TWI677516B - Liquid crystal alignment agent, liquid crystal alignment film, and liquid crystal display element - Google Patents

Abstract

The invention provides a liquid crystal display element with a small amount of outgassing from a liquid crystal alignment film and high reliability. The invention provides a liquid crystal alignment agent containing a polymer (P). The polymer (P) is selected from the group consisting of polyamidic acid, polyamidate, polyimide, and polyamidoamine. And has at least one of the following, and has a partial structure represented by the following formula (1). (A ¹ and A ² are hydrogen atoms or monovalent organic groups, the total number of carbon numbers 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 carbon number of 1 to 6 A monovalent hydrocarbon group, X ¹ is a single bond or a divalent organic group; "*" represents a bonding bond)

Description

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

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

In the past, liquid crystal display devices have developed various driving methods such as an electrode structure or physical properties of liquid crystal molecules used, such as a known twisted nematic (TN) type or a super twisted nematic (STN) type. , Vertical Alignment (VA) type, Multidomain Vertical Alignment (MVA) type, In Plane Switching (IPS type), Fringe Field Switching (FFS) type, optical compensation Various types of 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 polyamic acid, polyimide, polyimide, polyimide, polyester, polyorganosiloxane, etc. Among them, heat resistance, mechanical strength, and liquid crystal In terms of various properties such as affinity, polyfluorinated acid or polyimide is usually used.

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

Patent Document 1 proposes using an aromatic diamine in which an amine group protected by a tertiary butoxycarbonyl group (t-BOC group) is introduced in an ortho position with respect to a primary amine group, and the diamine is used to obtain the aromatic diamine. The polyamidic acid or polyimide is contained in a liquid crystal alignment agent. According to this technology, Patent Document 1 describes the following gist: the t-BOC group is deprotected by heating during film formation to generate an amine group, and the intramolecular reaction or intermolecular reaction (crosslinking) of the generated amine group Response) to improve reliability. [Prior Art Literature] [Patent Literature]

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

[Problems to be Solved by the Invention]

Patent Document 1 describes a technique using an amine group generated by heating during film formation, and it is considered that the reliability of a liquid crystal panel cannot be sufficiently improved because it is difficult to perform a crosslinking reaction.

In addition, when a thermally decomposable monomer is used, if a large amount of unreacted functional groups remain after heating, it is considered that a problem such as generation of bubbles in the panel may occur when the liquid crystal panel is lit for a long period of time. In order to suppress the occurrence of such a problem, it is required to reduce the amount of outgassing from the liquid crystal alignment film after the post-baking.

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

The present inventors and the like have actively studied in order to achieve the problems of the prior art as described above, and have attempted to introduce a specific structure thought to exhibit thermal decomposition properties into a polymer. Further, it was 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.

One aspect of the present invention is to provide a liquid crystal alignment agent, which contains at least one polymer selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamidine, 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 formula (1), A ¹ and A ² are each independently a hydrogen atom or a monovalent organic group, and the total number of carbon numbers 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; "*" represents a bonding bond)

Another aspect of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent, and a liquid crystal display element including the liquid crystal alignment film. [Effect of the invention]

According to the liquid crystal alignment agent containing the polymer (P), a liquid crystal alignment film having a small amount of outgassing can be formed. In addition, since the liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent containing the polymer (P), the quality degradation with use is small and the reliability is excellent.

Hereinafter, each component contained in a liquid crystal aligning agent, and other components arbitrarily mix | blended as needed are demonstrated.

<Polymer (P)> The liquid crystal alignment agent of the present invention contains a polymer (P) as a polymer component. The polymer (P) is selected from the group consisting of polyamic acid, polyamic acid ester, and polyimide. At least one of the group consisting of polyamine and polyamine is a main skeleton, and has a partial structure represented by the following formula (1). [Chemical 2] (In formula (1), A ¹ and A ² are each independently a hydrogen atom or a monovalent organic group; wherein the total number of carbon numbers of A ¹ and A ² is 0 to 7; 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; "*" represents a bonding bond)

Examples of the monovalent organic group of A ¹ and A ² in the formula (1) include: a monovalent hydrocarbon group; and for the methylene group of the monovalent hydrocarbon group, -O-, -S-, -CO-, -COO- , -COS- and other bivalent heteroatom-containing groups substituted; at least one of the hydrogen atoms of a monovalent hydrocarbon group is substituted with a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom, etc.) A group; a monovalent group having a heterocyclic ring and the like. As long as the total number of carbon numbers of A ¹ and A ^{2 is} in the range of 0 to 7, the carbon numbers of A ¹ and A ² are not particularly limited, but groups that are detached by heating during post-baking are allowed. From the viewpoint of reducing the amount of the compound remaining from "-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.

Herein, the "hydrocarbon group" in the present specification means a meaning including a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. The "chain hydrocarbon group" refers to a straight-chain hydrocarbon group and a branched hydrocarbon group that are composed of only a chain structure without a cyclic structure in the main chain. Among them, it may be saturated or unsaturated. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not containing an aromatic ring structure. However, it does not necessarily need to consist only of the structure of an alicyclic hydrocarbon, and also includes the hydrocarbon group which has a chain structure in a part. The "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not necessarily need to consist only of an aromatic ring structure, and may include a chain structure or an alicyclic hydrocarbon structure in part.

As specific examples of the monovalent hydrocarbon group, examples of the chain hydrocarbon group include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, and heptyl; alkenyl groups such as vinyl, propenyl, and butenyl ; Alkynyl groups such as ethynyl, propynyl, etc .; these groups may be linear or branched. Examples of the alicyclic hydrocarbon group include cyclohexyl and methylcyclohexyl. Examples of the aromatic hydrocarbon group include phenyl and tolyl. From the standpoint of ease of detachment of the group "-CHA ¹ A ² " due to heating, A ¹ and A ^{2 are} preferably a hydrogen atom therein, or a substituted or unsubstituted monovalent chain hydrocarbon group, It is more preferably a hydrogen atom or a substituted or unsubstituted alkyl group. In addition, A ¹ and A ² may be the same as 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. Specific examples of the alkyl group, the alkenyl group, and the alkynyl group include a group having 1 to 6 carbon atoms among the groups exemplified in A ¹ and A ² . R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

Examples of the divalent organic group of X ¹ include: a divalent hydrocarbon group; and for the methylene group of the divalent hydrocarbon group, -O-, -S-, -CO-, -COO-, -COS-, -NR ³ -,- CONR ^3- (wherein R ³ is a hydrogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms) such as a divalent heteroatom-containing group; at least one of the hydrogen atoms of the divalent hydrocarbon group is halogen A group substituted with an atom or the like; a divalent group having a heterocyclic ring or the like. Here, as specific examples of the divalent hydrocarbon group, examples of the chain hydrocarbon group include methylene, ethylidene, propanediyl, butanediyl, alkanediyl such as pentadiyl, and hexadiyl. These groups may be It is linear or branched. Examples of the alicyclic hydrocarbon group include cyclohexyl. Examples of the aromatic hydrocarbon group include phenylene, phenylene, and naphthyl. X ¹ is preferably a single bond or a substituted or unsubstituted divalent chain hydrocarbon group, and more preferably a single bond or a substituted or unsubstituted alkanediyl group.

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

The polyamidic acid, polyamidate, polyimide, and polyamidine as the polymer (P) can be synthesized according to a conventionally known method. Specific examples include a method using at least one carboxylic acid derivative selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic diester, tetracarboxylic diester dihalide, and dicarboxylic acid, and Diamine raw material to synthesize polymer (P).

[Polyamidoacid] The polyamidoacid as the polymer (P) can be obtained, for example, by reacting a tetracarboxylic dianhydride with a diamine. Specific methods include: [1] a method of synthesizing by polymerizing a tetracarboxylic dianhydride having a structure represented by the formula (1) in a raw material composition; [2] including a raw material composition A method for synthesizing a diamine having a structure represented by the formula (1); [3] A tetracarboxylic dianhydride having a structure represented by the formula (1) is included in a raw material composition, and A method of synthesizing a diamine having a structure represented by the formula (1) by polymerization. Among these methods, the method using [2] is preferred in terms of less restrictions on monomers.

