TW201700546A - Liquid crystal aligning agent, liquid crystal aligning film, liquid crystal member, production method for liquid crystal aligning film and silsesquioxane having good heat resistance and light resistance properties for substrate coating - Google Patents

Abstract

The present invention provides a liquid crystal aligning agent, liquid crystal aligning film, liquid crystal member, a production method for liquid crystal aligning film and a silsesquioxane, which have good coating properties on a substrate. The liquid crystal aligning agent of the present invention has a ladder-structured silsesquioxane (L) represented by the following formula (1), where E1 and E2 are each for monovalent organic group, and n is an integer of 2 or more; E1 and E2 in the different repeating units can be the same or different.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal element, method for producing liquid crystal alignment film, and sesquiterpene oxide

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal element, a method for producing a liquid crystal alignment film, and a compound.

The liquid crystal element includes a liquid crystal alignment film that controls alignment of liquid crystal molecules. The material constituting the liquid crystal alignment film is known as polyimide, polyamide, polyester, polyoxyalkylene, etc., and the liquid crystal alignment film containing the polyimide of these materials is heat resistance, mechanical strength, and liquid crystal molecules. Since it has excellent affinity, etc., it has been used for a long time (for example, refer patent document 1). In addition, in recent years, the use of a liquid crystal alignment agent containing a polyoxyalkylene obtained by reacting a decane compound is also increased in the light resistance and heat resistance (see, for example, Patent Document 2 and Patent Document 3). Patent Document 2 discloses that a polyoxyalkylene obtained by polycondensing an alkoxydecane compound in the presence of oxalic acid is used as a polymer component of a liquid crystal alignment agent. Further, Patent Document 3 discloses a liquid crystal alignment agent containing a polyoxyalkylene synthesized by a step of hydrolyzing or hydrolyzing/condensing a decane compound in the presence of an alkali metal compound or an organic base, or a hydrolyzate thereof. a condensate of a hydrolyzate. [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2010-97188 [Patent Document 2] Japanese Patent No. 5593611 [Patent Document 3] International Publication No. 2009/025388

[Problems to be Solved by the Invention] According to the method described in Patent Document 2, a random polyoxyalkylene is obtained, and a cage-type polyoxyalkylene is obtained according to the method described in Patent Document 3. However, the random type or the cage type polysiloxane has a low limit molecular weight, and when coating film is formed on a substrate, coating unevenness occurs, and there is a concern that the product yield is lowered or the display quality is lowered. With the recent high definition of liquid crystal panels, the demand for display quality has become stricter, and as a liquid crystal element, further improvement in electrical characteristics and liquid crystal alignment property is desired.

The present invention has been made in view of the above circumstances, and an object of the invention is to provide a liquid crystal alignment agent which is excellent in applicability to a substrate and which can obtain a liquid crystal alignment and electrical characteristics.

[Technical means for solving the problem] According to the present invention, the following means are provided.

[1] A liquid crystal alignment agent containing a sesquiterpene oxide [L] having a ladder structure represented by the following formula (1), [Chemical Formula 1] (In the formula (1), E ¹ and E ² are each independently a monovalent organic group, and n is an integer of 2 or more; and E ¹ and E ² in different repeating units may be the same or different).

[1-1] A liquid crystal alignment agent containing sesquiterpene oxide [L] satisfying the following requirements (A) to (C), (A) by gel permeation chromatography (Gel Permeation Chromatography, The weight average molecular weight (Mw) measured by GPC) is 5,000 or more; (B) The molecular weight distribution (Mw/Mn) expressed by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC is 3.8 or less; (C) The integral ratio of the peak of the ²⁹ Si-NMR spectrum derived from the partial structure represented by the following formula (4) is 70% to 99%; (In the formula (4), R ^a is a monovalent organic group having 1 or more carbon atoms, and "*" represents a bond with a ruthenium atom).

[2] A liquid crystal alignment agent containing sesquiterpene oxide [L] obtained by polymerizing a decane compound under two or more conditions of Condition 1, Condition 2, and Condition 3 described below, Condition 1: As the decane compound, a decane compound having one or two or more specific groups selected from -NHR ⁵ (wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; a group consisting of pyridyl, imidazolyl, cyano, imino, hydroxy, decyl, carboxyl, phosphonium, sulfo and anhydride groups; Condition 2: The decane compound in Condition 1 is acidic In the case of the specific group, the decane compound is hydrolytically condensed in the presence of a base, and in the case of having a basic group as the specific group, the decane compound is hydrolytically condensed in the presence of an acid; Condition 3: The decane compound is hydrolyzed and condensed in a solvent containing 10% by mass or more of water.

[3] A liquid crystal alignment film formed using the liquid crystal alignment agent of [1], [1-1] or [2]. [4] A liquid crystal element comprising the liquid crystal alignment film of [3]. [5] A method for producing a liquid crystal alignment film, comprising: a step of applying a liquid crystal alignment agent of [1], [1-1] or [2] onto a substrate to form a coating film; and coating The step of irradiating the substrate surface of the liquid crystal alignment agent with light is performed. [6] A sesquiterpene oxide having a ladder structure represented by the formula (1); wherein one or more of the plurality of E ¹ and E ² possessed by the sesquiterpene oxide are selected from the group consisting of a group of at least one of the group consisting of an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acrylonitrile group, a styryl group, an ethynyl group, a decyl group, an isocyanate group, an alcohol a hydroxyl group, a cyano group, -COOR ² , -CON(R ¹ R ² ), -PO(R ¹ ) ₂ , -SO ₃ R ² , -SO ₂ N(R ¹ R ² ) (wherein R ^{1 is} independently The ground is a hydrogen atom or a monovalent hydrocarbon group, R ² is a monovalent hydrocarbon group, a photo-alignment group, and a crosslinkable group.

[Effects of the Invention] According to the liquid crystal alignment agent containing sesquiterpene oxide [L], a liquid crystal alignment agent having good coating properties on a substrate can be obtained. Further, a liquid crystal element having excellent liquid crystal alignment properties and electrical characteristics can be obtained.

Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components arbitrarily formulated as needed will be described.

<Hexaphthalene oxide [L]> The liquid crystal alignment agent of the present invention contains a sesquiterpene oxide [L] having a ladder structure represented by the above formula (1). In the formula (1), the monovalent organic group of E ¹ and E ² is preferably a group containing at least one carbon atom, and may contain a hetero atom in the structure. Specific examples of the monovalent organic group include a monovalent hydrocarbon group having 1 to 20 carbon atoms, a group including a hetero atom-containing group between carbon-carbon bonds of the hydrocarbon group, and a hydrocarbon group and a hetero atom-containing group. A group formed by bonding, a group obtained by substituting at least one hydrogen atom of these groups with a substituent, and the like.

Here, in the present specification, the "organic group" is a group which may constitute a part of an organic compound, and may contain a hetero atom in the structure. The organic group is a concept containing a functional group such as an amine group or the like. The "hetero atom-containing group" may be a group having a hetero atom, and examples thereof include -O-, -CO-, -COO-, and -CONR ^a - (R ^a is a hydrogen atom or a carbon number of 1 to 6 alkyl, the same below), -NR ^a -, trivalent nitrogen atom, -NR ^a CONR ^a -, -OCONR ^a -, -S-, -COS-, -OCOO-, -SO ₂ -, phosphonium Base. Examples of the substituent include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amine group, a pyridyl group, an imidazolyl group, a fluorenyl group, a carboxyl group, a phosphoric acid group, a sulfo group, and a (meth)acryl fluorenyl group. Further, "(meth) propylene oxime" means "acryl oxime" and "methacryl oxime". The "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group which do not include a cyclic structure in the main chain but are composed only of a chain structure. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not including an aromatic ring structure. Among them, it is not necessary to be composed only of the structure of the alicyclic hydrocarbon, and also includes a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessary to constitute only the aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be contained in a part thereof.

As the group E ¹ and E ^2, preferably silicon alumoxane sesquichloride [L] has a plurality of at least one of E ¹ and E is selected from the group having the group ² consisting of at least one of: epoxy group An oxetanyl group, an acid anhydride group, a (meth) acrylonitrile group, a vinyl group (alkenyl group, a vinyl group in a styryl group, etc.), an ethynyl group, a decyl group, a -NHR ⁵ , an isocyanate group, an alcoholic hydroxyl group, a phenolic hydroxyl group, a cyano group, -COOR ¹ , -CON(R ¹ ) ₂ , -PO(R ¹ ) ₂ , -SO ₃ R ¹ and -SO ₂ N(R ¹ ) ₂ (wherein R ^{1 is} independently It is a hydrogen atom or a monovalent hydrocarbon group). R ^{1 is} preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms.

One or more of the plurality of E ¹ and E ² which the sesquiterpene oxide [L] has preferably has a group selected from the group consisting of a group having a pretilt expression ability, a photo-alignment group, and a crosslinkable group. At least one of the groups. By providing the group in the side chain, the obtained organic film can be provided with a function corresponding to each group. In particular, a sesquiterpene having a ladder structure represented by the above formula (1) is capable of arbitrarily controlling a group having a pretilt performance ability or a photoalignment property as compared with, for example, a cage type or a random type. The number of introduction of functional side chains such as a base or a crosslinkable group is preferable in that it is easy to adjust the controllability of the orientation and the reliability of the liquid crystal element.

The group having a pretilt performance ability is a group which imparts pretilt characteristics to the coating film without light irradiation, and specific examples thereof include an alkyl group having 3 to 20 carbon atoms and a fluorine having 3 to 20 carbon atoms. An alkyl group, an alkoxy group having 3 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, or a structure having two or more rings directly or via a linking group (hereinafter also referred to as "polycyclic structure"") group and so on. Specific examples of such a group include an alkyl group having 3 to 20 carbon atoms: n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-decyl group and n-decyl group. , n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, positive Examples of the fluoroalkyl group having 3 to 20 carbon atoms include a group obtained by substituting at least one hydrogen atom of the alkyl group exemplified by a fluorine atom, and the like; and an alkoxy group having 3 to 20 carbon atoms; Examples of the group include a group in which an oxygen atom is bonded to the alkyl group exemplified, and the like, and a group having a steroid skeleton having 17 to 51 carbon atoms may, for example, be a cholesteryl group or a cholesteryl group. a group of a lanthanyl group, etc.; a group having a polycyclic structure, for example, having 4,4'-exobiphenyl, 4,4'-bicyclohexylene, and the following formula (6-1) )~式(6-4) [化3] (In the formula, "*" represents a group or the like of a group represented by a bond). The sesquioxane [L] may have only one type of group having a pretilt performance ability, or may be two or more types.

