JP6807640B2 - Polymerizable compound substituted with halogen atom - Google Patents

Description

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element containing a polymerizable compound substituted with a halogen atom and a polymerizable compound substituted with a halogen atom.

Some liquid crystal display elements of a method (also called a vertical orientation (VA) method) in which liquid crystal molecules oriented perpendicularly to a substrate are made to respond by an electric field are subjected to ultraviolet rays while applying a voltage to the liquid crystal molecules in the manufacturing process. Some include the step of irradiating.
In such a vertically oriented liquid crystal display element, a photopolymerizable compound is added to the liquid crystal composition in advance, and the liquid crystal display element is used together with a vertically oriented film such as polyimide to irradiate the liquid crystal cell with ultraviolet rays while applying a voltage. , A technique for increasing the response speed of a liquid crystal (see, for example, Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display).

Normally, the tilting direction of liquid crystal molecules in response to an electric field is controlled by protrusions provided on the substrate, slits provided in display electrodes, and the like, but a liquid crystal is obtained by adding a photopolymerizable compound to the liquid crystal composition. By irradiating the cell with ultraviolet rays while applying a voltage, a polymer structure in which the tilted direction of the liquid crystal molecules is memorized is formed on the liquid crystal alignment film, so that the tilt direction of the liquid crystal molecules can be determined only by protrusions and slits. It is said that the response speed of the liquid crystal display element is faster than that of the control method.
It has also been reported that the response speed of the liquid crystal display element is increased by adding the photopolymerizable compound not in the liquid crystal composition but in the liquid crystal alignment film (SC-PVA type liquid crystal display) (for example, See Non-Patent Document 2).
On the other hand, as an added photopolymerizable compound, a certain polymerizable monomer is known (Patent Documents 2 to 6).

Japanese Unexamined Patent Publication No. 2003-307720 Japanese Unexamined Patent Publication No. 2008-239873 Japanese Unexamined Patent Publication No. 2011-844777 Japanese Unexamined Patent Publication No. 2012-240945 Special Table 2013-509457 UK Patent Application Publication GB2297549A

K.Hanaoka, SID 04 DIGEST, P.1200-1202 K.H Y.-J.Lee, SID 09 DIGEST, P.666-668

However, it is desired to further increase the response speed of the liquid crystal display element. Here, it is conceivable to increase the response speed of the liquid crystal display element by increasing the amount of the photopolymerizable compound added, but it is said that the conventional photopolymerizable compound is difficult to dissolve in the solvent used for the liquid crystal alignment agent. Has properties. Therefore, when the liquid crystal alignment agent is stored, there arises a problem of storage stability that the photopolymerizable compound is precipitated. Further, if the undissolved photopolymerizable compound remains, it becomes an impurity, which may cause a decrease in the reliability of the liquid crystal display element. For example, the liquid crystal display element may be burnt or an afterimage may occur, which may deteriorate the display quality.

An object of the present invention is to solve the above-mentioned problems of the prior art.
Specifically, an object of the present invention is to provide a liquid crystal alignment agent and a polymerizable compound having improved solubility in a liquid crystal.

As a result of diligent studies to achieve the above object, the present inventors have improved the storage stability in a varnish by using a novel polymerizable compound having a mother nucleus substituted with a halogen atom, and further, liquid crystal. It was found that the solubility in varnish was improved.

The present invention is based on such findings and has the following gist.
1. 1. A polymerizable compound having an aryl group at least monosubstituted with a halogen atom and two α-methylene-γ-butyrolactone groups.
2. 2. A polymerizable compound represented by the following formula [1].

In the formula [1], Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n1 and n2 are independently integers of 1 to 10.
3. 3. In the formula [1], Ar is a polymerizable compound having a structure represented by the following formulas [2] to [4]. (X represents a halogen group, and a fluorine group is particularly preferable. M _{1 to} m ₆ are independently integers of 0 to 4, and m ₇ and m ₈ are independently integers of 0 to 3, and m ₁ + M ₂ is 1 or more and 8 or less, m ₃ + m ₄ + m ₅ is 1 or more and 12 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 10 or less)

4. The polymerizable compound according to any one of 1 to 3 above, wherein X represents a fluorine group.
5. In formulas [2] to [4], X represents a fluorine group, m ₁ + m ₂ is 1 or more and 3 or less, m ₃ + m ₄ + m ₅ is 1 or more and 4 or less, and m ₆ + m ₇ + m ₈ is. The compound according to 4 above, which is 1 or more and 3 or less.
6. A polymerizable compound selected from the group consisting of compounds represented by the following formulas [5] to [7]. (n1 is an integer from 1 to 10.)

7. A polymerizable compound represented by the following formulas [1-1] to [1-5].

7-1. A polymerizable compound represented by the above formula [1-6].
8. A liquid crystal alignment agent containing the polymerizable compound according to any one of 1 to 7 above and at least one polymer selected from polyimide and a polyimide precursor.

According to the present invention, a polymerizable compound having a divalent organic group containing an aromatic ring having at least one halogen substituent and two α-methylene-γ-butyrolactone groups is a constituent component of the liquid crystal alignment film material. When used as, it has a high orientation-fixing ability, improves storage stability in a varnish, and further improves solubility in liquid crystal.

Hereinafter, the present invention will be described in more detail.
<Polymerizable compound>
The polymerizable compound of the present invention is represented by the following formula [1].

In the formula [1], Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ and n ₂ are independently integers of 1 to 10.
From the viewpoint of ease of synthesis, it is preferable that n1 and n2 are the same.
As Ar, those represented by the following formulas [2] to [4] are preferable.

In the formula, X represents a halogen group, and a fluorine group is particularly preferable. m _{1 to} m ₆ are independently integers of 0 to 4, m ₇ and m ₈ are independently integers of 0 to 3, m ₁ + m ₂ are 1 or more and 8 or less, and m ₃ + m ₄ + M ₅ is 1 or more and 12 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 10 or less.
In the formulas [2] to [4], X represents a fluorine group, m ₁ + m ₂ is 1 or more and 3 or less, m ₃ + m ₄ + m ₅ is 1 or more and 4 or less, and m ₆ + m ₇ + m ₈ is. It is preferably 1 or more and 3 or less from the viewpoint of ease of synthesis and economy. In each case, it is particularly preferable that the amount is 1 or more and 2 or less. Further, from the viewpoint of solubility, the substitution position of X is preferably a substitution position such that Ar becomes asymmetric.

The polymerizable compound of the present invention represented by the formula [1] can be synthesized by combining techniques in synthetic organic chemistry, and the synthesis method thereof is not particularly limited. For example, as shown in [Reaction Equation 1] below, cross-coupling using aryl halides [2-A] to [2-D], organometallic reagents [3-A] to [3-B], and a transition metal catalyst. After synthesizing the corresponding mother nuclei [4-A] to [4-C] by reacting, the ether compound [9] is synthesized by reacting with the corresponding halide [8] in the presence of a base to synthesize a metal reagent. Can be produced by reacting with an acrylic acid derivative [10] using.

Ar _1, Ar ₂ , and Ar ₃ are independently divalent organic groups having an aromatic ring, and at least one of Ar ₁ , Ar ₂ , and Ar ₃ has at least one halogen substituent. The halogen group is preferably an F atom. M is B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl. Hal is Cl or Br, I, OTf. PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group, and a 1,3-dioxolane group. n is an integer of 1-10. X ₁ is Cl, Br or I. X ₂ is Cl or Br. In addition, in this specification, Tf represents a triflate group, that is, a trifluoromersulfonyl group.

<Cross-coupling reaction, F-containing biaryl compound>
Examples of the F-containing biaryl compound [4-A] include the following biphenyl compounds [4-1] to [4-42] and phenylnaphthyl compounds [4-43] to [4-58].

The F group-containing biphenyl compound [4-A] such as the above [4-1] to [4-41] contains an aryl halide [2-A] and an organometallic reagent [3-A] as shown below. , Can be obtained by cross-coupling reaction using a metal catalyst.

In the formula, X represents F, Hal represents Br, I or OTf. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.

The amounts of the aryl halide [2-A] and the boronic acid derivative [3-A] represented by the cross-coupling reaction (Suzuki-Miyaura reaction) are not particularly limited, but the aryl halide [2-A] 1 It is preferable to use 1.0 to 1.5 equivalents of the boronic acid derivative [3-A] with respect to the equivalent amount. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used with respect to 1 equivalent of the boronic acid derivative [3-A].

The coupling reaction (Suzuki-Miyaura reaction) uses an appropriate metal complex and ligand as a catalyst. In some cases, the reaction proceeds without a ligand. Usually, a palladium complex or a nickel complex is used. As the catalyst, those having various structures can be used, but it is preferable to use a so-called low valence palladium complex or nickel complex, and in particular, a zero-valent complex having a tertiary phosphine or a tertiary phosphite as a ligand. Is preferable. It is also possible to use a suitable precursor that is easily converted to a zero-valent complex in the reaction system. Furthermore, in the reaction system, a complex that does not contain tertiary phosphine or tertiary phosphine as a ligand is mixed with tertiary phosphine or tertiary phosphite, and tertiary phosphine or tertiary phosphite is used as a ligand. It is also possible to generate a low valence complex. Examples of the tertiary phosphine or tertiary phosphine that is a ligand include triphenylphosphine, tri-o-tolylphosphine, diphenylmethylphosphine, phenyldimethylphosphine, 1,2-bis (diphenylphosphine) ethane, 1 , 3-Bis (diphenylphosphine) propane, 1,4-bis (diphenylphosphine) butane, 1,1'-bis (diphenylphosphine) ferrocene, trimethylphosphine, triethylphosphine, triphenylphosphine, etc. A complex containing a mixture of two or more of these ligands is also preferably used. It is also a preferable embodiment that a palladium complex containing no tertiary phosphine or tertiary phosphine, a complex containing tertiary phosphine or tertiary phosphite, and the above-mentioned ligand are used in combination as a catalyst. Examples of the complex that does not contain tertiary phosphine or tertiary phosphite used in combination with the above-mentioned ligands include bis (benzilidenacetone) palladium, tris (benzylideneacetone) dipalladium, bis (acetoformer) dichloropalladium, and bis (benzo Nitrile) Dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetethane complex, palladium-activated coal, nickel chloride, nickel iodide, etc., and as a complex already containing tertiary phosphine or tertiary phosphite as a ligand. Dimethylbis (triphenylphosphine) palladium, dimethylbis (diphenylmethylphosphine) palladium, (ethylene) bis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (triphenylphosphine) dichloropalladium, [1 , 3-Bis (diphenylphosphino) propane] nickel (II) dichloride, [1,2-bis (diphenylphosphino) ethane] nickel (II) dichloride and the like, but are not limited thereto. The amount of these palladium complex and nickel complex used may be a so-called catalytic amount, and generally, 20 mol% or less with respect to the substrate is sufficient, and usually 10 mol% or less.

Bases include inorganic bases such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, methylamine, and dimethyl. Amine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, colisine, etc. In addition to the amines of, sodium acetate, potassium acetate, lithium acetate and the like can also be used.

The solvent is one that is stable under the reaction conditions, is inert and does not interfere with the reaction. Water, alcohols, amines, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers _{(Et 2 O, i-Pr} 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic Hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesityrene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, etc.) , Carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetriform, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.

The F-containing biphenyl compound [4-A] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction to obtain high purity.

The solvent used for cleaning is not particularly limited, but is, for example, hydrocarbons such as hexane, heptane or toluene, halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4. -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof. Can be mentioned.

The solvent used for recrystallization is not particularly limited as long as the F-containing biphenyl compound [4-A] dissolves during heating and precipitates during cooling, and is not particularly limited. For example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1, 2 -Halogen hydrocarbons such as dichloroethane or chlorobenzene, ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile Classes, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof are mentioned, and ethyl acetate, tetrahydrofuran, toluene, and hexane are preferable.

Compound [4-42] can be purchased as a commercial product.

The F-containing phenylnaphthyl compound [4-A] such as the above [4-43] to [4-50] contains an aryl halide [2-A] and an organometallic reagent [3-A] as shown below. Can be obtained by performing a cross-coupling reaction using a metal catalyst such as Pd.

In the formula, X represents F. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.

The amount of the aryl halide [2-A] and the boronic acid derivative [3-A] represented by the cross-coupling reaction is not particularly limited, but is boron relative to 1 equivalent of the aryl halide [2-A]. It is preferable to use 1.0 to 1.5 equivalents of the acid derivative [3-A]. Further, 1.0 to 1.5 equivalents of aryl halide [2-A] may be used with respect to 1 equivalent of the boronic acid derivative [3-A].

The coupling reaction uses a suitable metal complex and ligand as catalysts. The types of catalysts and ligands are the same as in the F-containing biphenyl compound synthesis method.

The base is the same as the F-containing biphenyl compound synthesis method.

The solvent is the same as the F-containing biphenyl compound synthesis method.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.

The F-containing phenylnaphthyl compound [4-A] obtained as described above can be highly purified by purification by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction. The method is the same as the F-containing biphenyl compound synthesis method.

The F-containing phenyl-naphthyl compound [4-A] such as the above [4-51] to [4-58] contains an aryl halide [2-A] and an organometallic reagent [3-A] as shown below. ] Can be obtained by cross-coupling reaction using a metal catalyst such as Pd.

In the formula, X represents F. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.

The amount of the aryl halide [2-A] and the boronic acid derivative [3-A] represented by the cross-coupling reaction is not particularly limited, but is boron relative to 1 equivalent of the aryl halide [2-A]. It is preferable to use 1.0 to 1.5 equivalents of the acid derivative. Further, 1.0 to 1.5 equivalents of aryl halide may be used with respect to 1 equivalent of the boronic acid derivative [3-A].

The coupling reaction uses a suitable metal complex and ligand as catalysts. The types of catalysts and ligands are the same as in the F-containing biphenyl compound synthesis method.

The base is the same as the F-containing biphenyl compound synthesis method.

The solvent is the same as the F-containing biphenyl compound synthesis method.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.

The F-containing phenylnaphthyl compound [4-A] obtained as described above can be highly purified by purification by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction. The method is the same as the F-containing biphenyl compound synthesis method.

<Cross-coupling reaction, F-containing terphenyl compound>
Hereinafter, examples of the F-containing terphenyl compound [4-B] obtained by the coupling reaction of [Reaction Formula 1] include the following compounds. The F-containing terphenyl compound [4-B] has the same structure as the left and right benzene rings (A) with respect to the middle benzene ring (B) in the three-ring structure.

The F group-containing terphenyl compound [4-B] such as the above [4-59] to [4-99] contains an aryl halide [2-B] and an organometallic reagent [3-A] as shown below. ], Can be obtained by cross-coupling reaction using a metal catalyst.

In the formula, X represents F, Hal represents Br, I or OTf. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl.

The amount of the aryl halide [2-B] and the boronic acid derivative [3-A] represented by the cross-coupling reaction is not particularly limited, but is boron relative to 1 equivalent of the aryl halide [2-B]. It is preferable to use 2.0 to 2.5 equivalents of the acid derivative [3-A].

The coupling reaction uses a suitable metal complex and ligand as catalysts. The types of catalysts and ligands are the same as in the F-containing biphenyl compound synthesis method.

The base is the same as the F-containing biphenyl compound synthesis method.

The solvent is the same as the F-containing biphenyl compound synthesis method.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.

The F-containing terphenyl compound [4-B] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction. The method is the same as the F-containing biphenyl compound synthesis method.

Introducing different boronic acid derivatives [3-A] and [3-B] by using an aryl halide [2-C] having two different halogen groups selected from Cl, Br and I as a raw material. It is possible to obtain an F-containing terphenyl compound [4-C] having different structures of the benzene ring (A) and the benzene ring (C) as shown below.

The F group-containing terphenyl compound [4-C] such as the above [4-100] to [4-246] contains an aryl halide [2-C] and an organometallic reagent [3-A] as shown below. ], And a cross-coupling reaction using a metal catalyst is carried out, and the obtained aryl halide [2-D] and the organometallic reagent [3-B] are subjected to a cross-coupling reaction again. (In [Reaction Formula 1], the organometallic reagent [3-A] and the organometallic reagent [3-B] are organometallic reagents having different structures.)

In the formula, X represents F. M represents B (OH) ₂ or 4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl. [3-A] and [3-B] are different boronic acid derivatives.

The amount of the aryl halide [2-C] and the boronic acid derivative [3-A] represented by the cross-coupling reaction is not particularly limited, but is boron relative to 1 equivalent of the aryl halide [2-C]. It is preferable to use 1.0 to 1.2 equivalents of the acid derivative [3-A]. The same amount is preferably used for the subsequent Suzuki-Miyaura reaction.

The coupling reaction uses a suitable metal complex and ligand as catalysts. The types of catalysts and ligands are the same as in the F-containing biphenyl compound synthesis method.

The base is the same as the F-containing biphenyl compound synthesis method.

The solvent is the same as the F-containing biphenyl compound synthesis method.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably −50 to 150 ° C., and more preferably 40 to 120 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 40 hours, more preferably 0.5 to 24 hours.

The F-containing terphenyl compound [4-C] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction. The method is the same as the F-containing biphenyl compound synthesis method.