(Tetracarboxylic dianhydride) Examples of the tetracarboxylic dianhydride used in the synthesis of polyamic acid include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. . As specific examples of these tetracarboxylic dianhydrides, examples of the aliphatic tetracarboxylic dianhydride include 1, 2, 3, 4-butane tetracarboxylic dianhydride, and the like; and examples of the alicyclic tetracarboxylic dianhydride include : 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (Tetrahydro-2,5-dioxo-3-furyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -8-methyl-5- (tetrahydro-2,5-dioxo-3-furyl) -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-di 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, cyclopentanetetracarboxylic dianhydride, etc .; Examples of aromatic tetracarboxylic dianhydride: pyromellitic dianhydride In addition, tetracarboxylic dianhydride described in Japanese Patent Laid-Open No. 2010-97188 can also be used. In addition, the tetracarboxylic dianhydrides may be used singly or in combination of two or more kinds.

As a tetracarboxylic dianhydride used for the synthesis of a polyamic acid, it is preferable to contain an alicyclic tetracarboxylic dianhydride from the point which has good solubility or transparency with respect to a solvent. Among them, it is more preferable to include a compound selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxy 3-furyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8-methyl-5- (tetra Hydrogen-2,5-dioxo-3-furyl) -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, It is particularly preferred that at least one of the group consisting of 2,3,4-cyclobutanetetracarboxylic dianhydride is selected from the group consisting of 2,3,5-tricarboxycyclopentylacetic 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 in the group consisting of cyclohexanetetracarboxylic dianhydride and 1,2,3,4-cyclopentanetetracarboxylic dianhydride (hereinafter also referred to as "specific tetracarboxylic dianhydride"). As the tetracarboxylic dianhydride used in the synthesis of the polyamic acid, the specific tetracarboxylic dianhydride is preferably contained in an amount of 20 mol% or more with respect to the total amount of the tetracarboxylic dianhydride used in the synthesis, and more preferably The content is preferably 40 mol% or more, and particularly preferably 60 mol% or more.

(Diamine) It is preferable that the diamine used for the synthesis | combination of a polyamic acid contains the compound which has the structure represented by said Formula (1), and two primary amine groups (henceforth a "specific diamine").

Specific examples of the specific diamine include a compound represented by the following formula (c). [Chemical 3] (In 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 a structure represented by the formula (1) Partially structured monovalent organic groups, 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; n1 and n2 Are each 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), and m1 = 0 When m2 = 0, at least one of B ² and B ³ has a partial structure represented by the formula (1). When m1 = 0 and m2 = 1, B ¹ , B ^2, and B ³ At least one of them has a partial structure represented by the formula (1))

Specific examples of B ¹ in the formula (c) include, for example, 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 formula (1), respectively; “*” represents a combination 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 a group having one or more partial structures represented by the formula (1). It is preferably a monovalent group represented by the 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 to an alkanediyl group having 1 to 10 carbon atoms, and -O -A divalent group substituted. n1 and n2 are preferably 0 or 1, and more preferably 0.

Preferred specific examples of the specific diamine include, for example, a compound represented by the following formula (d). [Chemical 5] (In the formula (d), R ⁷ is a halogen atom or a monovalent hydrocarbon group having 1 to 6 carbon atoms, and n 3 is an integer of 0 to 2; A ¹ , A ² , Y ¹ , R ^1, and X ¹ are respectively Formula (1) has the same meaning)

In the formula (d), the illustrations and preferred specific examples of A ¹ , A ² , Y ¹ , R ^1, and X ¹ can be applied to the description of the formula (1), respectively. In the formula (d), with respect to the group represented by the formula (1), the bonding positions of two primary amine groups in the diaminophenyl group include the 2,4-position, 2,5- The 3,5-position, etc. are preferably the 3,5-position in terms of high reliability improvement effects. n3 is preferably 0 or 1, and more preferably 0.

Moreover, as a preferable specific example of a specific diamine, the compound represented by following formula (e) is mentioned. [Chemical 6] (In formula (e), Z ³ is a single bond or a divalent linking group, 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 a carbon A monovalent hydrocarbon group of 1 to 6; n4 and n5 are each independently an integer of 0 to 2; A ¹ , A ² , Y ¹ , R ¹ and X ¹ have the same meanings as the formula (1))

In the formula (e), the illustrations and preferred specific examples of A ¹ , A ² , Y ¹ , R ^1, and X ¹ can be applied to the description of the formula (1), respectively. Z ³ is preferably a divalent linking group, and preferred specific examples thereof can be applied to the description of the preferred examples of Z ¹ and Z ² in the formula (c). n4 and n5 are preferably 0 or 1, and more preferably 0.

Specific examples of the specific diamine include, for example, compounds represented by the following formulae (MDA-1) to (MDA-21). [Chemical 7]

[Chemical 8]

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

The diamine used in the synthesis of the polyamic acid may be only a specific diamine, or another diamine may be used together with the specific diamine. Examples of other diamines include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamine-based organosiloxanes. As specific examples of these diamines, examples of the aliphatic diamine include 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) cyclohexyl. Alkane etc.

Examples of the aromatic diamine include p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfide, 1,5-diaminonaphthalene, 2 2,2'-dimethyl-4,4'-diaminobiphenyl, 4,4'-diamino-2,2'-bis (trifluoromethyl) biphenyl, 2,7-diamino Hydrazone, 4,4'-diaminodiphenyl ether, 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl, 2,2-bis [4- (4- Aminophenoxy) phenyl] propane, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 4,4 '-(p-phenylene diisopropylidene) bisaniline, 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-indene-5-amine, 1- (4-aminophenyl) -2,3-dihydro-1,3,3-trimethyl-1H-indene-6- Amine, 3,5-diaminobenzoic acid, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, cholesteryloxy-2, 4-diaminobenzene, cholestenyl-2,4-diaminobenzene, cholesteryl 3,5-diaminobenzoate, cholestyl 3,5-diaminobenzoate Ester, 3,5-diaminobenzoic acid Stearyl alkyl esters, 3,6-bis (4-aminobenzyloxy) cholestane, 3,6-bis (4-aminophenoxy) cholestane, 4- (4'- Trifluoromethoxybenzyloxy) 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 Allylaniline, 4-aminobenzylamine, and the following formula (D-1) (In 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 Bond or alkanediyl 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 become 0 at the same time ) Represented compounds, etc .;

Examples of the diamine-based organosiloxane include 1,3-bis (3-aminopropyl) -tetramethyldisilaxane, etc. In addition, Japanese Patent Laid-Open No. 2010-97188 can also be used As described in Diamine.

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- (where the bond with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _{2c +1"} include, for example, methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n- Nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n Undecyl, n-icosyl and the like. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position with respect to the other groups.

Specific examples of the compound represented by the formula (D-1) include compounds represented by the following formulae (D-1-1) to (D-1-5). [Chemical 10]

Other diamines include, in addition to two primary amine groups, at least one structure selected from the group consisting of nitrogen-containing heterocycles, secondary amine groups, and tertiary amine groups (hereinafter also referred to as "nitrogen-containing Structure "). 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 formula (1) is obtained. Such a polymer is preferable because the effect of improving the reliability of the liquid crystal display element can be improved. 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-diamine group. Oxazole, N-methyl-3,6-diaminooxazole, 1,4-bis- (4-aminophenyl) -pyrazine, and the following formulae (D-2-1) to (D -2-6) Compounds and the like respectively indicated. [Chemical 11]

As the diamine used in the synthesis of the polyamidic acid, it is preferable that the blending ratio of the specific diamine is 1 mol% or more, and more preferably 3 mol% or more with respect to 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 use ratio of the specific diamine is not particularly limited, and it is preferably set to 90 mol% or less, and more preferably set to 80, in terms of improving various characteristics such as liquid crystal alignment and electrical characteristics by using other diamines. Molar% or less, Especially preferably, it is 70 mole% or less. The use ratio of the diamine having a nitrogen-containing structure to the total amount of diamines used in the synthesis is preferably 0.1 mol% or more, more preferably 1 mol% or more, and particularly preferably 2 mol. Ear%. The use ratio of the diamine having a nitrogen-containing structure is preferably 60 mol% or less, more preferably 50 mol% or less, and particularly preferably 40 mol% or less. In addition, other diamines may be used alone or in combination of two or more.

