TW201607973A - Liquid crystal alignment agent, liquid crystal alignment film and liquid crystal display element - Google Patents

Abstract

This invention obtains a liquid crystal display element with high reliability and less gas leakage amount from the liquid crystal alignment film. This invention provides a liquid crystal alignment agent containing polymers (P), in which at least one polymer is selected from the group consisting of polyamic acid, polyamic ester, polyimide and polyamide, and has a partial structure represented by formula (1). (A1 and A2 are a hydrogen atom or a monovalent group, and the total carbon number of A1 and A2 is from 0 to 7; Y1 is an oxygen atom or a sulfur atom; R1 is a hydrogen atom or a monovalent hydrocarbyl group containing from 1 to 6 carbons; X1 is a single bond or a bivalent organic group; and "*" represents a connection bond).

Description

Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element

The present invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display element.

Conventionally, liquid crystal display devices have developed various driving methods in which the electrode structure or the physical properties of liquid crystal molecules used are different. For example, a twisted nematic (TN) type or a super twisted nematic (STN) type is known. , Vertical Alignment (VA), Multidomain Vertical Alignment (MVA), Coplanar Switching (In PlaneSwitching, IPS), Fringe Field Switching (FFS), Optical Compensation Various liquid crystal display elements such as curved (Optically Compensatory Bend, OCB) type. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. The material of the liquid crystal alignment film is a polymer such as polyacrylic acid, polyimine, polyphthalate, polyamine, polyester or polyorganosiloxane, wherein heat resistance, mechanical strength, and liquid crystal are used. Polyuric acid or polyimine is usually used in terms of various properties such as affinity.

In recent years, liquid crystal panels have been used not only as display devices for personal computers and the like, but also for various applications such as liquid crystal televisions, car navigation systems, mobile phones, smart phones, and information displays. One of the important characteristics of the liquid crystal panel is that the quality of the liquid crystal panel is low and the reliability is high. In order to satisfy this characteristic, various liquid crystal alignment agents have been proposed (for example, see Patent Document 1).

Patent Document 1 proposes to use an aromatic diamine in which an amine group protected by a tertiary butoxycarbonyl group (t-BOC group) is introduced to an ortho position relative to a primary amine group, and is obtained by using the diamine. The polyamic acid or polyimine is contained in a liquid crystal alignment agent. According to this technique, Patent Document 1 describes that the t-BOC group is deprotected to form an amine group by heating at the time of film formation, and the intramolecular reaction or the intermolecular reaction (crosslinking) of the produced amine group is obtained. Reaction) to improve reliability. [Prior Art Document] [Patent Literature]

[Patent Document 1] International Publication No. 2013/115228

[Problems to be solved by the invention]

Patent Document 1 describes a technique in which an amine group formed by heating at the time of film formation is used, and it is considered that it is difficult to carry out a crosslinking reaction, and it is considered that the reliability of the liquid crystal panel cannot be sufficiently improved.

In the case where a thermally decomposable monomer is used, when a large amount of unreacted functional groups remain after heating, it is considered that a problem occurs in the case where bubbles are generated in the panel during long-term lighting of the liquid crystal panel. In order to suppress the occurrence of such an inconvenience, it is required that less gas escaping from the liquid crystal alignment film after post-baking.

The present invention has been made in view of the above problems, and an object thereof is to provide a liquid crystal alignment agent which can obtain a liquid crystal display element having a small amount of evolved gas from a liquid crystal alignment film and having high reliability. [Technical means to solve the problem]

The inventors of the present invention have actively studied in order to achieve the problems of the prior art as described above, and have attempted to introduce a specific structure which is considered to exhibit thermal decomposition into a polymer. Further, it has been found that the problem can be solved by using a polymer having the specific structure as a polymer component of a liquid crystal alignment agent, thereby completing the present invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element.

An aspect of the present invention provides a liquid crystal alignment agent containing at least one polymer selected from the group consisting of polylysine, polyphthalate, polyimine, and polyamine, and the polymerization At least a part of the substance is a polymer (P) having a partial structure represented by the following formula (1).

[Chemical 1] (In the formula (1), A ¹ and A ² are each independently a hydrogen atom or a monovalent organic group, and the total number of carbon atoms of A ¹ and A ² is 0 to 7; Y ¹ is an oxygen atom or a sulfur atom, and R ¹ Is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a single bond or a divalent organic group; "*" means a bond)

Another aspect of the present invention provides a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. [Effects of the Invention]

According to the liquid crystal alignment agent containing the polymer (P), a liquid crystal alignment film having a small amount of evolved gas can be formed. Further, since the liquid crystal display element of the present invention includes the liquid crystal alignment film formed using the liquid crystal alignment agent containing the polymer (P), the quality deterioration is small as the use, and the reliability is excellent.

Hereinafter, each component contained in the liquid crystal alignment agent and other components which are optionally blended as needed will be described.

<Polymer (P)> The liquid crystal alignment agent of the present invention contains a polymer (P) as a polymer component, and the polymer (P) is selected from the group consisting of polyglycine, polyphthalate, and polyimine. At least one of the group consisting of polyamines is used as a main skeleton, and has a partial structure represented by the following formula (1). [Chemical 2] (In the formula (1), A ¹ and A ² are each independently a hydrogen atom or a monovalent organic group; wherein, the total number of carbon atoms of A ¹ and A ² is 0 to 7; and Y ¹ is an oxygen atom or a sulfur atom. R ¹ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a single bond or a divalent organic group; "*" means a bond)

In the formula (1), the monovalent organic group of A ¹ and A ² may, for example, be a monovalent hydrocarbon group; and the methylene group to a monovalent hydrocarbon group may be -O-, -S-, -CO-, -COO- a group in which a divalent hetero atom-containing group such as -COS- is substituted; and at least one of hydrogen atoms possessed by the monovalent hydrocarbon group is substituted with a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or the like. a group; a monovalent group having a heterocyclic ring or the like. When the total number of carbon atoms of A ¹ and A ^{2 is} in the range of 0 to 7, the carbon number of A ¹ and A ² is not particularly limited, but a group which is desorbed by heating at the time of post-baking is used. From the viewpoint of reducing the amount of the compound remaining in the "-CHA ¹ A ² " in the alignment film, it is preferably 0 to 6, more preferably 0 to 4, and particularly preferably 0 to 3.

Here, the "hydrocarbon group" in the present specification means a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" means a linear hydrocarbon group and a branched hydrocarbon group which are not composed of a chain structure but a chain structure. Among them, it can be saturated or unsaturated. The "alicyclic hydrocarbon group" means a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. Among them, it is not necessarily required to be composed only of the structure of the alicyclic hydrocarbon, and also includes a hydrocarbon group having a chain structure in a part thereof. The "aromatic hydrocarbon group" means a hydrocarbon group containing an aromatic ring structure as a ring structure. Among them, it is not necessarily required to be composed only of an aromatic ring structure, and a structure of a chain structure or an alicyclic hydrocarbon may be contained in a part thereof.

Specific examples of the monovalent hydrocarbon group include, for example, an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group or a heptyl group; and an alkenyl group such as a vinyl group, a propenyl group or a butenyl group; An alkynyl group such as an ethynyl group or a propynyl group; these groups may be linear or branched. Further, examples of the alicyclic hydrocarbon group include a cyclohexyl group and a methylcyclohexyl group; and examples of the aromatic hydrocarbon group include a phenyl group and a tolyl group. From the viewpoint of easiness of detachment of the group "-CHA ¹ A ² " due to heating, A ¹ and A ^{2 are} preferably a hydrogen atom or a substituted or unsubstituted monovalent chain hydrocarbon group. More preferably, it is a hydrogen atom, or a substituted or unsubstituted alkyl group. Further, A ¹ and A ² may be the same or different from each other.

Examples of the monovalent hydrocarbon group having 1 to 6 carbon atoms of R ¹ include an alkyl group having 1 to 6 carbon atoms, an alkenyl group, an alkynyl group, a cyclohexyl group, and a phenyl group. Further, specific examples of the alkyl group, the alkenyl group and the alkynyl group include a group having 1 to 6 carbon atoms in the group exemplified in A ¹ and A ² . R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The divalent organic group of X ¹ may, for example, be a divalent hydrocarbon group; the methylene group to a divalent hydrocarbon group may be -O-, -S-, -CO-, -COO-, -COS-, -NR ³ -, - CONR ³ - (wherein, R ³ is a hydrogen atom or a monovalent hydrocarbon group having a carbon number of 1 to 6) group and the like divalent heteroatom-containing group for substitution; hydrogen atom divalent hydrocarbon group has at least one halogen a group substituted with an atom or the like; a divalent group having a hetero ring or the like. Here, as a specific example of the divalent hydrocarbon group, the chain hydrocarbon group may, for example, be an alkylene group such as a methylene group, an exoethyl group, a propylene group, a butyl group, a pentanediyl group or a hexamethylene group. These groups may be used. It is linear or branched. Further, examples of the alicyclic hydrocarbon group include a cyclohexylene group and the like; and examples of the aromatic hydrocarbon group include a stretched phenyl group, a stretched biphenyl group, and an extended naphthyl group. X ¹ is preferably a single bond, or a substituted or unsubstituted divalent chain hydrocarbon group, more preferably a single bond, or a substituted or unsubstituted alkanediyl group.

"*" in the formula (1) is preferably bonded to an aromatic ring. Examples of the aromatic ring to which the "*" in the formula (1) is bonded include a benzene ring, a naphthalene ring, a pyridine ring, a pyrimidine ring, a pyrazine ring, an imidazole ring, a thiol ring, and the like. It is preferably a benzene ring, a naphthalene ring or a pyridine ring. In terms of the ease of synthesis of the compound, Y ¹ is preferably an oxygen atom.

