WO2012002501A1

WO2012002501A1 - Liquid crystal alignment treatment agent, liquid crystal alignment film, and liquid crystal display element equipped with the liquid crystal alignment film

Info

Publication number: WO2012002501A1
Application number: PCT/JP2011/065072
Authority: WO
Inventors: 尚宏野田; 正人森内; 皇晶筒井
Original assignee: 日産化学工業株式会社
Priority date: 2010-06-30
Filing date: 2011-06-30
Publication date: 2012-01-05
Also published as: JPWO2012002501A1; KR20130088045A; CN103154808B; CN103154808A; TWI510519B; JP5761188B2; TW201215631A; KR101824279B1

Abstract

Disclosed are: a liquid crystal alignment treatment agent which enables the production of a liquid crystal alignment film that does not undergo the decrease in a voltage holding ratio even when exposed to light; and a novel diamine which can be used for the production of a polymer that can be contained in a liquid crystal alignment treatment agent. The liquid crystal alignment treatment agent comprises at least one polymer selected from the group consisting of a polyimide precursor produced from a diamine represented by formula [1] and a polyimide produced by the imidization of the polyimide precursor. (In formula [1], X represents an organic group represented by formula [2]; Y₁ and Y₂ independently represent a benzene ring or a cyclohexane ring; p and q independently represent an integer of 0 or 1; S₁ and S₂ independently represent a single bond or a bivalent linking group, wherein S₁ represents a single bond when p is 0 and S₂ represents a single bond when q is 0; and R₁ represents a hydrogen atom, a fluorine atom, an alkyl or fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group.) (In formula [2], C₁ and C₂ independently represent a single bond or a bivalent organic group; A represents a thermally detachable organic group; B₁ represents a bivalent organic group selected from -CH₂-, -O-, -NH- and -S-; n represents an integer of 0 or 1; and the direction of the bonding of X is not limited.)

Description

Liquid crystal aligning agent, liquid crystal alignment film, and liquid crystal display element using the same

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

The liquid crystal alignment film is a constituent member of a liquid crystal display element widely used as a display device, and plays a role of aligning liquid crystals in a certain direction. Currently, the main liquid crystal alignment film used industrially is formed from a liquid crystal alignment treatment agent comprising a polyamic acid (also referred to as polyamic acid) which is a polyimide precursor or a polyimide solution. Specifically, a liquid crystal alignment treatment agent is applied to a substrate, heated and fired, and then subjected to an alignment treatment. Surface treatment by rubbing, or alignment in which liquid crystal is aligned parallel or inclined with respect to the substrate surface. Processing.

In recent years, there has been a tendency for the substrate area to increase and the unevenness to increase due to the increase in size, definition, and cost of the substrate used in the panel. When forming an alignment film on such a substrate, printing defects such as pinholes occur during printing, uniform alignment processing becomes difficult with rubbing, and liquid crystal alignment defects occur. . Further, in the liquid crystal alignment treatment, the surface treatment is mainly performed by rubbing at present, but there are problems such as a defect in the liquid crystal alignment film, resulting in a display defect and generation of dust.

On the other hand, a liquid crystal alignment process using a photoreaction has been proposed as an alignment process method instead of the rubbing method. Specifically, a method of imparting liquid crystal alignment ability by forming a polymer film having a specific site causing a photoreaction such as polyvinyl cinnamate on the substrate surface and irradiating with polarized or non-polarized radiation ( The photo-alignment method) is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust, and viewing angle can be improved by alignment division (see Patent Documents 1 and 2).

For liquid crystal cells such as TN (Twisted Nematic) and STN (Super Twisted Nematic), the liquid crystal alignment film needs to have a function of tilting and aligning liquid crystal molecules at a predetermined angle (pretilt angle) with respect to the substrate surface ( (See Patent Document 15). In order to develop a pretilt angle, a liquid crystal alignment film using a polyamic acid having an alkyl side chain, a side chain of a steroid skeleton, a side chain having a ring structure, polyimide, or the like is known (Patent Documents 3 and 4). 5). In the liquid crystal alignment process using light, the pretilt angle is usually given by irradiation with radiation whose incident direction to the substrate surface is inclined normal to the substrate (see Patent Document 1).

JP-A-6-287453 JP-A-9-297313 Japanese Patent Laid-Open No. 05-043687 Japanese Patent Laid-Open No. 04-281427 Japanese Patent Laid-Open No. 02-223916

Conventionally, as described above, the main liquid crystal alignment film is formed of a liquid crystal alignment treatment agent composed of a polyimide precursor polyamic acid or a polyimide solution, but the preparation of a liquid crystal alignment film using a solution containing a soluble polyimide. The method has an advantage that good characteristics can be obtained as a liquid crystal alignment film even when firing at a relatively low temperature. However, when a polyimide containing a large amount of diamine having a side chain is used, there is a problem that the coating and film forming properties on the substrate are deteriorated.
In order to solve such a problem, the amount of the side chain is reduced by using a small amount of a diamine having a ring structure in the side chain that can obtain a relatively high pretilt angle in a small amount (for example, see Patent Document 5), and the substrate is supplied. A method for improving the applicability of the coating is also performed. Diamines having a ring structure in the side chain are often poorly soluble in polar solvents such as N-methylpyrrolidone (hereinafter also referred to as NMP), causing problems such as variations in the quality of the resulting polymer. It can happen.

Also, in materials used for photo-alignment, polymers having side chains including cinnamate groups are often used, and for vertical alignment, it is necessary to introduce a diamine having another side chain. is there. In general, side chains are often hydrophobic, and the affinity with polar solvents that have high wettability to the substrate is reduced, so polymers with many side chain sites can be coated and formed on the substrate. Have the problem of getting worse.

Also, along with the recent improvement in performance of liquid crystal display elements, liquid crystal display elements are used for large-screen, high-definition liquid crystal televisions and in-vehicle applications such as car navigation systems and meter panels. In such applications, in order to obtain high luminance, a backlight having a large calorific value may be used, and high stability with respect to the backlight is required. In particular, if the voltage holding ratio, which is one of the electrical characteristics, is reduced by the light irradiation of the backlight, a seizure defect (linear seizure) that is one of the display defects of the liquid crystal display element is likely to occur. A highly reliable liquid crystal display element cannot be obtained. Therefore, in the liquid crystal alignment film, in addition to good initial characteristics, for example, it is required that the voltage holding ratio does not easily decrease even after being exposed to light irradiation for a long time.

In view of the above situation, an object of the present invention is to provide a liquid crystal alignment treatment agent in which the polymer contained in the liquid crystal alignment treatment agent has good handling properties, excellent coating properties, and high reliability. In addition, the present invention provides a diamine having a side chain that is capable of providing a liquid crystal aligning agent having good solubility in a solvent used for obtaining a polymer and excellent printability, and is exposed to light irradiation. However, an object of the present invention is to provide a liquid crystal alignment film in which a decrease in voltage holding ratio is suppressed.

As a result of intensive studies to achieve the above object, the present inventors have completed the present invention. That is, the present invention has the following gist.
(1) Selected from the group consisting of a polyimide precursor obtained by reaction of a diamine component containing a diamine of the following formula [1] and a tetracarboxylic dianhydride, and a polyimide obtained by imidizing the polyimide precursor. A liquid crystal aligning agent comprising at least one polymer.

(In the formula, X is an organic group represented by the following formula [2], Y ₁ and Y ₂ independently represent a benzene ring or a cyclohexane ring. P and q are independently 0 or 1; S ₁ and S _{2 each} independently represents a single bond or a divalent linking group, and when p = 0, S ₁ is a single bond, and when q = 0, S ₂ is a single bond. ₁ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group.)

(Wherein C ₁ and C ₂ independently represent a single bond or a divalent organic group, A represents an organic group which can be removed by heat, and B ₁ represents —CH ₂ —, —O—, Represents a divalent organic group selected from —NH— and —S—, n represents 0 or 1, and the bonding direction of X is not limited.)

(2) The liquid crystal aligning agent according to the above (1), wherein the content of the diamine of the formula [1] in the diamine component is 5 to 95 mol%.
(3) The liquid crystal aligning agent according to the above (1) or (2), wherein A in the formula [2] is a tertiary butoxycarbonyl group represented by the formula [3].

(4) The liquid crystal aligning agent according to any one of (1) to (3), wherein C ₁ and C _{2 in} the formula [2] are divalent organic groups represented by the following formula [6].

(In the formula, S ₃ and S ₄ are each independently a divalent linking group, and R ₂ and R ₃ are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. )
(5) In the above formula [6], [—S ₄ —R ₃ —] is represented by the following formula [4], and either C ₁ or C ₂ has the structure of the formula [4] The liquid crystal aligning agent according to any one of 1) to (4).

(Wherein B ₂ represents a single bond, a phenyl group, —CH ₂ —, —O—, —NH—, —NR ₁₀ —, and —S—, and R ₁₀ represents carbon. Represents a divalent hydrocarbon of formula 1 to 6. The structure of the olefin of formula [4] may be either E or Z. The bond indicated by the broken line is the bond of C _{1 of} formula [2] Benzene ring or carbonyl carbon to which C ₂ is bonded.)

(6) The liquid crystal aligning agent according to any one of (1) to (4), wherein n = 0 in the formula [2].
(7) The liquid crystal aligning agent according to any one of (1) to (5), wherein in the formula [2], C ₁ is a single bond.
(8) The liquid crystal aligning agent according to any one of (1) to (7), wherein in the formula [2], B ₁ is —O— or NH—.
(9) The liquid crystal aligning agent according to the above (5), wherein in the formula [4], B ₂ is —O— or NH—.

(10) The liquid crystal according to any one of (1) to (9), wherein the diamine represented by the formula [1] is a compound of any one of the following formulas [1-a] to [1-k]. Alignment treatment agent.

(11) A liquid crystal alignment film using the liquid crystal aligning agent according to any one of (1) to (10).
(12) A liquid crystal alignment film using the liquid crystal alignment treatment agent according to any one of (1) to (10), wherein the alignment process is performed by light irradiation.
(13) A liquid crystal display device comprising the liquid crystal alignment film according to (11) or (12).

(14) A diamine having a structure represented by the following formula [1].

(Wherein C ₁ and C ₂ independently represent a single bond or a divalent organic group, A represents an organic group which can be removed by heat, and B ₁ represents —CH ₂ —, —O—, —NH— and —S— represent a divalent organic group selected, n represents 0 or 1, and the bonding direction of X is not limited.

(15) The diamine according to (14), wherein in formula [2], A is a tertiary butoxycarbonyl group represented by formula [3].

(16) The diamine according to (14) or (15), wherein in formula [2], C ₁ and C ₂ are divalent organic groups represented by the following formula [6].

(In the formula [6], S ₃ and S ₄ are independently a divalent linking group, and R ₂ and R ₃ are independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. .)

(17) In the above formula [6], [—S ₄ —R ₃ —] is represented by the following formula [4], and either C ₁ or C ₂ has the structure of the formula [4] The diamine according to any one of 14) to (16).

(Wherein B ₂ represents a single bond, a phenyl group, —CH ₂ —, —O—, —NH—, —NR ₁₀ —, and —S—, a divalent organic group selected, and R ₁₀ represents the number of carbon atoms. divalent structures olefin hydrocarbons representing the. formula [4] E of 1-6 bond represented by either good. dashed Z member is attached is C ₁ of the formula [2] Linked to benzene ring or carbonyl carbon to which C ₂ is bonded.)

(18) A diamine represented by any one of the following formulas [1-a] to [1-k].

(19) Polyamide, polyamic acid, or polyimide obtained by imidizing the polyamic acid, obtained using the diamine according to any one of (14) to (18) as a raw material.

The diamine used as a raw material for the liquid crystal alignment treatment agent of the present invention has very high solubility in a polar solvent such as NMP and has good handling during polymerization. A polyamic acid obtained from such a diamine, or the polyamic acid The liquid crystal aligning agent containing polyimide obtained by imidizing is excellent in coating and film forming properties, and further becomes a liquid crystal alignment film in which a decrease in voltage holding ratio is suppressed even when exposed to light irradiation. In addition, the diamine described above can provide a liquid crystal aligning agent suitable for the photo-alignment method.

<Diamine of the present invention>
As described above, the diamine used as a raw material for the liquid crystal aligning agent of the present invention is a diamine represented by the following formula [1] (hereinafter also referred to as the diamine of the present invention).

The diamine of the present invention has a phenylenediamine skeleton protected in the side chain structure by a thermally leaving group such as a tertiary butoxycarbonyl group (hereinafter also referred to as a Boc group). Usually, an amino group is a highly reactive organic group, so it is difficult to exist as it is as a part of the diamine side chain as it is, but the amino group can be made reactive by protecting it with a thermal leaving group. Can be reduced. In addition, when the amino group protected with a heat-leaving group is heated at about 150 ° C. or higher, the heat-leaving group is deprotected and can be converted into an amino group.

Also, amino groups are highly reactive organic groups and are known to react with functional sites such as unsaturated bonds, carboxylic acids, carboxylic anhydrides, epoxy compounds, and carbonyl groups. On the other hand, as shown in the figure below, when an amino group protected with a heat-eliminable group is placed in close proximity to a carbonyl-containing linking group such as an amide bond or an ester bond, it is more intramolecular than between diamine molecules. Reaction becomes easy to occur, and heterocyclic rings such as an imidazole ring, an oxazole ring, and a thiazole ring can be formed.

Thereby, the diamine of the present invention forms a heterocyclic ring by reacting the amino group generated by the heat treatment in the baking process of the liquid crystal aligning agent in the molecule, thereby generating a rigid side chain. The chain structure functions as a good induction site for the pretilt angle.

In addition, not all of the amino groups from which the thermal leaving group is removed are used in the cyclization reaction, and some of them are also used in the intermolecular reaction, improving the film strength and reducing the low molecular weight in the polymer. It contributes to the improvement of reliability by crosslinking with the component. Thus, the polyamic acid or polyimide using the diamine of the present invention is less prone to film scraping during rubbing treatment, and even when exposed to high temperature, backlight irradiation, etc. for a long time, the voltage holding ratio decreases and the ion density increases. Is difficult to wake up.
Furthermore, since the diamine of the present invention has a bulky Boc group as a thermally desorbable group, the solubility in an organic solvent (particularly a polar solvent such as NMP) at the time of (condensation) polymerization of the diamine is very high. Good handling during polymerization.
In addition, the polyimide precursor obtained using the diamine of the present invention and the liquid crystal alignment treatment agent using polyimide are excellent in coating and film forming properties, and the liquid crystal in which the decrease in voltage holding ratio is suppressed even when exposed to light irradiation. An alignment film can be obtained, and the liquid crystal alignment treatment agent can also be used in a photo-alignment method.

The diamine of the present invention has a side chain represented by the following formula [A].

In formula [A], X is an organic group represented by the following formula [2], Y ₁ and Y ₂ independently represent a benzene ring or a cyclohexane ring, and p and q are independently 0 or 1 represents an integer of ₁ and S ₁ and S _{2 each} independently represents a single bond or a divalent linking group. When p = 0, S ₁ is a single bond, and when q = 0, S ₂ is a single bond. R ₁ represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group. In the formula, DA represents a phenylenediamine skeleton.

Here, C ₁ and C ₂ independently represent a single bond or a divalent organic group, A represents an organic group that can be removed by heat, and B ₁ represents —CH ₂ —, —O—, — NH— and —S— represent a divalent organic group selected, and n represents 0 or 1. In the bonding direction of X, that is, in the above [A], C ₁ of X may be bonded to the Y ₁ side or may be bonded to the C ₁ side.

In the diamine of the present invention, DA has a phenylenediamine skeleton, and thus can be a diamine having a wide side chain amount and side chain density. However, when the molecular weight of the diamine skeleton is large, the molecular weight of the diamine increases, and the amount of monomer required for the polymer increases, making it difficult to use industrially. Further, when the diamine skeleton is an aliphatic diamine, the reactivity becomes too high, and problems such as precipitation due to salt formation and gelation occur during the preparation of the polymer.
The amino group of the phenylenediamine skeleton is preferably a primary amino group, but may be a secondary amino group, for example, an alkyl group having a relatively low molecular weight such as a methyl group, an ethyl group, a propyl group, or a butyl group. May be substituted with an amino group.

In the diamine of the present invention, the side chain site in the formula [1] is represented by the following formula [5], and this site is a part that determines the expression and the size of the pretilt angle. It is possible to obtain a preferable size of the corner.

In formula [5], Y ₁ and Y ₂ are each independently a benzene ring or a cyclohexane ring. The benzene ring and the cyclohexane ring may have a substituent if necessary. Moreover, as for the coupling | bonding position of a substituent, 1, 4-substitution is preferable in both a benzene ring and a cyclohexane ring. p and q independently represent an integer of 0 or 1. The cyclohexane ring preferably has a trans structure (so-called chair type).

In formula [5], S ₁ and S ₂ are each independently a single bond or a divalent linking group. When p = 0, S ₁ is a single bond, and when q = 0, S ₂ is a single bond. .
Specific examples of S ₁ and S ₂ are shown in (S-1) to (S-11), but are not limited thereto.

In the above formulas (S-5) to (S-8), (S-10), and (S-11), R ₄ and R ₅ are independently a hydrogen atom or a carbon number of 1 to 20, preferably 1 15 to 15 monovalent hydrocarbon groups.
Here, the monovalent hydrocarbon group is an alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, a t-butyl group, a hexyl group, an octyl group or a decyl group; a cycloalkyl such as a cyclopentyl group or a cyclohexyl group. Group: bicycloalkyl group such as bicyclohexyl group; vinyl group, 1-propenyl group, 2-propenyl group, isopropenyl group, 1-methyl-2-propenyl group, 1-, 2- or 3-butenyl group, hexenyl An alkenyl group such as a group; an aryl group such as a phenyl group, a xylyl group, a tolyl group, a biphenyl group and a naphthyl group; and an aralkyl group such as a benzyl group, a phenylethyl group and a phenylcyclohexyl group.