The photo-alignment group may be a group (photoreactive group) which exhibits photo-alignment properties by photoisomerization or photodimerization. Specific examples of the photo-alignment group include an azobenzene-containing group having azobenzene or a derivative thereof as a basic skeleton, and a cinnamic acid-containing group having cinnamic acid or a derivative thereof as a basic skeleton. a benzophenone-containing group having a chalcone-containing group as a basic skeleton, a benzophenone-containing group having benzophenone or a derivative thereof as a basic skeleton, or a coumarin or a coumarin thereof A coumarin-containing group or the like having a derivative as a basic skeleton. Among these groups, a group having a cinnamic acid structure is preferred. The crosslinkable group is preferably a group which can form a covalent bond between the same or different molecules by light or heat, and for example, a (meth)acrylic acid or a derivative thereof as a basic skeleton (methyl group) An acrylic group, a group having a vinyl group (alkenyl group, styryl group, etc.), an ethynyl group, an epoxy group, an oxetanyl group or the like. Among them, a (meth)acryl group-containing group and a styryl group are preferable.

Further, the sesquiterpene oxide [L] may include only one of a group having a pretilt performance ability, a photo-alignment group, and a crosslinkable group, and may contain two or more of these groups. Further, a group having a pretilt performance ability and a crosslinkable group such as a (meth)acryl fluorenyl group or a vinyl group may be contained in one E ¹ or one E ² . The group exhibited pretilt performance ability and showed crosslinkability. n in the formula (1) is 2 or more, preferably 5 or more, and more preferably 8 or more. The upper limit of n can be appropriately selected depending on the desired molecular weight.

(Synthesis of sesquiterpene oxide [L]) The synthesis method of sesquiterpene oxide [L] is not particularly limited as long as the sesquiterpene oxide having the structure represented by the above formula (1) is obtained. The sesquioxane [L] is preferably a hydrolysis condensate of a hydrolyzable decane compound. In terms of the high structural regularity of the obtained sesquiterpene oxide or the high controllability of the molecular weight and the molecular weight distribution, it is preferably used in the following conditions 1, 2, and 3; A method of polymerizing a decane compound under two or more conditions (hereinafter referred to as "method 1") or a method of polymerizing a decane compound containing a compound represented by the following formula (3) (hereinafter referred to as "method"2"). Condition 1: A decane compound having one or two or more specific groups selected from the group consisting of -NHR ⁵ , pyridyl, imidazolyl, cyano, imido, hydroxy, decyl, carboxyl In the group consisting of phosphonium, sulfo and anhydride groups. Condition 2: in the case where the decane compound of the condition 1 has an acidic group as the specific group, the decane compound is hydrolytically condensed in the presence of a base, and in the case of having a basic group as the specific group, The decane compound is hydrolytically condensed in the presence of an acid. Condition 3: The decane compound is hydrolyzed and condensed in a solvent containing 10% by mass or more of water. [Chemical 4] (In the formula (3), Ar ¹ is one selected from the group consisting of groups represented by the following formulas (ar-1) to (ar-8), and J ¹ is selected from the group consisting of One of the groups consisting of groups represented by (j-1) to (j-7); R ⁴ is a monovalent hydrocarbon group having 1 to 18 carbon atoms) (In the formula (ar-1) to (ar-8), "*" represents a bond bonded to a ruthenium atom) [Chem. 6] (In the formula (j-1) to the formula (j-7), R ⁶ is a single bond or an alkanediyl group having 1 to 5 carbon atoms; R ⁷ is an alkyl group having 1 to 5 carbon atoms; and X ⁴ is a hydrogen atom or An alkyl group having 1 to 6 carbon atoms; "*" means a bond with Ar ¹ )

In the method 1, the decane compound used in the polymerization preferably contains a decane compound having a polar group, and particularly preferably a decane compound having one or two or more specific groups (hereinafter also referred to as "specific decane compound"). The specific group is selected from the group consisting of -NHR ⁵ , pyridyl, imidazolyl, cyano, imido, hydroxy, decyl, carboxyl, phosphonium, sulfo and anhydride groups. Preferable examples of the specific decane compound include compounds represented by the following formula (2). [Chemistry 7] (In the formula (2), R ³ is an organic group having 2 to 18 carbon atoms, and the organic group has one or two or more selected from the group consisting of -NHR ⁵ , pyridyl, imidazolyl, cyano, imino, hydroxy a specific group in the group consisting of a mercapto group, a carboxyl group, a phosphonium group, a sulfo group, and an acid anhydride group; and X ¹ , X ² and X ³ are each independently a halogen atom, an alkoxy group having 1 to 18 carbon atoms or carbon a number of 1 to 18 decyloxy groups)

Examples of the halogen atom in X ¹ , X ² and X ³ of the formula (2) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Examples of the alkoxy group having 1 to 18 carbon atoms include the groups exemplified in the description of E ¹ and E ² . Examples of the decyloxy group having 1 to 18 carbon atoms include an ethoxycarbonyl group, a propenyloxy group, and a benzamidineoxy group. As X ¹ , X ² and X ³ , among these groups, a halogen atom, a methoxy group or an ethoxy group is preferred. Further, X ¹ , X ² and X ³ may be the same or different from each other.

The compound represented by the formula (2) may, for example, be at least one compound selected from the group consisting of 2-cyanoethyltriethoxydecane, 3- Aminopropyltriethoxydecane, 3-mercaptopropyltriethoxydecane, 1-methyl-3-(3-trimethoxydecylpropyl)-1H-imidazole-3-indene chloride, (3-Benzylmethoxypropyl)trimethoxydecane, trimethoxydecylpropylacetamide, ethyl 4-(2-(trimethoxydecyl)ethyl)benzenesulfonate, N- (3-propyltrimethoxydecane)imidazole, N-(3-trimethoxydecylpropyl)aspartic acid, 3-(m-dimethylaminophenoxy)propyltrimethoxynonane, Methyl 3-(trimethoxydecyl)propionate and a compound represented by the following formula (2-1). [化8]

Further, in the case where a specific decane compound is used for the polymerization, a specific decane compound may be added to the polymerization system to carry out polymerization, or a specific decane compound may be prepared by a reaction in the system to carry out polymerization.

As the decane compound used in the synthesis of the sesquiterpene oxide [L], the specific decane compound as described above may be used singly, but other decane compounds may be used in combination with the specific decane compound. The other decane compound may be a hydrolyzable decane compound, and specific examples thereof include tetramethoxy decane, tetraethoxy decane, trimethyl ethoxy decane, methyl trimethoxy decane, and the like. Methyl diethoxy decane, phenyl trimethoxy decane, phenyl triethoxy decane, dimethyl dimethoxy decane, dodecyl triethoxy decane, octadecyl triethoxy Alkoxydecane compounds such as decane, tridecafluorooctyltrimethoxydecane, 4-(chloromethyl)phenyltrimethoxydecane; 3-glycidoxypropyltrimethoxydecane, 3-glycidyloxy Epoxy-containing, etc., such as propyl triethoxy decane, 3-glycidoxy propyl methyl dimethoxy decane, 2-(3,4-epoxycyclohexyl)ethyl trimethoxy decane Decane compound; 3-(methyl)propenyloxypropyltrimethoxydecane, 3-(methyl)propenyloxypropyltriethoxydecane, 3-(methyl)propenyloxypropyl Methyl dimethoxy decane, 3-(methyl) propylene methoxy propyl methyl diethoxy decane, vinyl trimethoxy decane, vinyl triethoxy decane, An alkoxydecane compound containing an unsaturated bond such as vinyltrimethoxydecane; 1,6-bis(trimethoxydecyl)hexane, tris-(3-trimethoxydecylpropyl)isocyanuric acid Ester, 1,8-bis(trimethoxydecyl)octane, bis[3-(trimethoxydecyl)propyl]amine, triethoxydecylthiopropyltrimethoxydecane, etc. A decane compound of the above ruthenium atom or the like. Other decane compounds may be used alone or in combination of two or more. When the sesquioxane [L] is synthesized, the use ratio of the other decane compound is preferably 50% by mole or less based on the total of the decane compound used in the synthesis of the sesquioxane [L]. It is preferably set to 40 mol% or less.

The reaction of the method 1 is carried out by hydrolyzing and condensing one or two or more kinds of the above-described decane compounds, preferably in the presence of a catalyst and a solvent. As the catalyst to be used in the reaction, in the case of using a decane compound having a basic group such as an amine group as a specific decane compound, an acid is preferably used, and particularly preferably hydrochloric acid. On the other hand, when a decane compound having an acidic group such as a carboxyl group is used as the specific decane compound, a base is preferably used as the catalyst, and an alkali metal compound is more preferable, and sodium hydroxide is particularly preferable. The ratio of use of the catalyst is appropriately set depending on the type of the catalyst, the reaction conditions, and the like. For example, the total amount of the decane compound is preferably 0.01 to 6 moles, more preferably 1 to 2 moles. 6 times Moule.

The solvent used in the hydrolysis/condensation reaction of the decane compound is preferably an alcohol such as methanol, ethanol, isopropanol or butanol, water or a mixed solvent of these solvents, but is not limited thereto. The solvent used in the reaction preferably contains 10% by mass or more of water. More preferably, the content of water is 50% by mass or more, and more preferably 80% by mass or more. The use ratio of the solvent is preferably from 10 parts by mass to 10,000 parts by mass, and more preferably from 50 parts by mass to 1,000 parts by mass, based on 100 parts by mass of the total of the decane compound used in the reaction.

The hydrolysis/condensation reaction is preferably carried out by first mixing a decane compound in a solvent containing a catalyst and water, performing a reaction for 6 hours to 24 hours, and then heating at 50 to 70 ° C in an open system to evaporate the solvent. And implementation. The heating time is preferably from 0.5 to 24 hours, more preferably from 1 to 12 hours. The mixture may also be stirred during heating. Further, after completion of the reaction, it is preferred to carry out a treatment of converting relative ions in the molecule using an ion exchange resin. Then, if necessary, the reaction liquid is dried with a desiccant such as anhydrous calcium sulfate or molecular sieve, and the solvent is removed, whereby a sesquiterpene oxide having a ladder structure represented by the above formula (1) can be obtained. In the method 1, it is preferred to carry out the polymerization under the condition that at least the conditions 1 and 2 are satisfied, and it is more preferable to carry out the polymerization under the conditions satisfying the three conditions.

