KR20170001620A - Liquid crystal aligning agent, liquid crystal alignment film, liquid crystal device, manufacturing method for liquid crystal alignment film, and compound - Google Patents

Abstract

Provided in the present invention is a liquid crystal aligning agent having good coatability on substrates. The liquid crystal aligning agent comprises a silsesquioxane (L) having a ladder-type structure represented by formula (1). In the formula (1), E^1 and E^2 each independently represent a monovalent organic group; n is an integer of 2 or greater; and E^1 and E^2s on different repeating units may be identical or different.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment film, a liquid crystal alignment film, a liquid crystal device, a liquid crystal alignment film,

The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a liquid crystal device, a process for producing a liquid crystal alignment film, and a compound.

The liquid crystal device has a liquid crystal alignment film for controlling alignment of liquid crystal molecules. Polyimide, polyamide, polyester, polysiloxane, and the like are known as the materials for constituting the liquid crystal alignment film. Among them, a liquid crystal alignment film made of polyimide has long been known from heat resistance, mechanical strength and excellent affinity with liquid crystal molecules. (See, for example, Patent Document 1). In recent years, there have been increasing cases in which a liquid crystal aligning agent containing a polysiloxane obtained by reacting a silane compound is used for reasons such as good light resistance and heat resistance (see, for example, Patent Document 2 and Patent Document 3) . Patent Document 2 discloses that a polysiloxane obtained by polycondensing an alkoxysilane compound in the presence of oxalic acid is used as a polymer component of a liquid crystal aligning agent. Patent Document 3 discloses a liquid crystal aligning agent containing a polysiloxane synthesized through hydrolysis or hydrolysis / condensation of a silane compound in the presence of an alkali metal compound or an organic base, a hydrolyzate thereof or a condensate of a hydrolyzate ≪ / RTI >

Japanese Laid-Open Patent Publication No. 2010-97188 Japanese Patent Publication No. 5593611 International Publication No. 2009/025388

According to the method described in Patent Document 2, a random-type polysiloxane is obtained. According to the method described in Patent Document 3, a basket-type polysiloxane is obtained. However, the random or cage-type polysiloxane has a low molecular weight, and when the coating film is formed on the substrate, uneven coating may occur, which may result in lower product yield or lower display quality. With the recent trend toward higher definition of liquid crystal panels, the demand for display quality has become more stringent, and further improvements in electrical characteristics and liquid crystal orientation have been desired for liquid crystal devices.

It is an object of the present invention to provide a liquid crystal aligning agent which is obtained in view of the above circumstances and which is capable of obtaining a liquid crystal device having good applicability to a substrate and good liquid crystal alignability and electrical characteristics.

According to the present invention, the following means are provided.

[1] A liquid crystal aligning agent containing silsesquioxane [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; n is an integer of 2 or more;

E ¹ and E ² in different repeating units may be the same or different)

[1-1] A liquid crystal aligning agent comprising silsesquioxane [L] satisfying the following requirements (A) to (C).

(A) The weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) is 5000 or more.

(B) a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a 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 bonding bond to a silicon atom)

[2] A liquid crystal aligning agent comprising silsesquioxane [L] obtained by polymerizing a silane compound under conditions that satisfy at least two of the following conditions 1, 2 and 3.

Condition 1: As the silane compound, -NHR ⁵ (However, R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; the same applies hereinafter), a pyridyl group, an imidazole group, a cyano group, an imino group, a hydroxyl group, MER A silane compound having at least one specific group selected from the group consisting of a hydroxyl group, a hydroxyl group, a carboxyl group, a phosphoryl group, a sulfo group and an acid anhydride group.

Condition 2: In the case where the silane compound of the above-mentioned condition 1 has an acidic group as the specific group, the silane compound is hydrolyzed and condensed in the presence of a base, and when the silane compound has a basic group as the specific group, Decomposition and condensation.

Condition 3: The silane 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 aligning agent of the above [1], [1-1] or [2].

[4] A liquid crystal device comprising the liquid crystal alignment film according to [3] above.

[5] A process for forming a coating film by coating the liquid crystal aligning agent of the above-mentioned [1], [1-1] or [2] on a substrate and a step of irradiating the substrate surface coated with the liquid crystal aligning agent with light Wherein the liquid crystal alignment film has a thickness of 100 nm.

[6] A silsesquioxane having a ladder structure represented by the above formula (1). However, at least one of the plurality of E ¹ and E ² of silsesquioxane is preferably an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acryloyl group, a styryl group, an ethynyl group, a mercapto group, an isocyanate group alcoholic 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) ( However, R ¹ is , Each independently a hydrogen atom or a monovalent hydrocarbon group, and R ² is a monovalent hydrocarbon group), a photo-aligning group, and a crosslinking group.

According to the liquid crystal aligning agent containing the silsesquioxane [L], a liquid crystal aligning agent having good applicability to the substrate can be obtained. Further, a liquid crystal device having good liquid crystal alignability and electrical characteristics can be obtained.

1 is a ²⁹ Si-NMR spectrum of a polymer synthesized in Example.
2 is a schematic configuration diagram of an FFS type liquid crystal cell.
3 is a schematic plan view of a top electrode used for manufacturing a liquid crystal display element by photo-alignment treatment. (a) is a top view of the top electrode, and (b) is a partial enlarged view of the top electrode.
Fig. 4 is a diagram showing four driving electrodes.

(Mode for carrying out the invention)

Hereinafter, each component contained in the liquid crystal aligning agent of the present disclosure, and other components arbitrarily blended as necessary, will be described.

≪ Silsesquioxane [L] >

The liquid crystal aligning agent of the present disclosure contains silsesquioxane [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 monovalent organic groups include monovalent hydrocarbon groups of 1 to 20 carbon atoms, groups containing a heteroatom-containing group between the carbon-carbon bonds of the hydrocarbon group, groups in which the hydrocarbon group and the heteroatom-containing group are bonded, And a group obtained by substituting at least one hydrogen atom of the hydrogen atom with a substituent.

Herein, in the present specification, the "organic group" is a group capable of forming a part of an organic compound, and may include a hetero atom in the structure. This organic group is a concept including a functional group (for example, an amino group). The "heteroatom-containing group" may be a group having a heteroatom such as -O-, -CO-, -COO-, -CONR ^a - (wherein R ^a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, include, phospho group-light - they are the same or less), -NR ^a -, a valence 3 nitrogen ^{atoms, -NR a CONR a -, -OCONR} a -, -S-, -COS-, -OCOO-, -SO 2 . Examples of the substituent include a halogen atom, a nitro group, a cyano group, a hydroxyl group, an amino group, a pyridyl group, an imidazole group, a mercapto group, a carboxyl group, a phosphoric group, a sulfo group and a (meth) acryloyl group. Further, "(meth) acryloyl" means "acrylo" and "methacrylo".

The term "hydrocarbon group" means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The term "chain hydrocarbon group" means a straight chain hydrocarbon group and a branched hydrocarbon group which do not contain a cyclic structure in the main chain and are composed of only a chain structure. However, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only the structure of an alicyclic hydrocarbon and not containing an aromatic ring structure as the ring structure. However, it is not always necessary to be constituted by only the structure of alicyclic hydrocarbons, and some of them include those having a chain structure. The "aromatic hydrocarbon group" means a hydrocarbon group having an aromatic ring structure as a ring structure. However, it need not be constituted only of an aromatic ring structure, and a part thereof may contain a chain structure or a structure of an alicyclic hydrocarbon.

As E ¹ and E ² , at least one of a plurality of E ¹ and E ² of silsesquioxane [L] is preferably an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acryloyl group, a vinyl group , a vinyl group, etc.) of the styryl group, ethynyl group, a mercapto group, -NHR ^5, an isocyanate group, an alcoholic hydroxyl group, 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 each independently a hydrogen atom or a monovalent hydrocarbon group) Do. 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.

It is preferred that at least one of the plurality of E ¹ and E ² of the silsesquioxane [L] has at least one species selected from the group consisting of a group having a pretilt angle manifesting ability, a photo aligning group and a crosslinking group Do. By having these groups in the side chain, functions according to each group can be imparted to the resulting organic film. In particular, silsesquioxane having a ladder-like structure represented by the above formula (1) has, for example, a group having a pretilt angle manifesting ability or a photo-aligning group, a functional side chain termed a crosslinkable group Can be arbitrarily controlled, and it is suitable in that it is easy to control the controllability of the orientation direction and the reliability of the liquid crystal element.

The group having a pretilt angular expression ability is a group capable of imparting pretilt angularity to the coating film without depending on light irradiation, and specifically, for example, an alkyl group having 3 to 20 carbon atoms, a fluoroalkyl group having 3 to 20 carbon atoms, A group having 3 to 20 carbon atoms, an alkoxy group having 3 to 20 carbon atoms, a group having a steroid skeleton having 17 to 51 carbon atoms, and a group having a structure in which two or more rings are connected directly or via a linking group (hereinafter also referred to as a "polycyclic structure"). Specific examples thereof include alkyl groups having 3 to 20 carbon atoms such as n-propyl, n-butyl, n-pentyl, n-hexyl, n- , n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, Decyl group, n-eicosyl group and the like;

As the fluoroalkyl group having 3 to 20 carbon atoms, for example, a group in which at least one hydrogen atom of the above-exemplified alkyl group is substituted with a fluorine atom;

As the alkoxy group having 3 to 20 carbon atoms, for example, a group in which an oxygen atom is bonded to the above-mentioned alkyl group;

A group having a steroid skeleton having 17 to 51 carbon atoms such as a group having a cholestanyl group, a cholesteryl group or a lanostanyl group;

Examples of the group having a polycyclic structure include a 4,4'-biphenylene group, a 4,4'-bicyclohexylene group and the following formulas (6-1) to (6-4)

(Where " * " represents a combined hand)

A group having a group represented by each of R < 1 > The silsesquioxane [L] group having a pretilt angular expression ability may be either one kind or two or more kinds.

