 2 (F In accordance with a method described in Nakano, et.al., JPN.J.Appl.Phys.vol.19, p.2013 (1980)), a liquid crystal molecule is obtained by a crystal rotation method using He—Ne laser light The tilt angle from the substrate surface was measured. This measured value was defined as a pretilt angle. The liquid crystal display device of not irradiated with light, showing the respective pretilt angle of the liquid crystal display element and a liquid crystal display device of the dose 100,000J / ^{m 2} of dose 10,000 J / ^{m 2} in Table 2 below.

[Evaluation of heat resistance (heat resistance stability of voltage holding ratio)]
Among the liquid crystal display devices manufactured as described above, a liquid crystal cell irradiated with ultraviolet light was applied with a voltage of 5 V at 23 ° C. with an application time of 60 microseconds and a span of 167 milliseconds, and then 167 millimeters from the release of application. The voltage holding ratio (initial VHR) after 2 seconds was measured.
Subsequently, the liquid crystal display element after measurement of the initial VHR was allowed to stand for 5,000 hours in an oven set at a temperature of 120 ° C. Thereafter, the voltage holding ratio (VHR after heat stress) was measured in the same manner as described above. These voltage holding ratios [%] are shown in Table 2 below.
In addition, as a measuring apparatus, Toyo Technica Co., Ltd. make and VHR-1 were used.

[Manufacture of liquid crystal display element having patterned transparent electrode]
Each of the electrode surfaces of the glass substrate A and the substrate B each having ITO electrodes patterned in the slit shape as shown in FIG. On top of this, using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.), removing the solvent by heating (prebaking) on a hot plate at 80 ° C. for 1 minute, and then on a hot plate at 150 ° C. For 10 minutes (post-bake) to form a coating film having an average film thickness of 600 mm. The coating film was subjected to ultrasonic cleaning for 1 minute in ultrapure water and then dried in a clean oven at 100 ° C. for 10 minutes to obtain a substrate having a liquid crystal alignment film. This operation was repeated to obtain a pair (two) of substrates having a liquid crystal alignment film. The used electrode pattern is the same type as the electrode pattern in the PSA mode.

  Next, after applying an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm to the outer edges of the pair of substrates having the liquid crystal alignment film, the liquid crystal alignment film surfaces are overlapped and pressure-bonded so as to face each other. The adhesive was cured. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photo-curing adhesive to produce a liquid crystal cell. .

The above operation was repeated to produce three liquid crystal cells having patterned transparent electrodes. One of them was used for evaluation of the response speed of liquid crystal molecules described later. For the remaining two liquid crystal cells, 10,000 J / m ² or 100,000 J / m in a state where a voltage is applied between the conductive films by a method similar to the case of manufacturing a liquid crystal display element having a transparent electrode without pattern. After light irradiation with an irradiation amount of m ² , the response speed of liquid crystal molecules was evaluated.

[Evaluation of response speed of liquid crystal molecules]
For each of the liquid crystal display devices manufactured above, first, the luminance of light transmitted through the liquid crystal display device by irradiating a visible light lamp without applying a voltage was measured with a photomultimeter, and this value was 0% relative transmittance. It was. Next, the transmittance when AC 60 V was applied between the electrodes of the liquid crystal display element for 5 seconds was measured in the same manner as described above, and this value was defined as a relative transmittance of 100%. When 60 V AC is applied to each liquid crystal display element, the time until the relative transmittance shifts from 10% to 90% is measured, and this time is defined as the response speed, from voltage off to voltage on. The response of the liquid crystal molecules to the change of was evaluated. The liquid crystal display device of not irradiated with light, showing the liquid crystal display device of the dose 10,000 J / ^{m 2,} and each of the response speed of the liquid crystal display device of the dose 100,000J / ^{m 2} in Table 2 below.

[Examples 2 to 43 and Comparative Examples 1 and 2]
A liquid crystal aligning agent was prepared in the same manner as in Example 1 except that the types and amounts of the polymer [A], compound [D] and compound [E] contained in the liquid crystal aligning agent were changed as shown in Table 1 below. Prepared. Moreover, while using each of these liquid crystal aligning agents, the liquid crystal display element was manufactured similarly to Example 1, and the manufactured liquid crystal display element was evaluated. The evaluation results are shown in Table 2.

