TWI510519B - A liquid crystal alignment agent, a liquid crystal alignment film, and a liquid crystal display device using the same - Google Patents

Description

Liquid crystal alignment treatment 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 serves to orient the liquid crystal in a predetermined direction. The main liquid crystal aligning film which is currently used in the industry is formed by a liquid crystal aligning agent made of a solution of poly phthalic acid or polyimine of a polyimide precursor. Specifically, the substrate is coated with a liquid crystal alignment treatment agent, and after heating and firing, the orientation treatment is performed, and the surface treatment by rubbing or the liquid crystal is oriented parallel or oblique to the substrate surface. deal with.

In recent years, there has been a tendency for the substrate area to be enlarged and the unevenness to be large due to the increase in size, high definition, and cost reduction of the substrate used for the panel. When the alignment film is formed on such a substrate, printing defects such as pinholes occur during printing, and it is difficult to perform uniform orientation treatment during the rubbing treatment, causing problems such as poor alignment of the liquid crystal. Further, in the liquid crystal aligning treatment, surface treatment is mainly performed by friction, but the liquid crystal alignment film is caused to be defective, thereby causing display defects and generation of dust and the like.

On the other hand, as a method of changing the orientation treatment to the rubbing method, a liquid crystal aligning treatment using a photoreaction has been proposed. Specifically, a method of forming a film having a polymer which causes a specific portion of a photoreaction such as polyethylene cinnamate on a surface of a substrate, and imparting a directional energy to the liquid crystal by irradiating a polarized or non-polarized radiation is known (photo-alignment method) ). In this method, static gas or dust is not generated, uniform liquid crystal orientation can be achieved, and the viewing angle can be increased by directional division (see Patent Documents 1 and 2).

For a unit cell such as TN (Twisted Nematic) or STN (Super Twisted Nematic), the liquid crystal alignment film is required to have a function of tilting the liquid crystal molecules toward the substrate surface at a predetermined angle (inclination angle) (see Patent Document 15). It is known that a liquid crystal alignment film having a polyalkylene group such as a side chain of an alkyl group, a side chain of a steroid skeleton, a side chain having a ring structure, or a polyimine is used (Patent Documents 3, 4, and 5). . In the liquid crystal alignment treatment using light, the tilt angle is generally given by irradiation of radiation inclined to the substrate normal direction in the incident direction of the substrate surface (see Patent Document 1).

[Advanced technical literature] [Patent Literature]

[Patent Document 1] JP-A-6-287453

[Patent Document 2] JP-A-9-297313

[Patent Document 3] Japanese Patent Publication No. 05-043687

[Patent Document 4] Japanese Patent Publication No. 04-281427

[Patent Document 5] Japanese Patent Publication No. 02-223916

In the past, the main liquid crystal alignment film was formed as described above by a liquid crystal aligning agent formed from a solution of a polyimide or a polyimine of a polyimide precursor, but a solution containing a soluble polyimine was used. The method for preparing a liquid crystal alignment film has an advantage of obtaining good characteristics as a liquid crystal alignment film even at a relatively low temperature firing. However, when a polyimine containing a plurality of side chain-containing diamines is used, there is a problem that the film formation property of the substrate is deteriorated.

In order to solve such a problem, by using a small amount of a diamine having a ring structure in which a relatively high tilt angle is obtained in a small amount in the side chain (for example, refer to Patent Document 5), the amount of the side chain is reduced, and the coating property to the substrate is improved. The method can also be carried out. Most of the diamines having a ring structure in the side chain are inferior in solubility to a polar solvent such as N-methylpyrrolidone (hereinafter also referred to as NMP), and there may be a problem of unevenness in the quality of the obtained polymer.

Further, as a material used for light orientation, a polymer having a side chain such as a cinnamate group or the like is often used, and in order to be used in a vertical orientation, it is necessary to further introduce another diamine having a side chain. In general, there are many side chains which are hydrophobic, and it is desirable to reduce affinity with a polar solvent having high wettability to a substrate, and a polymer having a plurality of side chain sites may have problems in coating the substrate and forming film.