<F-containing etherification reaction>
As shown below, the F-containing ether compound [9] contains aromatic compounds [4-A] to [4-C] containing a phenolic hydroxyl group and an alkyl halide [8] in the presence of a base, if necessary. It can be obtained by reacting in the presence of an additive.

Ar _1, Ar ₂ , and Ar ₃ are independently divalent organic groups having an aromatic ring, and at least one of Ar ₁ , Ar ₂ , and Ar ₃ has at least one halogen substituent. The halogen group is preferably an F atom. n1 is an integer of 1-10. X ₁ is Cl, Br or I and PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group or a 1,3-dioxolane group.

As the base of the above reaction formula, inorganic bases such as sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium phosphate, potassium phosphate, sodium carbonate, potassium carbonate, lithium carbonate and cesium carbonate can be used. Preferred are sodium carbonate and potassium carbonate.

Additives can be used for the purpose of accelerating the reaction rate. As the additive, potassium iodide, sodium iodide, quaternary ammonium salt, crown ether and the like can be used.

The solvent is one that is stable under the reaction conditions, is inert and does not interfere with the reaction. Water, alcohols, amines, ketones such as acetone or methyl ethyl ketone, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i-Pr ₂ O, TBME, CPME, Tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetraline, etc.), halogen Hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetritale, propionitrile, butyronitrile, etc.) Can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more. Acetone, an aprotic polar organic solvent (DMF, DMSO, DMAc, NMP, etc.) is preferred.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably 40 to 150 ° C.

The reaction time is usually 0.05 to 100 hours, preferably 0.5 to 60 hours.

The F-containing ether compound [9] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction.

The solvent used for cleaning is not particularly limited, but is, for example, hydrocarbons such as hexane, heptane or toluene, halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4. -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof. Examples thereof are preferably alcohols such as methanol or ethanol and 2-propanol.

The solvent used for recrystallization is not particularly limited as long as the F-containing ether compound [9] dissolves during heating and precipitates during cooling, but is not particularly limited, and for example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1,2-dichloroethane. Alternatively, halogen-based hydrocarbons such as chlorobenzene, diethyl ethers, ethers such as tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, etc. Examples thereof include alcohols such as methanol or ethanol and 2-propanol and mixtures thereof, preferably alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol and 2-propanol, hexane or mixtures thereof.

<Lactone ring synthesis reaction>
The α-methylene-γ-butyrolactone compound [1] can be synthesized by combining techniques in synthetic organic chemistry, and the synthesis method is not particularly limited. As shown below, it can be synthesized by reacting an aldehyde or ketone, acetal, ketal with a metal reagent, or an acrylic acid derivative under acidic conditions (references: for example, P. Talaga, M. Schaeffer, C. Benezra). and JLStampf, Synthesis, 530 (1990)).

Ar _1, Ar ₂ , and Ar ₃ are independently divalent organic groups having an aromatic ring, and at least one of Ar ₁ , Ar ₂ , and Ar ₃ has at least one halogen substituent. The halogen group is preferably an F atom. n1 is an integer of 1-10. Examples of R include a hydrogen atom or a C1-4 alkyl group. PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxane group or a 1,3-dioxolane group. X ₂ is Cl or Br.

Examples of the acrylic acid derivative [10] represented by the above lactone ring synthesis include 2- (chloromethyl) acrylic acid, 2- (chloromethyl) methyl acrylate, 2- (chloromethyl) ethyl acrylate, and 2- (bromomethyl). ) Acrylic acid, methyl 2- (bromomethyl) acrylate, ethyl 2- (bromomethyl) acrylate and the like can be used.

The amount of the acrylic acid derivative [10] used is not particularly limited, but it is preferable to use 2.0 to 2.5 equivalents of the acrylic acid derivative with respect to 1 equivalent of the ether compound [9].

As the metal reagent, tin-based compounds such as tin powder, anhydrous tin chloride, tin chloride dihydrate, tin chloride pentahydrate, indium powder, zinc powder and the like can be used.

As the acid, an aqueous inorganic acid solution such as hydrochloric acid, sulfuric acid, phosphoric acid or ammonium chloride, an acidic resin such as Amberlyst 15, or an organic acid such as p-toluenesulfonic acid, acetic acid or formic acid can be used.

The solvent is one that is stable under the reaction conditions, is inert and does not interfere with the reaction. Water, alcohols, aprotic polar organic solvents (DMF, DMSO, DMAc, etc. NMP), ethers _{(Et 2 O, i-Pr} 2 O, TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (Pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, mesitylene, chlorobenzene, dichlorobenzene, nitrobenzene, tetralin, etc.), halogen-based hydrocarbons (chloroform, dichloromethane, tetrachloride, etc.) Carbon, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles (acetriform, propionitrile, butyronitrile, etc.) can be used. These solvents can be appropriately selected in consideration of the susceptibility of the reaction to occur, and in this case, the above-mentioned solvents can be used alone or in combination of two or more. Tetrahydrofuran and water are preferred.

The reaction temperature is not particularly limited, but is usually −90 to 200 ° C., preferably 20 to 100 ° C.

The reaction time is usually 0.05 to 200 hours, preferably 0.5 to 60 hours.

The α-methylene-γ-butyrolactone compound [1] obtained as described above can be purified by slurry washing, recrystallization, silica gel column chromatography or the like after the reaction.

The solvent used for cleaning is not particularly limited, but is, for example, hydrocarbons such as hexane, heptane or toluene, halogen-based hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, diethyl ether, tetrahydrofuran or 1,4. -Ethers such as dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, alcohols such as methanol or ethanol, 2-propanol, and mixtures thereof. Examples thereof are preferably alcohols such as methanol or ethanol and 2-propanol.

The solvent used for recrystallization is not particularly limited as long as the α-methylene-γ-butyrolactone compound [1] dissolves during heating and precipitates during cooling. For example, hydrocarbons such as hexane, heptane or toluene, chloroform, 1 , 2-Dichloroethane or halogen-based hydrocarbons such as chlorobenzene, diethyl ether, ethers such as tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, acetonitrile or propionitrile, etc. Nitriles, alcohols such as methanol or ethanol, 2-propanol and mixtures thereof, preferably alcohols such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol, 2-propanol, hexane or these. It is a mixture.

<Liquid crystal alignment agent>
The present application also provides a liquid crystal alignment agent and a liquid crystal alignment agent containing a polymerizable compound having improved solubility in a liquid crystal. The liquid crystal aligning agent of the present application is [I] at least one polymerizable compound selected from the group consisting of the compounds represented by the above formula [1] and [II] at least one polymer selected from polyimide and a polyimide precursor. Contains.

<[II] At least one polymer selected from polyimide and polyimide precursor>
[II] As at least one polymer selected from the polyimide and the polyimide precursor, a polyimide or a polyimide precursor that is used as a liquid crystal alignment agent and may be known in the past or in the future can be used.

[II] At least one polymer selected from the polyimide and the polyimide precursor preferably has (I) a side chain for vertically orienting the liquid crystal for a PSA type liquid crystal display.
<< (I) Side chain that orients the liquid crystal vertically >>
(I) The side chain that orients the liquid crystal vertically (hereinafter, also referred to as side chain A) is a side chain that has the ability to orient the liquid crystal molecules perpendicularly to the substrate, and if it has this ability, Its structure is not limited. As such a side chain, for example, a long-chain alkyl group or fluoroalkyl group, a cyclic group having an alkyl group or a fluoroalkyl group at the terminal, a steroid group and the like are known, and are preferably used in the present invention. .. These groups may be directly bonded to the main chain of the polyimide or the polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.

As the side chain A, for example, one represented by the following formula (a) can be exemplified.
In the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ¹ is an alkylene group having 2 to 6 carbon atoms, −O−, −COO−, −OCO−, respectively. -NHCO-, -CONH-, or an alkylene-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ independently represent a phenylene group or a cycloalkylene group, and R ⁵ is a hydrogen atom. Represents an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or a large cyclic substituent comprising them.

R ¹ in the formula (a) is an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO-, -CONH-, or an alkylene-ether having 1 to 3 carbon atoms. Represents a group. Among these, from the viewpoint of easiness of synthesis, -O-, -COO-, -CONH-, and an alkylene-ether group having 1 to 3 carbon atoms are preferable.

R ² , R ³ and R ⁴ in the formula (a) independently represent a phenylene group or a cycloalkylene group, respectively. From the viewpoint of ease of synthesis and ability to orient the liquid crystal vertically, the combination of l, m, n, R ² , R ³ and R ⁴ shown in the table below is preferable.

R ⁵ in the formula (a) represents a hydrogen atom or an alkyl group having 2 to 24 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or a macrocyclic substituent composed thereof. When at least one of l, m, and n is 1, the structure of R ⁵ is preferably a hydrogen atom or an alkyl group having 2 to 14 carbon atoms or a fluorine-containing alkyl group, and more preferably a hydrogen atom or a carbon atom number. 2 to 12 alkyl groups or fluorine-containing alkyl groups.
Further, l, m, n is both 0, preferably of the alkyl group or a fluorine-containing alkyl group having 12 to 22 carbon atoms, an aromatic ring, an aliphatic ring, a heterocyclic ring, or from them as the structure of R ⁵ It is a large cyclic substituent, more preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

The ability to orient the liquid crystal vertically depends on the structure of the side chain A described above, but in general, as the amount of the side chain A contained in the polymer increases, the ability to orient the liquid crystal vertically increases and decreases. Go down. Further, the side chain A containing a cyclic structure tends to orient the liquid crystal vertically even with a small content as compared with the side chain A of a long-chain alkyl group.

The abundance of the side chain A in the polyimide or the polyimide precursor used in the present invention is not particularly limited as long as the liquid crystal alignment film can orient the liquid crystal vertically. However, in the liquid crystal display element provided with the liquid crystal alignment film, when it is desired to increase the response speed of the liquid crystal, it is preferable that the abundance of the side chain A is as small as possible within the range in which the vertical alignment can be maintained. ..

[II] The polyimide or the polyimide precursor has (II) a photoreactive side chain in addition to the above-mentioned (I) side chain for vertically orienting the liquid crystal for SC-PVA type liquid crystal display. Is good.

<(II) Photoreactive side chain>
The photoreactive side chain (hereinafter, also referred to as side chain B) is a crosslinkable side chain having a functional group (hereinafter, also referred to as a photocrosslinking group) capable of reacting with irradiation with ultraviolet rays to form a covalent bond. , A photoradical generation side chain having a functional group that generates radicals by irradiation with ultraviolet rays, and its structure is not limited as long as it has this ability.
Among such side chains, for example, a side chain containing a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyle group, a chalconyl group, a coumarin group, a maleimide group, a stillben group or the like is known as a photocrosslinking group. It is also suitably used in the present invention. Further, a specific structure that generates radicals by irradiation with ultraviolet rays is also preferably used. These groups may be directly bonded to the main chain of the polyimide or the polyimide precursor as long as they have the above-mentioned ability, or may be bonded via an appropriate bonding group.

Examples of the side chain B include those represented by the following formulas (b-1) to (b-3).
In formula (b-1), R ⁶ is -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH). ₃ )-, -CON (CH ₃ )-, -N (CH ₃ ) CO-, where R ⁷ is cyclic, unsubstituted or substituted with a fluorine atom from 1 to 20 carbon atoms. Represents alkylene, where any −CH ₂ − of alkylene may be replaced by −CF ₂ − or −CH = CH −, where any of the following groups are not adjacent to each other. It may be replaced by a group; -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, carbocycle, heterocycle. R ⁸ is -CH _2- , -O-, -COO-, -OCO-, -NHCO-, -NH-, -N (CH ₃ )-, -CON (CH ₃ )-, -N (CH ₃ ) It represents either CO-, a carbocycle, or a heterocycle, where R ⁹ is a styryl group, -CR ¹⁰ = CH ₂ , a carbocycle, a heterocycle, or a structure represented by the following formula R9-1 to R9-31. Represents, and R ¹⁰ represents a methyl group that may be substituted with a hydrogen atom or a fluorine atom.

May be bonded group of the represented by R ⁶ in formula (b-1) is to form a normal organic synthetic techniques, from the viewpoint of ease of _synthesis, -CH 2 -, - O-, -COO-, -NHCO-, -NH-, -CH ₂ O- are preferable.

Carbocycles within the definition of formula (b-1) wherein R ⁷ in, the heterocyclic, although the specific examples thereof include the following structures, but not limited thereto.

Formula (b-1) Among the linking groups represented by ^{R 8} in, _-CH 2 from the viewpoint of ease of synthesis -, - O -, - COO -, - OCO-, NHCO -, - It is preferably NH-, a carbocycle, or a heterocycle. Specific examples of carbocyclic and heterocyclic, carbocyclic in the definition of R ^7, is similar to the heterocyclic ring.

R ⁹ in the formula (b-1) represents a styryl group, −CR ¹⁰ = CH ₂ , a carbocycle, a heterocycle or a structure represented by the above formula R9-1 to R9-31, and R ¹⁰ is a hydrogen atom or Represents a methyl group that may be substituted with a fluorine atom.

Among these, from the viewpoint of photoreactivity, it is more preferable that R ⁹ is a styryl group, -CH = CH ₂ , -C (CH ₃ ) = CH _2, or the above formula R9-2, R9-12 or R9-15. .. When R ⁹ is −CH = CH ₂ or −C (CH ₃ ) = CH ₂ , and R ⁸ is −OCO−, an acrylic group or a methacrylic group is formed, which is also preferable.

The side chain represented by the formula (b-2) is a side chain having a cinnamoyl structure and a methacrylic structure at the same time. In formula (b-2), R ¹⁰ represents a group selected from -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-. R ¹¹ is an alkylene group, a divalent carbon ring or a heterocycle formed from 1 to 30 carbon atoms, and one or more hydrogen atoms of the alkylene group, the divalent carbon ring or the heterocycle are , Fluorine atom or organic group may be replaced. ^In the case ^{R 11} are the any of the groups listed below are not adjacent to each other, -CH ₂ - may be replaced by these groups; -O -, - NHCO -, - CONH -, - COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ¹² represents any of -CH _2- , -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-, and a single bond. R ¹³ represents a photocrosslinkable group such as a cinnamoyl group, a chalcone group, and a coumarin group. R ¹⁴ is a single bond or an alkylene group, a divalent carbocycle or a heterocycle formed from 1 to 30 carbon atoms, and one or more of the alkylene group, the divalent carbocycle or the heterocycle. The hydrogen atom of is replaced with a fluorine atom or an organic group. ^{Further, R 14} is the if any of the following groups not adjacent to each other, -CH ₂ - may be replaced by these groups; -O -, - NHCO -, - CONH -, - COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ¹⁵ represents a photopolymerizable group selected from either an acrylic group or a methacrylic group.
Specific examples of the side chain represented by the formula (b-2) include the following structures (in the formula, R represents a hydrogen atom or a methyl group which may be substituted with fluorine. ).

Formula (b-3) is a side chain that generates radicals by irradiation with ultraviolet rays. In formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from phenylene, naphthylene, and biphenylene, which may be substituted with an organic group or a hydrogen atom may be replaced with a halogen atom. good. R ₁₆ and R ₁₇ are independently alkyl groups, alkoxy groups, benzyl groups, and phenethyl groups having 1 to 10 carbon atoms, respectively. In the case of alkyl groups and alkoxy groups, rings are formed by R ₁₆ and R _17. You may be. T ₁ and T ₂ are independently single-bonded or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N (CH ₃ ). -, -CON (CH ₃ )-, -N (CH ₃ ) CO-bonding group, S is an alkylene group having 1 to 20 carbon atoms substituted or substituted with a fluorine atom (however, of the alkylene group). -CH _2- or -CF ₂ --may be arbitrarily replaced by -CH = CH-, and may be replaced by any of the following groups when they are not adjacent to each other. -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, divalent carbon ring, divalent heterocycle.), N2 is 0 or 1, and Q Represents a structure selected from the following groups.

In the formula, R represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and R ₃ represents −CH _2- , −NR−, −O−, −S−.
Specific examples of the side chain represented by the formula (b-3) include the following structures.

The abundance of the side chain B is not particularly limited as long as the response speed of the liquid crystal in the liquid crystal display element can be increased. When it is desired to increase the response speed of the liquid crystal in the liquid crystal display element, it is preferable to increase the response speed as much as possible within a range that does not affect other characteristics.

<Polyamic acid>
Polyamic acid, which is a kind of polyimide precursor having a side chain A, is said to be obtained by either one of the raw materials diamine and tetracarboxylic acid anhydride having the side chain A or both having the side chain A. It can be obtained by reacting the raw materials. Of these, a method using a diamine compound having a side chain A is preferable because of ease of raw material synthesis.
As for the polyamic acid having side chain A and side chain B, only one of the raw materials diamine and tetracarboxylic acid anhydride has side chain A and side chain B, or one of them has only side chain A. And the other has only side chain B, or one has side chain A and side chain B and the other has side chain A, or one has side chain A and side chain B It can be obtained by reacting the raw materials by having and the other having a side chain B, or both having a side chain A and a side chain B. Of these, a method using a diamine compound having a side chain A, a diamine compound having a side chain B, and a tetracarboxylic acid having no side chain A or side chain B is preferable from the viewpoint of ease of raw material synthesis.
Hereinafter, the diamine compound having the side chain A will be described, and then the diamine compound having the side chain B will be described.

