TWI647226B - Polymeric compound squeeze by halogen atom - Google Patents

Abstract

The present invention provides a halogenated atom-substituted polymerizable compound which is used in a solvent of a liquid crystal alignment agent or which improves solubility in a liquid crystal.

The present invention provides a formula (1) wherein Ar is a divalent organic group containing an aromatic ring having at least one halogen substituent, and n ₁ and n _{2 are} each independently an integer of 1 to 10. a polymerizable compound containing an aromatic ring having at least one halogen substituent, and a polymerizable compound and at least one selected from the group consisting of polyimine and polyimine precursors, as the halogen group is preferably a F group. A liquid crystal alignment agent for polymers.

Description

Polymeric compound substituted by halogen atom

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

In a liquid crystal display device in which a liquid crystal molecule which is vertically aligned with a substrate is responsive to an electric field (also referred to as a vertical alignment (VA) method), a voltage is applied to the liquid crystal molecules while the manufacturing process is included. The step of ultraviolet light.

In the liquid crystal display device of such a vertical alignment type, a photopolymerizable compound is added to the liquid crystal composition in advance, and is used together with a vertical alignment film such as polyimide or the like. Generally, when a voltage is applied to the liquid crystal cell and ultraviolet rays are irradiated, the liquid crystal can be accelerated. The technique of the response speed (for example, refer to Patent Document 1 and Non-Patent Document 1) is known (PSA (Polymer sustained Alignment) type liquid crystal display).

The tendency direction of the liquid crystal molecules which are generally responsive to the electric field can be controlled by a protrusion provided on the substrate or a slit provided on the display electrode, and the liquid crystal of the photopolymerizable compound is added to the liquid crystal composition. When the ultraviolet ray is applied while applying a voltage, the polymer structure in which the liquid crystal molecules tend to be stored is formed on the liquid crystal alignment film, so that the direction of the liquid crystal molecules is controlled only by the protrusions or slits. In comparison, the response speed of the liquid crystal display element becomes faster.

In addition, it has been reported that even if a photopolymerizable compound is not added to the liquid crystal composition, it can be added to the liquid crystal alignment film to increase the response speed of the liquid crystal display element (SC-PVA liquid crystal display) ( For example, refer to Non-Patent Document 2).

On the other hand, several polymerizable monomers are known as a photopolymerizable compound (Patent Documents 2 to 6).

[Previous Technical Literature] [Patent Document]

[Patent Document 1] JP-A-2003-307720

[Patent Document 2] JP-A-2008-239873

[Patent Document 3] JP-A-2011-84477

[Patent Document 4] JP-A-2012-240945

[Patent Document 5] Japanese Patent Publication No. 2013-509457

[Patent Document 6] British Patent Application Publication No. GB 2297549A

[Non-patent literature]

[Non-Patent Document 1] K. Hanaoka, SID 04 DIGEST, P.1200-1202

[Non-Patent Document 2] K. H Y. -J. Lee, SID 09 DIGEST, P.666-668

However, it is also expected that the response speed of the liquid crystal display element can be further fast. Here, it is considered that the response speed of the liquid crystal display element can be accelerated by increasing the amount of addition of the photopolymerizable compound, and the conventional photopolymerizable compound has a property of being hardly soluble in a solvent used for the liquid crystal alignment agent. Therefore, when the liquid crystal alignment agent is stored, there is a problem that the storage stability of the photopolymerizable compound is precipitated. In addition, when the undissolved photopolymerizable compound remains as an impurity, it may become a cause of lowering the reliability of the liquid crystal display element. For example, if a burn-in or afterimage is generated on a liquid crystal display element, the display quality can be lowered.

The 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 or a polymerizable compound which improves solubility in liquid crystals.

The present inventors have repeated the detailed review results to achieve the above object, and found that by using a novel polymerizable compound having a mother core substituted with a halogen atom, the preservation stability in the paint can be improved, and the dissolution of the liquid crystal can be further improved. Sex.

The present invention has the following gist in the light of the findings.

A polymerizable compound which is a polymerizable compound having an aryl group substituted with at least one halogen atom and two α-methyl-γ-butyrolactone groups.

2. A polymerizable compound characterized by the following formula [1],

In the formula [1], Ar represents a divalent organic group containing an aromatic ring having at least one halogen substituent, and n1 and n2 are each independently an integer of from 1 to 10.

3. In the formula [1], Ar is a polymerizable compound formed by the structures represented by the following formulas [2] to [4]. (X represents a halogen group, particularly preferably a fluorine group. m ₁ to m _{6 are} each independently an integer of 0 to 4, m ₇ and m _{8 are} each independently an integer of 0 to 3, and m ₁ + m ₂ is 1 or more and 8 Hereinafter, 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. X represents a polymerizable compound according to any one of the above 1 to 3 of the fluorine group.

5. In the formulae [2] to [4], X represents a fluorine group, m ₁ + m ₂ is 1 or more and 3 or less, and m ₃ + m ₄ + m ₅ is 1 or more and 4 or less, and m ₆ + m ₇ + m ₈ The compound of the above 4 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].

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of the polymerizable compound according to any one of the above 1 to 7 and a polyimine and a polyimide precursor.

When the polymerizable compound described below is used as a constituent component of a liquid crystal alignment film material, the present invention can provide a higher alignment fixing ability, improve storage stability in painting, and further improve solubility in liquid crystal. . The polymerizable compound has a divalent organic group and two α-methyl-γ-butyrolactone groups, and the divalent organic group is an aromatic ring having at least one halogen substituent.

[Formation of the Invention]

The invention will be further described in detail below.

<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} each independently an integer of 1 to 10.

From the viewpoint of easy synthesis, it is preferable that n1 and n2 are the same.

As Ar, those represented by the following formulas [2] to [4] are preferred.

In the formula, X represents a halogen group, and particularly preferably a fluorine group. m ₁ to m _{6 are} each independently an integer of 0 to 4, m ₇ and m _{8 are} each independently an integer of 0 to 3, m ₁ + m ₂ is 1 or more and 8 or less, and m ₃ + m ₄ + m ₅ is 1 or more. 12 or less, m ₆ + m ₇ + m ₈ is 1 or more and 10 or less.

In the formulae [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 1 When it is 3 or more, it is preferable from the viewpoint of easiness of synthesis or economy. It is particularly good to be 1 or more and 2 or less. Further, from the viewpoint of solubility, the substitution position of X is preferably such that Ar becomes an asymmetric substitution position.

The polymerizable compound of the present invention represented by the above formula [1] can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited. For example, as shown in the following [Reaction Formula 1], by using a halogenated aryl [2-A] to [2-D] and an organometallic reagent [3-A] to [3-B], a transition metal catalyst is used. Cross-coupling reaction to synthesize the corresponding mother nucleus [4-A] After ~[4-C], the ether compound [9] is reacted with a corresponding halide [8] in the presence of a base, and a metal reagent can be produced by reacting with an acrylic acid derivative [10].

Ar ₁ , Ar ₂ and Ar _{3 are} each independently a divalent organic group having an aromatic ring, and at least one of Ar _{1 ,} Ar ₂ and Ar ₃ has at least one halogen substituent. As the halogen group, a F atom is preferred. 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-dioxanyl group, or a 1,3-difuranyl group. N is an integer from 1 to 10. X ₁ is Cl, Br or I. X ₂ is Cl or Br. In the present specification, Tf represents a trifluoromethanesulfonate group, that is, a trifluoromethylsulfonyl group.

<cross-coupling reaction, containing F-linked aryl compound>

Examples of the F-containing aryl compound [4-A] include the following biphenyl compounds [4-1] to [4-42] and phenylnaphthalene compounds [4-43] to [4-58].

The F-based biphenyl compound [4-A] as described in the above [4-1] to [4-41] can be used as described below by using a halogenated aryl group [2-A] and an organometallic reagent [3]. -A], the metal catalyst is obtained by cross-coupling reaction.

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

The amount of the halogenated aryl group [2-A] and the boronic acid derivative [3-A] represented by the above-mentioned cross-coupling reaction (Suzuki-Miyaura reaction) is not particularly limited, but is equivalent to 1 equivalent of halogenated aryl [2-A]. In other words, it is preferred to use a boric acid derivative [3-A] of 1.0 to 1.5 equivalents. Further, for one equivalent of the boronic acid derivative [3-A], a halogenated aryl [2-A] may be used in an amount of 1.0 to 1.5 equivalents.

In the above coupling reaction (Suzuki-Miyaura reaction), a suitable metal complex and a ligand can be used as a catalyst. According to the requirements, the reaction can be carried out even without a ligand. Palladium complexes or nickel complexes are generally used. As the catalyst, various structures can be used, but it is preferable to use a so-called low-valent palladium complex or a nickel complex, and it is preferable to use a tertiary phosphine or a tertiary phosphite as a zero-valent complex of a ligand. . Further, an appropriate precursor which tends to become a zero-valent complex can be used in the reaction system. Further, mixing a reaction body with a third-order phosphine or a tertiary phosphite as a ligand, and a tertiary phosphine or a tertiary phosphite, can produce a tertiary phosphine or a tertiary Phosphites act as low atomic valence bodies of ligands. Level 3 as phosphine or phosphite ligand stage 3 of the seat, for example, include triphenyl phosphine times, tri - o - toluene phosphinate, diphenylmethyl phosphinate, phenyl dimethylphosphinate, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphine)butane, 1,1'-bis(diphenyl A phosphine, a ferrocene, a trimethyl phosphite, a triethyl phosphite, a triphenyl phosphite, or the like may be used, and a complex containing two or more kinds of these ligands may be used. As a catalyst, a palladium complex which does not contain a tertiary phosphine or a tertiary phosphite, and a complex containing a tertiary phosphine or a tertiary phosphite are combined with the above-mentioned ligand, and the user is preferred. . Examples of the complex which does not contain a tertiary phosphine or a tertiary phosphite used in combination with the above-mentioned ligands include bis(xyleneacetone)palladium, ginseng (methylenebenzene)dipalladium, and bis(acetonitrile). Dichloropalladium, bis(benzonitrile)dichloropalladium, palladium acetate, palladium chloride, palladium chloride-acetonitrile, palladium-activated carbon, nickel chloride, nickel iodide, etc. Phosphine or a tertiary phosphite as a complex contained in a ligand, and examples thereof include dimethylbis(triphenylphosphinyl)palladium, dimethylbis(diphenylmethylphosphinyl)palladium, and Bis(triphenylphosphinyl)palladium, ruthenium (triphenylphosphinyl) palladium, bis(triphenylphosphinyl)dichloropalladium, [1,3-bis(diphenylphosphino)propane]nickel ( II) dichloride, [1,2-bis(diphenylphosphino)ethane]nickel(II) dichloride, etc., but is not limited thereto. The amount of the palladium complex and the nickel complex is preferably a so-called amount of the catalyst, and is generally 20 mol% or less for the substrate, and usually 10 mol% or less.

As the base, sodium hydroxide, potassium hydroxide, hydrogen hydroxide can be used. An inorganic base such as lithium, sodium hydrogencarbonate, potassium hydrogencarbonate, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate or methylamine, dimethylamine, trimethylamine, ethylamine, Diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, isopropylamine, diisopropylamine, triisopropylamine, butylamine, dibutylamine, Other than amines such as tributylamine, diisopropylethylamine, pyridine, imidazole, quinoline, and collidine, sodium acetate, potassium acetate, lithium acetate, or the like can be used.

As a solvent, it is stable under the reaction conditions, and inertness does not hinder 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.) can be used. ), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene) Etc.), halogen-based hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.) , nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected in consideration of the easiness of the reaction. In this case, one type of the above solvent may be used alone or two or more types may be used in combination.

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

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

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

The solvent to be used for the washing is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane or toluene, halogen hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, and diethyl ether. Ethers such as ethers, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, methanol or ethanol, 2-propanol, etc. Alcohols, and mixtures of these.

The solvent used for the recrystallization is not particularly limited as long as it contains a F-biphenyl compound [4-A] which is dissolved during heating and precipitates upon cooling, and examples thereof include hydrocarbons such as hexane, heptane or toluene. Halogen hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene; ethers such as diethyl ether, tetrahydrofuran or 1,4-dioxane; esters such as ethyl acetate; acetone or methyl A ketone such as ethyl ketone, a nitrile such as acetonitrile or propionitrile, an alcohol such as methanol or ethanol or 2-propanol, or a mixture thereof is preferably ethyl acetate, tetrahydrofuran, toluene or hexane.

The compound [4-42] is a commercially available product.

The F-phenylnaphthalene-containing compound [4-A] as described in the above [4-43] to [4-50] is a halogenated aryl group [2-A] and an organometallic reagent [3-A] as described below. It is obtained by performing a cross-coupling reaction using a metal catalyst such as Pd.

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

The amount of the halogenated aryl group [2-A] and the boronic acid derivative [3-A] shown in the above cross-coupling reaction is not particularly limited, but a boronic acid derivative is used for the halogenated aryl [2-A] 1 equivalent. 3-A] 1.0 to 1.5 equivalents is preferred. Further, for the boric acid derivative [3-A] 1 equivalent, The halogenated aryl [2-A] is used in an amount of 1.0 to 1.5 equivalents.

The above coupling reaction will use a suitable metal complex and a ligand as a catalyst. The type of the catalyst or the ligand is the same as that of the F-containing biphenyl compound.

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

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

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

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

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

The F-phenyl-naphthalene compound [4-A] of the above [4-51] to [4-58] can be used as described below, and the halogenated aryl group [2-A] can be used as an organometallic reagent [3-A]. 〕 using a metal catalyst such as Pd for cross-coupling reaction Got it.

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

The amount of the halogenated aryl group [2-A] and the boronic acid derivative [3-A] shown in the above cross-coupling reaction is not particularly limited, but for the halogenated aryl [2-A] 1 equivalent, it is derived by using boric acid. 1.0 to 1.5 equivalents are preferred. Further, it is preferred to use 1.0 to 1.5 equivalents of the halogenated aryl group for 1 equivalent of the boronic acid derivative [3-A].

The above coupling reaction can use a suitable metal complex and a ligand as a catalyst. The type of the catalyst or the ligand is the same as that of the F-containing biphenyl compound.

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

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

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

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

The F-phenylnaphthalene-containing compound [4-A] obtained as described above can be purified by slurry washing, recrystallization, gel column chromatography, etc. after the reaction. It is highly purified. This method is the same as the synthesis method of the F-containing biphenyl compound.

<cross-coupling reaction, F-containing biphenyl compound>

The following F-terphenyl compound [4-B] obtained by the coupling reaction of [Reaction formula 1] is exemplified below. The F-containing terphenyl compound [4-B] has the same structure as the benzene ring (A) in the intermediate benzene ring (B) in the 3-ring structure.

The F-based terphenyl compound [4-B] as described in the above [4-59] to [4-99] can be obtained by using a halogenated aryl group [2-B] and an organometallic reagent as shown below. 3-A], the metal catalyst is obtained by cross-coupling reaction.

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

The amount of the halogenated aryl group [2-B] and the boronic acid derivative [3-A] shown in the above cross-coupling reaction is not particularly limited, but for the halogenated aryl group [2-B] 1 equivalent, a boric acid derivative is used. [3-A] 2.0 to 2.5 equivalents is preferred.