As the polymer (P), polylysine, polyphthalate, polyimide, and polyamine can be synthesized according to a conventionally known method. Specific examples include a method of using at least one carboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester, tetracarboxylic acid diester dihalide, and dicarboxylic acid, and The raw material of the diamine is used to synthesize the polymer (P).

[Polyuric Acid] The polyamic acid as the polymer (P) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. Specific examples thereof include: [1] a method of synthesizing a tetracarboxylic dianhydride having a structure represented by the formula (1) in a raw material composition; [2] by including in a raw material composition a method of synthesizing a diamine having a structure represented by the formula (1); [3] comprising a tetracarboxylic dianhydride having a structure represented by the formula (1) and having a raw material composition A method of synthesizing a diamine having a structure represented by the formula (1), and the like. Among these methods, the method using [2] is preferable in terms of the small amount of monomer restriction.

(tetracarboxylic dianhydride) The tetracarboxylic dianhydride used for the synthesis of the polyamic acid is, for example, an aliphatic tetracarboxylic dianhydride, an alicyclic tetracarboxylic dianhydride, an aromatic tetracarboxylic dianhydride, or the like. . Specific examples of the tetracarboxylic dianhydride include aliphatic tetracarboxylic dianhydride: 1,2,3,4-butanetetracarboxylic dianhydride, and the like; and alicyclic tetracarboxylic dianhydride, for example, : 1,2,3,4-cyclobutane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro 8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[ 3.2.1] Octane-2,4-dione-6-spiro-3'-(tetrahydrofuran-2',5'-dione), 5-(2,5-dioxotetrahydro-3- Furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2:3,5:6- Anhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ] Monoalkane-3,5,8,10-tetraketone, cyclohexanetetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, etc.; aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride In addition, tetracarboxylic dianhydride or the like described in JP-A-2010-97188 may be used. Further, the tetracarboxylic dianhydride may be used alone or in combination of two or more.

The tetracarboxylic dianhydride used for the synthesis of the polyamic acid preferably contains an alicyclic tetracarboxylic dianhydride in terms of solubility in a solvent or transparency. More preferably, it comprises a compound selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo 3--3-furyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(four Hydrogen-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 2,4,6,8-tetracarboxybicyclo[3.3.0] Octane-2:4,6:8-dianhydride, 1,2,4,5-cyclohexanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride and 1, At least one of the group consisting of 2,3,4-cyclobutanetetracarboxylic dianhydride, particularly preferably comprising a component selected from the group consisting of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2, 4, 6 , 8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,4,5- At least one compound (hereinafter also referred to as "specific tetracarboxylic dianhydride") of a group consisting of cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride. The tetracarboxylic dianhydride used for the synthesis of the polyamic acid is preferably contained in an amount of 20 mol% or more of the specific tetracarboxylic dianhydride relative to the total amount of the tetracarboxylic dianhydride used in the synthesis. It is preferably contained in an amount of 40 mol% or more, and particularly preferably 60 mol% or more.

(Diamine) The diamine used in the synthesis of poly-proline is preferably a compound (hereinafter also referred to as "specific diamine") having a structure represented by the above formula (1) and two primary amine groups.

Specific examples of the specific diamine include a compound represented by the following formula (c). [Chemical 3] (In the formula (c), B ¹ is a divalent organic group having a partial structure represented by the formula (1), and B ² and B ³ are each independently a hydrogen atom or have the formula represented by the formula (1) a monovalent organic group of a partial structure, Z ¹ and Z ² are each independently a single bond or a divalent linking group, and R ⁵ and R ⁶ are each independently a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; n 1 and n 2 Each of them is independently an integer of 0 to 2, and m1 and m2 are each independently 0 or 1; wherein, in the case of m1=1, B ² has a partial structure represented by the formula (1), where m1=0 And when m2=0, at least one of B ² and B ³ has a partial structure represented by the formula (1), and in the case of m1=0 and m2=1, B ¹ , B ² and B ³ At least one of the structures having the formula (1)

In the above formula (c), examples of the specific example of B ¹ include a group represented by the following formula (b-1). [Chemical 4] (In the formula (b-1), R ⁴ is a nitrogen atom or a trivalent hydrocarbon group; A ¹ , A ² , Y ¹ , R ¹ and X ¹ have the same meanings as the above formula (1); respectively; key)

In the formula (b-1), the trivalent hydrocarbon group of R ⁴ is preferably an aromatic ring group. The monovalent organic group of B ² and B ³ may be any group having one or more partial structures represented by the above formula (1). It is preferably a monovalent group represented by the above formula (1). The divalent linking group of Z ¹ and Z ² is preferably -O-, -NH-, an alkanediyl group having 1 to 10 carbon atoms, or one or more methylene groups having an alkyldiyl group having 1 to 10 carbon atoms as -O. - a divalent group substituted. N1 and n2 are preferably 0 or 1, more preferably 0.

Preferable specific examples of the specific diamine include a compound represented by the following formula (d) and the like. [Chemical 5] (In the formula (d), R ⁷ is a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n3 is an integer of 0 to 2; and A ¹ , A ² , Y ¹ , R ¹ and X ¹ are respectively The formula (1) has the same meaning)

In the formula (d), the descriptions of the formula (1) can be respectively applied to the examples of A ¹ , A ² , Y ¹ , R ¹ and X ¹ and preferred specific examples. In the formula (d), the bonding position of the two primary amino groups in the diaminophenyl group relative to the group represented by the formula (1) may be 2, 4-position, 2, 5- The position, the 3, 5-position, etc. are preferably 3,5-position in terms of the effect of improving the reliability. N3 is preferably 0 or 1, more preferably 0.

Further, preferred specific examples of the specific diamine include compounds represented by the following formula (e). [Chemical 6] (In the formula (e), Z ³ is a single bond or a divalent linking group, and V ¹ is a hydrogen atom or a monovalent group represented by the formula (1), and R ⁸ and R ⁹ are each independently a halogen atom or carbon a monovalent hydrocarbon group of 1 to 6; n4 and n5 are each independently an integer of 0 to 2; and A ¹ , A ² , Y ¹ , R ¹ and X ¹ have the same meanings as the above formula (1), respectively)

In the formula (e), the descriptions of the formula (1) can be respectively applied to the examples of A ¹ , A ² , Y ¹ , R ¹ and X ¹ and preferred specific examples. Z ³ is preferably a divalent linking group, and a preferred example of the preferred examples of Z ¹ and Z ² in the formula (c) can be applied. N4 and n5 are preferably 0 or 1, more preferably 0.

Specific examples of the specific diamine include a compound represented by the following formula (MDA-1) to formula (MDA-21), and the like. [Chemistry 7]

[化8]

Further, the specific diamine may be used alone or in combination of two or more. Hereinafter, the compound represented by the formula (MDA-X) may also be referred to as "compound (MDA-X)".

The diamine used in the synthesis of polylysine may be only a specific diamine, or may be used in combination with a specific diamine in combination with a specific diamine. Examples of the other diamine include an aliphatic diamine, an alicyclic diamine, an aromatic diamine, and a diamine organic decane. Specific examples of the diamine include aliphatic m-xylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine. Examples of the alicyclic diamine include 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), and 1,3-bis(aminomethyl)cyclohexane. Alkane, etc.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl sulfide, 1,5-diaminonaphthalene, and 2 , 2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis(trifluoromethyl)biphenyl, 2,7-diamino Bismuth, 4,4'-diaminodiphenyl ether, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 2,2-bis[4-(4- Aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 4,4'-(p-phenylene diisopropylidene)diphenylamine, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy) Biphenyl, 2,6-diaminopyridine, N,N'-bis(4-aminophenyl)-benzidine, 1-(4-aminophenyl)-2,3-dihydro-1, 3,3-Trimethyl-1H-indole-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-indole-6- Amine, 3,5-diaminobenzoic acid, cholestyloxy-3,5-diaminobenzene, cholestyloxy-3,5-diaminobenzene, cholestyloxy-2, 4-diaminobenzene, cholesteneoxy-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoic acid, cholesteryl 3,5-diaminobenzoic acid Ester, 3,5-diaminobenzoic acid sheep甾alkyl ester, 3,6-bis(4-aminobenzimidyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'- Trifluoromethoxybenzylideneoxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4- Butylcyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 2,4-diamino-N,N-di Allyl aniline, 4-aminobenzylamine, and the following formula (D-1) [Chemical 9] (In the formula (D-1), X ^I and X ^II are each independently a single bond, -O-, -COO- or -OCO-, R ^I is an alkanediyl group having 1 to 3 carbon atoms, and R ^II is a single a bond or an alkanediyl group having 1 to 3 carbon atoms, a is 0 or 1, b is an integer of 0 to 2, c is an integer of 1 to 20, and n is 0 or 1; wherein a and b do not simultaneously become 0 ) the indicated compound, etc.;

Examples of the diamine-based organic siloxane include 1,3-bis(3-aminopropyl)-tetramethyldioxane and the like; in addition, Japanese Patent Laid-Open Publication No. 2010-97188 can be used. The diamines described therein.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _n -" in the formula (D-1) is preferably an alkyldiyl group having 1 to 3 carbon atoms, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein the bond with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _{2c +1"} include methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, and Sulfhydryl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, positive Pentadecyl, n-icosyl and the like. The two amine groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to the other groups.