Further, with the recent increase in the performance of liquid crystal display elements, liquid crystal display elements are used for applications such as car navigation systems or measuring instrument panels for large-screen and high-definition liquid crystal televisions or in-vehicle applications. In such a use, in order to obtain high brightness, it is sometimes necessary to use a backlight having a large amount of heat, and high stability for backlight is required. In particular, when the voltage holding ratio of the electric characteristic 1 is lowered by the light irradiation of the backlight, the printing failure (line burning) of the display failure of the liquid crystal display element is likely to occur, and the liquid crystal display element having high reliability cannot be obtained. . Therefore, in addition to the initial characteristics of the liquid crystal alignment film, for example, it is expected that the voltage holding ratio is not easily lowered after long-time exposure by light irradiation.

In view of the above circumstances, the present invention is intended to provide a liquid crystal aligning agent having excellent coatability and high reliability in that the polymer contained in the liquid crystal aligning agent is excellent in handleability. Moreover, the present invention provides a side chain-containing diamine which can improve the printability of a solvent to be obtained in a polymer, and which provides excellent printability, and provides a side chain-containing diamine, and provides exposure to light even when exposed to light. It is also possible to suppress a liquid crystal alignment film having a reduced voltage holding ratio.

The present inventors conducted detailed studies to achieve the above object, and as a result, completed the present invention. That is, the present invention has the following gist.

(1) A liquid crystal aligning agent characterized by containing a polyimine precursor obtained by reacting a diamine component containing a diamine of the following formula [1] with a tetracarboxylic dianhydride, and the polycondensation At least one polymer of the quinone imine precursor in a group of polyimine obtained by hydrazine imidization.

[Chemical 1]

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

[Chemical 2]

(wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents an organic group obtained by thermal detachment, and B ₁ represents a group selected from -CH ₂ -, -O-, -NH- And the divalent organic group of -S-, n represents 0 or 1, and the bonding direction of X is not limited.)

(2) The liquid crystal aligning agent of the above (1), wherein the diamine content of the formula [1] is 5 to 95 mol%.

(3) A liquid crystal aligning agent according to the above (1) or (2), wherein A in the above formula [2] is a third-stage butoxycarbonyl group represented by the formula [3].

[Chemical 3]

C (4) the formula [2] is _1, C ₂ represented by the following formula [6] as shown in the above-described divalent organic group (1) to (3) of the liquid crystal alignment treating agent according to any one.

[Chemical 4]

-S ₃ -R ₂ -S ₄ -R ₃ - [6]

(wherein, S ₃ and S ₄ are independent and represent a divalent linking group, and R ₂ and R ₃ are independent, and represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms.)

(5) [-S ₄ -R ₃ -] of the above formula [6] is represented by the following formula [4], and any one of C ₁ and C ₂ is the above (1) having the structure of the formula [4] The liquid crystal aligning agent according to any one of (4).

[Chemical 5]

Wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, and R ₁₀ represents a carbon number of 1 to The divalent hydrocarbon of 6. The structure of the olefin of the formula [4] may be either E or Z. The bond shown by the dotted line is bonded to the benzene ring or C ₂ bonded to C _{1 of} the formula [2]. Carbonyl carbon.)

(6) The liquid crystal aligning agent according to any one of (1) to (4) above, wherein n is 0.

(7) the formula [2], C ₁ is a single bond of the above-described liquid crystal alignment treating agent of (1) to (5) according to any one.

(8) the formula [2], B ₁ is -O- or NH- of the above-described liquid crystal alignment treating agent according to the (1) to (7) according to any one.

(9) The liquid crystal aligning agent described in the above (5), wherein B ₂ is -O- or NH- in the above formula [4].

