TWI709611B - Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display device, phase difference film and method for manufacturing the same, polymer and compound - Google Patents

Abstract

A liquid crystal alignment agent for obtaining a liquid crystal display device having various properties in good balance is provided. The liquid crystal alignment agent contains a polymer (P) obtained by using at least one compound (C') selected from a group consisted of a compound (C) and a compound (C1) for reaction. The compound (C) has a following structure (a) and a following structure (b). The compound (C1) has the following structure (a) and a following structure (b1), wherein a reactive group which participates in polymerization is not bonded on an aromatic ring group in the structure (a). (a): an aromatic amine structure obtained by bonding two or three aromatic ring groups to the same nitrogen atom. (b): a chain structure such as a bi-valent chain hydrocarbon group having 6 or more carbons. (b1): a structure such as a bi-valent chain hydrocarbon group having 1 to 5 carbons, -O-, and -S-, etc.

Description

Liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, phase difference Membrane and its manufacturing method, polymer and compound

The invention relates to a liquid crystal alignment agent, a liquid crystal alignment film, a liquid crystal display element, a retardation film, a method for manufacturing a retardation film, a polymer and a compound.

In the past, liquid crystal display elements have developed a variety of driving methods that differ in the electrode structure, the physical properties of the liquid crystal molecules used, and the manufacturing steps, such as known twisted nematic (TN) type or super twisted nematic (Super Twisted Nematic, Various liquid crystal display elements such as STN type, Vertical Alignment (VA) type, In-Plane Switching (IPS) type, Fringe Field Switching (FFS) type, etc. These liquid crystal display elements have a liquid crystal alignment film for aligning liquid crystal molecules. In terms of good properties such as heat resistance, mechanical strength, and affinity with liquid crystals, the material of the liquid crystal alignment film is usually polyamide acid or polyimide.

In addition, in recent years, with the advancement of high-definition liquid crystal display elements, the demand for reducing the residual image phenomenon or suppressing the decrease in contrast has increased. In order to meet the requirements, various liquid crystal alignment agents have been proposed (for example, refer to Patent Literature 1 to Patent Literature 6. ). These Patent Documents 1 to 6 describe that in the liquid crystal alignment agent, the diphenylamine unit is introduced into the liquid crystal alignment agent to achieve reduction in the accumulated charge in the liquid crystal display element, suppression of the decrease in contrast, and the like.

Specifically, Patent Document 1 discloses that polyamide acid or polyimide obtained by reacting diamine containing 4,4'-diaminodiphenylamine with tetracarboxylic dianhydride is contained in In the liquid crystal alignment agent. Patent Document 2 discloses that diamines containing oligoanilines such as (4-aminophenyl) (4-((4-aminophenyl)amino)phenylamine and the like are reacted with tetracarboxylic dianhydride The obtained polyimide is contained in the liquid crystal alignment agent. In addition, Patent Document 3 discloses that a compound having two or more diphenylamine units is added separately from a polymer such as polyimide or polyimide. Alternatively, polyamide acid obtained by reacting diamine having two or more diphenylamine units with tetracarboxylic dianhydride is included in the liquid crystal alignment agent.

Patent Document 4 discloses that 1,3-bis-4-(N,N-(4-aminophenyl)aminophenyl)propane is used as a compound having two diphenylamine structures in the molecule The polyamide acid obtained by reacting the diamine and tetracarboxylic dianhydride is contained in the liquid crystal alignment agent. In addition, Patent Document 5 and Patent Document 6 disclose that diamine containing N,N'-bis(4-aminophenyl)-N,N'-dimethylethylenediamine and tetracarboxylic dianhydride The polyamide acid obtained by the reaction is contained in the liquid crystal alignment agent.

In addition, a variety of optical materials are used in liquid crystal display elements. The retardation film is used for the purpose of eliminating the coloring of the display or the viewing angle dependence of the display color and contrast ratio that changes with the visual direction. The retardation film is known to include a liquid crystal alignment film formed on the surface of a substrate such as a triacetyl cellulose (TAC) film, and a liquid crystal alignment film formed on the surface of the liquid crystal alignment film by curing a polymerizable liquid crystal. Liquid crystal layer. In addition, in recent years, when the liquid crystal alignment film in the retardation film is produced, the following photo-alignment method is used: a radiation-sensitive organic thin film formed on the surface of a substrate is irradiated with polarized or non-polarized radiation. Provide liquid crystal alignment ability; a liquid crystal alignment agent for a retardation film useful for making a liquid crystal alignment film using the method is proposed (for example, refer to Patent Document 7).

[Prior Art Literature] [Patent Literature]

[Patent Document 1] Japanese Patent No. 4052307

[Patent Document 2] Japanese Patent Laid-Open No. 2000-44683

[Patent Document 3] Japanese Patent No. 4924832

[Patent Document 4] Japanese Patent Laid-Open No. 2011-207786

[Patent Document 5] Japanese Patent Laid-Open No. 2012-155311

[Patent Document 6] Japanese Patent No. 5130907

[Patent Document 7] Japanese Patent Laid-Open No. 2012-37868

However, in the case of using the liquid crystal alignment agent of Patent Document 1, the liquid crystal The direct current (DC) residual in the display element is not sufficiently alleviated, and there is a tendency for a long time until the residual image disappears. In addition, in the existing liquid crystal alignment agent containing a polymer using diamine having a plurality of diphenylamine units as a monomer, although the DC residual mitigation performance is improved, the aromatic concentration increases, so there is a problem of the liquid crystal alignment film Disadvantages such as low transmittance. In addition, AC (Alternating Current) residual image performance, which is one of the characteristics that affect the contrast of the liquid crystal display element, is insufficient, and various characteristics cannot be provided with good balance. In addition, with the diversification of liquid crystal display elements in recent years, liquid crystal display elements are conceived to be used in more severe conditions and are required to be excellent in heat resistance.

The liquid crystal display is manufactured by arranging a pair of substrates on which a liquid crystal alignment film is formed facing each other, and disposing liquid crystals between the pair of facing substrates. At this time, the pair of substrates are bonded together using a sealant such as epoxy resin. Here, in the touch panel type display panel represented by a smartphone or a tablet computer, in order to further expand the movable area of the touch panel and to take into account the miniaturization of the liquid crystal panel (element), an attempt is made to achieve a narrow frame. With the narrowing of the frame of the liquid crystal panel, uneven display may be visually recognized around the sealant, and the display quality may not be sufficiently satisfactory. In order to achieve high definition and long life of the liquid crystal display, a liquid crystal display element in which display unevenness (high bezel unevenness resistance) around the sealant is hard to be recognized is required.

The present invention is made in view of the above-mentioned problems, and one of the objects is to provide a liquid crystal alignment agent for obtaining a liquid crystal display element, the liquid crystal alignment film of the liquid crystal display element has good transmittance and has less display unevenness around the sealant. And well-balanced It has various characteristics such as after-image characteristics, high contrast, and heat resistance.

The inventors of the present invention actively studied in order to achieve the above-mentioned problems of the prior art, and found that by including a polymer having a specific structure as a polymer component in a liquid crystal alignment agent, the problem can be solved, thereby completing the present invention. Specifically, the present invention provides the following liquid crystal alignment agent, liquid crystal alignment film, liquid crystal display element, retardation film, retardation film manufacturing method, polymer, and compound.

One aspect of the present invention is to provide a liquid crystal alignment agent containing a polymer obtained by reacting at least one compound (C') selected from the group consisting of compound (C) and compound (C1) (P), the compound (C) has the following structure (a) and the following structure (b), the compound (C1) has the following structure (a) and the following structure (b1), and is in the structure The aromatic ring group in (a) is not bonded with a reactive group participating in polymerization.

(a) An aromatic amine structure in which two or three aromatic ring groups are bonded to the same nitrogen atom.

(b) Selected from a divalent chain hydrocarbon group having 6 or more carbon atoms, and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO- , -COO-, -COS- or -Si(CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) substituted with a chain structure in the group consisting of divalent groups.

(b1) Selected from a bivalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR ³ -, -NR ³ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted divalent groups, -O-, -S-, -CO-, -NR ³ CO- (R ³ is hydrogen Atom or monovalent organic group), -COO-, -COS-, and -Si(CH ₃ ) _2-

Another aspect of the present invention is to provide a liquid crystal alignment film formed using the liquid crystal alignment agent. In addition, a liquid crystal display element including the liquid crystal alignment film and a retardation film including the liquid crystal alignment film are provided. Furthermore, the other is to provide a method for manufacturing a retardation film, which includes: a step of coating the liquid crystal alignment agent on a substrate to form a coating film; a step of irradiating the coating film with light; The step of applying polymerizable liquid crystal to the irradiated coating film and curing it.

Another aspect of the present invention is to provide a compound represented by the following formula (1-1), a compound represented by the following formula (1-2), and a compound represented by the following formula (1-3). In addition, a polymer selected from the group consisting of polyamide, polyamide, and polyimide is provided. The polyamide, polyamide, and polyimide are selected At least one compound selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic acid diester compound, and tetracarboxylic acid diester dihalide, and a compound selected from the group consisting of the following formula (1-1), The compound represented by the following formula (1-2) and the diamine of at least one of the group consisting of the compound represented by the following formula (1-3) are used for reaction, and are obtained.

(In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently Ground is a single bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring and is bonded to a nitrogen atom, and B ¹ is a divalent organic group In the case of A ¹ , A ² and B ¹ , at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to the nitrogen atom; when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring. It is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹¹ includes a carbon number 6 or more At least one methylene group in the bivalent chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -(R is a hydrogen atom or a monovalent organic group) a divalent group substituted with a group; wherein, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least any of A ¹ and A ³ One is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group)

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group with 6 or more carbon atoms; A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are the same as those in the formula (1-1) The same meaning; where, when L ¹² is an alkanediyl group having 6 to 10 carbons, at least one of A ¹ and A ³ is a monovalent organic group, or a combination of B ¹ and B ² At least any one is a divalent organic group)

[化3]

(In formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group; wherein, at least 2 of A ⁷ , A ⁸ and A ⁹ One is an aromatic ring and is bonded to a nitrogen atom; L ⁴ is the structure (b1), L ⁵ is a single bond or a divalent organic group)

Using the liquid crystal alignment agent containing the polymer (P) as a polymer component, it is possible to obtain a liquid crystal that has less display unevenness around the sealant, and has a good balance of low residual image, high contrast, and heat resistance. Display components. In addition, a liquid crystal alignment film with good transmittance can be obtained. In addition, the polymer (P) has good solubility in solvents, and the storage stability of the liquid crystal alignment agent is also good.

10‧‧‧LCD display element

11a, 11b‧‧‧glass substrate

12‧‧‧LCD alignment film

13‧‧‧Top electrode

14‧‧‧Insulation layer

15‧‧‧Bottom electrode

16‧‧‧Liquid crystal layer

C1‧‧‧The part enclosed by the dotted line

d1‧‧‧Line width of electrode

d2‧‧‧The distance between the electrodes

Fig. 1 is a schematic configuration diagram of an FFS type liquid crystal cell.

2(a) and FIG. 2(b) are schematic plan views of the top electrode used when the liquid crystal display element is manufactured by the photo-alignment method. Fig. 2(a) is a top view of the top electrode, and Fig. 2(b) is a partially enlarged view of the top electrode.

Fig. 3 is a diagram showing four systems of drive electrodes.

4(a) and 4(b) are schematic plan views of top electrodes used when manufacturing liquid crystal display elements by rubbing treatment. Fig. 4(a) is a top view of the top electrode, and Fig. 4(b) is a partially enlarged view of the top electrode.

Hereinafter, each component contained in the liquid crystal alignment agent of the present invention and other components optionally blended as necessary will be described.

<Polymer (P)>

The liquid crystal alignment agent of the present invention includes a polymer (P) obtained by reacting at least one compound (C') selected from the group consisting of compound (C) and compound (C1) as a polymer component, and The compound (C) has the structure (a) and the structure (b), the compound (C1) has the structure (a) and the structure (b1), and is in the structure (a) No reactive group participating in polymerization is bonded to the aromatic ring group. In addition, below, the structure (a) is also referred to as "aromatic amine structure (a)", and the structure (b) is also referred to as "chain structure (b)".

. Compound (C) (Aromatic amine structure (a))

The aromatic amine structure (a) of the compound (C) is a structure in which two or three aromatic ring groups are bonded to the same nitrogen atom. The aromatic ring group may be a group obtained by removing a hydrogen atom from the ring portion of an aromatic ring. Specifically, examples include aromatic hydrocarbon rings such as a benzene ring, a toluene ring, a naphthalene ring, and an anthracene ring. Among the aromatic rings such as pyridine ring, pyrimidine ring, pyrazine ring, pyridazine ring, triazine ring and other aromatic heterocycles The group formed by removing the hydrogen atom from the ring part, etc. Among these groups, a benzene ring is preferable from the viewpoint of good affinity with liquid crystal.

The number of the aromatic amine structure (a) in the molecule of the compound (C) is 1 or 2 or more, and from the viewpoint of improving the performance of the residual DC mitigation, it is preferably 2 or more. In addition, from the viewpoint of the transmittance of the liquid crystal alignment film and the solubility of the polymer, two to four are more preferable, and two or three are particularly preferable.

(Chain structure (b))

The chain structure (b) of the compound (C) is a divalent chain hydrocarbon group with 6 or more carbons, or at least one methylene group in a divalent chain hydrocarbon group with 6 or more carbons is- O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) substituted Group.

The bivalent chain hydrocarbon group in the chain structure (b) refers to a hydrocarbon group that does not contain a cyclic structure in the main chain, but is composed of only a linear or branched chain structure. The divalent chain hydrocarbon group in the chain structure (b) has only to have 6 or more carbon atoms, and specific examples thereof include hexadiyl, heptanediyl, octanediyl, nonanediyl, and decanediyl. , Dodecanediyl, tetradecanediyl, eicosanediyl and other saturated hydrocarbon groups with 6 to 30 carbons; at least one carbon-carbon bond of the saturated hydrocarbon group with 6 to 30 carbons is a double bond or Unsaturated hydrocarbon groups with 6 to 30 carbon atoms in triple bonds, etc. These hydrocarbon groups may be linear or branched, and are preferably linear.

When the chain structure (b) is a divalent chain hydrocarbon group having 6 or more carbon atoms, the chain hydrocarbon group preferably has 6 to 30 carbon atoms, and more preferably 6 to 20 carbon atoms.

In the chain structure (b), at least one methylene group in a bivalent chain hydrocarbon group with 6 or more carbon atoms is used as -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) in the case of a group substituted, the number of substitutions may be one or more It can be set appropriately according to the carbon number. The number of carbons before the methylene group is substituted with the functional group is preferably 6-30, and more preferably 7-20.

The monovalent organic group of R includes, for example, a chain hydrocarbon group having 1 to 5 carbon atoms such as an alkyl group or an alkenyl group, and a chain hydrocarbon group having 1 to 5 carbon atoms having -O-, -CO- and other groups, protecting groups for amine groups, etc. Specific examples of the protecting group of the amino group include, for example, tertiary butoxycarbonyl, benzyloxycarbonyl, 1,1-dimethyl-2-haloethyloxycarbonyl, 1,1-dimethyl -2-cyanoethyloxycarbonyl, 9-fluorenylmethyloxycarbonyl, allyloxycarbonyl, 2-(trimethylsilyl)ethoxycarbonyl, etc., preferably tertiary butoxy Carbonyl.

The number of the chain structure (b) in the molecule of the compound (C) may be one or two or more. Preferably it is 1 to 5, More preferably, it is 1 to 3. In addition, the compound (C) preferably has an aromatic amine on the main chain of the compound (C), specifically the longest carbon chain in the compound (if it has a functional group, the longest carbon chain including the functional group) Structure (a) and chain structure (b).

In terms of reducing the surface unevenness of the liquid crystal alignment film, the molecular weight of the compound (C) is preferably 1,200 or less. Therefore, it is preferable to set the number of the aromatic amine structure (a) and the chain length of the chain structure (b) so that the molecular weight of the compound (C) is within the above range. More preferably, the molecular weight is 1,000 or less, and particularly preferably 800 or less.

. Compound (C1)

The compound (C1) has the aromatic amine structure (a) and the structure (b1). Among them, in the compound (C1), no reactive group participating in polymerization is bonded to the aromatic ring group in the aromatic amine structure (a). The reactive group differs according to the main skeleton of the polymer (P). For example, when the main skeleton of the polymer (P) is polyamide acid or polyimide, the reactive group is an acid anhydride group or For the primary amine group, in the case of polyester, the reactive group is a hydroxyl group or a carboxyl group, and in the case of polyamide, the reactive group is a carboxyl group or a primary amine group.

The description of the aromatic ring of the aromatic amine structure (a) possessed by the compound (C1) can be applied to the description of the compound (C). There is preferably one aromatic amine structure (a) in one molecule of the compound (C1).

The structure (b1) of the compound (C1) is selected from a divalent chain hydrocarbon group having 1 to 5 carbon atoms, and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO -, -NR ³ -, -NR ³ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -Substituted divalent group, -O-, -S-, -CO-,- A structure in the group consisting of NR ³ CO-, -COO-, -COS-, and -Si(CH ₃ ) _2- (R ³ is a hydrogen atom or a monovalent organic group). In addition, the compound (C1) may have only one type of these structures in the molecule, or may have two or more types in the molecule.