Specific examples of the compound represented by the formula (D-1) include a compound represented by the following formula (D-1-1) to formula (D-1-5), and the like. [化10]

The other diamine may further include at least one structure selected from the group consisting of a nitrogen-containing hetero ring, a secondary amine group, and a tertiary amine group in addition to the two primary amine groups (hereinafter also referred to as "nitrogen-containing" Structure ") diamine and the like. By using such a diamine having a nitrogen-containing structure as a raw material, a polymer having a corresponding nitrogen-containing structure and a structure represented by the above formula (1) can be obtained. According to such a polymer, the effect of improving the reliability of the liquid crystal display element can be improved, which is preferable. Specific examples of the diamine having a nitrogen-containing structure include, for example, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, and 3,6-diamino group. Carbazole, N-methyl-3,6-diaminocarbazole, 1,4-bis-(4-aminophenyl)-pyridazine, the following formula (D-2-1) to formula (D) -2-6) Compounds and the like respectively indicated. [11]

The diamine used in the synthesis of the polyamic acid is preferably a total of 1 mol% or more, more preferably 3 mol% or more, more preferably 3 mol% or more, based on the total amount of the diamine. It is preferably 5 mol% or more, and particularly preferably 10 mol% or more. The upper limit of the ratio of use of the specific diamine is not particularly limited, and it is preferably 90% by mole or less, and more preferably 80%, in terms of improving various properties such as liquid crystal alignment properties and electrical properties by using other diamines. The molar percentage is 5% or less, and particularly preferably 70% by mole or less. The proportion of the diamine having a nitrogen-containing structure is preferably 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 2 mol%, based on the total amount of the diamine used in the synthesis. More than 8% of the ear. The proportion of the diamine having a nitrogen-containing structure is preferably 60% by mole or less, more preferably 50% by mole or less, and particularly preferably 40% by mole or less. Further, other diamines may be used alone or in combination of two or more.

(Synthesis of Specific Diamine) Specific diamines can be synthesized by appropriately combining known methods. As an example, for example, a method of synthesizing a dinitro intermediate having a nitro group in place of a primary amine group in a specific diamine, and then using a suitable reduction system, the nitrate of the obtained dinitro intermediate is exemplified. The base is aminated. Further, the method of synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. For example, a method of reacting dinitroaniline with an alkyl chloroformic acid; a method of reacting dinitrobenzhydryl chloride with a hydroxyl group-containing compound having the structure represented by the above formula (1); A method of reacting an isocyanate group-containing compound such as dinitrophenyl isocyanate with a compound having a group "-CHA ¹ A ² " and a hydroxyl group.

(Synthesis of Polylysine) Polyproline can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above with a molecular weight modifier as needed. The ratio of the tetracarboxylic dianhydride to the diamine to be used in the synthesis reaction of the poly-proline is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride is 0.2 to 2 equivalents. More preferably, it is a ratio of 0.3 equivalent to 1.2 equivalent. Examples of the molecular weight modifier include acid monoanhydrides such as maleic anhydride, phthalic anhydride, and itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, and phenyl isocyanate. A monoisocyanate compound such as a naphthyl cyanate. The use ratio of the molecular weight modifier is preferably 20 parts by weight or less, and more preferably 10 parts by weight or less, based on 100 parts by weight of the total of the tetracarboxylic dianhydride and the diamine to be used.

The synthesis reaction of polylysine is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20 ° C to 150 ° C, and more preferably 0 ° C to 100 ° C. Further, the reaction time is preferably from 0.1 to 24 hours, more preferably from 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include an aprotic polar solvent, a phenol-based solvent, an alcohol, a ketone, an ester, an ether, a halogenated hydrocarbon, and a hydrocarbon. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (the first group of organic solvents), or selected from the first group of organic solvents are preferably used. One or more kinds of a mixture of one or more selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (the second group of organic solvents). In the latter case, the use ratio of the organic solvent of the second group is preferably 50% by weight or less, and more preferably 40% by weight based on the total amount of the organic solvent of the first group and the organic solvent of the second group. Hereinafter, it is especially preferably 30% by weight or less.

A particularly preferred organic solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, dimethyl hydrazine, gamma-butyl One or more of a group consisting of lactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol, and halogenated phenol is used as a solvent, or these agents are used within the range of the ratio. A mixture of more than one solvent and other organic solvents. The amount (a) of the organic solvent to be used is preferably in an amount of from 0.1% by weight to 50% by weight based on the total amount (a+b) of the reaction solution, and the total amount (b) of the tetracarboxylic dianhydride and the diamine.

A reaction solution obtained by dissolving polylysine was obtained in the manner as described above. The reaction solution may be supplied directly to the next step, or the polylysine may be separated and supplied to the next step, or the isolated polylysine may be purified and then supplied to the next step. These purification operations can be carried out in accordance with a known method.

[Polyurethane] Polyphthalate can be obtained, for example, by the following method: [I] a method of reacting a polylysine obtained by the synthesis reaction with an esterifying agent; [II] a method of reacting a tetracarboxylic acid diester with a diamine; [III] a method of reacting a tetracarboxylic acid diester dihalide with a diamine, and the like.

Here, examples of the esterifying agent used in the method [I] include a hydroxyl group-containing compound, an acetal compound, a halide, and an epoxy group-containing compound. Specific examples of the compound include a hydroxyl group-containing compound such as an alcohol such as methanol, ethanol or propanol, or a phenol such as phenol or cresol. Examples of the acetal compound include N,N-dimethyl group. Hydrazine diethyl acetal, N,N-diethylformamide diethyl acetal, etc.; halides, for example, methyl bromide, bromoethane, octadecane, methyl chloride, Examples of the epoxy group-containing compound include chloroacetyl octadecane and 1,1,1-trifluoro-2-iodoethane.

The tetracarboxylic acid diester used in the method [II] can be obtained by subjecting a tetracarboxylic dianhydride to ring opening using the alcohol. Further, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting a tetracarboxylic acid diester obtained in the above manner with a suitable chlorinating agent such as sulfinium chloride. In the case of obtaining a polyphthalate having a partial structure represented by the formula (1), in the method [II] and the method [III], by using the structure represented by the formula (1) Diamine As the at least a part of the diamine used in the reaction, a polyphthalate having a partial structure represented by the above formula (1) can be obtained. Further, the polyperurate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist. The reaction solution obtained by dissolving the polyamidate may be directly supplied to the next step, or the polyphthalate may be separated and then supplied to the next step, or the separated polyglycolate may be purified. Then provide it to the next step. These purification operations can be carried out in accordance with a known method.

[Polyimide] The polyimine as the polymer (P) can be obtained by subjecting polylysine synthesized in the above manner to dehydration ring closure and ruthenium imidization.

The polyimine may be a fully ruthenium imide formed by dehydration ring closure of the proline structure of the polyamic acid as a precursor thereof, or may be a dehydration ring only of a part of the structure of the proline. And a part of the quinone imide compound which has a structure of a proline and a quinone ring structure. The ruthenium iodide ratio of the polyimine is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 60% to 99%. The ruthenium imidization ratio is a ratio indicating the ratio of the number of guanidine structure to the total number of quinone ring structures of the polyimine and the total number of quinone ring structures. Here, a part of the quinone ring may also be an isoindole ring.

The dehydration ring closure of polylysine is preferably carried out by a method of heating polylysine; or dissolving polylysine in an organic solvent, adding a dehydrating agent and a dehydration ring-closing catalyst to the solution, A method of heating is required. Among them, a method using the latter is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of poly-proline, the dehydrating agent may be, for example, an acid anhydride such as acetic anhydride, propionic anhydride or trifluoroacetic anhydride. The amount of the dehydrating agent to be used is preferably from 0.01 mol to 20 mol based on 1 mol of the proline structure of the polyamic acid. Examples of the dehydration ring-closure catalyst include tertiary amines such as pyridine, trimethylpyridine, dimethylpyridine, and triethylamine. The amount of the dehydration ring-closure catalyst used is preferably set to 0.01 mol to 10 mol with respect to 1 mol of the dehydrating agent to be used. The organic solvent used for the dehydration ring-closure reaction is exemplified as an organic solvent exemplified as an organic solvent used for the synthesis of polyglycine. The reaction temperature of the dehydration ring closure reaction is preferably from 0 ° C to 180 ° C, more preferably from 10 ° C to 150 ° C. The reaction time is preferably from 1.0 to 120 hours, more preferably from 2.0 to 30 hours.

A reaction solution containing polyienimine was obtained in the manner described. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the dehydration agent and the dehydration ring closure catalyst can be removed from the reaction solution, and then supplied to the preparation of the liquid crystal alignment agent, or the polyphthalimide can be separated and then supplied to the liquid crystal alignment. The preparation of the agent, or the separation of the separated polyimine, may be further provided to the preparation of the liquid crystal alignment agent. These purification operations can be carried out in accordance with a known method. Further, the method for synthesizing the polyimine is not limited to the method, and can be carried out, for example, by hydrazylation of a polyphthalate.

[Polyinamide] The polyamine which is the polymer (P) can be obtained, for example, by reacting a dicarboxylic acid with a diamine. Examples of the dicarboxylic acid used in the reaction include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phthalic acid, isophthalic acid, and terephthalic acid. 5-decyloxyisophthalic acid and the like. Further, the dicarboxylic acid may be used alone or in combination of two or more. The diamine used in the reaction may be a specific diamine or a different diamine may be used together with a specific diamine.

The reaction of the dicarboxylic acid with the diamine is preferably carried out in a suitable organic solvent. At this time, the dicarboxylic acid can be subjected to hydrazine chlorination and then reacted with the diamine. The reaction temperature is preferably -100 ° C to 200 ° C, and more preferably -20 ° C to 150 ° C. Further, in the case where the dicarboxylic acid is directly supplied to the reaction with the diamine, it is preferred to set the reaction temperature to a temperature of room temperature (25 ° C) or higher, and to carry out the hydrazine chlorination of the dicarboxylic acid and then the diamine. In the case of carrying out the reaction, it is preferred to set the reaction temperature to a temperature lower than room temperature. The reaction time is preferably from 0.1 to 40 hours, more preferably from 0.5 to 20 hours.