The above coupling reaction uses a suitable metal complex and a ligand as a catalyst. The type of the catalyst or ligand is the same as that of the F-containing biphenyl compound.

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

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

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

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

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

When a halogenated aryl group [2-C] having two different halogen groups selected from the group consisting of Cl, Br and I is used as a raw material, each of the different boronic acid derivatives [3-A] and [3-B] can be used. The introduction was carried out to obtain an F-containing terphenyl compound [4-C] having a structure in which a benzene ring (A) and a benzene ring (C) were different as shown below.

F-based terphenyls such as the above [4-100]~[4-246] The compound [4-C] is a cross-coupling reaction of a halogenated aryl group [2-C] with an organometallic reagent [3-A] using a metal catalyst as shown below, and the resulting halogenated aryl group [2-D] It can be obtained by performing cross-coupling reaction with the organometallic reagent [3-B] again. (In [Reaction formula 1], the organometallic reagent [3-A] and the organometallic reagent [3-B] are organometallic reagents having a different structure)

Where 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 halogenated aryl group [2-C] and the boronic acid derivative [3-A] shown in the above cross-coupling reaction is not particularly limited, but a boronic acid derivative is used for the halogenated aryl [2-C] 1 equivalent. [3-A] 1.0 to 1.2 equivalents is preferred. In addition, the second Suzuki-Miyaura reaction is also used in the same amount.

The above coupling reaction uses a suitable metal complex and a ligand as a catalyst. Catalyst or ligand type and synthesis method of F-containing biphenyl compound the same.

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

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

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

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

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

<F-containing etherification reaction>

The F-containing ether compound [9] is an aromatic compound [4-A] to [4-C] having a phenolic hydroxyl group and a halogenated alkyl group [8] in the presence of a base, if necessary, in an additive, as shown below. In the presence of it, it is reversed.

Ar ₁ , Ar ₂ and Ar _{3 are} each independently a divalent organic group having an aromatic ring, and at least one of Ar _{1 ,} Ar ₂ and Ar ₃ has at least one halogen substituent. As the halogen group, a F atom is preferred. N1 is an integer from 1 to 10. X ₁ is Cl, Br or I, and PG is dimethyl acetal, diethyl acetal, 1,3-dioxyl or 1,3-difuranyl.

As the base of the above reaction formula, an inorganic base such as sodium hydride, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium citrate, potassium citrate, sodium carbonate, potassium carbonate, lithium carbonate or cesium carbonate can be used. Preferred is sodium carbonate or potassium carbonate.

The additive can be used for the purpose of promoting the reaction rate. As the additive, potassium iodide, sodium iodide, a fourth-order ammonium salt, a crown ether or the like can be used.

The solvent is stable under the reaction conditions and is inert and does not interfere with the reaction. Ketones such as water, alcohols, amines, acetone or methyl ethyl ketone, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.), ethers (Et ₂ O, i -Pr ₂ O) can be used. , TBME, CPME, tetrahydrofuran, dioxane, etc.), aliphatic hydrocarbons (pentane, hexane, heptane, petroleum ether, etc.), aromatic hydrocarbons (benzene, toluene, xylene, trimethylbenzene, chlorobenzene, Dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen hydrocarbons (chloroform, dichloromethane, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate) , butyl acetate, methyl propionate, etc.), nitriles (acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected in consideration of the ease of the reaction. In this case, one type of the above solvent may be used alone or two or more types may be used in combination. Preferred are acetone, aprotic polar organic solvents (DMF, DMSO, DMAc, NMP, etc.).

The reaction temperature is not particularly limited and is usually -90 to 200. °C, preferably 40~150 °C.

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

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

The solvent to be used for the washing is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane or toluene, halogen hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, and diethyl ether. Ethers such as ethers, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, methanol or ethanol, 2-propanol, etc. The alcohol and these mixtures are preferably alcohols such as methanol or ethanol or 2-propanol.

The solvent to be used for the recrystallization is not particularly limited as long as it is soluble in the F-containing ether compound [9] and can be precipitated during cooling, and examples thereof include hydrocarbons such as hexane, heptane or toluene. a halogen-based hydrocarbon such as chloroform, 1,2-dichloroethane or chlorobenzene; an ether such as diethyl ether, tetrahydrofuran or 1,4-dioxane; an ester such as ethyl acetate; acetone or methyl ethyl a ketone such as a ketone, a nitrile such as acetonitrile or propionitrile, an alcohol such as methanol or ethanol or 2-propanol, or a mixture thereof, preferably an alcohol such as ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol or 2-propanol. , hexane or these mixtures.

<Lactone ring synthesis reaction>

The α-methyl-γ-butyrolactone compound [1] can be synthesized by a combination of methods in organic synthetic chemistry, and the synthesis method is not particularly limited. As described below As shown, an aldehyde or a ketone, an acetal, a ketal can be synthesized by reacting a metal reagent with an acrylic acid under acidic conditions (Reference: For example, P. Talaga, M. Schaeffer, C. Benezra and JLStampf, Synthesis , 530 (1990)).

Ar ₁ , Ar ₂ and Ar _{3 are} each independently a divalent organic group having an aromatic ring, and at least one of Ar _{1 ,} Ar ₂ and Ar ₃ has at least one halogen substituent. As the halogen group, a F atom is preferred. N1 is an integer from 1 to 10. R may be a hydrogen atom or a C1-4 alkyl group. PG is a dimethyl acetal group, a diethyl acetal group, a 1,3-dioxanyl group or a 1,3-difuranyl group. X ₂ is Cl or Br.

As the acrylic acid derivative [10] represented by the above lactone ring synthesis, 2-(chloromethyl)acrylic acid, methyl 2-(chloromethyl)acrylate, ethyl 2-(chloromethyl)acrylate, 2- (Bromomethyl)acrylic acid, methyl 2-(bromomethyl)acrylate, ethyl 2-(bromomethyl)acrylate, and the like.

The amount of the acrylic acid derivative [10] to be used is not particularly limited, but it is preferably 2.0 to 2.5 equivalents based on the use of the acrylic acid derivative for the ether compound [9].

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

As the acid, an inorganic acid aqueous 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.

As a solvent, it is stable under the reaction conditions, which is inert without hindering the reaction. Use water, alcohols, 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, trimethylbenzene, chlorobenzene, dichlorobenzene, nitrobenzene, tetrahydronaphthalene, etc.), halogen Hydrocarbons (chloroform, methylene chloride, carbon tetrachloride, dichloroethane, etc.), lower fatty acid esters (methyl acetate, ethyl acetate, butyl acetate, methyl propionate, etc.), nitriles ( Acetonitrile, propionitrile, butyronitrile, etc.). These solvents can be appropriately selected in consideration of the easiness of the reaction. In this case, the above solvents may be used alone or in combination of two or more. Preferred is tetrahydrofuran and water.

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

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

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

The solvent to be used for the washing is not particularly limited, and examples thereof include hydrocarbons such as hexane, heptane or toluene, halogen hydrocarbons such as chloroform, 1,2-dichloroethane or chlorobenzene, and diethyl ether. Ethers such as ethers, tetrahydrofuran or 1,4-dioxane, esters such as ethyl acetate, ketones such as acetone or methyl ethyl ketone, nitriles such as acetonitrile or propionitrile, methanol or ethanol, 2-propanol, etc. The alcohol and these mixtures are preferably alcohols such as methanol or ethanol or 2-propanol.

The solvent used for the recrystallization may be such that the α-methyl-γ-butyrolactone compound [1] is dissolved during heating and precipitated upon cooling, and is not particularly limited, and examples thereof include hexane and heptane. Or a hydrocarbon such as toluene, a halogen-based hydrocarbon such as chloroform, 1,2-dichloroethane or chlorobenzene; an ether such as diethyl ether, tetrahydrofuran or 1,4-dioxane; or an ester such as ethyl acetate; a ketone such as acetone or methyl ethyl ketone, a nitrile such as acetonitrile or propionitrile, an alcohol such as methanol or ethanol or 2-propanol, or a mixture thereof, preferably ethyl acetate, tetrahydrofuran, toluene, methanol or ethanol, 2 An alcohol such as propanol, hexane or a mixture thereof.

<Liquid alignment agent>

The present invention provides a liquid crystal alignment agent or a liquid crystal alignment agent containing a polymerizable compound which improves solubility in a liquid crystal. The liquid crystal alignment agent of the present invention is at least one selected from the group consisting of at least one polymerizable compound selected from the group consisting of the compounds represented by the above formula [1] and [II] selected from the group consisting of polyimine and polyimine precursors. Kind of polymer.

<[II] at least one polymer selected from the group consisting of polyimine and polyimine precursors>

As at least one polymer selected from the group consisting of polyimine and polyimine precursors, a polyimide or a polyimide precursor which is conventionally known or known in the future can be used for a liquid crystal alignment agent.

[II] At least one polymer selected from the group consisting of polyimine and polyimine precursors is used for PSA liquid crystal display, and it is preferred to have (I) a chain in which liquid crystals are vertically aligned.

<<(I) The liquid crystal is vertically aligned to the side chain >>

The side chain in which the liquid crystal is vertically aligned (hereinafter also referred to as side chain A) is a side chain having the ability to vertically align liquid crystal molecules with respect to the substrate, and the structure is not particularly limited. . As such a side chain, for example, a long-chain alkyl group or a 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 applicable to the present invention. These groups may be directly bonded to the main chain of the polyimide or polyimine precursor, or may be bonded via a suitable bond, only having the above-mentioned ability.

The side chain A may be, for example, those represented by the following formula (a).

Further, in the formula (a), l, m and n each independently represent an integer of 0 or 1, and R ¹ represents an alkylene group having 2 to 6 carbon atoms, -O-, -COO-, -OCO-, -NHCO. -, -CONH-, or an alkyl-ether group having 1 to 3 carbon atoms, R ² , R ³ and R ⁴ each independently represent a phenyl or cycloalkyl group, and R ⁵ represents a hydrogen atom and a carbon atom. A 2 to 24 alkyl or fluoroalkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or a macrocyclic substituent formed by them.

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

R ² , R ³ and R ⁴ in the formula (a) each independently represent a phenyl group or a cycloalkyl group. From the viewpoint of easiness of synthesis and ability to vertically align the liquid crystal, it is preferred to use a combination of l, m, n, R ² , R ³ and R ⁴ as shown in the following table.

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 heterocyclic ring or a large cyclic substituent formed therefrom. 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, preferably a hydrogen atom or a carbon atom number of 2. An alkyl or fluoroalkyl group to 12.

Further, when all of l, m, and n are 0, the structure of R ⁵ is an alkyl group having 12 to 22 carbon atoms or a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the like. The macrocyclic substituent is preferred, and is preferably an alkyl group having 12 to 20 carbon atoms or a fluorine-containing alkyl group.

The ability to vertically align the liquid crystal differs depending on the structure of the side chain A. However, when the amount of the side chain A contained in the polymer is generally increased, the ability to vertically align the liquid crystal is increased, and if it is less, Will decrease. Further, the side chain A having a cyclic structure may have a tendency to vertically align the liquid crystal even in a small amount of the side chain A of the long-chain alkyl group.

The amount of the side chain A to be used in the polyimine or the polyimide precursor of the present invention is not particularly limited as long as the liquid crystal alignment film can form a liquid crystal in a vertical alignment range. However, in the liquid crystal display element including the liquid crystal alignment film, when the response speed of the liquid crystal is to be made faster, it is preferable to reduce the amount of the side chain A as much as possible while maintaining the vertical alignment.

[II] Polyimine or polyimine precursor, which is used in an SC-PVA liquid crystal display, and has (II) photoreactivity in addition to a side chain in which the liquid crystal of the above (I) is vertically aligned. Side chains are preferred.

<(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 forming a covalent bond by a reaction by ultraviolet irradiation. Or a photoradical free radical having a functional group capable of generating a radical by ultraviolet irradiation, having only this ability Its structure is not limited.

Among such side chains, for example, as a photocrosslinking group, a vinyl group, an acryl group, a methacryl group, a decyl group, a cinnamyl group, a chalcone group, a coumarin group, and a malayan group are known. A side chain such as an amine group or a thiol group can be suitably used in the present invention. Further, a specific structure which generates radicals by ultraviolet irradiation is also applicable. These groups may have only the above-mentioned capabilities, and may be directly bonded to the main chain of the polyimide or polyimine precursor, or may be bonded via a suitable bonding group.

Examples of the side chain B include those represented by the following formulas (b-1) to (b-3).

In the formula (b-1), R ⁶ represents -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH). Any of ₃ )-, -CON(CH ₃ )-, -N(CH ₃ )CO-, R ⁷ represents a cyclic, unsubstituted or substituted carbon atom with a carbon number of 1 to a carbon number of 20 a group in which any -CH ₂ - of the alkyl group may be substituted by -CF ₂ - or -CH=CH-, and may be substituted for each of the groups which are not listed next to each other; -O -, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, carbon ring, heterocyclic ring. R ⁸ represents -CH ₂ -, -O-, -COO-, -OCO-, -NHCO-, -NH-, -N(CH ₃ )-, -CON(CH ₃ )-, -N(CH ₃ ) Any of CO-, carbon ring or heterocyclic ring, R ⁹ represents a styryl group, a -CR ¹⁰ =CH ₂ group, a carbon ring, a hetero ring or a structure represented by the following formula R9-1 to R9-31, R ¹⁰ represents a hydrogen atom or a methyl group which may be substituted by a fluorine atom.

The aforementioned bonding group represented by R ⁶ in the formula (b-1) can be formed by a usual organic synthesis method, but from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, - NHCO-, -NH-, -CH ₂ O- is preferred.

Specific examples of the carbon ring and the hetero ring in the definition of R ⁷ in the formula (b-1) include the following structures, but are not limited thereto.

Among the above-mentioned bonding groups represented by R ⁸ in the formula (b-1), from the viewpoint of easiness of synthesis, -CH ₂ -, -O-, -COO-, -OCO-, NHCO- -NH-, carbon ring, or heterocyclic ring is preferred. Specific examples of the carbon ring and the hetero ring are the same as those of the carbon ring and the hetero ring defined by R ⁷ .

R ⁹ in the formula (b-1) represents a styryl group, -CR ¹⁰ =CH ₂ , a carbon ring, a heterocyclic ring or a structure represented by the above formula R9-1 to R9-31, and R ¹⁰ represents a hydrogen atom or a fluorine atom. A methyl group substituted by an atom.

It is also preferred from the viewpoint of photoreactivity 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-, it constitutes an acryl group or a methacryl group, and this is also preferable.

The side chain represented by the formula (b-2) is a side chain having both a cinnamino group structure and a methyl propyl fluorenyl structure. In the formula (b-2), R ¹⁰ represents a group selected from the group consisting of -CH ₂ -, -O-, -CONH-, -NHCO-, -COO-, -OCO-, -NH-, -CO-. R ¹¹ is an alkylene group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 1 to a carbon number of 30, and one or a plurality of hydrogen atoms of the alkylene group, the divalent carbon ring or the hetero ring may be fluorine. Substituted by an atom or an organic group. And, R ¹¹ in the below mentioned any of which is not adjacent to each other in the case, -CH ₂ - may be substituted with their group; -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 cinnamyl group, a chalcone group or a coumarin group. R ¹⁴ is a single bond, or an alkylene group, a divalent carbon ring or a heterocyclic ring formed by a carbon number of 1 to a carbon number of 30, or one or more of the alkylene group, the divalent carbon ring or the hetero ring. The hydrogen atom may be substituted by a fluorine atom or an organic group. Further, when R ¹⁴ is a group in which the following groups are not adjacent to each other, -CH ₂ - may be substituted with their groups; -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, -NHCONH-, -CO-. R ¹⁵ represents any photopolymerizable group selected from the group consisting of an acryl group and a methacryl group.