In the method 2, the decane compound containing the compound represented by the formula (3) is subjected to hydrolysis and condensation. In the formula (3), the monovalent hydrocarbon group of R ⁴ preferably has a carbon number of from 1 to 10, more preferably a methyl group or an ethyl group. R ^{6 is} preferably a single bond or a carbon number of 1 to 3. X ^{4 is} preferably a hydrogen atom or a methyl group. Specific examples of the compound represented by the formula (3) include p-styryltrimethoxydecane, p-styryltriethoxydecane, 4-vinylbiphenyltrimethoxynonane, and 4 - vinylcyclohexyltrimethoxydecane, 4-epoxyphenyltrimethoxydecane, and the like. Among them, p-styryltrimethoxydecane or p-styryltriethoxydecane is preferred. Further, the compounds represented by the formula (3) may be used alone or in combination of two or more.

The hydrolysis/condensation reaction of Process 2 is preferably carried out in the presence of a catalyst and a solvent. Examples of the catalyst used in the reaction include potassium carbonate, sodium hydrogencarbonate, and the like. The catalyst is preferably used in a ratio of from 0.01 to 6 moles per mole of the total amount of the decane compound. Examples of the solvent to be used in the reaction include ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran, and dioxane, alcohols such as methanol, ethanol, isopropanol, and butanol, water, and these solvents. Two or more kinds of mixed solvents and the like are not limited thereto. Regarding the content ratio of water, the description of the method 1 is applied. The reaction temperature is preferably from 10 ° C to 120 ° C, and more preferably from 30 ° C to 80 ° C. The reaction time is from 0.1 to 48 hours, preferably from 1 to 12 hours. Further, in the reaction of the method 2, another decane compound other than the compound represented by the formula (3) may be used in combination as the decane compound. The compounding ratio of the other decane compound is preferably 70% by mole or less, and more preferably 50% by mole or less based on the total amount of the decane compound used in the reaction.

The sesquioxane [L] obtained by the hydrolysis/condensation reaction described above preferably has a polystyrene-equivalent weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) at 5,000. Within the range of ~50,000. When Mw is less than 5,000, the coating property to the substrate tends to be deteriorated. Further, when a liquid crystal display element is manufactured by a liquid crystal dropping method (ODF (One Drop Filling) method), display unevenness (ODF unevenness) due to the outflow of the polymer in the liquid crystal layer may occur. On the other hand, when Mw exceeds 50,000, the polymer is liable to gel, and the storage stability of the liquid crystal alignment agent is deteriorated. In view of the above, the lower limit of the Mw of the sesquioxane [L] obtained by the hydrolysis/condensation reaction is preferably 6,000 or more, and particularly preferably 8,000 or more. The upper limit of Mw is preferably 45,000 or less, and more preferably 40,000 or less. Further, the molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) is preferably in the range of 1.0 to 3.8, more preferably in the range of 1.0 to 3.3. Further, it is preferably in the range of 1.0 to 3.0.

The integral ratio of the peak of the ²⁹ Si-NMR spectrum derived from the partial structure (T3 unit) represented by the following formula (4) in the sesquiterpene oxide [L] (hereinafter also referred to as "T3 peak integration ratio") ) is preferably from 70% to 99%. More preferably, it is 75% to 99%, and further preferably 80% to 99%. Further, the T3 peak integration ratio is a value indicating the content ratio of the T3 unit (R ^I SiO _3/2 ) in the _ruthenium- containing polymer, and the larger the value, the ratio of the T3 unit (R ^I SiO _3/2 ). The higher. [Chemistry 9] (In the formula (4), R ^a is a monovalent organic group having a carbon number of 1 or more, and "*" represents a bond with a ruthenium atom)

As the sesquiterpene oxide [L], in the case of obtaining E ¹ and E ² in the structure represented by the formula (1), it has a group selected from a group having a pretilt expression ability, a photo-alignment group, and cross-linking. In the case of a side chain modified polymer of at least one group (hereinafter also referred to as "functional functional group") in the group consisting of a group, the synthesis method is not particularly limited, and it can be carried out by organic chemistry. The common method is suitable for combination. For example, [I] a method of polymerizing a decane compound having a functional functional group with respect to at least one of a specific decane compound and another decane compound; [II] obtaining by the hydrolysis/condensation reaction described above A functional group having a sesquioxane [L], a method of reacting with a reactive compound having a group reactive with the functional group, and a functional functional group.

In the method of the above [I], the use ratio of the decane compound having a functional functional group is preferably set to 0.5 mol% based on the total of the decane compound used in the synthesis of the sesquioxane [L]. 50% by mole, more preferably 1% by mole to 30% by mole. Further, the decane compound having a functional functional group may be used alone or in combination of two or more.

Specific examples of the method of the above [II] include, for example, using ruthenium chloride having a functional functional group as a reactive compound, and having in the presence of a base (for example, sodium hydroxide or pyridine, triethylamine, etc.) A method of reacting an amine group or a sesquioxane [L] of a phenolic hydroxyl group; using an amine group-containing compound having a functional functional group or a hydroxyl group-containing compound as a reactive compound, and using a suitable condensing agent (for example) : 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide (EDC), etc., and sesquiterpene having a carboxyl group a method in which an oxane [L] is reacted; an epoxy group-containing compound having a functional functional group is used as a reactive compound, and an interlayer transfer catalyst (for example, tetramethyl ammonium bromide (TMAB) or the like) is used. a method of reacting with a sesquioxane [L] having a carboxyl group; using a carboxylic acid having a functional functional group as a reactive compound, in the presence of a base with a sesquioxide having a benzyl halide structure a method in which an alkane [L] is reacted; Using a thiol or amine having a functional functional group as a reactive compound, reacting with a sesquioxane [L] having an unsaturated double bond such as a styryl group or an alkenyl group in the presence of a radical initiator Method etc.

When the reactive compound has a group reactive with a functional group possessed by sesquioxane [L] and a functional functional group, the remaining structure is not particularly limited. Specific examples of the reactive compound include, for example, compounds represented by the following formulas (r-1) to (r-22), but are not limited thereto. [化10] [11] (In the formula (r-1) to the formula (r-22), R ¹⁵ is an alkyl group having 1 to 8 carbon atoms or a fluoroalkyl group; R ¹⁶ is a hydrogen atom or a methyl group; and R ¹⁷ is an alkyl group or a cyclohexyl group or Phenyl; Y ¹ is a single bond or a divalent linking group, Z ¹ is a carboxyl group, an epoxy group, a -COCl group, an amine group or a thiol group, and X ⁵ is a hydroxyl group or a chlorine atom; j is an integer of 0 to 12, h An integer from 1 to 20; k is an integer from 1 to 5)

When a sesquioxane having a functional group is reacted with a reactive compound, a sufficient amount of a functional functional group is introduced into the side chain of the sesquioxane, relative to the sesquiterpene oxide The total amount of the ruthenium atoms to be used is preferably from 1 mol% to 90 mol%, more preferably from 5 mol% to 50 mol%. Further, the reactive compounds may be used alone or in combination of two or more.

The sesquioxane [L] having a functional functional group in the side chain preferably has a weight average molecular weight (Mw) in terms of polystyrene measured by GPC in the range of 6,000 to 60,000. The lower limit of Mw is more preferably 8,000 or more, still more preferably 10,000 or more, and particularly preferably 12,000 or more. Further, the upper limit of Mw is more preferably 50,000 or less, still more preferably 45,000 or less. The molecular weight distribution (Mw/Mn) is preferably in the range of 1.0 to 3.8, more preferably in the range of 1.0 to 3.3, still more preferably in the range of 1.0 to 3.0.

The sesquiterpene oxide [L] contained in the liquid crystal alignment agent can be directly supplied to the preparation of the liquid crystal alignment agent in the form of a reaction solution obtained by dissolving the same, or in the reaction solution. The sesquioxane containing [L] is separated and then supplied to the preparation of the liquid crystal alignment agent. Alternatively, the sesquioxane [L] may be purified and then supplied to the preparation of the liquid crystal alignment agent. The separation and purification of sesquiterpene oxide [L] can be carried out according to a known method.

According to the liquid crystal alignment agent containing the sesquioxane [L], a liquid crystal alignment film having a sufficiently high crosslinking density of sesquioxanes is obtained by using a stanol group remaining at the terminal. In other words, when the crosslinking density of the sesquiterpene oxide in the liquid crystal alignment film is insufficient, when the liquid crystal cell is formed, there is a concern that the display quality is lowered due to the flow of the sesquioxane into the liquid crystal. In this respect, by using sesquioxane [L] in the alignment film material, as the crosslinking density is increased, the inflow of the film component in the liquid crystal is reduced, and the display quality can be ensured.

According to the above-described synthesis method, a polymer satisfying the following requirements (A) to (C) can be obtained as a sesquiterpene oxide [L]. By using a polymer which satisfies these requirements (A) to (C) as a polymer component of a liquid crystal alignment agent, it is excellent in coating property to a substrate, and liquid crystal element having good liquid crystal alignment property and electrical characteristics can be obtained. Preferably. (A) The weight average molecular weight (Mw) measured by GPC is 5,000 or more. (B) The molecular weight distribution (Mw/Mn) represented by the ratio of the weight average molecular weight (Mw) to the number average molecular weight (Mn) measured by GPC was 3.8 or less. (C) The integral ratio of the peak of the ²⁹ Si-NMR spectrum derived from the partial structure represented by the formula (4) is 70% to 99%.

In terms of sufficiently ensuring the effect, Mw is preferably 8000 or more, more preferably 10,000 or more, and still more preferably 12,000 or more in terms of the necessary condition (A). Further, with respect to the requirement (B), the molecular weight distribution is more preferably 3.3 or less, still more preferably 3.0 or less. The peak integration ratio of the necessary condition (C) is more preferably from 75% to 99%, and still more preferably from 80% to 99%. Further, regarding the ruthenium-containing polymer, the integral ratio of the peak of the ²⁹ Si-NMR spectrum obtained by the T3 peak integration ratio greater than the T2 peak integration ratio (for example, the partial structure represented by the above formula (4) is 70% or more ), soluble in water, having a large weight average molecular weight Mw (for example, Mw ≧ 5000) and a narrow molecular weight distribution (Mw/Mn) (for example, a molecular weight distribution of 3.8), and it can be judged that the main skeleton of the obtained ruthenium-containing polymer is Ladder structure. The sesquiterpene oxide [L] may be composed only of the ladder structure represented by the above formula (1), or may include a random or cage structure in a part thereof.