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

[Chemical 6]

[Chemistry 7]

(11) A liquid crystal alignment film using the liquid crystal alignment treatment agent according to any one of the above (1) to (10).

(12) A liquid crystal alignment film which is subjected to alignment treatment by light irradiation using the liquid crystal alignment film of the liquid crystal alignment treatment agent according to any one of the above (1) to (10).

(13) A liquid crystal display element comprising the liquid crystal alignment film according to (11) or (12) above.

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

[化8]

(wherein, X represents an organic group represented by the following formula [2], and Y ₁ and Y ₂ are independent, and represents a benzene ring or a cyclohexane ring. p and q are independent, and represent an integer of 0 or 1, and S ₁ , S ₂ is independent and 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 hydrogen, a fluorine atom, and an alkyl group having 1 to 22 carbon atoms. a fluoroalkyl group or a steroid group having 1 to 22 carbon atoms.)

[Chemistry 9]

(wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents an organic group obtained by thermal detachment, and B ₁ represents a group selected from -CH ₂ -, -O-, -NH- And a divalent organic group of -S-, n represents 0 or 1, and the bonding direction of X is not limited.

(15) In the formula [2], A represents the diamine described in the above (14) of the third-stage butoxycarbonyl group represented by the formula [3].

[化10]

(16) In the formula [2], C ₁ and C ₂ are the diamines of the above (14) or (15) which are divalent organic groups represented by the following formula [6].

[11]

-S ₃ -R ₂ -S ₄ -R ₃ -[6]

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

(17) [-S ₄ -R ₃ -] of the above formula [6] is represented by the following formula [4], and any one of C ₁ and C ₂ is the above (14) having the structure of the formula [4] The diamine described in any one of (16).

[化12]

Wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, and R ₁₀ represents a carbon number of 1 to The divalent hydrocarbon of 6. The structure of the olefin of the formula [4] may be either E or Z. The bond shown by the dotted line is bonded to the benzene ring or C ₂ bonded to C _{1 of} the formula [2]. Carbonyl carbon.)

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

[Chemistry 13]

[Chemistry 14]

(19) A polydecylamine obtained by using the diamine according to any one of the above (14) to (18) as a raw material, polylysine or a polyimine obtained by imidating the polyamic acid with ruthenium .

The diamine used as a raw material of the liquid crystal aligning agent of the present invention has a very high solubility in a polar solvent such as NMP, and is excellent in polymerization, and contains a polyamine obtained from the diamine or The liquid crystal aligning agent of the polyimine obtained by the ruthenium imidization of polyphthalic acid can have excellent coating and film forming properties, and can suppress the decrease of the voltage holding ratio even when exposed to light. membrane. Further, the above diamine may be provided as a liquid crystal aligning treatment agent which is also suitable for a photo-alignment method.

Type of implementation of the invention <Diamine of the invention>

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

[化15]

The diamine of the present invention has a pendant phenyldiamine skeleton which is protected by a thermal debonding group such as a third-stage butoxycarbonyl group (hereinafter also referred to as a Boc group) in a side chain structure. Usually, the amine group is a reactive organic group, so it is difficult to directly exist as a part of the side chain of the diamine, and the reactivity of the amine group can be lowered by protecting with a heat-releasing group. Further, when the amine group protected by the heat-releasing group is heated at about 150 ° C or higher, the thermally detachable group is deprotected to become an amine group.

Further, the amine group is known to be an organic group having high reactivity, and is reacted with a functional site such as an unsaturated bond, a carboxylic acid, a carboxylic acid anhydride, an epoxy compound or a carbonyl group. On the other hand, as shown in the figure below, when an amine group which is close to a bond group containing a carbonyl group such as a guanamine bond or an ester bond and is protected by a heat-releasing group is disposed, molecules are more likely to be caused than molecules of a diamine. The internal reaction can form a hetero ring such as an imidazole ring, an oxazole ring or a thiazole ring.

