JP2014102335A - Liquid crystal aligning agent - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal aligning agent that can reproduce a relatively low pretilt angle stably by photo-aligning method and is excellent in coating property (printability) even when a general-purpose solvent is used.SOLUTION: The liquid crystal aligning agent contains at least one kind of polymer selected from the group consisting of polyorganosiloxane, polyamide, poly(thio)ester and (meth)acrylic acid copolymer, the polymer containing a divalent group represented by the following formula (1). In the formula (1), Rto Reach independently represent a hydrogen atom, a halogen atom, C1-C12 alkyl group, or C2-C12 alkenyl group, Yand Yeach independently represent divalent organic group, and each "*" represents a bond.

Description

The present invention relates to a liquid crystal aligning agent.
Specifically, the present invention relates to a liquid crystal aligning agent that can impart good liquid crystal alignment by a photo-alignment method and has a high degree of freedom in selecting a substrate to be used.

In a liquid crystal display element, a retardation film having a liquid crystal layer, and the like, a liquid crystal alignment film is provided on the substrate surface in order to align liquid crystal molecules in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the surface of the organic film formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, if the liquid crystal alignment film is formed by rubbing treatment, dust and static electricity are likely to be generated during the rubbing process, so that dust adheres to the alignment film surface and causes display defects. In the case of a substrate having elements, there is also a problem that circuit yield of the TFT elements occurs due to the generated static electricity and causes a reduction in product yield. Therefore, as another means of aligning the liquid crystal in the liquid crystal display element, a photo-alignment method has been proposed which imparts liquid crystal alignment ability by irradiating a radiation-sensitive organic thin film formed on the substrate surface with polarized or non-polarized radiation. (See Patent Documents 1 to 4). This photo-alignment method is expected to be applied to a retardation film having a liquid crystal layer in addition to a liquid crystal display element.
Liquid crystal display elements include TN (Twisted Nematic) type, STN (Super Twisted Nematic) type, VA (Vertical Alignment) type and other liquid crystal display elements having vertical electric field type liquid crystal cells, and IPS (In-Plane Switching). 2. Description of the Related Art A lateral electric field type liquid crystal display element that generates an electric field in a direction parallel to a substrate by forming an electrode only on the side of a pair of opposed substrates such as an FFS (Fringe Field Switching) type is known. (Patent Documents 5 to 7). This horizontal electric field type liquid crystal display element has wider viewing angle characteristics than a vertical electric field type liquid crystal display element, and can display a high quality. Since the horizontal electric field type liquid crystal display element responds to the electric field only in the direction in which the liquid crystal molecules are parallel to the substrate, the change in the refractive index in the major axis direction of the liquid crystal molecules is not a problem. There is little change in the contrast and the contrast of the displayed color, so that high-quality display is possible regardless of the viewing angle. In order to obtain such an advantageous effect, since it is advantageous that the incident angle dependency of incident polarized light is small, in the horizontal electric field type liquid crystal display element, in the initial alignment characteristics when no electric field is applied. A low pretilt angle is desirable.

Also in a horizontal electric field type liquid crystal display element, in order to avoid the drawbacks of the rubbing method described above when providing liquid crystal alignment properties to the liquid crystal alignment film, it is desirable to use a photo alignment method. However, the liquid crystal aligning agent applicable to said photo-alignment method will contain an aromatic structure in a large ratio in order to provide photosensitivity to the polymer contained therein. However, when a liquid crystal alignment film containing an aromatic structure in a large proportion is used, the pretilt angle inevitably increases, and the advantageous effects as described above in the lateral electric field type liquid crystal display element are diminished.
As a liquid crystal alignment film material that stably expresses a relatively low pretilt angle by a photo-alignment method, a technique for introducing a cyclobutane ring into the main chain of polyimide has been proposed (Patent Document 8). This technique is based on the idea that the cyclobutane ring present in rigid polyimide is decomposed by light irradiation to form a concavo-convex shape in the polymer film, and the liquid crystal alignment ability is expressed by the concavo-convex shape. This technology is an old technology filed in 1997, but has not yet been put into practical use. The reason seems to be in the following two points.
(1) Although the said polyimide is formed by carrying out the thermal imidation process of the coating film formed from the solution containing the polyamic acid which is the precursor, this thermal imidation does not advance completely. Therefore, since a flexible amic acid structure remains in a part of the polymer, the cyclobutane ring is not sufficiently decomposed by light irradiation, so that the desired liquid crystal alignment ability cannot be obtained, and (2) polyamic acid In addition, since polyimide has poor solubility in a general-purpose organic solvent, only a specific aprotic polar solvent having extremely high solubility can be used as the solvent to ensure applicability. Since such a solvent erodes many general-purpose plastics, a liquid crystal aligning agent containing the solvent cannot be applied to a resin substrate, and does not meet the demand for weight reduction of a liquid crystal display element. As a result, application to a retardation film in which triacetyl cellulose (TAC) is frequently used is greatly limited.

JP 2003-307736 A JP 2004-163646 A JP 2002-250924 A JP 2004-83810 A U.S. Pat. No. 5,928,733 JP 56-91277 A JP 2008-46184 A JP-A-9-297313

"UV curable liquid crystal and its application", Liquid Crystal, Vol. 3 No. 1 (1999), pp34-42

The present invention has been made to overcome the above-described current situation.
An object of the present invention is to provide a liquid crystal aligning agent that can stably develop a relatively low pretilt angle by a photo-alignment method, and is excellent in coatability (printability) even when a general-purpose solvent is used. .

According to the present invention, the above objects and advantages of the present invention are:
At least one polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester and (meth) acrylic acid copolymer, provided that this polymer is represented by the following formula (1) 2 It is achieved by a liquid crystal aligning agent characterized by containing a valent group.

(In Formula (1), R ^{I to} R ^IV are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms;
Y ¹ and Y ² are each independently a divalent organic group, and “*” indicates a bond that is bonded to the polymer chain. )

Since the liquid crystal aligning agent of the present invention can stably develop a relatively low pretilt angle by a photo-alignment method, the liquid crystal aligning agent is particularly preferably applied to the formation of a liquid crystal alignment film used for a liquid crystal display element of a horizontal electric field type. Can do.
In addition, since the polymer contained in the liquid crystal aligning agent of the present invention is excellent in solubility, even when a general-purpose organic solvent is used, it is excellent in coatability and can form a highly uniform liquid crystal alignment film. it can.
The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be suitably applied to a liquid crystal display element (particularly a horizontal electric field type liquid crystal display element), a retardation film having a liquid crystal layer, and the like.

The cross-sectional schematic for demonstrating the structure of the electrode pair which the liquid crystal display element manufactured in the Example has. FIG. 3 is a schematic plan view for explaining a comb structure of a top electrode included in a liquid crystal display element manufactured in an example.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of this invention contains the polymer (henceforth "specific polymer") which has a bivalent group represented by the said Formula (1).
<Specific polymer>
The specific polymer in the present invention is at least one polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester, and (meth) acrylic acid copolymer, which has the formula (1) It has a bivalent group represented by these.
In the divalent group represented by the above formula (1), a bond marked with “*” is bonded to the polymer chain ”means that the divalent group is in the main chain of the polymer. It means that it exists, or exists as part of a cross-linking bond that couples polymer chains two-dimensionally or three-dimensionally. That is, the divalent group does not exist as a side chain of the polymer or a part thereof, or as a side chain of the crosslinked structure or a part thereof. However, in the specific polymer, the divalent group represented by the above formula (1) may be present in the main chain or the crosslinked structure of the polymer, and the side chain of the polymer or a part thereof or the side of the crosslinked structure. It is not prohibited to have the same type of structure as a chain or part thereof.
The content ratio of the divalent group represented by the above formula (1) in the specific polymer is preferably 1.0 × 10 ⁻⁴ mol / g or more, and 3.0 × 10 ^{−4 to} 2.0. It is more preferable that it is * 10 < ^-3 > mol / g.

The specific polymer is a polyamide obtained by reacting, for example, a diamine and a polyvalent carboxylic acid containing a compound represented by the following formula (C) (hereinafter referred to as “compound (C)”);
At least one compound selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound;
A polyvalent carboxylic acid containing a compound represented by the following formula (C);
A poly (thio) ester obtained by reacting with
At least one compound selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound, provided that at least a part of this compound is a compound represented by the following formula (E) (hereinafter referred to as “compound (E)”). )
A polyvalent carboxylic acid;
A poly (thio) ester obtained by reacting with
(Meth) acrylic acid obtained by addition polymerization of a mixture of a polymerizable unsaturated compound containing (meth) acrylic acid and a compound represented by the following formula (A) (hereinafter referred to as “compound (A)”) Copolymer;
It may be a polyorganosiloxane obtained by hydrolysis / condensation of a silane compound containing a compound represented by the following formula (S) (hereinafter referred to as “compound (S)”).

(In the formula (C), R ^{I to} R ^IV , Y ¹ and Y ² have the same meanings as in the above formula (1).)