The photo-aligning group may be a group (photoreactive group) that exhibits photo-alignment by photo-isomerization or photo-dimerization. As specific examples of photo-alignment groups, for example, azobenzene-containing groups having azobenzene or derivatives thereof as the basic skeleton, groups containing a cinnamic acid structure having basic skeleton of cinnamic acid or its derivatives, chalcones containing a chalcone or a derivative thereof as a basic skeleton A benzophenone-containing group having a benzophenone or a derivative thereof as a basic skeleton, and a coumarin-containing group having a coumarin or a derivative thereof as a basic skeleton. Among them, it is preferably a group containing a cinnamic acid structure.

The crosslinkable group is preferably a group capable of forming a covalent bond between the same or different molecules by light or heat and includes, for example, a (meth) acryl-containing group having a (meth) acrylic acid or a derivative thereof as a basic skeleton, An alkenyl group, a styryl group, etc.), an ethynyl group, an epoxy group, and an oxetanyl group. Among them, a (meth) acryl-containing group and a styryl group are preferable.

Further, the silsesquioxane [L] may have either a group having a pretilt angle manifesting ability, a photo-aligning group and a crosslinking group, or two or more of them. In addition, one E ¹ or one E ² may have a group having a pretilt angle manifesting ability and a crosslinkable group such as a (meth) acryloyl group or a vinyl group. These groups exhibit a pretilt angle manifesting ability and exhibit crosslinking properties. In the formula (1), n is 2 or more, preferably 5 or more, and more preferably 8 or more. The upper limit value of n can be appropriately selected depending on the desired molecular weight.

 (Synthesis of silsesquioxane [L]) [

The method of synthesizing silsesquioxane [L] is not particularly limited as long as silsesquioxane having the structure represented by the above formula (1) can be obtained. Preferably, silsesquioxane [L] is a hydrolytic condensation product of a hydrolyzable silane compound. The silane compound is polymerized under the conditions satisfying at least two of the following Condition 1, Condition 2 and Condition 3 in view of high structural regularity of the obtained silsesquioxane and high controllability of molecular weight and molecular weight distribution (Hereinafter referred to as "method 1") or a method of polymerizing a silane compound containing a compound represented by the following formula (3) (hereinafter referred to as "method 2").

Condition 1: The silane compound is selected from the group consisting of -NHR ⁵ , pyridyl, imidazole, cyano, imino, hydroxyl, mercapto, carboxyl, phospholyl, And a silane compound having one or more specific groups.

Condition 2: In the case where the silane compound of the above-mentioned condition 1 has an acidic group as the specific group, the silane compound is hydrolyzed and condensed in the presence of a base, and when the silane compound has a basic group as the specific group, Decomposition and condensation.

Condition 3: The silane compound is hydrolyzed and condensed in a solvent containing 10 mass% or more of water.

Wherein Ar ¹ is one kind selected from the group consisting of groups represented by each of the following formulas (ar-1) to (ar-8), J ¹ is a group represented by the following formula (j-1) To (j-7), R ⁴ is a monovalent hydrocarbon group of 1 to 18 carbon atoms,

(In the formulas (ar-1) to (ar-8), " * " represents a bonding hand bonding to a silicon atom)

(In the formulas (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, X 4 is a hydrogen atom, And " * " represents a hand bonded to Ar &^lt; ¹ >).

In the method 1, the silane compound used in the polymerization preferably contains a silane compound having a polar group. In particular, the silane compound having -NHR ⁵ , a pyridyl group, an imidazole group, a cyano group, an imino group, a hydroxyl group, (Hereinafter also referred to as " specific silane compound ") having at least one specific group selected from the group consisting of a carboxyl group, a carboxyl group, a phosphoryl group, a sulfo group and an acid anhydride group. Preferable examples of the specific silane compound include compounds represented by the following formula (2).

(In the formula (2), R ³ represents a group selected from the group consisting of -NHR ⁵ , a pyridyl group, an imidazole group, a cyano group, an imino group, a hydroxyl group, a mercapto group, a carboxyl group, a phosphoryl group, a sulfo group and an acid anhydride group X ¹ , X ² and X ³ are each independently a halogen atom, an alkoxy group having 1 to 18 carbon atoms or an organic group having 1 to 18 carbon atoms, Lt; / RTI >

Examples of the halogen atom in X ¹ , X ² and X ³ in the above 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 above. Examples of the acyloxy group having 1 to 18 carbon atoms include an acetyloxy group, a propionyloxy group and a benzoyloxy group. X ¹ , X ² and X ³ are preferably a halogen atom, a methoxy group or an ethoxy group. X ¹ , X ² and X ³ may be the same or different.

Examples of the compound represented by the formula (2) include 2-cyanoethyltriethoxysilane, 3-aminopropyltriethoxysilane, 3-mercaptopropyltriethoxysilane, 1-methyl- Imidazol-3-ium chloride, (3-benzoyloxypropyl) trimethoxysilane, trimethoxysilylpropylacetamide, ethyl 4- (2- (trimethoxysilyl) ethyl) benzene (3-trimethoxysilylpropyl) aspartic acid, 3- (m-dimethylaminophenoxy) propyltrimethoxysilane, methyl 3- (Trimethoxysilyl) propionate, and a compound represented by the following formula (2-1) can be given as preferred specific examples.

When a specific silane compound is used for the polymerization, the specific silane compound may be added to the polymerization system to perform polymerization, or the specific silane compound may be prepared by the reaction in the system to carry out the polymerization.

As the silane compound used in the synthesis of silsesquioxane [L], the specific silane compound as described above may be used alone, but other silane compounds may be used together with the specific silane compound. The other silane compounds may be hydrolyzable silane compounds. Specific examples thereof include tetramethoxysilane, tetraethoxysilane, trimethylethoxysilane, methyltrimethoxysilane, dimethyldiethoxysilane, phenyltrimethoxysilane , Alkoxy such as phenyltriethoxysilane, dimethyldimethoxysilane, dodecyltriethoxysilane, octadecyltriethoxysilane, tridecafluorooctyltrimethoxysilane, and 4- (chloromethyl) phenyltrimethoxysilane. Silane compounds;

3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, etc. An epoxy group-containing silane compound;

(Meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltrimethoxysilane, 3- (meth) acryloxypropyltriethoxysilane, 3- Unsaturated bond-containing alkoxysilane compounds such as silane, vinyltrimethoxysilane, vinyltriethoxysilane and p-styryltrimethoxysilane;

Bis (trimethoxysilyl) hexane, bis (trimethoxysilyl) hexane, tris- (3-trimethoxysilylpropyl) isocyanurate, 1,8- Silyl) propyl] amine, triethoxysilylthiopropyltrimethoxysilane and the like, and the like. The other silane compounds may be used alone or in combination of two or more.

In the synthesis of silsesquioxane [L], the other silane compounds are preferably used in an amount of 50 mol% or less based on the total amount of the silane compounds used in the synthesis of silsesquioxane [L] , And more preferably 40 mol% or less.

The reaction of the method 1 is carried out by hydrolysis and condensation of one or more silane compounds as described above, preferably in the presence of a catalyst and a solvent. When a silane compound having a basic group such as an amino group is used as the specific silane compound, an acid is preferably used, and hydrochloric acid is particularly preferable. On the other hand, when a silane compound having an acidic group such as a carboxyl group is used as the specific silane compound, it is preferable to use a base as the catalyst, more preferably an alkali metal compound, and particularly preferably sodium hydroxide. The use ratio of the catalyst should be appropriately set according to the kind of catalyst, reaction conditions such as temperature, and the like. For example, it is preferably 0.01 to 6 times by mole, more preferably 1 to 6 times It is mall.

As the solvent used in the hydrolysis-condensation reaction of the silane compound, it is preferable to use alcohols such as methanol, ethanol, isopropanol and butanol, water and a mixed solvent thereof, but 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 mass% or more, and more preferably 80 mass% or more. The use ratio of the solvent is preferably 10 to 10,000 parts by mass, more preferably 50 to 1,000 parts by mass based on 100 parts by mass of the total amount of the silane compounds used in the reaction.

The hydrolysis-condensation reaction is carried out by first mixing a silane compound in a solvent containing a catalyst and water, reacting the mixture for 6 to 24 hours, heating the mixture to 50 to 70 캜 in an open system, and evaporating the solvent . The heating time is preferably 0.5 to 24 hours, more preferably 1 to 12 hours. During the heating, the mixed solution may be stirred. After completion of the reaction, it is preferable to carry out a treatment for converting counter ions in the molecule using an ion exchange resin. Thereafter, the reaction solution is dried, if necessary, with a drying agent such as anhydrous calcium sulfate or molecular sieves, and then the solvent is removed to obtain a silsesquioxane having a ladder structure represented by the above formula (1). In the method 1, the polymerization is preferably carried out under the conditions at least satisfying the conditions 1 and 2. More preferably, the polymerization is carried out under the conditions satisfying the above three conditions.

In Method 2, the silane compound containing the compound represented by the formula (3) is hydrolyzed and condensed. In the formula (3), the monovalent hydrocarbon group of R ⁴ preferably has 1 to 10 carbon atoms, more preferably a methyl group or an ethyl group. R ⁶ is preferably a single bond or 1 to 3 carbon atoms. X ⁴ is preferably a hydrogen atom or a methyl group.