<Other components> The liquid crystal alignment agent of the present invention contains the sesquioxane [L] as described above, but may contain other components as needed.

One of the other components may be a polymer other than sesquiterpene oxide [L]. Examples of the other polymer include polyimine, polylysine, polyphthalate, and polyoxyalkylene having no structure represented by the above formula (1) (for example, cage type, random type, Double-decker type polyoxyalkylene), polyester, polyamine, cellulose derivative, polybenzoxazole precursor, polybenzoxazole, polyacetal, polystyrene derived A polymer, a poly(styrene-phenylmaleimide) derivative, a polymer having a poly(meth)acrylate or the like as a main skeleton. Further, (meth) acrylate means acrylate and methacrylate. The other polymer is preferably at least one polymer selected from the group consisting of polylysine, polyimine, and polyphthalate (hereinafter also referred to as "polymer" [P] ").

[Polyuric Acid] The polyamic acid as the polymer [P] can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. A well-known tetracarboxylic dianhydride can be used for the tetracarboxylic dianhydride used for the synthesis of poly-proline. Specific examples of the tetracarboxylic dianhydride include aliphatic 1,4,3,4-butanetetracarboxylic dianhydride, and the like, and examples of the alicyclic tetracarboxylic dianhydride are exemplified. : 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro -8-Methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6, 8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, cyclohexanetetracarboxylic dianhydride, etc.; aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride In addition, the tetracarboxylic dianhydride described in JP-A-2010-97188 can also be used. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

A well-known compound can be used for the diamine used for the synthesis of poly-proline. Specific examples of the diamine include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, and hexamethylenediamine; and alicyclic diamines. Examples thereof include 1,4-diaminocyclohexane and 4,4′-methylenebis(cyclohexylamine); and examples of the aromatic diamine include p-phenylenediamine and 4,4′-diamine. Diphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 4,4'-diaminodiphenyl ether, 4-aminophenyl-4'-aminobenzoate, 1,3-bis(4-aminophenoxy)propane, 2,2- Bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-(p-phenylenediphenylene)diphenylamine, 1,4-bis(4-aminobenzene) Oxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, N,N'-bis(4-aminophenyl)-benzidine, 1,4-bis-(4- Aminophenyl)-piperazine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-5-amine, 3,5-di Aminobenzoic acid, cholestyloxy-3,5-diaminobenzene, cholesteryl 3,5-diaminobenzoate, etc.; and diaminoorganomethoxy siloxanes, for example, 1,3 - bis(3-aminopropyl)-tetramethyldioxane; Except, in Japanese Patent Laid-Open may diamine described in Patent Publication No. 2010-97188. Further, these diamines may be used alone or in combination of two or more.

The polyamic acid can be obtained by reacting a tetracarboxylic dianhydride with a diamine, if necessary, together with a molecular weight modifier (for example, an acid mono-anhydride, a monoamine compound, a monoisocyanate compound, etc.). The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. . The synthesis reaction of poly-proline is preferably carried out in an organic solvent. The reaction temperature at this time is preferably from -20 ° C to 150 ° C, and the reaction time is preferably from 0.1 hour to 24 hours. As the organic solvent, it is preferably selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, γ-butyl One or more of the group consisting of lactone, tetramethyl urea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or one or more of these solvents are used and selected from the group consisting of alcohols, a mixture of more than one of the group consisting of a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. The reaction solution obtained by dissolving polylysine may be directly supplied to the preparation of the liquid crystal alignment agent, or the polylysine contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal alignment agent.

[Polyimide] The polyimine which is the polymer [P] can be obtained by subjecting polylysine synthesized in the above manner to dehydration ring closure and imidization of ruthenium. The polyimine may be a complete quinone imide formed by dehydrating and ring-closing the proline structure of the polyamic acid, or a partial quinone imine having a proline structure and a quinone ring structure. Compound. The ruthenium imidization ratio of the polyimine is preferably 30% or more, more preferably 40% to 99%. The ruthenium imidation ratio is a total of the number of the guanidine structure of the polyimine and the number of the quinone ring structure, and the ratio of the number of the quinone ring structure is expressed as a percentage. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closure catalyst to the solution, and heating as necessary. As the dehydrating agent, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, a tertiary amine such as pyridine, trimethylpyridine, dimethylpyridine or triethylamine can be used. The amount of the dehydration ring-closure catalyst to be used is preferably from 0.01 mol to 10 mol based on 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring closure reaction is exemplified as an organic solvent exemplified as a user of the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, and the reaction time is preferably from 1.0 hour to 120 hours. The reaction solution containing the polyimine may be directly supplied to the preparation of the liquid crystal alignment agent, or the polyimine may be separated and then supplied to the preparation of the liquid crystal alignment agent. In addition to this, polyimine can also be obtained by hydrazylation of polyphthalate.

[Polyurethane] The polyglycolate as the polymer [P] can be obtained, for example, by the following method: [I] reacting a polylysine obtained by the synthesis reaction with an esterifying agent Method; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine. The polyphthalate contained in the liquid crystal alignment agent may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist. Further, the reaction solution obtained by dissolving the polyamidate may be directly supplied to the preparation of the liquid crystal alignment agent, or the polyphthalate contained in the reaction solution may be separated and then supplied to the preparation of the liquid crystal alignment agent.

The polylysine, polyphthalate, and polyimine obtained in the above manner are preferably a solution having a concentration of 10 mPa·s to 800 mPa·s when it is made into a solution having a concentration of 10% by mass. The viscosity is more preferably a solution viscosity of 15 mPa·s to 500 mPa·s. Further, the solution viscosity (mPa·s) of the polymer is a concentration of 10% by mass prepared from a good solvent (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) using the polymer. The polymer solution was measured at 25 ° C using an E-type rotational viscometer. The polystyrene acid, the polyamidomate, and the polyimine contained in the liquid crystal alignment agent are preferably a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC) of 500 to 500 Å. 100,000, more preferably 1,000 to 50,000.

Preferred examples of the polymer component to be blended in the liquid crystal alignment agent include the following (i) and (ii). (i) A form in which sesquioxane [L] is contained as a polymer component alone. (ii) A form containing a sesquioxane [L] and a polymer [P] as a polymer component. In the case of the above (ii), sesquiterpene oxide [L] is preferable from the viewpoint of improving the coating property and reliability by the preparation of sesquioxane [L]. The blending ratio ([L]: [P]) to the polymer [P] is preferably from 1:99 to 80:20 in terms of mass ratio. More preferably, it is 10:90 - 75:25, and further preferably 20:80 - 70:30.

Further, as the other component, examples of the other additives include a compound having at least one epoxy group in the molecule, a functional decane compound, a compound having at least one oxetanyl group in the molecule, an antioxidant, and a surfactant. , light sensitizer, filler, antifoaming agent, dispersing agent, adhesion aid, antistatic agent, leveling agent, antibacterial agent, and the like. The blending ratio of these additives can be appropriately set within the range not impairing the effects of the present invention, depending on the compound to be used.

<Solvent> The liquid crystal alignment agent of the present invention is prepared as a sesquioxane [L] and, if necessary, other components, which are preferably a liquid composition which is dispersed or dissolved in a suitable solvent. Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethyl B. Indamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, Ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These organic solvents may be used singly or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total mass of the components other than the solvent of the liquid crystal alignment agent to the total mass of the liquid crystal alignment agent) can be appropriately selected in consideration of viscosity, volatility, etc., and is preferably 1 A range of % by mass to 10% by mass. In other words, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate as described later, and is preferably heated to form a coating film as a liquid crystal alignment film or a coating film to be a liquid crystal alignment film. At this time, when the solid content concentration is less than 1% by mass, the film thickness of the coating film is too small, and it is difficult to obtain a favorable liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by mass, the film thickness of the coating film becomes too large, and it is difficult to obtain a favorable liquid crystal alignment film, and the viscosity of the liquid crystal alignment agent increases and the coating property decreases. tendency. The temperature at which the liquid crystal alignment agent of the present invention is prepared is preferably from 10 ° C to 50 ° C.

[Liquid Crystal Alignment Film and Liquid Crystal Element] The liquid crystal alignment film of the present invention is formed using the liquid crystal alignment agent prepared in the above manner. Further, the liquid crystal element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal in the liquid crystal element is not particularly limited, and can be applied to a twisted nematic (TN) type, a super twisted nematic (STN) type, and an in-plane switching (In-Plane Switching, IPS). ), Fringe Field Switching (FFS) type, Vertical Alignment (VA) type, Multidomain Vertical Alignment (MVA) type, Polymer sustained alignment (PSA) type And many other modes.

The liquid crystal element can be produced by, for example, a method including the following steps 1 to 3. Step 1 uses different substrates depending on the desired drive mode. Steps 2 and 3 are common to each mode. [Step 1: Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. For the substrate, for example, glass such as float glass or soda glass; plastics such as polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, and poly(alicyclic olefin) may be used. Transparent substrate. In the case of manufacturing a liquid crystal display element of a TN type, an STN type, a VA type, an MVA type or a PSA type, two substrates provided with a patterned transparent conductive film are used. In the case of manufacturing an IPS type or FFS type liquid crystal display element, a substrate provided with an electrode including a transparent conductive film or a metal film patterned into a comb shape, and an opposite substrate not provided with an electrode are used. The transparent conductive film provided on the substrate surface may be a Neisser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), or an ITO film containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Wait. As the metal film, a film containing a metal such as chromium can be used. The application of the liquid crystal alignment agent on the substrate is preferably carried out by an offset printing method, a spin coating method, a roll coater method or an inkjet printing method.

After the liquid crystal alignment agent is applied, preheating (prebaking) is preferably performed for the purpose of preventing sag of the applied alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, and the prebaking time is preferably from 0.25 minutes to 10 minutes. Then, for the purpose of completely removing the solvent, in addition, in the case where the liquid crystal alignment agent contains the polymer [P], the structure of the proline which is present in the polymer [P] is subjected to thermal imine, if necessary. For the purpose of the purpose, the calcination (post-baking) step is carried out. The calcination temperature (post-baking temperature) at this time is preferably from 80 ° C to 300 ° C. The post-baking time is preferably from 5 minutes to 200 minutes. The film formed in the above manner preferably has a film thickness of 0.001 μm to 1 μm. After the liquid crystal alignment agent is applied onto the substrate, the organic solvent is removed to form a coating film which becomes a liquid crystal alignment film.