Specific examples of the side chain represented by the formula (b-2) include, for example, the following structures (wherein R represents a hydrogen atom or a methyl group which may be substituted by fluorine).

The formula (b-3) is a side chain which generates a radical by ultraviolet irradiation. In the formula (b-3), Ar ₄ represents an aromatic hydrocarbon group selected from a group consisting of a phenylene group, a naphthylene group, and a phenyl group, which may be substituted by an organic group, and a hydrogen atom may be substituted by a halogen atom. R ₁₆ and R ₁₇ each independently represent an alkyl group having 1 to 10 carbon atoms, an alkoxy group, or a benzyl group or a phenethyl group. When it is an alkyl group or an alkoxy group, R ₁₆ and R _{17 may} form a ring. T ₁ and T _{2 are} each independently a single bond or -O-, -COO-, -OCO-, -NHCO-, -CONH-, -NH-, -CH ₂ O-, -N(CH ₃ )-, - CON(CH ₃ )-, -N(CH ₃ )CO-binding group, S is an alkylene group having 1 to 20 carbon atoms which may be unsubstituted or substituted by a fluorine atom (however, the alkyl group-CH ₂ - or -CF ₂ - may be optionally substituted by -CH=CH-, and any of the groups exemplified below may be substituted for these groups; -O-, -COO-, -OCO-, -NHCO -, -CONH-, -NH-, a divalent carbon ring, a divalent hetero ring), n2 is 0 or 1, and Q represents a structure selected from the group below.

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-, or -S-.

Specific examples of the side chain represented by the formula (b-3) include the following structures.

The amount of the side chain B present is only a range which can be accelerated to the liquid crystal response speed in the liquid crystal display element, and is not particularly limited. In order to make the liquid crystal response speed in the liquid crystal display element faster, it is preferable as much as possible without affecting other characteristics.

<polylysine>

A polylysine having a polyimine precursor of a side chain A, which is one of a diamine and a tetracarboxylic anhydride as a raw material, and has a side chain A, or both sides have a side chain A, and the raw material is reacted and obtained. Among them, a method of using a diamine compound having a side chain A is preferred from the viewpoint of easiness of synthesis of a raw material and the like.

The polyamic acid having the side chain A and the side chain B is such that one of the diamine and the tetracarboxylic anhydride of the raw material has a side chain A and a side chain B, or only one side has a side chain A, and the other One has only a side chain B, or either side has a side chain A and a side chain B, and the other side has a side chain A, or either side has a side chain A and a side chain B, and the other side has a side chain B, or both have When the side chain A and the side chain B are obtained, it can be obtained by reacting the raw material. Among them, a method of 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 preferably used.

Hereinafter, the diamine compound having a side chain A will be described, and the diamine compound having a side chain B will be described next.

<Diamine compound having side chain A>

The diamine compound having a side chain A (hereinafter also referred to as diamine A) may have an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the like in the side chain of the diamine. An example of a diamine substituted with a large cyclic substituent. Specifically, a diamine having a side chain represented by the above formula (a) can be given. More specifically, for example, diamines represented by the following formulas (1), (3), (4), and (5) are exemplified, but are not limited thereto. Further, the definitions of l, m, n, and R ¹ to R ⁵ in the formula (1) are the same as those in the above formula (a).

In formula (3) or formula (4), A _{10 is} independently represented as -COO-, -OCO-, -CONH-, -NHCO-, -CH ₂ -, -O-, -CO-, or -NH- A ₁₁ represents a single bond or a phenyl group, and a represents a side chain A, and a' represents a large ring formed by a combination of any structure selected from an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, and a heterocyclic ring. Substitute.

In the formula (5), A ₁₄ is an alkyl group having 3 to 20 carbon atoms which may be substituted by a fluorine atom, A ₁₅ is a 1,4-cyclohexyl group, or a 1,4-phenylene group, and A ₁₆ is an oxygen atom. Or -COO-* (however, the bond with "*" is combined with A ₃ ), A ₁₇ is an oxygen atom, or -COO-* (but with a bond of "*" and (CH ₂ )a ₂ combined). Further, a ₁ is an integer of 0 or 1, and 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 amine groups (-NH ₂ ) in the formula (1) is not limited. Specifically, the second and third positions, the second and fourth positions, the second and fifth positions, the second and sixth positions, the third and fourth positions, and the third and fifth positions on the benzene ring may be mentioned with respect to the side chain bonding group. . Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the second, fourth, second, and fifth positions, or the third and fifth positions are preferred. In view of the easiness in synthesizing the diamine compound, the second, fourth or third and fifth positions are preferred.

The specific structure of the formula (1) is exemplified by the following formula [A-1] to the formula [A-24], but is not limited thereto.

In the formula [A-1] to the formula [A-5], each of A _{1 is} independently an alkyl group having 2 or more and 24 or less carbon atoms or a fluorine-containing alkyl group.

In the formula [A-6] and the formula [A-7], each of A _{2 is} independently -O-, -OCH ₂ - , -CH ₂ O-, -COOCH ₂ -, or -CH ₂ OCO-, and each of A ₃ An alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group independently having a carbon number of 1 or more and 22 or less.

In the formula [A-8]~[A-10], A _{4 is} independently -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, or -CH ₂ -, and A _{5 are} each 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.

In the formula [A-11] and the formula [A-12], A _{6 is} independently represented by -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH. ₂ O-, -OCH ₂ -, -CH ₂ -, -O-, or -NH-, A ₇ is a fluorine group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a methyl group, an acetamidine group Base, ethoxylated, or hydroxy.

In the formula [A-13] and the formula [A-14], A _{8 is} independently represented by an alkyl group having 3 or more and 12 or less carbon atoms, and the cis-trans isomerism of 1,4-cyclopentane is each trans-isomeric. Structure.

In the formula [A-15] and the formula [A-16], each of A _{9 is} independently represented by an alkyl group having 3 or more and 12 or less carbon atoms, and the cis-trans isomerism of 1,4-cyclopentane is each trans-isomeric. Structure.

Specific examples of the diamine represented by the formula (3) include the following formula [A-25] to the formula [A-30] (A ₁₂ represents -COO-, -OCO-, -CONH-, -NHCO-). And -CH ₂ -, -O-, -CO-, or -NH-, and A ₁₃ represents a diamine represented by an alkyl group having 1 or more and 22 or less carbon atoms or a fluorine-containing alkyl group), but is not limited thereto.

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

Among them, from the viewpoints of the ability to make the liquid crystal perpendicularly aligned 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 preferred.

The above diamine compound can be blended as a liquid crystal alignment when used as a liquid crystal alignment film Characteristics such as properties, pretilt angles, voltage holding characteristics, and accumulated charges can be used in one type or in a mixture of two or more types.

In the 100% by mole of the synthetic diamine component of the polyamic acid having the side chain A, the diamine A is from 5 to 70 mol%, preferably from 10 to 50 mol%, preferably from 20 to 50. Moer%.

<Diamine compound having side chain B>

Examples of the diamine compound having a side chain B (hereinafter also referred to as diamine B) include a vinyl group, an acrylic group, a methacryl group, a decyl group, a cinnamyl group, and a chalcone in the side chain of the diamine. A diamine which is a photocrosslinking group such as a keto group, a coumarin group, a maleidino group or a fluorenyl group, or a diamine having a specific structure which generates a radical by ultraviolet irradiation. Specific examples thereof include diamines having a side chain represented by the above formulas (b-1) to (b-3). Specific examples include the diamines 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 above formula (b-1)). , but not limited to this.

Formula (2) in the two group (-NH ₂₎ of the bonding position is not limited. Specifically, the second and third positions, the second and fourth positions, the second and fifth positions, the second and sixth positions, the third and fourth positions, and the third and fifth positions on the benzene ring may be mentioned. position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, the second, fourth, second, and fifth positions, or the third and fifth positions are preferred. Further, it is preferable to use the second or fourth position or the third and fifth positions in consideration of the easiness in synthesizing the diamine compound.

Specific examples thereof include the following compounds, but are not limited thereto.

Wherein X independently represents a bonding group selected from the group consisting of -C-, -O-, -NHCO-, -CONH-, -COO-, -OCO-, -NH-, and l, m, and n each independently represent 0 to 20 An integer, k represents an integer from 1 to 20, and R represents a hydrogen atom or a methyl group.

When the diamine compound is blended as a liquid crystal alignment film, the liquid crystal alignment property, the pretilt angle, the voltage holding property, the charge accumulation property, and the like, and the liquid crystal response speed in the case of a liquid crystal display element can be used in one type or in a mixture of two or more types.

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

<Other diamine compounds>

The polyamine acid used in the present invention may be used as a diamine component in combination with other diamine compounds other than diamine A and diamine B without impairing the effects of the present invention. The specific example is shown below.

P-phenylenediamine, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, m-phenylene Amine, 2,4-dimethyl-m-phenylenediamine, 2,5-diaminotoluene, 2,6-diaminotoluene, 2,5-diaminophenol, 2,4-di Aminophenol, 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'-diamino Biphenyl, 3,3'-dihydroxy-4,4'-diaminobiphenyl, 3,3'-dicarboxy-4,4'-diaminobiphenyl, 3,3'-di Fluorin-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'-di Aminodiphenylmethane, 3,4'-diaminodiphenylmethane, 2,2'-diaminodiphenylmethane, 2,3'-diaminodiphenylmethane, 4,4' -diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 2, 2'-Diaminodiphenyl ether, 2,3'-diaminodiphenyl ether, 4,4'-sulfonyldiphenylamine, 3,3'-sulfonyldiphenylamine, bis(4- Aminophenyl)decane, bis(3-amine Phenyl)decane, dimethyl-bis(4-aminophenyl)decane, dimethyl-bis(3-aminophenyl)decane, 4,4'-thiodiphenylamine, 3,3'-sulfur Diphenylamine, 4,4'-diaminodiphenylamine, 3,3'-diaminodiphenylamine, 3,4'-diaminodiphenylamine, 2,2'-diamino Diphenylamine, 2,3'-diaminodiphenylamine, N-methyl(4,4'-diaminodiphenyl)amine, N-methyl (3,3'-diamino Diphenyl)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'-diaminodiphenyl Ketone, 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-amino group Phenyl)propane, 1,3-bis(3-aminophenyl)propane, 1,4-bis(4-aminophenyl)butane, 1,4-bis(3-aminobenzene) Butane, bis(3,5-diethyl-4-aminophenyl)methane, 1,4-bis(4-aminophenoxy)benzene, 1,3-bis(4-aminobenzene) Oxy)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(methyl)diphenylamine, 4,4'-[1,3- Phenyl bis(methyl)diphenylamine, 3,4'-[1,4-phenylenebis(methyl)diphenylamine, 3,4'-[1,3-phenylene double (methyl) diphenylamine, 3,3'-[1,4-phenylenebis(methyl)diphenylamine, 3,3'-[1,3-phenylene bis(methyl) )]diphenylamine, 1,4-phenylene bis[(4-aminophenyl)methanone], 1,4-phenylene bis[(3-amino) Phenyl)methanone], 1,3-phenylene bis[(4-aminophenyl)methanone], 1,3-phenylphenylbis[(3-aminophenyl)methanone], 1 , 4-phenylphenyl bis(4-aminobenzoate), 1,4-phenylphenylbis(3-aminobenzoate), 1,3-phenylene bis(4-amine Benzoate), 1,3-phenylene bis(3-aminobenzoate), bis(4-aminophenyl)ethylene terephthalate, bis(3-aminobenzene) Ethylene 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-Exophenyl)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)m-xylyleneamine, N,N'-bis(3-aminophenyl)m-xylyleneamine, 9,10-bis(4-aminophenyl)anthracene, 4, 4'-bis(4-aminophenoxy)diphenylanthracene, 2,2'-bis[4-(4-aminophenoxy)phenyl]propane, 2,2'-bis[4- (4-amino group Oxy)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-aminophenoxyl) Methane, 1,2-bis(4-aminophenoxy)ethane, 1,3-bis(4-aminophenoxy)propane, 1,3-bis(3-aminophenoxy) Propane, 1,4-bis(4-aminophenoxy)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)decane, 1,9-bis(3-aminophenoxy)decane, 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-bis(3-aminophenoxy) An alicyclic diamine such as dodecane or the like, an alicyclic diamine such as bis(4-aminocyclohexyl)methane or bis(4-amino-3-methylcyclohexyl)methane, or a 1,3-diamine group Propane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctyl An aliphatic diamine such as an alkane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane or 1,12-diaminododecane.

When the other diamine compound is used as a liquid crystal alignment film, the liquid crystal alignment property, the pretilt angle, the voltage holding property, and the charge accumulation property can be used in one type or in a mixture of two or more types.

<tetracarboxylic dianhydride>

The tetracarboxylic dianhydride which reacts with the above diamine component in the synthesis of the polyamic acid used in the present invention is not particularly limited. Specific examples of this can be mentioned below.

From pyromellitic acid, 2,3,6,7-naphthalenetetracarboxylic acid, 1,2,5,6-naphthalenetetracarboxylic acid, 1,4,5,8-naphthalenetetracarboxylic acid, 2,3,6, 7-nonyltetracarboxylic acid, 1,2,5,6-nonane tetracarboxylic acid 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)anthracene, bis(3,4-dicarboxyphenyl)methane, 2,2-dual (3 , 4-dicarboxyphenyl)propane, 1,1,1,3,3,3-hexafluoro-2,2-bis(3,4-dicarboxyphenyl)propane, bis(3,4-dicarboxyl Phenyl) dimethyl decane, bis(3,4-dicarboxyphenyl)diphenyl decane, 2,3,4,5-pyridinetetracarboxylic acid, 2,6-bis(3,4-dicarboxybenzene Pyridine, 3,3',4,4'-diphenylphosphonium tetracarboxylic acid, 3,4,9,10-decanetetracarboxylic acid, 1,3-diphenyl-1,2,3,4 - cyclobutane tetracarboxylic acid, oxydiphthalic acid tetracarboxylic 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-tetrahydrofuran tetracarboxylic acid, 3,4-dicarboxy-1-cyclohexyl succinic acid, 2,3,5-tricarboxycyclopentyl acetic acid, 3,4-dicarboxy-1, 2,3,4-tetrahydro-1-naphthalene succinic acid, hydrazine [3,3,0] Alkane-2,4,6,8-tetracarboxylic acid, bicyclo[4,3,0]indole-2,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-2 ,4,7,9-tetracarboxylic acid, bicyclo[4,4,0]nonane-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-dioxotetrahydrofuran-3-yl)-1,2,3, 4-tetraqing hydrogen naphthalene-1,2-dicarboxylic acid, bicyclo[2,2,2]oct-7-ene-2,3,5,6-tetracarboxylic acid, 5-(2,5-di Oxotetrahydrofuran)-3-methyl-3-cyclohexane-1,2-dicarboxylic acid, tetracyclo[6,2,1,1,0,2,7]dodeca-4,5,9 , tetracarboxylic acid obtained from 10-tetracarboxylic acid, 3,5,6-tricarboxynorbornane-2:3,5:6 dicarboxylic acid, 1,2,4,5-cyclohexanetetracarboxylic acid or the like Diacid anhydride.