<Diamine compound having side chain A>
The diamine compound having a side chain A (hereinafter, also referred to as diamine A) has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocycle, or a large cyclic substituent composed thereof in the diamine side chain. Diamine can be taken as an example. Specifically, a diamine having a side chain represented by the formula (a) can be mentioned. More specifically, for example, diamines represented by the following formulas (1), (3), (4) and (5) can be mentioned, but the present invention is not limited thereto. The definitions of l, m, n, and R ^{1 to} R ^{5 in} the formula (1) are the same as those in the formula (a).

In formula (3) or formula (4), each of A ₁₀ independently has -COO-, -OCO-, -CONH-, -NHCO-, -CH _2- , -O-, -CO-, or -NH. -Represents-, A ₁₁ represents a single bond or a phenylene group, a represents a side chain A, and a'is an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, or a heterocyclic ring of any structure. Represents a large cyclic substituent consisting of a combination.

In formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted with a fluorine atom, and A ₁₅ is a 1,4-cyclohexylene group or 1,4-phenylene. A ₁₆ is an oxygen atom or -COO- * (where a bond with an "*" binds to A ₃ ), and A ₁₇ is an oxygen atom or -COO- * (provided that it is a group). , The coupling hand with "*" is (CH ₂ ) a ₂ ). Further, a ₁ is an integer of 0 or 1, a ₂ is an integer of ₂ to 10, and a ₃ is an integer of 0 or 1. )

The bonding position of the two amino groups (-NH ₂ ) in the formula (1) is not limited. Specifically, the positions 2, 3 and 2, 4 and 2, 5 and 2, 6 and 3, 4 and 3, 4 positions on the benzene ring with respect to the bonding group of the side chain. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. Considering the ease of synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable.

As a specific structure of the formula (1), diamines represented by the following formulas [A-1] to [A-24] can be exemplified, but the structure is not limited thereto.

Wherein [A-1] ~ formula _[A-5], A ₁ is each independently an alkyl group or a fluorine-containing alkyl group having 2 to 24 carbon atoms.
In the formulas [A-6] and [A-7], A ₂ independently represents -O-, -OCH _2- , -CH ₂ O-, -COOCH _2- , or -CH ₂ OCO-. , a ₃ are each independently, 1 or more carbon atoms 22 an alkyl group, an alkoxy group, a fluorine-containing alkyl group or fluorine-containing alkoxy group.
Wherein [A-8] ~ formula _[A-10], A ₄ are each independently, -COO -, - OCO -, - CONH -, - NHCO -, - COOCH 2 -, - CH 2 OCO -, - It represents CH ₂ O −, −OCH ₂ −, or −CH ₂ −, and A ₅ is independently an alkyl group having 1 or more and 22 or less carbon atoms, an alkoxy group, a fluorine-containing alkyl group, or a fluorine-containing alkoxy group.

Wherein [A-11] and the formula _[A-12], A ₆ are each independently, -COO -, - OCO -, - CONH -, - NHCO -, - COOCH 2 -, - CH 2 OCO -, - It represents CH ₂ O-, -OCH _2- , -CH _2- , -O-, or -NH-, and A ₇ is a fluorine group, cyano group, trifluoromethane group, nitro group, azo group, formyl group, acetyl group. , Acetoxy group, or hydroxyl group.
Wherein [A-13] and the formula _[A-14], A ₈ each independently is an alkyl group having 3 to 12 carbon atoms, 1,4-cyclohexylene cis - trans isomerism, trans respectively The body.
In the formulas [A-15] and [A-16], A ₉ is an alkyl group having 3 to 12 carbon atoms independently, and the cis-trans isomers of 1,4-cyclohexylene are trans isomers, respectively. The body.

Specific examples of the diamine represented by the formula (3) include the following formulas [A-25] to [A-30] (A ₁₂ is -COO-, -OCO-, -CONH-, -NHCO-. _{, -CH 2 -, - O -} , - CO-, or -NH- are _{shown, a 13} is be mentioned a diamine represented by an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms). It can, but it is not limited to this.

Specific examples of the diamine represented by the formula (4) include, but are not limited to, the diamines represented by the following formulas [A-31] to [A-32].

Among these, from the viewpoint of the ability to orient the liquid crystal vertically and the response speed of the liquid crystal, [A-1], [A-2], [A-3], [A-7], [A-14], [ The diamines of [A-16], [A-21] and [A-22] are preferable.
The above diamine compound may be used alone or in combination of two or more depending on the characteristics such as the liquid crystal orientation, the pretilt angle, the voltage holding characteristic, and the accumulated charge when the liquid crystal alignment film is formed.

Of the 100 mol% of the diamine component used for the synthesis of the polyamic acid having the side chain A, the diamine A is preferably 5 to 70 mol%, preferably 10 to 50 mol%, and more preferably 20 to 50 mol%. ..

<Diamine compound having side chain B>
As an example of a diamine compound having a side chain B (hereinafter, also referred to as diamine B), a vinyl group, an acrylic group, a methacryl group, an anthracenyl group, a cinnamoyle group, a chalconyl group, a coumarin group, a maleimide group, a stillben group, etc. Examples thereof include a diamine having a photobridge group of the above and a diamine having a specific structure for generating a radical by irradiation with ultraviolet rays. Specifically, a diamine having a side chain represented by the above formulas (b-1) to (b-3) can be mentioned. As a specific example, it is represented by the following general formula (2) (the definitions of R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ^{10 in} the formula (2) are the same as those in the formula (b-1)). Diamines can be mentioned, but are not limited to this.

The bonding position of the two amino groups (-NH ₂ ) in the formula (2) is not limited. Specifically, the positions 2, 3 and 2, 4 and 2, 5 and 2, 6 and 3, 4 and 3, 4 positions on the benzene ring with respect to the bonding group of the side chain. The position of 5 is mentioned. Of these, the 2,4 position, the 2,5 position, or the 3,5 position is preferable from the viewpoint of reactivity in synthesizing the polyamic acid. Considering the ease of synthesizing the diamine compound, the positions 2, 4 or 3, 5 are more preferable.
Specific examples thereof include, but are not limited to, the following compounds.

In the formula, X independently represents a linking group selected from -C-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, and l, m, n, are Each independently represents an integer of 0 to 20, k represents an integer of 1 to 20, and R represents a hydrogen atom or a methyl group.
One or two of the above diamine compounds may be used, depending on the liquid crystal orientation when used as a liquid crystal alignment film, pretilt angle, voltage holding characteristics, characteristics such as accumulated charge, and the response speed of the liquid crystal when used as a liquid crystal display element. It is also possible to mix and use more than one type.

Of the 100 mol% of the diamine component used for the synthesis of the polyamic acid, the diamine B is greater than 0% and 95 mol% or less, preferably 20-80 mol%, more preferably 40-70 mol%. Good.

<Other diamine compounds>
As the polyamic acid used in the present invention, other diamine compounds other than diamine A and diamine B can be used in combination as a diamine component as long as the effects of the present invention are not impaired. Specific examples are given below.

p-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylenediamine, 2,4-dimethyl-m-phenylenediamine, 2, 5-Diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-diaminophenol, 3,5-diaminophenol, 3,5-diaminobenzyl alcohol, 2,4-diaminobenzyl alcohol, 4 , 6-Diaminoresorcinol, 4,4'-diaminobiphenyl, 3,3'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 3,3'-dihydroxy -4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-difluoro-4,4'-biphenyl, 3,3'-trifluoromethyl-4, 4'-diaminobiphenyl, 3,4'-diaminobiphenyl, 3,3'-diaminobiphenyl, 2,2'-diaminobiphenyl, 2,3'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 3,3' -Diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diamino Diphenyl ether, 2,2'-diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldianiline, 3,3'-sulfonyldianiline, bis (4-aminophenyl) silane, bis (3-amino) Phenyl) silane, dimethyl-bis (4-aminophenyl) silane, dimethyl-bis (3-aminophenyl) silane, 4,4'-thiodianiline, 3,3'-thiodianiline, 4,4'-diaminodiphenylamine, 3, 3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diaminodiphenylamine, 2,3'-diaminodiphenylamine, N-methyl (4,4'-diaminodiphenyl) amine, N-methyl (3, 3'-diaminodiphenyl) amine, N-methyl (3,4'-diaminodiphenyl) amine, N-methyl (2,2'-diaminodiphenyl) amine, N-methyl (2,3'-diaminodiphenyl) amine, 4,4'-diaminobenzophenone, 3, 3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 1,4-diaminonaphthalene, 2,2'-diaminobenzophenone, 2,3'-diaminobenzophenone, 1,5-diaminonaphthalene, 1,6-diaminonaphthalene , 1,7-Diaminonaphthalene, 1,8-diaminonaphthalene, 2,5-diaminonaphthalene, 2,6 diaminonaphthalene, 2,7-diaminonaphthalene, 2,8-diaminonaphthalene, 1,2-bis (4-) Aminophenyl) ethane, 1,2-bis (3-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,3-bis (3-aminophenyl) propane, 1,4-bis ( 4aminophenyl) butane, 1,4-bis (3-aminophenyl) butane, bis (3,5-diamino-4-aminophenyl) methane, 1,4-bis (4-aminophenoxy) benzene, 1,3 -Bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenyl) benzene, 1,3-bis (4-aminophenyl) benzene, 1,4-bis (4-aminobenzyl) benzene, 1 , 3-bis (4-aminophenoxy) benzene, 4,4'-[1,4-phenylenebis (methylene)] dianiline, 4,4'-[1,3-phenylenebis (methylene)] dianiline, 3, 4'-[1,4-phenylenebis (methylene)] dianiline, 3,4'-[1,3-phenylenebis (methylene)] dianiline, 3,3'-[1,4-phenylenebis (methylene)] Dianiline, 3,3'-[1,3-phenylenebis (methylene)] dianiline, 1,4-phenylenebis [(4-aminophenyl) methanone], 1,4-phenylenebis [(3-aminophenyl) methanone ], 1,3-Phenylenebis [(4-aminophenyl) methanone], 1,3-phenylenebis [(3-aminophenyl) methanone], 1,4-phenylenebis (4-aminobenzoate), 1,4 -Phenylenebis (3-aminobenzoate), 1,3-phenylenebis (4-aminobenzoate), 1,3-phenylenebis (3-aminobenzoate), bis (4-aminophenyl) terephthalate, bis (3-amino) Phenyl) terephthalate, bis (4-aminophenyl) isophthalate, bis (3-aminophenyl) isophthalate, N, N'-(1,4-phenylene) bis (4-aminobenzamide), N, N'-( 1,3 -Phenylene) bis (4-aminobenzamide), N, N'-(1,4-phenylene) bis (3-aminobenzamide), N, N'-(1,3-phenylene) bis (3-aminobenzamide) , N, N'-bis (4-aminophenyl) terephthalamide, N, N'-bis (3-aminophenyl) terephthalamide, N, N'-bis (4-aminophenyl) isophthalamide, N, N' -Bis (3-aminophenyl) isophthalamide, 9,10-bis (4-aminophenyl) anthracene, 4,4'-bis (4-aminophenoxy) diphenylsulfone, 2,2'-bis [4- (4) -Aminophenoxy) phenyl] propane, 2,2'-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2'-bis (4-aminophenyl) hexafluoropropane, 2,2'- Bis (3-aminophenyl) hexafluoropropane, 2,2'-bis (3-amino-4-methylphenyl) hexafluoropropane, 2,2'-bis (4-aminophenyl) propane, 2,2'- Bis (3-aminophenyl) propane, 2,2'-bis (3-amino-4-methylphenyl) propane, 3,5-diaminobenzoic acid, 2,5-diaminobenzoic acid, bis (4-aminophenoxy) Methan, 1,2-bis (4-aminophenoxy) ethane, 1,3-bis (4-aminophenoxy) propane, 1,3-bis (3-aminophenoxy) propane, 1,4-bis (4-amino) Phenoxy) butane, 1,4-bis (3-aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,5-bis (3-aminophenoxy) pentane, 1,6-bis (4) −Aminophenoxy) hexane, 1,6-bis (3-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane, 1,7-bis (3-aminophenoxy) heptane, 1,8 -Bis (4-aminophenoxy) octane, 1,8-bis (3-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,9-bis (3-aminophenoxy) nonan, 1 , 10-bis (4-aminophenoxy) decane, 1,10-bis (3-aminophenoxy) decane, 1,11-bis (4-aminophenoxy) undecane, 1,11-bis (3-aminophenoxy) undecane , 1,12-bis (4-aminophenoxy) dodecane, 1,12- Aromatic diamines such as bis (3-aminophenoxy) dodecane, alicyclic diamines such as bis (4-aminocyclohexyl) methane, bis (4-amino-3-methylcyclohexyl) methane, 1,3-diaminopropane, 1 , 4-Diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1, Aliphatic diamines such as 11-diaminoundecane and 1,12-diaminododecane.

The other diamine compounds may be used alone or in combination of two or more depending on the characteristics such as the liquid crystal orientation, the pretilt angle, the voltage holding characteristic, and the accumulated charge when the liquid crystal alignment film is formed.

<Tetracarboxylic dianhydride>
In the synthesis of the polyamic acid used in the present invention, the tetracarboxylic dianhydride to be reacted with the above diamine component is not particularly limited. Specific examples are given below.

Pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6,7 -Anthracene tetracarboxylic acid, 1,2,5,6-anthracene tetracarboxylic acid, 3,3', 4,4'-biphenyltetracarboxylic acid, 2,3,3', 4'-biphenyltetracarboxylic acid, bis (3,4-dicarboxyphenyl) ether, 3,3', 4,4'-benzophenone tetracarboxylic acid, bis (3,4-dicarboxyphenyl) sulfone, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, 1,1,1,3,3,3-hexafluoro-2,2-bis (3,4-dicarboxyphenyl) propane, bis (3) , 4-dicarboxyphenyl) dimethylsilane, bis (3,4-dicarboxyphenyl) diphenylsilane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis (3,4-dicarboxyphenyl) Pyridine, 3,3', 4,4'-diphenylsulfonetetracarboxylic acid, 3,4,9,10-perylenetetracarboxylic acid, 1,3-diphenyl-1,2,3,4-cyclobutanetetracarboxylic acid, Oxydiphthaltetracarboxylic acid, 1,2,3,4-cyclobutanetetracarboxylic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid, 1,2 , 3,4-Tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid, 1,3-dimethyl-1,2, 3,4-Cyclobutanetetracarboxylic acid, 1,2,3,4-cycloheptanetetracarboxylic acid, 2,3,4,5-tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexylsuccinic acid, 2,3,5-tricarboxycyclopentylacetic acid, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid, bicyclo [3,3,0] octane-2,4,6 8-Tetracarboxylic Acid, Bicyclo [4,3,0] Nonan-2,4,7,9-Tetracarboxylic Acid, Bicyclo [4,4,0] Decane-2,4,7,9-Tetracarboxylic Acid, Bicyclo [4,4,0] decan-2,4,8,10-tetracarboxylic acid, tricyclo [6.3.0.0 <2,6>] undecane- 3,5,9,11-tetracarboxylic acid, 1,2,3,4-butanetetracarboxylic acid, 4- (2,5-dioxotetracarboxylic acid) -1,2,3,4-tetra Hydrinaphthalene-1,2-dicarboxylic acid, bicyclo [2,2,2] octo-7-ene-2,3,5,6-tetracarboxylic acid, 5- (2,5-dioxotetrahydrofuryl) -3 -Methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo [6,2,1,1,0,2,7] dodeca-4,5,9,10-tetracarboxylic acid, 3,5 Examples thereof include tetracarboxylic dianhydride obtained from 6-tricarboxynorbornane-2: 3,5: 6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid and the like.

The tetracarboxylic dianhydride may be used alone or in combination of two or more depending on the characteristics such as liquid crystal orientation, voltage holding characteristics, and accumulated charge when the liquid crystal alignment film is formed.

<Synthesis of polyamic acid>
A known synthetic method can be used to obtain a polyamic acid by reacting the diamine component with the tetracarboxylic dianhydride. Generally, it is a method of reacting a diamine component and a tetracarboxylic dianhydride in an organic solvent. The reaction of the diamine component with the tetracarboxylic dianhydride is advantageous in that it proceeds relatively easily in an organic solvent and no by-products are generated.

The organic solvent used in the above reaction is not particularly limited as long as it dissolves the produced polyamic acid. Further, even if it is an organic solvent that does not dissolve the polyamic acid, it may be mixed with the above solvent and used as long as the produced polyamic acid does not precipitate. Since the water content in the organic solvent inhibits the polymerization reaction and further causes the produced polyamic acid to be hydrolyzed, it is preferable to use a dehydrated and dried organic solvent.
Specific examples of organic solvents are given below.

N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3- Dimethyl-2-imidazolidinone, 3-methoxy-N, N-dimethylpropanamide, N-methylcaprolactam, dimethylsulfoxide, tetramethylurea, pyridine, dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, isopropyl alcohol, methoxymethyl Pentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cell solve, ethyl cell solve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, Ethyl glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, Propropylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monomethyl ether Propropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, Amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, d. Tylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether acetate, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl ethyl, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglime, 4-hydroxy-4-methyl-2-pentanone, 2-Ethyl-1-hexanol. These organic solvents may be used alone or in combination.