(Synthesis of Specific Diamine) The specific diamine can be synthesized by appropriately combining known methods. As an example thereof, a method such as synthesizing a dinitro intermediate having a nitro group instead of a primary amine group in a specific diamine, and then using a suitable reduction system to synthesize the nitrate of the obtained dinitro intermediate can be mentioned. Group is aminated. The method for synthesizing the dinitro intermediate can be appropriately selected depending on the target compound. For example, a method of reacting dinitroaniline with alkyl chloroformic acid; a method of reacting dinitrobenzidine chloride with a hydroxyl-containing compound having a structure represented by the 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, and the like.

(Synthesis of Polyamic Acid) Polyamic acid can be obtained by reacting a tetracarboxylic dianhydride and a diamine as described above together with a molecular weight regulator, if necessary. The use ratio of the tetracarboxylic dianhydride and the diamine provided for the synthesis reaction of the polyamic acid is preferably 1 equivalent to the amine group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes a ratio of 0.2 to 2 equivalents. The ratio is more preferably 0.3 equivalent to 1.2 equivalent. Examples of the molecular weight regulator include acid monoanhydrides such as maleic anhydride, phthalic anhydride, itaconic anhydride, monoamine compounds such as aniline, cyclohexylamine, and n-butylamine, phenyl isocyanate, and isocyanate. Monoisocyanate compounds such as naphthyl cyanate and the like. 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 tetracarboxylic dianhydride and diamine used.

The synthesis reaction of the polyamic acid is preferably performed 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. The reaction time is preferably from 0.1 to 24 hours, and more preferably from 0.5 to 12 hours.

Examples of the organic solvent used in the reaction include aprotic polar solvents, phenol-based solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. Among these organic solvents, one or more selected from the group consisting of an aprotic polar solvent and a phenol-based solvent (organic solvent of the first group), or an organic solvent selected from the group of the first group is preferably used. A mixture of one or more species with one or more species selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons (organic solvent of the second group). In the latter case, the use ratio of the organic solvent in the second group is preferably 50% by weight or less, and more preferably 40% by weight, relative to the total amount of the organic solvent in the first group and the organic solvent in the second group. Hereinafter, it is particularly preferably 30% by weight or less.

Particularly preferred organic solvents are preferably those selected from the group consisting of N-methyl-2-pyrrolidone, N, N-dimethylacetamidamine, N, N-dimethylformamidine, dimethylmethylene, and γ-butane. One or more of the group consisting of lactone, tetramethylurea, hexamethylphosphonium triamine, m-cresol, xylenol and halogenated phenol are used as a solvent, or these agents are used within the range of the ratio A mixture of one or more solvents with other organic solvents. It is preferable that the usage-amount (a) of an organic solvent is 0.1 weight%-50 weight% with respect to the total amount (a + b) of a reaction solution, and the total amount (b) of a tetracarboxylic dianhydride and a diamine.

In the manner as described above, a reaction solution obtained by dissolving polyamic acid was obtained. The reaction solution may be directly provided to the next step, or the polyamic acid may be separated and then provided to the next step, or the separated polyamino acid may be purified and then provided to the next step. These purification operations can be performed according to a known method.

[Polyamidate] Polyamidate can be obtained, for example, by the following method: [I] a method of reacting a polyamino acid obtained by the synthesis reaction with an esterifying agent; [II] using 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.

Examples of the esterifying agent used in the method [I] include a hydroxyl-containing compound, an acetal-based compound, a halide, and an epoxy-containing compound. As specific examples of these compounds, examples of the hydroxyl-containing compound include alcohols such as methanol, ethanol, and propanol; phenols such as phenol and cresol; and acetal compounds such as N, N-dimethylmethyl. Amine diethyl acetal, N, N-diethylformamide diethyl acetal, and the like; examples of the halide include bromomethane, bromoethane, bromooctadecane, methyl chloride, Chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, and the like; examples of the epoxy group-containing compound include propylene oxide and the like.

The tetracarboxylic acid diester used in the method [II] can be obtained by ring-opening a tetracarboxylic dianhydride using the alcohol. The tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained in the manner described above with an appropriate chlorinating agent such as thionyl chloride. In the case of obtaining a polyamidate having a partial structure represented by the formula (1), in the method [II] and the method [III], a method having a structure represented by the formula (1) is used. As at least a part of the diamine used in the reaction, a diamine can obtain a polyamidate having a partial structure represented by the formula (1). In addition, the polyamidate may have only a pseudoamidate structure, or may be a partially esterified product in which a pseudoamidate structure and a pseudoamidate structure coexist. The reaction solution obtained by dissolving the polyamidate can be directly provided to the next step, or the polyamidate can be separated and then provided to the next step, or the isolated polyamidate can be purified Provide it to the next step. These purification operations can be performed according to a known method.

[Polyimide] The polyimide as the polymer (P) can be obtained by dehydrating and ring-closing the polyamidic acid synthesized in the manner described above, and then being imidized.

The polyamidoimide may be a complete phosphonium imide obtained by dehydrating and ring-closing all the phosphonium acid structures of the polyphosphonium acid as a precursor thereof, or may be dehydrating and cyclizing only a part of the phosphonium structure. In addition, a part of the sulfonium imide compound in which the sulfonium acid structure and the sulfonium ring structure coexist. The fluorene imidization rate of the polyfluorene imine is preferably 30% or more, more preferably 50% to 99%, and particularly preferably 60% to 99%. The fluorene imidization ratio is a percentage expressed as a percentage of the number of fluorene imine ring structures relative to the total number of fluorene imine structures and the number of fluorene imine ring structures relative to the polyfluorene imine. Here, a part of the fluorene imine ring may be an isofluorene ring.

The dehydration ring closure of the polyamic acid is preferably performed by the following method: heating the polyamic acid; or dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydration ring closing catalyst to the solution, depending on A method of heating is required. Among these, the method using the latter is preferable.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to a solution of a polyamic acid, for example, an acid anhydride such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride can be used as the dehydrating agent. The amount of the dehydrating agent to be used is preferably 0.01 to 20 mol relative to 1 mol of the fluoric acid 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-closing catalyst used is preferably 0.01 mol to 10 mol relative to 1 mol of the dehydrating agent used. Examples of the organic solvent used in the dehydration ring-closure reaction include organic solvents exemplified as the organic solvent used in the synthesis of the polyamic acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0 ° C to 180 ° C, and more preferably 10 ° C to 150 ° C. The reaction time is preferably 1.0 to 120 hours, and more preferably 2.0 to 30 hours.

In this way, a reaction solution containing polyfluoreneimine was obtained. The reaction solution can be directly provided to the preparation of the liquid crystal alignment agent, or the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then provided to the preparation of the liquid crystal alignment agent, or the polyimide can be separated and then provided to the liquid crystal alignment agent Preparation of the agent, or the isolated polyfluorene imide may be purified and then provided to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to a known method. The method for synthesizing polyfluorene imine is not limited to the method described above, and it can be carried out, for example, by hydrazone imidization of a polyfluorene ester.

[Polyamine] The polyamine as 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, terephthalic acid, 5-decoxy isophthalic acid and the like. Moreover, a dicarboxylic acid may be used individually by 1 type selected from these, and may be used in combination of 2 or more type. The diamine used in the reaction may be a specific diamine alone, or other diamines may be used together with the specific diamine.

The reaction of a dicarboxylic acid and a diamine is preferably performed in a suitable organic solvent. In this case, the dicarboxylic acid may be subjected to ammonium chloride and then reacted with the diamine. The reaction temperature is preferably -100 ° C to 200 ° C, and more preferably -20 ° C to 150 ° C. In the case where the dicarboxylic acid is directly provided to the reaction with the diamine, the reaction temperature is preferably set to a temperature above room temperature (25 ° C), and the dicarboxylic acid is then subjected to fluorination with the diamine. When the reaction is performed, the reaction temperature is preferably set to a temperature lower than room temperature. The reaction time is preferably from 0.1 to 40 hours, and more preferably from 0.5 to 20 hours.

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

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

<Other components> The said liquid crystal aligning agent may contain other components other than a polymer (P) as needed. Examples of the other components include polymers other than the polymer (P), compounds having at least one epoxy group in the molecule (hereinafter referred to as "epoxy-containing compounds"), and functional silane compounds.