Specific examples of the compound represented by the formula (3) include p-styryltrimethoxysilane, p-styryltriethoxysilane, 4-vinylbiphenyltrimethoxysilane, 4-vinylcyclohexyltrimethoxysilane Ethoxy silane, 4-epoxy phenyltrimethoxy silane, and the like. Among them, p-styryltrimethoxysilane or p-styryltriethoxysilane is preferable. The compounds represented by the above formula (3) may be used singly or in combination of two or more kinds.

The hydrolysis-condensation reaction of the method 2 is preferably carried out in the presence of a catalyst and a solvent. The catalyst used in the reaction includes, for example, potassium carbonate, sodium hydrogencarbonate and the like. The use ratio of the catalyst is preferably 0.01 to 6 times by mole relative to the total amount of the silane compound. The solvent used in the reaction includes, for example, ethers such as ethylene glycol dimethyl ether, ethylene glycol diethyl ether, tetrahydrofuran and dioxane, alcohols such as methanol, ethanol, isopropanol and butanol, Mixed solvents of more than two kinds, and the like, but the present invention is not limited thereto. As for the content ratio of water, the description of Method 1 is applied. The reaction temperature is preferably 10 to 120 占 폚, more preferably 30 to 80 占 폚. The reaction time is 0.1 to 48 hours, preferably 1 to 12 hours. Further, in the reaction of the method 2, other silane compounds other than the compound represented by the formula (3) may be used as the silane compound. The mixing ratio of the other silane compound is preferably 70 mol% or less, more preferably 50 mol% or less, relative to the total amount of the silane compound used in the reaction.

The weight average molecular weight (Mw) in terms of polystyrene measured by gel permeation chromatography (GPC) of silsesquioxane [L] obtained by the above hydrolysis-condensation reaction is in the range of 5,000 to 50,000 desirable. If the Mw is less than 5,000, the coating property on the substrate tends to be poor. Further, when a liquid crystal display element is produced by a liquid dropping method (ODF method), there is a fear that display unevenness (ODF unevenness) due to outflow of the polymer into the liquid crystal layer may occur. On the other hand, when the Mw exceeds 50,000, the polymer tends to gel and the storage stability of the liquid crystal aligning agent is poor. From the above viewpoint, the lower limit of the Mw of the silsesquioxane [L] obtained by the above hydrolysis-condensation reaction is preferably 6,000 or more, particularly preferably 8,000 or more. The upper limit value of Mw is preferably 45,000 or less, and more preferably 40,000 or less. 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 1.0 to 3.3 , And more preferably in the range of 1.0 to 3.0.

(Hereinafter also referred to as "T3 peak enrichment") of the ²⁹ Si-NMR spectrum derived from the partial structure (T3 unit) represented by the following formula (4) in the silsesquioxane [L] , And preferably 70 to 99%. , More preferably 75 to 99%, and still more preferably 80 to 99%. Furthermore, T3 peak ever secretion, a value that indicates the content of T3 units (SiO _3/2 R ^I) in the silicon-containing polymer, the higher the value the higher the content of the T3 units (SiO _3/2 R ^I) .

(In the formula (4), R ^a is ^a monovalent organic group having 1 or more carbon atoms, and "*" represents a bonding bond to a silicon atom)

As the silsesquioxane [L], at least one kind selected from the group consisting of a group having a pretilt angle manifesting ability, a photo-aligning group and a crosslinking group is added to E ¹ and E ² in the structure represented by the formula (1) (Hereinafter also referred to as " functional functional group ") is obtained, the synthesis method thereof is not particularly limited, and can be carried out by suitably combining organic chemical methods. For example, a method of polymerizing at least one of [I] specific silane compounds and other silane compounds using a silane compound having a functional functional group, [II] a method of polymerizing silsesquioxane obtained by the hydrolysis- , A method of reacting a functional group having [L] with a reactive compound having a functional group and a functional group reactive with the functional group.

In the above method [I], the use ratio of the silane compound having a functional group is preferably 0.5 to 50 mol%, more preferably 1 to 5 mol% based on the total amount of the silane compounds used for synthesis of silsesquioxane [L] To 30 mol% is more preferable. The silane compound having a functional group may be used singly or in combination of two or more.

As a specific example of the above-mentioned method [II], there may be mentioned, for example, a method in which an acid chloride having a functional group is used as a reactive compound, silsesquioxane [L] having an amino group or a phenolic hydroxyl group and a base (for example, Pyridine, triethylamine, etc.);

As the reactive compound, an amino group-containing compound having a functional group or a hydroxyl group-containing compound is used, and a silsesquioxane having a carboxyl group [L] and a suitable condensing agent (for example, 1-ethyl- ) Carbodiimide (EDC));

A method in which an epoxy group-containing compound having a functional group is used as the reactive compound in the presence of a silsesquioxane having a carboxyl group [L] in the presence of an interlayer transfer catalyst (for example, tetramethylammonium bromide (TMAB));

A method of reacting silsesquioxane [L] having a benzyl halide structure with a carbonic acid having a functional functional group in the presence of a base as a reactive compound;

As a reactive compound, there can be mentioned a method of reacting silsesquioxane [L] having an unsaturated double bond such as a styryl group or an alkenyl group with a thiol or amine having a functional functional group in the presence of a radical initiator.

The remainder of the structure is not particularly limited as long as the reactive compound has a functional group and a functional group reactive with the functional group of the silsesquioxane [L]. 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.

(In the formulas (r-1) to (r-22), R ¹⁵ is an alkyl group or fluoroalkyl group having 1 to 8 carbon atoms; R ¹⁶ is a hydrogen atom or a methyl group; R ¹⁷ is an alkyl group, a cyclohexyl group, ego;

Y ¹ is a single bond or a divalent linking group, Z ¹ is a carboxyl group, an epoxy group, -COCl, an amino 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 is an integer of 1 to 20;

and k is an integer of 1 to 5)

In the reaction of the silsesquioxane having a functional group with the reactive compound, the ratio of the reactive compound to be used is preferably such that the functional group of the silicon atom contained in the silsesquioxane Is preferably from 1 to 90 mol%, more preferably from 5 to 50 mol%, based on the total. The reactive compounds may be used alone or in combination of two or more.

The weight average molecular weight (Mw) of the silsesquioxane [L] having a functional group as a side chain in terms of polystyrene measured by GPC is preferably 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. The upper limit value of Mw is more preferably 50,000 or less, and 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 1.0 to 3.3, and still more preferably 1.0 to 3.0.

When a reaction solution obtained by dissolving silsesquioxane [L] contained in the liquid crystal aligning agent is obtained, the silsesquioxane [L] may be directly supplied to the preparation of the liquid crystal aligning agent, It may be provided for preparation of a liquid crystal aligning agent after isolation. Further, the silsesquioxane [L] may be purified and then provided in the preparation of the liquid crystal aligning agent. Isolation and purification of silsesquioxane [L] can be carried out according to a known method.

The liquid crystal aligning agent containing silsesquioxane [L] is suitable because a liquid crystal alignment layer having a sufficiently high crosslinking density of silsesquioxane can be obtained by a silanol group remaining at the terminal. That is, when the cross-linking density of silsesquioxane in the liquid crystal alignment film is not sufficient, it is feared that when the liquid crystal cell is used, silsesquioxane flows into the liquid crystal to lower the display quality. In this respect, by using silsesquioxane [L] as an alignment film material, the flow of the film component into the liquid crystal is reduced along with the improvement of the crosslinking density, and the display quality can be ensured.

According to the above synthesis method, as the silsesquioxane (L), a polymer satisfying the following requirements (A) to (C) can be obtained. By using a polymer which satisfies the above requirements (A) to (C) as a polymer component of a liquid crystal aligning agent, it is suitable from the viewpoint of obtaining a liquid crystal device having good applicability to a substrate and good liquid crystal alignability and electrical characteristics Do.

(A) the weight average molecular weight (Mw) measured by GPC is 5000 or more.

(B) a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a 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 formula (4) is 70 to 99%.

From the viewpoint of sufficiently securing the above effect, Mw is preferably 8000 or more, more preferably 10,000 or more, and even more preferably 12000 or more with respect to Requirement (A). With respect to the requirement (B), the molecular weight distribution is more preferably 3.3 or less, and still more preferably 3.0 or less. The peak integral of the requirement (C) is more preferably 75 to 99%, and still more preferably 80 to 99%. The T3 peak integral ratio is larger than the T2 peak integral ratio (for example, the integral ratio of the peak of the ²⁹ Si-NMR spectrum derived from the partial structure represented by the above formula (4) is 70% or more) with respect to the silicon- , And is soluble in water and has a weight average molecular weight (Mw) of, for example, Mw ≧ 5,000 and a molecular weight distribution (Mw / Mn) of narrow Can be judged to be a ladder-type structure. The silsesquioxane [L] may be composed of only the ladder-like structure represented by the above formula (1), or may include a random or cage-type structure.

<Other components>

The liquid crystal aligning agent of the present disclosure contains silsesquioxane [L] as described above, but may contain other components as necessary.

One of the other components is other polymers other than silsesquioxane [L]. Examples of other polymers include polyimides, polyamic acids, polyamic acid esters, polysiloxanes having no structure represented by the above formula (1) (for example, a basket type, a random type and a double-decker type polysiloxane) , Polymers having a skeleton of polyamide, cellulose derivatives, polybenzoxazole precursors, polybenzoxazole, polyacetal, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives and poly (meth) acrylate have. Also, (meth) acrylate means to include acrylate and methacrylate. Among these polymers, at least one kind of polymer selected from the group consisting of polyamic acid, polyimide and polyamic acid ester (hereinafter also referred to as "polymer [P]") is preferable.