When the diamine component and the tetracarboxylic dianhydride component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride component is used as it is or is organic. A method of dispersing or dissolving the tetracarboxylic dianhydride component in a solvent and adding the dianide component, conversely a method of adding the diamine component to a solution in which the tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, Examples thereof include a method of adding alternately, and any of these methods may be used. When the diamine component or the tetracarboxylic dianhydride component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be reacted individually in sequence, or may be reacted individually, and have a low molecular weight. The bodies may be mixed and reacted to form a high molecular weight compound.

The temperature at which the diamine component and the tetracarboxylic dianhydride component are reacted can be selected from any temperature, and is, for example, in the range of −20 ° C. to 150 ° C., preferably −5 ° C. to 100 ° C. The reaction can be carried out at any concentration, for example, 1 to 50% by mass, preferably 5 to 30% by mass.

The ratio of the total number of moles of the tetracarboxylic dianhydride component to the total number of moles of the diamine component in the above polymerization reaction can be arbitrarily selected according to the molecular weight of the polyamic acid to be obtained. Similar to a normal polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polyamic acid produced. If you dare to show a preferable range, it is 0.8 to 1.2.

The method for synthesizing the polyamic acid used in the present invention is not limited to the above method, and as in the general method for synthesizing a polyamic acid, instead of the above-mentioned tetracarboxylic dianhydride, a tetracarboxylic having a corresponding structure is used. The corresponding polyamic acid can also be obtained by reacting with an acid or a tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide by a known method.

<Polyimide>
Examples of the method for imidizing the above-mentioned polyamic acid to obtain polyimide include thermal imidization in which the polyamic acid solution is heated as it is, and catalytic imidization in which a catalyst is added to the polyamic acid solution.
In the polyimide used in the present invention, the imidization ratio from polyamic acid to polyimide does not necessarily have to be 100%.

The temperature at which the polyamic acid is thermally imidized in the solution is 100 ° C. to 400 ° C., preferably 120 ° C. to 250 ° C., and it is preferable to remove the water generated by the imidization reaction from the system.

Catalytic imidization of polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to a solution of polyamic acid and stirring at -20 to 250 ° C., preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times, that of the amic acid group, and the amount of acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times that of the amic acid group. It is double. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine, and among them, pyridine is preferable because it has an appropriate basicity for advancing the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride and the like. Among them, acetic anhydride is preferable because it facilitates purification after completion of the reaction. The imidization rate by catalytic imidization can be controlled by adjusting the amount of catalyst, the reaction temperature, and the reaction time.

When the produced polyamic acid or polyimide is recovered from the reaction solution of polyamic acid or polyimide, the reaction solution may be poured into a poor solvent to precipitate. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellsolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water and the like. The polymer which has been put into a poor solvent and precipitated can be collected by filtration and then dried at normal temperature or by heating under normal pressure or reduced pressure. Further, when the operation of redistributing the polymer recovered by precipitation in an organic solvent and repeating the operation of recovering the precipitation 2 to 10 times, impurities in the polymer can be reduced. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these, because the purification efficiency is further improved.

<Liquid crystal alignment agent>
The liquid crystal aligning agent of the present invention has the above-mentioned [I] polymerizable compound; and at least one polymer selected from the above-mentioned [II] polyimide and polyimide precursor; but other than the [I] and [II] components. , It may have a resin component for forming a resin film. The content of the total resin component is preferably 1% by mass to 20% by mass, preferably 3% by mass to 15% by mass, and more preferably 3 to 10% by mass in 100% by mass of the liquid crystal aligning agent.

In the liquid crystal aligning agent used in the present invention, the above resin components may be a polyimide or polyimide precursor having all of the side chains A, or a polyimide or polyimide precursor having side chains A and B. , These may be a mixture thereof, and further, other polymers may be mixed. At that time, the content of the other polymer in the resin component is preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass.
Examples of such other polymers include a polyimide or polyimide precursor having no side chain B, and a polyimide or polyimide precursor having no side chain A and side chain B at the same time. Not limited.

The molecular weight of the polymer of the above resin component is the weight measured by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the coating film obtained from the polymer, the workability at the time of forming the coating film, and the uniformity of the coating film. The average molecular weight is preferably 5,000 to 1,000,000, more preferably 10,000 to 150,000.

<Solvent>
The organic solvent used for the liquid crystal alignment agent of the present invention is not particularly limited as long as it is an organic solvent that dissolves the above-mentioned resin component. This organic solvent may be one kind of solvent or two or more kinds of mixed solvents. If a specific example of the organic solvent is given, the organic solvent exemplified in the above-mentioned polyamic acid synthesis can be mentioned. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N, and N-dimethylpropanamide dissolve resin components. It is preferable from the viewpoint of sex.

Further, since the solvent shown below improves the uniformity and smoothness of the coating film, it is preferable to mix and use it with a solvent having high solubility of the resin component.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, Ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monobutyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether , Diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene Glycol monoacetate Monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether , Diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol acetate Monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropion Propyl acid, butyl 3-methoxypropanol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glyco Lumonoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, methyl lactate Examples thereof include esters, lactic acid ethyl esters, lactic acid n-propyl esters, lactic acid n-butyl esters, lactic acid isoamyl esters, and 2-ethyl-1-hexanol. A plurality of types of these solvents may be mixed. When these solvents are used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment agent.

The liquid crystal alignment agent may contain components other than the above. Examples thereof include a compound that improves the film thickness uniformity and surface smoothness when the liquid crystal alignment agent is applied, a compound that improves the adhesion between the liquid crystal alignment film and the substrate, and the like.

Examples of compounds that improve the uniformity of film thickness and surface smoothness include fluorine-based surfactants, silicone-based surfactants, and nonionic surfactants. More specifically, for example, Ftop EF301, EF303, EF352 (manufactured by Tochem Products), Megafvck F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Florard FC430, FC431 (manufactured by Sumitomo 3M Ltd.) ), Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (manufactured by Asahi Glass Co., Ltd.) and the like. When these surfactants are used, the ratio of their use is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part with respect to 100 parts by mass of the resin component contained in the liquid crystal alignment agent. It is a mass part.

Specific examples of the compound that improves the adhesion between the liquid crystal alignment film and the substrate include a functional silane-containing compound and an epoxy group-containing compound. For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane. , N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-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-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-aminopropyltrimethoxy Silane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neo Pentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol , N, N, N', N', -tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N', N', -tetraglycidyl -4,4'-diaminodiphenylmethane, 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane, 3- (N, N-diglycidyl) aminopropyltrimethoxysilane and the like can be mentioned. Further, in order to further increase the rubbing resistance of the resin using the present invention, phenol compounds such as 2,2'-bis (4-hydroxy-3,5-dihydroxymethylphenyl) propane and tetra (methoxymethyl) bisphenol are added. May be good. When these compounds are used, the amount is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, based on 100 parts by mass of the resin component contained in the liquid crystal alignment agent.
In addition to the above, the liquid crystal aligning agent used in the present invention includes a dielectric or a conductive substance for changing the electrical characteristics such as the dielectric constant and conductivity of the liquid crystal alignment film as long as the effects of the present invention are not impaired. The substance may be added.

<Liquid crystal alignment film>
For example, a cured film obtained by applying the liquid crystal alignment agent of the present invention to a substrate, drying it if necessary, and firing it can be used as it is as a liquid crystal alignment film. Further, the cured film is rubbed, polarized light or light of a specific wavelength is irradiated, an ion beam or the like is processed, or a voltage is applied to the liquid crystal display element after filling the liquid crystal as an alignment film for SC-PVA. It is also possible to irradiate the UV in this state.

At this time, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and glass plate, polycarbonate, poly (meth) acrylate, polyether sulphon, polyarylate, polyurethane, poly sulphon, polyether, polyetherketone, etc. Trimethylpentene, polyolefin, polyethylene terephthalate, (meth) acrylonitrile, triacetyl cellulose, diacetyl cellulose, acetate butylate cellulose and the like can be used. Further, it is preferable to use a substrate on which an ITO (Indium Tin Oxide) electrode for driving a liquid crystal is formed from the viewpoint of simplifying the process. Further, in the reflective liquid crystal display element, an opaque object such as a silicon wafer can be used if only one substrate is used, and in this case, a material that reflects light such as aluminum can also be used as the electrode.

The method for applying the liquid crystal alignment agent is not particularly limited, and examples thereof include printing methods such as screen printing, offset printing, and flexographic printing, an inkjet method, a spray method, a roll coating method, a dip, a roll coater, a slit coater, and a spinner. From the viewpoint of productivity, the transfer printing method is widely used industrially, and is preferably used in the present invention.

The coating film formed by applying the liquid crystal alignment agent by the above method can be fired to form a cured film. The drying step after applying the liquid crystal alignment agent is not always necessary, but if the time from coating to firing is not constant for each substrate, or if firing is not performed immediately after coating, a drying step is performed. Is preferable. The drying is not particularly limited as long as the solvent is removed to the extent that the shape of the coating film is not deformed by transporting the substrate or the like, and the drying means thereof is not particularly limited. For example, a method of drying on a hot plate having a temperature of 40 ° C. to 150 ° C., preferably 60 ° C. to 100 ° C. for 0.5 minutes to 30 minutes, preferably 1 minute to 5 minutes can be mentioned.

The firing temperature of the coating film formed by applying the liquid crystal alignment agent is not limited and can be carried out at any temperature of, for example, 100 to 350 ° C., but is preferably 120 ° C. to 300 ° C., more preferably 120 ° C. to 300 ° C. The temperature is 150 ° C to 250 ° C. The firing time can be any time from 5 minutes to 240 minutes. It is preferably 10 to 90 minutes, more preferably 20 to 90 minutes. The heating can be performed by a generally known method, for example, a hot plate, a hot air circulation furnace, an infrared furnace, or the like.

The thickness of the liquid crystal alignment film obtained by firing is not particularly limited, but is preferably 5 to 300 nm, more preferably 10 to 120 nm.

<Liquid crystal display element having a liquid crystal alignment film>
The liquid crystal display element of the present invention can be obtained by forming a liquid crystal alignment film on a substrate by the above method and then producing a liquid crystal cell by a known method. As a specific example of the liquid crystal display element, two substrates arranged so as to face each other, a liquid crystal layer provided between the substrates, and formed by the liquid crystal aligning agent of the present invention provided between the substrates and the liquid crystal layer. It is a vertical alignment type liquid crystal display element including a liquid crystal cell having the above liquid crystal alignment film. Specifically, the liquid crystal alignment agent of the present invention is applied onto two substrates and fired to form a liquid crystal alignment film, and the two substrates are arranged so that the liquid crystal alignment films face each other. By sandwiching a liquid crystal layer composed of liquid crystal between two substrates, that is, providing the liquid crystal layer in contact with the liquid crystal alignment film and irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays while applying a voltage. It is a vertically oriented liquid crystal display element including a liquid crystal cell to be manufactured. Using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention in this way, the polymerizable compound is polymerized by irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays while applying a voltage, and the light contained in the polymer. By reacting the reactive side chains with each other or the photoreactive side chains of the polymer with the polymerizable compound, the orientation of the liquid crystal is more efficiently fixed, and the response speed is remarkably excellent. It becomes.

The substrate used for the liquid crystal display element of the present invention is not particularly limited as long as it is a highly transparent substrate, but is usually a substrate on which a transparent electrode for driving a liquid crystal is formed. As a specific example, the same substrate as that described in the liquid crystal alignment film can be mentioned. A substrate provided with a conventional electrode pattern or protrusion pattern may be used, but in the liquid crystal display element of the present invention, the liquid crystal alignment agent of the present invention is used as the liquid crystal alignment agent for forming the liquid crystal alignment film. It is possible to operate even in a structure in which a line / slit electrode pattern of, for example, 1 to 10 μm is formed on one side substrate and no slit pattern or protrusion pattern is formed on the opposite substrate. The process can be simplified and high transmittance can be obtained.

Further, in a high-performance element such as a TFT type element, an element having an element such as a transistor formed between an electrode for driving a liquid crystal and a substrate is used.

In the case of a transmissive liquid crystal display element, it is common to use a substrate as described above, but in a reflective liquid crystal display element, an opaque substrate such as a silicon wafer may be used if only one side of the substrate is used. It is possible. At that time, a material such as aluminum that reflects light can be used for the electrodes formed on the substrate.

The liquid crystal alignment film is formed by applying the liquid crystal alignment agent of the present invention on this substrate and then firing it, and the details are as described above.

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display element of the present invention is not particularly limited, and the liquid crystal material used in the conventional vertical alignment method, for example, a negative type liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck Co., Ltd. Can be used.

As a method of sandwiching the liquid crystal layer between two substrates, a known method can be mentioned. For example, a pair of substrates on which a liquid crystal alignment film is formed is prepared, and spacers such as beads are sprayed on the liquid crystal alignment film of one substrate so that the surface on the side on which the liquid crystal alignment film is formed is on the inside. Another method is to bond the other substrate and inject the liquid crystal under reduced pressure to seal it. Further, a pair of substrates on which the liquid crystal alignment film is formed is prepared, spacers such as beads are sprayed on the liquid crystal alignment film of one substrate, liquid crystal is dropped, and then the surface on the side where the liquid crystal alignment film is formed is formed. A liquid crystal cell can also be produced by a method in which the other substrate is bonded and sealed so that the surface is on the inside. The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

In the process of producing a liquid crystal cell by irradiating the liquid crystal alignment film and the liquid crystal layer with ultraviolet rays while applying a voltage, for example, an electric field is applied to the liquid crystal alignment film and the liquid crystal layer by applying a voltage between electrodes installed on the substrate. Is applied, and an ultraviolet ray is irradiated while maintaining this electric field. Here, the voltage applied between the electrodes is, for example, 5 to 30 Vp-p, preferably 5 to 20 Vp-p. The dose of ultraviolet rays, for example 1~60J / cm ^2, preferably at 40 J / cm ² or less, more preferably 20 J / cm ² or less. It is preferable that the amount of ultraviolet irradiation is small because the decrease in reliability caused by the destruction of the liquid crystal and the members constituting the liquid crystal display element can be suppressed and the production efficiency is improved by reducing the ultraviolet irradiation time.

In this way, when ultraviolet rays are applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the polymerizable compound reacts to form a polymer, and the direction in which the liquid crystal molecules are tilted is memorized by the polymer. The response speed of the obtained liquid crystal display element can be increased. Further, when ultraviolet rays are applied to the liquid crystal alignment film and the liquid crystal layer while applying a voltage, the photoreactive side chains of the polymer and the photoreactive side chains of the polymer react with each other. , The response speed of the obtained liquid crystal display element can be increased.

Further, the liquid crystal alignment agent is not only useful as a liquid crystal alignment agent for manufacturing a vertically oriented liquid crystal display element such as a PSA type liquid crystal display or an SC-PVA type liquid crystal display, but also by a rubbing treatment or a photoalignment treatment. It can also be suitably used in the application of the produced liquid crystal alignment film.
Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples.

The abbreviations used in the preparation of the following liquid crystal alignment agents are as follows.
(Acid dianhydride)
BODA: Bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride.
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride.
PMDA: pyromellitic dianhydride TCA: 2,3,5-tricarboxycyclopentylacetic acid-1,4,2,3-dianhydride (diamine)

The vertically oriented diamine represented by the following formula DA-1 was synthesized by the method described in Japanese Patent No. 4085206.
The vertically oriented diamine represented by the following formula DA-2 was synthesized by the method described in Japanese Patent No. 4466373.
The vertically oriented diamine represented by the following formula DA-3 was synthesized by the method described in Japanese Patent No. 5273035.
The vertically oriented diamine represented by the following formula DA-4 was purchased from Tokyo Chemical Industry Co., Ltd.
The vertically oriented diamine represented by the following formula DA-5 was synthesized by the method described in WO2009 / 093704.
The photoreactive diamine represented by the following formula DA-6 was prepared as follows.
The diamine represented by the following formula DA-7 was purchased from Wako Pure Chemical Industries, Ltd.
The radical-generating diamine represented by the following formula DA-8 was prepared as follows.
The diamine represented by the following formula DA-9 was prepared by the method described in "(Raw Material Synthesis Example 3) Synthesis of DA-9" described later.

<Solvent>
NMP: N-methyl-2-pyrrolidone BCS: Butyl cellosolve THF: tetrahydrofuran DMF: N, N-dimethylformamide <Additive>
3AMP: 3-Picolylamine Hereinafter, the present invention will be described in detail with reference to Examples, but the present invention is not limited to these Examples.
<Polymerizable compound>
Polymerizable compounds represented by the following formulas RM1 to RM12 and RM13.

The molecular weight measurement conditions for polyimide are as follows.
Equipment: Room temperature gel permeation chromatography (GPC) equipment (SSC-7200) manufactured by Senshu Kagaku Co., Ltd.,
Column: Shodex column (KD-803, KD-805),
Column temperature: 50 ° C,
Eluent: N, N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr · H ₂ O) is 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphate) is 30 mmol / L, Tetrahydrofuran (THF) is 10 ml / L),
Flow velocity: 1.0 ml / min,
Standard samples for preparing calibration curves: Tosoh's TSK standard polyethylene oxide (molecular weight of about 9,000,000, 150,000, 100,000, 30,000) and Polymer Laboratory's polyethylene glycol (molecular weight of about 12,000, 4). 000, 1,000).