Specific examples of the bivalent chain hydrocarbon group having 1 to 5 carbon atoms in the structure (b1) include, for example, methylene, ethylene, propanediyl, butanediyl, pentadiyl, vinylene, Propylene diyl, butylene diyl, pentenediyl, etc. These hydrocarbon groups may be linear or branched, and are preferably linear.

In the structure (b1), at least one methylene group in a bivalent chain hydrocarbon group with 1 to 5 carbon atoms is used as -O-, -S-, -CO-, -NR ³ -, -NR ³ CO -, -COO-, -COS- or -Si(CH ₃ ) ₂ -In the case of a divalent group substituted by -, the number of substitutions may be one or more, and it may be appropriate according to the number of carbons set up. The description of the monovalent organic group of R ³ can be applied to the description of R of the compound (C).

The number of the structure (b1) in the molecule of the compound (C1) may be one or two or more. It is preferably two or more, and particularly preferably two. The description of the compound (C) can be applied to the molecular weight of the compound (C1).

The main skeleton of the polymer (P) includes, for example, polyamide, polyimide, polyamide, polyester, polyamide, polysiloxane, polyorganosiloxane, and cellulose. Derivatives, polyacetal derivatives, polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylate derivatives, etc. The polymer (P) can be used by appropriately selecting one kind or two or more kinds selected from these polymers according to the use of the liquid crystal alignment agent and the like. In addition, (meth)acrylate means to include acrylate and methacrylate. The polymer (P) may have the aromatic amine structure (a) and the chain structure (b) or structure (b1) in any of the main chain and the side chain of the polymer, and is preferably polymerized. The main chain of the substance has the structure.

Among them, the main skeleton of the polymer (P) is preferably at least one selected from the group consisting of polyamide acid, polyimide, and polyamide ester, and more preferably selected from the group consisting of polyamide acid, polyimide, and polyamide ester. At least one of the aromatic amine structure (a) and the chain structure (b) or the structure (b1) consisting of polyamide acid, polyimide, and polyamide ester. The polymer (P) preferably uses the compound (C') as a monomer and The obtained polymer.

Here, the "main chain" of the polymer in the present invention refers to the "dry" part containing the longest chain of atoms in the polymer. In addition, it is permissible that the "dry" part includes a ring structure. Therefore, the phrase "having the aromatic amine structure (a) and the chain structure (b) or structure (b1) in the main chain of the polymer" means that these structures constitute a part of the main chain. Among them, in the polymer (P), it is not excluded that the aromatic amine structure (a), the chain structure (b) and the structure (b1) also exist in parts other than the main chain, such as side chains (self-polymerizing On the branched part of the “stem” of the object).

[Polyamic acid (P)]

When the polymer (P) is polyamide (hereinafter also referred to as "polyamide (P)"), for example, it can be obtained by reacting tetracarboxylic dianhydride and diamine.

(Tetracarboxylic dianhydride)

Examples of the tetracarboxylic dianhydride used for synthesizing the polyamide acid (P) include aliphatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aromatic tetracarboxylic dianhydride. As a specific example of these tetracarboxylic dianhydrides, aliphatic tetracarboxylic dianhydrides include, for example, butane tetracarboxylic dianhydride, etc.; examples of alicyclic tetracarboxylic dianhydrides 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-dianhydride, bicyclo[3.3.0] Octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride, bicyclo[2.2.1]heptane-2,3,5,6-tetracarboxylic acid 2:3,5 ：6-dianhydride, 4,9-dioxatricyclo[5.3.1.0 ^2,6 ]undecane-3,5,8,10-tetraone, 1,2,4,5-cyclohexanetetra Carboxylic dianhydride, bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, ethylenediaminetetraacetic dianhydride, cyclopentanetetracarboxylic dianhydride, ethylenedi Ethylene glycol bis(anhydrotrimellitate), 1,3-propylene glycol bis(anhydrotrimellitate), etc.; aromatic tetracarboxylic acid Examples of the dianhydride include pyromellitic dianhydride. In addition to these, tetracarboxylic dianhydride described in JP 2010-97188 A can be used. In addition, the tetracarboxylic dianhydride used in the synthesis of polyamide acid may be used alone or in combination of two or more of these compounds.

The tetracarboxylic dianhydride used for synthesizing the polyamide acid (P) preferably contains a tetracarboxylic dianhydride selected from the group consisting of 1,2,3,4-rings in terms of allowing good liquid crystal alignment and solubility in solvents. Butane tetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxide -3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetra Hydro-2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4 -Diketone-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-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclic [ 5.3.1.0 ^2,6 ]Undecane-3,5,8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid At least one compound in the group consisting of dianhydride, cyclopentanetetracarboxylic acid dianhydride, 1,3-propanediol bis(trimellitic acid anhydride) and pyromellitic dianhydride (hereinafter also referred to as "specific four Carboxylic dianhydride"). Relative to the total amount of tetracarboxylic dianhydride used for the synthesis of polyamide acid, the usage amount of the specific tetracarboxylic dianhydride is preferably 5 mol% or more, more preferably 10 mol% or more, It is particularly preferable to set it as 20 mol% or more.

(Diamine)

The diamine used for synthesizing the polyamide acid (P) preferably contains a diamine selected from the group having the aromatic amine structure (a) and the chain structure (b) (hereinafter also referred to as "diamine (C)"), and at least one compound (C') in the group consisting of the compound (C1) having the structure (a1) and the structure (b1).

. Diamine (C)

The diamine (C) preferably has a structure capable of introducing the aromatic amine structure (a) and the chain structure (b) into the main chain of the polymer (P). Specifically, the following is preferable The compound represented by formula (1).

(In formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently A single bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom, and when B ¹ is a divalent organic group Below, at least two of A ¹ , A ² and B ¹ are bonded to a nitrogen atom by an aromatic ring; when B ² is a single bond, at least one of A ³ and A ⁴ is bonded by an aromatic ring Bonded to a nitrogen atom, when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹ includes the structure (b) Base)

Regarding the formula (1), the monovalent organic groups in A ¹ and A ³ include, for example, a monovalent hydrocarbon group, in which -O-, -COO-, -CO- are introduced between the carbon-carbon bonds in the monovalent hydrocarbon group , -NHCO-, -S-, -NH- and other functional groups formed by monovalent groups, as well as protecting groups for amine groups, etc. In addition, in A ¹ and A ³ , the hydrogen atom bonded to the carbon atom of the hydrocarbon group may be substituted with a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc.) or a hydroxyl group. Specific examples of the protective group of the amino group include the groups exemplified in the description of R of the chain structure (b). Preferably it is a tertiary butoxycarbonyl group.

Examples of the hydrocarbon group include chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups. Here, the "chain hydrocarbon group" in this specification is as described above. The "alicyclic hydrocarbon group" refers to a hydrocarbon group containing only an alicyclic hydrocarbon structure as a ring structure and not an aromatic ring structure. However, it does not need to be composed only of the structure of an alicyclic hydrocarbon, and a hydrocarbon group having a chain structure in a part thereof is also included. In addition, the "aromatic hydrocarbon group" refers to a hydrocarbon group containing an aromatic ring structure as a ring structure. However, it does not need to be composed only of an aromatic ring structure, and a chain structure or alicyclic hydrocarbon structure is also included in a part thereof.

As a specific example of the monovalent hydrocarbon group in A ¹ and A ³ , the chain hydrocarbon group includes, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, and decyl. , Dodecyl, tetradecyl, eicosyl and other C1-C30 alkyl groups; vinyl, propenyl, butenyl and other C2-C30 alkenyl groups; ethynyl, propynyl Such as alkynyl groups with 2 to 30 carbon atoms, etc.; these hydrocarbon groups may be linear or branched. In addition, examples of the alicyclic hydrocarbon group include cyclopentyl, cyclohexyl, norbornyl, adamantyl, etc.; examples of the aromatic hydrocarbon group include phenyl, tolyl, benzyl, and phenethyl.

The divalent organic groups in A ² , A ⁴ , B ¹ and B ² include, for example, a divalent hydrocarbon group, in which -O-, -COO-, -CO-,-are introduced between the carbon-carbon bonds in the divalent hydrocarbon group Divalent groups such as NHCO-, -S-, -NH- and other functional groups, and the hydrogen atoms bonded to carbon atoms in these groups may be substituted with halogen atoms or hydroxyl groups. Specific examples of the divalent hydrocarbon group include groups obtained by removing one hydrogen atom from each group exemplified in the monovalent hydrocarbon group. In addition, in the compound represented by the formula (1), the structure surrounding the nitrogen atom in the formula (1) corresponds to the aromatic amine structure (a).

It is preferable that at least one of B ¹ and B ² is a single bond, and it is more preferable that both B ¹ and B ² are single bonds.

L ¹ is a divalent group including the chain structure (b). Preferable specific examples of L ¹ include, for example, groups represented by the following formula (2) and the like.

(In formula (2), L ² and L ³ are each independently the structure (b); Q is a divalent group represented by the following formula (3) or formula (4); n is an integer of 0-4 ; "*" means the bond)

(In formula (3), A ⁵ is a hydrogen atom or a monovalent organic group; R ¹ and R ² are substituents, which may be the same or different from each other; "*" represents a bond)

(In formula (4), A ⁶ is a hydrogen atom or a monovalent organic group; "*" represents a bond)

In the above formula (3) and formula (4), the monovalent organic group of A ⁵ and A ⁶ can be applied to the description of the monovalent organic group of A ¹ and A ³ . Preferably, n in the formula (2) is 0 or 1.

Specific examples of the group represented by the formula (2) include groups represented by the following formulas (2-1) to (2-25), and the like.

[化8]

(In the formula, "*" means a bond)

Preferable specific examples of the compound represented by the formula (1) include, for example, a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2).

(In the formula (1-1), L ¹¹ is a formula containing at least one methylene group in a bivalent chain hydrocarbon group with 6 or more carbon atoms as -O-, -S-, -CO-, -NR-,- NRCO-, -COO-, -COS- or -Si(CH ₃ ) _2- (R is a hydrogen atom or a monovalent organic group) substituted with a divalent group; A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ^{2 have the} same meanings as in the above formula (1); wherein, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is hydrogen Atom, or at least one of B ¹ and B ² is a divalent organic group)

(In formula (1-2), L ¹² is a divalent group containing a divalent chain hydrocarbon group with 6 or more carbon atoms; A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are the same as those in the formula (1) The same meaning)

The L ¹¹ in the formula (1-1) may have only one methylene group that has at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbons as -O-, -S-, -CO-,- The group substituted by NR-, -NRCO-, -COO-, -COS-, or -Si(CH ₃ ) ₂ -may have a plurality of groups. Preferable specific examples of L ¹¹ include the group represented by the formula (2) (wherein, L ² and L ³ are a combination of at least one methylene group in a divalent chain hydrocarbon group having 6 or more carbon atoms with -O -, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted group), etc.

In the case where L ¹¹ contains an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom, and it is preferable that both A ¹ and A ³ are hydrogen atoms.

L ¹² in the above formula (1-2) may have only one divalent chain hydrocarbon group having a carbon number of 6 or more, or may have a plurality of them. Preferable specific examples of L ¹² include the group represented by the above formula (2) (where L ² and L ³ are a divalent chain hydrocarbon group having 6 or more carbon atoms) and the like.

When the alkanediyl group possessed by L ¹² has 6 to 10 carbon atoms, the compound represented by the formula (1-2) is preferably that at least one of A ¹ and A ³ is a monovalent organic group, or At least any of B ¹ and B ² is a divalent organic group. In the case where A ¹ and A ³ in the formula (1-1) are hydrogen atoms, L ¹² is preferably a group represented by the formula (2) where L ² and L ³ are carbon 7 or more The divalent chain hydrocarbon group is more preferably the divalent chain hydrocarbon group having 11 or more carbon atoms.

Preferred specific examples of the diamine (C) include, for example, compounds represented by the following formulas (DA-1) to (DA-10) and formula (DA-41). Moreover, the said diamine (C) can be used individually by 1 type or in combination of 2 or more types.

[化12]

(In the formula, Ph represents phenyl)

. Diamine (C1)

The diamine (C1) preferably has a structure capable of introducing the aromatic amine structure (a) and the structure (b1) into the main chain of the polymer (P). Specifically, the following formula ( 1-3) The compound represented.

(In formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, A ⁸ and A ⁹ are each independently a single bond or a divalent organic group; wherein, at least 2 of A ⁷ , A ⁸ and A ⁹ One is an aromatic ring and is bonded to a nitrogen atom; L ⁴ is the structure (b1), L ⁵ is a single bond or a divalent organic group)

Regarding the above formula (1-3), the description of the monovalent organic group of A ¹ and A ³ of the above formula (1) can be applied to the monovalent organic group of A ⁷ . The description of A ² and A ⁴ of the above formula (1) can be applied to the divalent organic groups of A ⁸ and A ⁹ . The divalent organic group of L ⁵ includes, for example, a divalent chain hydrocarbon group having 1 to 20 carbon atoms, and at least one methylene group in the chain hydrocarbon group is represented by -O-, -S-, -CO-,- NR ⁴ -, -NR ⁴ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted divalent groups, -O-, -S-, -CO-, -NR ⁴ CO -, -COO-, -COS-, and -Si(CH ₃ ) _2- (R ⁴ is a hydrogen atom or a monovalent organic group) and the like. Among these organic groups, L ⁵ is preferably structure (b1).

Preferred specific examples of the diamine (C1) include, for example, compounds represented by the following formulas (DA-22) to (DA-40). Moreover, the said diamine (C1) can be used individually by 1 type or in combination of 2 or more types.

[化15]

The diamine used in the synthesis of polyamide acid (P) may be only the diamine (C'), and diamine (C') may use other diamines other than the above.

Examples of other diamines that can be used here include aliphatic diamines, alicyclic diamines, aromatic diamines, and diamino organosiloxanes. As specific examples of these diamines, aliphatic diamines include, for example, metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, and hexamethylenediamine Etc.; for example, alicyclic diamines include: 1,4-diaminocyclohexane, 4,4'-methylenebis(cyclohexylamine), 1,3-bis(aminomethyl)cyclohexyl Alkanes, etc.; examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenyl Thioether, 4,4'-diaminodiphenylamine, 1,7-bis(4-aminophenoxy)heptane, 1,5-diaminonaphthalene, 2,2'-dimethyl -4,4'-diaminobiphenyl, 2,2'-bis(trifluoromethyl)-4,4'-diaminobiphenyl, 4,4'-diaminodiphenyl ether, 2 ,2-Bis[4-(4-aminophenoxy)phenyl]propane, 9,9-bis(4-aminophenyl)fluorene, 2,2-bis[4-(4-aminobenzene) (Oxy)phenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-(p-phenylene diisopropylidene) bisaniline, 4,4' -(Phenylenediisopropylidene)bisaniline, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, 2 ,6-Diaminopyridine, 2,4-diaminopyrimidine, 3,6-diaminocarbazole, N,N'-bis(4-aminophenyl)-benzidine, 1,4-bis -(4-Aminophenyl)-piperazine, 3,5-diaminobenzoic acid, dodecyloxy-2,4-diaminobenzene, tetradecyloxy-2,4- Diaminobenzene, pentadecyloxy-2,4-diaminobenzene, hexadecyloxy-2,4-diaminobenzene, octadecyloxy-2,4-diamine Benzene, dodecyloxy-2,5-diaminobenzene, tetradecyloxy-2,5-diaminobenzene, pentadecyloxy-2,5-diaminobenzene , Hexadecyloxy-2,5-diaminobenzene, octadecyloxy-2,5-diaminobenzene, cholesteryloxy-3,5-diaminobenzene, bile Stearyloxy-3,5-diaminobenzene, cholestyloxy-2,4-diaminobenzene, cholesteryloxy-2,4-diaminobenzene, 3,5 -Cholesteryl diaminobenzoate, cholesteryl 3,5-diaminobenzoate, lanosteryl 3,5-diaminobenzoate, 3,6-bis(4- Aminobenzyloxy)cholestane, 3,6-bis(4-aminophenoxy)cholestane, 4-(4'-trifluoromethoxybenzyloxy)cyclohexyl -3,5-diaminobenzoate, 4-(4'-trifluoromethylbenzyloxy)cyclohexyl-3,5-diaminobenzoate, 1,1-bis( 4-((aminophenyl)methyl)phenyl)-4-butylcyclohexane, 1,1-bis(4-((aminophenyl)methyl)phenyl)-4-heptyl Cyclohexane, 1,1-bis(4-((aminophenoxy)methyl)phenyl)-4-heptylcyclohexane, 1,1-bis(4-((aminophenyl) (Methyl)phenyl)-4-(4-heptylcyclohexyl)cyclohexane, 2,4-Diamino-N,N-diallylaniline, 4-aminobenzylamine, 3-aminobenzylamine, 1-(2,4-diaminophenyl)piperazine- 4-carboxylic acid, 1,3-bis(N-(4-aminophenyl)piperidinyl)propane, α-amino-ω-aminophenylalkylene, 1-(4-aminophenyl) )-2,3-Dihydro-1,3,3-trimethyl-1H-inden-5-amine, 1-(4-aminophenyl)-2,3-dihydro-1,3,3 -Trimethyl-1H-indene-6-amine, 4-aminophenyl-4'-aminobenzoate, 4,4'-[4,4'-propane-1,3-diylbis (Piperidine-1,4-diyl)) diphenylamine, 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine, the following formula (DA-18) The compound represented and the compound represented by the following formula (D-1), etc.; [化17]

(式(D-1)中，X^I及X^II分別獨立地為單鍵、-O-、*-COO-或者*-OCO-(*表示與式中的苯環鍵結的結合鍵)，R^I為碳數1~3的烷二基，R^II為單鍵或碳數1~3的烷二基，a為0或1，b為0~2的整數，c為1~20的整數，d為0或1；其中，a及b不會同時為0)

(In the formula (D-1), X ^I and X ^II are each independently a single bond, -O-, *-COO- or *-OCO- (* represents a bond to the benzene ring in the formula), R ^I is an alkanediyl group with 1 to 3 carbons, R ^II is a single bond or alkanediyl group with 1 to 3 carbons, a is 0 or 1, b is an integer from 0 to 2, and c is an integer from 1 to 20 , D is 0 or 1; where a and b will not be 0 at the same time)

Examples of diaminoorganosiloxanes include 1,3-bis(3-aminopropyl)-tetramethyldisiloxane, etc. In addition, Japanese Patent Laid-Open No. 2010-97188 can be used. The recorded diamine.