 [Polyamic acid]

The polyamic acid as the polymer [P] can be obtained, for example, by reacting a tetracarboxylic acid dianhydride with a diamine.

As the tetracarboxylic acid dianhydride used for the synthesis of the polyamic acid, a known tetracarboxylic dianhydride can be used. Specific examples thereof include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-butanetetracarboxylic dianhydride;

As the alicyclic tetracarboxylic acid dianhydride, for example, 1,2,3,4-cyclobutanetetracarboxylic acid 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, , 5,9b-hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [ 4,6,8-tetracarboxybicyclo [3.3.0] octane-2: 4, 6: 8-2 anhydride, cyclohexanetetracarboxylic acid dianhydride and the like;

As the aromatic tetracarboxylic acid dianhydride, for example, pyromellitic dianhydride and the like;

The tetracarboxylic acid dianhydride described in JP-A-2010-97188 can be used. The tetracarboxylic acid dianhydrides may be used singly or in combination of two or more.

As the diamine to be used for the synthesis of the polyamic acid, a known compound can be used. Specific examples of the diamine include aliphatic diamines such as meta-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, hexamethylenediamine and the like;

As the alicyclic diamine, for example, 1,4-diaminocyclohexane, 4,4'-methylenebis (cyclohexylamine) and the like;

As aromatic diamines, for example, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diamino-2,2'-dimethylbiphenyl, 4,4'- , 4'-diaminodiphenyl ether, 4-amino-phenyl-4'-aminobenzoate, 1,3-bis (4-aminophenoxy) Bis (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '- (p-phenylenediisopropylidene) bisaniline, 1,4-bis Phenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, N, N'-bis , 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 3,5-diaminobenzoic acid, cholestanyloxy- Diaminobenzene, 3,5-diaminobenzoic acid cholestanyl, and the like;

Examples of the diaminoorganosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisiloxane and the like, and diamines described in JP-A-2010-97188 can be used . These diamines may be used singly or in combination of two or more kinds.

The polyamic acid can be obtained by reacting a tetracarboxylic acid dianhydride and a diamine together with a molecular weight regulator (for example, an acid anhydride, a monoamine compound, a monoisocyanate compound or the like), if necessary. The ratio of the tetracarboxylic dianhydride and the diamine to be used in the synthesis reaction of the polyamic acid is preferably such that the amount of the acid anhydride group of the tetracarboxylic acid dianhydride is 0.2 to 2 equivalents based on 1 equivalent of the diamine amino group.

The synthesis reaction of the polyamic acid is preferably carried out in an organic solvent. The reaction temperature is preferably -20 ° C to 150 ° C, and the reaction time is preferably 0.1 to 24 hours. Examples of the organic solvent include N, N-dimethylacetamide, N, N-dimethylformamide, dimethylsulfoxide, gamma -butyrolactone, tetramethylurea, hexamethylphosphoric triamide , m-cresol, xylenol, and halogenated phenol may be used as a solvent, or at least one selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons It is preferable to use a mixture of at least one of them. The reaction solution obtained by dissolving the polyamic acid may be provided as it is in the preparation of the liquid crystal aligning agent as it is or may be provided in the preparation of the liquid crystal aligning agent after the polyamic acid contained in the reaction solution is isolated.

[Polyimide]

The polyimide as the polymer [P] can be obtained by subjecting the polyamic acid synthesized as described above to dehydration ring closure and imidization. The polyimide may be a completely imidized product in which all of the arid acid structure of the polyamic acid is subjected to dehydration ring closure or may be a partial imide product in which an arid acid structure and an imidazole ring structure coexist. The imide ratio of the polyimide is preferably 30% or more, more preferably 40 to 99%. The imidization rate is expressed as a percentage of the ratio of the number of imide ring structures to the sum of the number of amide structure and the number of imide ring structure of polyimide. Here, a part of the imide ring may be an isoimide ring.

The dehydration ring closure of the polyamic acid is preferably carried out by dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to the solution, and heating the polyamic acid as necessary. As the dehydrating agent, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol based on 1 mol of the acid structure of the polyamic acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine and triethylamine can be used. The amount of the dehydration ring-closing catalyst to be used is preferably 0.01 to 10 mol based on 1 mol of the dehydrating agent to be used. Examples of the organic solvent used in the dehydration ring-closure reaction include the organic solvents exemplified for use in the synthesis of polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 to 180 占 폚, and the reaction time is preferably 1.0 to 120 hours. The reaction solution containing the polyimide may be directly supplied to the preparation of the liquid crystal aligning agent, or may be provided after preparation of the liquid crystal aligning agent after the polyimide is isolated. In addition, the polyimide may be obtained by imidization of a polyamic acid ester.

 [Polyamic acid ester]

Examples of the polyamic acid ester as the polymer [P] include: [I] a method of reacting a polyamic acid obtained by the above synthesis reaction with an esterifying agent, [II] a method of reacting a tetracarboxylic acid diester with a diamine, ] A method in which a tetracarboxylic acid diester dihalide is reacted with a diamine. The polyamic acid ester to be contained in the liquid crystal aligning agent may have only an amide ester structure, or may be a partial esterified product in which the amide structure and the amide ester structure coexist. The reaction solution obtained by dissolving the polyamic acid ester may be directly supplied to the preparation of the liquid crystal aligning agent, or the polyamic acid ester contained in the reaction solution may be isolated and then provided in the preparation of the liquid crystal aligning agent.

The polyamic acid, polyamic acid ester and polyimide obtained as described above preferably have a solution viscosity of 10 to 800 mPa · s and a solution of 15 to 500 mPa · s It is more preferable to have a viscosity. The solution viscosity (mPa 占 퐏) of the polymer is preferably 10% by mass or less, more preferably 10% by mass or less, of a polymer prepared using a good solvent for the polymer (for example,? -Butyrolactone, N-methyl- Solution at 25 占 폚 using an E-type rotational viscometer. The weight average molecular weight in terms of polystyrene measured by gel permeation chromatography (GPC) of the polyamic acid, polyamic acid ester and polyimide contained in the liquid crystal aligning agent is preferably 500 to 100,000, more preferably 1,000 to 50,000 More preferable.

Preferable embodiments of the polymer component to be blended in the liquid crystal aligning agent include the following (i) and (ii).

(i) a sunscreens containing, as a polymer component, silsesquioxane [L] alone.

(ii) The sun containing silsesquioxane [L] and polymer [P] as a polymer component.

In the case of the above (ii), the blending ratio ([L]: [P]) of the silsesquioxane [L] and the polymer [P] is improved by improving the applicability and reliability by blending silsesquioxane [ From the viewpoint of obtaining the effect appropriately, it is preferable to set the mass ratio to 1:99 to 80:20. More preferably from 10:90 to 75:25, and even more preferably from 20:80 to 70:30.

As other components, other additives such as a compound having at least one epoxy group in the molecule, a functional silane compound, a compound having at least one oxetanyl group in the molecule, an antioxidant, a surfactant, An antistatic agent, a leveling agent, an antimicrobial agent, and the like. These compounding ratios can be suitably set in accordance with the compound to be used so long as they do not hinder the effects of the present disclosure.

<Solvent>

The liquid crystal aligning agent of the present disclosure is prepared as a liquid composition in which silsesquioxane [L] and other components as required are dispersed or dissolved in an appropriate solvent. Examples of the organic solvent to be used include organic solvents such as N-methyl-2-pyrrolidone,? -Butyrolactone,? -Butyrolactam, N, N-dimethylformamide, Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether , Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamylphosphate Propionate, isoamyl isobutyrate, di-isopentyl ether, ethylene carbonate, propylene carbonate, and the like. These may be used alone or in combination of two or more.

The solid concentration in the liquid crystal aligning agent (the ratio of the total mass of components other than the solvent of the liquid crystal aligning agent in the total mass of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, etc., Mass%. That is, the liquid crystal aligning agent of the present disclosure is applied to the surface of the substrate as described later, and preferably heated to form a coating film which is a liquid crystal alignment film or a liquid crystal alignment film. At this time, when the solid concentration is less than 1% by mass, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid concentration exceeds 10% by mass, the film thickness of the coating film becomes excessive, and it becomes difficult to obtain a good liquid crystal alignment film, and the viscosity of the liquid crystal aligning agent tends to increase and the coatability tends to decrease. The temperature at which the liquid crystal aligning agent of the present disclosure is prepared is preferably 10 to 50 占 폚.

 [Liquid Crystal Alignment Film and Liquid Crystal Device]

The liquid crystal alignment film of the present disclosure is formed by the liquid crystal aligning agent prepared as described above. Further, the liquid crystal device of the present disclosure comprises a liquid crystal alignment film formed using the above liquid crystal aligning agent. The mode of operation of the liquid crystal in the liquid crystal device is not particularly limited and can be applied to various modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type and PSA type.

The liquid crystal device can be manufactured by a method including the following steps 1 to 3, for example. Step 1 differs from substrate to substrate in accordance with a desired driving mode. Step 2 and step 3 are common to each mode.

[Process 1: Formation of coating film]

First, a liquid crystal aligning agent of the present disclosure is coated on a substrate, and then a coated film is formed on the substrate by heating the coated surface. Examples of the substrate include glass such as float glass and soda glass;

A transparent substrate made of plastic such as polyethylene terephthalate, polybutylene terephthalate, polyether sulfone, polycarbonate, and poly (alicyclic olefin) can be used. When a liquid crystal display element of TN type, STN type, VA type, MVA type or PSA type is manufactured, two substrates on which a patterned transparent conductive film is formed are used. In the case of manufacturing an IPS type or FFS type liquid crystal display device, a substrate on which electrodes made of a transparent conductive film or a metal film patterned in a comb-shaped pattern and an opposing substrate on which electrodes are not formed are used. As the transparent conductive film to be formed on the substrate surface, there can be used an NESA film (a registered trademark of PPG Corporation, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) have. As the metal film, for example, a film made of a metal such as chromium can be used. The application of the liquid crystal aligning agent to the substrate is preferably performed by an offset printing method, a spin coating method, a roll coating method, or an inkjet printing method.