[Other polymers] The other polymers may be used for improving solution characteristics or electrical characteristics. Examples of the other polymer include polyamidic acid that does not have the partial structure represented by the formula (1); polyimide that does not have the partial structure represented by the formula (1); Polyamines having a partial structure represented by formula (1); polyamines, polyorganosiloxanes, polyesters, cellulose derivatives, polyamines which do not have the partial structure represented by formula (1) Acetals, polystyrene derivatives, poly (styrene-phenylmaleimide) imine derivatives, poly (meth) acrylates, and the like. When other polymers are blended in the liquid crystal alignment agent, the blending ratio of the other polymers is preferably 50% by weight or less, and more preferably 0.1% to 40% by weight, relative to the total amount of polymers in the composition. % Is particularly preferably 0.1% to 30% by weight.

[Epoxy Group-Containing Compound] The epoxy group-containing compound can be used to improve the adhesion or electrical characteristics of the liquid crystal alignment film to the substrate surface. Here, as the epoxy-containing compound, for example, the following compounds are preferred: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopenta 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. Other examples of the epoxy group-containing compound include an epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598. When these epoxy group-containing compounds are formulated in a liquid crystal alignment agent, the compounding ratio of the epoxy group-containing compound is preferably 40 with respect to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent. It is more preferably 0.1 parts by weight to 30 parts by weight.

[Functional Silane Compound] The functional silane compound can be used for the purpose of improving the printability of a liquid crystal alignment agent. Examples of such a functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, and 2-aminopropyl Triethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxy Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxy Silylpropyltriethylene triamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetic acid Ester, 9-trimethoxysilyl-3,6-diazanonanoic acid methyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethyl Oxysilane, glycidyloxymethyltrimethoxysilane, 2-glycidyloxyethyltrimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, and the like. When these functional silane compounds are blended in a liquid crystal alignment agent, the blending ratio of the functional silane compounds is preferably 2 parts by weight or less, and more preferably 0.02 parts by weight to 100 parts by weight of the total polymer. 0.2 parts by weight.

In addition, as other components, additives other than those described above may be appropriately blended as long as the objects and effects of the present invention are not hindered. Specific examples of the additives other than the above include compounds having at least one oxetanyl group in the molecule, antioxidants, surfactants, defoamers, sensitizers, dispersants, and adhesion promoters. , Antistatic agent, leveling agent, antibacterial agent, etc.

[Solvent] The liquid crystal alignment agent of the present invention is prepared as a liquid composition obtained by dispersing or dissolving the polymer (P) and other components used as necessary in an appropriate organic solvent.

Examples of the organic solvent used include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, and N, N-dimethylethyl Amine, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, 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 Diethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisoamyl ether, ethylene carbonate, propylene carbonate and the like. These organic solvents may be used alone or in combination of two or more.

The solid content concentration in the liquid crystal alignment agent (the ratio of the total weight of components other than the solvent of the liquid crystal alignment agent to the total weight of the liquid crystal alignment agent) may be appropriately selected in consideration of viscosity, volatility, and the like, and is preferably 1 weight. % To 10% by weight. That is, 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 as 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 becomes too small, and it is difficult to obtain a good 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 good liquid crystal alignment film. In addition, the viscosity of the liquid crystal alignment agent tends to increase and the coating property tends to decrease. .

A particularly preferred range of the solid content concentration varies depending on the method used when the liquid crystal alignment agent is applied to the substrate. For example, when the spinner method is used, the solid content concentration (the ratio of the total weight of all 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% to 4.5% by weight. Range. When using the printing method, it is particularly preferable to set the solid content concentration to a range of 3% to 9% by weight, and thereby set the solution viscosity to a range of 12 mPa · s to 50 mPa · s. When using the inkjet method, it is particularly preferable to set the solid content concentration in the range of 1% to 5% by weight, and thereby set the solution viscosity to the range of 3 mPa · s to 15 mPa · s. The temperature when preparing the liquid crystal alignment agent is preferably 10 ° C to 50 ° C, and more preferably 20 ° C to 30 ° C.

<Liquid crystal alignment film and liquid crystal display element> The liquid crystal alignment film of this invention can be formed using the liquid crystal alignment agent prepared as mentioned above. 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 it can be applied to various driving modes such as TN type, STN type, IPS type, FFS type, VA type, MVA type, polymer sustained alignment (PSA) type, and the like.

The liquid crystal display element can be manufactured, for example, by a method including the following steps (1) to (3). Step (1) uses a different substrate according to the required driving mode. Steps (2) and (3) are shared in each driving mode.

[Step (1): Formation of Coating Film] First, the liquid crystal alignment agent of the present invention is coated on 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, STN, VA, MVA, or PSA type liquid crystal display element, two substrates provided with a patterned transparent conductive film are used as a pair, and in each substrate The formation 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, respectively. Here, the substrate can be, for example, glass such as float glass, soda glass, or polyethylene terephthalate, polybutylene terephthalate, polyether, polycarbonate, or poly (alicyclic olefin). ) And other plastic transparent substrates. The transparent conductive film provided on one side of the substrate may be a NESA film (registered trademark of the American PPG Corporation) containing tin oxide (SnO ₂ ), or an indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) Indium tin oxide (ITO) film, etc. In order to obtain a patterned transparent conductive film, for example, the following methods can be used: a method of forming a pattern by forming a transparent conductive film without a pattern, and then forming a pattern by photolithography; and a method of using a mask having a desired pattern when forming a transparent conductive film Wait. When the liquid crystal alignment agent is applied, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface on which the coating film is formed may be coated with a functional silane compound, a functional titanium compound, or the like in advance. Pre-processing.

After the liquid crystal alignment agent is applied, it is preferable to perform preheating (prebaking) for the purpose of preventing sagging of the applied alignment agent. The pre-baking temperature is preferably 30 ° C to 200 ° C, more preferably 40 ° C to 150 ° C, and particularly preferably 40 ° C to 100 ° C. The pre-baking time is preferably 0.25 minutes to 10 minutes, and more preferably 0.5 minutes to 5 minutes. Then, a sintering (post-baking) step is performed for the purpose of completely removing the solvent, and also for the purpose of performing thermal sulfidation of the fluorinated acid structure present in the polymer as necessary. The calcination temperature (post-baking temperature) at this time is preferably 80 ° C to 300 ° C, and more preferably 120 ° C to 250 ° C. The post-baking time is preferably 5 minutes to 200 minutes, and more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this way 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 with a comb-shaped transparent conductive film or a metal film, and an electrode not provided A liquid crystal alignment agent is coated on one side of the opposite substrate, and then each coated surface is heated to form a coating film. The material, coating method, heating conditions after coating, the patterning method of the transparent conductive film or metal film, the substrate pretreatment, and the preferred film thickness and thickness of the coating film to be used. 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 cases (1-1) and (1-2), after the liquid crystal alignment agent is coated on the substrate, the organic solvent is removed to form a coating film that becomes an alignment film. In this case, when the polymer contained in the liquid crystal alignment agent is polyamidic acid, or polyamidate, or a fluorinated polymer having a fluorinated imine ring structure and a fluorinated acid structure, It is also possible to perform a dehydration ring-closing reaction by further heating after the formation of the coating film, thereby forming a coating film that is further imidized.