When the tetracarboxylic dianhydride is blended as a liquid crystal alignment film, the liquid crystal alignment property, the voltage retention property, and the charge accumulation property can be used in one type or in combination of two or more types.

<Synthesis of polyaminic acid>

A known synthetic method can be used when the polyamine acid is obtained by the reaction of a diamine component and a tetracarboxylic dianhydride. A method of reacting a diamine component with a tetracarboxylic dianhydride in an organic solvent is generally employed. The reaction of the diamine component with the tetracarboxylic dianhydride is relatively easy to carry out in an organic solvent, and it is advantageous because no by-products are generated.

The organic solvent used in the above reaction is not particularly limited as long as it can dissolve only the produced polyamic acid. Further, even if it is an organic solvent in which polyamic acid is not dissolved, it can be used in the above solvent in the range in which the produced polyamic acid is not precipitated. Further, since the water in the organic solvent hinders the polymerization reaction and becomes a cause of the polyamic acid produced by the hydrolysis, it is preferred to use a dehydrated organic solvent.

Specific examples of the organic solvent are given below.

N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, N-methylformamide, N-methyl-2-pyrrolidine Ketone, N-ethyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxy-N,N-dimethylpropane decylamine, N-methyl caprolactam, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol , dipentene, ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl Ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbene Alcohol, 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, propylene glycol monomethyl ether acetate, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, diethyl Glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, 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, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, dioxins Alkane, n-hexane, n-pentane , n-octane, diethyl ether, cyclohexanone, ethyl ecarbonate, propyl carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, acetic acid Propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3- Ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl- 2-pentanone, 2-ethyl-1-hexanol. These organic solvents may be used singly 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 directly added or dispersed or a method of adding a solution of an organic solvent, and a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride component is dispersed or dissolved in an organic solvent, and a tetracarboxylic dianhydride component and a diamine component are alternately added. As the method and the like, any of these methods can be used. In addition, when the diamine component or the tetracarboxylic dianhydride component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed beforehand, or the reaction may be carried out in sequence, and further, a low molecular weight body which can be reacted separately may be used. After the mixing reaction, a high molecular weight body is obtained.

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

In the above polymerization reaction, the total number of moles of the diamine component may be any value selected by mixing the total molar ratio of the tetracarboxylic dianhydride component with the molecular weight of the obtained polyamic acid. As with the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the polylysine formed. And the preferred range is from 0.8 to 1.2.

The method for synthesizing the polyaminic acid used in the present invention is not limited to the above method, and is the same as the general method for synthesizing polyamic acid, and the tetracarboxylic acid or the corresponding structure is used instead of the above tetracarboxylic dianhydride. A tetracarboxylic acid derivative such as a tetracarboxylic acid dihalide can be reacted by a known method to obtain a corresponding polyamic acid.

<polyimine]

As the above-mentioned method for imidating polylysine by hydrazine to polyimine The method includes a ruthenium imidization in which a solution of a poly-proline acid is directly heated and a catalyst is added to a solution of a poly-proline.

For the polyimine used in the present invention, the ruthenium imidization rate from polyphthalic acid to polyimine is not necessarily 100%.

The temperature at which the polyaminic acid is thermally imidized in the solution is from 100 ° C to 400 ° C, preferably from 120 ° C to 250 ° C, and the water formed by the hydrazine imidization reaction is excluded from the system. It is better to perform on one side.

The ruthenium imidization of the polyptanic acid is carried out by adding a basic catalyst and an acid anhydride to the solution of the polyamic acid, and stirring can be carried out at -20 to 250 ° C, preferably at 0 to 180 ° C. The amount of the alkaline catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the prolyl group. 30 moles. The basic catalyst may, for example, be pyridine, triethylamine, trimethylamine, tributylamine or trioctylamine. Among them, pyridine is also preferred because it has moderate alkalinity for reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic anhydride. Among them, the use of acetic anhydride also makes it easier to purify the reaction after completion of the reaction. The imidization ratio of the imidization via the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, and the reaction time.

When the produced polyamic acid or polyimine is recovered from a reaction solution of polyglycolic acid or polyimine, only the reaction solution is poured into a weak solvent to precipitate. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated in a weak solvent is filtered and recovered, and then subjected to normal temperature or under normal pressure or reduced pressure. The person is heated to dry. Further, the polymer recovered by precipitation is redissolved in an organic solvent, and the operation of re-precipitation recovery is repeated 2 to 10 times to reduce impurities in the polymer. Examples of the weak solvent in this case include alcohols, ketones, and hydrocarbons. When three or more kinds of weak solvents selected from the group are used, the purification efficiency can be further improved, which is preferable.

<Liquid alignment agent> The liquid crystal alignment agent of the present invention has the above-mentioned [I] polymerizable compound; and the above [II] at least one polymer selected from the group consisting of polyimine and polyimine precursors, except for the components [I] and [II] In addition, a resin component for forming a resin film may be provided. The content of the total resin component is from 1% by mass to 20% by mass based on 100% by mass of the liquid crystal alignment agent, preferably from 3% by mass to 15% by mass, preferably from 3 to 10% by mass.

In the liquid crystal alignment agent used in the present invention, the above resin component is a polyimide or a polyimide precursor having a side chain A, or may be a polyimine or a group having a side chain A and a side chain B. The quinone imine precursor may also be a mixture thereof, and may be mixed with other polymers. In this case, the content of the other polymer in the resin component is preferably 0.5% by mass to 15% by mass, preferably 1% by mass to 10% by mass.

Examples of the other polymer include a polyimine or a polyimide precursor having no side chain B, and a polyimine or a polyimide precursor having no side chain A and side chain B. Etc., but not limited to this.

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

<solvent>

The organic solvent used in the liquid crystal alignment agent of the present invention is not particularly limited as long as it can dissolve only the organic solvent of the above resin component. The organic solvent may be one type of solvent or a mixed solvent of two or more types. Specific examples of the organic solvent include the organic solvents exemplified in the above polyamic acid synthesis. Among them, N-methyl-2-pyrrolidone, γ-butyrolactone, N-ethyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, 3-methoxyl -N,N-dimethylpropane decylamine is preferred from the viewpoint of solubility of the resin component.

Further, since the solvent shown below can improve the uniformity or smoothness of the coating film, it can be preferably used in a solvent having a high solubility in a resin component.

Examples thereof include isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, butyl cellosolve acetate, and ethyl group. Cellulolytic acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, B 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 Alcohol monoacetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, propylene glycol monomethyl ether Acid ester, 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, pentyl acetate, butyl butyrate Ester, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, diether ether, n-hexane, n-pentane, n-octane, diethyl ether, methyl lactate, Ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, 3-ethoxyl Methyl ethyl propionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, 3-methoxypropionic acid Butyl ester, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1-butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoethyl Acid ester, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol-1-monoethyl ether-2-acetate, dipropylene glycol, 2-(2- Propoxy) propanol, methyl lactate, ethyl lactate, n- propyl, n- butyl lactate, isopentyl lactate, 2-ethyl-hexyl alcohol and the like. These solvents can be mixed in a plurality of types. When these solvents are used, it is preferably from 5 to 80% by mass based on the total amount of the solvent contained in the liquid crystal alignment agent, and preferably from 20 to 60% by mass.

The liquid crystal alignment agent may contain components other than the above. In this example, a compound which improves the film thickness uniformity or surface smoothness when applied to a liquid crystal alignment agent, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate can be mentioned.

Examples of the compound for improving film thickness uniformity or surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a non-ionizing agent. Subsystem surfactants, etc. More specifically, for example, EFTOPEF301, EF303, EF352 (made by Tochem Products), Megafac F171, F173, R-30 (made by Dainippon Ink Co., Ltd.), FLUORADFC430, FC431 (manufactured by Sumitomo 3M), Asahi Guard AG710, SurflonS- 382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). When the surfactant is used, the use ratio is preferably 0.01 to 2 parts by mass, preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include a compound containing a functional decane or a compound containing an epoxy group. Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-urea Propyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyltri Ethoxy decane, N-triethoxymercaptopropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxyindolyl-1,4, 7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazaindolyl acetate, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-aminopropyl Triethoxy decane, N-phenyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltriethoxyhydrazine Alkane, N-bis(oxyethylene)-3-aminopropyltrimethoxydecane, N-bis(oxyethylene)-3-aminopropyltriethoxydecane, ethylene glycol diglycidyl ether, Polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol Diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetraglycidyl-2,4-hexanediol, N,N,N',N',-tetraglycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N, N',N',-tetraglycidyl-4,4'-diaminodiphenylmethane, 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane, 3 -(N,N-diglycidyl)aminopropyltrimethoxydecane, and the like. Further, in order to further improve the friction resistance of the resin of the present invention, 2,2'-bis(4-hydroxy-3,5-dihydroxymethylphenyl)propane or tetrakis(methoxymethyl)bisphenol may be added. Phenolic compound. When these compounds are used, it is preferably 0.1 to 30 parts by mass, preferably 1 to 20 parts by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment agent.

In the liquid crystal alignment agent to be used in the present invention, a dielectric body or the like for changing the electrical properties such as dielectric constant or conductivity of the liquid crystal alignment film may be added in addition to the above, without impairing the effects of the present invention. Conductive material.

<Liquid alignment film>

For example, after applying the liquid crystal alignment agent of the present invention to a substrate, the cured film obtained by drying and baking may be used as a liquid crystal alignment film as it is. Further, rubbing the cured film, irradiating polarized light, or light of a specific wavelength, etc. Alternatively, treatment with an ion beam or the like may be performed to apply UV to a liquid crystal display element after the liquid crystal is filled as an alignment film for SC-PVA.

In this case, the substrate to be used is not particularly limited as long as it has high transparency, and a glass plate, a polycarbonate, a poly(meth)acrylate, a polyether oxime, a polyallyl ester, or a polyamine group can be used. Formate, polyfluorene, polyether, polyether ketone, trimethylpentene, polyolefin, polyethylene terephthalate, (meth)acrylonitrile, triacetyl cellulose, diethyl hydrazine Cellulose, acetate butyrate cellulose, and the like. Further, when a substrate formed of an ITO (Indium Tin Oxide) electrode or the like to be liquid crystal driven is used, it is preferable from the viewpoint of simplification of the process. Further, in the reflective liquid crystal display device, an opaque material such as a germanium wafer can be used as the single-sided substrate, and a material such as aluminum or the like can be used as the electrode.

The coating method of the liquid crystal alignment agent is not particularly limited, and examples thereof include a printing method such as screen printing, offset printing, and flexographic printing, an inkjet method, a spray method, a roll coating method or dipping, a roll coater, and a slit coating. Machine, rotator, etc. From the production level, the transfer printing method is widely used in the industry, and is also applicable to the present invention.

The coating film formed by coating the liquid crystal alignment agent by the above method can be cured to form a cured film. Although the drying step after the application of the liquid crystal alignment agent is an unnecessary step, the drying step is preferably carried out when the time from the application to the baking is not constant depending on the substrate, or when the baking is not performed immediately after the application. This drying is only required to remove the solvent to the extent that the shape of the coating film is not deformed by substrate transfer or the like, and the drying method is not particularly limited. For example, it is preferably 40 ° C to 150 ° C, preferably 60 ° C to 100 ° C. The hot plate is carried out for 0.5 minutes to 30 minutes, more preferably for 1 minute to 5 minutes.

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

Further, 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 Liquid Crystal Alignment Film>

In the liquid crystal display device of the present invention, a liquid crystal alignment film can be formed on a substrate by the above method, and a liquid crystal cell can be produced by a known method. Specific examples of the liquid crystal display device include the above-described liquid crystal alignment layer having the two substrates arranged to face each other, the liquid crystal layer disposed between the substrates, and the liquid crystal alignment agent of the present invention provided between the substrate and the liquid crystal layer. A liquid crystal display element of a vertical alignment type of liquid crystal cells of a liquid crystal alignment film. Specifically, the liquid crystal display element is provided with a liquid crystal cell in which a liquid crystal alignment agent of the present invention is applied onto two substrates and a liquid crystal alignment film is formed by firing, and the liquid crystal alignment film is to be face to face. Two substrates are disposed, and a liquid crystal layer composed of a liquid crystal is sandwiched between the two substrates, that is, a liquid crystal layer is provided in contact with the liquid crystal alignment film, and the liquid crystal alignment film and the liquid crystal are provided. The layer is applied with a voltage and is irradiated with ultraviolet rays. By using the liquid crystal alignment film formed by the liquid crystal alignment agent of the present invention, while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, ultraviolet rays are irradiated to polymerize the polymerizable compound, and the photoreactive side chains of the polymer or When the side chain having the photoreactivity of the polymer reacts with the polymerizable compound, the alignment of the liquid crystal can be more efficiently immobilized, and the liquid crystal display element having a remarkable response speed can be obtained.

The substrate to be used in the liquid crystal display device of the present invention is not particularly limited as long as it is a substrate having high transparency, and is generally a substrate on which a transparent electrode for driving a liquid crystal on a substrate is formed. Specific examples include the same substrates described in the above liquid crystal alignment film. In the liquid crystal display device of the present invention, since the liquid crystal alignment agent of the present invention is used as the liquid crystal alignment agent for forming a liquid crystal alignment film, the liquid crystal alignment agent of the present invention can be used. In the above, for example, a line/slit electrode pattern of 1 to 10 μm is formed, and even if the structure of the opposite substrate is not formed with a slit pattern or a pattern of protrusions, an operation can be performed, and the liquid crystal display element of the structure can be manufactured. The process is simplified and high transmittance is obtained.

Further, for a high-function element such as a TFT type element, an element such as a triode is formed between an electrode to be driven by a liquid crystal and a substrate.

In the case of the transmissive liquid crystal display device, the substrate is generally used. However, in the reflective liquid crystal display device, an opaque substrate such as a germanium wafer can be used as the substrate on one side. At this time, a material such as aluminum which reflects light can be used in the electrode formed on the substrate.

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

The liquid crystal material constituting the liquid crystal layer of the liquid crystal display device of the present invention is not particularly limited, and a liquid crystal material used in the past vertical alignment method can be used. For example, a negative liquid crystal such as MLC-6608 or MLC-6609 manufactured by Merck can be used.

A well-known method is mentioned as a method of holding this liquid crystal layer between two board|substrate. For example, a pair of substrates for forming a liquid crystal alignment film may be prepared, and a spacer such as beads may be dispersed on the liquid crystal alignment film of one of the substrates, and the side surface of the liquid crystal alignment film may be formed inside, and the other substrate may be bonded to the liquid crystal. The method of sealing. Further, a pair of substrates for forming a liquid crystal alignment film is prepared, and a spacer such as a bead is dispersed on a liquid crystal alignment film of one of the substrates, and then a liquid crystal is dropped thereon, and then a side surface on which the liquid crystal alignment film is formed is formed inside, and the other substrate is bonded to be sealed. The liquid crystal unit can also be fabricated by the method. The spacer thickness at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

The step of producing a liquid crystal cell by applying a voltage to the liquid crystal alignment film and the liquid crystal layer while irradiating the ultraviolet ray is, for example, applying a voltage between the electrodes provided on the substrate to apply an electric field to the liquid crystal alignment film and the liquid crystal layer, and maintaining the electric field. A method of irradiating ultraviolet rays under an electric field. The voltage between the electrodes to be applied is, for example, 5 to 30 Vp-p, and preferably 5 to 20 Vp-p. The amount of ultraviolet radiation, for example, 1 ~ 60J / cm ^2, at 40J / cm ² or less is preferable, more preferably ² or less 20J / cm. When the amount of ultraviolet irradiation is small, the reliability of the destruction of the liquid crystal or the member constituting the liquid crystal display element can be suppressed, and the production efficiency can be improved after the ultraviolet irradiation is reduced, which is preferable.