Some or all of the hydrogen atoms of these monovalent hydrocarbon groups are halogen atoms, hydroxyl groups, thiol groups, amino groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amides. Group, nitro group, organooxy group, organosilyl group, organothio group, organoamino group, carbamate group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group, etc. May be. Further, these may have a ring structure.
When R ₄ and R ₅ have a bulky structure such as an aromatic ring or an alicyclic structure, the liquid crystal orientation may be reduced, or the monomer may become viscous and difficult to handle. , An alkyl group such as an ethyl group, a propyl group, or a butyl group, or a hydrogen atom is preferable, and a hydrogen atom is more preferable. Particularly preferred S ₁ and S ₂ are a single bond, —O—, —NHCO—, or —COO—.

In the formula [5], R ₁ represents a hydrogen atom, a fluorine atom, an alkyl group or a fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group. The alkyl group and the fluoroalkyl group may be linear or branched, and may form a condensed ring structure like a steroid group. When R ₁ is an alkyl group, it is preferably a straight chain and may have an appropriate substituent. From the viewpoint of ease of synthesis and availability, R ₁ is preferably an alkyl group. The number of carbon atoms of the alkyl group of R ₁ is not particularly limited. However, in the formula [5], when p and q are 0, that is, when there is no ring structure, the ability to develop a pretilt angle is low. It is preferable that R ₁ has 5 to 18 carbon atoms, and more preferably 7 to 15 carbon atoms.
In addition, when a benzene ring or a cyclohexane ring is introduced, the ability to develop a pretilt angle is improved. Therefore, R ₁ is preferably an alkyl group having a small number of carbon atoms. Preferable carbon number of R ₁ is 1 to 12, more preferably 3 to 10.

Preferred specific examples of the structure represented by the formula [5] are shown below.

From the viewpoint of ease of synthesis and availability of raw materials, the structure represented by the formula [5] has [5-1] to [5-3], [5-8], [5-14] to [5]. −19], [5-20], [5-44], [5-45] and the like are preferable, and [5-1], [5-2], [5-8] and the like are more preferable.
In the diaminobenzene skeleton in the formula [1], the bonding position of the amino group in the benzene ring is not limited. Specific amino group positions include 2, 3 positions, 2, 4 positions, 2, 5 positions, 2, 6 positions, 3, 4 positions, or 3, positions relative to the side chain substitution position. 5 positions. Among these, from the viewpoint of reactivity when synthesizing a polyamic acid, the 2,4, 2,5, or 3,5 positions are preferred. Considering the ease of synthesis, the positions 2 and 4 (Formula 1-1) or the positions 3 and 5 (Formula 1-2) are preferable.

As described above, the diamine of the present invention deprotects a heat-eliminable group such as a Boc group during firing, generates an amino group, and the resulting amino group undergoes a nucleophilic attack on the carbonyl carbon to form a complex. A thermal cyclization reaction occurs to form a ring. For this reason, the structure shown to following formula [2] is contained in the diamine of this invention.

Here, C ₁ and C ₂ independently represent a single bond or a divalent organic group, A represents an organic group that can be removed by heat, and B ₁ represents —CH ₂ —, —O—, — NH— and —S— represent a divalent organic group selected, n represents 0 or 1, and the direction of the bond portion of X is not limited.
The thermally desorbable group represented by A in the above formula [2] is the firing temperature of the liquid crystal aligning agent of the present invention, preferably 150 ° C. or more, more preferably 170 to 300 ° C., particularly preferably 180. The organic group is not particularly limited as long as it is an organic group that can be removed by heat at ˜250 ° C.
Examples of the thermal leaving group include carbamate-based organic groups represented by benzyloxycarbonyl group, 9-fluorenylmethyloxycarbonyl group, allyloxycarbonyl group, tertiary butoxycarbonyl group (Boc group) and the like. It is done. The Boc group is particularly preferred because it has a high efficiency of desorption by heat, desorbs at a relatively low temperature, and is a harmless gas when desorbed.

As preferred examples of the general formula [2], the following formulas [2-1] to [2-16] are shown.
B ₁ in the formula [2] represents a divalent organic group selected from —CH ₂ —, —O—, —NH—, and —S—, and is not particularly limited. From the viewpoint of the reaction yield and the electric yield of the alignment film, —O— or NH— is particularly preferable.
As for n in the formula [2], when the Boc group is removed and an amino group is generated by firing, a 5-membered heterocyclic ring is formed when n = 0, and a 6-membered heterocyclic group is formed when n = 1. Rings can be formed. However, when n = 1, the distance between the carbon of the amino group and the carbonyl group is long, and the cyclization reaction hardly occurs. Therefore, n = 0 is preferable from the viewpoint of the efficiency of the cyclization reaction.

In formula [2], C ₁ and C ₂ represent a single bond or a divalent organic group. The divalent organic group is not particularly limited and may be variously selected depending on easiness of synthesis and availability of raw materials. When C ₁ and C ₂ are divalent organic groups, they can be represented by the structure represented by the following formula [6].

In the formula [6], S ₃ and S ₄ are each independently a single bond or a divalent linking group, and R ₂ and R ₃ are independently a single bond or a divalent carbon atom having 1 to 20 carbon atoms. Hydrogen.
Specific examples of S ₃ and S ₄ are the same as those in the above formulas [S-1] to [S-11], but other linking groups may be used.

In the formula [6], when R ₂ and R ₃ are divalent hydrocarbons having 1 to 20 carbon atoms, specific examples are given below.
For example, methylene group, 1,1-ethylene group, 1,2-ethylene group, 1,1-propylene group, 1,2-propylene group, 1,3-propylene group, 1,2-butylene group, 1,4 Alkylene groups such as -butylene group, 2,3-butylene group, 1,6-hexylene group, 1,8-octylene group and 1,10-decylene group; 1,2-cyclopropylene group, 1,2-cyclohexane Cycloalkylene such as butylene, 1,3-cyclobutylene, 1,2-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,4-cyclohexylene Group: 1,1-ethenylene group, 1,2-ethenylene group, 1,2-ethenylenemethylene group, 1-methyl-1,2-ethenylene group, 1,2-ethenylene-1,1-ethylene group, , 2-Ethenylene-1,2-ethylene 1,2-ethenylene-1,2-propylene group, 1,2-ethenylene-1,3-propylene group, 1,2-ethenylene-1,4-butylene group, 1,2-ethenylene-1,2- Alkenylene groups such as butylene, 1,2-ethenylene-1,2-heptylene, 1,2-ethenylene-1,2-decylene; ethynylene, ethynylenemethylene, ethynylene-1,1-ethylene, Ethynylene-1,2-ethylene group, ethynylene-1,2-propylene group, ethynylene-1,3-propylene group, ethynylene-1,4-butylene group, ethynylene-1,2-butylene group, ethynylene-1,2 Alkynylene groups such as -heptylene group, ethynylene-1,2-decylene group, etc .; 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,2-naphthylene Group, 1,4-naphthylene group, 1,5-naphthylene group, 2,3-naphthylene group, 2,6-naphthylene group, 3-phenyl-1,2-phenylene group, 2,2′-diphenylene group, 2 Arylene groups such as 1,2′-dinaphth-1,1′-yl group; 1,2-phenylenemethylene group, 1,3-phenylenemethylene group, 1,4-phenylenemethylene group, 1,2-phenylene-1, 1-ethylene group, 1,2-phenylene-1,2-ethylene group, 1,2-phenylene-1,2-propylene group, 1,2-phenylene-1,3-propylene group, 1,2-phenylene- 1,4-butylene group, 1,2-phenylene-1,2-butylene group, 1,2-phenylene-1,2-hexylene group, methylene-1,2-phenylenemethylene group, methylene-1,3-phenylene Methylene group, methyle And a bifunctional hydrocarbon group composed of an arylene group such as chloro-1,4-phenylenemethylene group and an alkylene group.

In addition, a part or all of the hydrogen atoms of the divalent hydrocarbon group may be halogen atoms, hydroxyl groups, thiol groups, phosphate ester groups, ester groups, carboxyl groups, phosphate groups, thioester groups, amide groups, nitro groups, May be substituted with an organooxy group, organosilyl group, organothio group, organoamino group, carbamate group, acyl group, alkyl group, cycloalkyl group, bicycloalkyl group, alkenyl group, aryl group, aralkyl group, etc. . Further, these may have a ring structure.
In R ₂ and R ₃ , the smaller the number of carbon atoms, the more easily the monomer becomes solid, and the stability of the pretilt angle improves when used as a liquid crystal alignment film. Therefore, an alkylene group having 1 to 6 carbon atoms, An alkenylene group having 6 to 6 carbon atoms or an alkynylene group having 1 to 6 carbon atoms is preferable.
In the formula [6], the binding position of C ₁ is preferably 4-position or 5-position when viewed from the substitution position of the amino group protected by the Boc group, but after cyclization in both the 4-position and 5-position. Since the structure is the same, it is not particularly limited.

In the formula [6], when the structure of [—S ₄ —R ₃ —] is represented by the following formula [4] and either C ₁ or C ₂ has the structure of the formula [4]: The structure can be used in the photo-alignment method.

Here, B ₂ represents a divalent organic group selected from a single bond, a phenyl group, —CH ₂ —, —O—, —NH—, —NR ₁₀ —, and —S—, and R ₁₀ represents the number of carbon atoms. 1 to 6 divalent hydrocarbons are represented.

The olefin moiety of formula [4] may be either E-form or Z-form, and the broken line indicating the bond to olefin is the benzene ring to which C ₁ of general formula [2] is bonded, or C ₂ is bonded. Bonded to the carbonyl carbon.
The structure represented by the formula [4] is a site that causes various reactions by light. In the formula, B ₂ represents a divalent organic group selected from a single bond, a phenyl group, —CH ₂ —, —O—, —NH—, —NR ₁₀ —, and —S—. From the viewpoint of availability, —O— or —NH— is particularly preferable. R ₁₀ represents a divalent hydrocarbon having 1 to 6 carbon atoms.
The olefin moiety of the formula [4] is preferably E-form in C _{1 because of} easy synthesis. In this case, since the formula [2] is synonymous with the cinnamate derivative, it is particularly preferable from the viewpoint of easy photoreaction.
On the other hand, the olefin site in C ₂ is not particularly limited. Also, if the C ₂ comprises a structure that represented by the formula [4], the light reaction activity by cyclized by heat. On the other hand, when it is not cyclized, the photoreaction is unlikely to occur, and it is considered that the monomer, the liquid crystal alignment treatment agent and the liquid crystal alignment film using the monomer, are less affected by ultraviolet rays and the like than the conventional cinnamate system. In such a point, it is more preferable that C ₂ has the structure of the formula [4].

As preferred specific examples of the formula [2], the following formulas [2-17] to [2-32] are shown.

Formulas [2-17] to [2-20] and [2-25] to [2-28] are changed to formulas [2-33] to [2-40] shown below upon firing, whereby cinnamate It is considered that the same effect can be obtained.

Although the structure of especially preferable diamine is shown below, it is not limited to these.

In the formulas [7-1] to [7-6], B ₁ represents —O— or NH—, C ₁ and C _{2 each} independently represents a single bond or a divalent organic group, Y ₁ , Y ₂ is a benzene ring or a cyclohexyl ring, S ₁ and S ₂ are a single bond or a divalent linking group, p and q represent 0 or an integer of 1, and when p = 0, S ₁ is a single bond, and when q = 0, S ₂ is a single bond, and R ₁ represents a proton or an alkyl group having 1 to 22 carbon atoms.
Specific examples of the diamine structure are shown below.

Substituent X is used for substituted o-phenylenediamine, 2-aminophenol, 2-aminobenzenethiol, etc. (substrate) to protect thermally leaving groups such as Boc groups such as di-tert-butyl dicarbonate. A precursor having a desired structure can be synthesized by allowing the compound to act in a solvent. At this time, the yield and reaction rate can be improved by coexisting a base such as pyridine, 4-dimethylaminopyridine, or triethylamine as necessary. On the other hand, if these bases are allowed to coexist and react with each other, two units of the heat-eliminable group are introduced into the amino group or a product in which the heat-eliminable group is introduced into the hydroxyl group, It is preferable to adopt conditions more suitable for the substrate to be reacted.

When it is desired to direct the site represented by the formula [2], that is, the site where cyclization occurs to the diaminobenzene side, obtain a compound in which X is an unsubstituted or side chain substituent, Examples include a method in which a group is protected with a thermally leaving group, and dinitrobenzene is introduced to convert it into a diamine. Specific synthesis examples are shown below.

On the other hand, when it is desired to direct the site where cyclization occurs to the side chain side, X in the above formula is protected in advance, or is in an inactive substituent group that can be converted later, and a thermal leaving group. And a method in which a side chain is introduced into an amino group or a hydroxyl group adjacent to the amino group protected with, then X is converted into an active substituent and the like, and dinitrobenzene is introduced to convert it into a diamine. Specific synthesis examples are shown below.

An amide bond can be synthesized by a condensation reaction between a carboxylic acid and an amine, and an ester bond can be synthesized by a condensation reaction between the carboxylic acid and an alcohol or phenol. This reaction is a method of reacting a carboxylic acid halide with an amine, alcohol, or phenol in the presence of a base in a solvent that does not react with carboxylic acid, amine, and alcohol, or with a carboxylic acid in the presence of a condensing agent. , A method of reacting with amine, alcohol, or phenol.

The carboxylic acid halide can be obtained by reacting the carboxylic acid with an appropriate halogenating agent. From the viewpoint of versatility, the carboxylic acid halide used is preferably a carboxylic acid chloride, for example, carboxylic acid chloride. Carboxylic acid chloride is obtained by reacting carboxylic acid with a chlorinating agent. Examples of chlorinating agents include thionyl chloride, phosphonyl chloride, sulfuryl chloride, oxalyl chloride, phosphorus trichloride, diphosphorus pentachloride, etc., but thionyl chloride, chloride, etc. are versatile and easy to remove. Sulfuryl, oxalyl chloride and the like are preferable, and thionyl chloride and oxalyl chloride are particularly preferable.

The solvent used in the above reaction includes N-methyl-2-pyrrolidone, γ-butyrolactone, N, N-dimethylformamide, N, N-dimethylacetamide, tetrahydrofuran, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, tetrahydropyran, , 4-dioxane and the like. Bases used in the condensation reaction include organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, N-methylmorpholine, and in some cases, aqueous sodium hydroxide or water. A method using an aqueous solution of an inorganic base such as an aqueous potassium oxide solution (Schotten-Baumann method) is also included.

When the condensation reaction is performed in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1,3 , 5-Triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazol-1-yl) ) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate diphenyl, 4- (4,6- Dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride, n-hydrate, etc. There can be used.

In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The addition amount of the Lewis acid is preferably 0.1 to 1.0 times moles relative to number of moles of _{C 1.}
In the linking group represented by C ₁ and C ₂ in the general formula [2], a preferable C ₁ and C ₂ structure includes a divalent organic group represented by the following formula [6].

Here, S ₃ and S ₄ are each independently a single bond or a divalent linking group, and R ₂ and R ₃ are each independently a single bond or a divalent hydrocarbon having 1 to 20 carbon atoms. . Specific examples include diamines of formula [1-c], formula [1-i], and formula [1-h].

The diamine of the formula [4-c] can be synthesized according to the above-described method in which the cyclization site is directed to the side chain.

In the synthesis of the diamines of the formulas [4-i] and [4-h], they can be synthesized according to the method in which the cyclization site is directed to the diamine side, but the synthesis method can also be performed by other methods. There is no particular limitation.
When an olefin structure is introduced into the diamine, the same effect can be obtained with either the E (trans) isomer or the Z (cis) isomer. When the E-form is synthesized, it can be synthesized by using fumaric acid, and the Z-form can be synthesized by using maleic acid. There is also a method of synthesizing the E isomer by utilizing the isomerization reaction of the Z isomer, which is superior to the synthesis method via fumaric acid and can be synthesized with high yield. Regardless, the method using maleic acid is preferred.

In the diamine synthesis examples of the formula [4-i] and the formula [4-h], there is a step of forming an ether bond, but the ether bond is an alkyl halide or aryl halide and an alcohol in a solvent that does not react with them. It can be obtained by the Williamson ether synthesis method in which the reaction is carried out in the presence of a base. In addition, a method using a palladium catalyst or the like, a method using copper as a catalyst, or the like can be used. A preferred means is selected depending on the substrate to be reacted. The Williamson ether synthesis method is preferable in consideration of post-treatment after reaction and cost. The base to be used is not particularly limited, but an inorganic base such as sodium hydride, potassium hydride, potassium carbonate, sodium hydroxide, sodium alkoxide, potassium alkoxide, or an organic base such as triethylamine, trimethylamine, tributylamine, trioctylamine is used. it can.

By using the synthesis method described above and the like, the dinitrobenzene derivative [8] is synthesized, and the target diamine can be obtained by converting the nitro group to an amino group by a normal reduction reaction. The method for reducing the dinitro compound is not particularly limited, and usually palladium-carbon, platinum oxide, Raney nickel, platinum black, rhodium-alumina, platinum sulfide carbon, etc. are used as a catalyst, and ethyl acetate, toluene, tetrahydrofuran, dioxane, There is a method of performing reduction with hydrogen gas, hydrazine, hydrogen chloride or the like in a solvent such as alcohol. You may use an autoclave etc. as needed. On the other hand, when an unsaturated bond site is included in the structure, if palladium carbon, platinum carbon or the like is used, the unsaturated bond site may be reduced and become a saturated bond. Reduction conditions using a transition metal such as tin, tin chloride as a catalyst are preferred.