[Step (2): Alignment Process] In the case of manufacturing a TN, STN, IPS, or FFS liquid crystal display element, a process (alignment) for imparting liquid crystal alignment ability to the coating film formed in the step (1) is performed. deal with). As a result, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. Examples of the alignment treatment include a rubbing treatment and a photo-alignment treatment. The rubbing treatment is performed by rubbing a coating film in a certain direction with a roller wound with a cloth containing fibers such as nylon, rayon, and cotton, thereby imparting the coating film. Friction treatment of liquid crystal alignment ability; the photo alignment treatment irradiates a coating film formed on a substrate with light and imparts liquid crystal alignment ability to the coating film. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (1) may be directly used as a liquid crystal alignment film, but the coating film may be subjected to a rubbing treatment. In addition, the following treatment may also be performed on the liquid crystal alignment film after the rubbing treatment, so that the liquid crystal alignment film has different liquid crystal alignment capabilities in each region: by irradiating a part of the liquid crystal alignment film with ultraviolet rays, the A process of changing the pretilt angle of a part of the area; or a process of removing the resist film after forming a resist film on a part of the surface of the liquid crystal alignment film, and then performing a rubbing treatment in a direction different from the previous rubbing treatment. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. In the case of manufacturing a polymer sustained alignment (PSA) type liquid crystal display device, the following step (3) can be directly performed using the coating film formed in the step (1), but for the purpose of controlling the liquid crystal molecules The collapsing can be performed by a simple method for the purpose of alignment division, and can also be subjected to alignment processing such as weak friction processing. 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 having the liquid crystal alignment film formed as described above are prepared, and liquid crystal is disposed between the two substrates disposed opposite to each other, thereby manufacturing 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 conventionally known method. In this method, firstly, two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films face each other, and the peripheral portions of the two substrates are bonded together with a sealant. After filling the divided cell gap with liquid crystal, the injection hole is sealed to manufacture a liquid crystal cell. The second method is a method called a One Drop Fill (ODF) method. In this method, a predetermined portion of one of the two substrates on which the liquid crystal alignment film is formed is coated with a UV-curable sealant, for example, and liquid crystals are added dropwise to predetermined positions on the liquid crystal alignment film surface. Then, another substrate is bonded in a manner that the liquid crystal alignment film faces each other. Next, the liquid crystal is spread on 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 method, it is desirable to eliminate the liquid crystal by heating the liquid crystal cell manufactured as described above to a temperature at which the liquid crystal used obtains an isotropic phase, and then slowly cooling to room temperature. Flow alignment during filling.

As the sealant, for example, an epoxy resin containing a hardener and an alumina ball as a spacer can be used. Examples of the liquid crystal include nematic liquid crystals and dish liquid crystals. Among them, nematic liquid crystals are preferred. For example, Schiff base liquid crystals, azoxy liquid crystals, biphenyl liquid crystals, Phenylcyclohexane-based liquid crystal, ester-based liquid crystal, terphenyl-based liquid crystal, biphenylcyclohexane-based liquid crystal, pyrimidine-based liquid crystal, dioxane-based liquid crystal, bicyclooctane-based liquid crystal, cubane-based liquid crystal, etc. . In addition, these liquid crystals can also be used by adding the following substances: for example, cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonanoate, and cholesteryl carbonate ); Chiral agents sold under the trade names "C-15" and "CB-15" (Merck); p-decyloxymethylene-p-amino-2-methylbutane Ferroelectric liquid crystals such as cinnamate.

(3-2) In the case of manufacturing a PSA type liquid crystal display element, a liquid crystal cell is constructed in the same manner as in (3-1) above except that a photopolymerizable compound is injected or dropped together with the liquid crystal. Then, the liquid crystal cell is irradiated with light while a voltage is applied between the conductive films included in the pair of substrates. The voltage applied here may be, for example, 5 V to 50 V DC or AC. As the light to be irradiated, ultraviolet rays and visible rays including, for example, light having a wavelength of 150 to 800 nm can be used, and ultraviolet rays including light having a wavelength of 300 to 400 nm can be used. As a light source for irradiating light, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. The ultraviolet rays in the preferable 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, and the like. The amount of light irradiation is preferably 1,000 J / m ² to 200,000 J / m ² , and more preferably 1,000 J / m ² to 100,000 J / m ² .

Then, a liquid crystal display element can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell. Examples of the polarizing plate attached to the outer surface of the liquid crystal cell include a polarizing plate formed by sandwiching a polarizing film called an “H film” with a protective cellulose acetate film or a polarizing plate including the H film itself. The "H film" is a film formed by absorbing iodine while extending the orientation of polyvinyl alcohol. In addition, when the coating film is subjected to a rubbing treatment, the two substrates are arranged facing each other such that the rubbing directions in the respective coating films form a predetermined angle with each other, for example, orthogonally or anti-parallelly.

The liquid crystal display element of the present invention can be effectively applied to a variety of devices, such as: clocks, portable game consoles, word processors, notebook personal computers, car navigation systems, camcorders, and personal digital assistants. PDA), digital cameras, mobile phones, smart phones, various monitors, LCD TVs and other display devices.

[Examples] Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples.

In the following examples and comparative examples, the following methods were used to measure the fluorene imidization rate of polyfluorene imide in the polymer solution, the solution viscosity of the polymer solution, the weight average molecular weight of the polymer, and the epoxy equivalent. [Rhenimidization ratio of polyimide] A solution of polyimide was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethylimide. tetramethyl Silane as a standard material, was measured ¹ H- nuclear magnetic resonance ^{(1 H-Nuclear Magnetic Resonance,} 1 H-NMR) at room temperature. Based on the obtained ¹ H-NMR spectrum, the fluorene imidization ratio [%] was determined using the following formula (1).醯 Imidization rate [%] = (1-A ¹ / A ² × α) × 100 ... (1) (In the formula (1), A ¹ is a NH-group-derived compound that appears near a chemical shift of 10 ppm. Proton peak area, A ² is the peak area derived from other protons, α is the ratio of other protons to the number of one proton of the NH group in the polymer precursor (polyamic acid)) [Polymer solution Solution viscosity] The solution viscosity [mPa · s] of a polymer solution is a solution prepared at a polymer concentration of 10% by weight using a predetermined solvent, and measured at 25 ° C using an E-type rotary viscometer. [Weight average molecular weight of polymer] The weight average molecular weight is a polystyrene conversion value measured by gel permeation chromatography under the following conditions. Column: manufactured by Tosoh Co., Ltd., TSKgelGRCXLII Solvent: tetrahydrofuran Temperature: 40 ° C Pressure: 68 kgf / cm ² [epoxy equivalent] Measured 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)] A compound (MDA-1) was synthesized according to the following scheme 1. [Chemical 12]

A 0.5-liter four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring wing was charged with 16.5 g (0.090 mol) of 3,5-dinitroaniline and 14.2 under a nitrogen flow. g (0.180 mol) of pyridine and THF were dissolved, and the total amount was set to 80 ml. While cooling the flask in ice water, a solution prepared 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, followed by stirring for several minutes. The entire solution was transferred to a separating funnel, 1 equivalent of a hydrochloric acid solution was added, and after mixing, the aqueous layer was separated. Furthermore, after the operation of mixing 500 ml of pure water and the operation of taking out the water layer were performed 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 using an evaporator to obtain an intermediate (1) (yield: 95%).

Then, a 0.5-liter four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a thermometer, and a stirring blade was added with 4.80 g (0.020 mol) of the intermediate (1) and 25.4 g (0.400 mol) of Zinc, 4.28 g (0.080 mol) of ammonium chloride, 180 ml of THF, and 20 ml of EtOH were dissolved. While cooling the flask in ice water, 10 ml of pure water was added dropwise and the mixture was stirred. After the dropwise addition, the mixture was stirred at room temperature for 48 hours, and then filtered through celite. 100 ml of ethyl acetate was added to the filtrate, and the total amount was transferred to a separating funnel. The operation of mixing with 300 ml of pure water and the removal of the aqueous layer were performed three times, and then the lower organic layer was removed. , It was dried with anhydrous magnesium sulfate. The organic solvent was distilled off from the dried solution using 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)] Instead of using methylchloroformic acid and using ethylchloroformic acid and hexylchloroformic acid as starting materials, respectively, use In the same manner as the method for synthesizing the compound (MDA-1), a compound (MDA-2) and a compound (MDA-3) were obtained. [Chemical 13] [Chemical 14]

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

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

A 0.5-liter four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring wing was charged with 1.53 g (0.025 mol) of aminoethanol and 7.25 g (0.125 mol) under a nitrogen flow. Dissolve potassium fluoride, 17.3 g (0.125 mol) of potassium carbonate, and THF, and set the total amount to 80 ml. While cooling the flask in ice water, 3.20 g (0.026 mol) of propyl chloroformic 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 entire solution was transferred to a separating funnel, 500 ml of pure water was added and mixed, and the aqueous layer was separated. After this was performed three times in total, 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-dinitrobenzidine chloride, the compound (MDA-5) was obtained by the same method as the method for synthesizing the compound (MDA-1).