After application of the liquid crystal aligning agent, preheating (prebaking) is preferably performed for the purpose of preventing the flow of the liquid of the applied aligning agent or the like. The prebaking temperature is preferably 30 to 200 占 폚, and the prebaking time is preferably 0.25 to 10 minutes. Thereafter, when the liquid crystal aligning agent contains the polymer [P] for the purpose of completely removing the solvent, and if necessary, the post-baking (post Baking) process is performed. The firing temperature (post-baking temperature) at this time is preferably 80 to 300 占 폚. The post baking time is preferably 5 to 200 minutes. The film thickness of the film thus formed is preferably 0.001 to 1 mu m. After applying the liquid crystal aligning agent on the substrate, the organic solvent is removed to form a coating film which becomes the liquid crystal alignment film.

[Process 2: Orientation-imparting treatment]

In the case of producing a liquid crystal display element of TN type, STN type, IPS type or FFS type, the coating film formed in the above step 1 is subjected to treatment for imparting liquid crystal aligning ability. Accordingly, the alignment ability of the liquid crystal molecules is imparted to the coating film to form a liquid crystal alignment film. Examples of the orientation-imparting treatment include a rubbing treatment for rubbing the coating film in a predetermined direction with a roll formed of fibers such as nylon, rayon, and cotton, and a photo-alignment treatment for irradiating the coating film with polarized or unpolarized radiation have.

When the liquid crystal aligning ability is imparted to the coating film by the photo alignment treatment, ultraviolet rays and visible rays including light having a wavelength of, for example, 150 to 800 nm can be used as the radiation to be applied to the coating film. good. As the light source to be used, for example, a low pressure mercury lamp, a high pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser and the like can be used. The irradiation dose of the radiation is preferably 100 to 50,000 J / m 2, and more preferably 300 to 20,000 J / m 2. The light irradiation to the coating film may be performed while heating the coating film to enhance the reactivity. A liquid crystal alignment film suitable for a VA type liquid crystal display device can be suitably used for a liquid crystal display device of a PSA (Polymer Sustained Alignment) type.

[Step 3: Construction of liquid crystal cell]

Two substrates on which the liquid crystal alignment film is formed as described above are prepared, and the liquid crystal is arranged between the two substrates arranged opposite to each other to manufacture a liquid crystal cell. As a method of manufacturing the liquid crystal cell, for example, (1) two substrates are disposed opposite each other with a cell gap interposed therebetween so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded using a sealing agent A method in which a liquid crystal is injected and filled in a cell gap defined by a substrate surface and a sealant, and then the injection port is sealed; and (2) a liquid drop method (ODF method). As the sealing agent, for example, an epoxy resin containing an aluminum oxide sphere as a curing agent and a spacer can be used. Examples of the liquid crystal include nematic liquid crystal and smectic liquid crystal, and among them, nematic liquid crystal is preferable. Cholesteric liquid crystals, chiral agents, and strong dielectric liquid crystals may be added to these liquid crystals.

Then, if necessary, a polarizing plate is bonded to the outer surface of the liquid crystal cell to obtain the liquid crystal device of the present disclosure. As the polarizing plate to be bonded to the outer surface of the liquid crystal cell, a polarizing plate in which a polarizing film called "H film" in which iodine is absorbed while polyvinyl alcohol is oriented in a stretched polyvinyl alcohol is sandwiched by a cellulose acetate protective film or a polarizing plate made of H film itself .

The liquid crystal device of the present disclosure can be effectively applied to various devices and can be used for various applications such as a clock, a portable game, a word processor, a notebook type personal computer, a car navigation system, a camcorder, a PDA, A display device such as a telephone, a monitor, a liquid crystal television or the like, a light control film, and the like. The liquid crystal device formed using the liquid crystal aligning agent of the present disclosure may also be applied to a retardation film.

(Example)

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

In the following examples, the weight average molecular weight of the polymer, the imidization ratio of the polyimide, the solution viscosity of the polymer solution, the epoxy equivalent, and the T3 peak integral ratio were measured by the following methods. In the following examples, &quot; part &quot; and &quot;% &quot; are based on mass unless otherwise specified.

[Weight average molecular weight and number average molecular weight of polymer]; Is a polystyrene reduced value measured by GPC under the following conditions.

Column: TSKgelGRCXLII, manufactured by Tosoh Corporation

Solvent: tetrahydrofuran

Temperature: 40 ° C

Pressure: 68kgf / ㎠

[Imidization rate of polyimide]; The polyimide-containing solution was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature. The precipitate was dissolved in deuterated dimethyl sulfoxide and ¹ H-NMR was measured at room temperature using tetramethylsilane as a reference material. From the obtained ¹ H-NMR spectrum, the imidization ratio [%] was determined using the following equation (1).

Imidization ratio [%] = (1-A ¹ / A ² × α) × 100 (One)

(1), A ¹ is the peak area derived from the proton of the NH group near the chemical shift of 10 ppm, A ² is the peak area derived from the other proton, and? Is the proton 1 of the NH group in the polyamic acid The ratio of the number of other protons to the dog)

[Solution viscosity (mPa s) of polymer solution]; A solution prepared by using a predetermined solvent at a polymer concentration of 10% by mass was measured at 25 캜 using an E-type rotational viscometer.

[Epoxy equivalent]; Was measured in accordance with "hydrochloric acid-methyl ethyl ketone method" of JIS C2105.

[T3 peak antagonistic]; ²⁹ Si-NMR. &Lt; / RTI &gt; 2 g of a polysiloxane solution having a solid content concentration of 20% and tris (2,4-pentanedionato) chromium (III) dissolved in 0.8 g of heavy DMSO were taken as samples and analyzed with a nuclear magnetic resonance apparatus AVANCEIII 400 NMR using a bio-spin, Inc.) was subjected to ²⁹ Si-NMR measurement of the sample. Based on the difference in chemical shift of each spectrum obtained by the ²⁹ Si-NMR measurement, the integral value of each signal corresponding to the content ratio of each structure represented by each of the following formulas (T1) to (T3) I got it.

(In the formulas (T1) to (T3), R ^a represents ^a monovalent organic group having 1 or more carbon atoms, and "*" represents a bonding bond to a silicon atom)

&Lt; Synthesis of silsesquioxane [L] >

Silsesquioxane [L] was synthesized in the following procedure. Further, Method 1 was used in Synthesis Examples 1-1 to 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-aminopropyltriethoxysilane as a specific silane compound of the condition 1 was mixed with 60 ml of a 1.0 mol / L hydrochloric acid aqueous solution (containing water in an amount of 96 mass% of the entire solvent) and stirred at room temperature for 2 hours did. Then, the mixture was heated at 60 to 70 DEG C in an open system, and the solvent was evaporated to proceed polycondensation. Subsequently, the product was allowed to stand overnight at 100 占 폚 and then dissolved in 300 ml of water, and the obtained aqueous solution was lyophilized to obtain 4.24 g (yield: 94%) of a white powdery compound %).

Then, 0.20 g of the obtained polymer (L-1A) was dissolved in 50 mL of water, passed through a column packed with an anion exchange resin (Amberlite IRA-900), and further, 1 N NaOH aqueous solution did. Subsequently, the obtained solution was lyophilized to obtain 1.63 g (yield: 74%) of silsesquioxane having a partial structure represented by the following formula (s-1) (hereinafter referred to as "polymer (L-1)"). The polymer (L-1) thus obtained had a molecular weight distribution (PDI) of 2.0 and a T3 peak integral of 89%, which was found to be Mw = 13,000, Mn = 6,400 and a ratio Mw / Mn of Mw / Mn. From these physical properties, it was confirmed that the polymer (L-1) was a ladder type.

The storage stability was evaluated by the presence or absence of gelation when the polymer solution was allowed to stand at 20 占 폚 for 3 days. In the evaluation, the storage stability was judged as "good" when the gelation was not observed, and the case where the gelation was observed was judged as "poor". As a result, the polymer solution did not gel, and the storage stability was &quot; good &quot;.

 [Synthesis Example 1-2 and Synthesis Example 1-3]

Polymers (L-2) and (L-3)) were prepared in the same manner as in Synthesis Example 1-1, except that the type and amount of the monomers used were changed as shown in Table 1, Respectively. The physical properties of the obtained polymer are shown in Table 2 below.

[Synthesis Example 1-4]

4.35 g of 2-cyanoethyltriethoxysilane as a specific silane compound of the condition 1 were mixed in 5 mL of an aqueous sodium hydroxide solution having a concentration of 8% as a catalyst of the condition 2 and stirred for 13 hours. The resulting aqueous solution was heated to 50 to 60 캜 in an open system, and the solvent was evaporated to proceed polycondensation. The resulting powdery crude product was then added to 100 mL of water containing about 100 cm 3 of H ⁺ -type cation exchange resin and stirred at room temperature for 3 hours. After the cation exchange resin was filtered off, the resulting aqueous solution was concentrated to 20 mL with a rotary evaporator and then freeze-dried to obtain a silsesquioxane having a partial structure represented by the following formula (s-4) -4) &quot;) was obtained (yield: 70%). The obtained polymer (L-4) had a Mw of 8,000, a Mn of 4,000, a molecular weight distribution (PDI) of 2.0, and a T3 peak integral of 86%. From these properties, it was confirmed that the polymer (L-4) was a ladder type. The polymer solution was evaluated in terms of storage stability in the same manner as in Synthesis Example 1-1, and found to be &quot; good &quot;.