In this way, the diamine of the present invention forms a heterocyclic ring by reacting the amine group generated by the heat treatment in the firing process of the liquid crystal alignment treatment agent to form a heterocyclic ring, and the side chain is formed. The structure functions as an induced portion with a good inclination angle.

[Chemistry 16]

Further, not all of the amine groups desorbed from the heat-releasing group are used in the cyclization reaction, and some are also used in the intermolecular reaction to impart an increase in the strength of the film or to crosslink with a low molecular component in the polymer to impart a letter. Sexual improvement. Therefore, it is difficult to cause film peeling during rubbing treatment using the polyamine or polyimine of the diamine of the present invention, and it is difficult to cause a decrease in voltage holding ratio or ion even after exposure to high temperature, backlight irradiation or the like for a long period of time. Increase in density.

Further, when the diamine of the present invention is a thermally detachable group, since it has a bulky Boc group or the like, the solubility of the organic solvent in the (condensed) polymerization of the diamine, particularly for a polar solvent such as NMP, is extremely high. Make the rationality of the polymerization good.

Further, a liquid crystal aligning agent which is obtained by using the polyimine precursor or the polyimine obtained by using the diamine of the present invention is coated. The film forming property is excellent, and it is possible to suppress voltage holding even under exposure to light. A liquid crystal alignment film having a reduced rate, and a liquid crystal alignment treatment agent can also be used in the photo-alignment method.

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

[化17]

In the formula [A], X represents an organic group represented by the following formula [2], and Y ₁ and Y ₂ are independent, and represent a benzene ring or a cyclohexane ring, and p and q are independent, and represent an integer of 0 or 1, and S _1, S ₂ independently represents a single bond or a divalent linking group, p = 0 S ₁ is a single bond when, q = 0 when S ₂ is a single bond, R ₁ represents a hydrogen, a fluorine atom, having 1 to 22 carbon atoms An alkyl group, a fluoroalkyl group having 1 to 22 carbon atoms or a steroid group. In the formula, DA represents a phenylenediamine skeleton.

[化18]

Wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents an organic group obtained by thermal detachment, and B ₁ represents a group selected from —CH ₂ —, —O—, —NH—, and a divalent organic group of -S-, and n represents 0 or 1. The binding 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 is a diamine having a phenylenediamine skeleton, whereby a wide side chain amount or side chain density can be obtained. However, when the molecular weight of the diamine skeleton is large, the molecular weight of the diamine becomes large, and the amount of monomers necessary for the polymer increases, which is difficult to use in the industry. Further, when the diamine skeleton is an aliphatic diamine, the reactivity is too high, and there is a problem that precipitation or gelation occurs due to salt formation during preparation of the polymer.

The amine group having a phenylenediamine skeleton is preferably a first-order amine group, but may also be a second-stage amine group, for example, a methyl group having a relatively small molecular weight such as a methyl group, an ethyl group, a propyl group or a butyl group. Substituted as an amine group.

In the diamine of the present invention, the side chain portion in the formula [1] is represented by the following formula [5], and the portion is a portion for determining the inclination angle expression and the size, and the inclination angle is preferably obtained by optimization. size.

[Chemistry 19]

In the formula [5], Y ₁ and Y ₂ are independent and represent a benzene ring or a cyclohexane ring. The benzene ring and the cyclohexane ring may have a substituent as necessary. Further, the bonding position of the substituent is preferably substituted at the 1,4 position in any of the benzene ring and the cyclohexane ring. p and q are independent and represent an integer of 0 or 1. The cyclohexane ring is preferably a trans structure (so-called chair type).

In the formula [5], S ₁ and S ₂ are independent and represent 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 as shown in (S-1) to (S-11), but are not limited thereto.

[Chemistry 20]

In the above formulae (S-5) to (S-8), (S-10), and (in S-11, R ₄ and R ₅ are independently and represent hydrogen or a carbon number of 1 to 20, preferably 1 to 15 A monovalent hydrocarbon group.