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

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

A 0.5-liter four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring wing was charged with 6.00 g (0.100 mol) of diaminoethane and 3.16 g (0.040) under a nitrogen flow. mol) of pyridine and THF were dissolved, and the total amount was set to 80 ml. While cooling the flask in ice water, 2.16 g (0.020 mol) of ethyl chloroformic 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 entire solution was transferred to a separating funnel, 500 ml of pure water was added, and after mixing, the aqueous layer was separated. After this was performed three times in total, 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-dinitrobenzidine chloride, the compound (MDA-7) was obtained by the same method as the method for synthesizing the compound (MDA-1).

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

In a 0.5-liter four-necked flask equipped with a nitrogen introduction tube and a stirring wing, 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 entire solution was transferred to a separating funnel, 300 ml of ethyl acetate and 500 ml of a saturated ammonium chloride aqueous solution were added, and after mixing, the aqueous layer was separated. After the liquid separation operation was performed 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, a 0.5-liter four-necked flask equipped with a nitrogen introduction tube, a dropping funnel, a reflux cooling tube, a thermometer, and a stirring wing was charged with 6.08 g (0.020 mol) of 2- (4-nitro) under a nitrogen flow. 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 under reflux at 120 ° C for 2 hours. Then, the entire solution was transferred to a separating funnel, 300 ml of ethyl acetate and 500 ml of a saturated ammonium chloride aqueous solution were added, and after mixing, the aqueous layer was separated. After the liquid separation operation was performed 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 using an evaporator to obtain 2- (4-nitro) phenoxy-5-nitro-cyanobenzene (yield: 85%). Then, in a four-necked flask having a capacity of 0.5 liters, which includes a nitrogen introduction tube, a stirring blade, and a dropping funnel, 6.02 g (0.020 mol) of 2- (4-nitro) phenoxy-5- was added under a nitrogen stream. Nitro-cyanobenzene and 50 ml of dehydrated dichloromethane were stirred. Then, 10 ml of dehydrated methanol was added dropwise using a dropping funnel. The obtained solution was distilled off by an evaporator to obtain 2- (4-nitro) phenoxy-5-nitro-N-methoxycarbonylaniline (yield: 95%). Then, the same method as the synthetic method of obtaining the compound (MDA-1) from the intermediate (1) in Synthesis Example 1A was used to obtain the compound (MDA-11) (yield: 89%).

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

In a 0.5-liter four-necked flask equipped with a nitrogen introduction tube and a stirring blade, 2.94 g (0.020 mol) of the intermediate (2) obtained in Synthesis Example 5A and synthesis of 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 room Stir at temperature for 12 hours. Then, the entire solution was transferred to a separating funnel, 300 ml of ethyl acetate and 500 ml of a saturated ammonium chloride aqueous solution were added and mixed, and the aqueous layer was separated. After the liquid separation operation was performed 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 using an evaporator to obtain an intermediate (4) (yield: 88%). Then, the same method as the synthetic method of obtaining the compound (MDA-1) from the intermediate (1) in Synthesis Example 1A was used to obtain the compound (MDA-14) (yield: 80%).

<Synthesis of Polymer> [Synthesis Example 1: Synthesis of polyimide (PI-1)] 2,3,5-tricarboxycyclopentylacetic acid dianhydride (100 mol parts as tetracarboxylic dianhydride ( TCA), 60 mol parts of p-phenylenediamine (PDA), 20 mol parts of 3,5-diamino benzoic acid cholesteryl esters (3,5-diamino benzoic acid) cholestanyl (HCDA) and 20 moles of compound (MDA-1), dissolved in N-methyl-2-pyrrolidone (NMP), and reacted at 60 ° C for 6 hours. A solution containing 20% by weight of polyamic acid was obtained. A small amount of the obtained polyamic acid solution was added, and NMP was added to prepare a solution having a polyamic acid concentration of 10% by weight. The measured solution viscosity was 56 mPa · s. Next, NMP was added to the obtained polyamic acid solution to prepare a solution having a polyamic acid concentration of 7% by weight, and each was added to the total amount of tetracarboxylic dianhydride to be 1.0 times mole. The pyridine and acetic anhydride were dehydrated and closed at 110 ° C for 4 hours. After the dehydration ring-closing reaction, the solvent in the system is replaced with new NMP (by this operation, the pyridine and acetic anhydride used in the dehydration ring-closing reaction are removed from the system; the same applies below), thereby obtaining a 26% by weight Polyfluorene imine (PI-1) solution with an imidization rate of about 60%.

[Synthesis Example 2 to Synthesis Example 15, Synthesis Example 22] In addition to changing the types and amounts of the tetracarboxylic dianhydrides and diamines used, and the amounts of pyridine and acetic anhydride used in the fluorenimidization, the following were changed. Except as shown in Table 1, in the same manner as in Synthesis Example 1, polyamidoimine (PI-2) to polyamidoimine (PI-16) were synthesized. The measurement results of the fluorene imidation ratio of the obtained polymer are shown in Table 1 below. In addition, in Synthesis Example 8, 1.5 mol parts of aniline was prepared as a monoamine together with tetracarboxylic dianhydride and diamine.

[Table 1]

In Table 1, the numerical value in parentheses of the tetracarboxylic dianhydride represents a use ratio [mole part] with respect to a total of 100 mol parts of the tetracarboxylic dianhydride used in polymer synthesis. The numerical value in parentheses of a diamine and a monoamine shows the usage ratio [mole part] with respect to the total 100 mole parts of the tetracarboxylic dianhydride used for polymer synthesis. The abbreviations in Table 1 have the following meanings. In addition, "-" in Table 1 means a compound which does not use this column. <Tetracarboxylic dianhydride> t-1: 2,3,5-tricarboxycyclopentylacetic 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-furyl) -naphtho [1,2-c] furan-1,3-dione (MTDA ) T-5: pyromellitic dianhydride (PMDA) t-6: 1R, 2S, 4S, 5R-cyclohexanetetracarboxylic dianhydride (PMDA-HS) <diamine> d-1: the following formula Compound d-2 represented by (d-1): Compound d-3 represented by the following formula (d-2): p-phenylenediamine (PDA) d-4: 4,4'-diaminodiphenyl Methyl 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) ) -Tetramethyldisilaxane d-10: Cholesteryl 3,5-diaminobenzoate (HCDA) d-11: Cholesteryloxy-2,4-diaminobenzene (HCODA ) D-12: 3,6-bis (4-aminobenzyloxy) cholestane d-13: compound represented by the formula (D-1-5) d-14: 1,3 -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: compound represented by the following formula (mda-11) mda-12: represented by the following formula (mda-12) Compound mda-13: compound represented by the following formula (mda-13) mda-14: compound represented by the following formula (mda-14) [Chem. 21] <Monoamine> m-1: aniline

[Synthesis Example 16: Synthesis of Polyamic Acid (PA-1)] 100 mol parts of 1,2,3,4-cyclobutanetetracarboxylic dianhydride (CB) as tetracarboxylic dianhydride, 30 mol parts of the compound represented by the formula (d-1) as a diamine, 40 mol parts of 2,2'-dimethyl-4,4'-diaminobiphenyl, and 30 mol parts Ear compound (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 polyamidic acid (PA-1). The obtained polyamic acid solution was divided into a small amount, and the viscosity of the solution was 180 mPa · s.

[Synthesis Example 17: Synthesis of Polyamic Acid (PA-2)] The same procedure as in Synthesis Example 16 was performed except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 above. By the same operation, a solution containing 10% by weight of polyamidic acid (PA-2) was thus obtained. The obtained polyamic acid solution was divided into a small amount, and the viscosity of the solution obtained by the measurement was 210 mPa · s. [Synthesis Example 18: Synthesis of Polyamic Acid (PA-3)] Except changing the type and amount of the tetracarboxylic dianhydride and diamine used as shown in Table 1, the same procedure as in Synthesis Example 16 was performed. By the same operation, a solution containing 10% by weight of polyamic acid (PA-3) was thus obtained. The obtained polyamic acid solution was divided into a small amount, and the viscosity of the obtained solution was 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 2- (3,4-epoxy ring) was added. Hexyl) ethyltrimethoxysilane (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 the reaction was performed at 80 ° C. for 6 hours while stirring under reflux. After the reaction, the organic layer was taken out and washed with a 0.2% by weight ammonium nitrate aqueous solution until the washed water became neutral, and then the solvent and water were distilled off under reduced pressure to obtain reactivity as a thick transparent liquid. Polyorganosiloxane (EPS-1). As a result of ¹ H-NMR analysis of this reactive polyorganosiloxane, as a theoretical intensity, an epoxy-based peak was obtained around a chemical shift (δ) = 3.2 ppm, and it was confirmed that no epoxy group was generated during the reaction. Side effects. The weight average molecular weight Mw of the obtained reactive polyorganosiloxane was 3,500, and the epoxy equivalent was 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 4- Dodecyloxybenzoic acid and 0.10 g of UCAT 18X (trade name, manufactured by San-Apro) as a catalyst were reacted for 48 hours at 100 ° C while stirring. After the reaction, the solution obtained by adding ethyl acetate to the reaction mixture was washed three times with water, and the organic layer was dried with magnesium sulfate, and then the solvent was distilled off, thereby obtaining 9.0 g of a liquid crystal-aligning polyorganosiloxane (APS). -1). The weight average molecular weight Mw of the obtained polymer was 9,900.