(In the formula (E), R ^{I to} R ^IV , Y ¹ and Y ² each have the same meaning as in the above formula (1);
Z ¹ and Z ² are each independently a hydroxyl group, a thiol group, or an epoxy group. )

(In formula (S), R ^{I to} R ^IV , Y ¹ and Y ² each have the same meaning as in formula (1) above;
R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms;
X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom;
n1 and n2 are each independently an integer of 1 to 3. )

(In the formula (A), R ^{I to} R ^IV , Y ¹ and Y ² each have the same meaning as in the above formula (1);
R ³ and R ⁴ are each independently a water chain atom or a methyl group. )
As is clear from the above chemical formula, the divalent group represented by the formula (1) is derived from the compound (C), (E), (A) or (S). These compounds can be obtained by reacting a tetracarboxylic dianhydride represented by the following formula (T) with a primary amine compound.

(In formula (T), R ^{I to} R ^IV each have the same meaning as in formula (1) above.)
Examples of the tetracarboxylic dianhydride represented by the above formula (T) include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2, 3, 4-cyclobutane tetracarboxylic dianhydride etc. can be mentioned, One or more sorts chosen from these can be used.
The primary amine compound to be reacted with the tetracarboxylic dianhydride as described above will be described in the description of the compound (C), (E), (A) or (S).

[Synthesis of Compound (C)]
Compound (C) can be obtained, for example, by reacting a tetracarboxylic dianhydride represented by the above formula (T) with an amino acid. This amino acid is a compound having one primary amino group and one carboxy group in the molecule. In this case, the above formula (C) group Y ¹ in ^(hence the above equation (1) group in Y ¹⁾ becomes a divalent group obtained by removing the amino and carboxy groups from the amino acids.
Examples of the amino acid include glycine, alanine, leucine, isoleucine, phenylalanine, valine, 4-aminobutyric acid, and the like, and one or more selected from these can be used.
The reaction of the tetracarboxylic dianhydride represented by the above formula (T) with an amino acid can be carried out by heating a mixture of these compounds, preferably in an appropriate solvent.
The ratio of both compounds in this reaction is preferably 1.0 to 4.0 moles, and preferably 1.5 to 3.0 moles, as the ratio of amino acid to 1 mole of tetracarboxylic dianhydride. Is more preferably 1.8 to 2.5 mol.
The solvent used in this reaction is preferably an organic solvent, and for example, an aprotic polar solvent, phenol and derivatives thereof, alcohol, ketone, ester, ether, halogenated hydrocarbon, hydrocarbon, etc. are used. Can do.

Specific examples of these organic solvents include, for example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea as the aprotic polar solvent. Hexamethylphosphotriamide, pyridine, 2-picoline, 3-picoline, 4-picoline and the like;
Examples of the phenol derivative include m-cresol, xylenol, halogenated phenol and the like;
Examples of the alcohol include methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, and ethylene glycol monomethyl ether;
Examples of the ketone include acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone;
Examples of the ester include ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, and diethyl malonate;
Examples of the ether include diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate. Diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran 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, isoamylpropionate, isoamylisobutyrate, diisopentyl ether, and the like, and one selected from these It is preferable to use the above.

The use ratio of the solvent is preferably 50 to 5,000 parts by weight, more preferably 100 to 3,000 parts by weight with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and amino acid. 100 to 2,000 parts by weight is more preferable.
The reaction between the tetracarboxylic dianhydride and the amino acid is preferably 50 to 300 ° C, more preferably 80 to 200 ° C, preferably 0.1 to 20 hours, more preferably 0.1 to 10 hours. Done. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the above temperature and reaction time range.

[Synthesis of Compound (E)]
Among the compounds (E), a compound in which Z ¹ and Z ² are a hydroxy group or a thiol group is, for example, a tetracarboxylic dianhydride represented by the above formula (T), depending on the type of Z ¹ and Z ² Can be obtained by reaction of the product with aminoalcohol or aminothiol. In this case, the above formula (E) group in Y ^{1 (hence} the above equation (1) group in Y ¹⁾ is 2 obtained by removing the amino group from the amino alcohol or amino thiol, and hydroxyl or a thiol group, a It is a valent group.
Examples of the amino alcohol include 2-aminoethanol, 3-aminopropanol, 4-aminophenol, 4-aminobenzyl alcohol, 2- (4-aminophenyl) ethanol and the like;
Examples of the aminothiol include 3-thiolaniline, 4-thiolaniline, 1-thiol-3-aminopropane, and the like.
The reaction of tetracarboxylic dianhydride with amino alcohol or amino thiol can be carried out by heating a mixture of these compounds, preferably in a suitable solvent.

The use ratio of both compounds in this reaction is preferably 1.0 to 4.0 mol as the use ratio of amino alcohol or aminothiol to 1 mol of tetracarboxylic dianhydride, and 1.5 to 3. It is more preferably 0 mol, and particularly preferably 1.8 to 2.5 mol.
As the solvent used in this reaction, the same solvents as those exemplified above can be used as the solvent that can be used in the synthesis of compound (C). The proportion of the solvent used is preferably 50 to 5,000 parts by weight and 100 to 3,000 parts by weight with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and amino alcohol or aminothiol. More preferably, it is more preferably 100 to 2,000 parts by weight.
This reaction is preferably performed at a temperature of 50 to 300 ° C, more preferably 80 to 200 ° C, preferably for 0.1 to 10 hours, more preferably for 0.1 to 20 hours. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the above temperature and reaction time range.
Thus, a diol compound in which the groups Z ¹ and Z ² are each a hydroxyl group in the above formula (E) or a dithiol compound in which the groups Z ¹ and Z ² are each a thiol group is obtained.

The compound in which Z ¹ and Z ^{2 in the} compound (E) are each an epoxy group is, for example, a reaction between a diol compound or a dithiol compound obtained as described above, and a compound having an epoxy group and a halogen atom. Can be obtained. In this case, the radicals Y ¹ in (E) ^(hence the above equation (1) group in Y ¹⁾ includes a divalent group Y ¹ in the diol compound obtained as above or dithiol compound, an epoxy group And a divalent group obtained by removing an epoxy group and a halogen atom from a compound having a halogen atom is a divalent group formed by an ether bond.
Here, the epoxy group may be either an oxiranyl group or an oxetanyl group. Examples of the compound having an oxiranyl group and a halogen atom include epichlorohydrin, 2- (chloromethyl) -1,2-epoxypropane, 2- (chloromethyl) -1,2-epoxybutane, and 2- (bromomethyl). -1,2-epoxypropane, 2- (bromomethyl) -1,2-epoxybutane and the like;
Examples of the compound having an oxetanyl group and a halogen atom include 3- (chloromethyl) oxetane, 3- (chloromethyl) -3-methyloxetane, 3- (bromomethyl) oxetane, 3- (bromomethyl) -3-methyloxetane, and the like. ;
Examples of the compound having a (meth) acryl group and a halogen atom include (meth) acryl chloride, and one or more selected from these compounds can be used.

This reaction is performed by heating a mixture of the diol compound or dithiol compound obtained as described above and a compound having an epoxy group and a halogen atom, preferably in the presence of an appropriate catalyst, preferably in an appropriate solvent. This can be done.
The use ratio of the diol compound or dithiol compound and the compound having an epoxy group and a halogen atom is preferably 0.5 to 10 mol of the latter with respect to 1 mol of the former, 1.0 to 3.0 It is more preferable to use mol, and it is particularly preferable to use 1.8 to 2.5 mol.
Examples of the catalyst that can be used in this reaction include quaternary amine salts. Specific examples thereof include tetrabutylammonium chloride and tetrabutylammonium bromide. The ratio of the catalyst to be used is preferably 20 parts by weight or less, more preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the diol compound or dithiol compound.
The solvent used here is preferably an organic solvent, and the same solvents as exemplified above can be used as the solvent used in the synthesis of the compound (C).
The proportion of the solvent used is preferably 10 to 3,000 parts by weight, and 50 to 2,000 parts by weight with respect to 100 parts by weight of the total of the diol compound or dithiol compound and the compound having an epoxy group and a halogen atom. More preferably, it is more preferably 50 to 1,000 parts by weight.
This reaction is preferably performed at a temperature of -100 to 60 ° C, more preferably -80 to 40 ° C, preferably 0.5 to 30 hours, more preferably 2 to 15 hours. If desired, the reaction may be carried out while raising the reaction temperature stepwise or continuously within the above temperature and reaction time range.

[Synthesis of Compound (A)]
The compound (A) can be obtained, for example, by a reaction between a diol compound in which the groups Z ¹ and Z ² are hydroxyl groups in the above formula (E) and (meth) acrylic acid. In this case, the radicals ^{Y 1} in (A) (hence the above equation (1) group in ^{Y 1)} is the same as group ^{Y 1} in the compound used as a raw material (E). Here, (meth) acrylic acid is preferably subjected to a reaction after being converted to acid chloride by a known method.
The use ratio of the compound (E) which is a diol compound, and preferably (meth) acrylic acid acidified, is 0.5 to 10 mol of the use ratio of (meth) acrylic acid to 1 mol of compound (E). It is preferable to set it as 1.0-3.0 mol, and it is especially preferable to set it as 1.8-2.5 mol.
In the reaction, compound (E), which is a diol compound, is dissolved in an appropriate solvent, and acid chloride (meth) acrylic acid is preferably added dropwise in a state of being dissolved in an appropriate solvent as necessary. Can depend on the method.
As the solvent that can be used here, the same solvents as those exemplified above can be used as the solvent that can be used in the synthesis of the compound (C). The proportion of the solvent used is preferably such that the proportion of the total weight of the diol compound (E) and (meth) acrylic acid in the reaction solution is 0.5 to 50% by weight. More preferably, the ratio is 30% by weight.
The reaction is preferably performed at a temperature of −100 to 100 ° C., more preferably −20 to 40 ° C. Here, when (meth) acrylic acid is reacted as it is, the reaction temperature is preferably set to room temperature (25 ° C.) or higher;
When the reaction is performed after acidifying (meth) acrylic acid, the reaction temperature is preferably lower than room temperature. The reaction time is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is by dropping (preferably acid chloride) (meth) acrylic acid, the reaction time is measured after the end of dropping.