When the ultraviolet ray is irradiated to the liquid crystal alignment film and the liquid crystal layer, the polymerizable compound reacts to form a polymer, and the polymer can store the liquid crystal molecules in an oblique direction. Therefore, the obtained liquid crystal display element is obtained. The response speed is fast and variable. Further, when ultraviolet rays are applied while applying a voltage to the liquid crystal alignment film and the liquid crystal layer, side chains having photoreactivity of the polymer or side chains having photoreactivity of the polymer react with the polymerizable compound. The response speed of the resulting liquid crystal display element can be accelerated.

In addition, the liquid crystal alignment agent is useful not only as a liquid crystal alignment agent used for producing a liquid crystal display element of a vertical alignment type such as a PSA liquid crystal display or an SC-PVA liquid crystal display, but also a liquid crystal produced by rubbing treatment or photoalignment processing. The use of the alignment film is also good.

The invention is specifically described by way of examples, but the invention is not limited thereto.

[Examples]

The abbreviations used in the preparation of the liquid crystal alignment agent described below are as follows.

(acid dianhydride)

BODA: bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride.

CBDA: 1,2,3,4-cyclobutane tetracarboxylic dianhydride.

PMDA: pyromellitic dianhydride

TCA: 2,3,5-tricarboxycyclopentyl acetic acid-1,4,2,3-dianhydride

(diamine)

The vertical alignment diamine represented by the following formula DA-1 is synthesized by the method described in Patent No. 4085206.

The vertical alignment diamine represented by the following formula DA-2 is synthesized by the method described in Patent No. 4,463,373.

The vertical alignment diamine represented by the following formula DA-3 is synthesized by the method described in Patent No. 5,273,035.

The vertical alignment diamine represented by the following formula DA-4 is manufactured by Tokyo Chemical Industry Co., Ltd.

The vertical alignment diamine represented by the following formula DA-5 is synthesized by the method described in WO2009/093704.

The photoreactive diamine represented by the following formula DA-6 is prepared as shown below.

The diamine represented by the following formula DA-7 is manufactured by Wako Pure Chemical Industries Co., Ltd.

The radical-generating diamine represented by the following formula DA-8 was prepared as shown below.

The diamine represented by the following formula DA-9 can be prepared by the method described in "(Synthesis of Raw Material Synthesis Example 3) DA-9" described later.

<solvent>

NMP: N-methyl-2-pyrrolidone

BCS: butyl cellosolve

THF: tetrahydrofuran

DMF: N,N-dimethylformamide

<additive>

3AMP: 3-pyridylmethylamine

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited thereto.

<Polymerizable compound>

A polymerizable compound represented by the following formulas RM1 to RM12 and RM13.

Further, the molecular weight measurement conditions of the polyimine are as follows.

Device: a room temperature gel permeation chromatography (GPC) device (SSC-7200) manufactured by Senshu Scientific Co., Ltd.

Column: Shodex pipe column (KD-803, KD-805),

Column temperature: 50 ° C,

Dissolution: N,N'-dimethylformamide (as an additive, lithium bromide-hydrate (LiBr.H ₂ O) 30 mmol/L, phosphoric acid. anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) 10ml/L),

Flow rate: 1.0ml/min,

Standard sample for calibration curve preparation: TSK standard polyethylene oxide (molecular weight: about 9,000, 150,000, 100,000, 30,000) manufactured by Tosoh Co., Ltd., and polyethylene glycol manufactured by Polymer Laboratory (molecular weight: about 12,000, 4,000, 1,000) ).

Further, the ruthenium imidization ratio of polyimine was measured as shown below. 20 mg of polyimine powder was placed in an NMR sample tube (NMR sample tube standard manufactured by Kusano Scientific Co., Ltd. 5) 1.0 ml of dihydrogenated dimethyl hydrazine (DMSO-d ₆ , 0.05% TMS mixture) was added, and it was completely dissolved by ultrasonic waves. This solution was measured for proton NMR at 500 MHz by a NMR measuring instrument (JNW-ECA500) manufactured by JEOL Ltd. The ruthenium imidization rate is determined by using protons of a structure that has not changed before and after imidization as a reference proton, and the absorption peak integral value of the proton is used and the NH group derived from proline is present in the vicinity of 9.5 to 10.0 ppm. The proton absorption peak integral value is obtained by the following formula. In the following formula, x represents the integral value of the proton absorption peak derived from the NH group of proline, y represents the integral value of the absorption peak of the reference proton, and α represents the case of polyproline (the imidization ratio is 0%). The ratio of the number of reference protons in the proton of one NH group of proline.

醯 imidization rate (%) = (1-α.x/y) × 100

<Synthesis of diamine and polymerizable compound>

The products described in the following Synthesis Examples 1 to 12 were identified by ¹ H-NMR analysis (analysis conditions are as follows).

Device: Varian NMR System 400 NB (400MHz)

Determination of solvent: CDCl ₃ , DMSO-d ₆

Reference material: tetramethyl decane (TMS) (δ 0.0ppm for ¹ H)

(Synthesis of Raw Material Synthesis 1-1) Synthesis of DA-6 Precursor DA-6-1

21.2 g of 2-[4-(2-hydroxycarbonylvinyl)phenyl]-hexyl methacrylate, 300 mL of tetrahydrofuran, 2-(2,4-dinitrophenyl) was added to a 500 mL four-neck flask. 13.6 g of ethanol, 18.4 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride (EDC), and 0.8 g of 4-dimethylaminopyridine (DMAP). Stir at room temperature. After the completion of the reaction, the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer, and then dried and filtered, and then filtered, and the solvent was distilled off using a rotary evaporator, and the residue was washed with isopropyl alcohol and dried. 15.9 g of the objective DA-6-1 (yellow-white solid) was obtained (yield: 47%).

(Synthesis of Raw Material Synthesis 1-2) Synthesis of DA-6

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 placed in a 500 mL four-necked flask, and stirred while heating at 60 °C. After the reaction was completed, the reduced iron was filtered, and the organic layer was extracted with ethyl acetate. Anhydrous magnesium sulfate was added to the organic layer and dried to dryness, and anhydrous magnesium sulfate was filtered. The obtained filtrate was subjected to solvent distillation using a rotary evaporator. The residue was washed with isopropyl alcohol and dried to give 13.4 g of the object DA-6 (yellow white solid) (yield 95%). The results of the measurement of the obtained solid by ¹ H-NMR are shown below. From the results, it was confirmed that the obtained solid was the intended DA-6.

¹ H NMR (400MHz, [D _6] -DMSO): δ 7.64-7.66 (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)

(Synthesis of Raw Material Synthesis Example 2) Synthesis of DA-8

Synthesis of 1-(4-(2,4-dinitrophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylacetone

20.0-dinitrofluorobenzene 100.0 g ([Mw: 186.10 g/mol], 0.538 mol), 2-hydroxy-4'-(2-) was placed in a 2 L four-necked flask equipped with a stirrer and a nitrogen introduction tube. Hydroxyethoxy)-2-methylpropiophenone 120.6 g ([Mw: 224.25 g/mol], 0.538 mol), triethylamine 81.7 g ([Mw: 101.19 g/mol], 0.807 mol), THF 1000 g It was allowed to reflux for 24 hours. After the completion of the reaction, the mixture was concentrated on a rotary evaporator, ethyl acetate was added, and the mixture was washed with pure water and physiological saline several times, and dried over anhydrous magnesium sulfate.

After filtering anhydrous magnesium sulfate, it was taken out, concentrated by a rotary evaporator, and recrystallized by ethyl acetate and n-hexane to obtain 157.0 g ([Mw: 390.34 g/mol], 0.402 mol, yield: 75% of milky white individual. ). NMR spectroscopy confirmed that hydrogen atoms in the molecule ⁽¹ H-NMR spectroscopy). The measurement data is as follows.

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 to 7.31 (Ar: 1H ) 7.00 to 6.96 (Ar: 2H ), 4.65~4.63(-CH ₂ -: 2H ), 4.52~4.49(-CH ₂ -: 2H ), 4.16(-OH: 1H ), 1.66~1.60(-CH ₃ ×2, 6H )Total:18H

Synthesis of 1-(4-(2,4-diaminophenoxy)ethoxy)phenyl)-2-hydroxy-2-methylacetone (DA-8)

To a 1 L four-necked flask, 100.0 g ([Mw: 390.34 g/mol], 0.256 mol) of the dinitrobenzene derivative obtained in Step 1, and 10.0 g of iron-doped platinum carbon (3 wt% manufactured by Evonic Co., Ltd.) and THF were added. 500 ml, sufficiently degassed under reduced pressure and hydrogen substitution, and reacted at room temperature for 24 hours.

After the completion of the reaction, platinum carbon was removed by a membrane filter made of PTFE, and the filtrate was removed by a rotary evaporator to precipitate a solid. The obtained solid was washed with isopropyl alcohol, and dried under reduced pressure to give 72.7 g ([Mw: 330.38 g/mol], 0.220 mol yield: 86%) of the desired compound. ^{The 1} H-NMR spectrum measurement data is as follows.

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 ), 1.64~1.63(-CH ₃ ×2: 6H )Total:22H

(Synthesis of Raw Material Synthesis Example 3) Synthesis of DA-9

<Synthesis of DA-9-1>

In a 1000 mL four-necked flask, 600 g of THF, 120 g (310 mmol, 1.0 eq) of cholesterol and 33.3 g (329 mmol, 1.1 eq) of triethylamine were added, and 39.2-dinitrobenzoguanidine chloride (69.2 g (300 mmol) was added. ) Added over 1 hour. After the addition, after stirring overnight at room temperature, reprecipitation by water was carried out. The obtained solid was recrystallized from IPA and ethyl acetate to give 179 g (yield: 100%) of crude product of DA-9-1.

¹ H-NMR (CDCl ₃ , δ ppm): 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, 750 g of THF and 750 g of pure water were charged. Among them, 146 g (251 mmol) of DA-9-1 and 284 g (1497 mmol, 6.0 eq) of tin chloride were stirred at 70 ° C overnight. After the completion of the reaction, neutralization was carried out, and the precipitated tin was removed by filtration. Thereafter, it was recrystallized by liquid separation and IPA to obtain 76.3 g of DA-9 (yield: 58%).

¹ H-NMR (CDCl ₃ , δ ppm): 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>

In a 1 L four-necked flask equipped with a magnetic stirrer, THF 350 g and water 117 g were charged with 4-bromo-2-fluorophenol 58.3 g (305 mmol) and 4-(4,4,5,5-tetramethyl-1). , 3,2-dioxaborolan-2-yl)phenol 67.2 g (1.0 eq), potassium carbonate 84.8 g (2.0 eq), tris( o -toluene)phosphine 7.42 g (8 mol%), after nitrogen substitution 10.9 g (5 mol%) of bis(triphenylphosphinyl)palladium(II) chloride was added, and the reaction was carried out at 65 ° C for 15 hours.

After the completion of the reaction, the THF was concentrated under reduced pressure and diluted with ethyl acetate (466 g), and then, 268 g of a 3.0 M aqueous solution of HCl was added thereto, and insolubles such as Pd were removed by filtration, and the flask or the filtrate was washed with 233 g of ethyl acetate. Then, 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. After dehydration treatment with magnesium sulfate, activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added 2.92 g. The mixture was stirred at room temperature for about 30 minutes, and dried by filtration to give a crude material. The crude product was washed twice with 292 g of toluene at room temperature, and then dried by filtration to give RM1-A 42.0 g (yield: 67%, s.

¹ H-NMR (400 MHz) 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, 1 H).

<Synthesis of RM1-B>

In a 200 ml four-necked flask equipped with a magnetic stirrer, 80 ml of acetone 5.00 g (24.5 mmol) of the compound (RM1-A) obtained above and 12.0 g (2.2 eq) of 2-(4-bromobutyl)-1,3-difuran, and 13.8 g (4.0 eq) of potassium carbonate were added. The reaction was carried out at 60 ° C for 24 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, which were dried by filtration to obtain RM1-B 10.4 g (yield: 92%).

¹ H-NMR (400 MHz) 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 = 8.8 Hz, 2H).

<Synthesis of RM1>

A 100 ml four-necked flask equipped with a magnetic stirrer was placed in 40 ml of THF, and 2.90 g (6.30 mmol) of the compound (RM1-B) obtained above and 2.5 g (2.4 eq) of 2-(bromomethyl)acrylic acid were added and chlorinated. Tin (anhydrous) 2.8 g (2.4 eq), 12 ml of a 10% aqueous HCl solution was added, and the reaction was carried out at 70 ° C for 20 hours. Thereafter, the reaction solution was poured into pure water to precipitate crystals, which were dried by filtration to obtain a crude product. The obtained crude product was recrystallized from THF / EtOH to give RM1 2.2 g (yield: 69%).

¹ H-NMR (400 MHz) 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 = 8.8 Hz, 2H).

<Synthesis Example 2 - Synthesis of RM2 ->

<Synthesis of RM2-A>

Into a 1 L four-necked flask equipped with a magnetic stirrer, 281 g of THF was charged with 70.2 g (539 mmol) of 2-hydroxyethyl methacrylate and 76.4 g (1.4 eq) of triethylamine, and added dropwise with THF 35.1 under ice-cooling stirring. After 74.6 g (1.2 eq) of methanesulfonyl chloride diluted, it was stirred at room temperature for 2 hours. Thereafter, the salt precipitated from the reaction liquid was filtered, and 0.35 g of dibutylhydroxytoluene was added to the filtrate, followed by concentration and drying. Next, 281 g of ethyl acetate was added to the residue of the concentrate, and after adding 210 g of pure water, the insoluble matter was added, so that the activity was added. Carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd., Japan) 3.5 g, and stirred at room temperature for 30 minutes. Then, this was filtered, and it was confirmed that the insoluble matter was removed, and the aqueous phase was removed. Further, the organic phase was washed twice with 210 g of pure water, dehydrated with magnesium sulfate, and concentrated to dryness to obtain RM2-A 99.0 g (yield: 86%, trait: yellow liquid).

¹ H-NMR (400 MHz) 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, 1 H), 6.15 (m, 1 H).