[Synthesis Example 1-5]

Ladder silsesquioxane (polymer (L-5)) was obtained in the same manner as in Synthetic Example 1-4 except that the type and amount of the monomers used were changed as shown in Table 1 below. 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 monomers used were changed as shown in Table 1 and a mixed solution of an aqueous solution of sodium hydroxide and an aqueous solution of hydrogen peroxide was used as a catalyst, (Polymer (L-6)) was obtained. The physical properties of the obtained polymer are shown in Table 2 below.

[Synthesis Example 1-7]

9.00 g of p-styryltrimethoxysilane and 0.04 g of potassium carbonate as a compound represented by the above formula (3) were added to 7 mL (mass ratio 3/2) of a mixed solvent of tetrahydrofuran / water, and the mixture was stirred at 40 ° C for 2 hours . Subsequently, the precipitated viscous solid was dissolved in 15 mL of methylene chloride, and the obtained liquid was slowly added dropwise to 100 mL of methanol. The solids formed after dropwise addition were dried by filtration to obtain polymer (L-7) as silsesquioxane in a yield of 77%. The obtained polymer (L-7) had an Mw of 9,700, a Mn of 4,800, a molecular weight distribution (PDI) of 2.0, and a T3 peak integral of 92% and was soluble in water. A ²⁹ Si-NMR chart of the polymer (L-7) is shown in Fig. When the R ^a in the partial structure represented by the formula (4) is ^a styryl group, a peak in the T 3 unit appears near -80 ppm, a peak in the T2 unit is near -70 ppm, and a peak in the T1 unit is near -65 ppm . From the results shown in Fig. 1, the ratio of T3 units in polymer (L-7) was larger than that in T2 unit and T1 unit. From these results, it was confirmed that the polymer (L-7) was a ladder type.

[Synthesis Example 1-8]

Under nitrogen atmosphere, 3.17 g (0.025 mol) of chlorodimethoxysilane was added to 15 ml of xylene solution, and the solution was cooled to -15 캜. Subsequently, 25 mL of an acetone solution of 2.70 g (0.025 mol) of p-phenylenediamine was slowly added dropwise, and then stirred for 30 minutes. After stirring, 15 mL of acetone, 20 mL of xylene and 6 mL (10 mol / L) of hydrochloric acid were added dropwise in this order, followed by stirring at room temperature for 4 hours. Then, sodium sulfate was added to dehydrate, and sodium sulfate was removed by filtration. To the filtrate was added 2 parts of concentrated sulfuric acid, and the mixture was stirred at room temperature for 3 hours and then at 90 ° C for 3 hours. Subsequently, liquid separation was carried out with 50 mL of water, and the solvent of the organic layer was distilled off to obtain a polymer (L-8) as a silsesquioxane in a yield of 83%. The obtained polymer (L-8) had an Mw of 15,000, a Mn of 8,000, a molecular weight distribution (PDI) of 1.9 and a T3 peak integral of 82% and was soluble in water. From the above physical properties, it was confirmed that the polymer (L-8) was a ladder type.

&Lt; Synthesis of other polymer (polysiloxane) >

[Comparative Synthesis Example 1-1]

4.9 g (20 mmol) of 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane was dissolved in 50 g of cyclopentanone, and 0.2 g of triethylamine (TEA) and 5.0 g of water were added to 50 g of cyclopentanone And the mixture was stirred for 2 hours at 55 占 폚. The solvent was evaporated with a separator and the resulting solid was washed with acetone to obtain 3.30 g (yield: 93%) of cage silsesquioxane (hereinafter referred to as "polymer (R-1)") as a white powdery compound, ). 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 integral of 94%. Further, when this polymer solution was allowed to stand at 20 占 폚 for 3 days, gelation did not occur and storage stability was good.

[Comparative Synthetic Examples 1-2 to Comparative Synthetic Synthetic Examples 1-4]

(R-2) to a polymer (R-4) as cask silsesquioxane by carrying out the same operations as in Comparative Synthesis Example 1-1, except that the type and amount of the monomers used were changed as shown in Table 1 Respectively. The physical properties of the obtained polymer are shown in Table 2 below. With respect to the polymer (R-3) and the polymer (R-4), the polymer solution was allowed to stand at 20 캜 for 3 days, and as a result, gelation was observed and storage stability was poor.

[Comparative Synthesis Example 1-5]

51.3 g of hexylene glycol, 15.6 g of butyl cellosolve, 66.0 g of tetraethoxysilane and 6.9 g of dodecyltriethoxysilane were charged into a 500-mL four-neck reaction flask equipped with a reflux condenser and stirred. To this solution was added dropwise an oxalic acid solution containing 25.6 g of hexyleneglycol, 7.8 g of butyl cellosolve, 30.0 g of water and 0.3 g of oxalic acid as a catalyst at room temperature, and the mixture was stirred for 30 minutes after completion of dropwise addition. Thereafter, the solution was heated at a solution temperature of 70 占 폚 for 1 hour and then allowed to cool. To this solution, hexylene glycol (HG), butyl cellosolve (BC) and N-methyl-2-pyrrolidone (NMP) were added to give HG: BC: NMP = 30: 50: 20 Further, the solution was adjusted to have a SiO ₂ concentration of 3.5% by mass to obtain a solution containing a random polysiloxane (hereinafter referred to as "polymer (R-5)"). The polymer (R-5) obtained had Mw of 9,000, Mn of 2,650, a molecular weight distribution (PDI) of 3.4, and a T3 peak integral of about 0% (Table 2).

[Comparative Synthesis Example 1-6]

(R-6) as silsesquioxane was obtained by carrying out the same operations as in Synthesis Example 1-1, except that an aqueous solution of sodium hydroxide was used in place of the aqueous hydrochloric acid solution of 1.0 mol / L and the same concentration of sodium hydroxide was used. . The obtained polymer (R-6) had a Mw of 125,000, a Mn of 29,000, a molecular weight distribution (PDI) of 4.3 and a T3 peak integral of 62% . This polymer gelled after one day. The physical properties of the obtained polymer are shown in Table 2 below.

[Comparative Synthesis Example 1-7]

A polymer (R-7) was obtained as a silsesquioxane by performing the same operation as in Synthesis Example 1-4, except that an aqueous solution of hydrochloric acid having a copper concentration was used instead of the aqueous sodium hydroxide solution having a concentration of 8%. 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 T3 peak integral of 94% .

In Table 1, the numerical values of the monomers indicate the use ratio (mol%) of each compound to the sum of the monomers used in the reaction.

&Lt; Monomer &

MS3-1: 2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane

MS3-2: 3-methacryloxypropyltrimethoxysilane

MS3-3: Dodecyltriethoxysilane

MS3-4: 3-aminopropyltriethoxysilane

MS3-5: 2-Cyanoethyltriethoxysilane

MS3-6: 4- (Chloromethyl) phenyltrimethoxysilane

MS3-7: p-Styryltrimethoxysilane

MS3-8: 3-mercaptopropyltriethoxysilane

MS3-9: Chlorodymethoxysilane

MS4-1: Tetraethoxysilane

<Synthesis of silsesquioxane [L] of side chain modification type>

[Synthesis Example 2-1]

10 mL of thionyl chloride was added to 1.02 g (3.7 mmol) of 4- (4-n-pentylcyclohexyl) benzoic acid, and the mixture was heated to 60 ° C for 1 hour. Thereafter, thionyl chloride in the system was removed by vacuum distillation and removal to obtain a white acid chloride. This was dissolved in 20 g of tetrahydrofuran. Subsequently, 1.63 g of the polymer (L-1) was dissolved in a mixed solvent of 15 mL of water and 15 mL of tetrahydrofuran, 0.45 g (4.4 mmol) of triethylamine and 0.05 g of tetrabutylammonium bromide were added to the solution and stirred . This was placed under ice-cooling, and the inner temperature of the system was kept at 5 캜 or lower. To the solution, the acid chloride solution was added dropwise over a period of one hour, and stirring was carried out in an ice bath for 4 hours.

Then, 100 mL of cyclopentanone was added to the obtained reaction solution, and liquid separation was performed. Thereafter, 150 mL of N-methyl-2-pyrrolidone was added, and the mixture was concentrated with a double concentrator to obtain a polymer solution containing the polymer (L-11) of the side chain modification type. 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 integral of 91%. The evaluation of the storage stability was "good".

[Synthesis Example 2-2 and Synthesis Example 2-3]

(L-12) and a polymer (L-13) were obtained in the same manner as in Synthesis Example 2-1, except that the kind and amount of the reactive compound used were changed as shown in Table 3 below. 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 polymer (L-4) were dissolved in 20 mL of N-methyl- Pentanone in a mixed solvent of 40 mL. This was placed under ice-cooling, and the inner temperature of the system was kept at 5 캜 or lower. 0.81 g (4.2 mmol) of 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride and 0.1 g (catalytic amount) of dimethylaminopyridine were placed and reacted for 6 hours under ice cooling. Then, 100 mL of cyclopentanone was added to the obtained reaction solution, and liquid separation was performed. Thereafter, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer, and the mixture was concentrated with a double concentrator to obtain a polymer solution containing the polymer (L-14) of the side chain modification type. The physical properties of the obtained polymer are shown in Table 4 below.