[Synthesis Example 20: Synthesis of Polyamic Acid (PA-4)] The same procedure as in Synthesis Example 16 was performed except that the types and amounts of tetracarboxylic dianhydride and diamine used were changed as shown in Table 1 above. By the same operation, a solution containing 10% by weight of polyamidic acid (PA-4) was thus obtained. The obtained polyamic acid solution was divided into a small amount, and the viscosity of the obtained solution was 212 mPa · s. [Synthesis Example 21: Synthesis of Polyamic Acid (PA-5)] Except changing the type and amount of the tetracarboxylic dianhydride and diamine used as shown in Table 1, the same procedure as in Synthesis Example 16 was performed. By the same operation, a solution containing 10% by weight of polyamidic acid (PA-5) was thus obtained. The obtained polyamic acid solution was divided into a small amount, and the viscosity of the solution was 250 mPa · s.

[Example 1] <Preparation of liquid crystal alignment agent> Polyimide (PI-1) obtained as a polymer was added with NMP and butyl cellosolve (BC) as organic solvents, and the solvent composition was NMP. : BC = 50: 50 (weight ratio), solution with 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 (S1).

<Manufacture of VA-type liquid crystal cell> The prepared liquid crystal alignment agent was applied to a glass substrate with a transparent electrode including an ITO film (with a thickness of 1 mm) using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). ) On the transparent electrode surface, heating (pre-baking) on a hot plate at 80 ° C for 1 minute, and then heating (post-baking) on a hot plate at 200 ° C for 60 minutes to form a coating film with an average film thickness of 0.08 μm (LCD 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, the outer edge of the surface having the liquid crystal alignment film was coated with an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm, and then the liquid crystal alignment film faces were opposed to each other. In this way, a pair of substrates are overlapped and crimped to harden the adhesive. Next, a nematic liquid crystal (Merck, MLC-6608, manufactured by Merck) 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 light-curing adhesive to produce a VA type. LCD cell.

<Evaluation of reliability> The reliability of a liquid crystal display element was evaluated using the manufactured liquid crystal cell. Evaluation was performed as follows. 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 retention rate (VHR1) after 167 milliseconds after the application was released was measured. Next, the liquid crystal cell was left in an 80 ° C oven under a light emitting diode (LED) lamp for 200 hours, and then left at room temperature to naturally cool 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 retention rate (VHR2) was measured after 167 milliseconds since the application was released. As the measurement device, "VHR-1" manufactured by Toyo Technica (Stock) was used. The change rate (ΔVHR) of the VHR at this time was calculated according to the following formula (2), and the reliability was evaluated based on the ΔVHR. The evaluation was performed as follows: a case where ΔVHR was less than 1% was evaluated as reliability "good (◎)", a case where 1% or more and less than 2% was evaluated as reliability "good (○)", and 2% or more and A case where it is less than 3% is evaluated as a reliability “may (Δ)”, and a case where it is 3% or more is evaluated as a reliability “bad (×)”. As a result, ΔVHR = 1.9 [%] in Example 1, and the reliability was “good (○)”. ΔVHR [%] = (VHR1-VHR2) / (VHR1) × 100… (2)

<Evaluation of the amount of outgassing> When manufacturing a liquid crystal cell, the liquid crystal alignment agent (S1) was apply | coated to the board | substrate by the same operation, and pre-baking and post-baking were performed, and the coating film was formed on the board | substrate. For this post-baked substrate, thermal decomposition gas chromatography was used (JPS-700 manufactured by Japan Analytical Industries, thermal decomposition conditions were 590 ° C × 5 sec, and Gas Chromatography (GC) column BPX-5) To analyze the amount of outgassing. Regarding the amount of outgas, a calibration curve was prepared using a standard product, and the detected mass (%) was calculated from the mass comparison of the amounts of the thermally decomposed monomers introduced. The evaluation was performed as follows: A case where the amount of the detected substance was less than 4% was evaluated as "excellent (◎)", a case where 4% or more and less than 7% was evaluated as "good (○)", and 7% or more When it is less than 10%, it is evaluated as “possible (Δ)”, and when it is more than 10%, it is evaluated as “poor (×)”. As a result, in Example 1, the amount of outgassing 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 manner as in Example 1 was performed except that the composition of the liquid crystal alignment agent was changed to that shown in Table 2 below. Liquid crystal alignment agents were prepared separately. In addition, using each liquid crystal alignment agent, a liquid crystal cell was manufactured in the same manner as in Example 1, and the manufactured liquid crystal cell was evaluated. The evaluation results are shown in Table 2 below.

[Example 7] γ as an organic solvent was added so that the polyimide (PI-8) obtained as a polymer and the polyamidic acid (PA-1) had a solid content weight ratio of 20:80 -Butyrolactone (BL), NMP and butyl cellosolve (BC), a solution with a solvent composition of BL: NMP: BC = 70: 15: 15 (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 (S7).

<Manufacture of TN-type liquid crystal cell> Using the liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent was applied on the transparent electrode surface of a glass substrate with a transparent electrode including an ITO film. After heating (pre-baking) on a hot plate at 80 ° C for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 200 ° C for 10 minutes to form a coating film having an average film thickness of 0.08 μm. This coating film was rubbed with a friction machine having a roll wound with a rayon cloth at a roller rotation number of 400 rpm, a table moving speed of 30 mm / sec, and a gross press-in length of 0.4 mm to give the liquid crystal alignment ability. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then it was dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. In addition, the operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm was coated on the outer edge of the surface having the liquid crystal alignment film, and the friction directions were orthogonal. In a method, a pair of substrates are overlapped and crimped so that the liquid crystal alignment film faces are opposite to each other, so that the adhesive is hardened. Next, a nematic liquid crystal (Merck, 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 light-curing adhesive to produce TN. Type liquid crystal cell. <Evaluation of reliability and amount of outgas> Using the manufactured TN-type liquid crystal cell, the reliability and the amount of outgas were evaluated by the same method as in Example 1. As a result, ΔVHR = 0.6 [%] , The reliability is "excellent", and the amount of outgassing is 6%, which becomes the evaluation of "good".

[Example 8] <Preparation of Liquid Crystal Alignment Agent> A method in which polyimide (PI-9) and polyamidic acid (PA-2) obtained as polymers was 40:60 in terms of weight ratio of solid content Γ-butyrolactone (BL), NMP, and butyl cellosolve (BC) as organic solvents were added, and the solvent composition was BL: NMP: BC = 40: 40: 20 (weight ratio), and the solid content concentration was 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 prepared liquid crystal alignment agent was applied to a transparent electrode of a glass substrate with a transparent electrode including an ITO film using a liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.). On the surface, after heating (pre-baking) on a hot plate at 80 ° C. for 1 minute to remove the solvent, heating (post-baking) on a hot plate at 200 ° C. for 10 minutes to form a coating film having an average film thickness of 0.08 μm. This coating film was rubbed with a rubbing machine having a roll wound with a rayon cloth at a roll number of 1,000 rpm, a table moving speed of 20 mm / sec, and a gross press-in length of 0.4 mm to impart liquid crystal alignment ability. Then, ultrasonic cleaning was performed in ultrapure water for 1 minute, and then it was dried in a 100 ° C clean oven for 10 minutes, thereby obtaining a substrate having a liquid crystal alignment film. In addition, the operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm was applied to an outer edge of a surface having a liquid crystal alignment film, and the friction direction became antiparallel. In a manner, a pair of substrates are overlapped and crimped so that the liquid crystal alignment film faces are opposite to each other, so that the adhesive is hardened. Next, a nematic liquid crystal (Merck, 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 light-curable adhesive to manufacture IPS. / FFS type liquid crystal cell. <Evaluation of reliability and amount of outgas> Using the manufactured IPS / FFS type liquid crystal cell, the reliability and the amount of outgas were evaluated by the same method as in Example 1, and the result was: ΔVHR = 0.6 [ %], The reliability is "excellent", and the amount of outgassing is 6%, making it "good".