The imidization rate of polyimide was measured as follows. 20 mg of polyimide powder is placed in an NMR sample tube (NMR sampling tube standard φ5 manufactured by Kusano Kagaku Co., Ltd.), 1.0 ml of deuterated dimethyl sulfoxide (DMSO-d ₆ , 0.05% TMS mixture) is added, and ultrasonic waves are applied. It was completely dissolved over. This solution was subjected to 500 MHz proton NMR measurement with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidization rate is determined by using a proton derived from a structure that does not change before and after imidization as a reference proton, and the peak integrated value of this proton and the proton peak derived from the NH group of the amic acid appearing near 9.5 to 10.0 ppm. It was calculated by the following formula using the integrated value. In the following formula, x is the integrated proton peak value derived from the NH group of the amic acid, y is the integrated peak value of the reference proton, and α is the proton of the NH group of the amic acid in the case of polyamic acid (imidization rate is 0%). It is the number ratio of the reference protons to one.
Imidization rate (%) = (1-α · x / y) × 100

<Synthesis of diamines and polymerizable compounds>
The products described in Synthesis Examples 1 to 12 below were identified by ^{1 1} H-NMR analysis (analytical conditions are as follows).
Equipment: Varian NMR System 400 NB (400 MHz)
Measuring solvent: CDCl _3, DMSO-d ₆
Reference substance: Tetramethylsilane (TMS) (δ0.0 ppm for ¹ H)

(Raw Material Synthesis Example 1-1) Synthesis of DA-6 precursor DA-6-1

In a 500 mL four-necked flask, 21.2 g of 2-methylacrylic acid 6- [4- (2-hydroxycarbonylvinyl) phenyl] -hexyl ester, 300 mL of tetrahydrofuran, and 2- (2,4-dinitrophenyl) ethanol were placed. 13.6 g, 18.4 g of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (EDC) and 0.8 g of 4-dimethylaminopyridine (DMAP) were added, and the mixture was stirred at room temperature. After completion of the reaction, the organic layer is extracted with ethyl acetate, anhydrous magnesium sulfate is added to the organic layer, dehydrated and dried, and filtered. Then, the solvent is distilled off using a rotary evaporator, and the residue is washed with isopropyl alcohol and dried. As a result, 15.9 g of the target product DA-6-1 (yellowish white solid) was obtained (yield 47%).
(Raw Material Synthesis Example 1-2) Synthesis of DA-6

To a 500 mL four-necked flask, 7.6 g of DA-6-1, 150 mL of ethyl acetate, 150 ml of pure water, 8.4 g of reduced iron, and 6.5 g of ammonium chloride were added, and the mixture was stirred while heating at 60 ° C. After completion of the reaction, the reduced iron was filtered and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, dehydrated and dried, and anhydrous magnesium sulfate was filtered. The solvent was distilled off from the obtained filtrate using a rotary evaporator. The residue was washed with isopropanol and dried to obtain 13.4 g of the desired product DA-6 (yellowish white solid) (yield 95%). The results of measuring the obtained solid by ¹ H-NMR are shown below. From this result, it was confirmed that the obtained solid was the target DA-6.
^{1 1} H NMR (400 MHz, [D ₆ ] -DMSO): δ7.64-7.66 (d, 2H), 7.58-7.62 (d, 1H), 6.95-6.97 (d, 2H), 6.60-6.62 (d, 1H), 6.44-6.48 (d, 1H), 6.02 (s, 1H), 5.89 (s, 1H), 5.78-5.81 (d, 1H), 5.66 (s, 1H), 4.65 (s, 2H), 4.59 (s, 2H), 4.08-4.17 (m, 4H), 4.00-4.03 (t, 2H), 2.65-2.69 (t, 2H), 1.87 (s, 3H), 1.62-1.74 (m, 4H), 1.39 -1.45 (m, 4H)
(Raw Material Synthesis Example 2) Synthesis of DA-8

Step1 1-Synthesis of 4- (4- (2,4-dinitrophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanol In a 2L four-necked flask equipped with a stir bar and a nitrogen introduction tube, 2,4-dinitro 100.0 g of fluorobenzene ([Mw: 186.10 g / mol], 0.538 mol), 120.6 g of 2-hydroxy-4'-(2-hydroxyethoxy) -2-methylpropiophenone ([Mw:: 224.25 g / mol], 0.538 mol), 81.7 g of triethylamine ([Mw: 101.19 g / mol], 0.807 mol), and 1000 g of THF were added, and the mixture was refluxed for 24 hours. After completion of the reaction, the mixture was concentrated on a rotary evaporator, ethyl acetate was added, and the mixture was washed several times with pure water and physiological saline, and then dried over anhydrous magnesium sulfate.
Anhydrous magnesium sulfate was removed by filtration, concentrated on a rotary evaporator, and then recrystallized from ethyl acetate and normal hexane to produce 157.0 g of a milky white solid ([Mw: 390.34 g / mol], 0.402 mol, yield). : 75%) was obtained. It was confirmed by the nuclear magnetic resonance spectrum ( ¹ H-NMR spectrum) of the hydrogen atom in the molecule. The measurement data is shown below.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 8.75 (Ar: 1H), 8.48 to 8.45 (Ar: 1H), 8.09 to 8.05 (Ar: 2H), 7.34 ~ 7.31 (Ar: 1H) 7.00 to 6.96 (Ar: 2H), 4.55-4.63 (-CH _2- : 2H), 4.52-4.49 (-CH _2- : 2H), 4.16 (-OH: 1H), 1.66 to 1.60 (-CH ₃ x 2, 6H) Total: 18H

Synthesis of Step2 1- (4- (2,4-diaminophenoxy) ethoxy) phenyl) -2-hydroxy-2-methylpropanol (DA-8) 100. The dinitrobenzene derivative obtained in Step1 was placed in a 1L four-necked flask. Weigh 10.0 g of 0 g ([Mw: 390.34 g / mol], 0.256 mol) and iron-doped platinum carbon (3 wt% manufactured by Evonic), add 500 ml of THF, and perform degassing under reduced pressure and hydrogen substitution. It was thoroughly carried out and reacted at room temperature for 24 hours.
After completion of the reaction, platinum carbon was removed with a PTFE membrane filter, and the filtrate was removed with a rotary evaporator to precipitate a solid. The obtained solid was washed with isopropyl alcohol by heating and further dried under reduced pressure to obtain 72.7 g ([Mw: 330.38 g / mol], 0.220 mol yield) of the target compound, a light pink solid. : 86%) was obtained. ^{1 1} H-NMR spectrum measurement data is shown below.
^{1 1} H NMR (400 MHz, CDCl ₃ ) δ: 8.09 to 8.05 (Ar: 2H), 7.01 to 6.97 (Ar: 2H), 6.70 to 6.68 (Ar: 1H) , 6.12 (Ar: 1H), 4.36-4.33 (-CH _2- : 2H), 4.29-4.27 (-OH & -CH _2- : 3H), 3.7 (-NH) ₂ : 2H), 3.39 (-NH ₂ : 2H), 1.64 to 1.63 (-CH ₃ x 2: 6H) Total: 22H.
(Raw Material Synthesis Example 3) Synthesis of DA-9

<Synthesis of DA-9-1>
In a 1000 mL four-necked flask, 120 g (310 mmol, 1.0 eq) of cholesterol and 33.3 g (329 mmol, 1.1 eq) of triethylamine were charged in 600 g of THF, and 69.2 g (300 mmol) of 3,5-dinitrobenzoyl chloride was added over 1 hour. Was added. After the addition, the mixture was stirred overnight at room temperature and then reprecipitated with water. The obtained solid was recrystallized from IPA and ethyl acetate, respectively, to obtain 179 g of a crude product of DA-9-1 (crude yield: 100%).
^{1 1} H-NMR (CDCl ₃ , δppm): 9.22 (s, 1H), 9.16 (s, 2H), 5.46-5.44 (m, 1H), 5.00-4.95 ( m, 1H), 2.56-2.48 (m, 2H), 2.06-1.95 (m, 4H), 1.87-1.81 (m, 2H), 1.63-0. 86 (m, 32H), 0.70 (s, 3H).

<Synthesis of DA-9>
In a 2000 mL four-necked flask, 146 g (251 mmol) of DA-9-1 and 284 g (1497 mmol, 6.0 eq) of tin chloride were charged in 750 g of THF and 750 g of pure water, and the mixture was stirred at 70 ° C. overnight. After completion of the reaction, neutralization was performed and the precipitated tin was removed by filtration. Then, it was recrystallized by liquid separation and IPA to obtain 76.3 g of DA-9 (yield: 58%).
^{1 1} H-NMR (CDCl ₃ , δppm): 6.78 (s, 2H), 6.18 (s, 1H), 5.42-5.40 (m, 1H), 4.84-4.77 ( m, 1H), 3.67 (s, 4H), 2.43 (d, 2H), 1.63-0.86 (m, 38H), 0.69 (s, 3H).
<Synthesis Example 1-Synthesis of RM1->

<Synthesis of RM1-A>
4-Bromo-2-fluorophenol 58.3 g (305 mmol) and 4- (4,4,5,5-tetramethyl-1,3) in 350 g of THF and 117 g of water in a 1 L four-necked flask equipped with a magnetic stirrer. , 2-Dioxaborolan-2-yl) phenol 67.2 g (1.0 eq), potassium carbonate 84.8 g (2.0 eq), tri (o-tolyl) phosphine 7.42 g (8 mol%), after nitrogen replacement 10.9 g (5 mol%) of bis (triphenylphosphine) palladium (II) chloride was added, and the mixture was reacted at 65 ° C. for 15 hours.
After completion of the reaction, THF was distilled off by concentration under reduced pressure, diluted with 466 g of ethyl acetate, 268 g of a 3.0 MHCl aqueous solution was added, insoluble substances such as Pd were removed by filtration, and 233 g of ethyl acetate was used to wash the flask and filter. Was done. Subsequently, the aqueous phase was separated and the organic phase was recovered, the recovered organic phase was washed three times with 350 g of pure water, dehydrated with magnesium sulfate, and then activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical). 92 g was added, the mixture was stirred at room temperature for about 30 minutes, and filtered and dried to obtain a crude product. The crude product was washed with 292 g of toluene twice under room temperature conditions and then filtered and dried to obtain 42.0 g of RM1-A (yield: 67%, properties: light pink crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 6.80 ppm (dd, J = 2.0 Hz, J = 6.8 Hz, 2H), 6.97 ppm (t, J = 8.8 Hz, 1H), 7.21 ppm (dd, J = 2.0 Hz, J = 8.4 Hz, 1H), 7.35 ppm (dd, J = 2,4 Hz, J = 13.2 Hz, 1H), 7.42 ppm (dd, J = 2.0 Hz, J = 6.4 Hz, 2H), 9.49 ppm (s, 1H), 9.82 ppm (s, 1H).

<Synthesis of RM1-B>
5.00 g (24.5 mmol) of the compound (RM1-A) obtained above and 2- (4-bromobutyl) -1,3-dioxolane 12 in 80 ml of acetone in a 200 ml four-necked flask equipped with a magnetic stirrer. 0.0 g (2.2 eq) and 13.8 g (4.0 eq) of potassium carbonate were charged and reacted at 60 ° C. for 24 hours. Then, the reaction solution was put into pure water to precipitate crystals, and the reaction solution was filtered and dried to obtain 10.4 g of RM1-B (yield: 92%).
¹ H-NMR (400MHz) in CDCl ₃ : 1.60-1.67 ppm (m, 4H), 1.71-1.78 ppm (m, 4H), 1.82-1.93 ppm (m, 4H), 3.82-4.10 ppm (m, 12H) , 4.89 ppm (t, J = 4.6 Hz, 2H), 6.92-7.00 ppm (m, 3H), 7.20-7.30 ppm (m, 2H), 7.43 ppm (d, J = 8.8Hz, 2H).

<Synthesis of RM1>
2.90 g (6.30 mmol) of the compound (RM1-B) obtained above and 2.5 g (2.4eq) of 2- (bromomethyl) acrylic acid in 40 ml of THF in a 100 ml four-necked flask equipped with a magnetic stirrer. , 2.8 g (2.4 eq) of tin chloride (anhydride) was charged, 12 ml of a 10% HCl aqueous solution was added, and the mixture was reacted at 70 ° C. for 20 hours. Then, the reaction solution was put into pure water to precipitate crystals, and the mixture was filtered and dried to obtain a crude product. The obtained crude product was recrystallized in THF / EtOH to obtain 2.2 g of RM1 (yield: 69%).
¹ H-NMR (400MHz) in CDCl ₃ : 1.55-1.93 ppm (m, 12H), 2.61 ppm (dd, J = 7.6 Hz, J = 18.4 Hz, 2H), 3.09 ppm (dd, J = 6.8 Hz, J = 16.6 Hz, 2H), 4.00 ppm (t, J = 6.2 Hz, 2H), 4.08 ppm (t, J = 6.4 Hz, 2H), 4.35-4.60 ppm (m, 2H), 5.64 ppm (s, 2H) , 6.24 ppm (s, 2H), 6.93-7.01 ppm (m, 3H), 7.22-7.289 ppm (m, 2H), 7.45 ppm (d, J = 8.8Hz, 2H).
<Synthesis Example 2-Synthesis of RM2->

<Synthesis of RM2-A>
In a 1 L four-necked flask equipped with a magnetic stirrer, 70.2 g (539 mmol) of 2-hydroxyethyl methacrylate and 76.4 g (1.4 eq) of triethylamine were charged in 281 g of THF, and diluted with 35.1 g of THF under ice-cooling stirring. 74.6 g (1.2 eq) of methanesulfonyl chloride was added dropwise, and the mixture was stirred at room temperature for 2 hours. Then, the salt precipitated from the reaction solution was filtered, 0.35 g of dibutylhydroxytoluene was added to the filtrate, and the mixture was concentrated and dried. Next, when 281 g of ethyl acetate was added to the concentrate residue and 210 g of pure water was added, insoluble matter was generated. Therefore, 3.5 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added and at room temperature. The mixture was stirred for 30 minutes. Subsequently, this was filtered to confirm that the insoluble matter had been removed, and then the aqueous phase was removed. Further, the organic phase was washed twice with 210 g of pure water, dehydrated with magnesium sulfate, and then concentrated and dried to obtain 99.0 g of RM2-A (yield: 86%, properties: yellow liquid).
¹ H-NMR (400MHz) in CDCl ₃ : 1.93-1.94 ppm (m, 3H), 3.03 ppm (s, 3H), 4.39-4.41 ppm (m, 2H), 4.46-4.44 ppm (m, 2H), 5.61 -5.62 ppm (m, 1H), 6.15 (m, 1H).

<Synthesis of RM2-B>
10.4 g (54.4 mmol) of 4-bromo-2-fluorophenol and 6-hydroxy-2-naphthaleneboronic acid 9 in 72.8 g of THF and 31.2 g of pure water in a 300 ml four-necked flask equipped with a magnetic stirrer. .68 g (1.0 eq), potassium carbonate 15.1 g (2.0 eq), tri (o-tolyl) phosphine 1.32 g (8 mol%) were charged, and after nitrogen substitution, bis (triphenylphosphine) palladium (II) chloride 1.91 g (5 mol%) was added and reacted at 65 ° C. for 2 hours. Then, THF was removed by concentration under reduced pressure, diluted with 104 g of ethyl acetate, 47.8 g of a 3.0 M HCl aqueous solution was added, and the mixture was stirred. Subsequently, Pd was removed by filtration, and 52.0 g of ethyl acetate was washed with a filter or the like, and then the aqueous phase was separated. The recovered organic phase was washed 3 times with 72.8 g of pure water, dehydrated with magnesium sulfate, then 0.52 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for about 1 hour. It was filtered and dried. The crude product was washed with 72.8 g of toluene and then purified by silica gel column chromatography (ethyl acetate / toluene / hexane (= 1/1 / 2 vol)) to obtain 6.47 g of RM2-B (yield: 49). %, Properties: White solid).
¹ H-NMR (400MHz) in DMSO-d ₆ : 7.03-7.13 ppm (m, 3H), 7.42-7.40 ppm (m, 1H), 7.57 ppm (dd, J = 13 Hz, J = 2.2 Hz, 1H) , 7.67 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.72 ppm (d, J = 8.4 Hz, 1H), 7.80 ppm (d, J = 8.4 Hz, 1H), 8.01 ppm (s, 1H), 9.78 ppm (s, 1H), 9.96 ppm (s, 1H)

<Synthesis of RM2>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 6.07 g (23.9 mmol) of the compound (RM2-B) obtained above and 11.1 g of a polymerizable side chain (RM2-A) in 48.6 g of DMF (RM2-B). 2.2 eq) and 9.93 g (3.0 eq) of potassium carbonate were charged and reacted at 65 ° C. for 22 hours under a nitrogen atmosphere.
Then, the reaction solution was diluted with 48.6 g of ethyl acetate, the inorganic salt was removed by filtration, and the filtrate was washed with 42.5 g of ethyl acetate. The recovered organic phase was washed 3 times with 48.6 g of pure water, the organic phase was dehydrated with magnesium sulfate, and then concentrated and dried. After drying, 12.1 mg of 2,6-di-tert-butyl-p-cresol was added to the recovered crude product, 5.77 g of THF was added, and the mixture was heated at 45 ° C. to completely dissolve it, and 35.8 g of methanol was dissolved. Was added and recrystallization was performed at 5.0 ° C. However, since impurities were confirmed, 4.89 g of THF was added to the recovered solid and heated at 45 ° C. to completely dissolve the solid, and 24.9 g of methanol was added and recrystallized at room temperature to obtain 6.37 g of RM2. (Yield: 56%, Properties: White crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 1.89 ppm (s, 6H), 4.38-4.42 ppm (m, 4H), 4.46-2.47 ppm (m, 2H), 4.49-4.51 ppm (m, 2H) , 5.70-5.71 ppm (m, 2H), 6.05 ppm (d, J = 6.8 Hz, 2H), 7.22 ppm (dd, J = 9.0 Hz, J = 2.8 Hz, 1H), 7.33 ppm (t, J = 9.0) Hz, 1H), 7.40 ppm (d, J = 2.4 Hz, 1H), 7.59 ppm (d, J = 9.6 Hz, 1H), 7.70 ppm (dd, J = 12.8 Hz, J = 2.0 Hz, 1H), 7.80 ppm (dd, J = 8.6 Hz, J = 1.8 Hz, 1H), 7.88 ppm (t, J = 9.2 Hz, 2H), 8.15 ppm (s, 1H).