<Polymer of the present invention>
The polymer in the present invention refers to a polyimide precursor, a polyimide obtained by imidizing the polyimide precursor, and polyamide. Here, the polyimide precursor refers to a polyamic acid and a polyamic acid ester. The diamine of this invention can obtain the polyamic acid which has a specific structure in a side chain by making it react with tetracarboxylic acid or its derivative (s), such as tetracarboxylic acid, tetracarboxylic dihalide, and tetracarboxylic dianhydride. Moreover, polyamic acid ester can be obtained by reaction of tetracarboxylic acid diester dichloride and diamine, or by reacting tetracarboxylic acid diester and diamine in the presence of an appropriate condensing agent and a base. Furthermore, a polyimide having a specific structure in the side chain can be obtained by dehydrating and cyclizing the polyamic acid or heating the polyamic acid ester at a high temperature to promote dealcoholization and cyclization.

<Polyamic acid and polyamic acid ester>
The polyamic acid of this invention is obtained by reaction of the diamine component containing the diamine represented by Formula [1], and tetracarboxylic dianhydride. Further, the polyamic acid ester of the present invention is obtained by reacting a diamine component containing the diamine represented by the formula [1] and a tetracarboxylic acid diester dichloride in the presence of a base, or by reacting a tetracarboxylic acid diester and a diamine with an appropriate condensing agent. , And in the presence of a base. The polyimide of the present invention can be obtained by dehydrating and ring-closing this polyamic acid or by heating and ring-closing the polyamic acid ester. Any of such polyamic acid, polyamic acid ester, and polyimide is useful as a polymer for obtaining a liquid crystal alignment film.

In the diamine component (hereinafter also referred to as a diamine component) for obtaining a polyamic acid by reaction with the tetracarboxylic dianhydride, there is no limitation on the content ratio of the diamine represented by the formula [1]. In the liquid crystal alignment film of the present invention obtained using the polyamic acid or polyimide, the pretilt angle of the liquid crystal increases as the content ratio of the diamine represented by the formula [1] in the diamine component increases.
For the purpose of increasing the pretilt angle of the liquid crystal, 1 mol% or more of the diamine component is preferably a diamine represented by the formula [1]. Since the preferred content differs depending on the side chain structure of the formula [1] and the alignment mode of the liquid crystal, the preferred content cannot always be set. However, in the TN mode, the OCB mode, etc., it is necessary to take into account the horizontal alignment regulating force, so The content of the diamine represented by the formula [1] in the diamine component used in is preferably 1 to 50 mol%, particularly preferably 5 to 30 mol%.

For the purpose of vertically aligning the liquid crystal, 100 mol% of the diamine component may be a diamine represented by the formula [1]. Since the diamine of the formula [1] greatly reduces the polymerization viscosity of the polymer and the viscosity of the liquid crystal alignment treatment agent, the content for obtaining a required film thickness in flexographic printing or the like is 30 to 70 mol. % Is preferred.
Specific examples of diamines other than the diamine represented by formula (1) (hereinafter also referred to as other diamines) used when the diamine represented by formula (1) is less than 100 mol% in the diamine component. Is as follows.

Examples of alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4′-diaminodicyclohexylmethane, 4,4′-diamino-3,3′-dimethyldicyclohexylamine, isophorone Examples include diamines.
Examples of aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-diaminotoluene, 3,5-diaminotoluene, 1,4-diamino -2-methoxybenzene, 2,5-diamino-p-xylene, 1,3-diamino-4-chlorobenzene, 3,5-diaminobenzoic acid, 1,4-diamino-2,5-dichlorobenzene, 4,4 '-Diamino-1,2-diphenylethane, 4,4'-diamino-2,2'-dimethylbibenzyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane 4,4′-diamino-3,3′-dimethyldiphenylmethane, 2,2′-diaminostilbene, 4,4′-diaminostilbene, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminobenzophenone 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 3,5-bis (4-aminophenoxy) ) Benzoic acid, 4,4′-bis (4-aminophenoxy) bibenzyl, 2,2-bis [(4-aminophenoxy) methyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (3-aminophenyl) Enoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 1,1-bis (4-aminophenyl) cyclohexane, α, α′-bis (4-aminophenyl) -1,4- Diisopropylbenzene, 9,9-bis (4-aminophenyl) fluorene, 2,2-bis (3-aminophenyl) hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 4,4 ′ -Diaminodiphenylamine, 2,4-diaminodiphenylamine, 1,8-diaminonaphthalene, 1,5-diaminonaphthalene, 1,5-diaminoanthraquinone, 1,3-diaminopyrene, 1,6-diaminopyrene, 1,8- Diaminopyrene, 2,7-diaminofluorene, 1,3-bis (4-aminophenyl) tetramethyldisi Xanthone, benzidine, 2,2'-dimethylbenzidine, 1,2-bis (4-aminophenyl) ethane, 1,3-bis (4-aminophenyl) propane, 1,4-bis (4-aminophenyl) butane 1,5-bis (4-aminophenyl) pentane, 1,6-bis (4-aminophenyl) hexane, 1,7-bis (4-aminophenyl) heptane, 1,8-bis (4-aminophenyl) ) Octane, 1,9-bis (4-aminophenyl) nonane, 1,10-bis (4-aminophenyl) decane, 1,3-bis (4-aminophenoxy) propane, 1,4-bis (4- Aminophenoxy) butane, 1,5-bis (4-aminophenoxy) pentane, 1,6-bis (4-aminophenoxy) hexane, 1,7-bis (4-aminophenoxy) heptane 1,8-bis (4-aminophenoxy) octane, 1,9-bis (4-aminophenoxy) nonane, 1,10-bis (4-aminophenoxy) decane, di (4-aminophenyl) propane-1, 3-dioate, di (4-aminophenyl) butane-1,4-dioate, di (4-aminophenyl) pentane-1,5-dioate, di (4-aminophenyl) hexane-1,6-dioate, di (4-aminophenyl) heptane-1,7-dioate, di (4-aminophenyl) octane-1,8-dioate, di (4-aminophenyl) nonane-1,9-dioate, di (4-aminophenyl) ) Decane-1,10-dioate, 1,3-bis [4- (4-aminophenoxy) phenoxy] propane, 1,4-bis [4- (4-aminopheno) Phenoxy] butane, 1,5-bis [4- (4-aminophenoxy) phenoxy] pentane, 1,6-bis [4- (4-aminophenoxy) phenoxy] hexane, 1,7-bis [4- (4-aminophenoxy) phenoxy] heptane, 1,8-bis [4- (4-aminophenoxy) phenoxy] octane, 1,9-bis [4- (4-aminophenoxy) phenoxy] nonane, 1,10- And bis [4- (4-aminophenoxy) phenoxy] decane.

Examples of aromatic-aliphatic diamines include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, 4-amino-N-methylbenzylamine, 3-aminophenethylamine, 4-aminobenzylamine, Aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methylphenethylamine, 3- (3-aminopropyl) aniline, 4- (3-aminopropyl) aniline, 3- (3-methylaminopropyl) Aniline, 4- (3-methylaminopropyl) aniline, 3- (4-aminobutyl) aniline, 4- (4-aminobutyl) aniline, 3- (4-methylaminobutyl) aniline, 4- (4-methyl Aminobutyl) aniline, 3- (5-aminopentyl) aniline, 4- (5-aminopentyl) Aniline, 3- (5-methylaminopentyl) aniline, 4- (5-methylaminopentyl) aniline, 2- (6-aminonaphthyl) methylamine, 3- (6-aminonaphthyl) methylamine, 2- (6 -Aminonaphthyl) ethylamine, 3- (6-aminonaphthyl) ethylamine and the like.

Examples of heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2,7-diaminodibenzofuran, 3,6-diamino Examples thereof include carbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4-aminophenyl) -1,3,4-oxadiazole.
Examples of aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7 -Diamino-2,5-dimethylheptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane, 1,12-diamino Examples include dodecane, 1,18-diaminooctadecane, and 1,2-bis (3-aminopropoxy) ethane.

You may use together the diamine compound which has an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring, or the macrocyclic substituent which consists of them in a side chain. Specifically, diamines represented by the following formulas [DA1] to [DA26] are exemplified.

(R ₆ is an alkyl group or a fluorine-containing alkyl group having 1 to 22 carbon atoms.)

(S ₅ represents —COO—, —OCO—, —CONH—, —NHCO—, —CH ₂ —, —O—, —CO—, or —NH—, and R ₆ represents 1 to 22 carbon atoms. It has an alkyl group or a fluorine-containing alkyl group.)

(S ₆ represents —O—, —OCH ₂ —, —CH ₂ O—, —COOCH ₂ —, or —CH ₂ OCO—, and R ₇ represents an alkyl group or alkoxy group having 1 to 22 carbon atoms. A fluorine-containing alkyl group or a fluorine-containing alkoxy group.)

(S ₇ represents —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, or —CH ₂ —. R ₈ represents an alkyl group, an alkoxy group, a fluorine-containing alkyl group or a fluorine-containing alkoxy group having 1 to 22 carbon atoms.)

(S ₈ is —COO—, —OCO—, —CONH—, —NHCO—, —COOCH ₂ —, —CH ₂ OCO—, —CH ₂ O—, —OCH ₂ —, —CH ₂ —, —O — Represents — or —NH—, and R ₉ represents a fluorine group, a cyano group, a trifluoromethane group, a nitro group, an azo group, a formyl group, an acetyl group, an acetoxy group, or a hydroxyl group.

(R ₁₀ is an alkyl group having 3 to 12 carbon atoms, and the cis-trans isomerism of 1,4-cyclohexylene is a trans isomer.)

In the case of aligning with light, it is preferable to use a diamine of the general formula [1] in combination with the diamines of the above [DA-1] to [DA-26] because a more stable pretilt angle can be obtained. More preferred diamines that can be used in combination are those represented by the formulas [DA-10] to [DA-26], more preferably diamines of [DA-10] to [DA-16]. The preferred content of these diamines is not particularly limited, but is preferably 5 to 50 mol% in the diamine component, and is preferably 5 to 30 mol% in terms of printability.
Moreover, you may use the following diamine together.

(M is an integer of 0 to 3, and n is an integer of 1 to 5 in the formula [DA-34]).
By containing a diamine of formula [DA-27], formula [DA-28] or the like, the voltage holding characteristic when a liquid crystal alignment film is formed can be improved. Formulas [DA-29] to [DA-34 ] Is effective in reducing the accumulation of electricity.

Furthermore, diaminosiloxanes represented by the following formula [DA-35] can also be mentioned as other diamines.

(M is an integer from 1 to 10.)
Other diamine compounds may be used alone or in combination of two or more according to properties such as liquid crystal alignment properties, voltage holding properties, and accumulated charges when the liquid crystal alignment film is formed.

The tetracarboxylic dianhydride reacted with the diamine component to obtain the polyamic acid of the present invention is not particularly limited. Specific examples are given below.
Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4-cyclobutane. Tetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetra Carboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 1,2,4,5-cyclohexanetetracarboxylic Acid dianhydride, 3,4-dicarboxy-1-cyclohexylsuccinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, 1, , 3,4-Butanetetracarboxylic dianhydride, bicyclo [3,3,0] octane-2,4,6,8-tetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetra Carboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcycloocta-1,5-diene-1,2,5,6-tetracarboxylic dianhydride , Tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8-dianhydride, hexacyclo [6.6.0.1 ^{2 , 7} . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dianhydride, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2 3,4-tetrahydronaphthalene-1,2-dicarboxylic acid anhydride and the like.

Furthermore, in addition to the tetracarboxylic dianhydride having the alicyclic structure or aliphatic structure, the use of aromatic tetracarboxylic dianhydride improves the liquid crystal alignment and reduces the accumulated charge in the liquid crystal cell. This is preferable.
Aromatic tetracarboxylic dianhydrides include pyromellitic dianhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 2,2 ′, 3,3′-biphenyltetracarboxylic acid Dianhydride, 2,3,3 ′, 4-biphenyltetracarboxylic dianhydride, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,3,3 ′, 4-benzophenonetetra Carboxylic dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, bis (3,4-dicarboxyphenyl) sulfone dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride And 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

Tetracarboxylic dianhydride can be used alone or in combination of two or more depending on the liquid crystal alignment properties, voltage holding characteristics, accumulated charges, and the like when the liquid crystal alignment film is formed.
The tetracarboxylic acid dialkyl ester that is reacted with the diamine component to obtain the polyamic acid ester of the present invention is not particularly limited. Specific examples are given below.
Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1, 3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester, 1,2,3 , 4-Cyclopentanetetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofurantetracarboxylic acid dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1- Cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxy-1 2,3,4-tetrahydro-1-naphthalene succinic acid dialkyl ester, 1,2,3,4-butanetetracarboxylic acid dialkyl ester, bicyclo [3,3,0] octane-2,4,6,8-tetra Carboxylic acid dialkyl ester, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic acid dialkyl ester, 2,3,5-tricarboxycyclopentyl acetic acid dialkyl ester, cis-3,7-dibutylcycloocta-1,5-diene -1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo [4.2.1.0 ^2,5 ] nonane-3,4,7,8-tetracarboxylic acid-3,4: 7,8- Dialkyl ester, hexacyclo [6.6.0.1 ^2,7 . 0 ^3,6 . 1 ^9,14 . 0 ^10,13] hexadecane -4,5,11,12- tetracarboxylic acid-4,5: 11,12-dialkyl ester, 4- (2,5-di-oxo-tetrahydrofuran-3-yl) -1,2, Examples include 3,4-tetrahydronaphthalene-1,2-dicarboxylic dialkyl ester.

Examples of the aromatic tetracarboxylic acid dialkyl ester include pyromellitic acid dialkyl ester, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dialkyl ester, 2,2 ′, 3,3′-biphenyltetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-biphenyltetracarboxylic acid dialkyl ester, 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dialkyl ester, 2,3,3 ′, 4-benzophenone tetracarboxylic acid dialkyl ester, bis (3,4-dicarboxyphenyl) ether dialkyl ester, bis (3,4-dicarboxyphenyl) sulfone dialkyl ester, 1,2,5,6-naphthalenetetracarboxylic acid dialkyl ester, 2,3,6,7- Naphthalenetetracarboxylic acid dialkyl es Le and the like.

<Synthesis of polyamide>
The dicarboxylic acid reacted with the diamine component to obtain the polyamide of the present invention is not particularly limited. Specific examples of the dicarboxylic acid or its aliphatic dicarboxylic acid include malonic acid, succinic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, Examples include pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethylsuccinic acid, azelaic acid, sebacic acid, and suberic acid.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, and 1,3-cyclobutanedicarboxylic acid. Acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid Acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexane Dicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, 1,4- (2-nor Lunene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2, 5-dioxo-1,4-bicyclo [2.2.2] octane dicarboxylic acid, 1,3-adamantane dicarboxylic acid, 4,8-dioxo-1,3-adamantane dicarboxylic acid, 2,6-spiro [3. 3] Heptanedicarboxylic acid, 1,3-adamantanediacetic acid, camphoric acid and the like.

As aromatic dicarboxylic acids, o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid Acid, tetramethylterephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4 Anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 1,5-biphenylene dicarboxylic acid, 4,4 "-terphenyl dicarboxylic acid, 4,4'-diphenylmethane dicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenyl Lopandicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-bibenzyldicarboxylic acid, 4,4'-stilbene dicarboxylic acid, 4,4'-tolane Dicarboxylic acid, 4,4′-carbonyldibenzoic acid, 4,4′-sulfonyldibenzoic acid, 4,4′-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3′-p-phenylenedipropionic acid 4-carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 ′-[4,4 ′-(methylenedi-p-phenylene)] dipropionic acid, 4,4 ′-[4,4 ′-(oxydi) -P-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] butyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, bis (p- Cal And boxyphenyl) dimethylsilane.

Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazole dicarboxylic acid, 2-phenyl-4,5-thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2, Examples include 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, and 3,5-pyridinedicarboxylic acid.
The various dicarboxylic acids described above may have a structure of acid dihalide or acid anhydride. These dicarboxylic acids are preferably dicarboxylic acids that can give a polyamide having a linear structure, from the viewpoint of maintaining the orientation of liquid crystal molecules. Among these, terephthalic acid, isoterephthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4′-biphenyldicarboxylic acid, 4,4′-diphenylmethanedicarboxylic acid, 4,4′-diphenylethanedicarboxylic acid, 4,4 '-Diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 2,2-bis (phenyl) propanedicarboxylic acid, 4,4 caster-phenyldicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2 , 5-pyridinedicarboxylic acid or these acid dihalides are preferably used. Some of these compounds have isomers, but may be a mixture containing them. Two or more compounds may be used in combination.
In obtaining the polyamide of the present invention by reaction of a dicarboxylic acid and a diamine component, a known synthesis method can be used. Generally, this is a method in which a dicarboxylic acid and a diamine component are reacted in an organic solvent.

<Synthesis of polyamic acid>
As a method for obtaining the polyamic acid of the present invention by reaction of tetracarboxylic dianhydride and a diamine component, a known method can be used. In general, tetracarboxylic dianhydride and a diamine component are reacted in an organic solvent. The reaction of tetracarboxylic dianhydride and diamine is advantageous in that it proceeds relatively easily in an organic solvent and no by-product is generated.

The organic solvent used for the reaction of tetracarboxylic dianhydride and diamine is not particularly limited as long as the produced polyamic acid is soluble. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, N-methylcaprolactam, dimethyl sulfoxide, tetramethyl urea, pyridine, dimethyl sulfone, hexamethyl sulfoxide , Γ-butyrolactone, isopropyl alcohol, methoxymethylpentanol, dipentene, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, methyl cellosolve, ethyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl Carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethyl Glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipropylene glycol monoacetate monomethyl ether, dipropylene glycol Monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3-methoxybutyl acetate, tripropylene Glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n- Hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, Ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropion , 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy -N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide and the like. These may be used alone or in combination. Further, even a solvent that does not dissolve the polyamic acid may be used by mixing with the above solvent as long as the produced polyamic acid does not precipitate.