The divalent group represented by "-X ^I -(R ^I -X ^II ) _d -" in the formula (D-1) is preferably an alkanediyl group having 1 to 3 carbon atoms, *-O-, *- COO- or *-OC ₂ H ₄ -O- (wherein, the bond with "*" is bonded to the diaminophenyl group). Specific examples of the group "-C _c H _2c+1 "include, 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-nonadecane Group, n-eicosyl, etc. The two amino groups in the diaminophenyl group are preferably located at the 2,4-position or the 3,5-position relative to other groups.

Specific examples of the compound represented by the formula (D-1) include, for example, compounds represented by the following formulas (D-1-1) to (D-1-3).

In addition, the other diamines used for the synthesis of polyamide acid may be used alone or by appropriately selecting two or more of these compounds.

The diamine used in the synthesis of the polyamide acid (P) of the present invention is preferably relative to the total amount of the diamine used in the synthesis, and the use ratio of the diamine (C') is set to 0.5 mol% or more . If it is less than 0.5 mol%, there is a tendency that the effect of the present invention cannot be sufficiently obtained. It is more preferably 2 mol% or more, particularly preferably 5 mol% or more, and particularly preferably 10 mol% or more. In addition, the upper limit of the use ratio of the diamine (C′) can be arbitrarily set within the range of 100 mol% or less with respect to the total amount of the diamine used in the synthesis. In the case of realizing the improvement effects (such as printability, voltage retention, liquid crystal orientation, etc.) brought about by the addition of other diamines, it is preferable to set the use ratio of the diamine (C') to 95 mol %the following.

When the liquid crystal alignment agent of the present invention is used to manufacture TN type, STN type or In the case of a vertical alignment type liquid crystal display element, at least a part of the polymer (P) contained in the liquid crystal alignment agent may be a group having the ability to impart a pretilt angle to the coating film (hereinafter also referred to as "pretilt" Inclination performance base ") polymer. Examples of the pretilt expressive group include: C4-20 alkyl group, C4-20 fluoroalkyl group, C4-C20 alkoxy group, C17-51 group having a steroid skeleton , Groups with polycyclic structures, etc.

In order to obtain the polyamide acid (P) having a pretilt angle expressive group, it is preferable to include a diamine having a pretilt angle expressive group in the monomer composition in terms of ease of introduction of the pretilt angle expressive group Of the aggregation. Specifically, it can be synthesized by using a diamine having a pretilt angle expressive group as another diamine.

In the case of using a diamine having a pretilt angle expressive group when synthesizing polyamide acid (P), from the viewpoint of sufficiently exhibiting high pretilt angle characteristics, compared to all the diamines used in the synthesis, the The amount of diamine used is preferably 5 mol% or more, and more preferably 10 mol% or more.

In the case of imparting liquid crystal alignment ability to the coating film produced using the liquid crystal alignment agent of the present invention by the photo-alignment method, at least a part of the polymer (P) contained in the liquid crystal alignment agent can be made to have photo-alignment Sexually structured polymers. Here, the so-called photo-alignment structure is a concept including both a photo-alignment group and a decomposition type photo-alignment portion. Specifically, the photo-alignment structure can be a group that exhibits photo-alignment by photoisomerization, photodimerization, photolysis, etc., for example, a couple-containing group containing azobenzene or its derivative as a basic skeleton A nitrobenzene group, a group with a cinnamic acid structure containing cinnamic acid or its derivatives as the basic skeleton, a group containing chalcone or Chalcone-containing groups with its derivatives as the basic skeleton, benzophenone-containing groups with benzophenone or its derivatives as the basic skeleton, and coumarin or its derivatives as the basic skeleton Coumarin group, polyimide-containing structure containing polyimine or its derivative as the basic skeleton, etc.

For example, when polyamide acid, polyimide, and polyamide ester as the polymer (P) have a photo-alignment structure, it is preferable to have a decomposition type photo-alignment portion as the photo-alignment structure Specifically, a polymer having a bicyclo[2.2.2]octene skeleton or a cyclobutane skeleton is preferable. By having the specific skeleton as described above, the liquid crystal alignment of the coating film can be made more favorable. For example, a polyamide acid (P) having a bicyclo[2.2.2]octene skeleton or a cyclobutane skeleton can be obtained by containing bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxylic acid It is obtained by reaction of the tetracarboxylic dianhydride of at least any one of acid dianhydride and cyclobutane tetracarboxylic dianhydride, and the diamine containing the said diamine (C').

[Molecular weight regulator]

When synthesizing polyamide acid (P), it is also possible to synthesize a terminal-modified polymer by using an appropriate molecular weight modifier together with tetracarboxylic dianhydride and diamine as described above. By using the terminal modification type polymer, the coating properties (printability) of the liquid crystal alignment agent can be further improved without impairing the effects of the present invention.

Examples of the molecular weight modifier include acid monoanhydrides, monoamine compounds, and monoisocyanate compounds. As specific examples of these compounds, acid monoanhydrides include, for example, maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecane Base succinic anhydride, n-hexadecyl succinic anhydride, etc.; monoamine compounds include, for example: aniline, cyclohexylamine, n-butylamine, n-pentyl Amine, n-hexylamine, n-heptylamine, n-octylamine, etc.; monoisocyanate compounds include, for example, phenyl isocyanate, naphthyl isocyanate, 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 with respect to 100 parts by weight of the total of the tetracarboxylic dianhydride and diamine used.

The diamine (C) and diamine (C1) can be synthesized by appropriately combining common methods of organic chemistry. As an example of the method, for the compound represented by the formula (1), the following method can be cited: synthesizing a dinitro intermediate having a nitro group instead of the primary amino group in the formula, and then using an appropriate reduction The nitro group of the obtained dinitro intermediate is aminated.

The method of synthesizing the dinitro intermediate can be appropriately selected according to the target compound. As an example of the method, if the compound represented by the formula (1) is enumerated, for example, the following method can be enumerated: a secondary amine compound having corresponding A ¹ , A ² and L ¹ and a halogenated nitrobenzene Method of reaction; method of reacting halide with corresponding A ¹ , A ² and L ¹ with secondary amine compound containing nitrophenyl; method of making carboxylic acid with corresponding amino phenyl and nitro group , A method of reacting with a diol having a corresponding L ¹ ; a method of reacting a diamine compound having corresponding A ¹ , A ² and L ¹ with a halogenated nitrobenzene having a corresponding B ¹ ; Corresponding amino phenyl and nitro hydroxyl group-containing compounds, a method of reacting with a halide having a corresponding L ¹ , etc.

The reaction to obtain the nitro intermediate is preferably carried out in an organic solvent. Here, the organic solvent may be a solvent that does not affect the reaction, for example Examples include methanol, ethanol, tetrahydrofuran, toluene, dimethyl sulfide, dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone and the like. In addition, this reaction can also be carried out in the presence of a catalyst as necessary.

The reduction reaction of the dinitro intermediate is preferably carried out in an organic solvent using a catalyst such as palladium on carbon, platinum oxide, zinc, iron, tin, and nickel. Examples of the organic solvent used here include ethyl acetate, toluene, tetrahydrofuran, and alcohols. However, the synthesis procedure of diamine (C) and diamine (C1) is not limited to the above-mentioned method.

[Synthesis of Polyamide (P)]

The use ratio of the tetracarboxylic dianhydride to the diamine provided by the synthesis reaction of the polyamide acid (P) of the present invention is preferably 1 equivalent relative to the amino group of the diamine, and the acid anhydride group of the tetracarboxylic dianhydride becomes 0.2 equivalent~ The ratio of 2 equivalents is more preferably a ratio of 0.3 to 1.2 equivalents.

The synthesis reaction of polyamide acid is preferably carried out in an organic solvent. The reaction temperature at this time is preferably -20°C to 150°C, more preferably 0°C to 100°C. In addition, the reaction time is preferably 0.1 hour to 24 hours, more preferably 0.5 hour to 12 hours.

Here, the organic solvent includes, for example, aprotic polar solvents, phenolic solvents, alcohols, ketones, esters, ethers, halogenated hydrocarbons, and hydrocarbons. As specific examples of these organic solvents, aprotic polar solvents include, for example, N-methyl-2-pyrrolidone, N,N-dimethylacetamide, N,N-dimethylformamide, and dimethylformamide. Trimethylene, γ-butyrolactone, tetramethylurea, hexamethylphosphatidylamine, etc.; examples of phenolic solvents include phenol, m-cresol, xylenol, halogenated phenol, etc.; examples of alcohols include: Methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene Glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, etc.; examples of ketones include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc.; Examples of the ester include: ethyl lactate, butyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, diethyl oxalate , Diethyl malonate, isoamyl propionate, isoamyl isobutyrate, etc.; ethers include, for example, diethyl ether, diisoamyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol- N-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether, ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, Diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, etc.; halogenated hydrocarbons include, for example, dichloromethane, 1 , 2-Dichloroethane, 1,4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, etc.; the hydrocarbons include, for example, hexane, heptane, octane, benzene, toluene , Xylene, etc.

Among these organic solvents, it is preferable to use one or more selected from the group consisting of aprotic polar solvents and phenolic solvents (organic solvents of the first group), or organic solvents selected from the first group A mixture of one or more kinds and one or more kinds selected from the group consisting of alcohols, ketones, esters, ethers, halogenated hydrocarbons and hydrocarbons (organic solvents 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. The usage amount (α) of the organic solvent is preferably such that the total amount (β) of the tetracarboxylic dianhydride and diamine is 0.1% by weight to 50% by weight with respect to the total amount (α+β) of the reaction solution.

As described above, a reaction solution obtained by dissolving polyamide acid (P) is obtained. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, or the polyamide acid (P) contained in the reaction solution can be isolated and then supplied to the preparation of the liquid crystal alignment agent, or the isolated polyamide acid (P) can also be supplied to the preparation of the liquid crystal alignment agent. (P) After purification, it is provided to the preparation of the liquid crystal alignment agent. In the case where polyimide is made into polyimide by dehydration and ring closure of polyamic acid (P), the reaction solution may be directly supplied to the dehydration and ring-closure reaction, or the polyimide contained in the reaction solution ( P) is isolated and then supplied to the dehydration ring-closing reaction, or the isolated polyamide acid (P) can be purified and then supplied to the dehydration ring-closing reaction. The isolation and purification of polyamic acid can be performed according to a known method.

[Polyurate (P)]

The polyamide (hereinafter also referred to as polyamide (P)) as the polymer (P) can be obtained, for example, by the following method: [I] By making the polyamide obtained by the synthesis reaction A method of synthesizing by reacting amide acid (P) with a hydroxyl-containing compound, a halide, an epoxy-containing compound, etc.; [II] a method of reacting a tetracarboxylic acid diester with a diamine; and [III] A method of reacting tetracarboxylic acid diester dihalide and diamine.

In addition, the "tetracarboxylic acid diester" in the present specification refers to a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified, and the remaining two are carboxyl groups. The so-called "tetracarboxylic acid diester dihalide" refers to a compound in which two of the four carboxyl groups of the tetracarboxylic acid are esterified and the remaining two are halogenated.

Here, the hydroxyl group-containing compound used in the method [I] includes, for example, alcohols such as methanol, ethanol, and propanol; and phenols such as phenol and cresol. In addition, the halide example Examples include: bromomethane, bromoethane, bromooctadecane, chloromethane, chlorooctadecane, 1,1,1-trifluoro-2-iodoethane, etc., containing epoxy groups Examples of the compound include propylene oxide. The tetracarboxylic acid diester used in the method [II] can be obtained by ring-opening the tetracarboxylic dianhydride using the alcohols. In addition, the tetracarboxylic acid diester dihalide used in the method [III] can be obtained by reacting the tetracarboxylic acid diester obtained in the above-mentioned manner with an appropriate chlorinating agent such as sulfite chloride. The diamine used in the method [II] and the method [III] preferably contains the diamine (C′), and the other diamine may be used as needed. In addition, the polyamide (P) may have only an amide structure, or may be a partial ester product in which an amide structure and an amide structure coexist.

[Polyimide (P)]

The polyimide (hereinafter also referred to as polyimine (P)) as the polymer (P) can be prepared by dehydrating and ring-closing the polyimide (P) synthesized in the manner described above. Obtained by amination.

The polyimide (P) may be a complete amide compound obtained by dehydrating and ring-closing all the amide acid structure of the polyimide acid (P) as its precursor, or it may be only the amide Part of the amino acid structure undergoes dehydration and ring closure, and the partial amide acid structure and the amide ring structure coexist. The imidization rate of the polyimide contained in the liquid crystal alignment agent of the present invention is preferably 30% or more, more preferably 40% to 99%, and particularly preferably 50% to 99%. This imidization rate is the sum of the number of amide acid structures and the number of amide ring structures with respect to the polyimide, and the ratio of the number of amide ring structures is expressed as a percentage. Here, a part of the imine ring may be an isoimide ring.

The dehydration ring closure of polyamide acid is preferably carried out by the following method: the method of heating the polyamide acid; or the polyamide acid is dissolved in an organic solvent, and a dehydrating agent and a dehydration ring-closing catalyst are added to the solution. A method of heating is required. Among them, the latter method is preferred.

In the method of adding a dehydrating agent and a dehydration ring-closing catalyst to the polyamide acid solution, the dehydrating agent can be, for example, acid anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride. The amount of the dehydrating agent used is preferably 0.01 mol to 20 mol with respect to 1 mol of the amide structure of the polyamide acid. As the dehydration ring-closing catalyst, for example, tertiary amines such as pyridine, collidine, lutidine, and triethylamine can be used. The amount of the dehydration ring-closing catalyst 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-closing reaction include organic solvents exemplified as those used in the synthesis of polyamide acid. The reaction temperature of the dehydration ring-closing reaction is preferably 0°C to 180°C, more preferably 10°C to 150°C. The reaction time is preferably 1.0 hour to 120 hours, more preferably 2.0 hours to 30 hours.

The reaction solution containing polyimine (P) is obtained as described above. The reaction solution can be directly supplied to the preparation of the liquid crystal alignment agent, the dehydrating agent and the dehydration ring-closing catalyst can be removed from the reaction solution and then supplied to the preparation of the liquid crystal alignment agent, or the polyimide can be isolated and then supplied to the liquid crystal alignment agent Alternatively, the isolated polyimine can be purified and then supplied to the preparation of the liquid crystal alignment agent. These purification operations can be performed according to known methods. In addition to this, polyimide (P) can also be obtained by imidization of polyimide (P).

Polyamide acid and polyamide as polymer (P) obtained in the manner The ester and polyimide are preferably made into a solution with a concentration of 15% by weight, with 20mPa. s~1,800mPa. The solution viscosity of s is more preferably 50mPa. s~1,500mPa. The solution viscosity of s. In addition, the solution viscosity (mPa.s) of the polymer is based on a concentration of 15% by weight prepared with a good solvent for the polymer (such as γ-butyrolactone, N-methyl-2-pyrrolidone, etc.) The polymer solution is a value measured at 25°C using an E-type rotary viscometer.

The polystyrene conversion weight average molecular weight (Mw) measured by gel permeation chromatography (Gel Permeation Chromatography, GPC) of the polyamide acid, polyamide ester and polyimide is preferably 1,000 to 500,000 , More preferably 2,000 to 300,000. In addition, the molecular weight distribution (Mw/Mn) represented by the ratio of Mw and the number average molecular weight (Mn) in terms of polystyrene measured by GPC is preferably 15 or less, and more preferably 10 or less. By being within the molecular weight range, good alignment and stability of the liquid crystal display element can be ensured.