[Synthesis Example 2-5 and Synthesis Example 2-6]

Polymer (L-15) and polymer (L-16) were obtained in the same manner as in Synthesis Example 2-4, except that the kind and amount of the reactive compound used were changed as shown in Table 3. 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 THF, and 2.56 g (18.5 mmol) of potassium carbonate was added. 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, and liquid separation was carried out. Thereafter, 100 mL of N-methyl-2-pyrrolidone was added to the organic layer, and the mixture was concentrated with a double concentrator to obtain a polymer solution containing the polymer (L-17) of the side chain modified form. The physical properties of the obtained polymer are shown in Table 4 below.

[Synthesis Example 2-8]

1.01 g (3.02 mmol) of the compound represented by the following formula (mc-7) was dissolved in 30 mL of toluene, and then 1.98 g of the polymer (L-7) and 9.85 mg of azobisisobutyronitrile were added thereto. Lt; / RTI &gt; After the reaction, 100 mL of N-methyl-2-pyrrolidone was added, and the mixture was concentrated with a double concentrator to obtain a polymer solution containing the polymer (L-18) of the side chain modification type. 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. Subsequently, 6.21 g (50 mol) of 1,2-epoxy-4-vinylcyclohexane and 0.1 g of hexachloride platinum (IV) acid were added in this order and the mixture was reacted at 80 DEG C for 2 hours. After the reaction, the catalyst was removed by filtration. 100 ml of cyclopentanone was added to the filtrate and concentrated to obtain 30 g of a cyclopentanone solution having a solid content concentration of 30% by mass. 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 DEG C for 4 hours. After stirring, 100 mL of water was added to perform liquid separation and purification. Subsequently, 30 mL of butyl cellosolve was added to the organic layer, and the mixture was concentrated to obtain a polymer solution containing the polymer (L-19) of the branched chain type. The physical properties of the obtained polymer are shown in Table 4 below.

&Lt; Synthesis of other polymer (side chain modified silsesquioxane) >

[Comparative Synthesis Example 2-1]

3.3 g of the polymer (R-1), 50 g of methyl isobutyl ketone, 1.02 g of 4- (4-n-pentylcyclohexyl) benzoic acid, 2,6- 50 mg of methoxyphenol and 0.6 g of trade name &quot; UCAT 18X &quot; (a curing accelerator of an epoxy compound manufactured by SANA PRO Co., Ltd.) were placed and reacted at 90 캜 for 48 hours. After completion of the reaction, methanol was added to the reaction mixture to form a precipitate, and the precipitate was dissolved in ethyl acetate. The resulting solution was washed three times with water and then the solvent was distilled off to obtain a side chain modified silsesquioxane (polymer -11)) as white powder. 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 integral of 94%. The evaluation of the storage stability was "good".

[Comparative Synthesis Example 2-2]

Polymer (R-12) was obtained in the same manner as in Comparative Synthesis Example 2-1 except that the kind and amount of the reactive compound used were changed as shown in Table 3 below. The physical properties of the obtained polymer are shown in Table 4 below.

In Table 3, the numerical value of the reactive compound indicates the use ratio (mol%) of the reactive compound with respect to the silicon atom possessed by 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 (methacryloyloxy) benzoic acid

MC-3: 4-phenoxycinnamic acid

MC-4: 4- (4-n-pentylcyclohexyl) aniline

MC-5: Compound represented by the following formula (mc-5)

MC-6: Compound represented by the following formula (mc-6)

MC-7: Compound represented by the following formula (mc-7)

&Lt; Synthesis of other polymer (polymer [P]) >

[Synthesis Example 3-1]

19.61 g (0.1 mole) of 1,2,3,4-cyclobutane tetracarboxylic acid dianhydride and 21.23 g (0.1 mole) of 4,4'-diamino-2,2'- -Pyrrolidone and reacted at room temperature for 6 hours to obtain a solution containing polyamic acid (PA-1).

[Synthesis Example 3-2]

(0.1 mole) of pyromellitic dianhydride and 19.6 g (0.1 mole) of 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride as acid dianhydrides, and 4,4'-diamino di 40 g (0.2 mol) of phenyl ether was dissolved in 458 g of N-methyl-2-pyrrolidone and the mixture was reacted at 40 占 폚 for 3 hours. Then, 356 g of N-methyl- 2) was obtained.

[Synthesis Example 3-3]

19.61 g (0.1 mole) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 22.8 g (0.1 mole) of 4-aminophenyl-4'-aminobenzoate were dissolved in N-methyl-2-pyrrolidone , And the mixture was reacted at room temperature for 12 hours to obtain a solution containing polyamic acid (PA-3).

[Synthesis Example 3-4]

22.4 g (0.1 mole) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 10.81 g (0.1 mole) of p-phenylenediamine were dissolved in 329.3 g of N-methyl-2-pyrrolidone, For 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure at 40 占 폚 for 15 hours to obtain 32 g of polyamic acid (PA-4).

17.5 g of the polyamic acid (PA-4) obtained by the above-mentioned synthesis was added thereto, 232.5 g of N-methyl-2-pyrrolidone, 3.8 g of pyridine and 4.9 g of acetic anhydride were added and reacted at 120 ° C for 4 hours . Subsequently, the reaction mixture was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of polyimide powder. This was dissolved in 135 g of N-methyl-2-pyrrolidone to obtain a polyimide (PI-1) in a 10 mass% solution.

&Lt; Evaluation of liquid crystal aligning agent and liquid crystal display element >

[Example 1]

(1) Preparation of liquid crystal aligning agent

An amount corresponding to 100 parts by mass of the solution containing polyamic acid (PA-1) in terms of polyamic acid (PA-1) contained therein was taken, and the amount of the polymer (L- (NMP: BC = 80: 20 (mass ratio)) and a solid content concentration of 3.5 (mass%) were added to 100 parts by mass of NMP- Mass% solution. This solution was filtered with a filter having a pore size of 1 탆 to prepare a liquid crystal aligning agent (A-1).

(2) Evaluation of printability

The liquid crystal aligning agent (A-1) prepared in (1) above was applied to the transparent electrode surface of a glass substrate with a transparent electrode made of ITO film using a liquid crystal alignment film printing machine (manufactured by Japan Photographic Print Co., Ltd.) (Pre-baked) on a hot plate for 1 minute to remove the solvent, and then heated on a hot plate at 230 DEG C for 10 minutes (post baking) to form a coating film having an average film thickness of 0.06 mu m. This coating film was observed under a microscope with a magnification of 20 times to examine whether or not there were unevenness in film thickness, unevenness in citron peel, and unevenness in line. The evaluation was conducted under the following conditions: no film thickness unevenness, uniformity of printing surface printing property "good" (good), printability "possible (Δ)" when citron peel unevenness was observed, unevenness of yuzu peel, (X) &quot; for printability. In this example, the film thickness irregularity was not observed, and the coated surface was uniform, and the printability was "good (O)".

(3) Evaluation of residual film ratio

The liquid crystal aligning agent (A-1) prepared in (1) above was coated on a glass substrate using a spinner and pre-baked for 1 minute on a hot plate at 80 ° C. Lt; 0 &gt; C for 1 hour (post-baking). Next, N-methyl-2-pyrrolidone (NMP) was applied to the film after post-baking by spin coating. The film thickness D1 (占 퐉) before spin coating of NMP and the film thickness D2 (占 퐉) after coating were measured by a scanning electron microscope and the residual film ratio (%) was calculated by the following formula (2).

(%) = [(D1-D2) / D1] x100 (2)

The higher the residual film ratio, the higher the crosslinking density of silsesquioxane. On the other hand, when the cross-linking density of silsesquioxane is low, the silsesquioxane in the liquid crystal alignment layer flows into the liquid crystal when the liquid crystal cell is used, and the display characteristics are likely to deteriorate. In the evaluation, the case where the residual film ratio was 90% or more was referred to as "good". The case where the film residual rate was 80% or more and less than 90% was referred to as "possible?". As a result, in this example, the film residual ratio was "good (O)".

(4) Production of liquid crystal cell

An FFS type liquid crystal display element 10 shown in Fig. 2 was produced. First, a bottom electrode 15 having no pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned in a comb are formed in this order on a glass substrate 11a having an electrode pad on one side And the opposing glass substrate 11b on which the electrodes are not formed are paired so that the surfaces having the transparent electrodes on the glass substrate 11a and the surfaces of the opposing glass substrate 11b The liquid crystal aligning agent (A-1) was applied using a spinner to form a coating film. Subsequently, this coating film was pre-baked on a hot plate at 80 DEG C for 1 minute, and then heated (post-baked) at 230 DEG C for 15 minutes in an oven whose inside was replaced with nitrogen to form a coating film having an average film thickness of 0.1 mu m.

A schematic plan view of the top electrode 13 used here is shown in Fig. 3 (a) is a top 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 this embodiment, a substrate having a top electrode having a line width d1 of 4 mu m and a distance d2 between electrodes is 6 mu m. As the top electrode 13, driving electrodes of four lines of electrode A, electrode B, electrode C and electrode D were used. Fig. 4 shows the configuration of the driving electrode used. The bottom electrode 15 functions as a common electrode acting on all the four driving electrodes, and each of the areas of the four driving electrodes becomes a pixel area.

Subsequently, a polarizing ultraviolet ray (300 J / m 2) containing a bright line of 313 nm was irradiated from the normal direction of the substrate to each surface of these coating films using a Hg-Xe lamp and a Glane Taylor prism to obtain a pair of substrates having a liquid crystal alignment film . At this time, the irradiation direction of the polarized ultraviolet ray is set to be from the normal direction of the substrate, and the direction of the line segment in which the polarized surface of the polarized ultraviolet ray is projected onto the substrate is set to be the direction of both arrows in Fig. I did.