[Synthesis of Compound (S)]
For example, the compound (S) is obtained by dehydrating a diol compound in which the groups Z ¹ and Z ² are each a hydroxyl group in the above formula (E) to form a double bond at the terminal, and then hydrolyzing the double bond by a hydrosilation reaction. It can be obtained by adding an alkoxysilane compound. In this case, the radicals ^{Y 1} in (S) (hence the above equation (1) group in ^{Y 1)} is the same as group ^{Y 1} in the compound used as a raw material (E).
The dehydration reaction of the diol compound can be performed by bringing the diol compound into contact with sulfuric acid, preferably in a suitable organic solvent.
Examples of organic solvents that can be used here include acetic acid, acetic anhydride, tetrahydrofuran, acetonitrile, chloroform, dichloromethane, diethyl ether, benzene, toluene, xylene, acetone, methyl ethyl ketone, dimethylformamide, dimethyl sulfoxide, hexane, and 1,4. -Dioxane etc. can be mentioned. The use ratio of the organic solvent is preferably 50 to 2,000 parts by weight, more preferably 100 to 1,000 parts by weight with respect to 100 parts by weight of the compound (E) which is a diol compound.
The use ratio of sulfuric acid is preferably 0.0001 to 100 parts by weight, and more preferably 0.001 to 10 parts by weight with respect to 100 parts by weight of the compound (E) which is a diol compound. Sulfuric acid is preferably added gradually to the reaction system.
The dehydration reaction of the diol compound is preferably performed at a temperature of 0 to 300 ° C, more preferably 25 to 150 ° C, and preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is performed by dropwise addition of sulfuric acid, the above reaction time starts to be measured after the completion of the dropwise addition.
The reaction of adding an alkoxysilane compound to the dehydrated product obtained as described above can be performed according to a known hydrosilation reaction.

The alkoxysilane compound used here is a compound having at least one H-Si bond and at least one alkoxy-Si bond. Specifically, for example, dimethylmethoxysilane, dimethylethoxysilane, Examples thereof include organohydrogensilanes such as methyldimethoxysilane, diethylmethoxysilane, and diphenylmethoxy, and one or more selected from these can be used.
The proportion of the alkoxysilane compound used is preferably 0.5 to 5.0 mol, more preferably 1.0 to 3.0 mol, as the proportion of the alkoxysilane compound relative to 1 mol of the dehydrated product. In particular, the amount is preferably 1.8 to 2.5 mol.
This hydrosilation reaction is preferably carried out in the presence of a suitable catalyst, preferably in a suitable organic solvent.
Examples of the catalyst that can be used here include chloroplatinic acid, Wilkinson complex (RhCl (P (C ₆ H ₅ ) ₃ ) ₃ ), karsted catalyst (vinyl siloxane complex of chloroplatinic acid), spire catalyst (chloroplatinic acid). Alcohol solution) and the like, and one or more selected from these can be used. The use ratio of the catalyst is preferably 0.01 to 200 micromol (μmol), more preferably 0.05 to 50 micromol, with respect to 1 mol.
Examples of the organic solvent that can be used here include hydrocarbons, halogenated hydrocarbons, ethers, esters, and the like. Among these, it is preferable to use hydrocarbons, and it is particularly preferable to use at least one selected from toluene, heptane, hexane, benzene, toluene, xylene and the like. The use ratio of the organic solvent is preferably 10 to 2,000 parts by weight, and more preferably 50 to 1,000 parts by weight with respect to 100 parts by weight of the dehydrated product.
The hydrosilation reaction is preferably performed at a temperature of 30 to 200 ° C., more preferably 50 to 120 ° C., preferably for 0.1 to 60 hours, more preferably for 0.5 to 40 hours.

[Production of specific polymer]
Next, the manufacturing method of the specific polymer in this invention is demonstrated.
(1) Manufacture of polyamide The polyamide which is an example of the specific polymer in the present invention can be obtained by reacting a diamine and a polyvalent carboxylic acid containing the compound (C) obtained as described above. . Here, it is preferable that the polyvalent carboxylic acid is subjected to a reaction after being acidified by a known method.
Examples of the diamine include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,2′-dimethyl-4,4′-diaminobiphenyl, 4,4′-diamino-2,2′-bis (trifluoro Methyl) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4- Aminophenyl) hexafluoropropane, 2- (2,4-diaminophenoxy) ethyl methacrylate, dodecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, octadecanoxy- 2,5-diaminobenzene, cholestanyloxy-3,5-diaminobenzene, co Stenyloxy-3,5-diaminobenzene, cholestanyloxy-2,4-diaminobenzene, cholestenyloxy-2,4-diaminobenzene, cholestanyl 3,5-diaminobenzoate, cholestenyl 3,5-diaminobenzoate, 1 , 1-bis (4-((aminophenyl) methyl) phenyl) -4-heptylcyclohexane, 1,1-bis (4-((aminophenoxy) methyl) phenyl) -4-heptylcyclohexane, and the like. One or more selected from these can be used.

As the polyvalent carboxylic acid, only the compound (C) may be used, or the compound (C) and another polyvalent carboxylic acid may be used in combination. Other polyvalent carboxylic acids used here are preferably dicarboxylic acids, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, isophthalic acid, terephthalic acid, 5-Decanoxyisophthalic acid can be mentioned, and one or more selected from these can be used.
When the compound (C) and other polyvalent carboxylic acid are used in combination, the proportion of the compound (C) used is 5 mol% or more with respect to the total of the compound (C) and the other polyvalent carboxylic acid. It is preferably 10 mol% or more.
When other polycarboxylic acid is used together with compound (C) in the production of polyamide, a part of the other polycarboxylic acid can be replaced with tetracarboxylic dianhydride. Examples of tetracarboxylic dianhydrides that can be used here include pyromellitic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl). Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) Naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5 '-Dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxy Norbornane-2: 3,5 6 dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10- tetraone, bicyclo [3.3.0] octane -2, Examples include 4,6,8-tetracarboxylic dianhydride.
The ratio of the polyvalent carboxylic acid and the diamine is such that the ratio of the diamine is 0.7 to 1.2 with respect to a total of 1 mol of carboxy groups (and acid anhydride groups, if any) of the polyvalent carboxylic acid. It is preferable to set it as a mol, and it is more preferable to set it as 0.9-1.1 mol.

In the reaction, the diamine is dissolved in a suitable solvent, the polyvalent carboxylic acid is preferably converted into an acid chloride, and then dropped in a suitable solvent (for example, tetrahydrofuran) as necessary. Can be.
As the solvent that can be used here, the same solvents as those exemplified above can be used as the solvent that can be used in the synthesis of the compound (C). The proportion of the solvent used is preferably such that the proportion of the total weight of polyvalent carboxylic acids and diamine in the reaction solution is 3 to 50% by weight.
The reaction is preferably performed at a temperature of −100 to 200 ° C., more preferably −20 to 150 ° C. Here, when the polyvalent carboxylic acids are reacted as they are, the reaction temperature is preferably a room temperature (25 ° C.) or higher;
When the polycarboxylic acid is reacted after acid chloride, the reaction temperature is preferably lower than room temperature. The reaction time is preferably 0.1 to 40 hours, more preferably 0.5 to 20 hours. When the reaction is by dropping polyvalent carboxylic acids (preferably acid chloride), the reaction time is measured after completion of the dropping.
Mw of the polyamide as the specific polymer in the present invention (meaning a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography, the same shall apply hereinafter) is preferably 1,000 to 500,000, more preferably. Is 5,000 to 300,000.

(2) Production of poly (thio) ester Poly (thio) ester which is an example of the specific polymer in the present invention includes at least one selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound, and a compound (C Or at least one compound selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound, provided that at least a part of the compound is represented by the following formula (E): It can be obtained by a method of reacting a polyvalent carboxylic acid with the compound represented.
Examples of the diol compound include 3,6-dihydroxycholestane, 3,5-dihydroxybenzoic acid-3-cholestanyl, 3,5-dihydroxybenzoic acid, ethylene glycol, 1,3-propanediol, and 1,4-butane. Diol, 1,3-butanediol, 1,4-cyclohexanediol, phenyl-1,2-ethanediol, dimethyl-2,3-butanediol, α, α′-p-xylylenediol, α, α′- m-xylylenediol, hydroquinone, methylhydroquinone, t-butylhydroquinone, chlorohydroquinone, 2-methoxyhydroquinone, phenylhydroquinone, 2,3-dimethylhydroquinone, 2,3,5,6-tetramethylhydroquinone, 2,3, 5,6-tetrachlorohydroquinone, resorcin, 2-methylreso Lucine, 4-hexylresorcin, 5-phenylresorcin, 1,4-dihydroxynaphthalene and the like;
Examples of the dithiol compound include benzene-1,4-dithiol, 2-methylpropane-1,1-dithiol, butane-1,1-dithiol, 2-methylbutane-1,1-dithiol, 3-methylbutane-1, 1-dithiol, pentane-1,1-dithiol, 2-methylpentane-1,1-dithiol, 3-methylpentane-1,1-dithiol, hexane-1,1-dithiol, 2-methylhexane-1,1 -Dithiol, 3-methylhexane-1,1-dithiol and the like;
Examples of the diepoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, and the like can be exemplified, and one or more selected from the above can be used.