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

In addition, the present invention is not limited to the above, but it is estimated that the liquid crystal alignment agent containing the polymer (P) having the structure represented by the above formula (1) is heated (post-baking) by the formation of a coating film. The group "-CHA ¹ A ² " in the structure represented by the formula (1) is detached to regenerate the isocyanate group, and is sufficiently crosslinked between the regenerated isocyanate group and a carboxyl group, a hydroxyl group, an amine group or the like in the system. reaction. It is presumed that it is difficult to cause a decrease in various characteristics accompanying use by the intermolecular or intramolecular crosslinking reaction, and as a result, a liquid crystal display element exhibiting excellent reliability is obtained.

<Other Components> The liquid crystal alignment agent may contain other components than the polymer (P) as needed. Examples of the other component include a polymer other than the polymer (P), a compound having at least one epoxy group in the molecule (hereinafter referred to as "epoxy group-containing compound"), a functional decane compound, and the like.

[Other Polymers] The other polymers can be used to improve solution properties or electrical properties. Examples of the other polymer include polylysine which does not have the partial structure represented by the formula (1); polyimine which does not have the partial structure represented by the formula (1); a partially-structured polyphthalate represented by the formula (1); a polyamine, a polyorganosiloxane, a polyester, a cellulose derivative, a poly having no partial structure represented by the formula (1) An acetal, a polystyrene derivative, a poly(styrene-phenylmaleimide) derivative, a poly(meth)acrylate, or the like. In the case where other polymers are formulated in the liquid crystal alignment agent, the compounding ratio of the other polymer is preferably 50% by weight or less, more preferably 0.1% by weight to 40% by weight based on the total amount of the polymer in the composition. % is particularly preferably from 0.1% by weight to 30% by weight.

[Epoxy group-containing compound] The epoxy group-containing compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. Here, examples of the epoxy group-containing compound include the following compounds: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromopentane Glycol diglycidyl ether, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane , N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N-diglycidyl-benzylamine, N,N-diglycidyl - Aminomethylcyclohexane, N,N-diglycidyl-cyclohexylamine, and the like. In addition to the above, examples of the epoxy group-containing compound may be an epoxy group-containing polyorganosiloxane having the disclosure of WO 2009/096598. In the case where the epoxy group-containing compound is formulated in a liquid crystal alignment agent, the compounding ratio of the epoxy group-containing compound is preferably 40% based on 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. It is more preferably from 0.1 part by weight to 30 parts by weight per part by weight.

[Functional decane compound] The functional decane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of such a functional decane compound include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyl group. Triethoxy decane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Baseline, 3-ureidopropyltrimethoxydecane, 3-ureidopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-triethoxy矽alkylpropyltriethylamine, 10-trimethoxydecyl-1,4,7-triazadecane, 9-trimethoxydecyl-3,6-diazepineacetic acid Ester, methyl 9-trimethoxydecyl-3,6-diazadecanoate, N-benzyl-3-aminopropyltrimethoxydecane, N-phenyl-3-aminopropyltrimethyl Oxaloxane, glycidoxymethyltrimethoxydecane, 2-glycidoxyethyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, and the like. In the case where the functional decane compound is blended in the liquid crystal alignment agent, the compounding ratio of the functional decane compound is preferably 2 parts by weight or less, more preferably 0.02 part by weight to 100 parts by weight based on the total of the polymer. 0.2 parts by weight.

Further, as other components, additives other than the above may be appropriately blended within a range that does not impair the object and effect of the present invention. Specific examples of the additives other than the above include a compound having at least one oxetanyl group in the molecule, an antioxidant, a surfactant, an antifoaming agent, a sensitizer, a dispersing agent, and an adhesion aid. , antistatic agents, leveling agents, antibacterial agents, etc.

[Solvent] The liquid crystal alignment agent of the present invention is prepared by preparing a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in a suitable organic solvent.

Examples of the organic solvent to be used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N,N-dimethylformamide, and N,N-dimethyl B. Indamine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxy propionate, Ethylene glycol methyl ether, ethylene glycol ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethyl carbonate, propyl carbonate, and the like. These organic solvents may be used singly or in combination of two or more.

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

The range of the particularly preferable solid content concentration differs depending on the method used when the liquid crystal alignment agent is applied onto the substrate. For example, in the case of the rotator method, the solid content concentration (the ratio of the total weight of all the components other than the solvent in the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) is particularly preferably 1.5% by weight to 4.5% by weight. The scope. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3 to 9 wt%, thereby setting the solution viscosity to a range of 12 mPa·s to 50 mPa·s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to a range of 1% by weight to 5% by weight, thereby setting the solution viscosity to a range of 3 mPa·s to 15 mPa·s. The temperature at which the liquid crystal alignment agent is prepared is preferably from 10 ° C to 50 ° C, and more preferably from 20 ° C to 30 ° C.

<Liquid Crystal Alignment Film and Liquid Crystal Display Element> The liquid crystal alignment film of the present invention can be formed using the liquid crystal alignment agent prepared in the above manner. Further, the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The driving mode of the liquid crystal display element is not particularly limited, and can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, and polymer sustained alignment (PSA) type.

The liquid crystal display element can be manufactured, for example, by a method including the following steps (1) to (3). Step (1) uses different substrates depending on the desired driving mode. Step (2) and step (3) are shared in each drive mode.

[Step (1): Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is applied onto a substrate, and then the coated surface is heated to form a coating film on the substrate. (1-1) In the case of manufacturing a TN type, STN type, VA type, MVA type or PSA type liquid crystal display element, two substrates each having a patterned transparent conductive film are provided as a pair, in each substrate The surface of the transparent conductive film is preferably coated with the prepared liquid crystal alignment agent by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. Here, as the substrate, for example, glass such as float glass or soda glass may be used; and polyethylene terephthalate, polybutylene terephthalate, polyether oxime, polycarbonate, poly(alicyclic olefin) may be used. ) A transparent substrate such as plastic. The transparent conductive film provided on one side of the substrate may be a Neisser (NESA) film containing tin oxide (SnO ₂ ) (registered trademark of PPG, USA), and containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ). Indium Tin Oxide (ITO) film or the like. In order to obtain a patterned transparent conductive film, for example, a method of forming a pattern by photolithography after forming a transparent conductive film without a pattern, and a method of using a mask having a desired pattern when forming a transparent conductive film can be utilized. Wait. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the surface of the substrate and the transparent conductive film and the coating film, the surface on which the coating film is formed on the surface of the substrate may be coated with a functional decane compound or a functional titanium compound. Pretreatment.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing sag of the applied alignment agent. The prebaking temperature is preferably from 30 ° C to 200 ° C, more preferably from 40 ° C to 150 ° C, and particularly preferably from 40 ° C to 100 ° C. The prebaking time is preferably from 0.25 minutes to 10 minutes, more preferably from 0.5 minutes to 5 minutes. Then, for the purpose of completely removing the solvent, a calcination (post-baking) step is carried out for the purpose of thermally imidating the proline structure present in the polymer as needed. The calcination temperature (post-baking temperature) at this time is preferably 80 to 300 ° C, and more preferably 120 to 250 ° C. The post-baking time is preferably from 5 minutes to 200 minutes, more preferably from 10 minutes to 100 minutes. The film thickness of the film formed in the above manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(1-2) In the case of manufacturing an IPS type or FFS type liquid crystal display element, an electrode forming surface of a substrate including an electrode patterned as a comb-shaped transparent conductive film or a metal film, and an electrode not provided A liquid crystal alignment agent is applied to one surface of the counter substrate, and then each coated surface is heated to form a coating film. The material of the substrate and the transparent conductive film used at this time, the coating method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film The description (1-1) is the same. As the metal film, for example, a film containing a metal such as chromium can be used.

In any of the above (1-1) and (1-2), a coating film to be an alignment film is formed by applying a liquid crystal alignment agent onto a substrate and then removing the organic solvent. In this case, the polymer contained in the liquid crystal alignment agent is polyamic acid, or a polyphthalate, or a ruthenium-imided polymer having a quinone ring structure and a proline structure. Alternatively, the dehydration ring-closure reaction may be carried out by further heating after the formation of the coating film to form a coating film which is further imidized.

[Step (2): Alignment treatment] When a TN type, STN type, IPS type or FFS type liquid crystal display element is manufactured, a treatment for imparting liquid crystal alignment ability to the coating film formed in the step (1) is carried out (alignment) deal with). Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. The aligning treatment includes a rubbing treatment, a photo-alignment treatment, and the like, which is applied to the coating film by wiping the coating film in a predetermined direction by a roll wound with a cloth containing fibers such as nylon, rayon, or cotton. The rubbing treatment of the liquid crystal alignment ability; the photoalignment treatment irradiates the coating film formed on the substrate with light to impart a liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a VA liquid crystal display element, the coating film formed in the above step (1) can be directly used as the liquid crystal alignment film, but the coating film may be subjected to a rubbing treatment. In addition, the liquid crystal alignment film after the rubbing treatment may be further subjected to the following treatment so that the liquid crystal alignment film has different liquid crystal alignment ability in each region: the liquid crystal alignment film is irradiated by irradiating a part of the liquid crystal alignment film with ultraviolet rays. A process of changing the pretilt angle of a part of the region; or a process of removing the resist film after performing a rubbing treatment in a direction different from the previous rubbing treatment after forming a resist film on a part of the surface of the liquid crystal alignment film. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. In the case of producing a polymer sustained alignment (PSA) type liquid crystal display device, the following step (3) can be carried out directly using the coating film formed in the above step (1), but for controlling liquid crystal molecules The collapse is performed by a simple method for the purpose of the alignment division, and the alignment treatment such as weak rubbing treatment can be performed. A liquid crystal alignment film suitable for a VA type liquid crystal display element can also be suitably used for a PSA type liquid crystal display element.