<Synthesis of RM2-B>

In a 300 ml four-necked flask equipped with a magnetic stirrer, 72.8 g of THF and 31.2 g of pure water, 10.4 g (54.4 mmol) of 4-bromo-2-fluorophenol and 9.68 g of 6-hydroxy-2-naphthalene boronic acid (1.0 g) were charged. Eq), potassium carbonate 15.1 g (2.0 eq), tris( o -toluene)phosphine 1.32 g (8 mol%), after addition of nitrogen, bis(triphenylphosphinyl)palladium(II) chloride 1.91 g (5 mol) %), the reaction was carried out at 65 ° C for 2 hours. Thereafter, the THF was removed by concentration under reduced pressure, and the mixture was diluted with ethyl acetate (104 g), and then, 47.8 g of a 3.0 M aqueous HCl solution was added and stirred. Pd was further removed by filtration, and the filtrate was further washed with 52.0 g of ethyl acetate, and then the aqueous phase was separated. The recovered organic phase was washed three times with 72.8 g of pure water, and dehydrated with magnesium sulfate. After adding 0.52 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.), it was allowed to stand at room temperature for about 1 hour. Stir and filter dry. The crude product was repulped and washed with 72.8 g of toluene, and purified by silica gel column chromatography (ethyl acetate/toluene/hexane (=1/1/2 vol)) to obtain RM2-B 6.47 g. Rate: 49%, trait: white solid).

^{1 H-NMR (400MHz) in} DMSO-d 6: 7.03-7.13ppm (m, 3H), 7.42-7.40ppm (m, 1H), 7.57ppm (dd, J = 13Hz, J = 2.2Hz, 1H), 7.67ppm (dd, J = 8.6Hz, J = 1.8Hz, 1H), 7.72ppm (d, J = 8.4Hz, 1H), 7.80ppm (d, J = 8.4Hz, 1H), 8.01ppm(s, 1H ), 9.78ppm (s, 1H), 9.96ppm (s, 1H)

<Synthesis of RM2>

Into a 200 mL four-necked flask equipped with a magnetic stirrer, 48.6 g of DMF, 6.07 g (23.9 mmol) of the compound (RM2-B) obtained above and a polymerizable side chain (RM2-A) 11.1 g (2.2 eq). Potassium carbonate 9.93 g (3.0 eq) was reacted at 65 ° C for 22 hours under a nitrogen atmosphere.

Then, the reaction solution was diluted with 48.6 g of ethyl acetate, and then 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 three times with 48.6 g of pure water, and the organic phase was subjected to dehydration treatment with magnesium sulfate, followed by concentration and drying. 2,6-di- tert -butyl- p -cresol 12.1 mg was added to the recovered crude product after drying, and 5.77 g of THF was added thereto, and it was completely dissolved by heating at 45 ° C, and 35.8 g of methanol was added to recrystallize at 5.0 ° C. . However, since impurities were confirmed, 4.89 g of THF was added to the recovered solid, and after heating at 45 ° C to completely dissolve, 24.9 g of methanol was added and recrystallized at room temperature to obtain RM2 6.37 g (yield: 56%, Traits: white crystal).

¹ H-NMR (400MHz) in DMSO-d ₆ : 1.89ppm (s, 6H), 4.38-4.42ppm (m, 4H), 4.46-2.47ppm (m, 2H), 4.49-4.51ppm (m, 2H) , 5.70-5.71ppm (m, 2H), 6.05ppm (d, J = 6.8Hz, 2H), 7.22ppm (dd, J = 9.0Hz, J = 2.8Hz, 1H), 7.33ppm (t, J = 9.0 Hz, 1H), 7.40ppm (d, J = 2.4Hz, 1H), 7.59ppm (d, J = 9.6Hz, 1H), 7.70ppm (dd, J = 12.8Hz, J = 2.0Hz, 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>

2L four-necked flask equipped with a mechanical stirrer, THF 179g and pure water 76.6g, charged with 1,4-dibromo-2-fluorobenzene 25.5g (101mmol), 4-(4,4,5,5- Tetramethyl-1,3,2-dioxaborolan-2-yl)phenol 45.5 g (2.0 eq), potassium carbonate 41.7 g (3.0 eq), bis(triphenylphosphinyl)palladium (II) 2.12 g of chloride was stirred at 65 ° C for 24 hours under nitrogen atmosphere. Thereafter, the mixture was concentrated under reduced pressure, and then THF was evaporated, and then, the mixture was diluted with ethyl acetate (255 g), and 99.5 g of a 3.0 M aqueous HCl solution was added thereto, and insoluble matter such as Pd was removed by filtration. After removing the aqueous phase from the filtrate, the obtained organic phase was washed three times with 179 g of pure water. The recovered organic phase was dehydrated with magnesium sulfate, and 1.30 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for about 30 minutes, and then dried by filtration to obtain a crude product. . The recovered crude material was suspended in 153 g of toluene, and washed twice at 60 ° C for 1 hour to obtain RM3-A 22.4 g (yield: 79%, trait: pale pink crystal). .

¹ H-NMR (400 MHz) 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>

23.0 g (2.2 eq) of a polymerizable side chain (RM2-A 20.9 g (3.0 eq) of potassium carbonate was stirred at 65 ° C for 18 hours under a nitrogen atmosphere. After 18 hours, the polymerizable side chain (RM2-A) (0.2 eq/2) was added due to the remaining raw material, and the reaction was further carried out for 4 hours. After the reaction solution was diluted with 113 g of ethyl acetate, the inorganic salt was removed by filtration, and the filtrate was taken as B. 70.5 g of ethyl acetate was washed. The recovered organic phase was washed with 141 g of pure water, and a small amount of white crystals were formed. Therefore, 70.5 g of ethyl acetate was added, and further washed with 141 g of pure water, and the organic phase was dehydrated with magnesium sulfate, followed by filtration and drying. . To the recovered crude material, 0.71 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for about 30 minutes. After filtration and drying, 222 g of ethyl acetate was added and heated at 50 ° C. After completely dissolving, 98.2 g of hexane was added, and recrystallization was carried out at 2 ° C to obtain RM3 15.0 g (yield: 59%, trait: white crystal).

¹ H-NMR (400 MHz) 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, 73.4 g of DMF was charged with 9.18 g (45.0 mmol) of F-containing bisphenol compound (RM1-A) and 18.6 g (3.0 eq) of potassium carbonate, and a polymerizable side chain (RM2). -A) 20.7 g (2.2 eq), reacted at 62 ° C for 15 hours under nitrogen atmosphere. Thereafter, 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 recovered filtrate, and the mixture was washed three times with 91.8 g of pure water, and dehydrated with sodium sulfate. 0.46 g of activated carbon (brand: special egret dry product manufactured by ENVIRO Chemical Co., Ltd.) was further added, and after stirring at room temperature for about 30 minutes, the filtrate was filtered and the filtrate was concentrated to dryness. 9.2 mg of 2,6-di- tert -butyl- p -cresol was added to the concentrate, 184 g of IPA was added, and after heating to 57 ° C, it was completely dissolved, and recrystallization was carried out at room temperature to obtain RM4 13.4 g ( Yield: 70%, trait: light yellow crystal).

¹ H-NMR (400 MHz) 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) ), 5.69-5.70ppm (m, 2H), 6.03ppm (d, J = 4.8Hz, 2H), 7.03ppm (d, J = 8.8Hz, 2H), 7.25ppm (t, J = 8.8Hz, 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 ->

The synthesis was carried out in accordance with the description of paragraph [0179] of WO2012/002513.

<Synthesis Example 6 - Synthesis of RM6 ->

The synthesis was carried out in accordance with the description of 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, 90 g of NMP was charged with 9.00 g (44.1 mmol) of F-containing bisphenol compound (RM1-A) and 22.4 g (3.0 eq) of bromoacetaldehyde dimethyl acetal. 24.4 g (4.0 eq) of potassium carbonate and 2.2 g (0.30 eq) of potassium iodide were 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, followed by stirring for 8 hours. anti- After the completion of the reaction, the reaction solution was diluted with THF 99.0 g, and the filtrate was filtered. Next, the residue was diluted with 198 g of ethyl acetate, washed twice with 99.0 g of pure water, and then subjected to dehydration treatment with magnesium sulfate. Thereafter, 0.45 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added, and the mixture was stirred at room temperature for 1 hour. After filtration, the filtrate was concentrated under reduced pressure. Further, 19.8 g of THF was added to the obtained crude product, and after dissolving at 50 ° C, 60.3 g of IPA was added, and the mixture was stirred under ice cooling. The precipitated crystals were filtered and dried to obtain RM7-A 11.5 g (yield: 62%, trait: pale brown crystal)

¹ H-NMR (400 MHz) 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 = 13 Hz, J = 2.2 Hz 1H), 7.58 ppm (d, J = 8.4 Hz 2H)

<Synthesis of RM7>

Into a 500 mL four-necked flask equipped with a magnetic stirrer, 103 g of THF, 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. Further, 12.4 g (2.4 eq) of tin chloride and 36.2 g of a 10 wt% aqueous HCl solution were stirred at 70 ° C for 39 hours. After the completion of the reaction, 30 mg of 2,6-di- tert -butyl- p -cresol was added, and THF was evaporated under reduced pressure and diluted with ethyl acetate (104 g). After the separated aqueous phase was removed, the organic phase was washed at 6 ° C in pure water at 40 ° C.

3 times. After the organic phase was dehydrated with magnesium sulfate, 0.52 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added and stirred at room temperature for 1 hour, and the filtrate was filtered, and the filtrate was concentrated under reduced pressure. Further, 52 g of THF was added to the obtained crude product, and after dissolving at 60 ° C, 156 g of EtOH was added, and the mixture was stirred under ice cooling. Thereby, the precipitated crystals were filtered and dried to obtain 3.42 g of RM7 (yield: 30%, trait: white crystal).

^{1 H-NMR (400MHz) in} DMSO-d 6: 2.88-2.50ppm (m, 2H), 3.17-2.11ppm (m, 2H), 4.14ppm (dd, J = 5.6Hz, 11.2Hz, 1H), 4.28 -4.20 ppm (m, 2H), 4.33 ppm (dd, J = 2.8 Hz, 11.0 Hz, 1H), 5.00 - 4.95 ppm (m, 2H), 6.99 ppm (d, J = 6.8 Hz, 2H), 7.22 ppm (t, J = 8.8 Hz, 1H), 7.41 ppm (d, J = 8.4 Hz, 1H), 7.52 ppm (dd, J = 2 Hz, 12.8 Hz, 1H), 7.61 ppm (d, J = 2.0 Hz, 2H) )

<Synthesis Example 8 - Synthesis of RM8 ->

<Synthesis of RM8-A>

In a 200 mL four-necked flask equipped with a magnetic stirrer, NMP 15.3 g was charged with 10.0 g (53.7 mmol) of F-containing bisphenol compound (RM1-A), 20.4 g (3.0 eq) of potassium carbonate, and 1.61 g of potassium iodide (0.20 eq). In a nitrogen atmosphere, 16.6 g (2.2 eq) of 4-chlorobutyl aldehyde dimethyl acetal diluted with NMP 5.30 g was added dropwise at 80 ° C over 3 hours. After the dropwise addition for 19 hours, 2.25 g (0.3 eq) of 4-chlorobutyl aldehyde dimethyl acetal and 1.61 g (0.2 eq) of potassium iodide were added, and the reaction was further carried out for 25 hours. After the 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 three times with 60.0 g of pure water, and then subjected to dehydration treatment with magnesium sulfate. Thereafter, the solvent was removed by concentration under reduced pressure to give a crude material. The obtained crude product was added to 10 ml of THF and 70 g of MeOH, and the mixture was heated at 50 ° C, and crystals were precipitated by ice-cooling, and dried by filtration to give RM8-A 11.7 g (yield: 55%. Further, the filtrate was concentrated under reduced pressure, and the solvent was evaporated, and the crude material was added to 5 g of THF and 70 g of IPA and heated at 40 ° C, and crystals were precipitated by ice-cooling to obtain RM8-A 3.0 g (yield: 14%, trait: pale yellow solid).

¹ H-NMR (400 MHz) 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), 7.48ppm (dd, J = 13.2Hz, 2.4Hz, 1H), 7.56ppm (d, J = 8.8Hz, 2H)

<Synthesis of RM8>

Into a 300 mL four-necked flask equipped with a magnetic stirrer, 133 g of THF was charged with 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. Further, 13.8 g (2.4 eq) of tin chloride and 46.3 g of a 10 wt% aqueous HCl solution were reacted at 50 ° C for 5 hours. After 5 hours, 13.2 g of a 20 wt% aqueous HCl solution was added, and the reaction was carried out for 19 hours. After the completion of the reaction, the THF was evaporated under reduced pressure, and diluted with ethyl acetate (106 g), and then washed three times with 52.8 g of purified water. Further, 26.4 g of ethyl acetate and 79.2 g of pure water were further added, and the mixture was neutralized by adding sodium hydrogencarbonate. After the neutralization, the salt was removed, and 0.70 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added to the filtrate, and the mixture was stirred and filtered at room temperature. After the obtained solution was washed twice with 66 g of pure water, the solvent was removed by concentration under reduced pressure, and then THF (79.2 g) and 188 g of IPA were added, and the mixture was heated at 50 ° C, and crystals were precipitated by ice-cooling, and crystals were collected by filtration. The obtained crystals were added to 46.2 g of THF and 92.4 g of MeOH, and the mixture was heated at 50 ° C, and crystals were precipitated by ice-cooling, and dried by filtration to give 8.92 g (yield: 61%).

¹ H-NMR (400 MHz) 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, 1 H), 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>

4,4'-bisphenol 20.0 g (107 mmol) and potassium carbonate 44.6 g (3.0 eq) and potassium iodide 1.82 g (0.1 eq) were placed in a 300 mL four-necked flask equipped with a magnetic stirrer, 50.0 g of DMF. After heating at ° C, 39.8 g (2.2 eq) of 2-bromomethyl-1,3-difuran 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-difuran was further added, and the mixture was stirred for 18 hours. After the completion of the reaction, the reaction mixture was poured into 400 g of pure water and crystals were precipitated. After filtration, the filtrate was washed with MeOH (60.0 g) and filtered to give a white solid. The obtained white solid was suspended in 500 g of THF, and 1.00 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added, and the mixture was stirred at 60 ° C for 30 minutes, and then filtered while hot (45 ° C). Cooling the filtrate results, due to the precipitation of white crystals, Therefore, LM9-A 13.0 g (yield: 34%, trait: white solid) was obtained by filtration and drying.

^{1 H-NMR (400MHz) in} DMSO-d6: 3.85-3.93ppm (m, 4H), 3.95-3.99ppm (m, 4H), 4.03ppm (d, J = 4.0Hz, 4H), 5.21ppm (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>

Into a 300 mL four-necked flask equipped with a magnetic stirrer, 99.5 g of THF, 9.95 g (27.8 mmol) of the compound (RM9-A) obtained above, and 11.8 g of ethyl 2-(bromomethyl)acrylate (2.2 eq. ), 12.6 g (2.4 eq) of tin chloride, 34.8 g of a 10 wt% aqueous hydrochloric acid solution, and stirred at 60 ° C for 1.5 hours. After 1.5 hours, 9.95 g of a 20 wt% aqueous hydrochloric acid solution was added, and the mixture was further stirred for 21 hours to complete the reaction. Thereafter, THF was distilled off under reduced pressure, and 199 g of ethyl acetate was added to remove the aqueous phase. Next, the organic layer was washed twice with 59.7 g of pure water. The organic phase was recovered, and ethyl acetate was evaporated under reduced pressure. 0.48 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added, and the mixture was stirred for 1 hour, dehydrated with magnesium sulfate, and filtered to obtain a homogeneous filtrate. This concentration under reduced pressure was continued to adjust the amount of THF to 79.6 g, and after adding 159 g of MeOH at 55 ° C, it was stirred slightly under ice cooling. The crystals thus precipitated were filtered and dried to obtain RM9 8.4 g (yield: 74%, trait: white crystal).