<Other ingredients>

The liquid crystal alignment agent of the present invention contains the polymer (P) as described above, and may contain other components as necessary. 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 group-containing compounds"), functional silane compounds, Metal chelating compounds, hardening accelerators, surfactants, etc.

[Other polymers]

The other polymers can be used to improve solution properties or electrical properties. The other polymer may be, for example, a polymer obtained without using the compound (C'). The main skeleton is not particularly limited. Specifically, for example, polyamides, polyimines, polyamides, polyorganosiloxanes, polyesters, polyamides, cellulose derivatives, polyacetals, Polystyrene derivatives, poly(styrene-phenylmaleimide) derivatives, poly(meth)acrylates and other polymers.

In the case of adding other polymers to the liquid crystal alignment agent, the blending ratio of the other polymers is preferably 50 parts by weight or less with respect to 100 parts by weight of the total of the polymers contained in the liquid crystal alignment agent. It is preferable to set it as 0.1 weight part-40 weight part, and it is especially preferable to set it as 0.1 weight part-30 weight part or less.

In addition, when a photo-alignment method is used to impart liquid crystal alignment ability to a coating film formed using the liquid crystal alignment agent of the present invention, a polymer having a photo-alignment structure can be used as the other polymer. For example, in the case of a liquid crystal alignment agent for a retardation film, a polymer having a photoalignment group as a photoalignment structure can be preferably used. Specifically, a polymer having a cinnamic acid structure (cinnamic acid or its derivatives) can be introduced. The group of polymers and so on. Among them, the polyorganosiloxane having a cinnamic acid structure can be preferably used in terms of easy introduction of a photoalignment group into the polymer.

In addition, the polymer having a photo-alignment group can be synthesized by a conventionally known method. For example, as other polymers, polyorganosiloxanes with photo-alignment groups can be obtained by combining polyorganosiloxanes with epoxy groups and carboxylic acids with photo-alignment groups, preferably in ethers, esters, and ketones. In an organic solvent such as a quaternary ammonium salt, and in the presence of a catalyst such as a quaternary ammonium salt, it is synthesized.

In the case of using the photo-alignment method to impart the liquid crystal alignment ability to the coating film, relative to the total amount of the polymer used to prepare the liquid crystal alignment agent of the present invention, the photo-alignment The usage ratio of the polymer of the directional structure (in the case of the polymer (P) and other polymers having a photo-alignment structure, the total amount thereof) is preferably 3% by weight or more, more preferably 5% by weight % To 100% by weight, particularly preferably 10% to 100% by weight.

[Epoxy-containing compounds]

The epoxy group-containing compound can be used to improve the adhesion or electrical properties of the liquid crystal alignment film to the surface of the substrate. The epoxy group-containing compound includes, for example, the following compounds as preferred ones: ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether. Glycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromo neopentyl ether Alcohol 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, etc. In addition, as examples of the epoxy group-containing compound, the epoxy group-containing polyorganosiloxane described in International Publication No. 2009/096598 can be used.

When these epoxy group-containing compounds are added to the liquid crystal alignment agent, the blending ratio of the epoxy group-containing compound is preferably set to 100 parts by weight in total of the polymer contained in the liquid crystal alignment agent. It is 40 parts by weight or less, and more preferably 0.1 to 30 parts by weight.

[Functional Silane Compound]

The functional silane compound can be used for the purpose of improving the printability of the liquid crystal alignment agent. Examples of the functional silane compound include: 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyl Triethoxysilane, N-(2-aminoethyl)-3-aminopropyltrimethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxy Silane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-triethoxy Silylpropyl triethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonylacetic acid Ester, 9-trimethoxysilyl-3,6-diazepanonanoic acid methyl ester, N-benzyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltrimethyl Oxysilane, glycidoxymethyltrimethoxysilane, 2-glycidoxyethyltrimethoxysilane, 3-glycidoxypropyltrimethoxysilane, etc.

When these functional silane compounds are added to the liquid crystal alignment agent, the blending ratio of the functional silane compounds is preferably set to 2 parts by weight with respect to 100 parts by weight of the total polymer contained in the liquid crystal alignment agent Below, it is more preferable to set it as 0.02 weight part-0.2 weight part.

[Metal Chelating Compound]

The metal chelate compound is contained in the liquid crystal aligning agent (especially the liquid crystal for retardation film) in order to ensure the mechanical strength of the film formed by low-temperature treatment when the polymer component of the liquid crystal aligning agent has an epoxy structure. Alignment agent). The metal chelate compound is preferably an acetylacetone complex or an acetylacetate complex using a metal selected from aluminum, titanium, and zirconium. Specifically, for example, diisopropoxy Aluminum ethyl acetylacetate, aluminum tris (acetyl pyruvate), aluminum tris (ethyl acetyl acetic acid), diisopropoxy bis (ethyl acetyl acetate) titanium, diisopropoxy bis (ethyl (Acanthoxypyruvate) titanium, tri-n-butoxy ethyl acetyl zirconium acetate, di-n-butoxy bis (ethyl acetyl acetate) zirconium and the like. In the case of adding the metal chelate compound, the use ratio of the metal chelate compound is preferably 50 parts by weight or less, and more preferably 0.1 parts by weight to 40 with respect to 100 parts by weight of the total of the constituent components including the epoxy structure. Part by weight is particularly preferably 1 part by weight to 30 parts by weight.

[Hardening accelerator]

The curing accelerator is included in the liquid crystal alignment agent in order to ensure the mechanical strength of the formed liquid crystal alignment film and the temporal stability of the liquid crystal alignment when the polymer component in the liquid crystal alignment agent has an epoxy structure ( Especially in the liquid crystal alignment agent for retardation film). As the curing accelerator, for example, compounds having a phenol group, a silanol group, a thiol group, a phosphoric acid group, a sulfonic acid group, a carboxyl group, a carboxylic acid anhydride group, etc. can be used, and among them, a compound having a phenol group or a silanol group is preferable. As specific examples thereof, compounds having a phenol group include, for example, cyanophenol, nitrophenol, methoxyphenoxyphenol, thiophenoxyphenol, 4-benzylphenol, etc.; compounds having a silanol group Examples include: trimethylsilanol, triethylsilanol, 1,1,3,3-tetraphenyl-1,3-disiloxanediol, 1,4-bis(hydroxydimethylsilanol) Benzene, triphenylsilanol, tris(p-tolyl)silanol, diphenylsilanol, etc. In the case of adding a hardening accelerator, the use ratio of the hardening accelerator is preferably 50 parts by weight or less, and more preferably 0.1 to 40 parts by weight with respect to 100 parts by weight of the total of the constituent components including the epoxy structure. Especially preferably, it is 1 weight part-30 weight part.

[Surfactant]

The surfactant may be included in a liquid crystal alignment agent (especially a liquid crystal alignment agent for retardation film) for the purpose of improving the coating property of the liquid crystal alignment agent to the substrate. Examples of such surfactants include nonionic surfactants, anionic surfactants, cationic surfactants, amphoteric surfactants, silicone surfactants, polyalkylene oxide surfactants, fluorinated surfactants, etc. . The use ratio of the surfactant is preferably 10 parts by weight or less, and more preferably 1 part by weight or less with respect to 100 parts by weight of the total amount of the liquid crystal alignment agent.

In addition to the aforementioned components, other components include compounds having at least one oxetanyl group in the molecule, antioxidants, and the like.

<Solvent>

The liquid crystal alignment agent of the present invention is prepared as a liquid composition in which the polymer (P) and other components used as needed are preferably dispersed or dissolved in an appropriate solvent.

Examples of the organic solvent used include: N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactone, N,N-dimethylformamide, N,N-dimethylethyl Amide, 4-hydroxy-4-methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxy propionate, ethyl ethoxy propionate, Ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, ethylene glycol-isopropyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol Ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol Monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isobutyl Isoamyl acid, diisoamyl ether, ethylene carbonate, propylene carbonate, etc. These organic solvents can be used individually or in mixture of 2 or more types.

The solid content concentration in the liquid crystal alignment agent of the present invention (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) can be appropriately selected in consideration of viscosity, volatility, etc., preferably It is in the range of 1% by weight to 10% by weight. That is, the liquid crystal alignment agent of the present invention is applied to the surface of the substrate in the manner described below, preferably by heating, 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 increases and the coating properties tend to decrease. .

The particularly preferable range of the solid content concentration varies depending on the use of the liquid crystal alignment agent or the method used when the liquid crystal alignment agent is applied on the substrate. For example, when the liquid crystal alignment agent for the liquid crystal alignment film is applied on the substrate by the spinner method, the solid content concentration (the total weight of all components other than the solvent in the liquid crystal alignment agent is in the total weight of the liquid crystal alignment agent) The proportion) is particularly preferably in the range of 1.5% by weight to 4.5% by weight. In the case of using the printing method, it is particularly preferable to set the solid content concentration to a range of 3 wt% to 9 wt%, thereby setting the solution viscosity to 12 mPa. s~50mPa. The range of s. In the case of using the inkjet method, it is particularly preferable to set the solid content concentration to the range of 1 wt% to 5 wt%, thereby setting the solution viscosity to 3 mPa. s~15mPa. The range of s. Preparation of the liquid crystal alignment agent of the present invention The temperature at this time is preferably 10°C to 50°C, more preferably 20°C to 30°C. Regarding the liquid crystal alignment agent for retardation film, from the viewpoint of making the coatability of the liquid crystal alignment agent and the film thickness of the formed coating film appropriate, the solid content concentration of the liquid crystal alignment agent is preferably 0.2% by weight~ The range of 10% by weight is more preferably the range of 3% by weight to 10% by weight.

In addition, the inventors’ research results indicate that the use of a liquid crystal alignment agent containing the polymer (P) can form a coating film having a flat surface (good surface unevenness). The reason is not necessarily clear, but it is estimated as follows. If the aromatic amine structure (a) is introduced in order to improve the DC residual relaxation performance, in addition to the increase in crystallinity, the polymer becomes rigid, and it is considered that it becomes easy to aggregate (crystallize). In this case, it is assumed that the polymer chains are entangled with each other during the formation of the coating film, resulting in a decrease in the surface unevenness of the coating film. In contrast, in the polymer (P) obtained by using the compound (C) for the reaction, a chain structure (b) having a sufficiently long chain length is introduced as a spacer unit together with the aromatic amine structure (a). Here, the heating (post-baking) during the formation of the coating film loosens the entanglement of polymer chains, and it is considered that the surface unevenness of the coating film after heating becomes good. In addition, regarding the polymer (P) obtained by using the compound (C1) for the reaction, it is also presumed that the effect is obtained due to the same reason.

<Liquid crystal display element and retardation film>

The liquid crystal alignment film can be manufactured by using the liquid crystal alignment agent of the present invention described above. In addition, the liquid crystal alignment film formed using the liquid crystal alignment agent of the present invention can be preferably applied to liquid crystal alignment films for liquid crystal display elements and liquid crystal alignment films for retardation films. Hereinafter, the liquid crystal display element and retardation film of this invention are demonstrated.

[Liquid crystal display element]

The liquid crystal display element of the present invention includes a liquid crystal alignment film formed using the liquid crystal alignment agent. The operation mode of the liquid crystal display element of the present invention is not particularly limited. For example, it can be applied to TN type, STN type, VA type (including Vertical Alignment-Multidomain Vertical Alignment (VA-MVA) type, vertical Alignment-patterned vertical alignment (Vertical Alignment-Patterned Vertical Alignment, VA-PVA) type, etc.), IPS type, FFS type, Optically Compensatory Bend (Optically Compensatory Bend, OCB) type and other driving methods. The liquid crystal display element of the present invention can be manufactured by the following steps (I-1) to (I-3), for example. Step (I-1) uses different substrates according to the required operation mode. Step (I-2) and Step (I-3) are shared in each operation mode.

[Step (I-1): Formation of Coating Film]

First, the liquid crystal alignment agent of the present invention is coated on the substrate, and then the coated surface is heated, thereby forming a coating film on the substrate.

(I-1A) In the case of manufacturing liquid crystal display elements of, for example, TN type, STN type or VA type, first, two substrates provided with patterned transparent conductive films are used as a pair. On the conductive film formation surface, it is preferable to apply the liquid crystal alignment agent of the present invention separately by an offset printing method, a spin coating method, a roll coater method, or an inkjet printing method. The substrate can be, for example, glass such as float glass and soda glass; including polyethylene terephthalate, polybutylene terephthalate, polyether agglomerate, polycarbonate, poly(alicyclic Olefin) and other plastic transparent substrates. The transparent conductive film provided on one side of the substrate can use NESA film containing tin oxide (SnO ₂ ) (registered trademark of PPG in the United States), ITO containing indium oxide-tin oxide (In ₂ O ₃ -SnO ₂ ) 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 photoetching after forming a transparent conductive film without a pattern; a method of using a mask with a desired pattern when forming a transparent conductive film, etc. . When applying the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the transparent conductive film and the coating film, the surface of the substrate surface where the coating film is formed can also be pre-coated with functional silane compounds, functional titanium compounds, etc. Pretreatment.

After the liquid crystal alignment agent is applied, for the purpose of preventing sagging of the applied liquid crystal alignment agent, etc., it is preferable to perform preheating (prebaking). 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, more preferably 0.5 minutes to 5 minutes. Then, for the purpose of completely removing the solvent and thermally imidizing the amide structure existing in the polymer as necessary, a firing (post-baking) step is performed. The firing 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, more preferably 10 minutes to 100 minutes. The film thickness of the film formed in this manner is preferably 0.001 μm to 1 μm, and more preferably 0.005 μm to 0.5 μm.

(I-1B) In the case of manufacturing an IPS-type or FFS-type liquid crystal display element, the electrode formation surface of a substrate including electrodes patterned into a comb-shaped transparent conductive film or a metal film is provided with and without The opposite substrate surface of the electrode is respectively coated with the liquid crystal alignment agent of the present invention, and then each coated surface is heated, thereby forming a coating film. Regarding the substrate and transparent conductive film materials and coating methods used at this time The method, the heating conditions after coating, the patterning method of the transparent conductive film or the metal film, the pretreatment of the substrate, and the preferred film thickness of the formed coating film are the same as the above-mentioned (I-1A). For the metal film, for example, a film containing metal such as chromium can be used.

In either case of (I-1A) and (I-1B), after applying a liquid crystal alignment agent on a substrate, the organic solvent is removed to form a coating film that becomes an alignment film. At this time, the polymer contained in the liquid crystal alignment agent of the present invention is polyamide acid, or polyamide acid ester, or is an imidized polymer having an amide ring structure and an amide acid structure In the case of the coating film formation, the dehydration ring-closing reaction can be performed by further heating after the coating film is formed, and the coating film can be further imidized.

[Step (I-2): Alignment ability imparting processing]

In the case of manufacturing a TN-type, STN-type, IPS-type, or FFS-type liquid crystal display element, the coating film formed in the step (I-1) is subjected to a process of imparting liquid crystal alignment ability. Thereby, the alignment ability of the liquid crystal molecules is imparted to the coating film to become a liquid crystal alignment film. The treatment may include the following treatments: rubbing treatment, using a roll wrapped with a cloth containing fibers such as nylon, rayon, cotton, to wipe the coating film in a certain direction; and optical alignment treatment, irradiating the coating film with polarized light or non Polarized radiation. On the other hand, in the case of manufacturing a VA-type liquid crystal display element, the coating film formed in the step (I-1) may be directly used as a liquid crystal alignment film, or the coating film may be subjected to an alignment ability imparting treatment.

In the photo-alignment process, as the radiation irradiated to the coating film, for example, ultraviolet rays and visible rays including light with a wavelength of 150 nm to 800 nm can be used. When the radiation is polarized light, it may be linearly polarized light or partially polarized light. In addition, in the When the radiation of is linearly polarized or partially polarized, it may be irradiated from a direction perpendicular to the substrate surface, or from an oblique direction, or a combination of these irradiations may be performed. In the case of irradiating non-polarized radiation, the irradiated direction is an oblique direction.

As the light source used, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, etc. can be used. Ultraviolet rays in a preferred wavelength range can be obtained by means of using a light source in combination with, for example, a filter and a diffraction grating. The radiation exposure is preferably ^{100J / m 2 ~ 50,000J / m} 2, and more preferably ^{300J / m 2 ~ 20,000J / m} 2. In addition, in order to improve the reactivity, the coating film may be irradiated with light while heating the coating film. The temperature during heating is usually 30°C to 250°C, preferably 40°C to 200°C, and more preferably 50°C to 150°C.

In addition, the liquid crystal alignment film after the rubbing treatment can be further subjected to the following treatment to make the liquid crystal alignment film have different liquid crystal alignment capabilities in each region: by irradiating a part of the liquid crystal alignment film with ultraviolet rays, the liquid crystal alignment film The process of changing the pretilt angle; or the 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 rubbing treatment just now. In this case, the visual field characteristics of the obtained liquid crystal display element can be improved. The liquid crystal alignment film suitable for VA-type liquid crystal display elements can also be suitably used for polymer sustained alignment (PSA)-type liquid crystal display elements.