[Step (3): Construction of Liquid Crystal Cell] (3-1) Two substrates in which the liquid crystal alignment film was formed as described above were prepared, and liquid crystal was placed between the two substrates arranged in the opposite direction to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example. First, the first method is a previously known method. In this method, first, the two substrates are opposed to each other via a gap (cell gap) so that the respective liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together using a sealant, and the surface of the substrate and the sealant are bonded to each other. After the filled liquid crystal is injected into the divided cell gap, the injection hole is sealed, thereby manufacturing a liquid crystal cell. In addition, the second method is a method called a One Drop Fill (ODF) method. In the method, a predetermined portion on one of the two substrates on which the liquid crystal alignment film is formed, for example, an ultraviolet curable sealant is applied, and liquid crystal is dropped on a predetermined portion of the liquid crystal alignment film surface. Thereafter, another substrate is bonded in such a manner that the liquid crystal alignment film faces each other. Next, the liquid crystal is spread over the entire surface of the substrate, and then the entire surface of the substrate is irradiated with ultraviolet light to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using any of the methods, it is preferable to heat the liquid crystal cell produced in the above manner to a temperature at which the liquid crystal used is obtained to obtain an isotropic phase, and then gradually cool to room temperature, thereby eliminating the liquid crystal. Flow alignment when filling.

As the sealant, for example, an epoxy resin containing a curing agent and an alumina ball as a spacer can be used. Further, the liquid crystal may be a nematic liquid crystal or a discotic liquid crystal. Among them, a nematic liquid crystal is preferable, and for example, a Schiff base liquid crystal, an azoxy liquid crystal, or a biphenyl liquid crystal can be used. Phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclooctane liquid crystal, cubane liquid crystal, etc. . In addition, it is also possible to use the following substances in these liquid crystals: for example, cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate, etc. (cholesteric liquid crystal) a chiral agent sold under the trade names "C-15", "CB-15" (manufactured by Merck); p-methoxybenzylidene-p-amino-2-methylbutyrate Ferroelectric liquid crystals such as cinnamate.

(3-2) In the case of producing a PSA type liquid crystal display device, a liquid crystal cell is constructed in the same manner as in the above (3-1) except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with light in a state where a voltage is applied between the conductive films of the pair of substrates. The voltage applied here can be set to, for example, 5 V to 50 V DC or AC. Further, as the light to be irradiated, ultraviolet rays and visible rays including light having a wavelength of, for example, 150 nm to 800 nm may be used, and ultraviolet rays containing light having a wavelength of 300 nm to 400 nm are preferable. As the light source for illuminating light, for example, a low pressure mercury lamp, a high pressure mercury lamp, a xenon lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser or the like can be used. Further, the ultraviolet light in the preferred wavelength region can be obtained by a method in which a light source is used in combination with, for example, a filter, a diffraction grating, or the like. The irradiation amount of light is preferably from 1,000 J/m ² to 200,000 J/m ² , and more preferably from 1,000 J/m ² to 100,000 J/m ² .

Then, the liquid crystal display element can be obtained by attaching a polarizing plate to the outer surface of the liquid crystal cell. The polarizing plate to be bonded to the outer surface of the liquid crystal cell may be a polarizing plate in which a polarizing film called "H film" is sandwiched by a cellulose acetate protective film or a polarizing plate including the H film itself. The H film is a film obtained by absorbing iodine while extending the polyvinyl alcohol. Further, in the case where the coating film is subjected to the rubbing treatment, the two substrates are arranged at a predetermined angle with respect to each other in the rubbing direction of each of the coating films, for example, orthogonally or anti-parallel.

The liquid crystal display element of the present invention can be effectively applied to various devices, for example, can be used for: watches, portable game machines, word processors, notebook personal computers, car navigation systems, camcorders, personal digital assistants (Personal Digital Assistant, Display devices such as PDAs, digital cameras, mobile phones, smart phones, various monitors, and LCD TVs.

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

In the following examples and comparative examples, the oxime imidization ratio of the polyimine in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent were measured by the following methods. [rhodium imidization ratio of polyimine] The solution of polyimine is put into pure water, and the obtained precipitate is sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl hydrazine to tetramethyl Silane as a standard material, was measured ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear Magnetic Resonance,} 1 H-NMR) at room temperature. From the obtained ¹ H-NMR spectrum, the oxime imidization ratio [%] was determined using the following formula (1). Ruthenium amination rate [%]=(1-A ¹ /A ² ×α)×100 (1) (In the formula (1), A ¹ is an NH group derived from a chemical shift of 10 ppm. The peak area of protons, A ² is the peak area derived from other protons, and α is the ratio of the number of protons of other protons relative to the NH group in the precursor of the polymer (polyproline). Solution Viscosity] The solution viscosity [mPa·s] of the polymer solution was prepared by using a predetermined solvent to prepare a polymer concentration of 10% by weight, and was measured at 25 ° C using an E-type rotational viscometer. [Weight Average Molecular Weight of Polymer] The weight average molecular weight is a polystyrene equivalent value measured by gel permeation chromatography under the following conditions. Pipe column: manufactured by Tosoh (stock), TSKgelGRCXLII Solvent: tetrahydrofuran temperature: 40 ° C Pressure: 68 kgf / cm ² [epoxy equivalent] Determined by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105 Epoxy equivalent.

<Synthesis of Compound> [Synthesis Example 1A: Synthesis of Compound (MDA-1)] The compound (MDA-1) was synthesized according to the following Scheme 1. [化12]

16.5 g (0.090 mol) of 3,5-dinitroaniline, 14.2 was added under a nitrogen flow in a four-necked flask equipped with a nitrogen gas introduction tube, a dropping funnel, a reflux cooling tube, a thermometer and a stirring blade. G (0.180 mol) of pyridine and THF were dissolved to give a total amount of 80 ml. While cooling the flask in ice water, a solution obtained by dissolving 12.7 g (0.135 mol) of methyl chloroformic acid in 90 ml of dichloromethane was added dropwise and stirred. After the dropwise addition, the mixture was stirred at room temperature for 24 hours, and then 600 ml of ethyl acetate was added and stirred for several minutes. The whole solution was transferred to a separatory funnel, and 1 equivalent of a hydrochloric acid solution was added, and after mixing, the aqueous layer was separated. Further, after the operation of mixing with 500 ml of pure water and the operation of taking out the aqueous layer were carried out three times, the lower organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain an intermediate (1) (yield: 95%).

Then, 4.80 g (0.020 mol) of the intermediate (1) and 25.4 g (0.400 mol) were added to a four-necked flask having a nitrogen gas introduction tube, a dropping funnel, a thermometer, and a stirring blade of 0.5 liter. Zinc, 4.28 g (0.080 mol) of ammonium chloride, 180 ml of THF, and 20 ml of EtOH were dissolved. The flask was cooled while being cooled in ice water, and 10 ml of pure water was added dropwise thereto and stirred. After the dropwise addition, the mixture was stirred at room temperature for 48 hours, and then filtered over Celite. After adding 100 ml of ethyl acetate to the filtrate and transferring the total amount to the separatory funnel, the operation of mixing with 300 ml of pure water and the operation of taking out the aqueous layer were carried out three times, and then the lower organic layer was taken out. It was dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain a compound (MDA-1) (yield: 87%).

[Synthesis Example 2A, Synthesis Example 3A: Synthesis of Compound (MDA-2) and Compound (MDA-3)] Except that ethylchloroformic acid and hexylchloroformic acid were used as starting materials instead of methylchloroformic acid, respectively. The compound (MDA-2) and the compound (MDA-3) were obtained in the same manner as in the synthesis of the compound (MDA-1). [Chemistry 13] [Chemistry 14]

[Synthesis Example 4A: Synthesis of Compound (MDA-4)] Instead of using methyl chloroformic acid, butyl chloroformic acid was used instead of 3,5-dinitroaniline, and 2,4-dinitroaniline was used as The compound (MDA-4) was obtained by the same method as the synthesis of the compound (MDA-1) except for the starting material. [化15]

[Synthesis Example 5A: Synthesis of Compound (MDA-5)] The compound (MDA-5) was synthesized according to the following Scheme 5. [Chemistry 16]

1.53 g (0.025 mol) of aminoethanol and 7.25 g (0.125 mol) were added to a four-necked flask equipped with a nitrogen gas introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring blade in a volume of 0.5 liter. Potassium fluoride, 17.3 g (0.125 mol) of potassium carbonate, THF were dissolved to give a total amount of 80 ml. While the flask was cooled in ice water, 3.20 g (0.026 mol) of propylchloroformic acid was added dropwise and stirred. After the dropwise addition, the mixture was stirred at room temperature for 24 hours, and then filtered through Celite. After 300 ml of ethyl acetate was added to the filtrate, the solution was transferred to a separatory funnel, and 500 ml of pure water was added thereto, and after mixing, the aqueous layer was separated. After the total of the above three times, the lower organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain an intermediate (2) (yield: 85%). Then, using the intermediate (2) and 3,5-dinitrobenzimid chloride, the compound (MDA-5) was obtained by the same method as the synthesis of the compound (MDA-1).

[Synthesis Example 6A: Synthesis of Compound (MDA-6)] A compound was obtained by the same method as the synthesis of the compound (MDA-5) except that aminobutanol was used as a starting material instead of the aminoethanol. MDA-6). [化17]

[Synthesis Example 7A: Synthesis of Compound (MDA-7)] The compound (MDA-7) was synthesized according to the following Scheme 7. [化18]

6.00 g (0.100 mol) of diaminoethane and 3.16 g (0.040) were placed under a nitrogen flow in a four-necked flask equipped with a nitrogen gas introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring blade. The pyridine and THF were dissolved to give a total amount of 80 ml. While the flask was cooled in ice water, 2.16 g (0.020 mol) of ethylchloroformic acid was added dropwise and stirred. After the dropwise addition, the mixture was stirred at room temperature for 24 hours, and then filtered through Celite. After 300 ml of ethyl acetate was added to the filtrate, the solution was completely transferred to a separatory funnel, 500 ml of pure water was added, and after mixing, the aqueous layer was separated. After the total of the above three times, the lower organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain an intermediate (3) (yield 81%). Then, using the intermediate (3) and 3,5-dinitrobenzimid chloride, a compound (MDA-7) was obtained by the same method as the synthesis of the compound (MDA-1).