[Step 2: Orientation ability imparting treatment] When a TN type, STN type, IPS type or FFS type liquid crystal display element is manufactured, a process of imparting a liquid crystal alignment ability to the coating film formed in the above step 1 is performed. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment ability imparting treatment include a rubbing treatment in which a coating film is wound in a predetermined direction by a roll wound with a cloth containing fibers such as nylon, rayon, or cotton, and a light alignment treatment is performed to irradiate the coating film with polarized light or Non-polarized radiation. When the liquid crystal alignment ability is imparted to the coating film by the photo-alignment treatment, the radiation to be applied to the coating film may be, for example, ultraviolet light or visible light containing light having a wavelength of 150 nm to 800 nm, and may be polarized or non-polarized. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. The irradiation amount of the radiation is preferably from 100 J/m ² to 50,000 J/m ² , and more preferably from 300 J/m ² to 20,000 J/m ² . Further, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a polymer sustained alignment (PSA) type liquid crystal display element.

[Step 3: Construction of Liquid Crystal Cell] Two substrates in which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. For example, the method of manufacturing the liquid crystal cell is as follows: (1) aligning the two substrates via the cell gap so that the respective liquid crystal alignment films face each other, and bonding the peripheral portions of the two substrates with the sealant on the surface of the substrate And a method of sealing the injection hole after filling the liquid crystal into the cell gap divided by the sealant; (2) liquid crystal dropping method (ODF method). As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. The liquid crystal may be a nematic liquid crystal or a discotic liquid crystal, and among them, a nematic liquid crystal is preferable. Further, for example, a cholesteric liquid crystal, a chiral agent, a ferroelectric liquid crystal, or the like may be added to these liquid crystals.

Next, the liquid crystal element of the present invention can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell as needed. The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film or a polarizing plate including the H film itself. The H film "is formed by absorbing iodine while extending the polyvinyl alcohol.

The liquid crystal element of the present invention can be effectively applied to various devices, for example, can be used for: a clock, a portable game machine, a word processor, a note type personal computer, a car navigation system. ), camcorder, personal digital assistant (PDA), digital camera, mobile phone, smart phone, various monitors, LCD TV and other display devices, or dimming film. Further, a liquid crystal element formed using the liquid crystal alignment agent of the present invention can also be applied to a retardation film.

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

In the following examples, the weight average molecular weight of the polymer, the oxime imidization ratio of the polyimine, the solution viscosity of the polymer solution, the epoxy equivalent, and the T3 peak integration ratio were measured by the following methods. In addition, the "part" and "%" in the following examples are the quality standards unless otherwise specified. [Weight average molecular weight and number average molecular weight of the polymer]: a polystyrene equivalent value measured by GPC under the following conditions. Pipe column: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII Solvent: tetrahydrofuran temperature: 40 ° C Pressure: 68 kgf / cm ² [醯imination rate of polyimine]: Put the solution containing polyimine into pure water, The obtained precipitate was sufficiently dried under reduced pressure at room temperature, dissolved in deuterated dimethyl hydrazine, and tetramethyl decane was used as a reference material, and ¹ H-nuclear magnetic resonance (Nuclear Magnetic Resonance) was measured at room temperature. , NMR). From the ¹ H-NMR spectrum obtained, the oxime imidization ratio [%] was determined using the following formula (1).醯imination rate [%]=(1-A ¹ /A ² ×α)×100 (1) (In the formula (1), A ¹ is an NH group derived from a chemical shift of 10 ppm. The peak area of protons, A ² is the peak area derived from other protons, and α is the ratio of the number of protons of other protons to the NH group in polyperuric acid. [Solid viscosity of polymer solution (mPa·s) ]: A solution prepared to have a polymerization concentration of 10% by mass using a predetermined solvent was measured at 25 ° C using an E-type rotational viscometer. [Epoxy equivalent]: Measured according to "hydrochloric acid-methyl ethyl ketone method" of JIS C2105. [T3 peak integration ratio]: It was determined by ²⁹ Si-NMR in the following manner. 2 g of a polyaluminoxane solution having a solid concentration of 20% and tris(2,4-pentanedione) chromium (III) were dissolved in 0.8 g of dimethylsulfoxide-d6. As a sample, a ²⁹ NMR measurement of the sample was carried out using a nuclear magnetic resonance apparatus AVANCE type III400 NMR apparatus (Bruker BioSpin). The content ratio of each structure represented by each of the following formulas (T1) to (T3) of polysiloxane is determined based on the difference in chemical shift of each spectrum obtained by the ²⁹ Si-NMR measurement. The integral value of each signal. [化12] (In the formula (T1) to the formula (T3), R ^a is a monovalent organic group having 1 or more carbon atoms, and "*" represents a bond with a ruthenium atom)

<Synthesis of sesquiterpene oxide [L]> The sesquiterpene oxide [L] was synthesized by the following procedure. Further, Method 1 was used in Synthesis Example 1-1 to Synthesis Example 1-6 and Synthesis Example 1-8, and Method 2 was used in Synthesis Example 1-7. [Synthesis Example 1-1] 4.43 g (20 mmol) of 3-aminopropyltriethoxydecane as a specific decane compound of Condition 1 was mixed in a 1.0 mol/L 60 mL aqueous hydrochloric acid solution (containing a solvent as a whole) In 96% by mass of water), it was stirred at room temperature for 2 hours. Then, heating is carried out at 60 ° C to 70 ° C in an open system to evaporate the solvent to carry out polycondensation. Next, the product was allowed to stand at 100 ° C, dissolved in 300 mL of water, and the obtained aqueous solution was freeze-dried, thereby obtaining 4.24 g (yield 94%) of a white powdery compound (hereinafter referred to as "Polymer (L-1A)"). Then, 0.20 g of the obtained polymer (L-1A) was dissolved in 50 mL of water, and a column packed with an anion exchange resin (Amberlite IRA-900) was passed to transport a catalyst as Condition 2 1 N aqueous solution of NaOH. Then, the obtained solution was freeze-dried, whereby 1.63 g (yield 74%) of a sesquiterpene oxide having a partial structure represented by the following formula (s-1) (hereinafter referred to as "polymer" was obtained. (L-1)"). The obtained polymer (L-1) had Mw=13,000, Mn=6,400, a molecular weight distribution (PDI) represented by a ratio of Mw to Mn (Mw/Mn)=2.0, and a peak integration ratio of T3 of 89%, soluble. In the water. Based on these physical properties, it was confirmed that the polymer (L-1) was a ladder type. In addition, the storage stability was evaluated based on the presence or absence of gelation when the polymer solution was allowed to stand at 20 ° C for 3 days. The case where gelation was not observed was evaluated as "good" in storage stability, and the case where gelation was observed was evaluated as "poor". As a result, the polymer solution was not gelled, and the storage stability was "good". [Chemistry 13]

[Synthesis Example 1-2 and Synthesis Example 1-3] The ladder type was obtained by performing the same operation as in Synthesis Example 1-1 except that the type and amount of the monomer to be used were changed as described in Table 1 below. Sesquiterpene oxide (polymer (L-2) and polymer (L-3)). The physical properties of the obtained polymer are shown in Table 2 below. [Synthesis Example 1-4] 4.35 g of 2-cyanoethyltriethoxydecane as a specific decane compound of Condition 1 was mixed with 5 mL of a sodium hydroxide having a concentration of 8% as a catalyst of Condition 2 The mixture was stirred for 13 hours in an aqueous solution. The obtained aqueous solution is heated at 50 to 60 ° C in an open system to evaporate the solvent to carry out polycondensation. Then, the resulting powdery crude product was added to 100 mL of water to which about 100 cm ^{3 of} a H ⁺ type cation exchange resin was added, and stirred at room temperature for 3 hours. After the cation exchange resin was separated by filtration, the obtained aqueous solution was concentrated to 20 mL with a rotary evaporator, and then freeze-dried, whereby 1.95 g (yield 70%) of the following formula was obtained ( The sesquioxane having a partial structure represented by s-4) (hereinafter referred to as "polymer (L-4)"). The obtained polymer (L-4) had Mw of 8,000, Mn of 4,000, a molecular weight distribution (PDI) of 2.0, and a T3 peak integration ratio of 86%, which was soluble in water. Based on these physical properties, it was confirmed that the polymer (L-4) was a ladder type. Further, with respect to the polymer solution, the storage stability was evaluated in the same manner as in Synthesis Example 1-1, and as a result, it was "good". [Chemistry 14]

[Synthesis Example 1-5] A ladder type sesquiterpene oxide (polymerization) was obtained by performing the same operation as in Synthesis Example 1-4 except that the type and amount of the monomer to be used were changed as described in Table 1 below. Body (L-5)). The physical properties of the obtained polymer are shown in Table 2 below. [Synthesis Example 1-6] Except that the type and amount of the monomer to be used were changed as described in Table 1 below, and a mixed solution of a sodium hydroxide aqueous solution and an aqueous hydrogen peroxide solution was used as a catalyst, The same operation as in Synthesis Example 1-4 was carried out to obtain ladder type sesquiterpene oxide (polymer (L-6)). The physical properties of the obtained polymer are shown in Table 2 below.

[Synthesis Example 1-7] 9.00 g of p-styryltrimethoxydecane and 0.04 g of potassium carbonate as a compound represented by the above formula (3) were added to a mixed solvent of tetrahydrofuran/water of 7 mL (mass The mixture was mixed in a ratio of 3/2), and polymerization was carried out at 40 ° C for 2 hours. Then, the precipitated viscous solid was dissolved in 15 mL of dichloromethane, and the obtained liquid was slowly added dropwise to 100 mL of methanol. After the dropwise addition, the resulting solid was collected by filtration and dried, whereby a polymer (L-7) as a sesquiterpene oxide was obtained in a yield of 77%. The obtained polymer (L-7) had a Mw of 9,700, an Mn of 4,800, a molecular weight distribution (PDI) of 2.0, and a T3 peak integral ratio of 92%, and was soluble in water. The ²⁹ Si-NMR chart of the polymer (L-7) is shown in Fig. 1. Further, in the partial structure represented by the formula (4), the peak of the T3 unit in the case where R ^a is a styryl group appears in the vicinity of -80 ppm, the peak of the T2 unit appears in the vicinity of -70 ppm, and the peak of the T1 unit appears. Now near -65 ppm. According to the results of Fig. 1, the proportion of the T3 unit of the polymer (L-7) is larger than that of the T2 unit and the T1 unit. Based on these results, it was confirmed that the polymer (L-7) was a ladder type.