¹ H-NMR (400 MHz) 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), 4.25ppm (dd, J = 2.6Hz, J = 11.0Hz, 2H), 5.78-5.79ppm (m, 2H), 6.10-6.08ppm (m, 2H), 7.00ppm (d, J = 8.4Hz, 4H) , 7.55ppm (d, J = 8.4Hz)

<Synthesis Example 10 - Synthesis of RM10 ->

<Synthesis of RM10-A>

40.0 g (53.7 mmol) of 4,4'-bisphenol and 18.4 g (2.2 eq) of 4-chlorobutyl aldehyde dimethyl acetal were placed in a 200 mL four-necked flask equipped with a magnetic stirrer and 20.0 g of NMP. 22.3 g (3.0 eq) of potassium carbonate and 1.78 g (0.2 eq) of potassium iodide were stirred at 80 ° C for 3 hours. Thereafter, 2.45 g (0.3 eq) of 4-chlorobutyl aldehyde dimethyl acetal was added, followed by stirring for 16 hours. After the reaction, the reaction solution was diluted with 50.0 g of ethyl acetate. After the inorganic salt was filtered, the filtrate was diluted with ethyl acetate (50.0 g), and purified at 50 ° C in pure water. Wash 50.0g 3 times. Thereafter, the organic phase was subjected to dehydration treatment with sodium sulfate, and concentrated under reduced pressure to a total weight of 68.0 g, and the precipitated crystals were filtered. To the crude was added 5.0 g of THF and 20.0 g of MeOH, dissolved at 50 ° C, cooled, and stirred slightly. The precipitated crystals were filtered and dried to give RM10-A 15.8 g (yield: 70%, trait: white solid).

¹ H-NMR (400 MHz) 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>

Into a 500 mL four-necked flask equipped with a magnetic stirrer, 56.4 g of THF, 14.8 g (35.4 mmol) of the compound (RM10-A) obtained above, and 15.0 g of ethyl 2-(bromomethyl)acrylate (2.2 eq. There were 16.1 g (2.4 eq) of tin chloride, 0.39 g (5 mol%) of 2,6-di- tert -butyl- p -cresol, and 51.8 g of a 20 wt% aqueous HCl solution, and the mixture was stirred at 60 ° C for 3 hours. After the reaction, the reaction liquid was concentrated under reduced pressure, and then 148 g of pure water was added thereto, and the precipitated crystals were filtered, and washed twice with 148 g of pure water. Further, 118 g of THF and 118 g of MeOH were added to the crystals, and the mixture was dissolved at 50 ° C, and then cooled to room temperature and stirred slightly. The crystals thus obtained were filtered to give a crude material. Further, 237 g of THF and 237 g of IPA were added to the crude product, and the mixture was dissolved at 60 ° C, and then cooled to room temperature and stirred slightly. The crystals thus precipitated were filtered, washed three times with THF (74.0 g), and dried under reduced pressure to give RM10 7.20 g (yield: 44%, trait: white crystals).

¹ H-NMR (400 MHz) 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), 4.61-4.67ppm (m, 2H), 5.72-5.73ppm (m, 2H), 6.04-6.05ppm (m, 2H), 6.98ppm (d, J = 8.8Hz, 4H), 7.52ppm (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, 20 g of NMP was charged with 10.0 g (35.7 mmol) of F-containing terphenyl compound (RM3-A) and 13.3 g (2.2 eq) of bromoacetaldehyde dimethyl acetal. 14.8 g (3.0 eq) of potassium carbonate and 1.78 g (0.30 eq) of potassium iodide were 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, followed by stirring for 12 hours. Thereby, the reaction solution was diluted with 100 g of THF due to the end of the reaction, and the inorganic salt was filtered. Thereafter, the THF was distilled off under reduced pressure. Next, 200 g of pure water was added to the reaction liquid, and the precipitated crystals were filtered. The obtained crystals were suspended in 100 g of THF, and dissolved at an internal temperature of 50 ° C, and then 200 g of IPA was added, and the mixture was stirred under ice cooling. The crystals thus precipitated were filtered and dried to obtain 11.9 g of RM11-A (yield: 73%, trait: pale brown crystal).

¹ H-NMR (400 MHz) 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), 7.58-7.52ppm (m, 5H), 7.70ppm (d, J = 8.8Hz, 2H)

<Synthesis of RM11>

Into a 500 mL four-necked flask equipped with a magnetic stirrer, 110 g of THF, 11.0 g (24.2 mmol) of the compound (RM11-A) obtained above, and 10.3 g (2.2 eq) of ethyl 2-(bromomethyl)acrylate were added. 11.0 g (2.4 eq) of tin chloride and 38.6 g of a 10 wt% aqueous HCl solution were reacted at an internal temperature of 40 ° C for 18 hours. After 18 hours, 11.0 g of a 20 wt% aqueous HCl solution was added, followed by stirring for 6 hours. Thereafter, 27 mg of 2,6-di- tert -butyl- p -cresol was added, and THF was distilled off under reduced pressure, and then 110 g of pure water was added thereto, and the precipitated crystals were filtered. Next, the obtained crystal was suspended in 1100 g of THF, and the insoluble matter which was not dissolved at 60 ° C was filtered, and 0.55 g of activated carbon (brand: special egret dry product, manufactured by ENVIRO Chemical Co., Ltd.) was added to the filtrate, and the mixture was stirred at 60 ° C for about 30 minutes. After the filtration of the activated carbon, the filtrate was concentrated under reduced pressure and the THF was reduced to 110 g, the crystals which precipitated were filtered and dried to give RM 114.67 g (yield: 39%, </ RTI>

¹ H-NMR (400 MHz) 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) , 7.01-7.04ppm (m, 4H), 7.59-7.52ppm (m, 5H), 7.71ppm (d, J = 8.8Hz, 2H)

<Synthesis Example 12 - Synthesis of RM12 ->

<Synthesis of RM12-A>

In a 200 ml eggplant-shaped flask with a cooling tube, 4.0 g (14.3 mmol) of F-containing terphenyl compound (RM3-A), 6.3 g (2.1 eq) of 4-bromobutyl-1,3-difuran, and carbonic acid were added. Potassium 8.3g (4.0eq), and acetone 100ml The mixture was reacted while stirring under reflux for 24 hours. After the 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 give RM12-A 5.9 g (yield: 77%, </ RTI>

¹ H-NMR (400 MHz) 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>

To a 100 ml eggplant-shaped flask equipped 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, and chlorination were added. 2.6 g (2.5 eq) of tin (anhydrous) and 11 ml of a 10% aqueous HCl solution were used as a mixture, and the mixture was stirred at 70 ° C for 20 hours to cause a reaction. After the completion of the reaction, the reaction solution was poured into 500 ml of pure water to obtain white crystals. The white crystals obtained were purified by recrystallization (hexane/chloroform, 5/1) to give 2.4 g of RM12 (yield: 73%, trait: white crystals).

¹ H-NMR (400 MHz) 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), and after reacting at 60 ° C for 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (10.7 g) were added, and the reaction was carried out for 10 hours at room temperature to obtain polylysine. Solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (5.7 g) and pyridine (2.9 g) as a ruthenium amide catalyst were added, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-1. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 12,000, and a weight average molecular weight of 33,000.

To the obtained polyimine powder (A)-1 (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 50 ° C for 5 hours and dissolved. To the 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 alignment 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), DA-2 (4.00 g, 10.0 mmol) in NMP (34.8 g) After dissolving and reacting at 60 ° C for 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (11.6 g) were added, and the reaction was carried out for 10 hours at room temperature to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (5.3 g) and pyridine (2.7 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 50 ° C. Hour response. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-2. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 15,000, and a weight average molecular weight of 41,000.

To the obtained polyimine powder (A)-2 (6.0 g), NMP (44.0 g) was added, and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (38.9 g), and reacted at 60 ° C for 3 hours, and then added. CBDA (2.27 g, 11.6 mmol) and NMP (13.0 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (3.1 g) as a ruthenium imidization catalyst, and pyridyl were added. Pyridine (12.1 g) was reacted at 50 ° C for 3 hours. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-3. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 15,000, and a weight average molecular weight of 36,000.

The obtained polyimine powder (A)-3 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-2 (4.00 g, 10.0 mmol) were dissolved in NMP (32.8 g), and reacted at 60 ° C for 3 hours, and then added. CBDA (2.27 g, 11.6 mmol) and NMP (10.9 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (3.7 g) and pyridine (14.4 g) as a ruthenium catalyst were added, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-4. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 25,000, and a weight average molecular weight of 45,000.

The obtained polyimine powder (A)-4 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-8 (2.97 g, 9.0 mmol) were dissolved in NMP (24.9 g), and reacted at 80 ° C for 3 hours, and then added. CBDA (1.74 g, 8.9 mmol) and NMP (8.3 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (36 g) and diluting to 6 mass%, acetic anhydride (4.0 g) as a ruthenium amide catalyst and pyridine (2.1 g) were added, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-5. The polyimine has a hydrazine imidation ratio of 60%, a number average molecular weight of 20,000, and a weight average molecular weight of 43,000.

The obtained polyimine powder (A)-5 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-3 (2.61 g, 6.0 mmol) were dissolved in NMP (34.5 g), and reacted at 60 ° C for 3 hours, and then added. CBDA (2.27 g, 11.6 mmol) and NMP (11.5 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (5.3 g) and pyridine (2.7 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-6. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 17,000, and a weight average molecular weight of 35,000.

The obtained polyimine powder (A)-6 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-8 (3.00 g, 9.1 mmol) were dissolved in NMP (23.5 g), and reacted at 60 ° C for 3 hours, CBDA (1.43g, 7.3 Methyl) and NMP (7.8 g) were reacted at room temperature for 10 hours to give a polyaminic acid solution.

After adding NMP to the polyamic acid solution (36 g) and diluting to 6 mass%, acetic anhydride (3.6 g) as a ruthenium amide catalyst and pyridine (1.9 g) were added, and the reaction was carried out at 50 ° C for 3 hours. . The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-7. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 16,000, and a weight average molecular weight of 36,000.

The obtained polyimine powder (A)-7 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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), DA-1 (3.04 g, 8.0 mmol) were dissolved in NMP (33.9 g), and reacted at 60 ° C for 3 hours, CBDA (2.27 g, 11.6 mmol) and NMP (11.3 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (5.4 g) and pyridine (2.8 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 50 ° C for 3 hours. reaction. Put the reaction solution into The resulting precipitate was separated by filtration in methanol (700 mL). The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-8. The polyimine has a hydrazine imidation ratio of 60%, a number average molecular weight of 18,000, and a weight average molecular weight of 40,000.

The obtained polyimine powder (A)-8 (6.0 g) was added to NMP (44.0 g), and the mixture was stirred at 50 ° C for 5 hours to be dissolved. To the 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 alignment 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) were dissolved in NMP (29.5 g). After reacting at 60 ° C for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.5 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (6.4 g) and pyridine (3.3 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-9. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 10,000, and a weight average molecular weight of 31,000.

The obtained polyimine powder (A)-9 (6.0 g) was added to NMP (44.0 g) was stirred at 50 ° C for 5 hours to dissolve. To the 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 alignment agent D9.

<Synthesis Example 22 - Synthesis of Liquid Crystal Aligning Agent D10 ->

To 3.0 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 liquid crystal alignment agent D10 was obtained by stirring at room temperature for 5 hours.

<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) were dissolved in NMP (20.7 g) After reacting at 60 ° C for 3 hours, PMDA (2.53 g, 11.6 mmol) and NMP (9.9 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (6.1 g) and pyridine (3.2 g) as a ruthenium amide catalyst were added, and the mixture was carried out at 50 ° C for 3 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-10. The polyimine had a hydrazine imidation ratio of 60%, a number average molecular weight of 9000, and a weight average molecular weight of 25,000.

The obtained polyimine powder (A)-10 (6.0 g) was added to NMP (44.0 g) was stirred at 50 ° C for 5 hours to dissolve. To the 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 alignment agent D11.

<Synthesis Example 24 - Synthesis of Liquid Crystal Aligning Agent D12 ->

To 3.0 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 liquid crystal alignment agent D12 was obtained by stirring at room temperature for 5 hours.

<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), DA-4 (1.52 g, 10.0 mmol) were dissolved in NMP (30.0 g), and reacted at 80 ° C for 5 hours, and then added. CBDA (0.94 g, 4.8 mmol) and NMP (10.0 g) were reacted at 40 ° C for 10 hours to obtain a polyaminic acid solution.

After adding NMP to the polyamic acid solution (50 g) and diluting to 6 mass%, acetic anhydride (4.7 g) and pyridine (3.7 g) as a ruthenium catalyst were added, and the mixture was carried out at 80 ° C for 3 hours. reaction. The reaction solution was poured into methanol (700 ml), and the obtained precipitate was separated by filtration. The precipitate was washed with methanol, and dried under reduced pressure at 100 ° C to obtain a polyimine powder (A)-11. The polyimine has a hydrazine imidation ratio of 55%, a number average molecular weight of 20,000, and a weight average molecular weight of 40,000.

The obtained polyimine powder (A)-11 (6.0 g) was added to NMP (44.0 g) was stirred at 50 ° C for 5 hours to dissolve. To the 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 alignment 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), DA-2 (2.40 g, 6.0 mmol) were dissolved in NMP (26.4 g), and reacted at 60 ° C for 3 hours, and then added. CBDA (2.27 g, 11.6 mmol) and NMP (13.2 g) were reacted at room temperature for 10 hours to obtain a polyaminic acid solution. The polyaminic acid solution had a number average molecular weight of 20,000 and a weight average molecular weight of 40,000.

NMP (40.0 g) and BCS (30.0 g) were added to the polyamic acid solution (30 g), and the mixture was stirred at room temperature for 5 hours to obtain a liquid crystal alignment agent D14.

<Synthesis Example 27 - Synthesis of RM13 ->

<Synthesis of RM13-A>

In a 300 mL four-necked flask equipped with a magnetic stirrer, RM1-A 9.0 g (44.1 mmol) was charged in NMP 18.1 g, and washed with NMP 17.9 g, then 18.3 g (3.0 eq) of potassium carbonate was added to NMP 18.0 g. Washed together. This was stirred at 80 ° C, and 17.6 g (2.2 eq) of 2-(2-bromoethyl)-1,3-difuran was added dropwise thereto over 30 minutes, followed by stirring for 18 hours. After 18 hours, 2.4 g (0.3 eq) of 2-(2-bromoethyl)-1,3-difuran was further added, and the reaction was further carried out for 3.5 hours to confirm the disappearance of the intermediate. After the completion of the reaction, a large amount of water was added to the reaction liquid at room temperature, and the crystal of the target was precipitated while dissolving potassium carbonate and filtered. The recovered crystals were washed twice with pure water and filtered to dryness to obtain 17.8 g of crude RM13-A (yield: 100%, trait: pale brown crystals).