When synthesizing a poly (thio) ester by reaction of at least one selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound and a polyvalent carboxylic acid containing the compound (C), a polyvalent carboxylic acid As for, only a compound (C) may be used and a compound (C) and other polyvalent carboxylic acid may be used together. As other polyvalent carboxylic acids used here, the same polyvalent carboxylic acids as those exemplified above can be used as polyvalent carboxylic acids that can be used together with the compound (C) in the synthesis of polyamide. Further, a part or all of the polyvalent carboxylic acid may be replaced with tetracarboxylic dianhydride. The tetracarboxylic dianhydrides that can be used here are the same as those exemplified above as tetracarboxylic dianhydrides that can be used in the production of polyamide.
When the compound (C) and other polyvalent carboxylic acid are used in combination, the proportion of the compound (C) used is 5 mol% or more with respect to the total of the compound (C) and the other polyvalent carboxylic acid. It is preferably 10 mol% or more.
The use ratio of at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound and the polyvalent carboxylic acid containing the compound (C) depends on the amount and amount of the carboxy group of the polyvalent carboxylic acid. In this case, the usage ratio of at least one selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound is 0.7 to 1.2 mol with respect to a total of 1 mol of twice the amount of the acid anhydride group. It is preferable that the amount be 0.9 to 1.1 mol.
The synthesis reaction of poly (thio) ester by reacting at least one selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound and a polyvalent carboxylic acid containing compound (C) is performed in place of diamine. In addition, at least one selected from the group consisting of a diol compound, a dithiol compound, and a diepoxy compound is used in the same manner as the synthesis of the polyamide.

The synthesis of the poly (thio) ester is at least one compound selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound, provided that at least a part of this compound is a compound represented by the following formula (E) As the compound (E) used in the case of reacting with a polycarboxylic acid, a diepoxy compound in which both Z ¹ and Z ² in the above formula (E) are epoxy groups is preferable. The compound (E) which is a diepoxy compound may be used alone, or the compound (E) and other diepoxy compounds may be used in combination. As other diepoxy compounds used here, the same compounds as those exemplified above as diepoxy compounds that can be used in the former method for synthesizing poly (thio) esters can be used. When the compound (E) and other diepoxy compounds are used in combination, the use ratio of the compound (E) is preferably 5 mol% or more based on the total of the compound (E) and other diepoxy compounds, More preferably, it is 10 mol% or more.
The compound (E) which is the diepoxy compound and the other diepoxy compounds are each preferably a dioxiranyl compound.
As the polyvalent carboxylic acid in this reaction, those exemplified above as the polyvalent carboxylic acid that can be used together with the compound (C) in the synthesis of polyamide can be used. Further, a part or all of the polyvalent carboxylic acid may be replaced with tetracarboxylic dianhydride. The tetracarboxylic dianhydrides that can be used here are the same as those exemplified above as tetracarboxylic dianhydrides that can be used in the production of polyamide.
The use ratio of the compound (E) to the polyvalent carboxylic acid is such that the amount of the carboxy group possessed by the polyvalent carboxylic acid and, if present, the amount of the compound (E) based on a total of 1 mol of the double amount of the acid anhydride group. As a ratio, it is preferable to set it as 0.7-1.2 mol, and it is more preferable to set it as 0.9-1.1 mol.
In the synthesis reaction of poly (thio) ester by reacting compound (E) with polyvalent carboxylic acid, compound (E) (or a mixture of compound (E) and another diepoxy compound) is used instead of diamine. Others can be performed in substantially the same manner as the synthesis of the polyamide.
The Mw of the poly (thio) ester as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

(3) Production of (meth) acrylic acid copolymer The (meth) acrylic acid copolymer which is an example of the specific polymer in the present invention is a polymerizable unsaturated compound containing (meth) acrylic acid and the compound (A). Can be obtained by addition polymerization.
In this case, only the (meth) acrylic acid and the compound (A) may be used as the unsaturated compound, and in addition to the (meth) acrylic acid and the compound (A), other polymerizable unsaturated compounds are used in combination. May be. Examples of other polymerizable unsaturated compounds that can be used here include conjugated dienes, aromatic vinyl compounds, (meth) acrylic acid esters, α, β-unsaturated nitrile compounds, maleimide compounds, and the like. . Specific examples thereof include, for example, 1,3-butadiene, 2-methyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene, and 2-chloro-1,3-butadiene as the conjugated diene. Etc .;
Examples of the aromatic vinyl compound include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, chlorostyrene, divinylbenzene and the like;
Examples of the (meth) acrylic acid ester include methyl (meth) acrylate, ethyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, hydroxymethyl (meth) acrylate, hydroxyethyl (meth) acrylate (meth) acrylic acid 4- (4-n-propylcyclohexyl) phenyl and the like;
Examples of the α, β-unsaturated nitrile compound include acrylonitrile, methacrylonitrile, α-chloroacrylonitrile, α-ethylacrylonitrile, vinylidene cyanide and the like:
Examples of the maleimide compound include N-cyclohexylmaleimide and N-phenylmaleimide, and one or more selected from the above can be used.
In the (meth) acrylic acid copolymer,
The content ratio of the repeating unit derived from (meth) acrylic acid is preferably 0.1 to 80% by weight, more preferably 5 to 60% by weight;
The content ratio of the repeating unit derived from the compound (A) is preferably 0.1 to 15% by weight, more preferably 0.5 to 10% by weight.

The (meth) acrylic acid copolymer can be synthesized, for example, by known solution polymerization using the polymerizable unsaturated compound as described above. This solution polymerization can be carried out in an organic solvent in the presence of a suitable polymerization initiator, preferably in the presence of a suitable chain transfer agent.
Examples of the organic solvent include alcohol, ether, glycol ether, ethylene glycol alkyl ether acetate, diethylene glycol alkyl ether, propylene glycol monoalkyl ether, propylene glycol alkyl ether acetate, propylene glycol alkyl ether propionate, aromatic hydrocarbon, and ketone. Esters can be used. The use ratio of the organic solvent is preferably 120 to 600 parts by weight, and more preferably 150 to 400 parts by weight with respect to 100 parts by weight of the total of the polymerizable unsaturated compounds.
Examples of the polymerization initiator include cumene hydroperoxide, benzoyl peroxide, t-butyl hydroperoxide, acetyl peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, azo Bisisobutyronitrile, 1,1′-azobis (cyclohexanecarbonitrile), 2,2′-azobis (2,4-dimethylvaleronitrile) and the like can be mentioned, and one or more selected from these Can be used. The use ratio of the polymerization initiator is preferably 2 to 10 parts by weight, and more preferably 3 to 8 parts by weight with respect to 100 parts by weight of the total of the polymerizable unsaturated compounds.
Examples of the chain transfer agent include xanthogen compounds, thiuram compounds, phenol derivatives, allyl compounds, halogenated hydrocarbon compounds, vinyl ether compounds, triphenylethane, pentaphenylethane, acrolein, metaacrolein, thioglycolic acid, thiomalic acid, 2 -Ethylhexyl thioglycolate, (alpha) -methyl styrene dimer etc. can be mentioned, 1 or more types selected from these can be used. The ratio of the chain transfer agent to be used is preferably 3 parts by weight or less, more preferably 0.1 to 1.5 parts by weight, based on 100 parts by weight of the total amount of the polymerizable unsaturated compounds.
The solution polymerization for synthesizing the (meth) acrylic acid copolymer is preferably 50 to 100 ° C., more preferably 60 to 90 ° C., preferably 30 to 500 minutes, more preferably 60 to 300 minutes. Performed in reaction time.
The Mw of the (meth) acrylic acid copolymer as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

(4) Production of polyorganosiloxane The polyorganosiloxane which is an example of the specific polymer in the present invention is a hydrolysis / condensation of a silane compound containing the compound (S), preferably in the presence of an appropriate organic solvent and a catalyst. By doing so, it can be obtained.
As the silane compound, only the compound (S) may be used, or the compound (S) and another silane compound may be used in combination. Examples of other silane compounds that can be used here include tetramethoxysilane, tetraethoxysilane, methyltrimethoxysilane, methyltriethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, and 3- (meth). Acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, allyltrimethoxysilane, allyltriethoxysilane, octadecyltrimethoxysilane, octadecyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, 3-mercapto Propyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, mercaptomethyltrimethoxysilane, mercaptomethyltriethoxysilane, dimethyldimethoxysilane Dimethyldiethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropyltriethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane, 3-glycidyl Examples include loxypropyldimethylmethoxysilane, 3-glycidyloxypropyldimethylethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane. One or more selected from these can be used.