The monovalent hydrocarbon group may, for example, be 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 group such as a cyclopentyl group or a cyclohexyl group; Bicycloalkyl such as hexyl; vinyl, 1-propenyl, 2-propenyl, isopropenyl, 1-methyl-2-propenyl, 1-, 2- or 3-butenyl, hexenyl, etc. An aryl group such as a phenyl group, a xylyl group, a xylyl group, a biphenyl group or a naphthyl group; an aralkyl group such as a benzyl group, a phenylethyl group or a phenylcyclohexyl group; and the like.

And a part or all of the hydrogen of the monovalent hydrocarbon group may be a halogen atom, a hydroxyl group, a thiol group, an amine group, a phosphate group, an ester group, a carboxyl group, a phosphate group, a thioester group, a decyl group, a nitro group, an organic group. Substituents such as oxy, organoindenyl, organothio, organoamine, urethane, decyl, alkyl, cycloalkyl, bicycloalkyl, alkenyl, aryl, aralkyl, and the like. Moreover, these may also be a ring structure.

When R ₄ and R ₅ are a structure having a high volume such as an aromatic ring or an alicyclic structure, there is a possibility that the liquid crystal orientation is lowered or the shape of the monomer becomes a sticky state, which makes it difficult to handle, so that methyl and B are used. An alkyl group such as a propyl group or a butyl group or hydrogen is preferred, and hydrogen is preferred. Particularly preferably, S ₁ and S ₂ are a single bond, -O-, -NHCO- or -COO-.

In the formula [5], R ₁ represents hydrogen, a fluorine atom, an alkyl group having 1 to 22 carbon atoms or a fluoroalkyl group or a steroid group. The alkyl group or the fluoroalkyl group may be linear or branched, and may also form a condensed ring structure such as a steroid group. When R ₁ represents an alkyl group, it is preferably a linear chain or a suitable substituent. From the viewpoint of ease of synthesis or ease of handling, R ₁ is preferably an alkyl group. The number of carbon atoms of the alkyl group of R ₁ is not particularly limited. When p and q in the formula [5] are 0, that is, a ring-free structure, the expression of the tilt angle can be lowered, so that a long-chain alkyl group is preferable. Preferably, R _{1 has} a carbon number of 5 to 18, more preferably 7 to 15.

Further, when a benzene ring or a cyclohexane ring is introduced, since the tilt angle can be increased, R ₁ is preferably an alkyl group having a small carbon number. Preferably, R _{1 has} a carbon number of from 1 to 12, more preferably from 3 to 10.

Preferred specific structures of the formula [5] are as follows, for example.

From the viewpoints of ease of synthesis or ease of starting materials, the structure shown in the formula [5] is [5-1] to [5-3], [5-8], [5-14] to [5-19 ], [5-20], [5-44], [5-45], etc., preferably [5-1], [5-2], [5-8], etc. are preferred.

With respect to the diamine benzene skeleton in the formula [1], the position of the amine bond in the benzene ring is not limited. Specific specific amine group positions include a position of 2, 3 for a side chain, a position of 2, 4, a position of 2, 5, a position of 2, 6, a position of 3, 4, or 3, 5 position. Among them, from the viewpoint of reactivity in synthesizing polyamic acid, it is preferred to have a position of 2, 4, a position of 2, 5, or a position of 3, 5. When the ease of synthesis is added, it is preferable that the position of 2, 4 (formula 1-1) or the position of 3, 5 (formula 1-2) is preferable.

[Chem. 21]

As described above, the diamine of the present invention is subjected to deprotection of a thermal debonding group such as a Boc group at the time of firing to produce an amine group, and the resulting amine is subjected to nuclear attack by carbonyl carbon to form a heterocyclic ring to cause a thermal cyclization reaction. Therefore, the structure represented by the following formula [2] in the diamine of the present invention is contained in the diamine.