[Synthesis Example 8A: Synthesis of Compound (MDA-11)] The compound (MDA-11) was synthesized according to the following Scheme 8. [Chemistry 19]

In a four-necked flask equipped with a nitrogen gas introduction tube and a stirring blade with a capacity of 0.5 liter, 10.7 g (0.050 mol) of 2-phenoxybenzoic acid and 100 ml of mixed acid were added under a nitrogen stream, and placed in an oil bath at 60 ° C. Stir for 6 hours. Then, sodium hydroxide was added for neutralization. The solution was transferred to a separatory funnel, 300 ml of ethyl acetate and 500 ml of a saturated aqueous solution of ammonium chloride were added, and after mixing, the aqueous layer was separated. After the liquid separation operation was carried out three times in total, the organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain 2-(4-nitro)phenoxy-5-nitrobenzoic acid (yield: 80%). Then, in a four-necked flask having a nitrogen gas introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring blade of 0.5 liter, 6.08 g (0.020 mol) of 2-(4-nitro) was added under a nitrogen stream. Phenoxy-5-nitrobenzoic acid, 6.61 g (0.024 mol) of diphenylphosphoryl azide (DPPA), 2.87 g (0.028 mol) of triethylamine, 100 ml of dehydrated toluene, After stirring at room temperature for 3 hours, it was heated to reflux at 120 ° C for 2 hours. Then, the solution was completely transferred to a separatory funnel, 300 ml of ethyl acetate and 500 ml of a saturated aqueous ammonium chloride solution were added, and after mixing, the aqueous layer was separated. After the liquid separation operation was carried out three times in total, the organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain 2-(4-nitro)phenoxy-5-nitro-cyanatobenzene (yield: 85%). Then, 6.02 g (0.020 mol) of 2-(4-nitro)phenoxy-5- was added under a nitrogen flow in a four-necked flask having a nitrogen gas introduction tube, a stirring blade, and a dropping funnel of 0.5 liter. Nitro-cyanate benzene, 50 ml of dehydrated dichloromethane, was stirred. Then, 10 ml of dehydrated methanol was added dropwise using a dropping funnel. The resulting solution was distilled off using an evaporator to obtain 2-(4-nitro)phenoxy-5-nitro-N-methoxycarbonylaniline (yield: 95%). Then, using the same method as the synthesis method of obtaining the compound (MDA-1) from the intermediate (1) in Synthesis Example 1A, the compound (MDA-11) was obtained (yield: 89%).

[Synthesis Example 9A: Synthesis of Compound (MDA-14)] The compound (MDA-14) was synthesized according to the following Scheme 9. [Chemistry 20]

In a four-necked flask having a nitrogen gas introduction tube and a stirring blade having a capacity of 0.5 liter, 2.94 g (0.020 mol) of the intermediate (2) obtained in Synthesis Example 5A and 6.08 g (0.020 mol) were added under a nitrogen stream. 2-(4-Nitro)phenoxy-5-nitrobenzoic acid obtained in Example 8A, 5.75 g (0.030 mol) of 1-ethyl-3-(3-dimethylaminopropyl) carbon 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (EDC), 0.49 g (0.004 mol) of 4-dimethylaminopyridine (DMAP), in the chamber Stir for 12 hours at room temperature. Then, the whole solution was transferred to a separatory funnel, and 300 ml of ethyl acetate and 500 ml of a saturated aqueous ammonium chloride solution were added and mixed, and the aqueous layer was separated. After the liquid separation operation was carried out three times in total, the organic layer was taken out and dried over anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution by an evaporator to obtain an intermediate (4) (yield: 88%). Then, using the same method as the synthesis method of obtaining the compound (MDA-1) from the intermediate (1) in Synthesis Example 1A, the compound (MDA-14) was obtained (yield: 80%).

<Synthesis of Polymer> [Synthesis Example 1: Synthesis of Polyimine (PI-1)] 2,3,5-tricarboxycyclopentyl acetic acid dianhydride having 100 mol parts as tetracarboxylic dianhydride ( TCA), 60 moles of p-phenylenediamine (PDA) as a diamine, 20 moles of 3,5-diamino benzoic acid (3,5-diamino benzoic acid) Cholestanyl, HCDA), and 20 moles of compound (MDA-1), dissolved in N-methyl-2-pyrrolidone (NMP), reacted at 60 ° C for 6 hours. A solution containing 20% by weight of polylysine was obtained. The obtained polyaminic acid solution was fractionated, and NMP was added to prepare a solution having a polyglycine concentration of 10% by weight, and the obtained solution had a viscosity of 56 mPa·s. Then, NMP was added to the obtained polyaminic acid solution to prepare a solution having a polyglycine concentration of 7 wt%, and each was added in an amount of 1.0 mol per mol of the total amount of the tetracarboxylic dianhydride to be used. The pyridine and acetic anhydride were subjected to a dehydration ring-closure reaction at 110 ° C for 4 hours. After the dehydration ring closure reaction, the solvent in the system is replaced with a new NMP (by this operation, the pyridine and acetic anhydride used in the dehydration ring closure reaction are removed to the outside of the system; the same applies hereinafter), thereby obtaining 26% by weight. A solution of polyamidolimine (PI-1) having a ruthenium imidization rate of about 60%.

[Synthesis Example 2 to Synthesis Example 15 and Synthesis Example 22] The types and amounts of the tetracarboxylic dianhydride and the diamine to be used, and the amounts of pyridine and acetic anhydride used for the ruthenium imidization were changed as follows. In the same manner as in the above Synthesis Example 1, polyimine (PI-2) to polyimine (PI-16) were synthesized in the same manner as in the above Table 1. The measurement results of the ruthenium iodization ratio of the obtained polymer are shown together in Table 1 below. Further, in Synthesis Example 8, 1.5 mol parts of aniline was blended as a monoamine together with tetracarboxylic dianhydride and diamine.

[Table 1]

In Table 1, the numerical value in the parentheses of the tetracarboxylic dianhydride indicates the use ratio [mol%] with respect to 100 moles of the total of the tetracarboxylic dianhydride used in the synthesis of the polymer. The numerical values in the parentheses of the diamine and the monoamine indicate the use ratio [mol%] with respect to 100 moles of the total of the tetracarboxylic dianhydride used in the synthesis of the polymer. The abbreviations in Table 1 are respectively the following meanings. Further, "-" in Table 1 means a compound which does not use this column. <tetracarboxylic dianhydride> t-1: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride (TCA) t-2: 2,4,6,8-tetracarboxybicyclo[3.3.0]octane -2:4,6:8-dianhydride (BODA) t-3: 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) t-4:1,3,3a,4,5 , 9b-hexahydro-8-methyl-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-c]furan-1,3-dione (MTDA T-5: pyromellitic dianhydride (PMDA) t-6:1R, 2S, 4S, 5R-cyclohexane tetracarboxylic dianhydride (PMDA-HS) <diamine> d-1: the following formula (d-1) Compound d-2 represented by the formula d-3: p-phenylenediamine (PDA) d-4: 4,4'-diaminodiphenyl Methane d-5:4,4'-diaminodiphenyl ether d-6:2,2'-dimethyl-4,4'-diaminobiphenyl d-7:2,2'- Bis(trifluoromethyl)-4,4'-diaminobiphenyl d-8:3,5-diaminobenzoic acid (35DAB) d-9: 1,3-bis(3-aminopropyl) )-tetramethyldioxane d-10: cholesteryl 3,5-diaminobenzoate (HCDA) d-11: cholestyloxy-2,4-diaminobenzene (HCODA) D-12: 3,6-bis(4-aminobenzimidyloxy)cholestane d-13: the compound d-14:1,3 represented by the formula (D-1-5) -diamine 4-{4-[trans-4-(trans-4-n-pentylcyclohexyl)cyclohexyl]phenoxy}benzene (the compound represented by the formula (D-1-2)) d- 15: 1,4-benzenedicarboxylic acid bis(4-aminophenyl)mda-11: a compound mda-12 represented by the following formula (mda-11): represented by the following formula (mda-12) Compound mda-13: Compound mda-14 represented by the following formula (mda-13): a compound represented by the following formula (mda-14) [Chem. 21] <monoamine> m-1: aniline

[Synthesis Example 16: Synthesis of Polyproline (PA-1)] 100 parts by mole of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride, 30 moles of the compound represented by the formula (d-1) as a diamine, 40 mole parts of 2,2'-dimethyl-4,4'-diaminobiphenyl, and 30 moles The compound of the ear (MDA-1) was dissolved in a mixed solvent of NMP and γ-butyrolactone (γBL) (NMP: γBL = 10:90 (weight ratio)), and reacted at 40 ° C for 3 hours to obtain A solution containing 10% by weight of polylysine (PA-1). The obtained polyaminic acid solution was divided into a small amount, and the obtained solution had a viscosity of 180 mPa·s.