When the compound (S) and other silane compounds are used in combination, the use ratio of the compound (S) is preferably 5 mol% or more based on the total of the compound (S) and other silane compounds, More preferably, it is 10 mol% or more.
Examples of the organic solvent that can be used for synthesizing the polyorganosiloxane include hydrocarbons, ketones, esters, ethers, alcohols, and the like, and one or more selected from these can be used. it can. As specific examples of these organic solvents, it is possible to use the same hydrocarbons, ketones, esters, ethers or alcohols as those exemplified above among the solvents that can be used in the synthesis of the compound (C). it can. As the organic solvent, it is preferable to use a water-insoluble organic solvent. The use ratio of the organic solvent 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 compound.
Examples of the catalyst that can be used include acids, bases, organic bases, titanium compounds, and zirconium compounds. Of these, it is preferable to use a base.
Examples of the base include organic bases and basic alkali metal compounds. Specific examples thereof include organic bases such as 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;
A quaternary organic amine such as tetramethylammonium hydroxide can be used. Of these organic bases, triethylamine, tri-n-propylamine, tri-n-butylamine, pyridine, 4-dimethylaminopyridine or tetramethylammonium hydroxide is preferably used. Examples of the basic alkali metal compound include sodium hydroxide, potassium hydroxide, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide and the like.

The use ratio of the catalyst can be preferably 0.01 to 3 mol, and more preferably 0.05 to 1 mol, with respect to 1 mol of the total amount of the silane compound used as a raw material.
The proportion of water used in the synthesis of the polyorganosiloxane is preferably 0.5 to 100 mol, more preferably 1 to 30 mol, with respect to 1 mol of the total amount of silane compounds used as raw materials.
The polyorganosiloxane synthesis reaction is preferably carried out at a temperature of 0 to 200 ° C., more preferably 10 to 150 ° C., preferably for a reaction time of 0.1 to 40 hours, more preferably 0.5 to 20 hours. .
The Mw of the polyorganosiloxane as the specific polymer in the present invention is preferably 1,000 to 500,000, more preferably 5,000 to 300,000.

  As the specific polymer in the present invention, it is preferable to use one or more selected from the group consisting of polyamide, polyester and polyorganosiloxane, from the viewpoint of ease of monomer synthesis.

<Other ingredients>
The liquid crystal aligning agent of this invention contains the above specific polymers as an essential component. The liquid crystal aligning agent of this invention may contain the other component used arbitrarily besides a specific polymer.
Examples of other components that can be used here include polymers other than specific polymers, compounds having at least one epoxy group in the molecule (hereinafter also referred to as “epoxy compounds”), functional silane compounds, and the like. Can be mentioned.

[Polymers other than specific polymers]
Polymers other than the specific polymer can be used for improving solution properties and electrical properties. Such other polymer is a polymer having no divalent group represented by the above formula (1). For example, polyamic acid, imidized polymer of polyamic acid, polyamic acid ester, polyester, polyamide, poly One or more selected from the group consisting of siloxane, cellulose derivative, polyacetal, polystyrene and derivatives thereof, poly (styrene-phenylmaleimide) and derivatives thereof, and poly (meth) acrylate, represented by the above formula (1) The polymer does not have a divalent group.
The proportion of the polymer other than the specific polymer used may be 50% by weight or less with respect to the total of the polymers (the total of the polymers other than the specific polymer and the specific polymer; the same shall apply hereinafter). It is preferably 20% by weight or less, more preferably 10% by weight or less. Particularly preferably, no polymer other than the specific polymer is contained.

[Epoxy compound]
Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3 -Bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylme N, N-diglycidyl-benzylamine, N, N-diglycidyl-aminomethylcyclohexane, N, N-diglycidyl-cyclohexylamine, etc., and using one or more selected from these Can do.
The use ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

[Functional silane compounds]
Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9- Triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxy Methyltriethoxysilane, 2-glycidoxyethyltrimeth Sisilane, 2-glycidoxyethyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. can be used, and one or more selected from these can be used can do.
The use ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

<Preparation of liquid crystal aligning agent>
The liquid crystal aligning agent of this invention is comprised as a solution-like composition formed by melt | dissolving and containing the specific polymer and the other component arbitrarily used as needed, Preferably in an organic solvent.
Examples of the organic solvent used in the liquid crystal aligning agent of the present invention include benzyl alcohol, tetrahydrofuran, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether. Acetate, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol ethyl methyl ether, propylene glycol methyl ether, propylene glycol ethyl ether, propylene glycol propyl ether, propylene glycol butyl ether, Lopylene glycol methyl ether acetate, propylene glycol ethyl ether acetate, propylene glycol propyl ether acetate, propylene glycol butyl ether acetate, propylene glycol methyl ether propionate, propylene glycol ethyl ether propionate, propylene glycol propyl ether propionate, propylene glycol butyl ether Propionate, toluene, xylene, methyl ethyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone,

Methyl acetate, ethyl acetate, propyl acetate, butyl acetate, ethyl 2-hydroxypropionate, methyl 2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, methyl hydroxyacetate, hydroxyethyl acetate, hydroxy Butyl acetate, methyl lactate, ethyl lactate, propyl lactate, butyl lactate, methyl 3-hydroxypropionate, ethyl 3-hydroxypropionate, propyl 3-hydroxypropionate, butyl 3-hydroxypropionate, 2-hydroxy-3-methylbutane Methyl acetate, methyl methoxyacetate, ethyl methoxyacetate, propyl methoxyacetate, butyl methoxyacetate, methyl ethoxy acetate, ethyl ethoxy acetate, propyl ethoxy acetate, butyl ethoxy acetate, methyl propoxyacetate, propoxy Ethyl acetate, propyl propoxyacetate, butyl propoxyacetate, methyl butoxyacetate, ethyl butoxyacetate, propyl butoxyacetate, butyl butoxyacetate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, 2- Butyl methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, propyl 2-ethoxypropionate, butyl 2-ethoxypropionate, methyl 2-butoxypropionate, ethyl 2-butoxypropionate, 2-butoxy Propyl propionate, butyl 2-butoxypropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 3- Methyl toxipropionate, ethyl 3-ethoxypropionate, propyl 3-ethoxypropionate, butyl 3-ethoxypropionate, methyl 3-propoxypropionate, ethyl 3-propoxypropionate, propyl 3-propoxypropionate, 3-propoxy Butyl propionate, methyl 3-butoxypropionate, ethyl 3-butoxypropionate, propyl 3-butoxypropionate, butyl 3-butoxypropionate,

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, diethyl Examples include lenglycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. One or more selected from the above can be used according to the specific polymer used and the type of substrate to which the liquid crystal aligning agent of the present invention is applied.

Since the specific polymer in the present invention has high solubility in a general-purpose organic solvent, even when a solvent that does not erode a lightweight resin substrate is selected and used, it exhibits excellent coating properties. Therefore, the liquid crystal aligning agent of the present invention has an advantage that the degree of freedom of substrate selection is high. The liquid crystal aligning agent of this invention is especially advantageous at the point which can use a general purpose TAC film as a board | substrate, when applying to a phase difference film, because the freedom degree of board | substrate selection is high.
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 in 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. However, it is preferably in the range of 1 to 10% by weight. By setting the solid content concentration in this range, it is possible to form a liquid crystal alignment film having an appropriate film thickness with good coating properties, which is preferable.
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.

<Use of liquid crystal aligning agent of this invention>
A liquid crystal aligning film can be formed using the liquid crystal aligning agent of the present invention as described above. The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention is suitable as a liquid crystal display element having a liquid crystal cell of TN type, STN type, IPS type, FFS type, etc .;
In order to form a liquid crystal alignment film using the liquid crystal aligning agent of the present invention, for example, a step of coating the liquid crystal aligning agent of the present invention on a substrate to form a coating film (coating film forming step), and It can depend on the method of passing through the process (liquid crystal orientation provision process) which provides liquid crystal orientation to a coating film. Here, examples of the step of imparting liquid crystal alignment include rubbing treatment or light irradiation treatment.
Hereinafter, the case where the liquid crystal aligning agent of this invention is applied to a liquid crystal display element and the case where it applies to a phase difference film are demonstrated in order.