¹ H-NMR (400 MHz) in DMSO-d ₆ : 7.57 ppm (d, J = 8.8 Hz, 2H), 7.49 ppm (dd, J = 2.2 Hz, J = 13.0 Hz, 1H), 7.38 ppm (d, J) =10.0 Hz, 1H), 7.21 ppm (t, J = 8.8 Hz, 1H), 6.99 ppm (d, J = 8.4 Hz, 2H), 5.02-4.99 ppm (m, 2H), 4.18 ppm (t, J = 6.6 Hz, 2H), 4.10 ppm (t, J = 6.6 Hz, 2H), 3.94-3.91 ppm (m, 4H), 3.82-3.78 ppm (m, 4H), 2.09-2.02 ppm (m, 4H).

<Synthesis of RM13>

RM13-A 15.0g (37.1mmol), tin (II) chloride anhydrate 16.9g (2.4eq), 2-(bromomethyl)acrylic acid After 15.9 g (2.2 eq) of the base, 52.5 g of a 10 wt% aqueous HCl solution was added dropwise at 45 to 30 ° C over 45 minutes. Thereafter, the mixture was stirred at room temperature for 7 days to allow the starting materials and the intermediate to disappear. After adding 300 g of toluene to the reaction liquid, the mixture was separated into two phases, and the hydrochloric acid phase was removed by hot time separation (50 ° C). The organic phase was generally recovered in a flask, and dropped into 300 g of a 6 wt% aqueous KOH solution, and the jacket was separable at 50 ° C in a separable flask. In the middle, since insoluble matter was generated at the interface, 150 g of a 6 wt% aqueous KOH solution was added. After the alkali phase was removed, the organic phase was washed three times with 300 g of pure water to recover the organic phase. In this case, 0.75 g of activated carbon (brand: special egret dry product manufactured by ENVIRO Chemical Co., Ltd.), sodium sulfate 30.0 g, and THF 105 g were added, and the mixture was stirred at room temperature for 30 minutes, and then subjected to solid-liquid separation to recover a filtrate. This was concentrated to dryness, and then 45.0 g of MeOH was added, and the mixture was washed at room temperature for 1 hour. After filtering this, the obtained filtrate was washed with 7.5 g of MeOH and dried under reduced pressure to give RM 13 7.6 g (yield: 45%, </

¹ H-NMR (400 MHz) in DMSO-d ₆ : 7.59 ppm (d, J = 8.8 Hz, 2H), 7.51 ppm (dd, J = 2.0 Hz, J = 12.8 Hz, 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 = 5.0 Hz, 2H), 5.74 ppm (d, J = 2.0 Hz, 2H), 4.81-4.75 ppm (m, 2H), 4.20 ppm (t, J = 6.2 Hz, 2H), 4.13 ppm (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 of the 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 the mixture was stirred and dissolved at room temperature for 3 hours. The liquid crystal alignment agent D15 was prepared.

The obtained liquid crystal alignment agent D15 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 2>

In the same manner as in Example 1, except that the amount of the polymerizable compound RM1 was set to 0.09 g (15% by mass for the solid content), the liquid crystal alignment agent D16 was prepared in the same manner as in Example 1.

The obtained liquid crystal alignment agent D16 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed. <Reference Example 1>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D17 was prepared.

The obtained liquid crystal alignment agent D17 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Reference Example 2>

In the same manner as in Example 2 except that the polymerizable compound RM1 obtained in Synthesis Example 2 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D18 was prepared.

The obtained liquid crystal alignment agent D18 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Reference Example 3>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D19 was prepared.

The obtained liquid crystal alignment agent D19 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Reference Example 4>

In the second embodiment, the liquid crystal alignment agent D20 was prepared in the same manner as in Example 2 except that the polymerizable compound RM1 obtained in Synthesis Example 3 was used instead of the polymerizable compound RM1.

The obtained liquid crystal alignment agent D20 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Reference Example 5>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D21 was prepared.

The obtained liquid crystal alignment agent D21 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Reference Example 6>

In the second embodiment, the liquid crystal alignment agent D22 was prepared in the same manner as in Example 2 except that the polymerizable compound RM1 obtained in Synthesis Example 4 was used instead of the polymerizable compound RM1.

The obtained liquid crystal alignment agent D22 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 3>

In the same manner as in Example 2, the liquid crystal alignment agent D23 was prepared in the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 14 was used instead of the liquid crystal alignment agent D1.

The obtained liquid crystal alignment agent D23 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 4>

In the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 15 was used instead of the liquid crystal alignment agent D1, the liquid crystal alignment agent D24 was prepared.

The obtained liquid crystal alignment agent D24 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 5>

In the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 16 was used instead of the liquid crystal alignment agent D1, the liquid crystal alignment agent D25 was prepared.

The obtained liquid crystal alignment agent D25 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 6>

In the same manner as in Example 2, the liquid crystal alignment agent D26 was prepared in the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 17 was used instead of the liquid crystal alignment agent D1.

The obtained liquid crystal alignment agent D26 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 7>

With respect to Example 1, the liquid crystal alignment agent D1 was used in the same manner as in Example 2 except that the liquid crystal alignment agent D6 obtained in Synthesis Example 18 was used. The liquid crystal alignment agent D27 was prepared.

The obtained liquid crystal alignment agent D27 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 8>

In the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 19 was used instead of the liquid crystal alignment agent D1, the liquid crystal alignment agent D28 was prepared.

The obtained liquid crystal alignment agent D28 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 9>

In the same manner 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, the liquid crystal alignment agent D29 was prepared.

The obtained liquid crystal alignment agent D29 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 10>

In the same manner 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, the liquid crystal alignment agent D30 was prepared.

The obtained liquid crystal alignment agent D30 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 11>

In the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 25 was used instead of the liquid crystal alignment agent D1, the liquid crystal alignment agent D31 was prepared in the same manner as in Example 2.

The obtained liquid crystal alignment agent D31 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 12>

In the same manner as in Example 2 except that the liquid crystal alignment agent D1 obtained in Synthesis Example 26 was used instead of the liquid crystal alignment agent D1, the liquid crystal alignment agent D32 was prepared.

The obtained liquid crystal alignment agent D32 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 13>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 7 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D33 was prepared.

The obtained liquid crystal alignment agent D33 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 14>

For Example 1, the substituted polymerizable compound RM1 was used in the synthesis. The liquid crystal alignment agent D34 was prepared in the same manner as in Example 1 except for the polymerizable compound RM8 obtained in Example 8.

The obtained liquid crystal alignment agent D34 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Comparative Example 1>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D35 was prepared.

The obtained liquid crystal alignment agent D35 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Comparative Example 2>

In the second embodiment, the liquid crystal alignment agent D36 was prepared in the same manner as in Example 2 except that the polymerizable compound RM1 obtained in Synthesis Example 5 was used instead of the polymerizable compound RM1.

The obtained liquid crystal alignment agent D36 was stored in a freezer at -20 ° C for 1 day, and allowed to stand at room temperature for 3 hours to be thawed, and then precipitates were confirmed.

<Comparative Example 3>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D37 was prepared.

The obtained liquid crystal alignment agent D37 was stored in a freezer at -20 ° C. After standing at room temperature for 3 hours to cause thawing, it was confirmed that precipitates were observed.

<Comparative Example 4>

In the second embodiment, the liquid crystal alignment agent D38 was prepared in the same manner as in Example 2 except that the polymerizable compound RM1 obtained in Synthesis Example 6 was used instead of the polymerizable compound RM1.

The obtained liquid crystal alignment agent D38 was stored in a freezer at -20 ° C for 1 day, and allowed to stand at room temperature for 3 hours to be thawed, and then precipitates were confirmed.

<Comparative Example 5>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 9 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D39 was prepared.

The obtained liquid crystal alignment agent D39 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Comparative Example 6>

In the same manner as in Example 1, except that the polymerizable compound RM1 obtained in Synthesis Example 10 was used instead of the polymerizable compound RM1, the liquid crystal alignment agent D40 was prepared.

The obtained liquid crystal alignment agent D40 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<Example 15> <Production of liquid crystal cell>

Using the liquid crystal alignment agent D15 obtained in Example 1, the liquid crystal cell of the SC-PVA method was produced by the procedure shown below.

The liquid crystal alignment agent D15 obtained in Example 1 was spin-coated on an ITO surface of an ITO electrode substrate having a line size of 100 μm × 300 μm and an ITO electrode pattern of 5 μm each, at 80 ° C. The hot plate was dried for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a liquid crystal alignment film having a thickness of 100 nm.

Further, the liquid crystal alignment agent D1 was spin-coated on the ITO surface on which the electrode pattern was not formed, and dried on a hot plate at 80 ° C for 90 seconds, and then fired in a hot air circulating oven at 200 ° C for 30 minutes to form a film thickness. 100 nm liquid crystal alignment film.

On the two substrates described above, a 4 μm bead spacer was spread on the liquid crystal alignment film of one of the substrates, and then a sealant (solvent-type thermosetting epoxy resin) was applied thereon. Next, the side surface of the liquid crystal alignment film on the other substrate was formed as an inner side, and after bonding to the previous substrate, the sealant was cured to produce an empty container. In the empty container, liquid crystal MLC-6608 (trade name, manufactured by Merck & Co., Inc.) was injected by a reduced pressure injection method to prepare a liquid crystal cell. The produced liquid crystal cell was placed in a hot air circulating oven of 120 degrees for 1 hour, and liquid crystal realignment treatment was performed.

The response speed of the obtained liquid crystal cell was measured by the following method. Thereafter, in a state where a DC voltage of 15 V was applied to the liquid crystal cell, UV 10 J/cm ² irradiation through a 365 nm band pass filter was irradiated from the outside of the liquid crystal cell. Thereafter, the response speed was measured again, and the response speed before and after the UV irradiation was compared. Further, the pretilt angle of the pixel portion was measured for the container after UV irradiation. Further, the container which was not irradiated with UV was left for one day, and then subjected to a polarizing microscope observation of the liquid crystal cell. When the solubility of the polymerizable compound is low, it is likely to be precipitated in the liquid crystal cell to cause a bright spot. The results are shown in Table 1.

<Method for measuring response speed>

First, a liquid crystal cell is disposed between a group of polarizing plates for a measuring device comprising a backlight and a group of polarizing plates and a light amount detector in a crossed Nicols state. The pattern of the line/space ITO electrode formed at this time is an angle of 45° for the crossed Nicols. A rectangular wave having a voltage of ±6 V and a frequency of 1 kHz is applied to the liquid crystal cell, and the brightness is detected by the light amount detector to be saturated and read by the analyzer, and the brightness when the voltage is not applied is 0%. The voltage of ±4V and the saturation luminance value are taken as 100%, and the time required for the change of the luminance from 10% to 90% is taken as the response speed.

<Measurement of pretilt angle>

An LCD analyzer LCA-LUV42A manufactured by Mingling Technica was used.

<Example 16 to Example 28>

In the same manner as in Example 21 except that the liquid crystal alignment agent D15 was used instead of the liquid crystal alignment agent D15, the response speed before and after the UV irradiation was compared. The measurement of the pretilt angle was also performed. Moreover, the observation result of the bright spot in the liquid crystal cell was also performed.

<Example 29>

To the liquid crystal alignment agent D10 (10.0 g) obtained in Synthesis Example 22, 0.06 g of RM13 synthesized in Synthesis Example 27 (10% by mass of the solid content of the liquid crystal alignment agent D10) was added, and the mixture was allowed to stand at room temperature for 3 hours. The liquid crystal alignment agent D41 was prepared by stirring and dissolving.

The obtained liquid crystal alignment agent D41 was stored in a freezer at -20 ° C for one day, and after being allowed to stand at room temperature for 3 hours to be thawed, no precipitate was observed.

<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 speed before and after UV irradiation. Further, the measurement of the pretilt angle and the bright spot observation in the liquid crystal cell were performed.

<Reference Example 7 to Reference Example 12>

The same operation as in Example 16 was carried out, except that each of the liquid crystal alignment agents D17 to D22 was used instead of the liquid crystal alignment agent D15, and the response speed before and after the UV irradiation was compared. The measurement of the pretilt angle was also performed. And the result of the bright spot observation in the liquid crystal cell is performed.

Further, in Reference Examples 7, 8, 11, and 12, in place of the hot air circulating oven of 200 ° C, a hot air circulating oven of 140 ° C was used.

<Comparative Example 7 to Comparative Example 12>

Replace liquid crystal alignment agent D15, use each liquid crystal alignment agent D35~D40 The same operation as in Example 15 was carried out, and the response speed before and after the UV irradiation was compared. The measurement of the pretilt angle was also performed. And the result of the bright spot observation in the liquid crystal cell is performed.

Comparative Examples 15 and 16 and Comparative Examples 7 and 8, especially in Comparative Example 16 and Comparative Example 8, have the same skeleton (F substitution (RM1) for RM1 and RM5. No (RM5) phase Iso), it was found that the solubility in the paint can be improved by the introduction of a halogen group. Moreover, it was found that the solubility in the liquid crystal was also improved by the observation of the bright spots in the liquid crystal cell.

In the same manner, Comparative Example 27 and Comparative Example 11 (having F substitution (RM7) for RM7 and RM9. No difference (RM9)), Example 28 and Comparative Example 12 (F substitution for RM8 and RM10) (RM8). When there is no difference (RM10), it is known that the solubility to liquid crystal is improved. Further, it is known from Reference Example 9 and Reference Example 10 that even if it has a terphenyl skeleton which is rigid and has low solubility, the solubility of the polymerizable compound can be improved by the introduction of a halogen group, and the liquid crystal alignment agent can be improved. The preservation stability is also improved.

In the same manner, the high solubility of the polymerizable compound was confirmed from Reference Examples 7, 8, 11, and 12. Therefore, it has been found that the halogen-substituted polymerizable compound exhibits improved solubility of the polymerizable compound, high storage stability of the liquid crystal alignment agent, and improved solubility in liquid crystal. Further, it was confirmed that the liquid crystal alignment agent to which the polymerized compound substituted with a halogen is added is the same as the liquid crystal alignment unit of the SC-PVA type, and exhibits the same inclination angle as the liquid crystal alignment agent to which the polymerizable compound not substituted by halogen is added.

Claims (6)

A polymerizable compound characterized by the following formula [1]; (In the formula [1], Ar is formed by the structures shown in the following formulas [2] to [4]; (In the formulae [2] to [4], X represents a halogen substituent, m ₁ to m _{6 are} each independently an integer of 0 to 4, and m ₇ and m _{8 are} each independently an integer of 0 to 3, m ₁ + m ₂ It 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). The polymerizable compound of claim 1, wherein X represents a fluorine group. The polymerizable compound according to claim 1, wherein in the formulae [2] to [4], X represents a fluorine group, m ₁ + m ₂ is 1 or more and 3 or less, and m ₃ + m ₄ + m ₅ is 1 or more and 4 or less. m ₆ + m ₇ + m ₈ is 1 or more and 3 or less. The polymerizable compound of the above formula 1, wherein the polymerizable compound represented by the formula [1] is a group selected from the group consisting of the compounds represented by the following formulas [5] to [7]; (n1 is an integer of 1 to 10) The polymerizable polymer of the formula (1), wherein the polymerizable compound represented by the formula [1] is selected from the group consisting of polymerizable compounds represented by the following formulas [1-1] to [1-6]. A liquid crystal alignment agent comprising the polymerizable compound according to any one of claims 1 to 5, and at least one polymer selected from the group consisting of polyimine and polyimine precursors.