[Example 9] <Preparation of liquid crystal alignment agent> A method of obtaining polyimide (PI-10) and polyorganosiloxane (APS-1) as a polymer in a ratio of 95: 5 by weight of solid content Add NMP and butyl cellosolve (BC) as organic solvents to make a solution with 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] To 10 g of nematic liquid crystal (Merck, MLC-6608), 0.3% by weight of the following formula (pc-1) was added. The indicated photopolymerizable compound was mixed to obtain a liquid crystal composition LC1. [Chemical 22]

<Manufacture of PSA-VA liquid crystal cell> Using the liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent was applied to two glass substrates each having an 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 FIG. 1 to FIG. 3, and is divided into a plurality of regions. A heating plate at 80 ° C. After heating (pre-baking) for 1 minute to remove the solvent, it is heated (post-baking) for 10 minutes on a 200 ° C hot plate to form a coating film with an average film thickness of 800 Å. In addition, the operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. 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, the outer edge of the surface having the liquid crystal alignment film was coated with an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm, and then the liquid crystal alignment film faces were opposed to each other. In this way, a pair of substrates are overlapped and crimped to harden the adhesive. Then, the prepared liquid crystal composition LC1 is filled between a pair of substrates from a liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curable adhesive. Then, in a state where a voltage was applied between the conductive films of the obtained liquid crystal cell, light irradiation was performed at an irradiation amount of 100,000 J / m ² . Thus, a PSA-VA type liquid crystal cell was obtained. <Evaluation of reliability and amount of outgas> Using the manufactured PSA-VA type liquid crystal cell, the reliability and the amount of outgas were evaluated by the same method as in Example 1, and the result was: ΔVHR = 0.4 [ %], Reliability was "excellent", and the amount of outgassing was 2%, which was evaluated as "excellent".

[Example 12] <Preparation of liquid crystal alignment agent> To obtain polyamic acid (PA-3) as a polymer, NMP and butyl cellosolve (BC) as organic solvents were added, and the solvent composition was NMP: BC = 50: 50 (weight ratio), solution with 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 (S12).

<Manufacturing of IPS / FFS type liquid crystal cell using photo-alignment method> Using the liquid crystal alignment film printer (manufactured by Japan Photo Printing Co., Ltd.), the prepared liquid crystal alignment agent was applied to a substrate having a transparent electrode including an ITO film. The transparent electrode surface of the glass substrate was heated (pre-baked) on a hot plate at 80 ° C. for 1 minute to remove the solvent. Then, a Hg-Xe lamp was used to irradiate polarized ultraviolet light including a bright line of 254 nm from the substrate normal at an irradiation amount of 700 mJ / cm ² , and then heated (post-baked) on a hot plate at 200 ° C. for 10 minutes. , Forming a coating film having an average film thickness of 800 Å provided to the liquid crystal alignment film. In addition, the operation was repeated to obtain a pair (two pieces) of substrates having a liquid crystal alignment film. Then, for one of the pair of substrates, an epoxy resin adhesive with alumina balls having a diameter of 5.5 μm was applied to an outer edge of a surface having a liquid crystal alignment film to polarize the polarized ultraviolet rays. The direction in which the surface is projected onto the substrate becomes parallel, and a pair of substrates are overlapped and crimped so that the liquid crystal alignment film faces face each other, so that the adhesive is hardened. Next, a nematic liquid crystal (Merck, 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 light-curable adhesive to manufacture IPS. / FFS type liquid crystal cell.

<Evaluation of reliability and amount of outgas> Using the IPS / FFS type liquid crystal cell manufactured by the photo-alignment method described above, the same method as in Example 1 was used to evaluate the reliability and amount of outgas, and the result was : ΔVHR = 0.5 [%], reliability was "excellent", and the amount of outgassing was 3%, which was evaluated as "excellent".

[Example 13 to Example 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. In addition, using each liquid crystal alignment agent, a liquid crystal cell was manufactured in the same manner as in Example 12, and the manufactured liquid crystal cell was evaluated. The evaluation results are shown in Table 2 below.

[Table 2]

In Table 2, the numerical value of the amount of polymer represents the use ratio [part 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 "possible", and the amount of outgassing was also small. In contrast, in Comparative Examples 1 to 3, and Comparative Example 5, the reliability was evaluated as “bad”, and in Comparative Example 4, the amount of outgassing was large and evaluated as “bad”. In addition, 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 evaluation was lower than the examples is not certain, but one of the factors is considered to be: In the case of a tertiary alkyl structure, decarboxylation is mainly performed to generate an amine group. Therefore, the cross-linking reaction is more difficult to proceed than in the example. In addition, in the case of Comparative Example 4 in which a diamine having a linear structure of 10 carbon atoms was used as a thermally decomposable monomer, an outgas was easily generated due to the excessively long carbon chain.

1‧‧‧ITO electrode

2‧‧‧ Slit

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 an example. FIG. 3 is a view showing an electrode pattern of a transparent electrode film used in an example.

Claims (7)

A liquid crystal alignment agent comprising at least one polymer selected from the group consisting of polyamic acid, polyamidate, polyimide, and polyamidamine, and at least a part of the polymer has the following Polymer (P) having a partial structure represented by formula (1), In the formula (1), A ¹ and A ² are each independently a hydrogen atom or a substituted or unsubstituted monovalent chain hydrocarbon group, and the total number of carbons of A ¹ and A ² is 0 to 7; 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, X ¹ is a single bond or a divalent organic group; “*” indicates a bonding bond; the polymer (P) is A polymer having a partial structure derived from a diamine represented by the following formula (e), In the formula (e), Z ³ is a single bond or a divalent linking group, 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 a carbon number a monovalent hydrocarbon group having 1 to 6; N4 and n5 are each independently an integer of 0 to ^{2; a 1, a 2, Y} 1, R 1 and X ^1, respectively, in the formula (1) have the same meaning as the polymerization (P) is a polymer having a partial structure derived from an acid anhydride selected from 2,3,5-tricarboxycyclopentylacetic dianhydride, 2,4,6,8-tetracarboxybicyclo [ 3.3.0] octane-2: 4,6: 8-dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride At least one of the group consisting of anhydride and 1,2,4,5-cyclohexanetetracarboxylic dianhydride. According to the liquid crystal alignment agent described in item 1 of the scope of patent application, the polymer (P) is a polymer having a partial structure derived from a diamine represented by the following formula (c), In 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 a portion represented by the formula (1) Structured monovalent organic groups, 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; n1 and n2 are respectively Is independently an integer of 0 to 2, m1 and m2 are independently 0 or 1; wherein, when 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 when m1 = 0 and m2 = 1, B ¹ , B ^2, and B ³ At least one of them has a partial structure represented by the formula (1). According to the liquid crystal alignment agent described in claim 1 or 2, the polymer (P) is a polymer having a partial structure derived from 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 n 3 is an integer of 0 to 2; A ¹ , A ² , Y ¹ , R ^1, and X ¹ are respectively as described above. Formula (1) has the same meaning. According to the liquid crystal alignment agent described in item 3 of the scope of patent application, among the diaminophenyl groups of the compound represented by the formula (d), two primary amine groups are represented by the formula (1). Structure is bonded to the 3,5-position. According to the liquid crystal alignment agent described in item 1 or item 2, the polymer (P) has a structure represented by the formula (1) and is selected from the group consisting of a nitrogen-containing heterocyclic ring, a secondary amine group, and At least one nitrogen-containing structure in the group consisting of a secondary amine group. A liquid crystal alignment film is formed using the liquid crystal alignment agent according to any one of claims 1 to 5 in the scope of patent application. A liquid crystal display element includes the liquid crystal alignment film according to item 6 of the patent application scope.