<Application to liquid crystal display elements>
(1) Coating film formation process When applying the liquid crystal aligning agent of this invention to the liquid crystal display element which has a liquid crystal cell of a vertical electric field system, such as TN type and STN type, the patterned transparent conductive film is provided. Two substrates are used as a pair, and the liquid crystal aligning agent of this invention is apply | coated on each transparent conductive film formation surface, and a coating film is formed. When the liquid crystal aligning agent of the present invention is applied to a liquid crystal display element having a transverse electric field type liquid crystal cell such as an IPS type or an FFS type, a transparent conductive film or a metal film is patterned in a comb shape on one side. A pair of a substrate having a pair of electrodes and a counter substrate on which no electrode is provided, and a coating film obtained by applying the liquid crystal aligning agent of the present invention to the comb-shaped electrode forming surface and one surface of the counter substrate, respectively. Form.
In any of the above cases, examples of the substrate include glass such as float glass and soda glass;
A transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, or polycarbonate can be used. As the transparent conductive film, for example, an ITO film made of In ₂ O ₃ —SnO _{2 or} a NESA (registered trademark) film made of SnO ₂ can be used. As the metal film, for example, a film made of a metal such as chromium can be used. For patterning the transparent conductive film and the metal film, for example, a method of forming a pattern by a photo-etching method or a sputtering method after forming a transparent conductive film without a pattern, or having a desired pattern when forming the transparent conductive film For example, a method using a mask can be used.
After applying a functional silane compound, titanate, etc. on the substrate and the electrode in advance in order to further improve the adhesion between the substrate and the electrode and the coating film when applying the liquid crystal aligning agent on the substrate. A pretreatment for heating may be performed.
The liquid crystal aligning agent can be applied onto the substrate by an appropriate application method such as an offset printing method, a spin coating method, a roll coater method, or an ink jet printing method. After coating, the coated surface can be preheated (prebaked) and then baked (postbaked) to form a coating film. The prebaking condition is, for example, a heating time of 0.1 to 5 minutes at a heating temperature of 40 to 120 ° C., and the postbaking condition is, for example, a heating temperature of 120 to 300 ° C., preferably 150 to 250 ° C. The heating time is 5 to 200 minutes, preferably 10 to 100 minutes. The film thickness of the coating film after post-baking is preferably 0.001 to 1 μm, and more preferably 0.005 to 0.5 μm.

(2) Liquid crystal alignment imparting step [rubbing treatment step]
The coating film formed by the above (1) coating film forming step can be subjected to a rubbing treatment to impart a liquid crystal alignment ability to the coating film to form a liquid crystal alignment film.
The rubbing treatment is performed by rubbing the coating film formed in the above (1) coating film forming step with a roll in which a cloth made of long fibers such as nylon, rayon, and cotton is wound in a certain direction. Thereby, the orientation ability of a liquid crystal molecule is provided to a coating film, and it can be set as a liquid crystal aligning film.

[Light irradiation treatment process]
The coating film formed by the above-mentioned (1) coating film forming step can impart a liquid crystal alignment ability to the liquid crystal alignment film by irradiating polarized light thereto.
As light to be irradiated here, for example, ultraviolet rays or visible rays including light having a wavelength of 150 to 800 nm can be used. Ultraviolet light containing light having a wavelength of 200 to 400 nm is preferable. As a light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, a Hg-Xe lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable wavelength region can be obtained by means of using the light source in combination with, for example, a filter, a diffraction grating, or the like.
When the light used for light irradiation is polarized (linearly polarized or partially polarized), it can be irradiated from a direction perpendicular to the coating surface or from an oblique direction to give a pretilt angle. Good. On the other hand, when irradiating non-polarized light, the irradiation is preferably performed from an oblique direction with respect to the coating surface.
The irradiation dose of light, preferably 1,000~10,000J / ^{m 2,} more preferably from 1,500~7,000J / ^{m 2.} In a known liquid crystal alignment film material that imparts liquid crystal alignment by utilizing photodecomposition of a cyclobutane ring, a large irradiation amount exceeding 10,000 J / m ² is required as the light irradiation amount. The liquid crystal aligning agent of the present invention can impart good liquid crystal alignment even when the light irradiation amount is, for example, 5,000 J / m ² or less, and particularly good liquid crystal alignment even when it is 3,000 J / m ² or less. Is obtained.

(3) Manufacture of a liquid crystal display element A liquid crystal display element can be manufactured as follows using a pair of board | substrate with which the liquid crystal aligning film was formed as mentioned above.
First, a liquid crystal cell having a structure in which a liquid crystal is sandwiched in a gap (cell gap) in which a pair of substrates on which a liquid crystal alignment film is formed is opposed to each other is configured.
To configure the liquid crystal cell,
The two substrates on which the liquid crystal alignment film is formed are bonded so that the liquid crystal alignment film surface faces each other by the sealant disposed on the periphery thereof, and the liquid crystal is placed in the cell gap defined by the liquid crystal alignment film surface and the sealant. Filling and filling the injection hole;
For example, an ultraviolet curable sealant is disposed at a predetermined position on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is disposed at predetermined positions on the liquid crystal alignment film surface. The other substrate can be bonded and pressure-bonded so that the liquid crystal alignment film faces, and the liquid crystal is spread on the front surface of the liquid crystal alignment film, and then the entire surface of the substrate is irradiated with ultraviolet rays to cure the sealant. .
In any of the above cases, when the rubbing treatment is performed at the time of forming the liquid crystal alignment film, the rubbing directions of the liquid crystal alignment films on the two substrates are orthogonal or anti-parallel;
When the polarized light is irradiated during the formation of the liquid crystal alignment film, the direction in which the polarization plane of the irradiated light is projected on the two substrate surfaces is orthogonal or antiparallel.
Each is preferably arranged.
And a liquid crystal display element can be manufactured by bonding a polarizing plate on the outer surface of a liquid crystal cell in a predetermined direction.
As the sealant, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.

As the liquid crystal, nematic liquid crystal or smectic liquid crystal can be used. Of these, nematic liquid crystal is preferable. Specific examples include Schiff-based liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, phenyl cyclohexane liquid crystals, ester liquid crystals, terphenyl liquid crystals, biphenyl cyclohexane liquid crystals, pyrimidine liquid crystals, dioxane liquid crystals, and bicyclooctane liquid crystals. And Cuban liquid crystal. For example, cholesteric liquid crystals such as cholestyl chloride, cholesteryl nonate, and cholesteryl carbonate;
Chiral agents such as those sold under the product names “C-15” and “CB-15” (Merck);
Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be added and used.
As a polarizing plate to be bonded to the outer surface of the liquid crystal cell, for example, a polarizing plate in which a polarizing film called “H film” in which iodine is absorbed while stretching and aligning polyvinyl alcohol is sandwiched between cellulose acetate protective films, or H Examples thereof include a polarizing plate made of the film itself.

<Application to retardation film>
(1) Coating film forming step As a substrate used when the liquid crystal aligning agent of the present invention is applied to a retardation film, triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polyamide, polyimide A transparent substrate made of a synthetic resin such as polymethyl methacrylate or polycarbonate can be suitably exemplified. Of these, TAC is generally used as a protective layer for a polarizing film in a liquid crystal display device.
In many cases, the retardation film is used in combination with a polarizing film. At this time, it is necessary to attach the retardation film by precisely controlling the angle with respect to the polarization axis of the polarizing film in a specific direction so that the desired optical characteristics can be exhibited. Accordingly, here, if a liquid crystal alignment film having liquid crystal alignment ability in the direction of a predetermined angle is formed on the TAC film, the step of bonding the retardation film on the polarizing film while controlling the angle can be omitted. This can contribute to the improvement of the productivity of the liquid crystal display element. Formation of a liquid crystal alignment film having a liquid crystal alignment ability in a predetermined angle direction can be performed by a photo-alignment method using the liquid crystal aligning agent of the present invention.
Therefore, by using a TAC film as a substrate, it is possible to enjoy the above-mentioned advantages, contribute to the reduction in size and weight of the liquid crystal display element, and is preferable in that it can be applied to a flexible display. .
The liquid crystal aligning agent can be applied onto the substrate in the same manner as in the case of application to a liquid crystal display element.
In addition, the film thickness of the coating film formed here becomes like this. Preferably it is 1-1000 nm, More preferably, it is 5-500 nm.

(2) Liquid crystal orientation imparting step The rubbing treatment step or the light irradiation treatment step is performed on the coating film formed in the above (1) coating film forming step in the same manner as in the case of application to a liquid crystal display element. As a result, liquid crystal alignment is imparted to the coating film to form a liquid crystal alignment film.

(3) Production of Retardation Film A polymerizable liquid crystal coating film is then formed on the liquid crystal alignment film formed on the substrate as described above, and then the polymerizable liquid crystal coating film is heated and By performing one or more treatments selected from light irradiation, a liquid crystal layer is formed to form a retardation film.
The polymerizable liquid crystal applied on the liquid crystal alignment film is a liquid crystal compound or liquid crystal composition that is polymerized by at least one treatment of heating and light irradiation. As such a polymerizable liquid crystal, for example, a nematic liquid crystal compound described in Non-Patent Document 1 (“UV curable liquid crystal and its application”, liquid crystal, Vol. 3, No. 1 (1999), pp 34 to 42) is used. In addition, a cholesteric liquid crystal; a discotic liquid crystal; a twisted nematic alignment type liquid crystal to which a chiral agent is added may be used. The polymerizable liquid crystal may be a mixture of a plurality of liquid crystal compounds. The polymerizable liquid crystal may further be a composition containing a known polymerization initiator, an appropriate solvent, and the like.
In order to apply the polymerizable liquid crystal as described above on the liquid crystal alignment film, an appropriate application method such as a bar coater method, a roll coater method, a spinner method, a printing method, or an ink jet method can be employed.