<Synthesis Example 3-Synthesis of RM3->

<Synthesis of RM3-A>
In a 2L four-necked flask equipped with a mechanical stirrer, 25.5 g (101 mmol) of 1,4-dibromo-2-fluorobenzene, 4- (4,4,5,5-tetramethyl) in 179 g of THF and 76.6 g of pure water -1,3,2-dioxaborolan-2-yl) phenol 45.5 g (2.0 eq), potassium carbonate 41.7 g (3.0 eq), bis (triphenylphosphine) palladium (II) chloride 2.12 g The mixture was stirred at 65 ° C. for 24 hours under a nitrogen atmosphere. Then, THF was distilled off by concentration under reduced pressure, the reaction solution was diluted with 255 g of ethyl acetate, 99.5 g of a 3.0 M HCl aqueous solution was added, and insoluble matter such as Pd was removed by filtration. After removing the aqueous phase from the filtrate, the obtained organic phase was washed 3 times with 179 g of pure water. The recovered organic phase is dehydrated with magnesium sulfate, 1.30 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) is added, and the mixture is stirred under room temperature conditions for about 30 minutes, and then filtered and dried to remove the crude product. Obtained. The recovered crude product was suspended in 153 g of toluene, washed twice with repulp at 60 ° C. for 1 hour, and filtered and dried to obtain 22.4 g of RM3-A (yield: 79%, properties: light pink). crystal).
¹ H-NMR (400MHz) in DMSO-d6: 6.85-6.88 ppm (m, 4H), 7.41 ppm (dd, J = 1.2 Hz J = 8.4 Hz, 2H), 7.46-7.49 ppm (m, 3H), 7.57 ppm (d, J = 8.8 Hz, 2H), 9.65 ppm (s, 2H).

<Synthesis of RM3>
In a 500 mL four-necked flask equipped with a mechanical stirrer, 23.0 g (2.2 eq) of the polymerizable side chain (RM2-A) and 14.1 g (50.2 mmol) of the compound (RM3-A) obtained above in 113 g of DMF. ), Potassium carbonate (20.9 g (3.0 eq)) was charged, and the mixture was stirred at 65 ° C. for 18 hours under a nitrogen atmosphere. After 18 hours, since the raw material remained, a polymerizable side chain (RM2-A) (0.2eq / 2) was added and the reaction was carried out for another 4 hours. Then, the reaction solution was diluted with 113 g of ethyl acetate, the inorganic salt was removed by filtration, and the filtrate was washed with 70.5 g of ethyl acetate. As a result of washing the recovered organic phase with 141 g of pure water, a small amount of white crystals were generated. Therefore, 70.5 g of ethyl acetate was added, and the organic phase was further washed twice with 141 g of pure water, and the organic phase was dehydrated with magnesium sulfate. , Filtered and dried. Add 0.71 g of activated carbon (brand: special Shirasagi dry product, manufactured by Nippon Enviro Chemical) to the recovered crude product, stir for about 30 minutes under room temperature conditions, filter dry, add 222 g of ethyl acetate, and heat at 50 ° C. The mixture was completely dissolved, 98.2 g of hexane was added, and the mixture was recrystallized at 2 ° C. to obtain 15.0 g of RM3 (yield: 59%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d6: 1.89 ppm (s, 6H), 4.30-4.33 ppm (m, 4H), 4.45-4.46 ppm (m, 4H), 5.71 ppm (s, 2H), 6.05 ppm (s, 2H), 7.07-7.10 ppm (m, 4H), 7.52-7.56 ppm (m, 5H), 7.70 ppm (d, J = 8.4 Hz, 2H).

<Synthesis Example 4-Synthesis of RM4->

<Synthesis of RM4>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 9.18 g (45.0 mmol) of F-containing biphenol compound (RM1-A), 18.6 g (3.0 eq) of potassium carbonate, and a polymerizable side chain in 73.4 g of DMF. 20.7 g (2.2 eq) of (RM2-A) was charged and reacted at 62 ° C. for 15 hours under a nitrogen atmosphere. Then, the reaction solution was diluted with 138 g of ethyl acetate, and the inorganic salt was removed by filtration. Further, 45.9 g of ethyl acetate was added to the collected filtrate, washed 3 times with 91.8 g of pure water, and dehydrated with sodium sulfate. Subsequently, 0.46 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added and stirred at room temperature for about 30 minutes, which was filtered, and the filtrate was concentrated and dried. 9.2 mg of 2,6-di-tert-butyl-p-cresol was added to the concentrate, 184 g of IPA was added, and the mixture was completely dissolved by heating to 57 ° C., and recrystallized under room temperature conditions. RM4 13. 4 g was obtained (yield: 70%, properties: pale yellow crystals).
¹ H-NMR (400MHz) in DMSO-d6: 1.87-1.88 ppm (m, 6H), 4.27-4.29 ppm (m, 2H), 4.34-4.37 ppm (m, 2H), 4.43-4.46 ppm (m, 4H) ), 5.69-5.70 ppm (m, 2H), 6.03 ppm (d, J = 4.8 Hz, 2H), 7.03 ppm (d, J = 8.8 Hz, 2H), 7.25 ppm (t, J = 8.8 Hz, 1H) , 7.39 ppm (dd, J = 1.6 Hz, J = 8.4 Hz, 1H), 7.50 ppm (dd, J = 2.0 Hz, J = 13 Hz, 1H), 7.58 ppm (d, J = 8.8 Hz, 2H).

<Synthesis Example 5-Synthesis of RM5->
It was synthesized according to the description in paragraph [0179] of WO2012 / 002513.
<Synthesis Example 6-Synthesis of RM6->
It was synthesized according to the description in paragraph [0163] of WO2012 / 133820.

<Synthesis Example 7-Synthesis of RM7->

<Synthesis of RM7-A->
In a 200 mL four-necked flask equipped with a magnetic stirrer, 9.00 g (44.1 mmol) of F-containing biphenol compound (RM1-A), 22.4 g (3.0 eq) of bromoacetaldehyde dimethyl acetal, and 24. Potassium carbonate in 18 g of NMP. 4 g (4.0 eq) and 2.2 g (0.30 eq) of potassium iodide were charged and stirred at 120 ° C. for 18 hours. After 18 hours, 7.45 g (1.0 eq) of bromoacetaldehyde dimethyl acetal and 1.4 g (0.2 eq) of potassium iodide were added, and the mixture was further stirred for 8 hours. After completion of the reaction, the reaction solution was diluted with 99.0 g of THF, the inorganic salt was filtered, and the filtrate was concentrated under reduced pressure. Next, this residue was diluted with 198 g of ethyl acetate, washed twice with 99.0 g of pure water, and then dehydrated with magnesium sulfate. Then, 0.45 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added, and the mixture was stirred at room temperature for 1 hour, filtered, and the filtrate was concentrated under reduced pressure. Subsequently, 19.8 g of THF was added to the obtained crude product and dissolved at 50 ° C., 60.3 g of IPA was added, and the mixture was stirred under ice-cooling. The crystals precipitated thereby were filtered and dried to obtain 11.5 g of RM7-A (yield: 62%, properties: light brown crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 3.36 ppm (m, 12H), 4.01 ppm (d, J = 5.2 Hz, 2H), 4.08 ppm (d, J = 5.2 Hz, 2H), 4.74-4.69 ppm (m, 2H), 7.03 ppm (d, J = 11.6 Hz 2H), 7.25 ppm (t, J = 8.8 Hz 1H), 7.40-7.37 ppm (m, 1H), 7.51 ppm (dd, J = 13Hz, J = 2.2 Hz 1H), 7.58 ppm (d, J = 8.4 Hz 2H)

<Synthesis of RM7>
10.4 g (27.2 mmol) of the compound (RM7-A) obtained above and 11.6 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate in 103 g of THF in a 500 mL four-necked flask equipped with a magnetic stirrer. ), 12.4 g (2.4 eq) of tin chloride, and 36.2 g of a 10 wt% HCl aqueous solution were charged, and the mixture was stirred at 70 ° C. for 39 hours. After completion of the reaction, 30 mg of 2,6-di-tert-butyl-p-cresol was added, THF was distilled off under reduced pressure, and the mixture was diluted with 104 g of ethyl acetate. After removing the separated aqueous phase, the organic phase was washed 3 times with 62.4 g of pure water at 40 ° C. Next, after dehydrating the organic phase with magnesium sulfate, 0.52 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) is added, stirred at room temperature for 1 hour, filtered, and the filtrate is concentrated under reduced pressure. I left. Subsequently, 52 g of THF was added to the obtained crude product and dissolved at 60 ° C., 156 g of EtOH was added, and the mixture was stirred under ice-cooling. As a result, the precipitated crystals were filtered and dried to obtain 3.42 g of RM7 (yield: 30%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 2.88-2.50 ppm (m, 2H), 3.17-2.11 ppm (m, 2H), 4.14 ppm (dd, J = 5.6 Hz, 11.2 Hz, 1H), 4.28 -4.20ppm (m, 2H), 4.33ppm (dd, J = 2.8 Hz, 11.0 Hz, 1H), 5.00-4.95ppm (m, 2H), 6.99ppm (d, J = 6.8 Hz, 2H), 7.22ppm (t, J = 8.8Hz, 1H), 7.41ppm (d, J = 8.4Hz, 1H), 7.52 ppm (dd, J = 2Hz, 12.8Hz, 1H), 7.61ppm (d, J = 2.0Hz, 2H) )

<Synthesis Example 8-RM8 Synthesis->

<Synthesis of RM8-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of F-containing biphenol compound (RM1-A), 20.4 g (3.0 eq) of potassium carbonate, and 1 potassium iodide in 15.3 g of NMP. .61 g (0.20 eq) was charged, and 16.6 g (2.2 eq) of 4-chlorobutylaldehyde dimethyl acetal diluted with NMP 5.30 g at 80 ° C. under a nitrogen atmosphere was added dropwise over 3 hours. After 19 hours of dropping, 2.25 g (0.3 eq) of 4-chlorobutylaldehyde dimethyl acetal and 1.61 g (0.2 eq) of potassium iodide were added, and the mixture was further reacted for 25 hours. After completion of the reaction, the reaction solution was diluted with 80.0 g of ethyl acetate, and potassium carbonate was removed by filtration. Further, 20.0 g of ethyl acetate was added, and the mixture was washed 3 times with 60.0 g of pure water and then dehydrated with magnesium sulfate. Then, the solvent was removed by concentration under reduced pressure to obtain a crude product. 10 g of THF and 70 g of MeOH were added to the obtained crude product, and the mixture was heated at 50 ° C., ice-cooled to precipitate crystals, and filtered and dried to obtain 11.7 g of RM8-A (yield: 55%, properties). : White solid). Further, the filtrate was concentrated under reduced pressure to remove the solvent, and the crude product was heated at 40 ° C. by adding 5 g of THF and 70 g of IPA, and ice-cooled to precipitate crystals, and 3.0 g of RM8-A was obtained (yield). 14%, properties: pale yellow solid).
¹ H-NMR (400MHz) in DMSO-d ₆ : 1.77-1.67 ppm (m, 8H), 3.23 ppm (s, 12H), 4.01 ppm (t, J = 6 Hz, 2H), 4.08 ppm (t, J) = 6 Hz, 2H), 4.44-4.41 ppm (m, 2H), 6.97 ppm (d, J = 6.8 Hz, 2H), 7.19 ppm (t, J = 8.8 Hz, 1H), 7.38 ppm (d, J = 7.6 Hz, 1H), 7.48 ppm (dd, J = 13.2 Hz, 2.4 Hz, 1H), 7.56 ppm (d, J = 8.8 Hz, 2H)

<Synthesis of RM8>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 13.2 g (30.3 mmol) of the compound (RM8-A) obtained above and 12.9 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate in 133 g of THF. ), 13.8 g (2.4 eq) of tin chloride, and 46.3 g of a 10 wt% HCl aqueous solution were charged and reacted at 50 ° C. for 5 hours. After 5 hours, 13.2 g of a 20 wt% HCl aqueous solution was added, and the mixture was reacted for 19 hours. After completion of the reaction, THF was distilled off under reduced pressure, diluted with 106 g of ethyl acetate, and then washed with water 3 times with 52.8 g of pure water. Subsequently, 26.4 g of ethyl acetate and 79.2 g of pure water were further added, and sodium hydrogen carbonate was added for neutralization. After neutralization, the salt was removed by filtration, 0.70 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added to the filtrate, and the mixture was stirred at room temperature and filtered. The obtained solution was washed twice with 66 g of pure water, the solvent was removed by concentration under reduced pressure, 79.2 g of THF and 158 g of IPA were added, heated at 50 ° C., and ice-cooled to precipitate crystals, which were then filtered. The crystals were recovered. The obtained crystals were heated at 50 ° C. by adding 46.2 g of THF and 92.4 g of MeOH, the crystals were precipitated by ice-cooling, and 8.92 g of RM8 was obtained by filtration drying (yield: 61%). , Properties: white crystals).
¹ H-NMR (400MHz) in CDCl3: 2.02-1.87 ppm (m, 8H), 2.67-2.60 ppm (m, 2H), 3.15-3.08 ppm (m, 2H), 4.13-4.02 ppm (m, 4H), 4.65-4.60 ppm (m, 2H), 5.66 ppm (s, 2H), 6.25 ppm (d, J = 2.4 Hz, 2H), 6.94 ppm (d, J = 8.8 Hz, 2H), 6.99 ppm (t, J) = 8.6 Hz, 1H) 7.28-7.22 ppm (m, 2H), 7.44 ppm (d, J = 8.8 Hz, 2H)

<Synthesis Example 9-Synthesis of RM9->

<Synthesis of RM9-A>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 20.0 g (107 mmol) of 4,4'-biphenol, 44.6 g (3.0 eq) of potassium carbonate, and 1.82 g (0.82 g) of potassium iodide in 50.0 g of DMF. 1eq) was charged and heated to 100 ° C., 39.8 g (2.2 eq) of 2-bromomethyl-1,3-dioxolane diluted with 10.0 g of DMF was added dropwise, and the mixture was stirred at the same temperature for 6 hours. After 6 hours, 5.38 g (0.3 eq) of 2-bromomethyl-1,3-dioxolane was further added, and the mixture was stirred for 18 hours. After completion of the reaction, the reaction solution was added to 400 g of pure water to precipitate crystals, filtered, and the filtrate was slurry-washed with 60.0 g of MeOH and filtered again to obtain a white solid. The obtained white solid was suspended in 500 g of THF, 1.00 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical Co., Ltd.) was added, and the mixture was stirred at 60 ° C. for 30 minutes and then filtered by heat (45 ° C.). As a result of cooling the filtrate, white crystals were precipitated. Therefore, 13.0 g of RM9-A was obtained by filtration and drying (yield: 34%, properties: white solid).
¹ H-NMR (400MHz) in DMSO-d6: 3.85-3.93 ppm (m, 4H), 3.95-3.99 ppm (m, 4H), 4.03 ppm (d, J = 4.0 Hz, 4H), 5.21 ppm (t, J = 4.0 Hz, 2H), 7.01 ppm (d, J = 8.8 Hz, 4H), 7.53 ppm (d, J = 8.4 Hz, 4H)