Further, since water in the organic solvent inhibits the polymerization reaction and further causes hydrolysis of the produced polyamic acid, it is preferable to use a dehydrated and dried organic solvent as much as possible.
When the tetracarboxylic dianhydride and the diamine component are reacted in an organic solvent, the solution in which the diamine component is dispersed or dissolved in the organic solvent is stirred, and the tetracarboxylic dianhydride is used as it is or in an organic solvent. A method of adding by dispersing or dissolving, a method of adding a diamine component to a solution in which tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, and alternately adding a tetracarboxylic dianhydride and a diamine component. Any of these methods may be used. Further, when the tetracarboxylic dianhydride or diamine component is composed of a plurality of types of compounds, they may be reacted in a premixed state, may be individually reacted sequentially, or may be further reacted individually. May be mixed and reacted to form a high molecular weight product.

In this case, the polymerization temperature can be selected from -20 to 150 ° C., but is preferably in the range of −5 to 100 ° C. The reaction can be carried out at any concentration, but if the concentration is too low, it is difficult to obtain a high molecular weight polymer, and if the concentration is too high, the viscosity of the reaction solution becomes too high and uniform stirring is difficult. Therefore, the total concentration of the tetracarboxylic dianhydride and the diamine component in the reaction solution is preferably 1 to 50% by mass, more preferably 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and then an organic solvent can be added.
In the polyamic acid polymerization reaction, the ratio of the total number of moles of tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably 0.8 to 1.2, preferably 0.9 to 1.1. Is more preferable. Similar to the normal polycondensation reaction, the closer the molar ratio is to 1.0, the higher the molecular weight of the polyamic acid produced.

<Synthesis of polyimide>
The polyimide of the present invention is a polyimide obtained by dehydrating and ring-closing the above polyamic acid, and is useful as a polymer for obtaining a liquid crystal alignment film.
In the polyimide of the present invention, the dehydration cyclization rate (imidation rate) of the amic acid group is not necessarily 100%, and can be arbitrarily adjusted according to the application and purpose.
Examples of the method for imidizing the polyamic acid include a thermal imidization method in which the polyamic acid solution is heated as it is, and a catalytic imidation method in which a catalyst is added to the polyamic acid solution.
The temperature at which the polyamic acid is thermally imidized in the solution is 100 to 400 ° C., preferably 120 to 250 ° C., and is preferably carried out while removing water generated by the imidization reaction from the system.

The catalytic imidation of the polyamic acid can be carried out by adding a basic catalyst and an acid anhydride to the polyamic acid solution and stirring at -20 to 250 ° C, preferably 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 mol times, preferably 2 to 20 mol times the amidic acid group, and the amount of the acid anhydride is 1 to 50 mol times, preferably 3 to 30 mol times the amido group. 30 mole times. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, trioctylamine and the like. Among them, pyridine is preferable because it has basicity suitable for proceeding with the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, pyromellitic anhydride, and the like. Among them, use of acetic anhydride is preferable because purification after completion of the reaction is facilitated. The imidization rate by catalytic imidation can be controlled by adjusting the amount of catalyst, reaction temperature, reaction time, and the like.

<Synthesis of polyamic acid ester>
As a method of synthesizing a polyamic acid ester, a reaction between a tetracarboxylic acid diester dichloride and a diamine, a method in which a tetracarboxylic acid diester and a diamine are reacted in the presence of an appropriate condensing agent and a base, or a polyamic acid in advance. And a method of esterifying a carboxylic acid in an amic acid using a polymer reaction.
Specifically, tetracarboxylic acid diester dichloride and diamine are reacted in the presence of a base and an organic solvent at −20 to 150 ° C., preferably 0 to 50 ° C., for 30 minutes to 24 hours, preferably 1 to 4 hours. Can be synthesized.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine and the like can be used. However, pyridine is preferable because the reaction proceeds gently. The addition amount of the base is preferably 2 to 4 moles relative to the tetracarboxylic acid diester dichloride because it can be easily removed and a high molecular weight product can be easily obtained.
When the condensation polymerization is performed in the presence of a condensing agent, triphenyl phosphite, dicyclohexylcarbodiimide, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride, N, N′-carbonyldiimidazole, dimethoxy-1, 3,5-triazinylmethylmorpholinium, O- (benzotriazol-1-yl) -N, N, N ′, N′-tetramethyluronium tetrafluoroborate, O- (benzotriazole-1- Yl) -N, N, N ′, N′-tetramethyluronium hexafluorophosphate, diphenyl (2,3-dihydro-2-thioxo-3-benzoxazolyl) phosphonate, 4- (4,6 -Dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate and other condensing agents can be used wear.

In the method using the condensing agent, the reaction proceeds efficiently by adding Lewis acid as an additive. As the Lewis acid, lithium halides such as lithium chloride and lithium bromide are preferable. The amount of Lewis acid added is preferably 0.1 to 1.0 times the molar amount of the diamine component.
As the solvent used in the above reaction, the same solvent as used for polymerizing the above polyamic acid can be used, and N-methyl-2-pyrrolidone, γ-butyrolactone, etc. are preferable from the viewpoint of the solubility of the monomer and polymer. You may use these 1 type or in mixture of 2 or more types. The concentration of the polymer at the time of synthesis is preferably 1 to 30% by mass and more preferably 5 to 20% by mass from the viewpoint that the polymer is hardly precipitated and a high molecular weight product is easily obtained. In order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, the solvent used for the synthesis of the polyamic acid ester is preferably dehydrated as much as possible, and it is preferable to carry out the reaction in a nitrogen atmosphere to prevent outside air from being mixed.

<Recovery of polymer>
When recovering the produced polymer from a reaction solution such as polyamic acid, polyamic acid ester, polyimide, etc., it is preferable to add the reaction solution to a poor solvent to cause precipitation. Examples of the poor solvent used for precipitation include methanol, acetone, hexane, butyl cellosolve, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, and water. The polymer deposited in a poor solvent and collected can be recovered by filtration, and then dried at normal temperature or under reduced pressure at room temperature or by heating. In addition, when the polymer collected by precipitation is redissolved in an organic solvent, reprecipitated, and recovered, the impurities in the polymer can be reduced by repeating the operation 2 to 10 times. Examples of the poor solvent at this time include alcohols, ketones, hydrocarbons, and the like, and it is preferable to use three or more kinds of poor solvents selected from these because purification efficiency is further improved.
The molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is determined by the GPC (Gel Permeation Chromatography) method in consideration of the strength of the obtained coating film, the workability during coating film formation, and the uniformity of the coating film. The weight average molecular weight measured in (1) is preferably 5,000 to 1,000,000, and more preferably 10,000 to 150,000.

<Liquid crystal aligning agent>
The liquid-crystal aligning agent of this invention is a coating liquid for forming a liquid crystal aligning film, and is a solution in which the resin component for forming a resin film melt | dissolved in the organic solvent. Here, the resin component contains at least one polymer selected from the polymers of the present invention described above. The content of the resin component in the liquid crystal aligning agent is preferably 1 to 20% by mass, more preferably 3 to 15% by mass, and particularly preferably 3 to 10% by mass.
All of the resin components may be the polymer of the present invention, or other polymers may be mixed. In this case, the content of the other polymer in the resin component is 0.5 to 15% by mass, preferably 1 to 10% by mass.
Examples of such other polymers include polyamic acid or polyimide obtained by using a diamine compound other than the specific diamine compound as a diamine component to be reacted with the tetracarboxylic dianhydride component.

The organic solvent used for the liquid-crystal aligning agent of this invention will not be specifically limited if it is an organic solvent in which a resin component is dissolved. Specific examples are given below.
N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, N-ethylpyrrolidone, N-vinylpyrrolidone, dimethylsulfoxide, tetramethylurea, pyridine, Dimethylsulfone, hexamethylsulfoxide, γ-butyrolactone, 3-methoxy-N, N-dimethylpropanamide, 3-ethoxy-N, N-dimethylpropanamide, 3-butoxy-N, N-dimethylpropanamide, 1,3 -Dimethyl-imidazolidinone, ethyl amyl ketone, methyl nonyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropyl ketone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme, 4-hydroxy-4 Such as methyl-2-pentanone and the like. These may be used alone or in combination.

The liquid crystal aligning agent of this invention may contain components other than the above. Examples thereof include compounds that improve the adhesion between the liquid crystal alignment film and the substrate, such as a solvent-rich substance that improves film thickness uniformity and surface smoothness when a liquid crystal alignment treatment agent is applied.
The following are mentioned as a specific example of the solvent (poor solvent) which improves the uniformity of film thickness and surface smoothness.
For example, isopropyl alcohol, methoxymethylpentanol, methyl cellosolve, ethyl cellosolve, butyl cellosolve, methyl cellosolve acetate, ethyl cellosolve acetate, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoacetate Isopropyl ether, ethylene glycol monobutyl ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tert-butyl ether, dipropylene glycol monomethyl ether, diethylene glycol, diethylene glycol monoacetate, diethylene glycol dimethyl ether, dipro Lenglycol monoacetate monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monoacetate monoethyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monoacetate monopropyl ether, 3-methyl-3 -Methoxybutyl acetate, tripropylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, amyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methylcyclohexene, propyl ether, dihexyl Ether, 1-hexanol, n-hexane, n-pentane, n-octane Diethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, methyl 3-methoxypropionate, methyl ethyl 3-ethoxypropionate, Ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, propyl 3-methoxypropionate, butyl 3-methoxypropionate, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1 -Butoxy-2-propanol, 1-phenoxy-2-propanol, propylene glycol monoacetate, propylene glycol diacetate, propylene glycol-1-monomethyl ether-2-acetate, propylene glycol- Low 1-monoethyl ether-2-acetate, dipropylene glycol, 2- (2-ethoxypropoxy) propanol, lactate methyl ester, lactate ethyl ester, lactate n-propyl ester, lactate n-butyl ester, lactate isoamyl ester Examples include solvents having surface tension.
These poor solvents may be used alone or in combination. When the solvent is used, it is preferably 5 to 80% by mass, more preferably 20 to 60% by mass, based on the total amount of the solvent contained in the liquid crystal alignment treatment agent.

Examples of the compound that improves the uniformity of the film thickness and the surface smoothness include a fluorine-based surfactant, a silicone-based surfactant, and a nonionic surfactant.
More specifically, for example, F-top EF301, EF303, EF352 (manufactured by Tochem Products), MegaFuck F171, F173, R-30 (manufactured by Dainippon Ink), Florard FC430, FC431 (manufactured by Sumitomo 3M) Asahi Guard AG710, Surflon S-382, SC101, SC102, SC103, SC104, SC105, SC106 (Asahi Glass Co., Ltd.). The use ratio of these surfactants is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass with respect to 100 parts by mass of the resin component contained in the liquid crystal aligning agent. .

Specific examples of the compound for improving the adhesion between the liquid crystal alignment film and the substrate include the following functional silane-containing compounds and epoxy group-containing compounds.
For example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyltrimethoxysilane, N-ethoxy Carbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4,7-triazadecane, 10-to Ethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N-bis (oxyethylene) -3-amino Propyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether , Polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 1,3,5,6-tetra Glycidyl-2,4-hexanediol, N, N, N ′, N ′,-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N Examples include ', N',-tetraglycidyl-4,4'-diaminodiphenylmethane.

Furthermore, in addition to improving the adhesion between the substrate and the film, it is preferable to contain the following phenoplast type additives for the purpose of preventing electrical characteristics from being deteriorated by the backlight. Specific phenoplast type additives are shown below.

When a compound that improves the adhesion to the substrate is used, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass with respect to 100 parts by mass of the resin component. is there. If the amount used is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected, and if it exceeds 30 parts by mass, the orientation of the liquid crystal may deteriorate.
In the liquid crystal alignment treatment agent of the present invention, in addition to the above, within the range that does not impair the effects of the present invention, the dielectric, conductive, A substance, and further, a crosslinkable compound for the purpose of increasing the hardness and density of the liquid crystal alignment film may be added.

<Liquid crystal alignment film and liquid crystal display element>
The liquid crystal alignment treatment agent of the present invention can be used as a liquid crystal alignment film without applying an alignment treatment in a vertical alignment application or the like after being applied onto a substrate and baked and then subjected to an alignment treatment by rubbing treatment or light irradiation. In this case, the substrate to be used is not particularly limited as long as it is a highly transparent substrate, and a glass substrate, an acrylic substrate, a plastic substrate such as a polycarbonate substrate, or the like can be used. In addition, it is preferable to use a substrate on which an ITO electrode or the like for driving liquid crystal is formed from the viewpoint of simplification of the process. In the reflective liquid crystal display element, an opaque material such as a silicon wafer can be used as long as it is only on one side of the substrate. In this case, a material that reflects light such as aluminum can be used for the electrode.
The method for applying the liquid crystal aligning agent is not particularly limited, but industrially, it is generally performed by a method such as screen printing, offset printing, flexographic printing, or inkjet. Other coating methods include dip, roll coater, slit coater, spinner and the like, and these may be used depending on the purpose.

Firing after applying the liquid crystal aligning agent on the substrate can be carried out by heating means such as a hot plate at 50 to 300 ° C., preferably 80 to 250 ° C., and the solvent can be evaporated to form a coating film. . The thickness of the coating film formed after baking is disadvantageous in terms of power consumption of the liquid crystal display element if it is too thick, and if it is too thin, the reliability of the liquid crystal display element may be lowered. The thickness is preferably 10 to 100 nm. When the liquid crystal is horizontally or tilted, the fired coating film is treated by rubbing or irradiation with polarized ultraviolet rays.
The liquid crystal display element of the present invention is a liquid crystal display element obtained by obtaining a substrate with a liquid crystal alignment film from the liquid crystal aligning agent of the present invention by the method described above, and then preparing a liquid crystal cell by a known method.

To give an example of liquid crystal cell production, prepare a pair of substrates on which a liquid crystal alignment film is formed, spray spacers on the liquid crystal alignment film of one substrate, and make the liquid crystal alignment film surface inside. Examples include a method of bonding the other substrate and injecting the liquid crystal under reduced pressure, or a method of sealing the liquid crystal after dropping the liquid crystal on the liquid crystal alignment film surface on which the spacers are dispersed, and the like. . The thickness of the spacer at this time is preferably 1 to 30 μm, more preferably 2 to 10 μm.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the interpretation of the present invention is not limited to these examples.

<Example 1>
Synthesis of 2- (tert-butoxycarbonylamino) -4-octanamidophenyl 3,5-diaminobenzoate (HC-01)

Step 1 Synthesis of 4-octanamide-2-nitrophenol

To a 500 mL (milliliter) four-necked flask, 15.9 g (103 mmol) of 4-amino-2-nitrophenol, 300 mL of tetrahydrofuran, and 7.9 g (103 mmol) of pyridine were added. The system was cooled to 0 ° C., 16.3 g (103 mmol) of n-octanoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 50 mL of pure water was added and stirred. After completion of the reaction, ethyl acetate was added to separate the organic layer, and the organic layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The obtained solid was recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7 (volume ratio, the same applies hereinafter)) to obtain 27.0 g of a light yellow solid (yield) 94%).

Second Step 4-Synthesis of Octanamide-2-aminophenol

To a 500 mL four-necked flask, 15.0 g (53.5 mmol) of N- (3-nitro-4-hydroxyphenyl) octanamide, 40 mL of ethanol, and 1.0 g of 5% palladium carbon were added, and the room temperature was kept under a hydrogen atmosphere. And stirred. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 13.0 g of a white solid (yield 97%).

Step 3 Synthesis of 4-octanamide-2-tert-butoxycarbonylaminophenol

In a 300 mL four-necked flask, 12.5 g (49.9 mmol) of N- (3-amino-4-hydroxyphenyl) octanamide, 200 mL of tetrahydrofuran, and 11.9 g (54.9 mmol) of di-tert-butyl dicarbonate And 0.61 g (4.99 mmol) of 4-dimethylaminopyridine were added and stirred at room temperature. After completion of the reaction, ethyl acetate was added and washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 3 (volume ratio, the same in the following examples)), and a mixed solvent of ethyl acetate and n-hexane (1: 9) was used. Was used for recrystallization to obtain 16.5 g of white solid (yield 94%).

Step 4 Synthesis of 2- (tert-butoxycarbonylamino) -4-octanamidophenyl 3,5-dinitrobenzoate

To a 300 mL four-necked flask, 7.0 g (20.0 mmol) of HC-03-1, 80 mL of tetrahydrofuran, and 1.6 g (20.0 mmol) of pyridine were added. The system was cooled to 0 ° C., 5.5 g (20.0 mmol) of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 10 mass% potassium carbonate aqueous solution was added to adjust the pH to 8-9, ethyl acetate was added to separate the organic layer, and the organic layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 4) and recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 5.9 g of a pale yellow solid. Obtained (yield 54%).

Step 5 Synthesis of HC-01

In a 500 mL four-necked flask, 5.9 g (10.8 mmol) of 2- (tert-butoxycarbonylamino-4-octanamidophenyl) 3,5-dinitrobenzoate, 150 mL of tetrahydrofuran, and 5% palladium / carbon were added. 0.6 g was added and stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 5.2 g of a gray solid (yield 99%). The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-01.
The compounds in the examples of the present invention were identified by ¹ H-NMR ( ¹ H nuclear magnetic resonance, Varian, model: INOVA400).
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 9.92 (s, 1H), 8.73 (s, 1H), 7.89 (s, 1H), 7.40-7.43 ( d, 1H), 6.99-7.01 (d, 1H), 6.58 (s, 2H), 6.09 (s, 1H), 5.04 (s, 4H), 2.27-2 .31 (t, 2H), 1.56-1.60 (t, 2H), 1.40 (s, 9H), 1.25-1.29 (m, 8H), 0.85-0.88 (T, 3H)

<Example 2>
Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide (HC-02)

Step 1 Synthesis of 3-tert-butoxycarbonylamino-4-aminonitrobenzene

To a 300 mL four-necked flask, 25.0 g (163 mmol) of 3,4-diaminonitrobenzene, 250 mL of tetrahydrofuran, and 35.6 g (163 mmol) of di-tert-butyl dicarbonate were added and stirred under reflux for 4 hours in a nitrogen atmosphere. After completion of the reaction, the solvent was removed with a rotary evaporator, and the resulting solid was washed with methanol and recrystallized using a mixed solvent of ethyl acetate and n-hexane (5: 5) to obtain 33.8 g of a yellow solid. (Yield 82%).