The coating film of the polymerizable liquid crystal formed as described above is subjected to at least one treatment selected from heating and light irradiation to cure the coating film and form a liquid crystal layer. It is preferable to perform these treatments in a superimposed manner because good alignment can be obtained.
The heating temperature of the coating film should be appropriately selected depending on the type of polymerizable liquid crystal used. For example, when using RMS03-013C manufactured by Merck, it is preferable to heat at a temperature in the range of 40 to 80 ° C. The heating time is preferably 0.5 to 5 minutes.
As irradiation light, non-polarized ultraviolet rays having a wavelength in the range of 200 to 500 nm can be preferably used. The irradiation dose of light, preferably in the 50~10,000mJ / cm ^2, and more preferably a 100~5,000mJ / cm ^2.
The thickness of the liquid crystal layer to be formed is appropriately set depending on desired optical characteristics. For example, when manufacturing a half-wave plate for visible light having a wavelength of 540 nm, a thickness is selected such that the retardation of the formed retardation film is 240 to 300 nm. The thickness is selected such that the phase difference is 120 to 150 nm. The thickness of the liquid crystal layer from which the desired retardation is obtained varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, the thickness for manufacturing a quarter-wave plate is in the range of 0.6 to 1.5 μm.

A retardation film can be produced as described above.
The retardation film manufactured using the liquid crystal aligning agent of this invention can be applied suitably as a retardation film of a liquid crystal display element.

In the following synthesis examples, the necessary amounts of compounds used in the following synthesis examples and examples were secured by repeating the synthesis on the scale described below as necessary.
<Synthesis of Monomer Having Divalent Group Represented by Formula (1)>
[Synthesis of Compound (E)]
Synthesis Example E-1
Compound (E-1) was synthesized according to the following scheme E-1.

  In a 2 L three-necked flask equipped with a reflux tube, 196.11 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 152 g of 3-aminopropanol and 1,000 mL of dimethylformamide were mixed, and then 2 ° C. at 40 ° C. The reaction was stirred for 4 hours and then refluxed for 4 hours. After the reaction, distilled water was added to the reaction mixture for crystallization, and the solid was collected by filtration. The recovered solid was washed with ethanol, and then heated to 60 ° C. under reduced pressure and dried to obtain 301 g of compound (E-1).

Synthesis Example E-2
Compound (E-2) was synthesized according to the following scheme E-2.

  In a 2 L three-necked flask equipped with a reflux tube, 196.11 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 220 g of 4-aminophenol and 1,000 mL of pyridine were mixed, and then at 40 ° C. for 2 hours. The reaction was stirred and then refluxed for 4 hours. After the reaction, distilled water was added to the reaction mixture for crystallization, and the solid was collected by filtration. The recovered solid was washed with ethanol, and then heated to 60 ° C. under reduced pressure and dried to obtain 359 g of compound (E-2).

Synthesis Example C-1
Compound (C-1) was synthesized according to the following scheme C-1.

  In a 2 L three-necked flask equipped with a reflux tube, 196.11 g of 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 180 g of β-alanine and 1,000 mL of dimethylformamide were mixed, and then at 40 ° C. for 2 hours. The reaction was stirred and then refluxed for 4 hours. After the reaction, distilled water was added to the reaction mixture for crystallization, and the solid was collected by filtration. The recovered solid was washed with ethanol, and then heated to 60 ° C. under reduced pressure and dried to obtain 311 g of compound (C-1).

Synthesis Example S-1
Compound (S-1) was synthesized according to the following scheme S-1.

In a 2 L three-necked flask equipped with a dropping funnel, 310.3 g of the compound (E-1) synthesized in the same manner as in Synthesis Example E-1 and 800 mL of acetic acid were charged. Here, 200 mL of sulfuric acid was slowly dropped from the dropping funnel. During the dropping, the flask was cooled in an ice bath, and the internal temperature was kept so as not to exceed 10 ° C. After completion of the dropping, the reaction was performed at room temperature for 6 hours. After completion of the reaction, 2,000 mL of ethyl acetate was added to the reaction mixture. Distilled water 500mL was added here, and liquid separation washing operation which carries out liquid separation washing and discards an aqueous layer was performed. This separation washing operation was repeated, and a total of four separation washing operations were performed. Subsequently, the solvent was removed by distillation under reduced pressure to obtain a liquid crude product. This crude product was dissolved in ethyl acetate and purified with a silica column, and then the solvent was removed under reduced pressure to obtain 155 g of compound (S-1a).
In a 1,000 mL three-necked flask equipped with a reflux tube and a nitrogen introduction tube, 27.4 g of the compound (S-1a) obtained above, 50 mL of toluene and chloroplatinic acid hexahydrate at a concentration of 0.2 mol / L Charge 5 μL of a Japanese isopropanol solution, bubbling it with a nitrogen stream for about 10 minutes to replace the nitrogen in the system, add 18.1 g of dimethylmonomethoxysilane, and react under reflux for 10 hours under nitrogen. Went. After completion of the reaction, the reaction mixture was passed through a silica gel short column, further purified with a silica column, and then the solvent was removed under reduced pressure to obtain 8.2 g of compound (S-1).

<Synthesis of specific polymer>
[Polyamide synthesis]
Synthesis example PA-1
A reaction vessel equipped with a stirrer, thermometer, dropping funnel and reflux condenser was charged with 100 mol% of 1,4-diaminobenzene, and tetrahydrofuran was added and dissolved so that the total concentration of this compound was 20 wt%. . Further, triethylamine was charged in an amount corresponding to 300 mol% with respect to the number of moles of 1,4-diaminobenzene, and mixed at room temperature. A solution prepared by dissolving 100 mol% of the compound (C-1) obtained in Synthesis Example C-1 above in acid chloride with thionyl chloride in tetrahydrofuran at a concentration of 20 wt% was slowly dropped from the dropping funnel. The polymerization reaction was carried out at room temperature for 4 hours. After completion of the reaction, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The recovered precipitate was washed with methanol, and then dried at 40 ° C. under reduced pressure for 15 hours to obtain polyamide (PA-1).

[Synthesis of polyester]
Synthesis Examples PE-1 to PE-4
In the above synthesis example PA-1, in place of 1,4-diaminobenzene, the types and molar ratios of the dihydroxy compounds or diepoxy compounds described in Table 1 are used as the polyvalent carboxylic acids and the compounds of the types and molar ratios described in Table 1 Were used in the same manner as in Synthesis Example PA-1 except that polyesters (PE-1) to (PE-4) were obtained.

Synthesis example PE-5
In a reaction vessel equipped with a stirrer, a thermometer and a reflux condenser, 31 g of the compound (E-1) obtained in Synthesis Example E-1 was dissolved in 211.2 g of N-methylpyrrolidone. Pyromellitic dianhydride (21.8 g) was added thereto, and a reaction was carried out at 40 ° C. for 12 hours to obtain a solution containing 20% by weight of polyester (PE-5).

Abbreviations of compound names in Table 1 have the following meanings, respectively.
DA-1: 1,4-diaminobenzene EP-1: 1,4-diglycidyloxybenzene CA-1: terephthalic acid CA-2: 2,2-bis (4- (4-carboxyphenoxy) phenyl) propane PYA : Pyromellitic dianhydride

[Synthesis of polyorganosiloxane]
Synthesis example PS-1
In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux condenser, 45.47 g of the compound (S-1) obtained in Synthesis Example S-1 was charged, and 181.88 g of methyl isobutyl ketone was added and dissolved. did. To this, 1.01 g of triethylamine was added and mixed at room temperature. Next, 36 g of deionized water was dropped from the dropping funnel, and the reaction was performed at 80 ° C. for 6 hours.
After completion of the reaction, the organic layer was taken out, washed with 0.2 wt% ammonium nitrate aqueous solution until the washed waste water became neutral, and then the solvent and water were distilled off under reduced pressure to remove polysiloxane (PS -1) 40 g was obtained.

[Synthesis of polyamic acid]
Comparative Synthesis Example p-1
In a reaction vessel equipped with a stirrer and a thermometer, 41.0 g of 2,2-bis [4- (4-aminophenoxy) phenyl] propane and 1,2,3,4-cyclobutanetetracarboxylic dianhydride 19 .2 g was dissolved in 343.5 g of N-methylpyrrolidone and reacted at room temperature for 10 hours to obtain a solution containing polyamic acid (p-1).

<Preparation and evaluation of liquid crystal aligning agent>
[Application to liquid crystal display elements]
Example 1
(1) Preparation of liquid crystal aligning agent As a polymer, 100 parts by weight of the polymer (polyamide (PA-1)) obtained in Synthesis Example PA-1 was added to N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC). It melt | dissolved in the mixed solvent (NMP: BC = 50: 50 (mass ratio)), and was set as the solution of solid content concentration 6.5 weight%. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering through a filter having a pore size of 0.2 μm.
(2) Evaluation of printability The liquid crystal aligning agent prepared above was applied to the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a liquid crystal alignment film printer (Nissha Printing Co., Ltd.). After removing the solvent by heating (pre-baking) for 1 minute on an 80 ° C. hot plate, heating (post-baking) for 10 minutes on a 200 ° C. hot plate to form a coating film having an average film thickness of 600 mm. When this coating film was observed with a microscope with a magnification of 20 times to check for the presence of printing unevenness and pinholes, neither printing unevenness nor pinholes were observed, and the printability was “good”.