[Synthesis Example 17: Synthesis of poly-proline (PA-2)] The synthesis and the synthesis were carried out except that the type and amount of the tetracarboxylic dianhydride and the diamine used were changed as shown in Table 1 above. The same operation was carried out, thereby obtaining a solution containing 10% by weight of poly-proline (PA-2). The obtained polyaminic acid solution was divided into a small amount, and the obtained solution had a viscosity of 210 mPa·s. [Synthesis Example 18: Synthesis of poly-proline (PA-3)] The synthesis and the synthesis were carried out except that the type and amount of the tetracarboxylic dianhydride and the diamine to be used were changed as shown in Table 1 above. The same operation was carried out, thereby obtaining a solution containing 10% by weight of poly-proline (PA-3). The obtained polyaminic acid solution was fractionated, and the obtained solution had a viscosity of 230 mPa·s.

[Synthesis Example 19: Synthesis of polyorganosiloxane (APS-1)] In a reaction vessel equipped with a stirrer, a thermometer, a dropping funnel, and a reflux cooling tube, 100.0 g of a 2-(3,4-epoxy ring) was added. Hexyl)ethyltrimethoxydecane (ECETS), 500 g of methyl isobutyl ketone and 10.0 g of triethylamine were mixed at room temperature. Then, 100 g of deionized water was added dropwise from the dropping funnel for 30 minutes, and then the reaction was carried out at 80 ° C for 6 hours while stirring under reflux. After completion of the reaction, the organic layer was taken out and washed with a 0.2% by weight aqueous solution of ammonium nitrate until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain reactivity in the form of a viscous transparent liquid. Polyorganosiloxane (EPS-1). ¹ H-NMR analysis of the reactive polyorganosiloxane gave a peak based on an epoxy group at a chemical shift (δ) = 3.2 ppm as determined by theoretical strength, and it was confirmed that no epoxy group was produced in the reaction. Side reaction. The resulting reactive polyorganosiloxane had a weight average molecular weight Mw of 3,500 and an epoxy equivalent of 180 g/mole. Then, in a 200 mL three-necked flask, 10.0 g of reactive polyorganosiloxane (EPS-1), 30.28 g of methyl isobutyl ketone as a solvent, and 3.98 g of a reactive compound were added. Dodecyloxybenzoic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro Co., Ltd.) as a catalyst were reacted at 100 ° C for 48 hours while stirring. After completion of the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed with water three times, and the organic layer was dried over magnesium sulfate, and then the solvent was evaporated to obtain 9.0 g of a liquid crystal-aligned polyorganosiloxane (APS). -1). The obtained polymer had a weight average molecular weight Mw of 9,900.

[Synthesis Example 20: Synthesis of poly-proline (PA-4)] The synthesis and the synthesis were carried out except that the type and amount of the tetracarboxylic dianhydride and the diamine used were changed as shown in Table 1 above. The same operation was carried out, thereby obtaining a solution containing 10% by weight of poly-proline (PA-4). The obtained polyaminic acid solution was divided into a small amount, and the obtained solution had a viscosity of 212 mPa·s. [Synthesis Example 21: Synthesis of Polyproline (PA-5)] The synthesis and the synthesis of the tetracarboxylic dianhydride and the diamine were changed as shown in Table 1 above. The same operation was carried out, thereby obtaining a solution containing 10% by weight of poly-proline (PA-5). The obtained polyaminic acid solution was divided into a small amount, and the obtained solution had a viscosity of 250 mPa·s.

[Example 1] <Preparation of liquid crystal alignment agent> In the polyimine (PI-1) obtained as a polymer, NMP and butyl cellosolve (BC) as an organic solvent were added to prepare a solvent composition of NMP. : BC = 50:50 (weight ratio), and a solution having a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S1).

<Manufacture of VA-type liquid crystal cell> The prepared liquid crystal alignment agent was applied to a glass substrate (thickness of 1 mm) having a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.). The transparent electrode surface was heated (prebaked) on a hot plate at 80 ° C for 1 minute, and further heated (post-baked) on a hot plate at 200 ° C for 60 minutes to form a coating film having an average film thickness of 0.08 μm. (Liquid crystal alignment film). This operation was repeated to obtain a pair (two pieces) of glass substrates having a liquid crystal alignment film on a transparent conductive film. Then, for one of the pair of substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the liquid crystal alignment film surface is opposite. The method is to crimp and bond a pair of substrates to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6608) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a VA type. Liquid crystal cell.

<Evaluation of Reliability> The reliability of the liquid crystal display element was evaluated using the liquid crystal cell manufactured as described above. Evaluation was performed in the following manner. First, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR1) after 167 milliseconds from the application release was measured. Then, the liquid crystal cell was allowed to stand in an 80 ° C oven irradiated with a light emitting diode (LED) lamp for 200 hours, and then allowed to stand at room temperature and naturally cooled to room temperature. After cooling, a voltage of 5 V was applied to the liquid crystal cell with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio (VHR2) after 167 milliseconds from the application release was measured. Further, the measuring device was "VHR-1" manufactured using Toyo Technica Co., Ltd. The rate of change (ΔVHR) of the VHR at this time is calculated from the following equation (2), and the reliability is evaluated based on ΔVHR. The evaluation was performed in such a manner that the case where ΔVHR is less than 1% is evaluated as "excellent (?)", and the case where 1% or more and less than 2% is evaluated as "good (○)", and 2% or more The case of less than 3% was evaluated as reliability "may (?)", and the case of 3% or more was evaluated as reliability "poor (x)". As a result, in Example 1, ΔVHR was 1.9 [%], and the reliability was "good (○)". ΔVHR[%]=(VHR1-VHR2)/(VHR1)×100...(2)

<Evaluation of the amount of evolved gas> When the liquid crystal cell was produced, the liquid crystal alignment agent (S1) was applied onto the substrate by the same operation, and prebaking and post-baking were performed to form a coating film on the substrate. For the post-baking substrate, thermal decomposition gas chromatography (JPS-700 manufactured by Nippon Analytical Industries Co., Ltd., thermal decomposition conditions: 590 ° C × 5 sec, Gas Chromatography (GC) column BPX-5) was used. To analyze the amount of evolved gas. With respect to the amount of the evolved gas, a standard curve was prepared using a standard product, and the mass (%) of the detected substance was calculated by comparing the mass of the amount of the thermally decomposable monomer introduced. The evaluation was performed as follows: the case where the detected substance mass was less than 4% was evaluated as "excellent (?)", and the case where 4% or more and less than 7% was evaluated as "good (?)", and 7% or more The case of less than 10% was evaluated as "may (Δ)", and the case of 10% or more was evaluated as "bad (x)". As a result, in Example 1, the amount of evolved gas was small, and it was evaluated as "excellent (?)".

[Example 2 to Example 6, Example 10 to Example 11 and Comparative Example 1 to Comparative Example 5] The same procedure as in Example 1 was carried out except that the composition of the liquid crystal alignment agent was changed as shown in Table 2 below. A liquid crystal alignment agent was separately prepared. Further, a liquid crystal cell was produced in the same manner as in Example 1 using each liquid crystal alignment agent, and the produced liquid crystal cell was evaluated. The evaluation results thereof are shown in Table 2 below.

[Example 7] γ as an organic solvent was added so that the polyimine (PI-8) and the polyamic acid (PA-1) obtained as a polymer had a solid content by weight ratio of 20:80. Butyrolactone (BL), NMP and butyl cellosolve (BC) were prepared into a solution having a solvent composition of BL:NMP:BC=70:15:15 (weight ratio) and a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S7).

<Production of TN-type liquid crystal cell> The liquid crystal alignment agent prepared by applying the liquid crystal alignment agent to the transparent electrode surface of the glass substrate with the transparent electrode containing the ITO film was used using a liquid crystal alignment film printing machine (manufactured by Nippon Photographic Co., Ltd.). After heating (prebaking) on a hot plate at 80 ° C for 1 minute to remove the solvent, the film was heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 0.08 μm. With respect to this coating film, a rubbing machine having a roller wound with a rayon cloth was used, and a rubbing treatment was performed at a roll rotation number of 400 rpm, a table moving speed of 30 mm/sec, and a hair press-in length of 0.4 mm to impart a liquid crystal alignment ability. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and is orthogonal to the rubbing direction. In the method, a pair of substrates are superposed and pressure-bonded so that the liquid crystal alignment film faces are opposed to each other to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6221) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce a TN. Liquid crystal cell. <Evaluation of the reliability and the amount of the evolved gas> Using the TN-type liquid crystal cell manufactured as described above, the reliability and the amount of the evolved gas were evaluated by the same method as in the above-described Example 1, and as a result, ΔVHR = 0.6 [%] The reliability was "excellent" and the amount of evolved gas was 6%, which became a "good" evaluation.

[Example 8] <Preparation of liquid crystal alignment agent> A method in which a polyimine (PI-9) and a polyaminic acid (PA-2) obtained as a polymer were 40:60 in terms of a solid content by weight ratio Γ-butyrolactone (BL), NMP and butyl cellosolve (BC) were added as an organic solvent to prepare a solvent composition of BL:NMP:BC=40:40:20 (weight ratio), and a solid concentration of 6.0. % by weight solution. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S8).

<Manufacture of IPS/FFS type liquid crystal cell> The liquid crystal alignment agent was applied to a transparent electrode of a glass substrate with a transparent electrode containing an ITO film using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.) The surface was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent, and then heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 0.08 μm. The coating film was subjected to a rubbing treatment using a rubbing machine having a roll wound with a rayon cloth at a number of rolls of 1000 rpm, a table moving speed of 20 mm/sec, and a hair press-in length of 0.4 mm to impart liquid crystal alignment ability. Then, ultrasonic cleaning was performed for 1 minute in ultrapure water, followed by drying in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. Further, the above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and the rubbing direction becomes antiparallel. In a manner, the pair of substrates are overlapped and crimped in such a manner that the liquid crystal alignment film faces are opposed to each other to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6221) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce IPS. /FFS type liquid crystal unit. <Evaluation of the reliability and the amount of the evolved gas> Using the manufactured IPS/FFS type liquid crystal cell, the reliability and the amount of the evolved gas were evaluated by the same method as in the above-described Example 1, and the result was: ΔVHR = 0.6 [ %], the reliability is "excellent", and the amount of evolved gas is 6%, which is a "good" evaluation.