Second Step Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminonitrobenzene

To a 300 mL four-necked flask, 18.3 g (95.0 mmol) of 4-amylbenzoic acid, 150 mL of tetrahydrofuran and 20 mL of dimethylformamide were added, the system was cooled to 0 ° C., and 14.1 g (119 mmol) of thionyl chloride. The mixture was returned to room temperature and stirred for 2 hours to prepare a 4-amylbenzoic acid chloride solution. On the other hand, 20.0 g (79.0 mmol) of 3-tert-butoxycarbonylamino-4-aminonitrobenzene, 100 mL of tetrahydrofuran, and 7.5 g (95.0 mmol) of pyridine were added to a 500 mL four-necked flask. The solution was cooled to 0 ° C., and the 4-amylbenzoic acid chloride solution prepared above was slowly added dropwise and stirred at room temperature. After completion of the reaction, the solvent was removed with a rotary evaporator, ethyl acetate was added, and the mixture was washed with a 10 mass% aqueous sodium hydrogen carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was washed with methanol and recrystallized using a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 24.7 g of a yellow solid (yield 73%).

Third Step N-4- (4-Amylbenzoylamino) -3-tert-butoxycarbonylamino Synthesis of aniline

In a 500 mL four-necked flask, 20.0 g (46.8 mmol) of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminonitrobenzene, 200 mL of tetrahydrofuran, and 2.0 g of 10% palladium carbon In addition, the mixture was stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon is removed by filtration, the solvent is distilled off using a rotary evaporator, redissolved in acetone, activated carbon is added and stirred for a while at room temperature, and then the activated carbon is filtered and acetone is distilled off. By vacuum drying, 17.7 g of a light yellowish green glassy solid was obtained (yield 95%).

Fourth Step Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzamide

In a 300 mL four-necked flask, 10.0 g (25.2 mmol) of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminoaniline, 150 mL of tetrahydrofuran, 20 mL of dimethylformamide, and 2.2 of pyridine. 4 g (30.2 mmol) was added. The system was cooled to 0 ° C., 5.8 g (25.2 mmol) of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, the solvent was removed with a rotary evaporator, ethyl acetate was added, and the mixture was washed with a 10 mass% aqueous sodium hydrogen carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was washed with methanol and recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 11.8 g of a pale yellow solid (yield 79%).

Step 5 Synthesis of HC-02

In a 300 mL four-necked flask, 10.0 g (16.9 mmol) of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzamide, 100 mL of tetrahydrofuran, and 10% 1.0 g of palladium carbon was added and stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7), and further dispersed and washed with n-hexane to obtain 8.6 g of a white solid (yield 96%). . The results of ¹ H-NMR of the obtained solid are shown below. From this result, it was confirmed that the target product was HC-02.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 10.0 (s, 1H), 9.71 (s, 1H), 8.62 (s, 1H), 8.01 (d, 1H) , 7.89-7.87 (d, 2H), 7.54-7.52 (dd, 1H), 7.42-7.40 (d, 1H), 7.37-7.35 (d, 2H), 6.30 (d, 2H), 6.00-5.90 (t, 1H), 4.96 (s-br, 4H), 2.68-2.64 (m, 2H), 1 .64-1.57 (m, 2H), 1.45 (s, 9H), 1.39-1.17 (m, 4H), 0.89-0.85 (t, 3H)

<Example 3>
Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzamide (HC-03)

Step 1 Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 2,4-dinitrobenzamide

To a 300 mL four-necked flask, 4.10 g (19.4 mmol) of 2,4-dinitrobenzoic acid, 150 mL of dichloromethane, and 20 mL of dimethylformamide were added, the system was cooled to 0 ° C., and 2.46 g of oxalyl chloride ( 19.4 mmol) was slowly added, and the mixture was returned to room temperature and stirred for 2 hours to prepare a 2,4-dinitrobenzoic acid chloride solution. Meanwhile, in a 500 mL four-necked flask, 7.00 g (17.6 mmol) of 4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminoaniline, 100 mL of tetrahydrofuran, and 2.09 g (26.4 mmol) of pyridine were added. The system was cooled to 0 ° C., and the 2,4-dinitrobenzoic acid chloride solution prepared above was slowly added dropwise and stirred at 40 ° C. in a nitrogen atmosphere. After completion of the reaction, the solvent was removed with a rotary evaporator, ethyl acetate was added, and the mixture was washed with a 10 mass% aqueous sodium hydrogen carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with methanol and recrystallized using a mixed solvent of dichloroethane and n-hexane (2: 8) to obtain 6.56 g of a light yellow solid (yield 63%).

Second Step Synthesis of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzamide

In a 300 mL four-necked flask, 6.00 g (10.2 mmol) of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 2,4-dinitrobenzamide, 100 mL of tetrahydrofuran, and 10% 0.60 g of palladium carbon was added and stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with a mixed solvent of methanol and 2-propanol, and then recrystallized using a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 4.88 g of a light yellow solid (yield). Rate 90%). The results of ¹ H-NMR of the individual obtained are shown below. From this result, it was confirmed that the target product was HC-02.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 10.4 (s, 1H), 9.56 (s, 1H), 8.63 (s, 1H), 8.01 (d, 1H) 7.89-7.87 (d, 2H), 7.54-7.52 (dd, 1H), 7.42-7.40 (d, 1H), 7.37-7.35 (d, 1H), 7.28 (d, 1), 6.72 (d, 1H), 6.75 (d, 1H), 6.40 (s-br, 2H), 5.84 (s, 1H), 5.44 (s-br, 2H), 2.68-2.64 (m, 2H), 1.64-1.57 (m, 2H), 1.45 (s, 9H), 1.39- 1.17 (m, 4H), 0.89-0.85 (t, 3H)

<Example 4>
Synthesis of N-4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide (HC-04)

Step 1 Synthesis of 2-tert-butoxycarbonylamino-4-nitrophenol

In a 300 mL four-necked flask, 12.3 g (79.8 mmol) of 2-amino-4-nitrophenol, 250 mL of tetrahydrofuran, 14.2 g (87.9 mol) of di-tert-butyl dicarbonate, and 4-dimethyl 2.00 g (7.98 mol) of aminopyridine was added and stirred at room temperature. After completion of the reaction, ethyl acetate was added and washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was purified by silica gel column chromatography (ethyl acetate: hexane = 1: 1) and recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 15.0 g of a pale yellow solid. Obtained (yield 73%).

Second Step Synthesis of 4- (4-Amylbenzoyloxy) -3-tert-butoxycarbonylamino nitrobenzene

To a 200 mL four-necked flask, 6.4 g (32.8 mol) of 4-amylbenzoic acid and 60 mL of tetrahydrofuran were added, the system was cooled to 0 ° C., and 4.3 g (35.3 mol) of thionyl chloride was added. The mixture was returned to room temperature and stirred for 1 hour to prepare a 4-amylbenzoic acid chloride solution. Meanwhile, 6.3 g (25.2 mmol) of 2-tert-butoxycarbonylamino-4-nitrophenol, 60 mL of tetrahydrofuran, and 4.0 g (50.4 mmol) of pyridine were added to a 500 mL four-necked flask, and the system was cooled. The temperature was then brought to 0 ° C., and the 4-amylbenzoic acid chloride solution prepared earlier was slowly added dropwise and stirred at room temperature. After completion of the reaction, 10% by mass potassium carbonate aqueous solution was added to adjust the pH to 8-9. Ethyl acetate was added to separate the organic layer, and the organic layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (7: 3) to obtain 6.9 g of a yellow solid (yield 64%).

Step 3 Synthesis of 4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylamino aniline

To a 300 mL four-necked flask, add 8.8 g (20.5 mol) of 4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminonitrobenzene 2, 100 mL of tetrahydrofuran, and 0.9 g of 5% palladium carbon. The mixture was stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (7: 3) to obtain 6.8 g of a white solid (yield 84%).

Step 4 Synthesis of N-4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzamide

In a 300 mL four-necked flask, 6.8 g (17.1 mmol) of 4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminoaniline, 100 mL of tetrahydrofuran, and 1.5 g (18.8 mmol) of pyridine added. The system was cooled to 0 ° C., 4.6 g (20.0 mol) of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, 10% by mass potassium carbonate aqueous solution was added to adjust the pH to 8-9. Ethyl acetate was added to separate the organic layer, and the organic layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 11.0 g of a pale yellow solid.
(Yield 99%).

Synthesis of the fifth step HC-04

In a 300 mL four-necked flask, 11.0 g (18.6 mmol) of N-4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzamide, 100 mL of tetrahydrofuran, and 5% 1.0 g of palladium carbon was added and stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 9.7 g of a gray solid (yield 98%). The results of ¹ H-NMR of the individual obtained are shown below. From this result, it was confirmed that it was the target product, HC-04.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 9.99 (s, 1H), 8.88 (s, 1H), 799-8.01 (m, 3H), 7.48- 7.51 (d, 1H), 7.34-7.38 (d, 2H), 7.10-7.11 (d, 1H), 6.26 (s, 2H), 5.96 (s, 1H), 4.93 (s-br, 4H), 2.63-2.67 (t, 2H), 1.55-1.59 (t, 2H), 1.22-1.34 (m, 13H), 0.81-0.84 (t, 3H),

Example 5 Synthesis of 2-methyl-6-tert-butoxycarbonylaminophenyl 3,5-diaminobenzoate (HC-05)

Step 1 Synthesis of 6-tert-butoxycarbonylamino-m-cresol

To a 300 mL four-necked flask was added 6.2 g (50.3 mmol) of 6-amino-m-cresol, 150 mL of tetrahydrofuran, and 14.2 g (55.3 mmol) of di-tert-butyl dicarbonate. Stir. After completion of the reaction, ethyl acetate was added and washed with water and saturated brine. Then, it dried with magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator to obtain 11.2 g of a white solid (yield 99%).

Second Step 3-Methyl-6-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzoate

To a 300 mL four-necked flask, 11.2 g (50.2 mmol) of 6-tert-butoxycarbonylamino-m-cresol, 200 mL of tetrahydrofuran, and 4.0 g (50.2 mmol) of pyridine were added. The system was cooled to 0 ° C., 11.5 g (50.2 mmol) of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, the reaction solution was poured into a mixed solvent of methanol and water (9: 1) to precipitate a solid, and the solid was filtered. Subsequently, the solid was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 20.2 g of a yellow solid (yield 97%).

Synthesis of the third step HC-05

To a 300 mL four-necked flask, add 10.0 g (24.0 mmol) of 3-methyl-6-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzoate, 100 mL of tetrahydrofuran, and 1.0 g of 5% palladium / carbon. And stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 8.7 g of a gray solid (yield 99%). The results of ¹ H-NMR of the individual obtained are shown below. From this result, it was confirmed that it was the target product, HC-05.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 8.63 (s, 1H), 7.43-7.45 (d, 2H), 6.99-7.02 (d, 1H), 6.93 (s, 1H), 6.57 (s, 2H), 6.08 (s, 1H), 5.04 (s, 4H), 2.27 (s, 1H), 1.37 (s , 9H)

<Example 6>
Synthesis of 4- (4-amylbenzoylamino) -2-tert-butoxycarbonylamino 3,5-diaminobenzoate (HC-06)

First Step Synthesis of 4- (4-Amylbenzoylamino) -2-nitrophenol

To a 200 mL four-necked flask, 12.5 g (64.9 mmol) of 4-amylbenzoic acid, 100 mL of tetrahydrofuran, and 20 mL of DMF (N, N-dimethylformamide) are added, and the system is cooled to 0 ° C. 7.80 g (65.5 mol) of thionyl was added and stirred at 60 ° C. for 2 hours to prepare a 4-amylbenzoic acid chloride solution. On the other hand, 10.0 g (64.9 mmol) of 4-amino-2-nitrophenol, 150 mL of tetrahydrofuran and 6.3 g (64.9 mmol) of pyridine were added to a 300 mL four-necked flask, and the system was cooled. The temperature was brought to 0 ° C., and the 4-amylbenzoic acid chloride solution prepared previously was slowly added, and the mixture was returned to room temperature and stirred for 1 day under a nitrogen atmosphere. After completion of the reaction, the solvent was removed by an evaporator, ethyl acetate was added, 50 mL of pure water was added and stirred, the organic layer was separated, and the organic layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was purified by column chromatography (mixed solvent of ethyl acetate and n-hexane (8: 2), and again dispersed and washed with a mixed solvent of ethyl acetate and n-hexane (2: 8). 15.6 g of a yellow solid was obtained (73% yield).

Second Step Synthesis of 4- (4-Amylbenzoylamino) -2-aminophenol

To a 200 mL four-necked flask, 10.0 g (30.5 mol) of 4- (4-amylbenzoylamino) -2-nitrophenol, 100 mL of tetrahydrofuran, and 1.0 g of 10% palladium carbon were added. Stir at room temperature. After completion of the reaction, palladium carbon was removed by filtration, the solvent was distilled off using a rotary evaporator, redissolved with acetone, and activated carbon was added and stirred. Thereafter, the activated carbon was removed by filtration, and the solvent was distilled off from the filtrate using a rotary evaporator to obtain 8.4 g of a light brown candy-like solid (yield 93%).

Step 3 Synthesis of 4- (4-amylbenzoylamino) -2-tert-butoxycarbonylaminophenol

In a 200 mL four-necked flask, 6.0 g (20.1 mmol) of 4- (4-amylbenzoylamino) -2-aminophenol, 100 mL of tetrahydrofuran, and 4.4 g (20.1 mmol) of di-tert-butyl dicarbonate. ) And 0.16 g (2.01 mmol) of pyridine were added and stirred at room temperature. After completion of the reaction, the solvent was distilled off with a rotary evaporator, ethyl acetate was added, and the mixture was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 5.8 g of a white solid (yield 72%).

Step 4 Synthesis of 4- (4-Amylbenzoylamino) -2-tert-butoxycarbonylaminophenyl-3,5-dinitrobenzoate

To a 200 mL four-necked flask, 5.00 g (12.5 mmol) of 4-amylbenzoylamino-2-tert-butoxycarbonylaminophenol, 80 mL of tetrahydrofuran, and 0.99 g (12.5 mmol) of pyridine were added. The system was cooled to 0 ° C., 2.9 g (12.5 mmol) of 3,5-dinitrobenzoyl chloride was added, and the mixture was stirred at room temperature. After completion of the reaction, ethyl acetate was added, and the mixture was washed successively with 10% by mass aqueous sodium hydrogen carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with a mixed solvent of methanol and 2-propanol (3: 7) and recrystallized using a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 5.09 g of a pale yellow solid. Obtained (yield 90%).

Synthesis of the fifth step HC-06

In a 100 mL four-necked flask, 4.52 g (7.59 mmol) of 4- (4-amylbenzoylamino) -2-tert-butoxycarbonylamino 3,5-dinitrobenzoate, 50 mL of 1,4-dioxane, and 10 0.45 g of% palladium carbon was added and stirred at room temperature in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of dichloroethane and n-hexane (5: 5) to obtain 3.62 g of a light gray solid (yield 90%). The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-07.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 9.82 (s, 1H), 8.73 (s, 1H), 7.96-7.85 (dd, 3H), 7.40- 7.43 (d, 1H), 7.37-7.35 (d, 2H), 6.99-7.01 (d, 1H), 6.54 (s, 2H), 6.12 (s, 1H), 4.99 (s-br, 4H), 2.68-2.64 (m, 2H), 1.65 to 1.56 (m, 2H), 1.46 (s, 9H), 1 .37-1.16 (m, 4H), 0.88-0.84 (t, 3H)

<Example 7>
[4- (4-Amylbenzoylamino) -2- (tert-butoxycarbonylamino) phenyl] Synthesis of 2- (2,4-diaminophenyl) acetamide (HC-07)

First Step [4- (4-Amylbenzoylamino) -3- (tert-butoxycarbonylamino) phenyl] Synthesis of (2,4-dinitrophenyl) acetamide

To a 100 mL four-necked flask, 3.0 g (12.3 mmol) of 2,4-dinitrophenylacetic acid, 50 mL of dichloromethane, and 5 mL of dimethylformamide were added, the system was cooled to 0 ° C., and 1.6 g of oxalyl chloride ( 12.3 mmol) was slowly added, and the mixture was returned to room temperature and stirred for 2 hours to prepare a 2,4-dinitrophenylacetic acid chloride solution. Meanwhile, in a 200 mL four-necked flask, 4.5 g (11.2 mmol) of N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylamino aniline, 50 mL of dichloromethane, and 1.1 g (13 4 mmol), the system was cooled to 0 ° C., and the 2,4-dinitrobenzoic acid chloride solution prepared above was slowly added dropwise and stirred at room temperature under a nitrogen atmosphere. After completion of the reaction, the solvent was removed with a rotary evaporator, ethyl acetate was added, and the mixture was washed successively with a 10% by mass aqueous sodium hydrogen carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with methanol, and recrystallized using a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 5.2 g of light yellow solid (yield 77%).