<Synthesis of RM9>
In a 300 mL four-necked flask equipped with a magnetic stirrer, 9.95 g (27.8 mmol) of the compound (RM9-A) obtained above and 11.8 g (2) of ethyl 2- (bromomethyl) acrylate in 99.5 g of THF. .2 eq), 12.6 g (2.4 eq) of tin chloride, and 34.8 g of a 10 wt% hydrochloric acid aqueous solution were charged, and the mixture was stirred at 60 ° C. for 1.5 hours. After 1.5 hours, 9.95 g of a 20 wt% hydrochloric acid aqueous solution was added, and the mixture was further stirred for 21 hours to complete the reaction. Then, THF was distilled off under reduced pressure, 199 g of ethyl acetate was added, and the aqueous phase was removed. Next, the organic layer was washed twice with 59.7 g of pure water. The organic phase was recovered, ethyl acetate was distilled off under reduced pressure, 149 g of THF was added, and the mixture was stirred under reflux. Subsequently, 0.48 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added, stirred for 1 hour, dehydrated with magnesium sulfate, and then filtered to obtain a uniform filtrate. Subsequently, this was concentrated under reduced pressure to bring the amount of THF to 79.6 g, 159 g of MeOH was added at 55 ° C., and the mixture was stirred with ice for a while. The precipitated crystals were filtered and dried to obtain 8.4 g of RM9 (yield: 74%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d6: 2.82-2.89 ppm (m, 2H), 3.10-3.18 ppm (m, 2H), 4.14 ppm (dd, J = 5.4 Hz, J = 11.0 Hz, 2H), 4.25 ppm (dd, J = 2.6 Hz, J = 11.0 Hz, 2H), 5.78-5.79 ppm (m, 2H), 6.10-6.08 ppm (m, 2H), 7.00 ppm (d, J = 8.4 Hz, 4H) , 7.55 ppm (d, J = 8.4 Hz)

<Synthesis Example 10-Synthesis of RM10->

<Synthesis of RM10-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (53.7 mmol) of 4,4'-biphenol, 18.4 g (2.2 eq) of 4-chlorobutylaldehyde dimethyl acetal, and potassium carbonate in 20.0 g of NMP. 22.3 g (3.0 eq) and 1.78 g (0.2 eq) of potassium iodide were charged and stirred at 80 ° C. for 3 hours. Then, 2.45 g (0.3 eq) of 4-chlorobutylaldehyde dimethyl acetal was added, and the mixture was further stirred for 16 hours. After the reaction, the reaction solution was diluted with 50.0 g of ethyl acetate, the inorganic salt was filtered, the filtrate was diluted with 50.0 g of ethyl acetate, and this was washed 3 times with 50.0 g of pure water at 50 ° C. .. Then, this organic phase was dehydrated with sodium sulfate, concentrated under reduced pressure to a total weight of 68.0 g, and the precipitated crystals were filtered. 5.0 g of THF and 20.0 g of MeOH were added to the crude product, dissolved at 50 ° C., cooled, and stirred for a while. The precipitated crystals were filtered and dried to obtain 15.8 g of RM10-A (yield: 70%, properties: white solid).
¹ H-NMR (400MHz) in DMSO-d6: 1.66-1.75 ppm (m, 8H), 3.24 ppm (s, 12H), 4.00 ppm (t, J = 6.2 Hz, 4H), 4.42 ppm (t, J = 5.2 Hz, 2H), 6.97 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm (d, J = 8.4 Hz, 4H)

<Synthesis of RM10>
In a 500 mL four-necked flask equipped with a magnetic stirrer, 14.8 g (35.4 mmol) of the compound (RM10-A) obtained above and 15.0 g (2) of ethyl 2- (bromomethyl) acrylate in 56.4 g of THF. .2 eq), 16.1 g (2.4 eq) of tin chloride, 0.39 g (5 mol%) of 2,6-di-tert-butyl-p-cresol, 51.8 g of 20 wt% HCl aqueous solution, and 3 at 60 ° C. Stirred for hours. After the reaction, the reaction solution was concentrated under reduced pressure, 148 g of pure water was added, and the precipitated crystals were filtered and washed twice with 148 g of pure water. Subsequently, 118 g of THF and 118 g of MeOH were added to the crystals and dissolved at 50 ° C., and then allowed to cool to room temperature and stirred for a while. The crystals thus obtained were filtered to obtain a crude product. Further, 237 g of THF and 237 g of IPA were added to this crude product and dissolved at 60 ° C., then cooled to room temperature and stirred for a while. The precipitated crystals were filtered, washed 3 times with 74.0 g of THF, and dried under reduced pressure to obtain 7.20 g of RM10 (yield: 44%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d6: 1.75-1.85 ppm (m, 8H), 2.60-2.68 ppm (m, 2H), 3.08-3.15 ppm (m, 2H), 4.03 ppm (t, J = 5.2) Hz, 4H), 4.61-4.67 ppm (m, 2H) 5.72-5.73 ppm (m, 2H), 6.04-6.05 ppm (m, 2H), 6.98 ppm (d, J = 8.8 Hz, 4H), 7.52 ppm ( d, J = 8.8 Hz, 4H)

<Synthesis Example 11-Synthesis of RM11->

<Synthesis of RM11-A>
In a 200 mL four-necked flask equipped with a magnetic stirrer, 10.0 g (35.7 mmol) of F-containing terphenyl compound (RM3-A), 13.3 g (2.2 eq) of bromoacetaldehyde dimethyl acetal, and potassium iodide 14 in 20 g of NMP. 8.8 g (3.0 eq) and 1.78 g (0.30 eq) of potassium iodide were charged and stirred at 100 ° C. for 13 hours. After 13 hours, 4.82 g (0.8 eq) of bromoacetaldehyde dimethyl acetal and 4.93 g (1.0 eq) of potassium carbonate were added, and the mixture was further stirred for 12 hours. As a result, the reaction was completed, so the reaction solution was diluted with 100 g of THF, the inorganic salt was filtered, and then THF was distilled off under reduced pressure. Next, 200 g of pure water was added to the reaction solution, and the precipitated crystals were filtered. Subsequently, the obtained crystals were suspended in 100 g of THF, dissolved at an internal temperature of 50 ° C., 200 g of IPA was added, and the mixture was ice-cooled and stirred. The precipitated crystals were filtered and dried to obtain 11.9 g of RM11-A (yield: 73%, properties: light brown crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 3.58-3.36 ppm (m, 12H), 4.04 ppm (d, J = 5.2 Hz, 4H), 4.74-4.71 ppm (m, 2H), 7.10-7.06 ppm (m, 4H), 7.58-7.52 ppm (m, 5H), 7.70 ppm (d, J = 8.8 Hz, 2H)

<Synthesis of RM11>
11.0 g (24.2 mmol) of the compound (RM11-A) obtained above, 10.3 g (2.2 eq) of ethyl 2- (bromomethyl) acrylate in 110 g of THF in a 500 mL four-necked flask equipped with a magnetic stirrer. ), 11.0 g (2.4 eq) of tin chloride, and 38.6 g of a 10 wt% HCl aqueous solution were charged and reacted at an internal temperature of 40 ° C. for 18 hours. After 18 hours, 11.0 g of a 20 wt% HCl aqueous solution was added, and the mixture was further stirred for 6 hours. Then, 27 mg of 2,6-di-tert-butyl-p-cresol was added, THF was distilled off under reduced pressure, 110 g of pure water was added, and the precipitated crystals were filtered. Next, the obtained crystals were suspended in 1100 g of THF, the insoluble matter left undissolved at 60 ° C. was filtered, and then 0.55 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical) was added to the filtrate, and 60 The mixture was stirred at ° C. for about 30 minutes. Subsequently, the activated carbon was filtered and the filtrate was concentrated under reduced pressure to reduce the amount to 110 g of THF, and then the precipitated crystals were filtered and dried to obtain 4.67 g of RM11 (yield: 39%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d6: 2.86 ppm (d, J = 17.6 Hz, 2H), 3.15 ppm (dd, J = 8.2 Hz, 17.4 Hz, 2H), 4.17 ppm (dd, J = 5.4 Hz) , 11 Hz, 2H), 4.29 ppm (dd, J = 2.6 Hz, 11 Hz, 2H), 4.99-4.96 ppm (m, 2H), 5.79-5.78 ppm (m, 2H), 6.10-6.09 ppm (m, 2H), 7.01-7.04 ppm (m, 4H), 7.59-7.52 ppm (m, 5H), 7.71 ppm (d, J = 8.8 Hz, 2H)

<Synthesis Example 12-Synthesis of RM12->

<Synthesis of RM12-A>
4.0 g (14.3 mmol) of F-containing terphenyl compound (RM3-A), 6.3 g (2.1 eq) of 4-bromobutyl-1,3-dioxolane, 8.3 g of potassium carbonate in a 200 ml eggplant flask with a cooling tube. (4.0 eq) and 100 ml of acetone were added to form a mixture, which was reacted under reflux conditions with stirring for 24 hours. After completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain a white solid. This white solid was purified by recrystallization (hexane / tetrahydrofuran, 5/1) to obtain 5.9 g of RM12-A (yield: 77%, properties: white crystals).
¹ H-NMR (400MHz) in CDCl ₃ : 1.62 ppm (m, 4H), 1.77 ppm (m, 4H), 1.91 ppm (m, 4H), 3.87 ppm (m, 4H), 4.04 ppm (m, 8H) , 4.90 ppm (m, 2H), 7.00 ppm (m, 4H), 7.50-7.80 ppm (m, 7H).

<Synthesis of RM12>
In a 100 ml eggplant flask with a cooling tube, 3.0 g (5.6 mmol) of the compound (RM12-A) obtained above, 2.3 g (2.5 eq) of 2- (bromomethyl) acrylic acid, 35 ml of THF, tin chloride (anhydrous). Product) 2.6 g (2.5 eq) and 11 ml of a 10% HCl aqueous solution were added to prepare a mixture, and the mixture was stirred at 70 ° C. for 20 hours to react. After completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain white crystals. The obtained white crystals were purified by recrystallization (hexane / chloroform, 5/1) to obtain 2.4 g of RM12 (yield: 73%, properties: white crystals).
¹ H-NMR (400MHz) in CDCl ₃ : 1.50-1.90 ppm (m, 12H), 2.60 ppm (m, 2H), 3.10 ppm (m, 2H), 4.03 ppm (m, 4H), 4.58 ppm (m, 2H), 5.65 ppm (m, 2H), 6.23 ppm (m, 2H), 6.94 ppm (m, 4H), 7.50-7.80 ppm (m, 7H).

<Synthesis Example 13-Synthesis of Liquid Crystal Aligning Agent D1->
BODA (2.00 g, 8.0 mmol), DA-2 (2.40 g, 6.0 mmol), DA-4 (0.94 g, 6.2 mmol), DA-6 (1.77 g, 3.8 mmol), DA-8 (1.32 g, 4.0 mmol) was dissolved in NMP (32.2 g), reacted at 60 ° C. for 3 hours, and then CBDA (2.27 g, 11.6 mmol) and NMP (10. 7 g) was added and reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (5.7 g) and pyridine (2.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -1. The imidization ratio of this polyimide was 60%, the number average molecular weight was 12,000, and the weight average molecular weight was 33000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -1 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D1.

<Synthesis Example 14-Synthesis of Liquid Crystal Aligning Agent D2->
BODA (2.00 g, 8.0 mmol), DA-8 (3.30 g, 10.0 mmol) and DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (34.8 g) at 60 ° C. After reacting for 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (11.6 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -2. The imidization ratio of this polyimide was 60%, the number average molecular weight was 15,000, and the weight average molecular weight was 41,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -2 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D2.

<Synthesis Example 15-Synthesis of Liquid Crystal Aligning Agent D3->
BODA (2.00 g, 8.0 mmol), DA-6 (4.67 g, 10.0 mmol) and DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (38.9 g) at 60 ° C. After reacting for 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (13.0 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (3.1 g) and pyridine (12.1 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -3. The imidization ratio of this polyimide was 60%, the number average molecular weight was 15,000, and the weight average molecular weight was 36,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -3 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D3.

<Synthesis Example 16-Synthesis of Liquid Crystal Aligning Agent D4->
BODA (2.00 g, 8.0 mmol), DA-7 (2.64 g, 10.0 mmol) and DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (32.8 g) at 60 ° C. After reacting in 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (10.9 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (3.7 g) and pyridine (14.4 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain polyimide powder (A) -4. The imidization ratio of this polyimide was 60%, the number average molecular weight was 25,000, and the weight average molecular weight was 45,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -4 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D4.

<Synthesis Example 17-Synthesis of Liquid Crystal Aligning Agent D5->
TCA (1.35 g, 6.0 mmol), DA-1 (2.28 g, 6.0 mmol) and DA-8 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g) at 80 ° C. After reacting in 3 hours, CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (36 g) to dilute it to 6% by mass, acetic anhydride (4.0 g) and pyridine (2.1 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -5. The imidization ratio of this polyimide was 60%, the number average molecular weight was 20000, and the weight average molecular weight was 43000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -5 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D5.

<Synthesis Example 18-Synthesis of Liquid Crystal Aligning Agent D6->
BODA (2.00 g, 8.0 mmol), DA-8 (4.63 g, 14.0 mmol) and DA-3 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g) at 60 ° C. After reacting in 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (5.3 g) and pyridine (2.7 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -6. The imidization ratio of this polyimide was 60%, the number average molecular weight was 17,000, and the weight average molecular weight was 35,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -6 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D6.

<Synthesis Example 19-Synthesis of Liquid Crystal Aligning Agent D7->
BODA (1.30 g, 5.2 mmol), DA-9 (2.09 g, 3.9 mmol) and DA-8 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g) at 60 ° C. After reacting in 3 hours, CBDA (1.43 g, 7.3 mmol) and NMP (7.8 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (36 g) to dilute it to 6% by mass, acetic anhydride (3.6 g) and pyridine (1.9 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -7. The imidization ratio of this polyimide was 60%, the number average molecular weight was 16000, and the weight average molecular weight was 36000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -7 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D7.

<Synthesis Example 20-Synthesis of Liquid Crystal Aligning Agent D8->
BODA (2.00 g, 8.0 mmol), DA-8 (3.96 g, 12.0 mmol) and DA-1 (3.04 g, 8.0 mmol) were dissolved in NMP (33.9 g) at 60 ° C. After reacting in 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (11.3 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (5.4 g) and pyridine (2.8 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -8. The imidization ratio of this polyimide was 60%, the number average molecular weight was 18,000, and the weight average molecular weight was 40,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -8 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D8.

<Synthesis Example 21-Synthesis of Liquid Crystal Aligning Agent D9->
BODA (2.00 g, 8.0 mmol), DA-1 (2.28 g, 6.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-5 (1.45 g, 6.0 mmol) After dissolving in NMP (29.5 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.5 g) are added and reacted at room temperature for 10 hours to form a polyamic acid solution. Got
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (6.4 g) and pyridine (3.3 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -9. The imidization ratio of this polyimide was 60%, the number average molecular weight was 10,000, and the weight average molecular weight was 31,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -9 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D9.

<Synthesis Example 22-Synthesis of Liquid Crystal Aligning Agent D10->
To 7.0 g of the liquid crystal alignment agent D8 obtained in Synthesis Example 20, 3.0 g of the liquid crystal alignment agent D9 obtained in Synthesis Example 21 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent D10. It was.

<Synthesis Example 23-Synthesis of Liquid Crystal Aligning Agent D11->
BODA (2.00 g, 8.0 mmol), DA-1 (1.52 g, 4.0 mmol), DA-4 (1.22 g, 8.0 mmol), DA-8 (2.64 g, 8.0 mmol) After dissolving in NMP (20.7 g) and reacting at 60 ° C. for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.9 g) are added and reacted at room temperature for 10 hours to form a polyamic acid solution. Got
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (6.1 g) and pyridine (3.2 g) were added as imidization catalysts, and the mixture was reacted at 50 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -10. The imidization ratio of this polyimide was 60%, the number average molecular weight was 9000, and the weight average molecular weight was 25,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -10 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D11.

<Synthesis Example 24-Synthesis of Liquid Crystal Aligning Agent D12->
To 7.0 g of the liquid crystal alignment agent D8 obtained in Synthesis Example 20, 3.0 g of the liquid crystal alignment agent D11 obtained in Synthesis Example 23 was added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent D12. It was.

<Synthesis Example 25-Synthesis of Liquid Crystal Aligning Agent D13->
BODA (3.75 g, 15.0 mmol), DA-1 (3.81 g, 10.0 mmol) and DA-4 (1.52 g, 10.0 mmol) were dissolved in NMP (30.0 g) at 80 ° C. CBDA (0.94 g, 4.8 mmol) and NMP (10.0 g) were added, and the mixture was reacted at 40 ° C. for 10 hours to obtain a polyamic acid solution.
NMP was added to this polyamic acid solution (50 g) to dilute it to 6% by mass, acetic anhydride (4.7 g) and pyridine (3.7 g) were added as imidization catalysts, and the mixture was reacted at 80 ° C. for 3 hours. This reaction solution was put into methanol (700 ml), and the obtained precipitate was filtered off. The precipitate was washed with methanol and dried under reduced pressure at 100 ° C. to obtain a polyimide powder (A) -11. The imidization ratio of this polyimide was 55%, the number average molecular weight was 20000, and the weight average molecular weight was 40,000.
NMP (44.0 g) was added to the obtained polyimide powder (A) -11 (6.0 g), and the mixture was dissolved by stirring at 50 ° C. for 5 hours. To this solution, 6.0 g of 3AMP (1 wt% NMP solution), NMP (14.0 g) and BCS (30.0 g) were added, and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D13.