[Synthesis Example 1-8] Under a nitrogen atmosphere, 15 mL of a xylene solution was added to 3.17 g (0.025 mol) of chlorodimethoxydecane, and the mixture was cooled to -15 °C. Then, 25 ml of a 2.70 g (0.025 mol) solution of p-phenylenediamine in acetone was slowly added dropwise, followed by stirring for 30 minutes. After stirring, 15 mL of acetone, 20 mL of xylene, and 6 mL (10 mol/L) of hydrochloric acid were successively added dropwise, and the mixture was stirred at room temperature for 4 hours. Then, sodium sulfate was added for dehydration, and sodium sulfate was removed by filtration. Two drops of concentrated sulfuric acid were added to the filtrate, and the mixture was stirred at room temperature for 3 hours, and then stirred at 90 ° C for 3 hours. Then, the liquid layer was washed with 50 ml of water, and the solvent of the organic layer was distilled off, whereby a polymer (L-8) as a sesquiterpene oxide was obtained in a yield of 83%. The obtained polymer (L-8) had Mw of 15,000, Mn of 8,000, a molecular weight distribution (PDI) of 1.9, and a peak integration ratio of T3 of 82%, which was soluble in water. From the above physical properties, it was confirmed that the polymer (L-8) was a ladder type.

<Synthesis of Other Polymer (Polyoxane)> [Comparative Synthesis Example 1-1] 4.9 g (20 mmol) of 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane was dissolved in 50 g of cyclopentanone was slowly added dropwise to a solution obtained by dissolving 0.2 g of triethylamine (TEA) and 5.0 g of water in 50 g of cyclopentanone, and mixing them. Stir at ° C for 2 hours. The solvent was evaporated by an evaporator, and the resulting solid was washed with acetone to obtain 3.30 g (yield 93%) of a caged sesquiterpoxide as a white powdery compound (hereinafter referred to as "polymer (R-1)" "). The obtained polymer (R-1) had Mw of 3,500, Mn of 2,100, a molecular weight distribution (PDI) of 1.7, and a T3 peak integration ratio of 94%. Further, after the polymer solution was allowed to stand at 20 ° C for 3 days, it was not gelled, and the storage stability was good.

[Comparative Synthesis Example 1-2 to Comparative Synthesis Example 1-4] The same operation as in Comparative Synthesis Example 1-1 was carried out except that the type and amount of the monomer to be used were changed as described in Table 1 below. A polymer (R-2) to a polymer (R-4) as a cage sesquiterpene gas was obtained. The physical properties of the obtained polymer are shown together in Table 1 below. Further, in the polymer (R-3) and the polymer (R-4), after the polymer solution was allowed to stand at 20 ° C for 3 days, gelation was observed, and storage stability was poor.

[Comparative Synthesis Example 1-5] In a 500 mL four-neck reaction flask equipped with a reflux tube, 51.3 g of hexanediol, 15.6 g of butyl cellosolve, 66.0 g of tetraethoxynonane, and 6.9 g were charged. Stirring was carried out with dodecyltriethoxydecane. To the solution, an oxalic acid solution obtained by mixing 25.6 g of hexanediol, 7.8 g of butyl cellosolve, 30.0 g of water, and 0.3 g of oxalic acid as a catalyst was added dropwise at room temperature. Stir for 30 minutes. Then, it was heated at a solution temperature of 70 ° C for 1 hour and then left to cool. Add hexyleneglycol (HG), butyl cellosolve (BC) and N-methyl-2-pyrrolidone (NMP) to the solution, HG:BC:NMP= 30:50:20 (mass ratio) was prepared so that the concentration in terms of SiO _{2 was} 3.5% by mass, and a solution containing a random polysiloxane (hereinafter referred to as "polymer (R-5)") was obtained. The obtained polymer (R-5) had a Mw of 9,000, a Mn of 2,650, a molecular weight distribution (PDI) of 3.4, and a T3 peak integration ratio of about 0% (Table 2).

[Synthesis Example 1-6] A sesquiterpene oxide was obtained by the same operation as in Comparative Synthesis Example 1-1 except that the same concentration of aqueous sodium hydroxide solution was used instead of the 1.0 mol/L aqueous hydrochloric acid solution. Polymer (R-6). The obtained polymer (R-6) had a Mw of 125,000, an Mn of 29,000, a molecular weight distribution (PDI) of 4.3, and a T3 peak integration ratio of 62% (Table 2). Based on these physical properties, the polymer (R-6) was confirmed. ) is a random type. The polymer gelled after one day. The physical properties of the obtained polymer are shown in Table 2 below.

[Comparative Synthesis Example 1-7] A sesquiterpene oxygen was obtained by performing the same operation as Comparative Synthesis Example 1-4 except that the aqueous solution of sodium hydroxide having a concentration of 8% was used instead of the aqueous solution of hydrochloric acid having the same concentration. Alkane polymer (R-7). The obtained polymer (R-7) had a Mw of 60,000, a Mn of 15,000, a molecular weight distribution (PDI) of 4.0, and a peak integration ratio of T3 of 94% (Table 2). Based on these physical properties, the polymer (R-7) was confirmed. ) is a random type.

[Table 1]

In Table 1, the numerical value of the monomer indicates the use ratio (mol%) of each compound with respect to the total of the monomers used in the reaction. <Monomer> MS3-1: 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane MS3-2: 3-methylpropenyloxypropyltrimethoxydecane MS3-3: ten Dialkyltriethoxydecane MS3-4: 3-Aminopropyltriethoxydecane MS3-5: 2-cyanoethyltriethoxydecane MS3-6: 4-(Chloromethyl)benzene Trimethoxymethoxydecane MS3-7: p-styryltrimethoxydecane MS3-8: 3-mercaptopropyltriethoxydecane MS3-9: chlorodimethoxydecane MS4-1: Tetraethoxydecane

[Table 2]

<Synthesis of side chain modified sesquiterpene oxide [L]> [Synthesis Example 2-1] 10 mL of 1.02 g (3.7 mmol) of 4-(4-n-pentylcyclohexyl)benzoic acid was mixed. Thionine chloride was heated at 60 ° C for 1 hour. Then, the sulfinium chloride in the system was removed by distillation under reduced pressure to obtain white ruthenium chloride. It was dissolved in 20 g of tetrahydrofuran. Then, 1.63 g of the polymer (L-1) was dissolved in a mixed solvent of 15 ml of water and 15 mL of tetrahydrofuran, and 0.45 g (4.4 mmol) of triethylamine and 0.05 g of bromination were added to the solution. Tetrabutylammonium was stirred. This was placed under ice cooling to set the internal temperature in the system to 5 ° C or lower. In the solution, the hydrazine chloride solution was added dropwise for one hour, and the mixture was stirred for 4 hours in an ice bath. Then, 100 mL of cyclopentanone was added to the obtained reaction liquid, and liquid separation extraction was performed. Then, 150 mL of N-methyl-2-pyrrolidone was added and concentrated by an evaporator to obtain a polymer solution containing a side chain-modified polymer (L-11). The obtained polymer (L-11) had Mw of 19,000, Mn of 9,600, a molecular weight distribution (PDI) of 2.0, and a T3 peak integration ratio of 91%. In addition, the evaluation of storage stability was "good".

[Synthesis Example 2-2 and Synthesis Example 2-3] A polymer was obtained by performing the same operation as in Synthesis Example 2-1 except that the type and amount of the carboxylic acid to be used were changed as described in Table 3 below. (L-12) and polymer (L-13). The physical properties of the obtained polymer are shown in Table 4 below. [Synthesis Example 2-4] 0.69 g (2.8 mmol) of 4-(4-n-pentylcyclohexyl)aniline as a reactive compound (side chain component), and 1.95 g of a polymer (L-4), Dissolved in 20 mL of N-methyl-2-pyrrolidone and 40 mL of cyclopentanone in a mixed solvent. This was placed under ice cooling to set the internal temperature in the system to 5 ° C or lower. 0.81 g (4.2 mmol) of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride and 0.1 g (catalyst amount) of dimethylaminopyridine were added. The reaction was carried out for 6 hours under ice cooling. Then, 100 mL of cyclopentanone was added to the obtained reaction liquid, and liquid separation extraction was performed. Then, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer, and the mixture was concentrated by an evaporator to obtain a polymer solution containing a side chain-modified polymer (L-14).

[Synthesis Example 2-5 and Synthesis Example 2-6] The polymerization was separately obtained by performing the same operation as in Synthesis Example 2-4 except that the type and amount of the reactive compound to be used were changed as described in Table 3 below. Body (L-15) and polymer (L-16). The physical properties of the obtained polymer are shown in Table 4 below. [Synthesis Example 2-7] 1.01 g (3.7 mmol) of 4-(4-n-pentylcyclohexyl)benzoic acid as a reactive compound (side chain component) was dissolved in 30 mL of tetrahydrofuran (THF). Add 2.56 g (18.5 mmol) of potassium carbonate. Then, 2.51 g of the polymer (L-5) was added, and the mixture was stirred at room temperature for 3 hours. After stirring, the solid was removed by filtration. Then, 100 mL of cyclopentanone was added to the obtained filtrate to carry out liquid separation extraction. Then, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer, and the mixture was concentrated by an evaporator to obtain a polymer solution containing a side chain-modified polymer (L-17). The physical properties of the obtained polymer are shown in Table 4 below. [Synthesis Example 2-8] 1.01 g (3.02 mmol) of a compound represented by the following formula (mc-7) was dissolved in 30 mL of toluene, followed by addition of 1.98 g of a polymer (L-7) and 9.85 mg. Azobisisobutyronitrile was stirred at 70 ° C for 3 hours. After the reaction, 100 mL of N-methyl-2-pyrrolidone was added and concentrated by an evaporator to obtain a polymer solution containing a side chain-modified polymer (L-18). The physical properties of the obtained polymer are shown in Table 4 below.