Synthesis of the second step HC-07

In a 100 mL four-necked flask, 4.5 g (7.43 mmol) of N- [4- (4-amylbenzoylamino) -3- (tert-butoxycarbonylamino) phenyl] (2,4-dinitrophenyl) acetamide, 50 mL of 1,4-dioxane and 0.45 g of platinum oxide were added, and the mixture was stirred at room temperature in a hydrogen atmosphere. After completion of the reaction, platinum oxide was removed by filtration, and the solvent was distilled off using a rotary evaporator. Recrystallization was performed using a mixed solvent of residual ethyl acetate and n-hexane (5: 5) to obtain 3.6 g of a light brown solid (yield 89%). The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-07.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 9.98 (s, 1H), 9.67 (s, 1H), 8.68 (s, 1H), 8.00 (d, 1H) 7.85-7.83 (d, 2H), 7.53-7.50 (m, 1H), 7.32-7.28 (m, 2H), 7.22 (d, 2H), 6 .43-6.40 (d, 1H), 6.00-5.90 (d, 1H), 4.96 (s-br, 2H), 3.52 (s-br, 2H), 3.08 (S, 2H), 2.67-2.65 (m, 2H), 1.62-1.55 (m, 2H), 1.46 (s, 9H), 1.39-1.17 (m , 4H), 0.89-0.85 (t, 3H)

<Example 8>
Synthesis of (Z) -3,5-dinitrobenzyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate (HC-08)

Step 1 Synthesis of 2- (tert-butoxycarbonylamino) aniline

To a 500 mL four-necked flask were added 50.0 g (462 mmol) of O-phenylenediamine, 300 mL of tetrahydrofuran, and 100.8 g (462 mmol) of di-tert-butyl dicarbonate, and the mixture was refluxed for 4 hours under a nitrogen atmosphere. After completion of the reaction, the solvent was removed with a rotary evaporator, and the resulting solid was dispersed and washed with methanol and recrystallized with a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 77.0 g (yield) of a light brown solid. 80%).

Step 2 Synthesis of 2-butenedioic acid (2Z)-, 3,5-dinitrobenzyl ester

To a 500 mL four-necked flask, 25.0 g (126 mmol) of 3,5-dinitrobenzyl alcohol, 300 mL of chloroform, and 19.1 g (189 mmol) of triethylamine were added, and the system was cooled to 0 ° C. in a nitrogen atmosphere. 14.8 g (151 mmol) of acid was added, stirred for 2 hours, returned to room temperature, and reacted for 6 hours. After completion of the reaction, the mixture was cooled again to 10 ° C., 200 mL of 10% by weight aqueous sodium hydrogen carbonate solution was added and stirred for 1 hour, the aqueous layer was separated, the aqueous layer was washed with dichloroethane, cooled again to 10 ° C., 10 A mass% aqueous hydrochloric acid solution was added to adjust the pH to 4 to 5, and a white solid was precipitated. The obtained solid was dissolved in ethyl acetate and extracted, and then the ethyl acetate layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with ethanol and recrystallized with a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 32.1 g (yield 86%) of a white solid.

Step 3 (Z) -3,5-dinitrobenzyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate

In a 300 mL four-necked flask, weigh 10.00 g (33.7 mmol) of 2-butenedioic acid (2Z)-, 3,5-dinitrobenzyl ester, 200 mL of THF, and 1.71 g (16.9 mmol) of triethylamine. , And 13.99 g (50.6 mmol) of 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate (DMT-MM) were added at room temperature. After stirring for 30 minutes, 7.67 g (36.8 mmol) of 2- (tert-butoxycarbonylamino) aniline was added little by little, and the mixture was reacted at room temperature for 6 hours under a nitrogen atmosphere.
After completion of the reaction, the reaction solution was concentrated on a rotary evaporator, 200 ml of ethyl acetate was added, and the mixture was stirred at 50 ° C. for 1 hour, and then insoluble matters were filtered and washed with water and saturated brine in this order. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized from methanol to obtain a light yellow solid 14.59 (yield 89%).

Synthesis of the fourth step HC-08

In a 300 mL four-necked flask, 10.0 g (20.6 mmol) of (Z) -3,5-dinitrobenzyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate, reduced iron 11.5 g (200 mmol), 10 mass% ammonium chloride aqueous solution 107 g (ammonium chloride 200 mmol), and toluene 150 mL were added, and the mixture was reacted with stirring at 70 ° C. for 1 day in a nitrogen atmosphere with a mechanical stirrer. After completion of the reaction, ethyl acetate was added, iron was filtered, and the organic layer of the filtrate was washed with water and saturated brine. Then, it dried with magnesium sulfate, magnesium sulfate was removed by filtration, activated carbon was added to the organic layer, and it stirred for a while. Thereafter, the activated carbon was removed by filtration, and the solvent was distilled off with a rotary evaporator. Purification was performed by column chromatography (a mixed solvent of ethyl acetate and dichloroethane (3: 7)) and dried under reduced pressure to obtain 8.0 g (yield 91%) of a pale yellow glassy solid.
The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-08.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.78 (s-br, 1H), 7.56-7.53 (d, 1H), 7.38-7.37 (dd, 1H), 7. 20-7.12 (m, 2H), 7.04-6.92 (q, 2H), 6.93 (s-br, 1H), 6.10 (d, 2H), 5.98-5. 97 (t, 1H), 5.01 (s, 2H), 3.63 (s-br, 4H), 1.51 (s, 9H)

<Example 9>
(E)-(2,4-Diaminophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate (HC-09) and 2- (2,4-diamino) Synthesis of phenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobutanoate (HC-10)

Step 1 Synthesis of 2- (2,4-dinitrophenoxy) ethanol

To a 300 mL four-necked flask, add 13.6 g (134 mmol) of triethylamine, 50 mL of ethylene glycol, and 150 mL of tetrahydrofuran, cool to 10 ° C. under a nitrogen atmosphere, and further add 25.0 g (134 mmol) of 2,4-dinitrofluorobenzene. In addition, the mixture was heated to 60 ° C. and reacted for 16 hours. After completion of the reaction, the solvent was removed by a rotary evaporator, ethyl acetate was added, washed with water and saturated brine, and dried over magnesium sulfate. Thereafter, magnesium sulfate was removed by filtration, and the solvent was distilled off by a rotary evaporator. Recrystallization was performed with a mixed solvent of methanol and 2-propanol (3: 7), and the mixture was dispersed and washed with n-hexane to obtain 26.0 g (yield 85%) of a white solid.

Second step (1)
Synthesis of 2-butenedioic acid (2E)-, 2- (2,4-dinitrophenoxy) ethanol ester (method utilizing isomerization reaction from maleic anhydride)

To a 300 mL four-necked flask, 10.0 g (43.8 mmol) of 2- (2,4-dinitrophenoxy) ethanol was weighed, 200 mL of chloroform and 4.43 g (43.8 mmol) of triethylamine were added, and anhydrous in an ice bath. 5.15 g (52.6 mmol) of maleic acid was added, slowly returned to room temperature, and stirred for 6 hours. After completion of the reaction, 100 mL of ethyl acetate was added, and the mixture was washed successively with a 10 mass% hydrochloric acid aqueous solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dissolved in 200 mL of 1,4-dioxane, 1.00 g of hydrochloric acid was added, and the mixture was stirred at 100 ° C. for 2 hours. Then, the solvent was distilled off with a rotary evaporator, and recrystallization was performed with a mixed solvent of ethyl acetate and hexane (7: 3) to obtain 12.86 g (yield 90%) of a white solid.

Second step (2)
Synthesis of 2-butenedioic acid (2E)-, 2- (2,4-dinitrophenoxy) ethanol ester

To a 300 mL four-necked flask were added fumaryl chloride 10.0 (65.7 mmol) and chloroform 150 mL, and the system was cooled to 0 ° C. in a nitrogen atmosphere, and 2- (2,4-dinitrophenoxy) ethanol was further cooled. 10.0 g (43.8 mmol) of a dimethylacetamide solution (DMAc 50 mL) and a chloroform solution of 4.43 g (43.8 mmol) of triethylamine were slowly added, stirred for 2 hours, returned to room temperature, and reacted for 1 day. After completion of the reaction, 50 mL of water was added, the mixture was cooled again to 10 ° C., 100 mL of a 10% by mass aqueous sodium hydrogen carbonate solution was added and stirred for 1 hour, the aqueous layer was separated, and the aqueous layer was washed with ethyl acetate. Thereafter, after cooling to 10 ° C., a 10 mass% hydrochloric acid aqueous solution was added to adjust the pH to 4 to 5, and a white solid was precipitated. The obtained solid was dissolved in ethyl acetate and extracted, and then the ethyl acetate layer was washed with water and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was dispersed and washed with ethanol and recrystallized with a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 12.1 g (yield 85%) of a white solid.

Step 3 (E)-(2,4-dinitrophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate

To a 200 mL four-necked flask was added 10.0 g (30.7 mmol) of 2-butenedioic acid (2E)-, 2- (2,4-dinitrophenoxy) ethanol ester, 100 mL of chloroform, and 30 mL of DMF, and further under a nitrogen atmosphere, After slowly adding 4.3 g (33.8 mmol) of oxalyl chloride at 0 ° C., the mixture was returned to room temperature and stirred for 2 hours. Subsequently, 9.6 g (46.1 mmol) of 2- (tert-butoxycarbonylamino) aniline was added, and the mixture was reacted at room temperature for 24 hours under a nitrogen atmosphere. After completion of the reaction, ethyl acetate was added to separate the organic layer, and the organic layer was washed sequentially with water, 10% by mass hydrochloric acid aqueous solution, 10% by mass sodium hydrogen carbonate aqueous solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized with a mixed solvent of ethyl acetate and n-hexane (3: 7) and dispersed and washed with ethanol to obtain 12.1 g of light yellow solid (yield 76%).

Synthesis of the fourth step HC-09

In a 200 mL four-necked flask, 5.0 g (9.68 mmol) of (E)-(2,4-dinitrophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate Then, 5.4 g (96.8 mmol) of reduced iron, 51.8 g (ammonium chloride 96.8 mmol) of 10 mass% ammonium chloride aqueous solution and 70 mL of toluene were added, and the mixture was stirred at 70 ° C. for 1 day in a nitrogen atmosphere with a mechanical stirrer. It was made to react. After completion of the reaction, ethyl acetate was added, iron was filtered, and the organic layer of the filtrate was washed with water and saturated brine. Then, it dried with magnesium sulfate, magnesium sulfate was removed by filtration, activated carbon was added to the organic layer, and it stirred for a while. Thereafter, the activated carbon was removed by filtration, and the solvent was distilled off with a rotary evaporator. Purification was performed by column chromatography (mixed solvent of ethyl acetate and dichloroethane (5: 5)) and dried under reduced pressure to obtain 3.5 g of light yellow glassy solid (yield 80%).
The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-09.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.80 (s-br, 1H), 7.61-7.59 (d, 1H), 7.40-7.38 (d, 1H), 7. 21-7.14 (m, 2H), 6.99 (s-br, 1H), 6.94-6.81 (q, 2H), 6.69-6.67 (d, 1H), 6. 15-6.13 (d, 1H), 6.09-6.07 (dd, 1H), 4.54-4.52 (t, 2H), 4.21-4.19 (t, 2H), 3.66 (s-br, 4H), 1.52 (s, 9H)

Step 5 Synthesis of HC-10

In a 300 mL four-necked flask, 5.0 g of (E)-(2,4-dinitrophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate (9. 68 mmol), tetrahydrofuran (50 mL), and 10% palladium carbon (0.50 g) were added, and the mixture was stirred at room temperature in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and then the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (2: 8) to obtain 4.00 g of a white solid (yield 90%).
The results of ¹ H-NMR of the obtained individual are shown below. From this result, it was confirmed that it was the target product, HC-09.
¹ H NMR (400 MHz, CDCl ₃ ): δ 8.21 (s-br, 1H), 7.43-7.42 (d, 1H), 7.37-7.36 (d, 1H), 7. 16-7.08 (m, 3H), 6.57-6.56 (d, 1H), 6.05-6.03 (d, 1H), 5.97-5.96 (dd, 1H), 4.38-4.35 (t, 2H), 4.14-4.11 (t, 2H), 3.22 (s-br, 4H), 2.76-2.74 (t, 2H), 2.59-2.56 (t, 2H), 1.46 (s, 9H)

<Characteristic evaluation of liquid crystal alignment film>
The abbreviations of the compounds used in the present specification are as follows.
<Tetracarboxylic dianhydride>
CBDA: 1,2,3,4-cyclobutanetetracarboxylic dianhydride PMDA: pyromellitic dianhydride CBDE: 1,2,3,4-cyclobutanetetracarboxylic acid dimethyl ester

<Diamine>
p-PDA: p-phenylenediamine 3-ABA: 3-aminobenzylamine 2,4-DAA: N, N-diallylamino 2,4-diaminobenzene C14DAB: 4-tetradecyloxy-1,3-diaminobenzene C16DAB : 4-hexadecyloxy-1,3-diaminobenzene CAB-2: N- (4- (trans-4-n-heptylcyclohexyl) benzoyl) amino 2,4-diaminobenzene PCH-7AB: N- (4- (Trans-4-n-heptylcyclohexyl) phenoxy) 2,4-diaminobenzene m-TDA: m-tolyl 3,5-diaminobenzoate HC-01: 2- (tert-butoxycarbonylamino) -4-octanamide Phenyl 3,5-diaminobenzoate HC-02: N-4- (4-amino Rubenzoylamino) -3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide HC-03: N-4- (4-amylbenzoylamino) -3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzamide HC -04: N-4- (4-amylbenzoyloxy) -3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide HC-05: 2-methyl-6-tert-butoxycarbonylaminophenyl 3,5-diamino Benzoate

HC-06: 4- (4-Amylbenzoylamino) -2-tert-butoxycarbonylamino 3,5-diaminobenzoate HC-07: [4- (4-Amylbenzoylamino) -2- (tert-butoxycarbonylamino) ) Phenyl] 2- (2,4-diaminophenyl) acetamide HC-08: (Z) -3,5-dinitrobenzyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2- Enoate HC-09: (E)-(2,4-diaminophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenylamino) -4-oxobut-2-enoate HC-10: 2- (2, 4-Diaminophenoxy) ethyl 4- (2- (tert-butoxycarbonylamino) phenyl Mino) -4-oxobutanoate HC-11: 4- (trans-4-amylcyclohexanecarboxyamino) -3- (tert-butoxycarbonylamino) phenyl 3,5-diaminobenzamide HC-12: 4- [4 -(Trans-4-pentylcyclohexyl) benzamide] -3- (tert-butoxycarbonylamino) phenyl 3,5-diaminobenzamide

<Condensation agent>
DMT-MM: 4- (4,6-dimethoxy-1,3,5-triazin-2-yl) 4-methoxymorpholium chloride n-hydrate <organic solvent>
NMP: N-methyl-2-pyrrolidone γ-BL: γ-butyrolactone BC: Butyl cellosolve DPM: Dipropylene glycol monomethyl ether

<Measurement of molecular weight>
The molecular weight of the polymer obtained by the polymerization reaction was determined by measuring the polyimide with a GPC (room temperature gel permeation chromatography) apparatus, and calculating the number average molecular weight and the weight average molecular weight as converted values of polyethylene glycol and polyethylene oxide.
GPC device: manufactured by Shodex (GPC-101)
Column: manufactured by Shodex (series of KD803 and KD805)
Column temperature: 50 ° C
Eluent: N, N-dimethylformamide (as additives, lithium bromide-hydrate (LiBr · H 2 O) 30 mmol / L, phosphoric acid / anhydrous crystal (o-phosphoric acid) 30 mmol / L, tetrahydrofuran (THF ) Is 10 mL / L)
Flow rate: 1.0 mL / min Standard sample for preparing calibration curve: TSK standard polyethylene oxide (molecular weight: about 900,000, 150,000, 100,000, 30,000) manufactured by Tosoh Corporation and polyethylene glycol manufactured by Polymer Laboratory (Molecular weight about 12,000, 4,000, 1,000).

<Measurement of imidization ratio>
The imidation ratio of polyimide in the synthesis example was measured as follows. Add 20 mg of polyimide powder to an NMR sample tube (NMR sampling tube standard made by Kusano Kagaku), add 0.53 mL of deuterated dimethyl sulfoxide (DMSO-d6, 0.05 mass% TMS mixture), and apply ultrasonic waves. And completely dissolved. 500 MHz proton NMR of this solution was measured with an NMR measuring instrument (JNW-ECA500) manufactured by JEOL Datum. The imidation rate is determined based on protons derived from structures that do not change before and after imidation as reference protons, and the peak integrated value of these protons and proton peaks derived from NH groups of amic acid appearing in the vicinity of 9.5 to 10.0 ppm. It calculated | required by the following formula | equation using the integrated value.

Imidization rate (%) = (1−α · x / y) × 100

In the above formula, x is a proton peak integrated value derived from NH group of amic acid, y is a peak integrated value of reference proton, α is one NH group proton of amic acid in the case of polyamic acid (imidation rate is 0%) Is the number ratio of the reference proton to.

<Production of liquid crystal cell>
About the liquid crystal aligning agent prepared by the Example and the comparative example, the liquid crystal cell was produced as follows.
A liquid crystal alignment treatment agent is spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C. for 70 seconds, and then baked on a hot plate at 210 ° C. for 10 minutes to form a coating film having a thickness of 100 nm. I let you. For the liquid crystal alignment treatment by rubbing, this coating film surface was rubbed with a rubbing apparatus having a roll diameter of 120 mm using a rayon cloth under the conditions of a roll rotation speed of 1000 rpm, a roll traveling speed of 50 mm / sec, and an indentation amount of 0.3 mm. A substrate with a film was obtained. The liquid crystal alignment treatment with light was performed by irradiating the coating surface with linearly polarized UV light (UV wavelength: 313 nm, equivalent to 500 mJ) at an angle of 40 ° with respect to the normal line of the plate.

After preparing two substrates with a liquid crystal alignment film subjected to the liquid crystal alignment treatment in this manner, a spacer of 6 μm is sprayed on the surface of the one liquid crystal alignment film, and then a sealant is printed thereon, and another sheet is obtained. The substrates are bonded so that the liquid crystal alignment film faces each other and the rubbing direction is perpendicular (twisted nematic liquid crystal cell), or for those irradiated with UV, the directions of irradiated polarized light are parallel (vertical). Orientation mode), the sealing agent was cured to produce an empty cell. In this empty cell, liquid crystal MLC-2003 (Merck) is injected in the twisted nematic cell by vacuum injection, and liquid crystal MLC-6608 (Merck) is injected in the vertical alignment mode, and the injection port is sealed. Thus, a twisted nematic liquid crystal cell was obtained.
A method for measuring physical properties and evaluating characteristics of each liquid crystal cell produced was described below.
The results of the composition of each liquid crystal alignment treatment agent in Examples 1 to 9 and Comparative Examples 1 to 3, the measurement of physical properties of each liquid crystal alignment film, and the evaluation of the characteristics are shown in Tables 2 to 4. .