(3) Manufacture of liquid crystal display element A glass substrate having two systems of electrode pairs in which a bottom electrode having no pattern, a silicon nitride film, and a top electrode patterned in a comb-like shape are laminated in this order on one side, and an electrode A counter glass substrate not provided is paired, and the liquid crystal aligning agent prepared above is applied to each of the surface having the electrode of the glass substrate and one surface of the counter glass substrate using a spinner, and a hot plate at 80 ° C. Then, after prebaking for 1 minute, it was heated (postbaked) at 200 ° C. for 1 hour in an oven in which the inside of the chamber was replaced with nitrogen to form a coating film having an average film thickness of 1,000 mm.
Hereinafter, each of the two electrode pairs is referred to as “electrode A” and “electrode B”, respectively. A schematic cross-sectional view of these electrode pairs and a schematic plan view of the top electrode are shown in FIGS. 1 and 2, respectively. FIG. 2B is an enlarged view of a portion surrounded by a broken line in FIG.
Each surface of the coating film formed above is irradiated with polarized ultraviolet rays 2,500 J / m ² containing a 254 nm emission line from the normal direction of the substrate using a high-pressure mercury lamp and a Grand Taylor prism, respectively, and a liquid crystal alignment film A pair of substrates were obtained.
An epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface of the substrate having the liquid crystal alignment film by screen printing, and the liquid crystal alignment film surfaces of the pair of substrates are made to face each other. Then, the polarizing plane of polarized ultraviolet light was superposed and pressure-bonded so that the directions projected onto the substrate were parallel, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, liquid crystal “MLC-6221” manufactured by Merck Co., Ltd. was filled into the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature.
Next, the liquid crystal display element was manufactured by bonding a polarizing plate on both outer surfaces of the substrate. At this time, one of the polarizing plates is stuck so that the polarization direction thereof is parallel to the direction of projection of the polarization plane of the polarized ultraviolet light of the liquid crystal alignment film onto the substrate surface, and the other one has the polarization direction first. The polarizing plate was attached so as to be orthogonal to the polarization direction of the polarizing plate.

(4) Evaluation of liquid crystal alignment The presence or absence of an abnormal domain in the change in brightness when a voltage of 5 V was turned ON / OFF (applied / released) was observed with a microscope with a magnification of 50 times for the liquid crystal display element manufactured above. . When the abnormal domain was not observed, the liquid crystal alignment was “good”, and when the abnormal domain was observed, the liquid crystal alignment was “bad”. The liquid crystal alignment of the liquid crystal display element was “good”. .

Examples 2-5 and 7
In Example 1 above, a liquid crystal aligning agent was prepared and evaluated in the same manner as in Example 1 except that the types of polymers used for preparing the liquid crystal aligning agent were as shown in Table 2.
The evaluation results are shown in Table 2.

Example 6
In Example 1, the liquid crystal aligning agent was prepared as follows, and various evaluations were performed in the same manner as in Example 1 except that the liquid crystal aligning agent was used.
(1) Preparation of liquid crystal aligning agent N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) are added to the solution containing the polyester (PE-5) prepared in Synthesis Example PE-5, and the solvent composition ratio Was a solution having NMP: BC = 50: 50 (mass ratio) and a solid concentration of 6.5% by weight. After sufficiently stirring this solution, a liquid crystal aligning agent was prepared by filtering through a filter having a pore size of 0.2 μm.
The evaluation results are shown in Table 2.

Comparative Example 1
In Example 6 above, Example 6 was used except that the solution containing polyamic acid (p-1) obtained in Comparative Synthesis Example p-1 was used instead of the solution containing polyester (PE-5). Similarly, a liquid crystal aligning agent was prepared and evaluated.
The evaluation results are shown in Table 2.
In Comparative Example 1, although evaluation of the liquid crystal alignment was slightly bright and dark, many abnormal domains were observed and the liquid crystal was considered not to be uniformly aligned. .

[Application to retardation film]
Example 8
The liquid crystal aligning agent prepared in Example 1 was applied to one surface of a TAC film as a substrate using a bar coater, and baked in an oven at 120 ° C. for 2 minutes to form a coating film having a thickness of 100 nm. . Next, the surface of the coating film was irradiated with polarized ultraviolet rays 2,500 J / m ² containing a 254 nm emission line perpendicularly from the substrate normal line using a high-pressure mercury lamp and a Grand Taylor prism to form a liquid crystal alignment film.
Next, the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) was filtered through a filter having a pore diameter of 0.2 μm, and then applied onto the liquid crystal alignment film using a bar coater, and then the oven temperature was set to 50 ° C. Was baked for 1 minute to form a polymerizable liquid crystal film. By irradiating this polymerizable liquid crystal film with non-polarized ultraviolet rays of 1,000 mJ / cm ² including a 365 nm emission line using a Hg-Xe lamp, the polymerizable liquid crystal is polymerized and cured, thereby causing a phase difference. A film was produced.

(2) Evaluation of retardation film i) Liquid crystal orientation The orientation of the retardation film produced above was observed by visual observation under a crossed Nicol and observation with a polarizing microscope (magnification 50 times). When no abnormal domain is observed by both visual observation and polarization microscope observation, the liquid crystal orientation is excellent “A”;
The liquid crystal orientation is good by visual observation, but when the abnormal domain is observed by polarizing microscope observation, the liquid crystal orientation is good “B”;
When an abnormality in the liquid crystal alignment is observed by visual observation, the liquid crystal alignment is poor "C"
As evaluated. As a result, the liquid crystal orientation of this retardation film was evaluated as excellent “A”.
ii) Adhesiveness About the retardation film manufactured above, it cut | incised at 1 mm space | interval with the cutter knife using the equal interval spacer with a guide, and formed the 10 * 10 lattice pattern. Next, after the cellophane tape was adhered to the lattice pattern, the cellophane tape was peeled off from the lattice pattern.
Here, when the cut portion of the lattice pattern after the cellophane tape is peeled off is observed, and no peeled portion is observed along the cut line or at the intersection portion of the lattice pattern, the adhesion is excellent “A”. :
When the number of grids in which peeling points are observed is 14 or less, the adhesion is good “B”;
When the number of grids in which peeling points were observed was 15 or more, the adhesion was poor “C”.
As evaluated. As a result, the adhesiveness of this retardation film was evaluated as excellent “A”.

a: Glass substrate b: Liquid crystal alignment film c: Top electrode (comb structure)
d: Silicon nitride film e: Bottom electrode (no pattern)
f: Direction of polarization plane of polarized ultraviolet light

Claims (11)

At least one polymer selected from the group consisting of polyorganosiloxane, polyamide, poly (thio) ester and (meth) acrylic acid copolymer, provided that this polymer is represented by the following formula (1) 2 A liquid crystal aligning agent comprising a valent group.
(In Formula (1), R ^{I to} R ^IV are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 12 carbon atoms, or an alkenyl group having 2 to 12 carbon atoms;
Y ¹ and Y ² are each independently a divalent organic group, and “*” indicates a bond that is bonded to the polymer chain. ) The liquid crystal aligning agent of Claim 1 whose said polymer is the polyorganosiloxane obtained by hydrolyzing and condensing the silane compound containing the compound represented by a following formula (S).
(In formula (S), R ^{I to} R ^IV , Y ¹ and Y ² each have the same meaning as in formula (1) above;
R ¹ and R ² are each independently an alkyl group having 1 to 12 carbon atoms or an aryl group having 6 to 12 carbon atoms;
X ¹ and X ² are each independently an alkoxy group having 1 to 12 carbon atoms or a halogen atom;
n1 and n2 are each independently an integer of 1 to 3. ) The polymer is
Diamine,
A polyvalent carboxylic acid containing a compound represented by the following formula (C);
The liquid crystal aligning agent of Claim 1 which is the polyamide obtained by making this react.
(In the formula (C), R ^{I to} R ^IV , Y ¹ and Y ² have the same meanings as in the above formula (1).) The polymer is
At least one compound selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound;
A polyvalent carboxylic acid containing a compound represented by the following formula (C);
The liquid crystal aligning agent of Claim 1 which is the poly (thio) ester obtained by making this react.
(In the formula (C), R ^{I to} R ^IV , Y ¹ and Y ² have the same meanings as in the above formula (1).) The polymer is
At least one compound selected from the group consisting of a diol compound, a dithiol compound and a diepoxy compound, provided that at least a part of this compound is a compound represented by the following formula (E):
A polyvalent carboxylic acid;
The liquid crystal aligning agent of Claim 1 which is the poly (thio) ester obtained by making this react.
(In the formula (E), R ^{I to} R ^IV , Y ¹ and Y ² each have the same meaning as in the above formula (1);
Z ¹ and Z ² are each independently a hydroxyl group, a thiol group, or an epoxy group. )   The liquid crystal aligning agent as described in any one of Claims 1-5 used in order to form the liquid crystal aligning film in the phase difference film of a liquid crystal display element.   The liquid crystal aligning agent as described in any one of Claims 1-5 used in order to form the liquid crystal aligning film in the liquid crystal cell of a liquid crystal display element.   A liquid crystal alignment film formed from the liquid crystal aligning agent according to claim 1.   A retardation film for a liquid crystal display device, comprising a liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 6.   A liquid crystal cell of a liquid crystal display device comprising a liquid crystal alignment film formed from the liquid crystal alignment agent according to claim 7.   A liquid crystal alignment film comprising a step of applying a liquid crystal aligning agent according to any one of claims 1 to 7 on a substrate to form a coating film, and then irradiating the coating film with light. Forming method.