[化22]

Wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents an organic group obtained by thermal detachment, and B ₁ represents a group selected from —CH ₂ —, —O—, —NH—, and - Divalent organic group of -S-, n represents 0 or 1, and the direction of the bonding portion of X is not limited.

The heat-releasing group represented by A in the above formula [2] is only the firing temperature of the liquid crystal aligning agent of the present invention, preferably 150 ° C or higher, more preferably 170 to 300 ° C, and particularly preferably 180 to 250. The organic group which can be detached by heat at ° C is not particularly limited.

Examples of the heat-releasing group include a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, an allyloxycarbonyl group, and a tertiary-stage butoxycarbonyl group (Boc group). The formate is an organic group. The Boc group is particularly preferable from the viewpoint of good heat removal efficiency, detachment at a relatively low temperature, and harmless gas at the time of detachment.

Preferred examples of the general formula [2] are as shown in the following formulas [2-1] to [2-16].

Further, B ₁ in the formula [2] represents a divalent organic group selected from the group consisting of -CH ₂ -, -O-, -NH-, and -S-, and is not particularly limited, but is derived from a cyclization reaction. The yield, the electrical characteristics of the oriented film, and the like are particularly preferable as -O- or NH-.

With respect to n in the formula [2], when the Boc group is detached by firing to produce an amine group, a 5-membered ring heterocyclic ring can be formed when n = 0, and a 6-membered ring heterocyclic ring can be formed when n = 1. However, when n = 1, the carbon of the amine group and the carbonyl group are far apart and it is difficult to cause a cyclization reaction. Therefore, n = 0 is preferable from the viewpoint of the efficiency of the cyclization reaction.

[化23]

[Chem. 24]

In the 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 various options can be made depending on the ease of synthesis or the ease of starting materials. When C ₁ and C ₂ are a divalent organic group, they can be represented by the structure represented by the following formula [6].

[化25]

-S ₃ -R ₂ -S ₄ -R ₃ -[6]

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

Specific examples of S ₃ and S ₄ are the same as the above-described formulas [S-1] to [S-11], but may be other linking groups.

In the formula [6], when R ₂ and R ₃ are a divalent hydrocarbon having 1 to 20 carbon atoms, the following specific examples can be mentioned.

For example, methyl, 1,1-extended ethyl, 1,2-extended ethyl, 1,1-extended propyl, 1,2-extended propyl, 1,3-extended propyl, 1, 2-alkylene, 1,4-tert-butyl, 2,3-butylene, 1,6-exexyl, 1,8-extenyl, 1,10-extended alkyl; 1,2-cyclopropyl, 1,2-cyclobutyl, 1,3-cyclobutyl, 1,2-cyclopentyl, 1,1-cyclohexyl, 1,2-ring a cycloalkyl group such as a hexyl group or a 1,4-cyclohexyl group; a 1,1-vinyl group, a 1,2-vinyl group, a 1,2-vinyl group, a methyl group, a 1-methyl-1,2- Stretching vinyl, 1,2-extended vinyl-1,1-extended ethyl, 1,2-extended vinyl-1,2-extended ethyl, 1,2-extended vinyl-1,2-extended 1, 1,2-vinyl-1,3-propanyl, 1,2-vinyl-1,4-butyl, 1,2-vinyl-1,2-butyl, 1,2-Extended vinyl-1,2-propenyl, 1,2-vinyl-1,2-extenylene, etc.; ethynyl, ethynyl, methyl, ethynyl -1,1-Extended ethyl, ethynyl-1,2-extended ethyl, ethynyl-1,2-propanyl, ethynyl-1,3-propanyl, ethynyl-1 , 4-butylene, ethynyl-1,2-butylene, ethynyl-1,2-heptenyl, ethynyl -1,2-Extenction group, etc.; 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,2-anthranyl, 1,4-stretch Naphthyl, 1,5-anthranyl, 2,3-naphthyl, 2,6-anthranyl, 3-phenyl-1,2-phenylene, 2,2'-diphenyl 2,2'-dinaphthyl-1,1'-yl isobaric; 1,2-phenyl extended methyl, 1,3-phenyl extended methyl, 1,4-phenyl extended methyl, 1 , 2-phenylene-1,1-extended ethyl, 1,2-phenylene-1,2-extended ethyl, 1,2-phenylene-1,2-extended propyl, 1,2 - phenyl-1,3-propanyl, 1,2-phenyl-1,4-butylene, 1,2-phenylene-1,2-butylene, 1,2-extension Phenyl-1,2-dimethylphenyl, methyl-1,2-phenyl extended methyl, methyl-1,3-phenyl extended methyl, methyl-1,4-phenyl extended A difunctional hydrocarbon group formed by a methyl group and the like.