<Synthesis Example 26-Synthesis of Liquid Crystal Aligning Agent D14->
BODA (2.00 g, 8.0 mmol), DA-6 (6.53 g, 14.0 mmol) and DA-2 (2.40 g, 6.0 mmol) were dissolved in NMP (26.4 g) at 60 ° C. After reacting in 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (13.2 g) were added, and the mixture was reacted at room temperature for 10 hours to obtain a polyamic acid solution. The number average molecular weight of this polyamic acid solution was 20000, and the weight average molecular weight was 40,000.
NMP (40.0 g) and BCS (30.0 g) were added to this polyamic acid solution (30 g), and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal aligning agent D14.

<Synthesis Example 27-Synthesis of RM13->

<Synthesis of RM13-A>
In a 300 ml four-necked flask equipped with a magnetic stirrer, 9.0 g (44.1 mmol) of RM1-A in 18.1 g of NMP was charged, co-washed with 17.9 g of NMP, and then 18.3 g (3.0 eq) of potassium carbonate. Was added, and the mixture was co-washed with 18.0 g of NMP. While stirring this at 80 ° C., 17.6 g (2.2 eq) of 2- (2-bromoethyl) -1,3-dioxolane was added dropwise over 30 minutes, and then the mixture was stirred for 18 hours. After 18 hours, 2.4 g (0.3 eq) of 2- (2-bromoethyl) -1,3-dioxolane was further added, and the mixture was further reacted for 3.5 hours to confirm the disappearance of the intermediate. After completion of the reaction, a large amount of water was added to the reaction solution at room temperature to dissolve potassium carbonate, and crystals of the target substance were precipitated and filtered. The recovered crystals were subjected to slurry washing twice with pure water and filtered and dried to obtain 17.8 g of a crude product of RM13-A (yield: 100%, properties: light brown crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 7.57ppm (d, J = 8.8Hz, 2H), 7.49ppm (dd, J = 2.2 Hz, J = 13.0Hz, 1H), 7.38ppm (d, J) = 10.0Hz, 1H), 7.21ppm (t, J = 8.8Hz, 1H), 6.99ppm (d, J = 8.4Hz, 2H), 5.02-4.99ppm (m, 2H), 4.18ppm (t, J = 6.6Hz, 2H), 4.10ppm (t, J = 6.6Hz, 2H), 3.94-3.91ppm (m, 4H), 3.82-3.78ppm (m, 4H), 2.09-2.02ppm (m, 4H).

<Synthesis of RM13>
RM13-A 15.0 g (37.1 mmol), tin (II) chloride anhydride 16.9 g (2.4 eq), 2- (bromomethyl) acrylic acid in 135 g of THF in a 500 ml four-necked flask equipped with a magnetic stirrer. After adding 15.9 g (2.2 eq) of ethyl, 52.5 g of a 10 wt% HCl aqueous solution was added dropwise at 20 to 30 ° C. over 45 minutes. Then, the mixture was stirred at room temperature for 7 days to eliminate the raw materials and intermediates. Next, 300 g of toluene was added to the reaction solution to divide it into two phases, and the hydrochloric acid phase was removed by a hot separation solution (50 ° C.). The organic phase was once collected in a flask, and 300 g of a 6 wt% KOH aqueous solution was added dropwise to a separable flask with a jacket in a stirred state at 50 ° C. Since insoluble matter was generated at the interface on the way, 150 g of a 6 wt% KOH aqueous solution was added. Next, after removing the alkaline phase, the organic phase was washed with 300 g of pure water three times, and then the organic phase was recovered. To this was added 0.75 g of activated carbon (brand: special Shirasagi dry product manufactured by Nippon Enviro Chemical), 30.0 g of sodium sulfate, and 105 g of THF, and after stirring at room temperature for 30 minutes, solid-liquid separation was performed to recover the filtrate. This was concentrated to dryness, 45.0 g of MeOH was added, and then the slurry was washed at room temperature for 1 hour. This was filtered, and the obtained filtrate was washed with 7.5 g of MeOH and then dried under reduced pressure to obtain 7.6 g of RM13 (yield: 45%, properties: white crystals).
¹ H-NMR (400MHz) in DMSO-d ₆ : 7.59 ppm (d, J = 8.8Hz, 2H), 7.51 ppm (dd, J = 2.0 Hz, J = 12.8Hz, 1H), 7.40 ppm (dd, J = 1.6 Hz, J = 8.0 Hz, 1H), 7.34 ppm (t, J = 9.0 Hz, 1H), 7.01 ppm (d, J = 8.8 Hz, 2H), 6.05 ppm (dd, J = 2.6 Hz, J = 5.0Hz, 2H), 5.74ppm (d, J = 2.0Hz, 2H), 4.81-4.75ppm (m, 2H), 4.20ppm (t, J = 6.2Hz, 2H), 4.13ppm (t, J = 6.2) Hz, 2H), 3.21-3.12ppm (m, 2H), 2.79-2.71ppm (m, 2H), 2.17-2.08ppm (m, 4H).

<Example 1>
0.06 g (10% by mass with respect to solid content) of the polymerizable compound RM1 obtained in Synthesis Example 1 was added to 10.0 g of the liquid crystal alignment agent D1 obtained in Synthesis Example 13 and stirred at room temperature for 3 hours. To dissolve the liquid crystal aligning agent D15.
When the obtained liquid crystal alignment agent D15 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 2>
In Example 1, the liquid crystal aligning agent D16 was prepared by the same method as in Example 1 except that the amount of the polymerizable compound RM1 was 0.09 g (15% by mass with respect to the solid content).
When the obtained liquid crystal alignment agent D16 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 1>
In Example 1, the liquid crystal alignment agent D17 was prepared by the same method as in Example 1 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D17 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 2>
In Example 2, the liquid crystal alignment agent D18 was prepared by the same method as in Example 2 except that the polymerizable compound RM2 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D18 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 3>
In Example 1, the liquid crystal alignment agent D19 was prepared by the same method as in Example 1 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D19 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 4>
In Example 2, the liquid crystal alignment agent D20 was prepared by the same method as in Example 2 except that the polymerizable compound RM3 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D20 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 5>
In Example 1, the liquid crystal alignment agent D21 was prepared by the same method as in Example 1 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D21 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Reference example 6>
In Example 2, the liquid crystal alignment agent D22 was prepared by the same method as in Example 2 except that the polymerizable compound RM4 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D22 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 3>
In Example 1, the liquid crystal alignment agent D23 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D2 obtained in Synthesis Example 14 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D23 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 4>
In Example 1, the liquid crystal alignment agent D24 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D3 obtained in Synthesis Example 15 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D24 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 5>
In Example 1, the liquid crystal alignment agent D25 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D4 obtained in Synthesis Example 16 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D25 was stored in a freezer at −20 ° C. for 1 day, left at room temperature for 3 hours and thawed, no precipitate was confirmed.

<Example 6>
In Example 1, the liquid crystal alignment agent D26 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D5 obtained in Synthesis Example 17 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D26 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 7>
In Example 1, the liquid crystal alignment agent D27 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D6 obtained in Synthesis Example 18 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D27 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 8>
In Example 1, the liquid crystal alignment agent D28 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D7 obtained in Synthesis Example 19 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D28 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 9>
In Example 1, the liquid crystal alignment agent D29 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D10 obtained in Synthesis Example 22 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D29 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 10>
In Example 1, the liquid crystal alignment agent D30 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D12 obtained in Synthesis Example 24 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D30 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 11>
In Example 1, the liquid crystal alignment agent D31 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D13 obtained in Synthesis Example 25 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D31 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 12>
In Example 1, the liquid crystal alignment agent D32 was prepared by the same method as in Example 2 except that the liquid crystal alignment agent D14 obtained in Synthesis Example 26 was used instead of the liquid crystal alignment agent D1.
When the obtained liquid crystal alignment agent D32 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 13>
In Example 1, the liquid crystal alignment agent D33 was prepared by the same method as in Example 1 except that the polymerizable compound RM7 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D33 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Example 14>
In Example 1, the liquid crystal alignment agent D34 was prepared by the same method as in Example 1 except that the polymerizable compound RM8 obtained in Synthesis Example 8 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D34 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Comparative example 1>
In Example 1, the liquid crystal alignment agent D35 was prepared by the same method as in Example 1 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D35 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Comparative example 2>
In Example 2, the liquid crystal alignment agent D36 was prepared by the same method as in Example 2 except that the polymerizable compound RM5 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D36 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, precipitates were confirmed.

<Comparative example 3>
In Example 1, the liquid crystal alignment agent D37 was prepared by the same method as in Example 1 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D37 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, precipitates were confirmed.

<Comparative example 4>
In Example 2, the liquid crystal alignment agent D38 was prepared by the same method as in Example 2 except that the polymerizable compound RM6 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D38 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, precipitates were confirmed.

<Comparative example 5>
In Example 1, the liquid crystal alignment agent D39 was prepared by the same method as in Example 1 except that the polymerizable compound RM9 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D39 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.

<Comparative Example 6>
In Example 1, the liquid crystal alignment agent D40 was prepared by the same method as in Example 1 except that the polymerizable compound RM10 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1.
When the obtained liquid crystal alignment agent D40 was stored in a freezer at −20 ° C. for 1 day, left at room temperature for 3 hours and thawed, no precipitate was confirmed.

<Example 15>
<Manufacturing of liquid crystal cell>
Using the liquid crystal alignment agent D15 obtained in Example 1, an SC-PVA liquid crystal cell was produced by the procedure as shown below.
The liquid crystal aligning agent D15 obtained in Example 1 was spin-coated on the ITO surface of an ITO electrode substrate having an ITO electrode pattern having a pixel size of 100 μm × 300 μm and a line / space of 5 μm, respectively, and hot-coated at 80 ° C. After drying on a plate for 90 seconds, it was fired in a hot air circulation oven at 200 ° C. for 30 minutes to form a liquid crystal alignment film having a film thickness of 100 nm.
Further, the liquid crystal aligning agent D1 is spin-coated on the ITO surface on which the electrode pattern is not formed, dried on a hot plate at 80 ° C. for 90 seconds, and then baked in a hot air circulation oven at 200 ° C. for 30 minutes to obtain a film thickness. A 100 nm liquid crystal alignment film was formed.
A 4 μm bead spacer was sprayed on the liquid crystal alignment film of one of the above two substrates, and then a sealant (solvent type thermosetting type epoxy resin) was printed on the bead spacer. Next, the surface of the other substrate on which the liquid crystal alignment film was formed was turned inside, and after bonding with the previous substrate, the sealant was cured to prepare an empty cell. A liquid crystal MLC-6608 (trade name manufactured by Merck & Co., Inc.) was injected into this empty cell by a vacuum injection method to prepare a liquid crystal cell. The produced liquid crystal cell was then placed in a hot air circulation oven at 120 degrees for 1 hour to reorient the liquid crystal.
The response speed of the obtained liquid crystal cell was measured by the following method. Then, with a DC voltage of 15 V applied to the liquid crystal cell, UV was irradiated from the outside of the liquid crystal cell through a bandpass filter of 365 nm at 10 J / cm ² . Then, the response speed was measured again, and the response speed before and after UV irradiation was compared. In addition, the pre-tilt angle of the pixel portion of the cell after UV irradiation was measured. In addition, the cells not irradiated with UV were left for one day, and then the liquid crystal cells were observed with a polarizing microscope. When the solubility of the polymerizable compound is low, it is considered that precipitation is likely to occur even in the liquid crystal cell and bright spots are generated. The results are shown in Table 5.

<Measurement method of response speed>
First, in a measuring device composed of a backlight, a set of polarizing plates in a cross Nicol state, and a photodetector in this order, a liquid crystal cell was arranged between the set of polarizing plates. At this time, the pattern of the ITO electrode on which the line / space was formed was set to an angle of 45 ° with respect to the cross Nicol. Then, a square wave with a voltage of ± 6 V and a frequency of 1 kHz is applied to the above liquid crystal cell, and the change until the brightness observed by the light amount detector is saturated is captured by an oscilloscope, and the brightness when no voltage is applied is obtained. A voltage of 0% and ± 4V was applied, the saturated brightness value was set to 100%, and the time required for the brightness to change from 10% to 90% was defined as the response speed.

<Measurement of pre-tilt angle>
An LCD analyzer LCA-LUV42A manufactured by Meiryo Technica was used.
<Examples 16 to 28>
The same operation as in Example 21 was performed except that the liquid crystal alignment agent shown in Table 1 was used instead of the liquid crystal alignment agent D15, and the response speeds before and after UV irradiation were compared. The pre-tilt angle was also measured. In addition, the bright spot observation results in the liquid crystal cell were also performed.

<Example 29>
0.06 g (10% by mass) of RM13 synthesized in Synthesis Example 27 (10% by mass with respect to the solid content of the liquid crystal alignment agent D10) was added to the liquid crystal alignment agent D10 (10.0 g) obtained in Synthesis Example 22 at room temperature. The liquid crystal alignment agent D41 was prepared by stirring and dissolving for 3 hours.
When the obtained liquid crystal alignment agent D41 was stored in a freezer at −20 ° C. for 1 day and left at room temperature for 3 hours to thaw, no precipitate was confirmed.
<Example 30>
The liquid crystal alignment agent D41 prepared in Example 29 was subjected to the same operation as in Example 15 to compare the response speeds before and after UV irradiation. In addition, the pretilt angle was measured and the bright spot in the liquid crystal cell was observed.

<Reference Example 7 to Reference Example 12>
The same operation as in Example 16 was performed except that the liquid crystal aligning agents D17 to D22 were used instead of the liquid crystal aligning agent D15, and the response speeds before and after UV irradiation were compared. The pre-tilt angle was also measured. In addition, the bright spot observation results in the liquid crystal cell were also performed.
In Reference Examples 7, 8, 11 and 12, a hot air circulation oven at 140 ° C. was used instead of the hot air circulation oven at 200 ° C.

<Comparative Example 7 to Comparative Example 12>
The same operation as in Example 15 was performed except that the liquid crystal aligning agents D35 to D40 were used instead of the liquid crystal aligning agent D15, and the response speeds before and after UV irradiation were compared. The pre-tilt angle was also measured. In addition, the bright spot observation results in the liquid crystal cell were also performed.

Comparing Examples 15 and 16 with Comparative Examples 7 and 8, especially when comparing Example 16 and Comparative Example 8, when they have the same skeleton (RM1 and RM5 have F substitution (RM1) and none). (Difference in (RM5))), it can be seen that the solubility in varnish is improved by the introduction of the halogen group. Further, by observing the bright spots in the liquid crystal cell, it can be seen that the solubility in the liquid crystal is also improved.
From the same viewpoint, Example 27 and Comparative Example 11 (difference between RM7 and RM9 with and without F substitution (RM7) and without F substitution (RM9)), Example 28 and Comparative Example 12 (RM8 and RM10 are different). Comparing the difference between with and without F substitution (RM8) and without F substitution (RM10), it can be seen that the solubility in the liquid crystal is improved. Further, from Reference Example 9 and Reference Example 10, even if the terphenyl skeleton is more rigid and less soluble than the biphenyl skeleton, the introduction of the halogen group improves the solubility of the polymerizable compound, and the liquid crystal alignment agent It can be confirmed that the storage stability is also improved.
Similarly, high solubility of the polymerizable compound was confirmed from Reference Examples 7, 8, 11 and 12. Therefore, it can be seen that the halogen-substituted polymerizable compound improves the solubility of the polymerizable compound, the liquid crystal alignment agent exhibits high storage stability, and the solubility in the liquid crystal is also improved. Further, the liquid crystal alignment agent to which the halogen-substituted heavy synthetic compound is added can exhibit a tilt angle in the SC-PVA type liquid crystal cell in the same manner as the liquid crystal alignment agent to which the halogen-substituted polymerizable compound is added. confirmed.

Claims (7)

A polymerizable compound having an aryl group at least monosubstituted with a halogen atom and two α-methylene-γ-butyrolactone groups, wherein Ar is a halogen-substituted compound in the following formula [1] (in the formula [1]). A polymerizable compound which is a divalent organic group containing an aromatic ring having at least one group, and n ₁ and n ₂ are the same and are integers of 1 to 10).

In the above formula [1], Ar is the following formulas [2] to [4] (in the formula, X represents a halogen substituent, m _{1 to} m ₆ are independently integers of 0 to 4, and m ₇ and m ₈ is an integer of 0 to 3, m ₁ + m ₂ is 1 or more and 8 or less, m ₃ + m ₄ + m ₅ is 1 or more and 12 or less, and m ₆ + m ₇ + m ₈ is 1 or more and 10 The polymerizable compound according to claim 1, which has a structure represented by (the following).

The polymerizable compound according to claim 2, wherein X represents a fluorine group. In formulas [2] to [4], X represents a fluorine group, m ₁ + m ₂ is 1 or more and 3 or less, m ₃ + m ₄ + m ₅ is 1 or more and 4 or less, and m ₆ + m ₇ + m ₈ is. The polymerizable compound according to claim 2, which is 1 or more and 3 or less. A polymerizable compound selected from the group consisting of compounds represented by the following formulas [5] to [7] (in the formula, n1 is an integer of 1 to 10).

The following formula [1-1] - [1-6] with a compound heavy polymerizable compound that will be selected from the group consisting represented.

A liquid crystal alignment agent containing the polymerizable compound according to any one of claims 1 to 6 and at least one polymer selected from polyimide and a polyimide precursor.