[Step (I-3): Construction of liquid crystal cell]

Prepare two substrates with liquid crystal alignment films formed in the manner described above, and arrange them in opposite directions Liquid crystals are arranged between the two substrates to manufacture a liquid crystal cell. In order to manufacture a liquid crystal cell, the following two methods can be mentioned, for example. The first method is a previously known method. First, the two substrates are arranged to face each other through a gap (cell gap) so that the liquid crystal alignment films are opposed to each other. The peripheral parts of the two substrates are bonded together using a sealant, and the cells are divided by the surface of the substrate and the sealant. After injecting and filling the liquid crystal into the void, the injection hole is sealed, thereby manufacturing a liquid crystal cell. In addition, the second method is a method called One Drop Fill (ODF) method. For example, apply a UV-curable sealant to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and then drop liquid crystal on predetermined locations on the surface of the liquid crystal alignment film. The alignment film is bonded to another substrate in an opposing manner, and the liquid crystal is spread on the entire surface of the substrate, and then ultraviolet light is irradiated to the entire surface of the substrate to harden the sealant, thereby manufacturing a liquid crystal cell. In the case of using either method, it is desirable to heat the liquid crystal cell manufactured in the manner described above until the temperature at which the liquid crystal used obtains the isotropic phase, and then slowly cool to room temperature, thereby removing Flow alignment during liquid crystal filling.

As the sealing agent, for example, an epoxy resin containing a curing agent and alumina balls as spacers can be used. In addition, the liquid crystals include nematic liquid crystals and smectic liquid crystals. Among them, nematic liquid crystals are preferable. For example, Schiff base liquid crystals, azo oxides can be used. (azoxy) liquid crystal, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl cyclohexane liquid crystal, pyrimidine liquid crystal, dioxane liquid crystal, bicyclic Octane-based liquid crystal, cubane-based liquid crystal Wait. In addition, the following substances can also be added to these liquid crystals for use: for example, cholesteryl chloride, cholesteryl nonanoate, cholesteryl carbonate and other cholesteric liquid crystals. ); Chiral agent sold as trade names "C-15" and "CB-15" (manufactured by Merck); p-decyloxybenzylidene-p-amino-2 -Ferroelectric liquid crystals such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate, etc.

Next, the liquid crystal display element of the present invention can be obtained by bonding a polarizing plate to the outer surface of the liquid crystal cell. Examples of the polarizing plate bonded to the outer surface of the liquid crystal cell include: a polarizing plate formed by sandwiching a polarizing film called "H film" with a cellulose acetate protective film, or a polarizing plate containing the H film itself. The "H "Film" is a film formed by absorbing iodine while extending and aligning polyvinyl alcohol.

[Retardation film]

In the case of using the liquid crystal alignment agent of the present invention to produce a retardation film, the generation of dust or static electricity can be suppressed in the step, and a uniform liquid crystal alignment film can be formed, and it can be used when irradiating radiation. In terms of arbitrarily forming a plurality of regions with different liquid crystal alignment directions on the substrate with a mask, it is preferable to use a photo-alignment method. Specifically, it can be manufactured by going through the following steps (II-1) to (II-3).

[Step (II-1): Formation of coating film using liquid crystal alignment agent]

First, the liquid crystal alignment agent of the present invention is coated on a substrate to form a coating film. this The substrate used in the premises can be suitably exemplified: including triacetyl cellulose (TAC), polyethylene terephthalate, polybutylene terephthalate, polyether sulfide, polyamide, polyimide, polyimide Transparent substrate of synthetic resin such as methyl methacrylate and polycarbonate. Among these substrates, TAC is generally used as a protective layer of a polarizing film in a liquid crystal display element. In addition, polymethyl methacrylate can be preferably used as a substrate for a retardation film in terms of low hygroscopicity of the solvent, good optical properties, and low cost. In addition, for the substrate used in the coating of the liquid crystal alignment agent, in order to improve the adhesion between the substrate surface and the coating film, a conventionally known pretreatment may be performed on the surface of the substrate where the coating film is formed.

In many cases, a retardation film is used in combination with a polarizing film. At this time, in order to be able to exhibit the required optical properties, the angle of the polarization axis of the retardation film with respect to the polarizing film must be precisely controlled to a specific direction and the retardation film must be bonded. Therefore, here, by forming a liquid crystal alignment film having liquid crystal alignment ability in a predetermined angle direction on a substrate such as a TAC film or polymethyl methacrylate, it is possible to omit the need to control the angle of the retardation film while controlling the angle of the retardation film. The step of attaching to the polarizing film. In addition, this can contribute to improving the productivity of the liquid crystal display element. In order to form a liquid crystal alignment film having a liquid crystal alignment ability in a direction of a predetermined angle, it is preferable to use the liquid crystal alignment agent of the present invention and perform the photo-alignment method.

Appropriate coating methods can be used to apply the liquid crystal alignment agent on the substrate. For example, roll coater method, spinner method, printing method, inkjet method, bar coater method, extrusion die method, direct gravure coater ( direct gravure coater method, chamber doctor coater method, indirect gravure coater (offset gravure coater method, single roll kiss coater method, reverse kiss coater method using small diameter gravure rolls, three reverse roll coater method, Four reverse roll coater method, slot die method, air doctor coater method, positive rotation roll coater method, blade coater method , Knife coater method, impregnation coater method, MB coater method, MB reverse coater method, etc.

After coating, the coated surface is heated (baked) to form a coating film. The heating temperature at this time is preferably 40°C to 150°C, and more preferably 80°C to 140°C. The heating time is preferably 0.1 minute to 15 minutes, more preferably 1 minute to 10 minutes. The thickness of the coating film formed on the substrate is preferably 1 nm to 1,000 nm, and more preferably 5 nm to 500 nm.

[Step (II-2): Light irradiation step]

Then, by irradiating the coating film formed on the substrate in the above manner with light, the coating film is provided with liquid crystal alignment ability. Here, the description of the wavelength of the irradiated light, the type of light, and the light source used can be applied to the description of the optical alignment processing in the step (I-2). Light irradiation amount is preferably set to ^{0.1mJ / cm 2 ~ 1,000mJ / cm} 2, and more preferably set to ^{1mJ / cm 2 ~ 500mJ / cm} 2, particularly preferably to ^{2mJ / cm 2 ~ 200mJ / cm} 2.

[Step (II-3): Formation of Liquid Crystal Layer]

Then, the polymerizable liquid crystal is coated and cured on the coating film irradiated with light in the manner described above. Thus, a coating film (liquid crystal layer) containing polymerizable liquid crystal is formed. Here The polymerizable liquid crystal used is a liquid crystal compound or liquid crystal composition polymerized by at least one of heating and light irradiation. As the polymerizable liquid crystal, a conventionally known liquid crystal can be used. Specifically, for example, Non-Patent Document 1 ("Ultraviolet (UV) Curable Liquid Crystal and Its Application", "Liquid Crystal" Vol. 3 No. 1 (1999) , Page 34~page 42) described in the nematic liquid crystal. In addition, it may also be: cholesteric liquid crystal; discotic liquid crystal; twisted nematic liquid crystal added with a chiral agent, etc. The polymerizable liquid crystal may be a mixture of multiple liquid crystal compounds. The polymerizable liquid crystal may further contain a known polymerization initiator, a suitable solvent, and the like.

In order to coat the above-mentioned polymerizable liquid crystal on the coating film formed using the liquid crystal alignment agent, for example, an appropriate coating method such as a bar coater method, a roll coater method, a spinner method, a printing method, and an inkjet method can be used.

Then, the coating film of the polymerizable liquid crystal formed as described above is subjected to one or more treatments selected from heating and light irradiation to harden the coating film to form a liquid crystal layer. It is preferable to perform these treatments overlappingly to obtain good alignment.

The heating temperature of the coating film can be appropriately selected according to the type of polymerizable liquid crystal used. For example, when RMS03-013C manufactured by Merck is used, it is preferable to heat at a temperature in the range of 40°C to 80°C. The heating time is preferably 0.5 minutes to 5 minutes.

Irradiation light can preferably use non-polarized ultraviolet rays having a wavelength in the range of 200 nm to 500 nm. The amount of light irradiation is preferably 50 mJ/cm ² to 10,000 mJ/cm ² , and more preferably 100 mJ/cm ² to 5,000 mJ/cm ² .

The thickness of the formed liquid crystal layer is appropriately set according to the required optical characteristics. For example, in the case of manufacturing a 1/2-wavelength plate of visible light with a wavelength of 540nm, the thickness of the formed retardation film is selected to be 240nm~300nm, and if it is a quarter-wavelength plate, the retardation is selected to be 120nm~ 150nm thickness. The thickness of the liquid crystal layer to obtain the target retardation varies depending on the optical characteristics of the polymerizable liquid crystal used. For example, in the case of RMS03-013C manufactured by Merck, the thickness used to manufacture the quarter-wave plate is in the range of 0.6 μm to 1.5 μm.

The retardation film obtained in this manner can be preferably used as a retardation film of a liquid crystal display element. The driving method of the liquid crystal display element using the retardation film manufactured using the liquid crystal alignment agent of the present invention is not limited. For example, it can be applied to various known methods such as TN type, STN type, IPS type, FFS type, and VA type. The retardation film is used by sticking the retardation film on the outer surface of the polarizing plate arranged on the visibility side of the liquid crystal display element on the substrate side surface. Therefore, it is preferable to set the phase difference film substrate as a TAC or acrylic base material, and make the phase difference film substrate also function as a protective film of the polarizing film.

Here, there is a roll-to-roll method as a method of producing retardation films on an industrial scale. This method is a method in which the following treatments are carried out in continuous steps, and the film after these steps is made into a wound body for recovery. The treatment is: the film is rolled out from the wound body of a long base film , A process of forming a liquid crystal alignment film on the rolled film; a process of coating a polymerizable liquid crystal on the liquid crystal alignment film and curing; and a process of laminating a protective film if necessary. The retardation film formed by using the liquid crystal alignment agent of the present invention has good adhesion to the substrate, and it is also difficult to peel off the liquid crystal alignment film and the substrate when it is made into a roll for storage. Therefore, it is possible to suppress Decrease in product yield when using the roll-to-roll method to manufacture retardation films.

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, note type personal computers, car navigation systems, etc. system), camcorder (camcorder), personal digital assistant (Personal Digital Assistant, PDA), digital camera (digital camera), mobile phone, smart phone, various monitors, LCD TV, information display and other display devices.

[Example]

Hereinafter, the present invention will be further described in detail through examples, but the present invention is not limited to these examples.

In the following examples and synthesis examples, the following methods are used to measure the weight average molecular weight Mw, the imidization rate and epoxy equivalent of the polymer, and the solution viscosity of the polymer solution.

[Weight average molecular weight of polymer Mw]

Mw is a polystyrene conversion value measured by GPC under the following conditions.

Column: manufactured by Tosoh (stock), TSKgelGRCXLII

Solvent: N,N-dimethylformamide solution containing tetrahydrofuran, or lithium bromide and phosphoric acid

Temperature: 40℃

Pressure: 68kgf/cm ²

[The imidization rate of polymer]

The polyimide-containing solution was poured into pure water, and the resulting precipitate was sufficiently dried under reduced pressure at room temperature, and then dissolved in deuterated dimethyl sulfide, using tetramethyl silane as the reference substance, at room temperature ¹ H-Nuclear Magnetic Resonance (NMR) was measured. From the obtained ¹ H-NMR spectrum, the following mathematical formula (EX-1) was used to determine the imidization rate.

The imidization rate (%)=(1-E ¹ /E ² ×α)×100…(EX-1)

(In the mathematical formula (EX-1), E ¹ is the peak area of the proton derived from the NH group that appears near the chemical shift of 10 ppm, E ² is the peak area derived from other protons, and α is the peak area of the other protons relative to the polymer The ratio of the number of protons of the NH group in the precursor (polyamide acid))

[Epoxy equivalent]

The epoxy equivalent is measured by the hydrochloric acid-methyl ethyl ketone method described in JIS C 2105.

[Solution viscosity of polymer solution]

The solution viscosity (mPa·s) of the polymer solution is measured at 25°C using an E-type rotary viscometer.

<Synthesis of Compound (C)> [Synthesis Example 1-1: Synthesis of Compound (DA-1)]

The compound (DA-1) was synthesized according to the following scheme 1. In addition, in the formula, Bn represents a benzyl group (the same applies hereinafter).

[化20]

The first stage of the reaction is the use of Williamson reaction (Williamson reaction) for synthesis. First, in a 2L three-necked flask equipped with a dropping funnel, 83.7 g (0.2 mol) of N-benzyl-4-hydroxyaniline, 46 g (0.42 mol) of 1,5-dibromopentane, and 121.5 cesium fluoride were mixed. g (0.8 mol) and 800 mL of dimethylformamide were dissolved, and the reaction was carried out by stirring at 60°C for 4 hours. After the reaction, 2000 mL of ethyl acetate was added for extraction, and 200 mL of distilled water was added for separation and purification. After repeating the extraction and purification 5 times, the solvent was removed from the organic layer by distillation under reduced pressure, thereby obtaining 76.4 g of a dibenzyl intermediate (compound represented by the formula (DA-1-1)) ( 0.16 mol).

The second stage of the reaction is synthesized by Ullmann condensation reaction. Under nitrogen flow, add 76.4 g (0.16 mol) of the bibenzyl intermediate (DA-1-1), 81.5 g (0.33 mol) of 4-iodonitrobenzene, and phenanthroline in a 2L three-necked flask (phenanthroline) 59g (0.33 mol), tripotassium phosphate 139g (0.65 mol), copper iodide 9.4g (0.05 mol) And 600 mL of dimethylacetamide, mixed and dissolved them, and stirred for 24 hours under reflux to perform the reaction. After the completion of the reaction, the reaction liquid was filtered to remove the catalyst, and the filtrate was poured into 2000 mL of distilled water to precipitate crystals. The precipitated solid was recovered by filtration, fully washed with ethanol, and recrystallized in tetrahydrofuran to obtain 35 g (0.05 mole) of the nitro intermediate (the compound represented by the formula (DA-1-2)) ear).

The third stage of the reaction is synthesis by hydrogen reduction reaction. Under nitrogen flow, add 35 g of the nitro intermediate (DA-1-2), 3 g of 5% Pd/C, 50 mL of ethanol, 50 mL of tetrahydrofuran and 35 mL of hydrazine monohydrate in a 500 mL three-necked flask, and then add hydrogen again The displacement is carried out at room temperature in the presence of hydrogen. The reaction was followed by high performance liquid chromatography (High Performance Liquid Chromatography, HPLC), and filtration was performed after confirming the progress of the reaction. 1000 mL of ethyl acetate was added to the filtrate, and 100 mL of distilled water was added to perform liquid separation and purification. After repeating the extraction and purification 5 times, the solvent was removed from the organic layer by distillation under reduced pressure, thereby depositing a solid. The precipitated solid was recrystallized in a mixed solvent of tetrahydrofuran and ethanol to obtain 18.5 g (0.04 mol) of compound (DA-1).

[Synthesis Example 1-2: Synthesis of Compound (DA-2)]

According to the following scheme 2, the compound (DA-2) was obtained using the same synthesis reaction recipe as that of the compound (DA-1).

[化21]

[Synthesis Example 1-3: Synthesis of Compound (DA-3)]

According to the following Scheme 3, the compound (DA-3) was obtained using the same synthesis reaction recipe as that of the compound (DA-1). In addition, the second-stage reaction is synthesized using the method described in Non-Patent Document 2 (The Journal of Organic Chemistry, 2002, 67, 6479).

[Synthesis Example 1-4: Synthesis of Compound (DA-4)]

According to the following Scheme 4, the compound (DA-4) was obtained using the same synthesis reaction recipe as the compound (DA-1). In addition, the second stage of the reaction is synthesis by hydrolysis, and the third stage is by the condensation reaction of 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide hydrochloride. synthesis.

[Synthesis Example 1-5: Synthesis of Compound (DA-5)]

According to the following Scheme 5, the compound (DA-5) was obtained using the same synthesis reaction formula as the compound (DA-1).

[化24]

[Synthesis Example 1-6: Synthesis of Compound (DA-6)]

According to the following Scheme 6, the compound (DA-6) was obtained using the same synthesis reaction formula as that of the compound (DA-1).

[Synthesis Example 1-7: Synthesis of Compound (DA-7)]

According to the following Scheme 7, the compound (DA-7) was obtained using the same synthesis reaction recipe as that of the compound (DA-1).

[化26]

[Synthesis Example 1-8: Synthesis of DA-8]

According to the following Scheme 8, the compound (DA-8) was obtained using the same synthesis reaction formula as the compound (DA-1). In addition, the first step in the synthesis of the mononitromonoiodine intermediate (the compound represented by the formula (DA-8-1)) is to use the Friedel-Crafts reaction to synthesize The second stage is the synthesis using the reduction reaction of the silyl carbonyl group of triethylsilane in the presence of trifluoromethanesulfonic acid as a strong acid.

[化27]

[Synthesis Example 1-9: Synthesis of Compound (DA-9)]

According to the following Scheme 9, the compound (DA-9) was obtained using the same synthesis reaction recipe as that of the compound (DA-1).