[Example 9] <Preparation of liquid crystal alignment agent> A method of obtaining a polyimine (PI-10) and a polyorganosiloxane (APS-1) as a polymer to have a solid content by weight ratio of 95:5 The organic solvent NMP and butyl cellosolve (BC) were added to prepare a solution having a solvent composition of NMP: BC = 50:50 (weight ratio) and a solid content concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S9).

<Preparation of Liquid Crystal Composition> [Preparation of Liquid Crystal Composition LC1] For 10 g of nematic liquid crystal (manufactured by Merck, MLC-6608), 0.3% by weight of the following formula (pc-1) was added. The photopolymerizable compound shown is mixed to obtain a liquid crystal composition LC1. [化22]

<Manufacture of PSA-VA type liquid crystal cell> Using the liquid crystal alignment film printing machine (manufactured by Japan Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent was applied to two glass substrates each having the ITO electrode 1 (substrate A, On each electrode surface of the substrate B), the ITO electrode 1 is patterned into a slit shape (slit portion 2) as shown in FIGS. 1 to 3, and is divided into a plurality of regions, and a heating plate at 80 ° C After heating (prebaking) for 1 minute to remove the solvent, it was heated (post-baked) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 800 Å. Further, the above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Further, the pattern of the electrodes used is the same pattern as the electrode pattern in the PSA mode. Then, for one of the pair of substrates, an epoxy resin adhesive having an alumina ball having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film, and then the liquid crystal alignment film surface is opposite. The method is to crimp and bond a pair of substrates to harden the adhesive. Then, the prepared liquid crystal composition LC1 was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive. Then, light was applied at a dose of 100,000 J/m ² in a state where a voltage was applied between the conductive films of the obtained liquid crystal cells. Thereby, a PSA-VA type liquid crystal cell was obtained. <Evaluation of the reliability and the amount of the evolved gas> Using the PSA-VA type liquid crystal cell manufactured as described above, the reliability and the amount of the evolved gas were evaluated by the same method as in the above-described Example 1, and as a result, ΔVHR = 0.4 [ %], the reliability is "excellent", and the amount of evolved gas is 2%, which is an "excellent" evaluation.

[Example 12] <Preparation of liquid crystal alignment agent> In the case of obtaining polyglycine (PA-3) as a polymer, NMP and butyl cellosolve (BC) as an organic solvent were added to prepare a solvent composition of NMP: A solution having a BC = 50:50 (weight ratio) and a solid concentration of 6.0% by weight. This solution was filtered using a filter having a pore size of 1 μm, thereby preparing a liquid crystal alignment agent (S12).

<Manufacturing of IPS/FFS Type Liquid Crystal Cell Using Photo-Alignment Method> The liquid crystal alignment agent prepared by applying the liquid crystal alignment film to a transparent electrode having an ITO film was applied using a liquid crystal alignment film printer (manufactured by Nippon Photoprint Co., Ltd.). The transparent electrode surface of the glass substrate was heated (prebaked) on a hot plate at 80 ° C for 1 minute to remove the solvent. Then, using a Hg-Xe lamp, a polarized ultraviolet ray containing a bright line of 254 nm was irradiated from the substrate normal line at an irradiation dose of 700 mJ/cm ² , and then heated (post-baked) for 10 minutes on a hot plate at 200 ° C. A coating film having an average film thickness of 800 Å imparted to the liquid crystal alignment film was formed. Further, the above operation was repeated to obtain a pair of (two pieces) substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive having a diameter of 5.5 μm is applied to the outer edge of the surface having the liquid crystal alignment film to polarize the polarized ultraviolet rays. The direction in which the surface is projected onto the substrate is parallel, and the pair of substrates are superposed and pressure-bonded so that the liquid crystal alignment film faces face each other to harden the adhesive. Then, a nematic liquid crystal (manufactured by Merck Co., Ltd., MLC-6221) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an acrylic photocurable adhesive to produce IPS. /FFS type liquid crystal unit.

<Evaluation of the reliability and the amount of the evolved gas> Using the IPS/FFS liquid crystal cell manufactured by the above-described photoalignment method, the reliability and the amount of the evolved gas were evaluated by the same method as in the first embodiment, and the result was : ΔVHR = 0.5 [%], the reliability was "excellent", and the amount of evolved gas was 3%, which was an "excellent" evaluation.

[Examples 13 to 14] A liquid crystal alignment agent was prepared in the same manner as in Example 12 except that the composition of the liquid crystal alignment agent was changed to that shown in Table 2 below. Further, a liquid crystal cell was produced in the same manner as in Example 12 using each liquid crystal alignment agent, and the produced liquid crystal cell was evaluated. The evaluation results thereof are shown in Table 2 below.

[Table 2]

In Table 2, the numerical value of the amount of the polymer indicates the use ratio [parts by weight] of each polymer with respect to 100 parts by weight of the total of the polymers used in the preparation of the liquid crystal alignment agent.

As shown in Table 2, in Examples 1 to 14, the reliability was evaluated as "excellent" to "may", and the amount of evolved gas was also small. On the other hand, in Comparative Example 1 to Comparative Example 3 and Comparative Example 5, the reliability was evaluated as "poor", and in Comparative Example 4, the amount of evolved gas was large, and it was evaluated as "poor". Further, in Comparative Example 2, Comparative Example 3, and Comparative Example 5 in which a thermally decomposable monomer having a tertiary alkyl structure was used, the reason why the reliability was evaluated lower than that of the examples was not determined, but one of the factors was considered to be: In the case of the tertiary alkyl structure, the decarboxylation is mainly carried out to form an amine group, so that the crosslinking reaction is difficult to carry out as compared with the examples. Further, in the case of Comparative Example 4 using a diamine having a linear structure having a carbon number of 10 as a thermally decomposable monomer, it is presumed that an escape gas is likely to be generated due to an excessively long carbon chain.

1‧‧‧ITO electrode
2‧‧‧Slits
A, B‧‧‧ substrate

FIG. 1 is a view showing an electrode pattern of a transparent electrode film used in Examples and Comparative Examples. Fig. 2 is a view showing an electrode pattern of a transparent electrode film used in the examples. 3 is a view showing an electrode pattern of a transparent electrode film used in Examples.

1‧‧‧ITO electrode

2‧‧‧Slits

Claims (9)

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polylysine, polyphthalate, polyimine, and polyamine, at least a portion of the polymer having the following a partially structured polymer (P) represented by the formula (1), (In the formula (1), A ¹ and A ² are each independently a hydrogen atom or a monovalent organic group, and the total number of carbon atoms of A ¹ and A ² is 0 to 7; Y ¹ is an oxygen atom or a sulfur atom, and R ¹ It is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and X ¹ is a single bond or a divalent organic group; "*" indicates a bond). The liquid crystal alignment agent according to claim 1, wherein the polymer (P) is a partially structured polymer having a diamine represented by the following formula (c). (In the formula (c), B ¹ is a divalent organic group having a partial structure represented by the formula (1), and B ² and B ³ are each independently a hydrogen atom or have the formula represented by the formula (1) a monovalent organic group of a partial structure, Z ¹ and Z ² are each independently a single bond or a divalent linking group, and R ⁵ and R ⁶ are each independently a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms; n 1 and n 2 Each of them is independently an integer of 0 to 2, and m1 and m2 are each independently 0 or 1; wherein, in the case of m1=1, B ² has a partial structure represented by the formula (1), where m1=0 And when m2=0, at least one of B ² and B ³ has a partial structure represented by the formula (1), and in the case of m1=0 and m2=1, B ¹ , B ² and B ³ At least any one of them has a partial structure represented by the formula (1). The liquid crystal alignment agent according to the first or second aspect of the invention, wherein the polymer (P) is a partially structured polymer having a diamine represented by the following formula (d), (In the formula (d), R ⁷ is a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n3 is an integer of 0 to 2; and A ¹ , A ² , Y ¹ , R ¹ and X ¹ are respectively The formula (1) has the same meaning). The liquid crystal alignment agent according to claim 3, wherein in the diaminophenyl group of the compound represented by the formula (d), two primary amino groups are represented by the formula (1) The structure is bonded to the 3,5-position. The liquid crystal alignment agent according to any one of the first aspect, wherein the polymer (P) is a diamine represented by the following formula (e). Partially structured polymer, (In the formula (e), Z ³ is a single bond or a divalent linking group, and V ¹ is a hydrogen atom or a monovalent group represented by the formula (1), and R ⁸ and R ⁹ are each independently a halogen atom or carbon The monovalent hydrocarbon group of 1 to 6; n4 and n5 are each independently an integer of 0 to 2; and A ¹ , A ² , Y ¹ , R ¹ and X ¹ have the same meanings as the above formula (1), respectively. The liquid crystal alignment agent according to any one of the preceding claims, wherein the polymer (P) is a polymer having a partial structure derived from an acid anhydride, wherein the acid anhydride is 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 2,4,6,8-tetracarboxybicyclo[3.3.0]octane-2:4,6:8-dianhydride, 1,2 a mixture of 3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, and 1,2,4,5-cyclohexanetetracarboxylic dianhydride At least one of the groups. The liquid crystal alignment agent according to any one of the preceding claims, wherein the polymer (P) has a structure represented by the formula (1) and is selected from the group consisting of nitrogen-containing impurities. At least one nitrogen-containing structure of the group consisting of a ring, a secondary amine group, and a tertiary amine group. A liquid crystal alignment film formed by using the liquid crystal alignment agent according to any one of the first to seventh aspects of the invention. A liquid crystal display element comprising the liquid crystal alignment film according to item 8 of the patent application.