Further, a part or all of the hydrogen of the above divalent hydrocarbon group may be a halogen atom, a hydroxyl group, a thiol group, a phosphate group, an ester group, a carboxyl group, a phosphate group, a thioester group, a decylamino group, a nitro group, an organooxy group. Substituted with an organic fluorenyl group, an organic thio group, an organic amine group, a urethane group, a decyl group, an alkyl group, a cycloalkyl group, a bicycloalkyl group, an alkenyl group, an aryl group, an aralkyl group or the like. Moreover, these may also be a ring structure.

When R ₂ and R ₃ have a small carbon number, the monomer tends to become a solid. When used as a liquid crystal alignment film, the stability of the tilt angle can be improved. Therefore, the alkyl group having 1 to 6 carbon atoms and the carbon number 1 to 1 are used. The alkenyl group of 6 or the alkynyl group having 1 to 6 carbon atoms is preferred.

In the formula [6], as the bonding position of C ₁ , the position of the substitution of the amine group protected by the Boc group is preferably 4 or 5, and any of the 4 and 5 positions is after cyclization. The structure is the same, and is not particularly limited.

Further, with respect to the formula [6], the structure of [-S ₄ -R ₃ -] is represented by the following formula [4], and when either of C ₁ and C ₂ has the structure of the formula [4], it becomes light-oriented. The structure used in the law.

[Chem. 26]

Wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, and R ₁₀ represents a carbon number of 1 to 6 Divalent hydrocarbons.

The olefin moiety of the formula [4] may be either E or Z, and the dotted line indicating the bond to the olefin is bonded to the benzene ring to which C _{1 of} the general formula [2] is bonded or the carbonyl carbon to which C ₂ is bonded.

The structure represented by the formula [4] becomes a site where various reactions are caused by light. Wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, starting from the ease of synthesis or starting materials From a sexual point of view, it is particularly good to use -O- or -NH-. R ₁₀ represents a divalent hydrocarbon having 1 to 6 carbon atoms.

Formula [4] portion olefin, preferably C ₁ in a view to ease of synthesis of E isomer. In this case, the formula [2] is synonymous with the cinnamic acid ester derivative, and therefore it is particularly preferable from the viewpoint of the ease of photoreaction.

On the other hand, the olefin moiety in C ₂ is not particularly limited. Further, when C ₂ is a structure represented by the formula [4], it can be photoreactive by thermal cyclization. On the other hand, if the cyclization is not carried out, the photoreaction is less likely to occur, and the influence of the ultraviolet ray deterioration or the like of the monomer or the liquid crystal aligning agent or the liquid crystal aligning film using the same may be considered to be less than that of the conventional cinnamate system. From such a viewpoint, it is preferred that C ₂ is a structure of the formula [4].

Preferred examples of the formula [2] include the following formulas [2-17] to [2-32].

[化27]

Formulas [2-17] to [2-20] and [2-25] to [2-28] become the following formulas [2-33] to [2-40] at the time of firing, taking into account The same effect as cinnamic acid ester can be obtained.

[化28]

The structure of the particularly preferred diamine is shown below, but is not limited thereto.