[化28]

[Synthesis Example 1-10: Synthesis of Compound (DA-10)]

According to the following Scheme 10, the compound (DA-10) was obtained using the same synthesis reaction formula as the compound (DA-1). In addition, the first stage in the synthesis of the mononitro monohydroxy intermediate (the compound represented by the formula (DA-10-1)) is synthesis by Friedel-Crafts reaction, and the second stage is by It is synthesized by the deprotection reaction of the methoxy group of lithium bromide, and the third stage is synthesis using the reduction reaction of the silyl carbonyl group of triethylsilane in the presence of trifluoromethanesulfonic acid as a strong acid.

[化29]

<Synthesis of Compound (C1)> [Synthesis Example 1-11: Synthesis of Compound (DA-22)]

According to the following scheme 11, compound (DA-22) was obtained. In addition, in the first stage of synthesis, an intermediate (a compound represented by the following formula (DA-22-1)) is obtained by Knoevenagel reaction. The second stage uses the same method as the compound (DA-1) to perform reduction.

[化30]

[Synthesis Example 1-12: Synthesis of Compound (DA-23)]

According to the following Scheme 12, the compound (DA-22-1) is reduced in the presence of zinc with water as a catalyst to obtain the compound (DA-23).

<Synthesis of polymers> . Synthesis of polyamide acid [Synthesis Example 2-1: Synthesis of Polymer (PAm-1)]

In the reaction vessel, tetracarboxylic dianhydride and diamine were added at the mixing ratio (mole part) described in Table 1 below and the total weight was 30 g, and further N-methyl-2-pyrrolidone (N- 170 g of methyl-2-pyrrolidone, NMP) was dissolved and reacted at 60°C for 6 hours. Then, the resulting reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. Wash the recovered precipitate with methanol After washing, it was dried under reduced pressure at 40°C for 15 hours, thereby obtaining a polymer (PAm-1). In addition, regarding tetracarboxylic dianhydride, the numerical values in Table 1 indicate the use ratio (mol %) relative to the total amount of tetracarboxylic dianhydride used in the reaction, and regarding diamines, the numerical values in Table 1 indicate relative The use ratio (mol%) of the total amount of diamine used in the reaction. Then, the obtained polymer (PAm-1) was dissolved in NMP so as to become 15% by weight, and the viscosity of each solution was measured. The measurement results are shown in Table 1 below. In addition, the obtained polymer solution did not undergo gelation after being allowed to stand at 20°C for 3 days, and the storage stability was good.

[Synthesis example 2-2~Synthesis example 2-18: Synthesis of polymer (PAm-2)~polymer (PAm-18)]

Except that the mixing ratio of tetracarboxylic dianhydride and diamine was changed to the values described in Table 1 and Table 2 below, the same operations as in Synthesis Example 2-1 were performed to obtain polymers (PAm-2) ~ polymerization物(PAm-18). The results of measuring the solution viscosity of each polymer in the same manner as in Synthesis Example 2-1 are shown in Table 1 and Table 2 below. In addition, for each polymer solution obtained as described above, after being allowed to stand at 20°C for 3 days, no gelation was performed except for the polymer (PAm-14), and the storage stability was good. The polymer (PAm-14) gelled and its fluidity disappeared.

. Synthesis of polyimide [Synthesis Example 3-1: Synthesis of Polymer (PIm-1)]

Tetracarboxylic dianhydride and diamine were added in the mixing ratio (mole part) described in the following Table 2 so that the total weight became 30 g, and 170 g of NMP was added, and synthesized by the same operation as Synthesis Example 2-1 Polyamide acid. Then, add 200g NMP was added with pyridine and acetic anhydride in the amounts shown in Table 2 below (numerical values indicate molar parts with respect to 100 molar parts in total of acid dianhydride), and dehydration ring-closure reaction was performed at 80°C for 6 hours. Then, the reaction mixture was poured into a large amount of excess methanol to precipitate the reaction product. After washing the recovered precipitate with methanol, it was dried under reduced pressure at 40°C for 15 hours to obtain a polymer (PIm-1).

Then, the obtained polymer (PIm-1) was dissolved in NMP so as to be 15% by weight, and the viscosity of each solution was measured. In addition, the imidization rate was also measured. These measurement results are shown in Table 2 below. Furthermore, the obtained polymer solution did not undergo gelation after being allowed to stand at 20°C for 3 days, and the storage stability was good.

[Synthesis Example 3-2: Synthesis of Polymer (PIm-2)]

Except that the mixing ratio of tetracarboxylic dianhydride and diamine was changed to the value described in Table 2 below, the same operation as in Synthesis Example 3-1 was performed to obtain a polymer (PIm-2). The results of the measurement of the solution viscosity of the polymer (PIm-2) in the same manner as in Synthesis Example 3-1 and the measurement results of the imidization rate are shown in Table 2 below. In addition, the obtained polymer solution did not undergo gelation after being allowed to stand at 20°C for 3 days, and the storage stability was good.

The abbreviations of the compounds in Table 1 and Table 2 have the following meanings. In addition, in Table 2, the numerical values of pyridine and acetic anhydride represent molar parts with respect to a total of 100 molar parts of tetracarboxylic dianhydride used in the reaction.

(Tetracarboxylic dianhydride)

AN-1: 1,2,3,4-cyclobutane tetracarboxylic dianhydride

AN-2: Pyromellitic dianhydride

AN-3: 2,3,5-Tricarboxycyclopentylacetic dianhydride

AN-4: Ethylenediaminetetraacetic acid dianhydride

AN-5: 5-(2,5-dioxotetrahydrofuran-3-yl)-8-methyl-3a,4,5,9b-tetrahydronaphtho[1,2-c]furan-1,3 -Diketone

AN-6: Bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic acid 2:4,6:8-dianhydride

AN-7: 1,3-propanediol bis(trimellitic anhydride)

AN-8: 1,2,3,4-cyclopentanetetracarboxylic dianhydride

(Diamine)

DA-11: 1,7-bis(4-aminophenoxy)heptane

DA-12: 4,4'-diaminodiphenylamine

DA-13: A compound represented by the following formula (DA-13)

DA-14: A compound represented by the following formula (DA-14)

DA-15: A compound represented by the following formula (DA-15)

DA-16: 4,4'-Diaminodiphenylmethane

DA-17: 4-Aminophenyl-4'-aminobenzoate

DA-18: The compound represented by the formula (DA-18)

DA-19: 4-(4-aminophenoxycarbonyl)-1-(4-aminophenyl)piperidine

DA-20: 4-(tetradecyloxy)benzene-1,3-diamine

DA-21: 3,5-diaminobenzoic acid cholesteryl ester

[化32]

. Synthesis of Polyorganosiloxane Containing Optical Orientation Group [Synthesis Example 4-1: Synthesis of Polymer (PSi-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-epoxycyclohexyl) ethyl trimethoxysilane, 500 g of methyl isobutyl ketone, and three 10.0 g of ethylamine was mixed at room temperature. To this, after adding 100 g of deionized water dropwise from the dropping funnel for 30 minutes, the reaction was performed at 80° C. for 6 hours while mixing under reflux. After the reaction, the organic layer was taken out, and the organic layer was 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 form a viscous transparent liquid The form obtains the polyorganosiloxane with oxocyclopropyl. The ¹ H-NMR analysis of the polyorganosiloxane with oxepan groups showed that the chemical shift (δ)=3.2 ppm was around, and the peak based on the oxepan groups was obtained as the theoretical strength. It was confirmed that the reaction was in progress There is no side reaction of oxocyclopropyl. The epoxy equivalent of the polyorganosiloxane having an oxepan group was measured, and the result was 186 g/equivalent.

Then, in a 100 mL three-necked flask, 9.3 g of the obtained polyorganosiloxane with oxirane, 26 g of methyl isobutyl ketone, 3 g of 4-phenoxy cinnamic acid and UCAT 18X (commercial Name, manufactured by San-Apro (Stock) 0.10 g, react for 12 hours while stirring at 80°C. After the reaction, the precipitate formed by putting the reaction mixture into methanol was recovered, and the precipitate was dissolved in ethyl acetate to prepare a solution. After the solution was washed three times with water, the solvent was distilled off to give a white The powder is formed to obtain 6.3 g of polyorganosiloxane (PSi-1) having an oxocyclopropyl and cinnamic acid structure. For this polyorganosiloxane (PSi-1), the weight average molecular weight Mw in terms of polystyrene measured by GPC was 3,500.

[Example 1-1: Optically aligned FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

As a polymer, 50 parts by weight of the polymer (PAm-4) obtained in Synthesis Example 2-4 and 50 parts by weight of the polymer (PAm-11) obtained in Synthesis Example 2-11 were dissolved in the γ-butane Mixed solvent of ester (γ-butyrolactone, GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) (GBL: NMP: BC=40:40:20 (weight ratio)) In the solution, a solid content concentration of 3.5% by weight was prepared. The solution was filtered with a filter having a pore diameter of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of surface unevenness of coating film

Using a spinner, the prepared liquid crystal alignment agent was coated on a glass substrate, and after pre-baking on a hot plate at 80°C for 1 minute, it was heated in an oven at 200°C in which nitrogen was replaced in the library (after Baking) for 1 hour, thereby forming a coating film with an average film thickness of 1,000 Å. The coating film was observed by an atomic force microscope (Atomic Force Microscope, AFM), and the center average roughness (Ra) was measured. The evaluation was performed as follows: when Ra is less than 2.0 nm, the surface unevenness is evaluated as "good", The case of 2.0 nm or more and less than 5.0 nm was evaluated as "acceptable", and the case of 5.0 nm or more was evaluated as "bad". In this example, Ra=0.8 nm, and the surface unevenness is "good".

(3) Evaluation of transmittance

For the obtained coating film, the light transmittance (%) at a wavelength of 400 nm was evaluated using a spectrophotometer (150-20 type dual beam manufactured by Hitachi, Ltd.). The evaluation was performed as follows: the case where the light transmittance was 97% or more was evaluated as “good”, the case where the light transmittance was more than 95% and less than 97% was evaluated as “acceptable”, and the case where the light transmittance was less than 95% was evaluated as “bad”. As a result, the light transmittance of this coating film was 99.0%, and the transmittance was "good".

(4) Evaluation of orientation

For the obtained coating film, a Hg-Xe lamp and a Glan-Taylor prism were used to irradiate a polarized ultraviolet 300 J/m ² containing a bright line of 313 nm from the normal direction of the substrate to perform alignment treatment. For the glass substrate with an alignment film, a liquid crystal alignment film inspection device (LayScan) manufactured by MORITEX was used to measure the refractive index anisotropy (nm). The evaluation was performed as follows: the case of 0.020 nm or more was evaluated as "good", the case of less than 0.020 nm and 0.010 nm or more as "acceptable", and the case of less than 0.010 as "bad". As a result, the refractive index anisotropy of this substrate was 0.037 nm, and the orientation was "good".

(5) Manufacturing of FFS-type liquid crystal display elements using optical alignment method

The FFS type liquid crystal display element 10 shown in FIG. 1 was produced. First, will be in the single mask There is an electrode pair and a glass substrate 11a on which a bottom electrode 15 without a pattern, a silicon nitride film as an insulating layer 14, and a top electrode 13 patterned into a comb-tooth shape are formed in this order, and the electrode pair without electrodes The opposite glass substrate 11b is a pair. On the surface of the glass substrate 11a with the transparent electrode and one surface of the opposite glass substrate 11b, using a spinner, the liquid crystal alignment agent prepared in (1) is applied to form a coating film. . Then, the coating film was pre-baked on a hot plate at 80°C for 1 minute, and then heated (post-baked) at 230°C for 15 minutes in an oven that replaced the inside of the library with nitrogen. The average film thickness was 1,000Å coating film. The schematic plan view of the top electrode 13 used here is shown in FIG. 2(a) and FIG. 2(b). In addition, FIG. 2(a) is a plan view of the top electrode 13, and FIG. 2(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 2(a). In this embodiment, a substrate having a top electrode with an electrode line width d1 of 4 μm and a distance d2 between the electrodes of 6 μm is used. In addition, the top electrode 13 is a four-system drive electrode using electrode A, electrode B, electrode C, and electrode D. Fig. 3 shows the structure of the drive electrode of the liquid crystal display element. In this case, the bottom electrode 15 acts as a common electrode on all the driving electrodes of the 4 systems, and the regions of the driving electrodes of the 4 systems are pixel regions.

Then, for each surface of these coating films, using Hg-Xe lamp and Glan Taylor horn, irradiated with 313nm bright line polarized ultraviolet light 300J/m ² from the normal direction of the substrate to obtain a pair of liquid crystal alignment films. Substrate. At this time, the irradiation direction of the polarized ultraviolet rays is set from the normal direction of the substrate, and the direction of the line segment projecting the polarized surface of the polarized ultraviolet rays onto the substrate becomes the direction of the double-headed arrow in Figure 2(a) and Figure 2(b) After setting the direction of the polarization plane, perform light irradiation treatment.

Then, on the outer periphery of the surface with the liquid crystal alignment film of one of the substrates, an epoxy resin adhesive added with alumina balls with a diameter of 5.5 μm was coated by screen printing, and then a pair of The liquid crystal alignment film of the substrate faces each other, and the polarizing surface of the polarized ultraviolet light is projected onto the substrate in parallel, overlapping and pressure-bonded, and the adhesive is thermally cured at 150°C for 1 hour. Then, the liquid crystal "MLC-6221" manufactured by Merck was filled into the substrate gap from the liquid crystal injection port, and the liquid crystal injection port was sealed with an epoxy resin adhesive. Then, in order to remove the flow alignment during liquid crystal injection, it was heated to 150°C and then slowly cooled to room temperature.

Then, the FFS type liquid crystal display element was manufactured by bonding polarizing plates to both outer sides of the substrate. At this time, one of the polarizing plates is attached so that its polarization direction is parallel to the projection direction of the polarized ultraviolet rays of the liquid crystal alignment film on the substrate surface, and the other is attached so that its polarization direction is the same as the previous polarizing plate. Attached in a way orthogonal to the polarization direction.

The above method was repeated to produce a total of 5 FFS-type liquid crystal display elements, which were provided in the following evaluation of liquid crystal orientation, heat resistance, frame unevenness, residual image characteristics, and contrast characteristics. One. However, ultraviolet irradiation under voltage application is not performed in either case. In addition, regarding the liquid crystal cell used in the evaluation of the contrast characteristic, no polarizing plate was bonded.

(6) Evaluation of liquid crystal orientation

For the manufactured FFS type liquid crystal display element, use a microscope to observe when it is turned on at a magnification of 50 times. Turn off (ON, OFF) (apply, release) the brightness when 5V voltage The presence or absence of abnormal areas that are changing. The evaluation was performed in the following manner: the case where the abnormal area was not observed was evaluated as "good" for the liquid crystal alignment, and the case where the abnormal area was observed was evaluated as "bad" for the liquid crystal alignment. The liquid crystal alignment in this liquid crystal display element was "good".

(7) Evaluation of voltage retention

For the manufactured FFS type liquid crystal display element, after applying a voltage of 5V at 23°C with an application time of 60 microseconds and a span of 167 milliseconds, the voltage retention rate (VHR) after 167 milliseconds from the release of the application was measured. As a result, The voltage retention rate is 99.4%. In addition, the measuring device used VHR-1 manufactured by Toyo Technica (stock).

(8) Evaluation of heat resistance

The voltage holding ratio was measured in the same manner as the evaluation of the voltage holding ratio in (7), and the value was taken as the initial VHR (VHR _BF ). Then, the liquid crystal display element after the initial VHR measurement was allowed to stand in an oven at 100°C for 500 hours. Then, after the liquid crystal display element was left to stand at room temperature and left to cool to room temperature, the voltage holding ratio was measured in the same manner as described above, and the value was taken as VHR _AF . In addition, the rate of change (ΔVHR(%)) of the voltage holding ratio before and after the application of thermal stress was obtained from the following mathematical formula (EX-2).

△VHR(%)=((VHR _BF -VHR _AF )÷VHR _BF )×100…(EX-2)

The heat resistance is evaluated in the following way: the change rate △VHR is less than 4% The case was evaluated as "good" in heat resistance, the case with 4% or more and less than 5% was evaluated as "acceptable" in heat resistance, and the case with 5% or more was evaluated as "poor" in heat resistance. As a result, ΔVHR was 2.9%, and the heat resistance of the liquid crystal display element was "good".

(9) Resistance to unevenness around the sealant (resistant to frame unevenness)

The FFS type liquid crystal display element manufactured as described above was stored under the conditions of 25° C. and 50% RH for 30 days, and then was driven with an AC voltage of 5V to observe the lighting state. The evaluation was carried out in the following manner: If the brightness difference (more black or more white) is not visible around the sealant, it is evaluated as "excellent"; if it is visible, it is 5 after lighting If the brightness difference disappears within minutes, it is evaluated as “good”; if the brightness difference disappears within 5 minutes and within 20 minutes, it is evaluated as “acceptable”; if the brightness difference is still recognized even after 20 minutes, it is evaluated as "bad". As a result, the brightness difference of this liquid crystal display element was not recognized, and it was judged as "good".