[Synthesis Example 2-9] To 5.15 g of the polymer (L-8), 30 mL of toluene was added and dissolved. Then, 6.21 g (50 mol) of 1,2-epoxy-4-vinylcyclohexane and 0.1 g of hexachloroplatinic (IV) acid were successively added, and the reaction was carried out at 80 ° C for 2 hours. After the reaction, filtration was carried out to remove the catalyst. 100 mL of cyclopentanone was added to the filtrate for concentration, whereby 30 g of a cyclopentanone solution having a solid content concentration of 30% by mass was obtained. To the obtained solution, 4.12 g (15 mmol) of 4-(4-n-pentylcyclohexyl)benzoic acid and 0.5 g of tetrabutylammonium bromide were added, and the mixture was stirred at 110 ° C for 4 hours. After stirring, 100 mL of water was added to carry out liquid separation purification. Then, 30 mL of butyl cellosolve was added to the organic layer and concentrated to obtain a polymer solution containing the side chain-modified polymer (L-19). The physical properties of the obtained polymer are shown in Table 4 below.

<Synthesis of Other Polymer (Side Chain Modified Sesquierane)> [Comparative Synthesis Example 2-1] 3.3 g of a polymer (R-1) and 50 g of a glass were placed in a 100 mL three-necked flask. Isobutyl ketone, 1.02 g of 4-(4-n-pentylcyclohexyl)benzoic acid, 50 mg of 2,6-di-t-butyl-4-methoxyphenol, and a trade name of 0.6 g "UCAT 18X" (manufactured by San-Apro Co., Ltd., a hardening accelerator for an epoxy compound) was reacted at 90 ° C for 48 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the solution obtained by dissolving the precipitate in ethyl acetate was washed with water three times, and then the solvent was distilled off, thereby obtaining 3.1 g of a side chain modification type. A white powder of a semi-oxane (polymer (R-11)). The polymer (R-11) had Mw of 4,500, Mn of 2,800, a molecular weight distribution (PDI) of 1.6, and a T3 peak integration ratio of 94%. In addition, the evaluation of storage stability was "good". [Comparative Synthesis Example 2-2] A polymer (R-12) was obtained by performing the same operation as in Comparative Synthesis Example 2-1 except that the type and amount of the carboxylic acid to be used were changed as described in Table 3 below. . The physical properties of the obtained polymer are shown in Table 4 below.

[table 3]

In Table 3, the numerical value of the reactive compound indicates the use ratio (% by mole) of the reactive compound with respect to the ruthenium atom of the polymer used in the reaction. The abbreviations of the reactive compounds in Table 3 are as follows. MC-5 to MC-7 have the following structures. <Reactive Compound> MC-1: 4-(4-n-pentylcyclohexyl)benzoic acid MC-2: 3,5-bis(methacryloxy)benzoic acid MC-3:4-phenoxy Cinnamate MC-4: 4-(4-n-pentylcyclohexyl)aniline MC-5: Compound MC-6 represented by the following formula (mc-5): a compound represented by the following formula (mc-6) MC-7: a compound represented by the following formula (mc-7) [Chem. 15]

[Table 4]

<Synthesis of Other Polymer (Polymer [P])> [Synthesis Example 3-1] 19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 21.23 g ( 0.1 mol% of 4,4'-diamino-2,2'-dimethylbiphenyl was dissolved in 367.6 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 6 hours to obtain A solution of polyaminic acid (PA-1). [Synthesis Example 3-2] 21.8 g (0.1 mol) of pyromellitic dianhydride as an acid dianhydride and 19.6 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic acid The dianhydride and 40 g (0.2 mol) of 4,4'-diaminodiphenyl ether as a diamine were dissolved in 458 g of N-methyl-2-pyrrolidone and carried out at 40 ° C for 3 hours. After the reaction, 356 g of N-methyl-2-pyrrolidone was added, whereby a solution containing polyglycine (PA-2) was obtained. [Synthesis Example 3-3] 19.61 g (0.1 mol) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 22.8 g (0.1 mol) of 4-aminophenyl-4' The aminobenzoic acid ester was dissolved in 382 g of N-methyl-2-pyrrolidone, and reacted at room temperature for 12 hours to obtain a solution containing polyglycine (PA-3).

[Synthesis Example 3-4] 22.4 g (0.1 mol) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 10.81 g (0.1 mol) of p-phenylenediamine were dissolved in 329.3 g of N In the methyl-2-pyrrolidone, the reaction was carried out at 60 ° C for 6 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate was washed with methanol, and dried at 40 ° C for 15 hours under reduced pressure, whereby 32 g of polyamine (PA-4) was obtained. 17.5 g of the polylysine (PA-4) obtained in the synthesis was weighed, and 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added thereto at 120 ° C. The reaction was carried out for 4 hours to carry out oxime imidization. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate a reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours, whereby 15 g of a powder of polyimine was obtained. This was dissolved in 135 g of N-methyl-2-pyrrolidone to obtain a 10% by mass solution of polyimine (PI-1).

<Evaluation of liquid crystal alignment agent and liquid crystal display element> [Example 1] (1) Preparation of liquid crystal alignment agent A solution containing polyglycine (PA-1) was weighed and converted into polylysine contained therein. (PA-1) is equivalent to 100 parts by mass, and 100 parts by mass of the polymer (L-13) obtained in the Synthesis Example 2-3 is further added thereto, and further N-methyl-2-pyrrolidone is added ( NMP) and butyl cellosolve (BC) were prepared as a solution having a solvent composition of NMP: BC = 80:20 (mass ratio) and a solid concentration of 3.5% by mass. This solution was filtered with a filter having a pore size of 1 μm to prepare a liquid crystal alignment agent (A-1).

(2) Evaluation of printability The liquid crystal alignment agent (A-1) prepared in the above (1) was applied to a transparent film containing an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). The transparent electrode surface of the glass substrate of the electrode was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 230 ° C for 10 minutes to form an average film thickness. It is a coating film of 0.06 μm. The coating film was observed with a microscope having a magnification of 20 times to investigate the uneven thickness of the film, the unevenness of the orange peel, and the presence or absence of linear unevenness. The film thickness unevenness and the uniformity of the coating surface were evaluated as "good (○)", and the unevenness of the orange peel was evaluated as "printability" (△), and orange peel was observed. The case of unevenness of defects and unevenness of the line was evaluated as "bad (x)" in printability. In the present Example, film thickness unevenness was not observed, and the coating surface was uniform, and the printability was "good (○)".

(3) Evaluation of Residual Film Rate The liquid crystal alignment agent (A-1) prepared in the above (1) was applied onto a glass substrate by a spinner, and prebaked on a hot plate at 80 ° C for 1 minute. The coating film was formed by heating (post-baking) in a 230 ° C oven in which the inside of the chamber was purged with nitrogen for 1 hour. Then, N-methyl-2-pyrrolidone (NMP) was applied by spin coating on the film after post-baking. The film thickness D1 [μm] before spin coating NMP and the film thickness D2 [μm] after coating were measured by a scanning electron microscope, and the residual film ratio (%) was calculated by the following formula (2). Residual film rate (%) = [(D1 - D2) / D1] × 100 (2) The higher the residual film ratio, the higher the crosslinking density of sesquiterpene oxide. On the other hand, when the crosslinking density of sesquiterpene is low, in the case of forming a liquid crystal cell, sesquioxane in the liquid crystal alignment film flows into the liquid crystal, and display characteristics are liable to lower. The case where the residual film ratio was 90% or more was evaluated as "good (○)", the case where 80% or more and less than 90% was evaluated as "may (?)", and the case where less than 80% was evaluated as "poor (X) )". As a result, in this example, the residual film ratio was "good (?)".

(4) Production of liquid crystal cell The FFS type liquid crystal display element 10 shown in Fig. 2 was produced. First, a pair of glass substrates 11a having electrode pairs on one side and a pair of opposite glass substrates 11b having no electrodes are formed, and the electrode pairs are sequentially formed with a bottom electrode 15 having no pattern and nitridation as the insulating layer 14. The ruthenium film and the top electrode 13 patterned into a comb-tooth shape are coated on the surface of the glass substrate 11a having the transparent electrode and one surface of the opposite glass substrate 11b by using a rotator to coat the (1) The prepared liquid crystal alignment agent (A-1) was formed into a coating film. Then, the coating film was prebaked on a hot plate at 80 ° C for 1 minute, and then heated (post-baked) at 230 ° C for 15 minutes in an oven in which the inside of the chamber was purged with nitrogen to form an average film thickness of 0.1. Μm coating film. A schematic plan view of the top electrode 13 used herein is shown in Figs. 3(a) and 3(b). 3(a) is a plan view of the top electrode 13, and FIG. 3(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 3(a). In the present embodiment, a substrate having a top electrode having an electrode having a line width d1 of 4 μm and a distance d2 between electrodes of 6 μm was used. Further, the top electrode 13 is a four-system driving electrode using the electrode A, the electrode B, the electrode C, and the electrode D. The configuration of the driving electrodes used is shown in FIG. The bottom electrode 15 operates as a common electrode that acts on all of the drive electrodes of the four systems, and the regions of the drive electrodes of the four systems become pixel regions.

Then, using Hg-Xe lamps and Glan-Taylor prisms on each surface of these coating films, 300 M/m ² of polarized ultraviolet rays containing 313 nm bright lines were irradiated from the normal direction of the substrate to obtain inclusions. A pair of substrates of a liquid crystal alignment film. In this case, the irradiation direction of the polarized ultraviolet light is set from the normal direction of the substrate, and the direction of the polarizing surface is set such that the direction in which the polarizing surface of the polarized ultraviolet light is projected onto the line segment on the substrate becomes the direction of the double arrow in FIG. 3( b ). Then, light irradiation treatment is performed. Next, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied by screen printing on the outer periphery of the surface of the one of the substrates including the liquid crystal alignment film, thereby forming a pair of substrates. The liquid crystal alignment film faces each other, and the pressure is applied to the substrate so that the direction in which the polarized surface of the polarized ultraviolet light is projected onto the substrate is overlapped, and the adhesive is thermally cured at 150 ° C for 1 hour. Then, the liquid crystal "MLC-6221" manufactured by Merck was filled in the substrate gap from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin. Then, in order to remove the flow alignment at the time of liquid crystal injection, it was heated to 150 ° C and then slowly cooled to room temperature. Then, an FFS type liquid crystal display element was fabricated by laminating a polarizing plate on both outer sides of the substrate. At this time, one of the polarizing plates is attached such that the polarizing direction thereof is parallel to the direction in which the polarizing surface of the polarized ultraviolet ray of the liquid crystal alignment film is parallel to the projection surface of the substrate surface, and the other is that the polarizing direction becomes the same as that of the polarizing plate. The polarization directions of the polarizing plates are attached in a manner orthogonal to each other.