Next, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 占 퐉 was applied to the periphery of the surface having one liquid crystal alignment film in the above-mentioned substrate by screen printing, and then the liquid crystal alignment film faces of the pair of substrates were opposed to each other, The polarizing surfaces of the polarized ultraviolet rays were superimposed on each other in such a manner that the directions of projection of the polarizing surfaces of the polarizing ultraviolet rays were parallel to each other, and the adhesive was thermally cured at 150 占 폚 for 1 hour. Subsequently, a liquid crystal "MLC-6221" manufactured by Merck Ltd. was filled in the gap between the substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy resin adhesive. Thereafter, in order to remove the flow orientation at the time of injecting the liquid crystal, it was heated to 150 DEG C and then gradually cooled to room temperature.

Next, a polarizing plate was bonded to both outer sides of the substrate to produce an FFS type liquid crystal display element. One of the polarizing plates is adhered so that the polarizing direction of the polarizing plate is parallel to the projection direction of the polarizing plane of the polarized ultraviolet ray of the liquid crystal alignment film to the substrate surface and the other polarizing direction is perpendicular to the polarizing direction of the polarizing plate did.

(5) Evaluation of voltage preservation and maintenance rate

A voltage of 1 V was applied to the FFS type liquid crystal display device manufactured in (4) above at a temperature of 23 캜 for an application time of 0.5 microseconds and a span of 2,000 milliseconds. Thereafter, a voltage holding and maintaining ratio (VHR ) Were measured. As a measuring apparatus, VHR-1 (manufactured by Toyotecnica Co., Ltd.) was used. In the evaluation, the case where the voltage holding and maintaining ratio is 95% or more is defined as "good", the case where the voltage holding and maintaining ratio is 90% or more and less than 95% is defined as "possible" and the case where the voltage holding and maintaining ratio is less than 90% As a result, in this embodiment, the voltage holding and sustaining rate was "good (O)".

(6) Evaluation of alignment of liquid crystal

With respect to the liquid crystal display device manufactured as described above, the presence or absence of an abnormal domain in the change of light and dark when a voltage of 5 V was applied / released was observed by an optical microscope. In the evaluation, the liquid crystal alignability was evaluated as &quot; good (o) &quot; when no abnormal domains were observed, the liquid crystal alignability was evaluated as & X) &quot;. As a result, no abnormal domains were observed in this liquid crystal display element, and the liquid crystal alignment property was "good (O)".

[Examples 2 to 13 and Comparative Examples 1 and 2]

A liquid crystal aligning agent was prepared in the same manner as in Example 1, except that the kind and the amount of the polymer used in Example 1 were changed as shown in Table 5 below, and various evaluations were conducted using the liquid crystal aligning agent. The evaluation results are shown in Table 5 below.

In Table 5, the numerical values of the polymer [P] are the same as in Example 1 except that the blending ratio of each polymer to 100 parts by mass of silsesquioxane (silsesquioxane [L] used as a liquid crystal aligning agent or silsesquioxane as another polymer) (Parts by mass).

As shown in Table 5, all of Examples 1 to 13 including silsesquioxane [L] were &quot; good &quot; or &quot; acceptable &quot; in evaluation of printability, residual film ratio, voltage storage retention and liquid crystal alignability. In contrast, Comparative Examples 1 and 2 were inferior to those in Examples.

10: Liquid crystal display element
11a and 11b:
12: liquid crystal alignment film
13: Top electrode
14: Insulating layer
15: bottom electrode
16: liquid crystal layer

Claims (15)

A liquid crystal aligning agent containing silsesquioxane [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; n is an integer of 2 or more;
E ¹ and E ² in different repeating units may be the same or different). The method according to claim 1,
A liquid crystal aligning agent having an integral ratio of peaks in a ²⁹ Si-NMR spectrum derived from a partial structure represented by the following formula (4) in the silsesquioxane [L]: 70 to 99%

(In the formula (4), R &lt; ^a &gt; represents ^a monovalent organic group having at least 1 carbon atom and &quot; * &quot; represents a bonding bond to a silicon atom). 3. The method according to claim 1 or 2,
Wherein at least one of a plurality of E ¹ and E ² of the silsesquioxane [L] is an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acryloyl group, a vinyl group, an ethynyl group, -NHR ^5, an isocyanate group, an alcoholic hydroxyl group, 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 (provided that 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) My. 3. The method according to claim 1 or 2,
Wherein at least one of a plurality of E ¹ and E ² of the silsesquioxane [L] has at least one kind selected from the group consisting of a group having a pretilt angle manifesting ability, a photo aligning group and a crosslinking group Orientation agent. A liquid crystal aligning agent containing silsesquioxane [L] satisfying the following requirements (A) to (C)
(A) a weight average molecular weight (Mw) of 5000 or more as measured by gel permeation chromatography;
(B) a molecular weight distribution (Mw / Mn) represented by a ratio of a weight average molecular weight (Mw) to a number average molecular weight (Mn) measured by gel permeation chromatography 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 &lt; ^a &gt; represents ^a monovalent organic group having at least 1 carbon atom and &quot; * &quot; represents a bonding bond to a silicon atom). 6. The method according to claim 1 or 5,
The silsesquioxane [L] is a liquid crystal aligning agent which is a hydrolyzed condensation product of a silane compound containing a compound represented by the following formula (3)

[Wherein Ar ¹ is one kind selected from the group consisting of groups represented by each of the following formulas (ar-1) to (ar-8), J ¹ is a group represented by the following formula (j-1) ) To (j-7), respectively;
R &lt; ⁴ &gt; is a monovalent hydrocarbon group of 1 to 18 carbon atoms);

(In the formulas (ar-1) to (ar-8), "*" represents a bonding hand bonding to a silicon atom, and "* 1" represents a bonding hand bonding to J ¹ );

(In the formulas (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, X ⁴ is a hydrogen atom, An alkyl group having 1 to 6 carbon atoms;
And &quot; * &quot; represents a hand bonded to Ar ¹ ). 6. The method according to claim 1 or 5,
The silsesquioxane [L] is a liquid crystal aligning agent which is a hydrolyzed condensate of a silane compound containing a compound represented by the following formula (2)

(In the formula (2), R ³ represents -NHR ⁵ (wherein R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a pyridyl group, an imidazole group, a cyano group, an imino group, An organic group having 2 to 18 carbon atoms and having at least one specific group selected from the group consisting of a hydroxyl group, a carboxyl group, a phosphoryl group, a sulfo group and an acid anhydride group;
X ¹ , X ² and X ³ are each independently a halogen atom, an alkoxy group having 1 to 18 carbon atoms or an acyloxy group having 1 to 18 carbon atoms. 6. The method according to claim 1 or 5,
The silsesquioxane [L] is a compound obtained by polymerizing a silane compound under conditions that satisfy at least two of the following conditions 1, 2, and 3: Liquid crystal aligning agent:
Condition 1: As the silane compound, -NHR ⁵ (R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a pyridyl group, an imidazole group, a cyano group, an imino group, a hydroxyl group, a mercapto group, A silane compound having at least one specific group selected from the group consisting of a phosphorus group, a phosphoryl group, a sulfo group and an acid anhydride group;
Condition 2: In the case where the silane compound of the above-mentioned condition 1 has an acidic group as the specific group, the silane compound is hydrolyzed and condensed in the presence of a base, and when the silane compound has a basic group as the specific group, Decomposition and condensation;
Condition 3: The silane compound is hydrolyzed and condensed in a solvent containing 10% by mass or more of water. A liquid crystal aligning agent containing silsesquioxane [L] obtained by polymerizing a silane compound under conditions that satisfy at least two of the following conditions 1, 2, and 3:
Condition 1: As the silane compound, -NHR ⁵ (R ⁵ is a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), a pyridyl group, an imidazole group, a cyano group, an imino group, a hydroxyl group, a mercapto group, A silane compound having at least one specific group selected from the group consisting of a phosphorus group, a phosphoryl group, a sulfo group and an acid anhydride group;
Condition 2: In the case where the silane compound of the above-mentioned condition 1 has an acidic group as the specific group, the silane compound is hydrolyzed and condensed in the presence of a base, and when the silane compound has a basic group as the specific group, Decomposition and condensation;
Condition 3: The silane compound is hydrolyzed and condensed in a solvent containing 10% by mass or more of water. 10. The method according to any one of claims 1, 5 and 9,
Further, a liquid crystal aligning agent comprising at least one polymer [P] selected from the group consisting of polyimide, polyamic acid and polyamic acid ester. 11. The method of claim 10,
Wherein a mixing ratio ([L]: [P]) of the silsesquioxane [L] and the polymer [P] is 1:99 to 80:20 in terms of a mass ratio. 10. A liquid crystal alignment film formed using the liquid crystal aligning agent according to any one of claims 1, 5, and 9. A liquid crystal device comprising the liquid crystal alignment film according to claim 12. A method for manufacturing a liquid crystal display device, comprising the steps of: applying a liquid crystal aligning agent according to any one of claims 1, 5, and 9 on a substrate to form a coated film; irradiating the substrate surface coated with the liquid crystal aligning agent with light, Wherein the liquid crystal alignment film is formed on the substrate. Silsesquioxane having a ladder-like structure represented by the following formula (1): &lt; EMI ID =

(In the formula (1), E ¹ and E ² are each independently a monovalent organic group; n is an integer of 2 or more;
However, at least one of the plurality of E ¹ and E ² of silsesquioxane is preferably an epoxy group, an oxetanyl group, an acid anhydride group, a (meth) acryloyl group, a styryl group, an ethynyl group, a mercapto group, an isocyanate group alcoholic 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) ( However, R ¹ is , Each independently a hydrogen atom or a monovalent hydrocarbon group, and R ² is a monovalent hydrocarbon group), a photo-aligning group, and a crosslinking group.

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