(10) Evaluation of residual image characteristics (DC residual image evaluation)

The manufactured photo-alignment liquid crystal display element is placed in an environment of 25° C. and 1 atmosphere. The bottom electrode was used as a common electrode for all driving electrodes of the 4 systems, and the potential of the bottom electrode was set to 0V potential (ground potential). The electrode B and the electrode D and the common electrode were short-circuited to be a 0V applied state, and a combined voltage including an AC voltage of 3.5V and a DC voltage of 1V was applied to the electrode A and the electrode C for 2 hours. After 2 hours, an AC voltage of 1.5V was immediately applied to all electrodes A to D. Next, the measurement was performed from the moment when the AC 1.5V voltage was applied to all the driving electrodes until the driving stress application area (the pixel area of electrode A and electrode C) and the driving stress non-application area (electrode B and The pixel area of electrode D) The time until the temperature difference is used as the afterimage erasing time. In addition, the shorter the time, the harder it is to produce afterimages. The afterimage erasing time is less than 30 seconds as "good", the case where the afterimage erasing time is less than 30 seconds is evaluated as "acceptable", and the case of 120 seconds or more is evaluated as "bad". The afterimage erasing time of the liquid crystal display element was 1 second, and the afterimage characteristic was evaluated as "good".

(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)

After driving the manufactured FFS liquid crystal cell (liquid crystal cell without a polarizing plate) for 30 hours at an AC voltage of 10V, a device with a polarizer and an analyzer arranged between the light source and the light quantity detector was used to measure The minimum relative transmittance (%) expressed by the mathematical formula (EX-3).

Minimum relative transmittance (%)=(β-B ₀ )/(B ₁₀₀ -B ₀ )×100…(EX-3)

(In the mathematical formula (EX-3), B ₀ is the amount of light transmission under the blank and crossed Nicols; B ₁₀₀ is the amount of light transmission under the blank and parallel Nicols; β is the amount of light transmitted under the crossed Nicols. Under the ear, the liquid crystal display element is clamped between the polarizer and the analyzer to achieve the smallest light transmission)

The black level in the dark state is represented by the minimum relative transmittance of the liquid crystal display element. The smaller the black level in the dark state, the better the contrast characteristics. Those with a minimum relative transmittance of less than 0.5% were evaluated as “good”, those with 0.5% or more and less than 1.0% were evaluated as “acceptable”, and those with 1.0% or more were evaluated as “bad”. As a result, the minimum relative transmittance of the liquid crystal display element was 0.2%, and the contrast characteristic was judged to be "good".

[Example 1-2, Example 1-3, and Comparative Example 1-1]

Except that the type and amount of the polymer used in the preparation of the liquid crystal alignment agent are respectively set as described in the following Table 3, the liquid crystal alignment agent was prepared in the same manner as in Example 1-1 to produce a liquid crystal display. Components for evaluation. The evaluation results are shown in Table 3 below.

[Example 2-1: Rubbing FFS type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

The polymer (PAm-1) obtained in Synthesis Example 2-1 as a polymer was dissolved in a compound containing γ-butyrolactone (GBL), N-methyl-2-pyrrolidone (NMP) and butyl cellosolve (BC) In the mixed solvent of (GBL:NMP:BC=40:40:20 (weight ratio)), the solid content concentration is 3.5% by weight. The solution was filtered with a filter having a pore diameter of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of surface unevenness of coating film

Using a spinner, the prepared liquid crystal alignment agent was coated on a glass substrate, and after pre-baking on a hot plate at 80°C for 1 minute, it was heated in an oven at 200°C in which nitrogen was replaced in the library (post-baking) ) 1 hour, thereby forming a coating film with an average film thickness of 1,000 Å. With respect to this coating film, the surface unevenness of the coating film was evaluated in the same manner as in (2) of Example 1-1. As a result, the Ra of the coating film was 0.9 nm, and the surface unevenness was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as (3) of Example 1-1. As a result, the transmittance of the coating film was 98.5%, and the transmittance was "good".

(4) Evaluation of friction resistance

With respect to the obtained coating film, a rubbing machine having a roll wound with cotton cloth was used to perform 7 rubbing treatments at a roll rotation speed of 1000 rpm, a table moving speed of 20 cm/sec, and a bristle press length of 0.4 mm. Use an optical microscope to observe the immortality on the resulting substrate The foreign matter (fragments of the coating film) caused by the grinding was rubbed, and the number of foreign matter in the area of 500 μm×500 μm was measured. The evaluation was carried out as follows: the case where the number of foreign objects was 3 or less was evaluated as "good", the case where 4 or more and 7 or less was evaluated as "acceptable", and the case where 8 or more was evaluated as friction resistance Sexual "bad". As a result, no foreign matter was observed, and the friction resistance of the coating film was "good".

(5) Evaluation of orientation

With respect to the obtained glass substrate with an alignment film subjected to the rubbing alignment treatment, the alignment was evaluated in the same manner as (4) of Example 1-1. As a result, the refractive index anisotropy in this substrate was 0.031 nm, which was "good".

(6) Manufacturing of FFS-type liquid crystal display elements using the rubbing method

In the same manner as (5) of Example 1-1, the FFS type liquid crystal display element shown in FIG. 1 was produced. The schematic plan view of the top electrode 13 used here is shown in FIG. 4(a) and FIG. 4(b). In addition, FIG. 4(a) is a plan view of the top electrode 13, and FIG. 4(b) is an enlarged view of a portion C1 surrounded by a broken line in FIG. 4(a). In this embodiment, a substrate having a top electrode with an electrode line width d1 of 4 μm and a distance d2 between the electrodes of 6 μm is used.

Then, using cotton, rubbing treatment is performed on each surface of the coating film formed on the glass substrate to form the liquid crystal alignment film 12. In Fig. 4(b), the rubbing direction of the coating film formed on the glass substrate 11a is indicated by an arrow. These substrates were bonded via spacers with a diameter of 3.5 μm so that the rubbing directions of the substrates 11a and 11b were antiparallel, and liquid crystal MLC-6221 (manufactured by Merck) was injected to form a liquid crystal layer. 16. Furthermore, on the outside of the substrate 11a and the substrate 11b, two On the surface, polarizing plates (not shown in the figure) were bonded so that the polarization directions of the two polarizing plates were orthogonal to each other, thereby fabricating the liquid crystal display element 10.

(7) Evaluation of liquid crystal orientation

For the manufactured rubbed FFS type liquid crystal display element, the liquid crystal alignment was evaluated in the same manner as (6) of Example 1-1. As a result, the liquid crystal orientation in this liquid crystal display element was "good".

(8) Evaluation of voltage retention and heat resistance

For the manufactured rubbed FFS type liquid crystal display element, the voltage holding ratio (VHR _BF ) was measured in the same manner as (7) of Example 1-1, and the same as that of (8) of Example 1-1. ) In the same manner, the heat resistance of the liquid crystal display element was evaluated based on the rate of change of the voltage retention before and after the thermal stress was applied. As a result, VHR _BF was 99.4%. In addition, ΔVHR was 1.6%, and it was judged that the heat resistance was "good".

(9) Resistance to unevenness around the sealant (resistant to frame unevenness)

In the same manner as (9) of Example 1-1, the frame unevenness resistance was evaluated. As a result, the brightness difference of the liquid crystal display element was not recognized, and it was judged that the frame unevenness resistance was "excellent".

(10) Evaluation of residual image characteristics (DC residual image evaluation)

The DC residual image evaluation was performed in the same manner as in Example 1-1 (10). As a result, the afterimage erasing time of this liquid crystal display element was 2 seconds, which was evaluated as "good".

(11) Evaluation of contrast characteristics after driving stress (AC residual image evaluation)

AC residual image evaluation was performed in the same manner as in Example 1-1 (10). In addition, also in this case, evaluation was performed using a liquid crystal cell to which a polarizing plate was not bonded. its As a result, the minimum relative transmittance was 0.1%, and it was judged that the contrast characteristic was “good”.

[Example 2-2 to Example 2-15 and Comparative Example 2-1 to Comparative Example 2-5]

Except that the type and amount of the polymer used in the preparation of the liquid crystal alignment agent were set as described in Table 4 below, the liquid crystal alignment agent was prepared in the same manner as in Example 2-1, and the liquid crystal display element was manufactured. Make an evaluation. Among them, with regard to Comparative Examples 2-4, the liquid crystal orientation was poor, and the evaluation of the liquid crystal cell was not performed. The evaluation results are shown in Table 4 and Table 5 below.

As shown in Tables 3 to 5, in the liquid crystal alignment agent including the polymer obtained by using the compound (C′), good results were obtained regarding the surface unevenness, transmittance, rubbing resistance, and alignment properties of the coating film. In addition, in the liquid crystal display elements produced using these liquid crystal alignment agents, the alignment of liquid crystal molecules, voltage retention, heat resistance, frame unevenness resistance, residual image characteristics (DC residual image), and contrast characteristics (AC residual image ) All obtain good results, and have various characteristics in a well-balanced manner.

In contrast, in Comparative Example 2-1 using a diamine having no aromatic amine structure but only a chain structure, the residual image characteristic is "bad", and the frame unevenness resistance and heat resistance are inferior to the examples. As a result, it is not sufficient for the purpose of the invention. Minute.

In addition, in Comparative Example 1-1, Comparative Example 2-2, and Comparative Example 2-3 using diamines having only an aromatic amine structure, the heat resistance, frame unevenness resistance, and contrast characteristics of the liquid crystal display element were "bad" ". In addition, the polymer of Comparative Example 4 using PAm-14 has poor storage stability, surface unevenness, and transmittance of the coating film, and poor liquid crystal alignment, and therefore is not sufficient for use as a liquid crystal display element. Furthermore, in Comparative Example 2-5, the heat resistance and the frame unevenness resistance were "bad". In addition, if we comprehensively consider the transmittance, rub resistance, and orientation of the coating film, as well as the orientation of the liquid crystal in the liquid crystal display element, voltage retention, heat resistance, frame unevenness resistance, residual image characteristics, and contrast characteristics , Any comparative example becomes a worse result than the embodiment.

[Example 3-1: TN type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

As a polymer, 50 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 and 50 parts by weight of the polymer (PAm-16) obtained in Synthesis Example 2-16 were dissolved in a mixed solvent of NMP and BC In (NMP:BC=50:50 (weight ratio)), a solution having a solid content concentration of 6.5% by weight was prepared. After the solution was sufficiently stirred, it was filtered with a filter with a pore size of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of printability

Using a liquid crystal alignment film printer (manufactured by Nippon Printing Co., Ltd.), the liquid crystal alignment agent prepared in (1) was applied to the transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film at 80°C After heating (pre-baking) on the hot plate for 1 minute to remove the solvent, heating (post-baking) on the hot plate at 200°C for 10 minutes, the shape The average film thickness is 600Å. The coating film was observed with a microscope with a magnification of 20 times, and the presence or absence of uneven printing and pinholes was investigated. The evaluation was performed as follows: a case where neither printing unevenness nor pinholes was observed was evaluated as printability "good", and a case where at least one of printing unevenness and pinholes was slightly observed was evaluated as printing The printability is "good", and a case where at least one of a large amount of printing unevenness and pinholes is seen is evaluated as the printability "bad". In this example, neither uneven printing nor pinholes were observed, and the printability was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as (3) of Example 1-1. As a result, the transmittance of the coating film was 98.4%, which was “good”.

(4) Manufacturing of TN-type liquid crystal cell

Using a liquid crystal alignment film printer (manufactured by Nippon Photographic Printing Co., Ltd.), the liquid crystal alignment agent prepared in (1) was coated on the transparent electrode surface of a glass substrate with a transparent electrode containing an ITO film at 80°C After heating (pre-baking) on the hot plate 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 with an average film thickness of 600Å. The coating film was rubbed with a rubbing machine having a roll wound with rayon cloth at a roll rotation speed of 500 rpm, a table moving speed of 3 cm/sec, and a bristle press length of 0.4 mm to impart liquid crystal alignment ability. Then, ultrasonic washing was performed in ultrapure water for 1 minute, and then dried in a clean oven at 100° C. for 10 minutes, thereby obtaining a substrate with a liquid crystal alignment film. In addition, the operation was repeated to obtain a pair (2) of substrates having a liquid crystal alignment film.

Then, on one of the pair of substrates, a liquid crystal configuration After coating the outer edge of the film with an epoxy resin adhesive added with alumina balls with a diameter of 5.5 μm, a pair of substrates were overlapped and pressure-bonded with the liquid crystal alignment film faces facing each other to harden the adhesive. Then, a nematic liquid crystal (MLC-6221, manufactured by Merck) is filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port is sealed with an acrylic light-curing adhesive to produce TN Type liquid crystal cell.

(5) Evaluation of liquid crystal orientation

For the liquid crystal cell manufactured in (4), under a crossed Nicol, use a microscope to observe the connection at a magnification of 50 times. Whether there is an abnormal area when the 5V voltage is turned off. Evaluation was performed in the same manner as (6) of Example 1-1. As a result, the liquid crystal orientation in this liquid crystal display element was "good".

(6) Evaluation of pretilt angle stability

For the liquid crystal cell manufactured in (4), the angle of tilt of the liquid crystal molecules from the substrate surface was measured by the crystal rotation method using He-Ne laser light, and this value was used as the initial pretilt angle θ _IN . The crystal rotation method is based on Non-Patent Document 3 (TJ Schiffer et al., Journal of Applied Physics (Journal of Applied Physics, J. Appl. Phys.) No. 48, p. 1783 (1977)) and non-patent Document 4 (F. Nakano et al., "Japanese Journal of Applied Physics, JPN. J. Appl. Phys.) No. 19, p. 2013 (1980)) To proceed.

Then, an AC voltage of 5V was applied to the liquid crystal cell after the initial pretilt angle θ _IN was measured for 100 hours. Then, the pretilt angle was measured again by the same method as described above, and this value was used as the pretilt angle θ _AF after voltage application. These measured values are substituted into the following mathematical formula (EX-4), and the amount of change (Δθ(°)) of the pretilt angle before and after voltage application is obtained.

△θ=| θ _AF -θ _IN |…(EX-4)

The case where Δθ is less than 3% is evaluated as the pretilt angle stability "good", the case where 3% or more and less than 4% is evaluated as the pretilt angle stability "good", and the case where 4% or more is evaluated as the pretilt angle stability "Poor", as a result, the pretilt angle change rate of the liquid crystal display element was 1.6%, and it was judged that the pretilt angle stability was "good".

(7) Evaluation of voltage retention and heat resistance

The voltage holding ratio (VHR _BF ) was measured in the same manner as (7) of Example 1-1, and in the same manner as (8) of Example 1-1, based on the voltage before and after the application of thermal stress The change rate of the retention rate was used to evaluate the heat resistance of the liquid crystal display element. As a result, the VHR _BF was 98.6%. In addition, ΔVHR was 2.1%, and it was judged that the heat resistance was "good".

(8) Resistance to unevenness around the sealant (resistant to frame unevenness)

The frame unevenness resistance was evaluated in the same manner as (9) of Example 1-1. As a result, the brightness difference of this liquid crystal display element was not recognized, and it was judged as "good".

(9) Evaluation of residual image characteristics (DC residual image evaluation)

The DC residual image evaluation was performed in the same manner as in Example 1-1 (10). As a result, the afterimage erasing time of this liquid crystal display element was 12 seconds, which was evaluated as "good".

[Example 4-1: VA type liquid crystal display element] (1) Preparation of liquid crystal alignment agent

As a polymer, 20 parts by weight of the polymer (PIm-2) obtained in Synthesis Example 3-2 and 80 parts by weight of the polymer (PAm-3) obtained in Synthesis Example 2-3 were added to NMP and BC to prepare The solid content concentration is 6.5% by weight, and the mixing ratio of solvents is NMP:BC=50:50 (weight ratio). After the solution was sufficiently stirred, it was filtered with a filter with a pore diameter of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Evaluation of printability

Using the liquid crystal alignment agent prepared in (1), the printability was investigated in the same manner as in (2) of Example 3-1. Both printing unevenness and pinholes were not observed, and the printability was "good".

(3) Evaluation of transmittance

For the obtained coating film, the transmittance was evaluated in the same manner as (3) of Example 1-1. As a result, the coating film was 99.2%, and the transmittance of the coating film was "good".

(4) Manufacturing of VA-type liquid crystal cell

Using a liquid crystal alignment film printer (manufactured by Nippon Printing Co., Ltd.), the prepared liquid crystal alignment agent was coated on the transparent electrode surface of a glass substrate (thickness 1 mm) with a transparent electrode containing an ITO film. Then, it was heated (pre-baked) on a hot plate at 80°C for 1 minute, and then heated (post-baked) on a hot plate at 200°C for 60 minutes to form a coating film (liquid crystal alignment film) with an average film thickness of 800 Å. This operation was repeated to obtain a pair (2 pieces) of glass with a liquid crystal alignment film on the transparent conductive film Substrate. Next, for one of the pair of substrates, the outer edge of the surface with the liquid crystal alignment film was coated with an epoxy resin adhesive added with alumina balls with a diameter of 5.5 μm, and the liquid crystal alignment film surface was opposed A pair of substrates are overlapped and crimped in a way to harden the adhesive. Then, a nematic liquid crystal (Merck (Merck), MLC-6608) is filled between the pair of substrates from the liquid crystal injection port, and the liquid crystal injection port is sealed with an acrylic light-curing adhesive to produce a VA type Liquid crystal cell.