<Rubbing resistance evaluation>
When producing a substrate with a liquid crystal alignment film by the method described in <Preparation of liquid crystal cell> above, the rubbing conditions are changed by changing the indentation amount to 0.5 mm, and a liquid crystal alignment film for rubbing resistance evaluation is produced. The surface was observed with a confocal laser microscope, and the following evaluation was performed.
○: Scraping and rubbing scratches are not observed.
Δ: Scraping and rubbing scratches are observed.
X: A film | membrane peels or a rubbing damage | wound is observed visually.

<Measurement of pretilt angle>
The twisted nematic liquid crystal cell or antiparallel cell produced by the method described in <Preparation of liquid crystal cell> above was heated at 105 ° C. for 5 minutes, and then the pretilt angle was measured. The pretilt angle was measured by “Axo Scan” manufactured by Axo Metric, using the Mueller matrix method.

<Measurement of voltage holding ratio (VHR) and backlight aging resistance>
Voltage holding ratio in the initial state of the liquid crystal cell produced by the method described in <Preparation of liquid crystal cell> and backlight aging (the liquid crystal cell is mounted on the backlight for the LCD panel and driven at 10 V AC for 2 weeks) The subsequent voltage holding ratio was measured. The voltage holding ratio was measured by applying a voltage of 4 V for 60 μs at a temperature of 90 ° C., measuring the voltage after 16.67 ms, and calculating how much the voltage could be held as the voltage holding ratio. The voltage holding ratio was measured using a voltage holding ratio measuring device (VHR-1) manufactured by Toyo Technica.

(Example 10)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.72 g (1.50 mmol) of HC-01, and 28.2 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-1) concentration of 15 mass%.
30 g of this polyamic acid (PAA-1) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-1) and 74% of NMP. A liquid crystal alignment treatment agent-1 was obtained by making a solution with a mass% and BC of 20 mass%. The number average molecular weight of this polyamic acid was 14,300, and the weight average molecular weight was 41,200.

(Example 11)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.80 g (1.5 mmol) of HC-02, and 28.6 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-2) concentration of 15% by mass.
30 g of this polyamic acid (PAA-2) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-2) and 74% of NMP. A liquid crystal alignment treatment agent-2 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 12,300, and the weight average molecular weight was 26,700.

(Example 12)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.80 g (1.5 mmol) of HC-03, and 28.6 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-3) concentration of 15% by mass.
30 g of this polyamic acid (PAA-3) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-3) and 74% of NMP. A liquid crystal aligning agent-3 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 9,800, and the weight average molecular weight was 26,900.

(Example 13)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.80 g (1.5 mmol) of HC-04, and 28.6 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-4) concentration of 15 mass%.
30 g of this polyamic acid (PAA-4) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by weight of polyamic acid (PAA-4) and 74% by weight of NMP. % And BC as a 20% by mass solution to obtain Liquid Crystal Alignment Agent-4. The number average molecular weight of this polyamic acid was 11,300, and the weight average molecular weight was 25,800.

(Example 14)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.54 g (1.5 mmol) of HC-05, and 27.1 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-5) concentration of 15% by mass.
30 g of this polyamic acid (PAA-5) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, diluted to 6% by mass of polyamic acid (PAA-5), and 74% of NMP. A liquid crystal aligning agent-5 was obtained by making a solution with a mass% and BC of 20 mass%. The number average molecular weight of this polyamic acid was 12,600, and the weight average molecular weight was 30,200.

(Example 15)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.80 g (1.5 mmol) of HC-06, and 28.6 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-6) concentration of 15% by mass.
30 g of this polyamic acid (PAA-6) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, diluted to 6% by mass of polyamic acid (PAA-6), and 74% of NMP. A liquid crystal alignment agent-6 was obtained by making a solution with a mass% of 20% by mass of BC. The number average molecular weight of this polyamic acid was 12,700, and the weight average molecular weight was 27,700.

(Example 16)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.82 g (1.5 mmol) of HC-07, and 28.7 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-7) concentration of 15% by mass.
30 g of this polyamic acid (PAA-7) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-7) and 74% of NMP. A liquid crystal aligning agent-7 was obtained by making a solution with a mass% and BC of 20 mass%. The number average molecular weight of this polyamic acid was 10,200, and the weight average molecular weight was 26,500.

(Example 17)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.71 g (1.5 mmol) of HC-10, and 28.1 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-8) concentration of 15% by mass.
30 g of this polyamic acid (PAA-8) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-8) and 74% of NMP. A liquid crystal alignment treatment agent-8 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 9,900, and the weight average molecular weight was 23,500.

(Example 18)
As a diamine component, 2.00 g (5.60 mmol) of HC-05 and 17.4 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. Next, 1.08 g (5.49 mmol) of CBDA was added, returned to room temperature, and reacted for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamic acid (PAA-9) concentration of 15 mass%.
15 g of this polyamic acid (PAA-9) solution was transferred to a 50 mL Erlenmeyer flask, diluted by adding 15.0 g of NMP and 7.5 g of BC, and diluted to 6% by mass of polyamic acid (PAA-9) and 74% of NMP. A liquid crystal alignment agent-9 was obtained by making a solution with a mass% and BC of 20 mass%. The number average molecular weight of this polyamic acid was 21,200, and the weight average molecular weight was 50,900.

(Example 19)
As a diamine component in a 50 mL four-necked flask, 2.00 g (4.70 mol) of HC-08, 0.45 g (1.17 mmol) of PCH-7AB, and 20.3 g of NMP were added and cooled to about 10 ° C. . Next, 1.13 g (5.81 mmol) of CBDA was added, returned to room temperature, and reacted for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamic acid (PAA-10) concentration of 15 mass%.
20 g of this polyamic acid (PAA-10) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 20.0 g of NMP and 10.0 g of BC, diluted to 6% by mass of polyamic acid (PAA-10), and 74% of NMP. A liquid crystal alignment treatment agent-10 was obtained by making a solution with a mass% and BC of 20 mass%. The number average molecular weight of this polyamic acid was 13,300, and the weight average molecular weight was 428,000.

(Example 20)
As a diamine component in a 50 mL four-necked flask, 2.00 g (4.38 mol) of HC-09, 0.45 g (1.10 mmol) of PCH-7AB, and 19.7 g of NMP were added and cooled to about 10 ° C. . Next, 1.06 g (5.43 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-11) concentration of 15% by mass.
20 g of this polyamic acid (PAA-11) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 20.0 g of NMP and 10.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-11) and 74% of NMP. A liquid crystal alignment treatment agent-11 was obtained in the form of a solution containing 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 10,700, and the weight average molecular weight was 35,300.

(Example 21)
As a diamine component in a 100 mL four-necked flask, 0.307 g (2.52 mmol) of 3-ABA, 0.384 g (1.89 mmol) of 2,4-DAA, and 1.00 g (1.89 mol) of HC-02 And 12.3 g of NMP were added and cooled to about 10 ° C. Next, 0.412 g (1.89 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 0.964 g (4.91 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-12) concentration of 20 mass%.
To 15.0 g of a polyamic acid (PAA-12) solution, 22.5 g of NMP was added for dilution, and 1.96 g of acetic anhydride and 0.84 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellowish brown powder of polyimide (SPI-1). The number average molecular weight of this polyimide was 11,200, and the weight average molecular weight was 30,800. Further, the imidization ratio was 89%.
To 2.00 g of polyimide (SPI-1), 18.0 g of γ-BL was added and stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-1) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass, thereby obtaining a liquid crystal aligning agent-12.

(Example 22)
As a diamine component in a 100 mL four-necked flask, 3-ABA 0.307 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), HC-03 1.00 g (1.89 mol) And 12.3 g of NMP were added and cooled to about 10 ° C. Next, 0.412 g (1.89 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 0.964 g (4.91 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-13) concentration of 20 mass%.
To 15.0 g of a polyamic acid (PAA-13) solution, 22.5 g of NMP was added for dilution, and 1.96 g of acetic anhydride and 0.84 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain an orange powder of polyimide (SPI-2). The number average molecular weight of this polyimide was 9,800, and the weight average molecular weight was 23,500. Further, the imidization ratio was 89%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-2), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-2) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass, thereby obtaining a liquid crystal aligning agent-13.

(Example 23)
As a diamine component in a 100 mL four-neck flask, 0.308 g (2.52 mmol) of 3-ABA, 0.384 g (1.89 mmol) of 2,4-DAA, and 1.00 g (0.89 mol) of HC-04 And 12.3 g of NMP were added and cooled to about 10 ° C. Next, 0.412 g (1.89 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 0.964 g (4.91 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-14) concentration of 20 mass%.
To 15.0 g of a polyamic acid (PAA-14) solution, 22.5 g of NMP was added for dilution, and 1.96 g of acetic anhydride and 0.84 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellowish brown powder of polyimide (SPI-3). The number average molecular weight of this polyimide was 11,800, and the weight average molecular weight was 25,100. Moreover, the imidation ratio was 88%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-3), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-3) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass, thereby obtaining a liquid crystal aligning agent-14.

(Example 24)
As a diamine component in a 100 mL four-necked flask, 3-ABA 0.308 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), HC-06 1.00 g (0.89 mol) And 12.3 g of NMP were added and cooled to about 10 ° C. Next, 0.412 g (1.89 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 0.964 g (4.91 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-15) concentration of 20 mass%.
To 15.0 g of a polyamic acid (PAA-15) solution, 22.5 g of NMP was added for dilution, and 1.96 g of acetic anhydride and 0.84 g of pyridine were further added, followed by reaction at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellowish brown powder of polyimide (SPI-4). The number average molecular weight of this polyimide was 13,200, and the weight average molecular weight was 29,400. Moreover, the imidation ratio was 85%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-4), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-4) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass, thereby obtaining a liquid crystal aligning agent-15.

(Example 25)
As a diamine component in a 100 mL four-neck flask, 0.298 g (2.44 mmol) of 3-ABA, 0.372 g (1.83 mmol) of 2,4-DAA, and 1.00 g (0.83 mol) of HC-04 And 12.0 g of NMP were added and cooled to about 10 ° C. Next, 0.399 g (1.83 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 0.933 g (4.76 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-16) concentration of 20 mass%.
To 15.0 g of a polyamic acid (PAA-16) solution, 22.5 g of NMP was added for dilution, and 1.94 g of acetic anhydride and 0.83 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellowish brown powder of polyimide (SPI-5). The number average molecular weight of this polyimide was 10,700, and the weight average molecular weight was 22,800. The imidation ratio was 87%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-5), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-5) was 5 mass%, γ-BL was 65 mass%, and BC was A liquid crystal aligning agent-16 having 15% by mass and DPM of 15% by mass was obtained.

(Example 26)
In a 100 mL four-necked flask, 2.37 g (9.12 mmol) of CBDE, 0.813 g (7.52 mmol) of p-PDA, 1.00 g (1.88 mmol) of HC-02, and 30 NMP were used as diamine components. 0.7g and 0.475 g (4.70 mmol) of triethylamine were added and cooled to about 10 ° C. Next, 7.80 g (28.2 mmol) of DMT-MM was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid ester (PAE-1) concentration of 12 mass%.
To this polyamic acid (PAE-1) solution, 34.9 g of NMP was added and slowly poured into 500 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 300 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a white powder of polyamic acid ester (PAE-1). The number average molecular weight of this polyamic acid ester was 15,300, and the weight average molecular weight was 38,800.
18.0 g of γ-BL was added to 2.00 g of polyamic acid ester (PAE-1), and the mixture was stirred at room temperature for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (PAE-1) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass, thereby obtaining a liquid crystal aligning agent-17.

(Comparative Example 1)
As a diamine component, 1.45 g (13.5 mol) of p-PDA, 0.52 g (1.50 mmol) of C16DAB, and 28.2 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-17) concentration of 15% by mass.
30 g of this polyamic acid (PAA-17) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-17) and 74% of NMP. A liquid crystal alignment agent-18 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 18,300, and the weight average molecular weight was 43,200.

(Comparative Example 2)
As a diamine component, 1.45 g (13.5 mol) of p-PDA, 0.64 g (1.50 mmol) of CAB-2, and 28.2 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-18) concentration of 15% by mass.
30 g of this polyamic acid (PAA-18) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, diluted to 6% by mass of polyamic acid (PAA-18), and 74% of NMP. A liquid crystal alignment agent-19 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 97,000, and the weight average molecular weight was 19,200.

(Comparative Example 3)
To a 50 mL four-necked flask, as a diamine component, 2.00 g (8.26 mmol) of mTDA and 20.3 of NMP were added and cooled to about 10 ° C. Next, 1.59 g (8.09 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-19) concentration of 15% by mass.
15 g of this polyamic acid (PAA-19) solution was transferred to a 50 mL Erlenmeyer flask, diluted by adding 15.0 g of NMP and 7.5 g of BC, and diluted to 6% by mass of polyamic acid (PAA-19) and 74% of NMP. A liquid crystal alignment agent-20 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 22,000, and the weight average molecular weight was 49,600.

(Comparative Example 4)
As a diamine component in a 100 mL four-necked flask, 0.508 g (4.16 mmol) of 3-ABA, 0.634 g (3.12 mmol) of 2,4-DAA, 1.00 g (3.12 mmol) of C14DAB, and 17.7 g of NMP was added and cooled to about 10 ° C. Next, 0.680 g (3.12 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 1.59 g (8.11 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-20) concentration of 20 mass%.
30.0 g of NMP was added to 20.0 g of a solution of polyamic acid (PAA-20) for dilution, and 3.01 g of acetic anhydride and 1.29 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 200 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was recovered, further dispersed and washed twice with 150 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellowish brown powder of polyimide (SPI-6). The number average molecular weight of this polyimide was 10,700, and the weight average molecular weight was 22,800. Moreover, the imidation ratio was 88%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-6), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-6) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass to obtain a liquid crystal aligning agent-21.

(Comparative Example 5)
As a diamine component in a 100 mL four-necked flask, 0.386 g (3.16 mmol) of 3-ABA, 0.482 g (2.37 mmol) of 2,4-DAA, and 1.00 g (2.37 mmol) of CAB-2 And 14.4 g of NMP were added and cooled to about 10 ° C. Next, 0.517 g (2.37 mmol) of PMDA was added, the temperature was returned to room temperature, and the reaction was performed for 1 hour in a nitrogen atmosphere. Further, 1.21 g (6.16 mmol) of CBDA was added and reacted at room temperature in a nitrogen atmosphere for 16 hours to obtain a solution having a polyamic acid (PAA-21) concentration of 20 mass%.
To 15.0 g of a solution of polyamic acid (PAA-21), 22.5 g of NMP was added for dilution, and 2.10 g of acetic anhydride and 0.90 g of pyridine were further added and reacted at 50 ° C. for 3 hours. The reaction solution was cooled to about room temperature and then slowly poured into 150 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a yellow-orange powder of polyimide (SPI-7). The number average molecular weight of this polyimide was 9,900, and the weight average molecular weight was 28,800. Moreover, the imidation ratio was 91%.
12.00 g of γ-BL was added to 2.00 g of polyimide (SPI-7), and the mixture was stirred at 50 ° C. for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (SPI-7) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass to obtain a liquid crystal aligning agent-22.

(Comparative Example 6)
As a diamine component, 1.00 g (9.28 mol) of m-PDA, 0.883 g (2.32 mmol) of PCH-7AB and 23.3 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.23 g (11.4 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-22) concentration of 15 mass%.
20 g of this polyamic acid (PAA-22) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 20.0 g of NMP and 10.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-22) and 74% of NMP. A liquid crystal alignment agent-23 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 16,300, and the weight average molecular weight was 40,200.

(Comparative Example 7)
In a 100 mL four-necked flask, 2.98 g (11.4 mmol) of CBDE, 1.02 g (9.44 mmol) of p-PDA, 1.00 g (2.36 mmol) of CAB-2, and 36 NMP were used as diamine components. 0.6 g and triethylamine (0.60 g, 5.90 mmol) were added, and the mixture was cooled to about 10 ° C. Next, 9.80 g (35.4 mmol) of DMT-MM was added, returned to room temperature, and reacted for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamic acid ester (PAE-2) concentration of 12 mass%.
41.7 g of NMP was added to this polyamic acid (PAE-2) solution, and slowly poured into 500 mL of methanol cooled to about 10 ° C. with stirring to precipitate a solid. The precipitated solid was collected, further dispersed and washed twice with 300 mL of methanol, and dried under reduced pressure at 100 ° C. to obtain a light pink powder of polyamic acid ester (PAE-2). The number average molecular weight of this polyamic acid ester was 13,200, and the weight average molecular weight was 35,700.
18.0 g of γ-BL was added to 2.00 g of polyamic acid ester (PAE-2), and the mixture was stirred at room temperature for 20 hours. The polyimide was completely dissolved at the end of stirring. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to this solution, and the mixture was stirred at 50 ° C. for 20 hours. Polyimide (PAE-2) was 5 mass%, γ-BL was 65 mass%, BC Was 15% by mass and DPM was 15% by mass to obtain a liquid crystal aligning agent-24.