In Table 1, the abbreviations of the compounds are as follows.
<Compound [D]>
Compound (D-3): a mixture of compounds wherein n is an integer of 2 to 4 in the following formula (d-3)
(In formula (d-1), n is an integer of 2-4 each independently.)
Compound (D-4); trade name “AC-SQ TA100” (manufactured by Toagosei Co., Ltd.)
<Other ingredients>
Compound (F-1); 2,4,6-tris (3 ′, 5′-di-tert-butyl-4′-hydroxybenzyl) mesitylene Compound (F-2); N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenylmethane

As shown in Table 2, in Examples 1 to 43, even when light irradiation was performed at a relatively low dose of 10,000 J / m ² , the pretilt angle was shown and the response speed of the liquid crystal molecules was also high. It was fast enough. From these things, in Examples 1-43, it turned out that a desired pretilt angle characteristic can be provided with respect to a coating film with a smaller light irradiation amount.
Moreover, in Examples 1-43, it turned out that a high voltage holding ratio is maintained even after giving a high temperature stress for a long time, and it is excellent in long-term heat resistance.
On the other hand, in Comparative Example 1 containing no compound [D], even when the light irradiation was performed at 100,000 J / m ² , the pretilt angle and the response speed were almost the same as in the case of no light irradiation. Moreover, in the comparative example 2 which does not contain compound [E], the fall amount of the voltage retention after high temperature stress provision was large, and it was inferior to long-term heat resistance.

Claims (11)

Compound [E] having an epoxy group and a polymerizable unsaturated bond and having a molecular weight of 2,000 or less,
Compounds having two or more polymerizable unsaturated bonds [D] (provided that. Except those corresponding to the compound [E]) containing, as,
A liquid crystal aligning agent containing a polyorganosiloxane having two or more polymerizable unsaturated bonds as the compound [D] . The said compound [E] is a liquid crystal aligning agent of Claim 1 represented by following formula (1).
(In Formula (1), Z is an epoxy group, W is a group having a polymerizable unsaturated bond, and R ¹ is an (m + n) -valent organic group. M and n are each independently 1 It is an integer of ~ 8.) The said compound [E] is a liquid crystal aligning agent of Claim 1 or 2 which has group represented by following formula (2) as group which has the said polymerizable unsaturated bond.
(In Formula (2), R ² is a hydrogen atom or a methyl group, and Y ¹ and Y ² are each independently an oxygen atom or a sulfur atom. “*” Represents a bond.)   The liquid crystal alignment according to any one of claims 1 to 3, wherein the compound [E] is a reaction product of a compound having two or more epoxy groups and a carboxylic acid having the polymerizable unsaturated bond. Agent.   The compound [E] is a reaction product of a compound having two or more polymerizable unsaturated bonds and at least one selected from the group consisting of an amino compound having an epoxy group and a thiol compound having an epoxy group. The liquid crystal aligning agent according to any one of claims 1 to 3.   Furthermore, the liquid crystal aligning agent as described in any one of Claims 1 thru | or 5 containing at least 1 type of polymer [A] selected from the group which consists of a polyamic acid, a polyamic acid ester, a polyimide, and a polyorganosiloxane. The said compound [D] is a liquid crystal aligning agent as described in any one of Claims 1 thru | or 6 which has two or more groups represented by following formula (3) as a group which has the said polymerizable unsaturated bond.
(In Formula (3), R ³ is a hydrogen atom or a methyl group, Y ³ and Y ⁴ are each independently an oxygen atom or a sulfur atom. “*” Represents a bond.) The liquid crystal alignment as described in any one of Claims 1 thru | or 7 containing the compound which has two or more of the said polymerizable unsaturated bonds as said compound [D], and group represented by following formula (4). Agent.
(In the formula (4), Ac ¹ and Ac ² are independently a benzene ring or a cyclohexane ring, it may .X ^a may have a substituent is a single bond, 1 to 4 carbon atoms A divalent hydrocarbon group, an oxygen atom, a sulfur atom, or —COO—, where “*” represents a bond.) The 1st process of apply | coating the liquid crystal aligning agent as described in any one of Claim 1 thru | or 8 on this electrically conductive film of a pair of board | substrate which has an electrically conductive film, respectively, and then heating this, and forming a coating film. When,
A second step of constructing a liquid crystal cell by placing the pair of substrates on which the coating film is formed facing each other so that the coating film faces through a layer of liquid crystal molecules;
A third step of irradiating the liquid crystal cell with light while applying a voltage between the conductive films of the pair of substrates;
A method for producing a liquid crystal display element comprising: The liquid crystal aligning film formed using the liquid crystal aligning agent as described in any one of Claims 1 thru | or 8 . A liquid crystal display device comprising the liquid crystal alignment film according to claim 10 .