(5) Evaluation of liquid crystal orientation, voltage retention and heat resistance

For the liquid crystal cell manufactured in (4), the liquid crystal alignment was evaluated in the same manner as in Example 1-1 (6), and as a result, the liquid crystal alignment of the liquid crystal cell was "good". In addition, the voltage holding ratio (VHR _BF ) was measured in the same manner as (7) of Example 1-1, and heat resistance (before and after thermal stress application) was measured in the same manner as (8) of Example 1-1. The rate of change of the voltage holding rate). As a result, VHR _BF was 99.0%. In addition, ΔVHR was 2.3%, and it was judged that the heat resistance was "good".

(6) Resistance to unevenness around the sealant (resistant to frame unevenness)

The frame unevenness resistance was evaluated in the same manner as (9) of Example 1-1. As a result, the brightness difference of this liquid crystal cell was not recognized, and it was judged as "good".

[Example 5-1: Retardation film] (1) Preparation of liquid crystal alignment agent

100 parts by weight of the polymer (PAm-1) obtained in Synthesis Example 2-1 and 10 parts by weight of the polymer (PSi-1) obtained in Synthesis Example 4-1 were dissolved in a mixed solvent (NMP) containing NMP and BC ：BC=50:50 (weight ratio)), made into solid A solution with a concentration of 3.5% by weight. The solution was filtered with a filter having a pore diameter of 0.2 μm, thereby preparing a liquid crystal alignment agent.

(2) Manufacturing of retardation film

On one side of the TAC film as the substrate, the prepared liquid crystal alignment agent was coated using a bar coater, and baked in an oven at 120° C. for 2 minutes to form a coating film with a film thickness of 100 nm. Then, the surface of the coating film was irradiated perpendicularly with polarized ultraviolet rays of 10 mJ/cm ² including bright rays of 313 nm from the normal line of the substrate using a Hg-Xe lamp and a Glan Taylor beam. Then, after filtering the polymerizable liquid crystal (RMS03-013C, manufactured by Merck) with a filter with a pore size of 0.2 μm, the polymerizable liquid crystal was coated on the light-irradiated coating film using a bar coater , To form a coating film of polymerizable liquid crystal. After baking for 1 minute in an oven adjusted to a temperature of 50°C, use a Hg-Xe lamp to irradiate the coating film surface from a vertical direction with a non-polarized ultraviolet 1,000mJ/cm ² containing 365nm bright rays to make polymerizable The liquid crystal is cured to form a liquid crystal layer, thereby manufacturing a retardation film.

(3) Evaluation of liquid crystal orientation

With respect to the retardation film produced in (2), the presence or absence of abnormal regions was observed by visual observation under crossed Nicols and a polarizing microscope (magnification: 2.5 times), thereby evaluating the liquid crystal alignment (optical alignment). The evaluation is performed in the following manner: a case where the alignment is good under visual inspection and no abnormal area is observed with a polarizing microscope is evaluated as "good" for the liquid crystal alignment; The abnormal area was evaluated as "Yes" for the liquid crystal alignment; the abnormal area was evaluated by visual inspection and polarization microscope as the liquid crystal alignment "bad". As a result, this retardation film was evaluated as "good" for liquid crystal alignment.

(4) Adhesion

Using the retardation film produced in (2) above, the adhesion of the coating film formed with the liquid crystal alignment agent to the substrate was evaluated. First, using equal-spaced spacers with guides, a dicing knife is used to cut incisions from the surface of the phase difference film on the side of the liquid crystal layer to form 10 × 10 grid patterns in a range of 1 cm × 1 cm. The depth of each cut is set from the surface of the liquid crystal layer to half the thickness of the substrate. Then, after the cellophane was adhered so as to cover the entire surface of the lattice pattern, the cellophane was peeled off. The cut part of the lattice pattern after peeling was observed by visual observation under the crossed Nicols to evaluate the adhesiveness. The evaluation was carried out as follows: the part along the cut line and the intersection of the grid pattern was evaluated as the adhesion "good"; the part where peeling was observed relative to the total number of the grid pattern When the number of grids is less than 15%, the adhesion is evaluated as "possible"; the case where the number of grids where peeling is observed is 15% or more relative to the total number of grid patterns is evaluated as adhesion Sexual "bad". As a result, the retardation film was "good" in adhesion.

10‧‧‧LCD display element

11a, 11b‧‧‧glass substrate

12‧‧‧LCD alignment film

13‧‧‧Top electrode

14‧‧‧Insulation layer

15‧‧‧Bottom electrode

16‧‧‧Liquid crystal layer

Claims (18)

A liquid crystal alignment agent, characterized in that it contains a polymer (P) obtained by reacting at least one compound (C') selected from the group consisting of compound (C) and compound (C1), and The compound (C) has the following structure (a) and the following structure (b); (a) an aromatic amine structure in which two or three aromatic ring groups are bonded to the same nitrogen atom; and (b) Selected from divalent chain hydrocarbon groups with 6 or more carbons, and at least one methylene group in the chain hydrocarbon groups is -O-, -S-, -CO-, -NR-, -NRCO-,- A chain structure in a group consisting of divalent groups substituted by COO-, -COS- or -Si(CH ₃ ) ₂ -, wherein R is a hydrogen atom or a monovalent organic group; the compound (C1) Is a compound represented by the following formula (1-3),

In the formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond, a divalent hydrocarbon group, or a carbon-carbon bond introduced into the divalent hydrocarbon group- A divalent group consisting of one or more functional groups of O-, -COO-, -CO-, -NHCO-, -S- or -NH-, and the hydrogen atom bonded to the carbon atom of the group may be halogenated Atom or hydroxyl; among them, at least two of A ⁷ , A ⁸ and A ⁹ are aromatic rings bonded to the nitrogen atom; 2 or 3 aromatic ring groups are bonded to the same nitrogen atom The aromatic ring group in the aromatic amine structure is not bonded with a reactive group participating in polymerization, and L ⁴ is selected from a divalent chain hydrocarbon group having 1 to 5 carbon atoms and at least 1 of the chain hydrocarbon groups A structure in the group consisting of divalent groups substituted by a methylene group with -O-, -S-, -CO-, -NR ³ CO-, -COO- or -COS-, where R ³ is A hydrogen atom or a monovalent organic group, L ⁵ is a divalent chain hydrocarbon group with 1 to 20 carbons, or at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR ⁴ -, -NR ⁴ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted divalent group, R ⁴ is a hydrogen atom or a monovalent organic group. The liquid crystal alignment agent according to claim 1, wherein the compound (C) is a compound having two or more aromatic amine structures in the molecule. The liquid crystal alignment agent according to item 1 or item 2 of the scope of patent application, wherein the polymer (P) is selected from the group consisting of polyamide acid, polyamide acid ester, and polyimide At least one of them. The liquid crystal alignment agent described in item 1 or item 2 of the scope of patent application, wherein the compound (C) is a compound represented by the following formula (1),

In formula (1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently a single Bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring bonded to a nitrogen atom, and when B ¹ is a divalent organic group , At least two of A ¹ , A ² and B ¹ are bonded to the nitrogen atom by an aromatic ring; when B ² is a single bond, at least one of A ³ and A ⁴ is bonded by an aromatic ring For the nitrogen atom, when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹ includes those with 6 or more carbon atoms A bivalent chain hydrocarbon group, and at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -A bivalent group in a chain structure in a group consisting of a divalent group substituted with -Si(CH ₃ ) ₂ -, wherein R is a hydrogen atom or a monovalent organic group. The liquid crystal alignment agent according to claim 4, wherein at least any one of the B ¹ and the B ² is a single bond. The liquid crystal alignment agent described in item 4 of the scope of patent application, wherein the L ¹ is represented by the following formula (2),

In formula (2), L ² and L ³ are each independently selected from a divalent chain hydrocarbon group having 6 or more carbons, and at least one methylene group in the chain hydrocarbon group is represented by -O-, -S -, -CO-, -NR-, -NRCO-, -COO-, -COS-, or -Si(CH ₃ ) ₂ -The chain structure in the group consisting of substituted divalent groups, where R Is a hydrogen atom or a monovalent organic group; Q is a divalent group represented by the following formula (3) or formula (4); n is an integer from 0 to 4; "*" represents a bond;

In formula (3), A ⁵ is a hydrogen atom or a monovalent organic group; R ¹ and R ² are substituents, which may be the same or different from each other; "*" represents a bonding bond;

In formula (4), A ⁶ is a hydrogen atom or a monovalent organic group; "*" represents a bonding bond. The liquid crystal alignment agent described in claim 4, wherein the compound (C) is a compound represented by the following formula (1-1),

In the formula (1-1), L ¹¹ is a formula containing at least one methylene group in a bivalent chain hydrocarbon group with 6 or more carbon atoms as -O-, -S-, -CO-, -NR-, -NRCO -, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted with a divalent group of groups, wherein R is a hydrogen atom or a monovalent organic group; A ¹ , A ² , A ³ , A ^4. B ¹ and B ^{2 have the} same meaning as the above formula (1); wherein, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least one of A ¹ and A ³ is a hydrogen atom , Or at least one of B ¹ and B ² is a divalent organic group. The liquid crystal alignment agent described in item 4 of the scope of patent application, wherein the compound (C) is a compound represented by the following formula (1-2),

In the formula (1-2), L ¹² is a divalent group including a divalent chain hydrocarbon group having 6 or more carbons; A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are the same as those in the formula ( 1) The same meaning. The liquid crystal alignment agent according to item 1 or item 2 of the scope of patent application, wherein the polymer (P) is selected from the group consisting of tetracarboxylic dianhydride and a diamine containing the compound (C') At least one of the group consisting of polyamide acid, polyamide acid ester, and polyimide obtained by the reaction, and the tetracarboxylic dianhydride includes at least one selected from the group consisting of 1,2,3,4-cyclobutane Alkyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo -3-furanyl)-naphtho[1,2-c]furan-1,3-dione, 1,3,3a,4,5,9b-hexahydro-8-methyl-5-(tetrahydro -2,5-dioxo-3-furyl)-naphtho[1,2-c]furan-1,3-dione, 3-oxabicyclo[3.2.1]octane-2,4- Diketone-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-carboxynorbornane-2:3,5:6-dianhydride, 4,9-dioxatricyclic [5.3 .1.0 ^2,6 ]Undecane-3,5,8,10-tetraketone, bicyclo[3.3.0]octane-2,4,6,8-tetracarboxylic dianhydride, ethylenediaminetetraacetic acid At least one of anhydride, cyclopentanetetracarboxylic dianhydride, 1,3-propanediol bis(trimellitic anhydride ester), and pyromellitic dianhydride. The liquid crystal alignment agent according to item 1 or item 2 of the scope of patent application, wherein the molecular weight of the compound (C′) is 1,000 or less. A liquid crystal alignment film, characterized in that it is formed by using the liquid crystal alignment agent described in any one of items 1 to 10 in the scope of the patent application. A liquid crystal display element, characterized by comprising the liquid crystal alignment film as described in item 11 of the scope of patent application. A retardation film, characterized by comprising the liquid crystal alignment film as described in item 11 of the scope of patent application. A method for manufacturing a retardation film, which is characterized by comprising: coating the liquid crystal alignment agent as described in any one of items 1 to 10 of the scope of the patent application on a substrate to form a coating film; The step of irradiating the film with light; and the step of coating the polymerizable liquid crystal on the coating film irradiated with the light and curing it. A polymer characterized in that it is a polymer selected from the group consisting of polyamide acid, polyamide acid ester and polyimide, and it is selected from the group consisting of tetracarboxylic dianhydride, tetracarboxylic dianhydride, and tetracarboxylic acid dianhydride. At least one compound from the group consisting of a carboxylic acid diester compound and a tetracarboxylic acid diester dihalide, and includes a compound selected from the following formula (1-1), and the following formula (1-2) At least one diamine in the group consisting of the compound represented and the compound represented by the following formula (1-3) is obtained by reacting,

In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently Is a single bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring and is bonded to a nitrogen atom, and B ¹ is a divalent organic group In this case, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to the nitrogen atom; when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring. It is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹¹ includes a carbon number 6 or more At least one methylene group in the bivalent chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -A divalent group of a substituted group, wherein R is a hydrogen atom or a monovalent organic group; wherein, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least any of A ¹ and A ³ One is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group; [化9]

In the formula (1-2), L ¹² is a divalent group including a divalent chain hydrocarbon group having 6 or more carbons; A ¹ , A ² , A ³ , A ⁴ , B ¹ and B ² are the same as those in the formula ( 1-1) The same meaning; wherein, when L ¹² is an alkanediyl group having 6 to 10 carbon atoms, at least one of A ¹ and A ³ is a monovalent organic group, or at least one of B ¹ and B ² Any one is a divalent organic group;

In the formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond, a divalent hydrocarbon group, or a carbon-carbon bond introduced into the divalent hydrocarbon group- A divalent group consisting of one or more functional groups of O-, -COO-, -CO-, -NHCO-, -S- or -NH-, and the hydrogen atom bonded to the carbon atom of the group may be halogenated Atoms or hydroxyl groups; among them, at least two of A ⁷ , A ⁸ and A ⁹ are aromatic rings bonded to the nitrogen atom; 2 or 3 aromatic ring groups are bonded to the same nitrogen atom The aromatic ring group in the aromatic amine structure is not bonded with a reactive group participating in the polymerization, and L ⁴ is a divalent chain hydrocarbon group with 1 to 5 carbon atoms, or at least one of the chain hydrocarbon groups is The methyl group is a divalent group substituted by -O-, -S-, -CO-, -NR ³ CO-, -COO- or -COS-, wherein R ³ is a hydrogen atom or a monovalent organic group; L ³ is A divalent chain hydrocarbon group with 1 to 20 carbon atoms or at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR ⁴ -, -NR ⁴ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted with a divalent group, R ⁴ is a hydrogen atom or a monovalent organic group. A compound characterized in that it is represented by the following formula (1-1),

In formula (1-1), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently Is a single bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring and is bonded to a nitrogen atom, and B ¹ is a divalent organic group In this case, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to the nitrogen atom; when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring. It is bonded to a nitrogen atom, and when B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹¹ includes a carbon number 6 or more At least one methylene group in the bivalent chain hydrocarbon group is -O-, -S-, -CO-, -NR-, -NRCO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -A divalent group of a substituted group, wherein R is a hydrogen atom or a monovalent organic group; wherein, when L ¹¹ has an alkanediyl group having 1 to 5 carbon atoms, at least any of A ¹ and A ³ One is a hydrogen atom, or at least one of B ¹ and B ² is a divalent organic group. A compound characterized in that it is represented by the following formula (1-2), [化12]

In formula (1-2), A ¹ and A ³ are each independently a hydrogen atom or a monovalent organic group, A ² and A ⁴ are each independently a single bond or a divalent organic group; B ¹ and B ² are each independently Is a single bond or a divalent organic group; among them, when B ¹ is a single bond, at least one of A ¹ and A ² is an aromatic ring and is bonded to a nitrogen atom, and B ¹ is a divalent organic group In this case, at least two of A ¹ , A ² and B ¹ are aromatic rings and are bonded to the nitrogen atom; when B ² is a single bond, at least one of A ³ and A ⁴ is an aromatic ring. It is bonded to a nitrogen atom. When B ² is a divalent organic group, at least two of A ³ , A ⁴ and B ² are aromatic rings and are bonded to the nitrogen atom; L ¹² contains 6 or more carbon atoms A divalent group of a bivalent chain hydrocarbon group; wherein, when L ¹² is an alkanediyl group having 6 to 10 carbons, at least one of A ¹ and A ³ is a monovalent organic group, or B ¹ and B ^2, at least any one of a bivalent organic group. A compound characterized in that it is represented by the following formula (1-3),

In the formula (1-3), A ⁷ is a hydrogen atom or a monovalent organic group, and A ⁸ and A ⁹ are each independently a single bond, a divalent hydrocarbon group, or a carbon-carbon bond introduced into the divalent hydrocarbon group- A divalent group consisting of one or more functional groups of O-, -COO-, -CO-, -NHCO-, -S- or -NH-, and the hydrogen atom bonded to the carbon atom of the group may be halogenated Atoms or hydroxyl groups; among them, at least two of A ⁷ , A ⁸ and A ⁹ are aromatic rings bonded to the nitrogen atom; 2 or 3 aromatic ring groups are bonded to the same nitrogen atom The aromatic ring group in the aromatic amine structure is not bonded with a reactive group participating in the polymerization, and L ⁴ is a divalent chain hydrocarbon group with 1 to 5 carbon atoms, or at least one of the chain hydrocarbon groups is The methyl group is a divalent group substituted by -O-, -S-, -CO-, -NR ³ CO-, -COO- or -COS-, wherein R ³ is a hydrogen atom or a monovalent organic group; L ⁵ is A divalent chain hydrocarbon group with 1 to 20 carbon atoms or at least one methylene group in the chain hydrocarbon group is -O-, -S-, -CO-, -NR ⁴ -, -NR ⁴ CO-, -COO-, -COS- or -Si(CH ₃ ) ₂ -substituted with a divalent group, R ⁴ is a hydrogen atom or a monovalent organic group.

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