When Examples 10 to 18 are compared with Comparative Examples 1 and 2, it can be seen that Examples 10 to 18 have improved rubbing resistance, high VHR, and excellent backlight aging resistance.
When Example 17 and Comparative Example 3 are compared, Comparative Example 3 (structure in which no cyclization reaction occurs) has a smaller pretilt angle than that of Example 17, and improves rubbing resistance and VHR aging resistance. It can be seen that is excellent.
When comparing Examples 19 and 20 and Comparative Example 6. In Examples 19 and 20, the development of pretilt was confirmed, indicating that the liquid crystal aligning agent is useful in the photoalignment method.
When comparing Examples 21 to 25 and Comparative Examples 4 and 5, in Comparative Examples 4 and 5, when the liquid crystal alignment treatment agent was printed on the substrate, pinholes and oblique unevenness were confirmed. In Examples 21 to 25, printability was excellent, no such defects were confirmed, pretilt expression was confirmed, and the effect of improving the backlight aging resistance of VHR could be confirmed. .
When Example 26 and Comparative Example 7 were compared, Example 26 had good printability and resulted in improved rubbing resistance and VHR backlight aging resistance.

<Example 27>
Synthesis of 4- (trans-4-amylcyclohexanecarboxyamino) -3- (tert-butoxycarbonylamino) phenyl 3,5-diaminobenzamide (HC-11)

Step 1 Synthesis of 4- (trans-4-amylcyclohexanecarboxamide) -3- (tert-butoxycarbonylamino) nitrobenzene

In a 100 mL branched eggplant flask, 5.16 g (20.0 mmol) of trans-4-amylcyclohexanecarboxylic acid was weighed and dissolved by adding 50 mL of THF, and 3.33 g (28.0 mmol) of thionyl chloride in an ice bath. Was slowly added dropwise. Thereafter, the temperature was returned to room temperature and reacted for 2 hours to form 4-amylcyclohexanecarboxylic acid chloride.

On the other hand, 5.07 g (20.0 mmol) of 3-tert-butoxycarbonylamino-4-aminonitrobenzene was measured into a 200 mL four-necked flask, and 50.0 mL of THF and 4.05 g (40.0 mmol) of triethylamine were added thereto. The temperature was adjusted to 10 ° C. or lower at 4 ° C., and 4-amylcyclohexanecarboxylic acid chloride prepared previously was added dropwise under a nitrogen atmosphere. Then, it returned to room temperature and made it react under nitrogen atmosphere for 24 hours.
After completion of the reaction, ethyl acetate was added, and the mixture was washed successively with 10% by mass aqueous sodium hydrogen carbonate solution, acetic acid water, pure water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (6: 4) to obtain 5.31 g of a yellowish white solid (yield 61%).

Second Step 4- (trans-4-amylcyclohexanecarboxamide) -3- (tert-butoxycarbonylamino) aniline synthesis

In a 100 mL four-necked flask, 4- (trans-4-amylcyclohexylcarboxylamido) -3- (tert-butoxycarbonylamino) nitrobenzene 4.28 g (9.88 mmol), tetrahydrofuran 50 mL, pure water 50 mL, and 9.48 g (50.0 mmol) of tin chloride was added and refluxed for 24 hours under a nitrogen atmosphere. After completion of the reaction, 100 mL of ethyl acetate was added, a 10% by mass aqueous sodium hydrogen carbonate solution was added, and the precipitate was removed by filtration. Thereafter, the organic layer of the filtrate was separated, washed with pure water and saturated brine, and dried over anhydrous sodium sulfate. Anhydrous sodium sulfate was removed by filtration, and the solvent was removed by a rotary evaporator to obtain 3.95 g of a yellow solid (yield 99%).

Step 3 Synthesis of 4- (trans-4-amylcyclohexanecarboxylamido) -3- (tert-butoxycarbonylamino) phenyl 3,5-dinitrobenzamide

In a 200 mL four-necked flask, 4.79 g (11.9 mmol) of 4- (trans-4-amylcyclohexanecarboxylamido) -3- (tert-butoxycarbonylamino) aniline, 80 mL of tetrahydrofuran, and 1.10 g of pyridine. (13.9 mmol) was added, and a 10 mass% THF solution of 3.22 g (14.0 mmol) of 3,5-dinitrobenzoic acid chloride was slowly added dropwise in an ice bath at 10 ° C. or lower in a nitrogen atmosphere, and the mixture was returned to room temperature. The reaction was allowed to proceed for 24 hours. The system was cooled to 0 ° C., 5.8 g (14.0 mmol) of 3,5-dinitrobenzoyl chloride was further added, and the mixture was stirred at room temperature. After completion of the reaction, the solvent was removed with a rotary evaporator, ethyl acetate was added, and the mixture was washed with a 10 mass% aqueous sodium carbonate solution, water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 5.26 g of light yellow solid (yield 74%).

Synthesis of the fourth step HC-11

To a 300 mL four-necked flask, 5.00 g (8.37 mmol) of 4- (trans-4-amylcyclohexanecarboxylamido) -3- (tert-butoxycarbonylamino) phenyl 3,5-dinitrobenzamide, 30 mL of tetrahydrofuran, 30 mL of ethanol and 0.50 g of 5% palladium carbon were added, and the mixture was stirred at room temperature in a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9), and then dispersed and washed with n-hexane to obtain 4.20 g of a gray solid (yield 93%).
The results of ¹ H-NMR of the obtained solid are shown below. From this result, it was confirmed that it was the target product, HC-10.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 9.94 (s, 1H), 9.22 (s, 1H), 8.34 (s, 1H), 8.34-7.93 ( d, 1H), 7.48-7.746 (dd, 1H), 7.32-7.30 (d, 1H), 7.28 (d, 2H), 5.99-5.97 ( t, 1H), 4.93 (s-br, 4H), 2.29 (m, 1H), 1.88-1.81 (m, 4H), 1.47 (s, 9H) 1.47- 1.40 (m, 2H), 1.31-1.16 (m, 9H), 0.94-0.91 (m, 2H) 0.89-0.85 (t, 3H)

<Example 28>
Synthesis of 4- [4- (trans-4-pentylcyclohexyl) benzamide] -3- (tert-butoxycarbonylamino) phenyl 3,5-diaminobenzamide (HC-12)

First Step Synthesis of 4-[(trans-4-pentylcyclohexyl) benzamide] -3-tert-butoxycarbonylamino nitrobenzene

To a 100 mL eggplant flask with a branch, weigh 5.07 g (22.0 mmol) of 4- (trans-4-pentylcyclohexyl) benzoic acid, add 50 mL of THF and 1 mL of DMF, and 3.33 g of thionyl chloride in an ice bath. (28.0 mmol) was slowly added dropwise, returned to room temperature, and allowed to react for 2 hours to produce 4- (trans-4-pentylcyclohexyl) benzoic acid chloride.

On the other hand, 5.07 g (20.0 mmol) of 3-tert-butoxycarbonylamino-4-aminonitrobenzene was weighed into a 200 mL four-necked flask, and 50.0 mL of THF and 2.43 g (24.0 mmol) of triethylamine were added to the ice bath. The temperature was lowered to 10 ° C. or lower, and 4- (trans-4-pentylcyclohexyl) benzoic acid chloride prepared previously was added dropwise under a nitrogen atmosphere, returned to room temperature, and allowed to react for 24 hours under a nitrogen atmosphere.
After completion of the reaction, ethyl acetate was added, and the mixture was washed with 10% by mass aqueous sodium hydrogen carbonate solution, acetic acid water, pure water, and saturated brine. Then, it dried with magnesium sulfate, the magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (3: 7) to obtain 6.03 g of a yellowish white solid (yield 60%).

Second Step Synthesis of 4-[(trans-4-pentylcyclohexyl) benzamide] -3- (tert-butoxycarbonylamino) aniline

In a 200 mL four-necked flask, 6.03 g (11.8 mmol) of 4-[(trans-4-pentylcyclohexyl) benzamide] -3- (tert-butoxycarbonylamino) nitrobenzene, 50 mL of tetrahydrofuran, and 5% palladium carbon 0.60 g was added, and the mixture was stirred at room temperature for 24 hours under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was removed by a rotary evaporator to obtain 5.94 g of a white solid (yield 99%).

Step 3 Synthesis of 4-[(trans-4-pentylcyclohexyl) benzamide] -3- (tert-butoxycarbonylamino) phenyl 3,5-dinitrobenzamide

In a 200 mL four-necked flask, 5.94 g (12.4 mmol) 4-[(trans-4-pentylcyclohexyl) benzoylamide] -3- (tert-butoxycarbonylamino) aniline, 80 mL tetrahydrofuran, and 1 pyridine. .10 g (13.9 mmol) was added, and a 10 mass% THF solution of 3.22 g (14.0 mmol) of 3,5-dinitrobenzoic acid chloride was slowly added dropwise in an ice bath at 10 ° C. or lower in a nitrogen atmosphere. Then, it returned to room temperature and made it react for 24 hours. After completion of the reaction, the solvent was removed with a rotary evaporator, the residue was washed with methanol, and recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) to obtain 7.82 g of a pale yellow solid. Obtained (yield 94%).

Synthesis of the fourth step HC-11

In a 300 mL four-necked flask, 6.00 g (8.9 mmol) of 4-[(trans-4-amylcyclohexyl) benzamide) -3- (tert-butoxycarbonylamino) phenyl 3,5-dinitrobenzamide was dissolved in 60 mL of tetrahydrofuran. Then, 0.60 g of 5% palladium carbon was added, and the mixture was stirred at room temperature under a hydrogen atmosphere. After completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary evaporator. The residue was recrystallized using a mixed solvent of ethyl acetate and n-hexane (1: 9) and then dispersed and washed with n-hexane to obtain 5.45 g of a gray solid (yield 99%).
The results of ¹ H-NMR of the obtained solid are shown below. From this result, it was confirmed that it was the target product, HC-10.
¹ H NMR (400 MHz, [D ₆ ] -DMSO): δ 10.00 (s, 1H), 9.71 (s, 1H), 8.59 (s, 1H), 8.02-8.01 ( d, 1H), 7.89-7.87 (d, 2H), 7.54-7.51 (dd, 1H), 7.41-7.37 (dd, 3H), 6.31-6. 30 (d, 2H), 6.00-5.99 (t, 1H), 4.94 (s-br, 4H), 2.60-2.51 (t, 1H), 1.85-1. 81 (m, 4H), 1.51-1.45 (t, 2H) 1.45 (s, 9H), 1.32-1.2 (m, 10H) 1.10-1.00 (m, 2H) 0.89-0.86 (t, 3H)

(Example 29)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.81 g (1.5 mmol) of HC-11, and 28.6 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was performed in a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-23) concentration of 15 mass%.
30 g of this polyamic acid (PAA-23) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-23) and 74% of NMP. A liquid crystal aligning agent-25 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 10,100, and the weight average molecular weight was 22,500.

(Example 30)
As a diamine component, 1.46 g (13.5 mol) of p-PDA, 0.94 g (1.5 mmol) of HC-12, and 29.4 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.79 g (14.3 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-24) concentration of 15% by mass.
30 g of this polyamic acid (PAA-24) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-24) and 74% of NMP. A liquid crystal aligning agent-26 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 13,700, and the weight average molecular weight was 28,200.

(Example 31)
As a diamine component, 1.06 g (10.5 mol) of p-PDA, 2.48 g (4.5 mmol) of HC-11, and 36.4 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.88 g (14.7 mmol) of CBDA was added, the temperature was returned to room temperature, and the reaction was carried out under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-25) concentration of 15 mass%.
30 g of this polyamic acid (PAA-25) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, and diluted to 6% by mass of polyamic acid (PAA-25) and 74% of NMP. A liquid crystal alignment treatment agent-27 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 17,200, and the weight average molecular weight was 38,900.

(Example 32)
As a diamine component, 1.06 g (10.5 mol) of p-PDA, 2.82 g (4.5 mmol) of HC-12, and 38.3 g of NMP were added to a 50 mL four-necked flask and cooled to about 10 ° C. . Next, 2.88 g (14.7 mmol) of CBDA was added, the temperature was returned to room temperature, and the mixture was reacted under a nitrogen atmosphere for 24 hours to obtain a solution having a polyamic acid (PAA-26) concentration of 15% by mass.
30 g of this polyamic acid (PAA-26) solution was transferred to a 100 mL Erlenmeyer flask, diluted by adding 30.0 g of NMP and 15.0 g of BC, diluted to 6% by mass of polyamic acid (PAA-26), and 74% of NMP. A liquid crystal aligning agent-28 was obtained by making a solution with 20% by mass and 20% by mass BC. The number average molecular weight of this polyamic acid was 19,600, and the weight average molecular weight was 42,200.

The liquid crystal aligning agents of Examples 29 to 32 were evaluated in the same manner as described above. The results are shown in Tables 5-8.

<Side-chain diamine solubility test>
As a test for comparing the solubility of the monomers, 2.0 g of NMP was added to 0.5 g of the side chain diamine, and the mixture was stirred at 20 ° C. for 1 hour to prepare a 20 wt% solution. The evaluation criteria of the test are as follows: All dissolved: ○
There is unmelted residue: ×

The liquid crystal display element manufactured using the liquid crystal aligning agent of the present invention has high reliability, including a large-screen high-definition liquid crystal television, a TN liquid crystal display element, an STN liquid crystal display element, a TFT liquid crystal display element, VA It is useful as a liquid crystal display element, an IPS liquid crystal display element, an OCB liquid crystal display element, and the like.
The entire contents of the specification, claims, and abstract of Japanese Patent Application No. 2010-150054 filed on June 30, 2010 are incorporated herein as the disclosure of the specification of the present invention. Is.

Claims

At least one selected from the group consisting of a polyimide precursor obtained by reaction of a diamine component containing a diamine of the following formula [1] and tetracarboxylic dianhydride, and a polyimide obtained by imidizing the polyimide precursor. A liquid crystal aligning agent characterized by containing a polymer.

(In the formula, X is an organic group represented by the following formula [2], Y 1 and Y 2 independently represent a benzene ring or a cyclohexane ring. P and q are independently 0 or 1; S 1 and S 2 each independently represents a single bond or a divalent linking group, and when p = 0, S 1 is a single bond, and when q = 0, S 2 is a single bond. 1 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group.)

(Wherein C 1 and C 2 independently represent a single bond or a divalent organic group, A represents an organic group which can be removed by heat, and B 1 represents —CH 2 —, —O—, This represents a divalent organic group selected from —NH— and —S—, where n is 0 or 1. The bonding direction of X is not limited.
The liquid crystal aligning agent according to claim 1, wherein the content of the diamine of the formula [1] in the diamine component is 5 to 95 mol%.
The liquid crystal aligning agent according to claim 1 or 2, wherein A in the formula [2] is a tertiary butoxycarbonyl group represented by the formula [3].
The liquid crystal aligning agent according to any one of claims 1 to 3, wherein C 1 and C 2 in the formula [2] are divalent organic groups represented by the following formula [6].

(In the formula, S 3 and S 4 are each independently a divalent linking group, and R 2 and R 3 are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. )
5. [—S 4 —R 3 —] of the formula [6] is represented by the following formula [4], and either C 1 or C 2 has the structure of the formula [4]. The liquid-crystal aligning agent in any one of.

(Wherein B 2 represents a single bond, a phenyl group, —CH 2 —, —O—, —NH—, —NR 10 —, and —S—, and R 10 represents carbon. Represents a divalent hydrocarbon of formula 1 to 6. The structure of the olefin of formula [4] may be either E or Z. The bond indicated by the broken line is the bond of C 1 of formula [2] Benzene ring or carbonyl carbon to which C 2 is bonded.)
In the formula [2], n = 0, The liquid crystal aligning agent according to any one of claims 1 to 4.
6. The liquid crystal aligning agent according to claim 1 , wherein in the formula [2], C 1 is a single bond.
8. The liquid crystal aligning agent according to claim 1 , wherein in the formula [2], B 1 is —O— or NH—.
6. The liquid crystal aligning agent according to claim 5, wherein in the formula [4], B 2 is —O— or NH—.
10. The liquid crystal aligning agent according to claim 1, wherein the diamine represented by the formula [1] is a compound of any one of the following formulas [1-a] to [1-k].
A liquid crystal alignment film using the liquid crystal aligning agent according to any one of claims 1 to 10.
A liquid crystal alignment film using the liquid crystal alignment treatment agent according to any one of claims 1 to 10, wherein the alignment process is performed by light irradiation.
A liquid crystal display device comprising the liquid crystal alignment film according to claim 11.
A diamine having a structure represented by the following formula [1].

(In the formula, X is an organic group represented by the following formula [2], Y 1 and Y 2 independently represent a benzene ring or a cyclohexane ring. P and q are independently 0 or 1; S 1 and S 2 each independently represents a single bond or a divalent linking group, and when p = 0, S 1 is a single bond, and when q = 0, S 2 is a single bond. 1 represents a hydrogen atom, a fluorine atom, an alkyl group having 1 to 22 carbon atoms, a fluoroalkyl group having 1 to 22 carbon atoms, or a steroid group.)

(Wherein C 1 and C 2 independently represent a single bond or a divalent organic group, A represents an organic group which can be removed by heat, and B 1 represents —CH 2 —, —O—, Represents a divalent organic group selected from —NH— and —S—, n represents 0 or 1, and the bonding direction of X is not limited.
The diamine according to claim 14, wherein, in the formula [2], A is a tertiary butoxycarbonyl group represented by the formula [3].
The diamine according to claim 14 or 15, wherein in the formula [2], C 1 and C 2 are divalent organic groups represented by the following formula [6].

(In the formula, S 3 and S 4 are each independently a divalent linking group, and R 2 and R 3 are each independently a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms. )
[-S 4 -R 3- ] in the formula [6] is represented by the following formula [4], and either C 1 or C 2 has the structure of the formula [4]. The diamine in any one of.

(Wherein B 2 represents a single bond, a phenyl group, —CH 2 —, —O—, —NH—, —NR 10 —, and —S—, and R 10 represents carbon. Represents a divalent hydrocarbon of formula 1 to 6. The structure of the olefin of formula [4] may be either E or Z. The bond indicated by the broken line is the bond of C 1 of formula [2] Linked to the benzene ring or the carbonyl carbon to which C 2 is attached.)
Diamines represented by any of the following formulas [1-a] to [1-k].
A polyamide, polyamic acid, or polyimide obtained by imidizing the polyamic acid, obtained using the diamine according to any one of claims 14 to 18 as a raw material.