(5) Evaluation of voltage holding ratio The FFS type liquid crystal display element manufactured in the above (4) was subjected to application of a voltage of 1 V at an application time of 0.5 μsec and a span of 2,000 msec at 23 ° C. The voltage holding ratio (VHR) after 2000 milliseconds. Further, VHR-1 manufactured by Toyo Technica Co., Ltd. was used as a measuring device. The case where the voltage holding ratio was 95% or more was evaluated as "good (○)", the case where 90% or more and less than 95% was evaluated as "may (?)", and the case where less than 90% was evaluated as "poor (X) )". As a result, in this example, the result of the voltage holding ratio "good (○)" was obtained.

(6) Evaluation of liquid crystal alignment property The presence or absence of an abnormal region in the change in brightness and darkness when a voltage of 5 V was applied/released was observed with an optical microscope. The case where the abnormal region was not observed was evaluated as the liquid crystal alignment property "good (○)", and the case where the abnormal region was observed was evaluated as the liquid crystal alignment property "bad (x)". As a result, no abnormal region was observed in the liquid crystal display element, and the liquid crystal alignment property was "good (○)".

[Examples 2 to 13 and Comparative Example 1 and Comparative Example 2] In the first embodiment, the type and amount of the polymer were the same as those in the first embodiment except that they were as described in the following Table 5. In the manner of preparing a liquid crystal alignment agent, various evaluations were carried out using the liquid crystal alignment agent. The evaluation results are shown in Table 5 below.

[table 5]

In Table 5, the numerical value of the polymer [P] represents 100 masses of sesquiterpene oxide (sesquioxane [L] or sesquioxanes as other polymers) used in the preparation of the liquid crystal alignment agent. The blending ratio (parts by mass) of each polymer in terms of parts.

As shown in Table 5, Examples 1 to 13 containing sesquioxane [L] were "good" or "may" in the evaluation of printability, residual film ratio, voltage holding ratio, and liquid crystal alignment. . On the other hand, Comparative Example 1 and Comparative Example 2 were worse than the examples.

10‧‧‧Liquid display components
11a, 11b‧‧‧ substrate
12‧‧‧Liquid alignment film
13‧‧‧ top electrode
14‧‧‧Insulation
15‧‧‧ bottom electrode
16‧‧‧Liquid layer
A, B, C, D‧‧‧ electrodes
Part of the C1‧‧‧ dotted line
D1‧‧‧ electrode line width
D2‧‧‧Distance between electrodes

Figure 1 is a ²⁹ Si-NMR spectrum of a polymer synthesized in the examples. 2 is a schematic configuration diagram of a Fringe Field Switching (FFS) type liquid crystal cell. 3(a) and 3(b) are plan views schematically showing a top electrode for manufacturing a liquid crystal display element by photoalignment processing. Fig. 3(a) is a plan view of the top electrode, and Fig. 3(b) is a partially enlarged view of the top electrode. 4 is a view showing drive electrodes of four systems.

Claims (15)

A liquid crystal alignment agent containing a sesquiterpene oxide [L] having a ladder structure represented by the following formula (1), In the formula (1), E ¹ and E ² are each independently a monovalent organic group, and n is an integer of 2 or more; and E ¹ and E ² in different repeating units may be the same or different. The liquid crystal alignment agent according to the first aspect of the invention, wherein the peak of the ²⁹ Si-NMR spectrum derived from the partial structure represented by the following formula (4) in the sesquiterpene oxide [L] The integral ratio is 70% to 99%. In the formula (4), R ^a is a monovalent organic group having 1 or more carbon atoms, and * represents a bond with a ruthenium atom. The liquid crystal alignment agent according to claim 1, wherein one or more of the plurality of E ¹ and E ² which the sesquiterpene oxide [L] has has a group selected from the group consisting of the following groups At least one functional group: epoxy group, oxetanyl group, acid anhydride group, (meth) acrylonitrile group, vinyl group, ethynyl group, decyl group, -NHR ⁵ , isocyanate group, alcoholic hydroxyl group, phenolic hydroxyl group , cyano, -COOR ¹ , -CON(R ¹ ) ₂ , -PO(R ¹ ) ₂ , -SO ₃ R ¹ and -SO ₂ N(R ¹ ) ₂ , wherein R ^{1 is} independently a hydrogen atom Or a monovalent hydrocarbon group, and R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The liquid crystal alignment agent according to claim 1, wherein one or more of the plurality of E ¹ and E ² which the sesquiterpene oxide [L] has is selected from a group having a pretilt performance ability. At least one of the group consisting of a photo-alignment group and a cross-linking group. A liquid crystal alignment agent containing sesquiterpene oxide [L] satisfying the following requirements (A) to (C), (A) a weight average molecular weight Mw measured by gel permeation chromatography of 5,000 or more (B) The molecular weight distribution Mw/Mn represented by the ratio of the weight average molecular weight Mw to the number average molecular weight Mn measured by gel permeation chromatography is 3.8 or less; (C) is represented by the following formula (4) The integral ratio of the peak of the ²⁹ Si-NMR spectrum derived from the partial structure is 70% to 99%; In the formula (4), R ^a is a monovalent organic group having 1 or more carbon atoms, and * represents a bond with a ruthenium atom. The liquid crystal alignment agent according to any one of claims 1 to 5, wherein the sesquiterpene oxide [L] is a hydrolysis of a decane compound containing a compound represented by the following formula (3) Condensate, In the formula (3), Ar ¹ is one selected from the group consisting of groups represented by the following formulas (ar-1) to (ar-8), and J ¹ is selected from the following formula ( J-1) to one of the groups consisting of groups represented by the formula (j-7); R ⁴ is a monovalent hydrocarbon group having 1 to 18 carbon atoms; In the formula (ar-1) to the formula (ar-8), * represents a bond bonded to a ruthenium atom, and *1 represents a bond bonded to J ¹ , In the formulae (j-1) to (j-7), R ⁶ is a single bond or an alkanediyl group having 1 to 5 carbon atoms, R ⁷ is an alkyl group having 1 to 5 carbon atoms, and X ⁴ is a hydrogen atom or carbon. An alkyl group of 1 to 6; * represents a bond to Ar ¹ . The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the sesquiterpene oxide [L] is a hydrolysis of a decane compound containing a compound represented by the following formula (2) Condensate, In the formula (2), R ³ is an organic group having 2 to 18 carbon atoms, and the organic group has one or two or more selected from the group consisting of -NHR ⁵ , pyridyl, imidazolyl, cyano, imido, hydroxy, a specific group in the group consisting of a mercapto group, a carboxyl group, a phosphonium group, a sulfo group, and an acid anhydride group, wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; and X ¹ , X ² and X ³ are each independently The ground is a halogen atom, an alkoxy group having 1 to 18 carbon atoms or a decyloxy group having 1 to 18 carbon atoms. The liquid crystal alignment agent according to any one of the items 1 to 5, wherein the sesquiterpene oxide [L] is two of the following conditions 1, 2, and 3 A compound obtained by polymerizing a decane compound under the above conditions, Condition 1: a decane compound having one or two or more specific groups selected from -NHR ⁵ , pyridyl group a group consisting of imidazolyl, cyano, imino, hydroxy, decyl, carboxyl, phosphonium, sulfo and anhydride groups, wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Condition 2: in the case where the decane compound of the condition 1 has an acidic group as the specific group, the decane compound is hydrolytically condensed in the presence of a base, and in the case of having a basic group as the specific group, The decane compound is hydrolytically condensed in the presence of an acid; Condition 3: The decane compound is hydrolytically condensed in a solvent containing 10% by mass or more of water. A liquid crystal alignment agent containing sesquiterpene oxide [L] obtained by polymerizing a decane compound under two or more conditions of Condition 1, Condition 2, and Condition 3 described below, Condition 1: Containing one type Or two or more of the following specific decane compounds selected from the group consisting of -NHR ⁵ , pyridyl, imidazolyl, cyano, imido, hydroxy, decyl, carboxyl, phosphonium And a group consisting of a sulfo group and an acid anhydride group, wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; Condition 2: the decane compound in the condition 1 has an acidic group as the specific group In the case where the decane compound is hydrolytically condensed in the presence of a base, in the case of having a basic group as the specific group, the decane compound is hydrolytically condensed in the presence of an acid; Condition 3: in a mass of 10 The decane compound is hydrolyzed and condensed in a solvent of water of more than %. The liquid crystal alignment agent according to claim 9, which further comprises at least one polymer [P] selected from the group consisting of polyimine, polylysine, and polyphthalate. The liquid crystal alignment agent according to claim 10, wherein a ratio of the sesquioxane [L] to the polymer [P] is [L]: [P] is a mass ratio of 1: 99 to 80:20. A liquid crystal alignment film which is formed using the liquid crystal alignment agent according to any one of the first to eleventh aspects of the invention. A liquid crystal element comprising the liquid crystal alignment film according to claim 12 of the patent application. A method for producing a liquid crystal alignment film, which comprises the steps of: applying a liquid crystal alignment agent according to any one of claims 1 to 11 to form a coating film; and coating the same The substrate surface of the liquid crystal alignment agent is irradiated with light to impart a liquid crystal alignment ability to the coating film. A sesquioxane having a ladder structure represented by the following formula (1), In the formula (1), E ¹ and E ² are each independently a monovalent organic group, and n is an integer of 2 or more; wherein one or more of the plurality of E ¹ and E ² which the sesquiterpene oxide has A group selected from at least one of the group consisting of an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acrylonitrile group, a styryl group, an ethynyl group, a decyl group, an isocyanate group , alcoholic hydroxyl group, cyano group, -COOR ² , -CON(R ¹ R ² ), -PO(R ¹ ) ₂ , -SO ₃ R ² , -SO ₂ N(R ¹ R ² ), photoalignment group And a crosslinkable group, wherein R ^{1 is} independently a hydrogen atom or a monovalent hydrocarbon group, and R ² is a monovalent hydrocarbon group.