[化29]

[化30]

For the formula [7-1] to [7-6], B ₁ represents -O- or NH-, C ₁ and C ₂ are independent, and represent a single bond or a divalent organic group, and Y ₁ and Y ₂ represent a benzene ring or a cyclohexyl ring, S ₁ , S ₂ represents a single bond or a divalent linking group, p, q represents an integer of 0 or 1, when p=0, S ₁ represents a single bond, and when q=0, S ₂ represents a single bond, R ₁ It represents a proton or an alkyl group having 1 to 22 carbon atoms.

The structure of the diamine is specifically shown below, for example.

[化31]

[化32]

[化33]

<Synthesis of Diamine of the Present Invention>

[化34]

Substituent X in the substituted o-phenylene diamine, 2-aminophenol, 2-aminobenzenethiol (base), etc., will be used for thermal debonding such as Boc group such as di-tert-butyl dicarbonate The protected compound acts in a solvent to synthesize the precursor of the desired structure. At this time, it is possible to increase the yield or the reaction rate by coexisting a base such as pyridine, 4-dimethylaminopyridine or triethylamine. On the other hand, when these bases are coexisted, the reaction is carried out by introducing a thermal debonding group into an amine group of 2 units or introducing a thermally desorbable hydroxyl group-containing product. Therefore, a more suitable condition is employed for the substrate to be reacted. It is better.

[化35]

When the site represented by the formula [2] faces the diamine side of the moiety which is caused to cyclize, X is an unsubstituted or side chain substituent, and the amine group is protected by a heat-releasing group by the above-mentioned method. A method of converting dinitrobenzene into a diamine can be exemplified. Specific synthesis examples are shown below.

[化36]

On the other hand, when the moiety which causes cyclization faces the side chain side, the state of the above formula X or the inert substituent which can be changed later is protected in advance, and the amine group or hydroxyl group which is close to the amine group protected by the thermal detachment group is introduced. A side chain, followed by a method in which X is converted into an active substituent or the like, and dinitrobenzene is introduced, and converted into a diamine is exemplified. Specific synthesis examples are given below.

[化37]

In the condensation reaction of a carboxylic acid and an amine, an ester bond can be synthesized by performing a condensation reaction of a guanamine bond, a carboxylic acid, and an alcohol or a phenol. The reaction is carried out in a solvent which does not react with a carboxylic acid, an amine, and an alcohol, in the presence of a base, a method of reacting a carboxylic acid halide with an amine, an alcohol or a phenol, or a condensing agent to form a carboxylic acid and It can be obtained by a method in which an amine, an alcohol or a phenol is reacted.

The carboxylic acid halide can be obtained by reacting a carboxylic acid with a suitable halogenating agent. From the standpoint of widespread use, the carboxylic acid halide used is preferably a carboxylic acid chloride, for example a carboxylic acid chloride. The carboxylic acid chloride is obtained by reacting a carboxylic acid with a chlorinating agent. Examples of the chlorinating agent include arsenic chloride, phosphorus oxychloride, thiophosphorus chloride, ethylene dichloride, phosphorus trichloride, and phosphorus pentachloride, and the like, and the ease of use and the ease of removal are mentioned. In view of the above, it is preferred to use a ruthenium chloride, a ruthenium chloride or a ruthenium chloride, and particularly preferably a ruthenium chloride or a ruthenium chloride.

Further, examples of the solvent used in the above reaction include N-methyl-2-pyrrolidone, γ-butyrolactone, N,N-dimethylformamide, and N,N-dimethylacetamide. Tetrahydrofuran, chloroform, dichloroethane, dichloromethane, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, and the like. Examples of the base used in the condensation reaction include organic bases such as pyridine, 4-dimethylaminopyridine, triethylamine, trimethylamine, tributylamine, trioctylamine, and N-methylmorpholine, or A method of using an aqueous solution of an inorganic alkali such as an aqueous sodium hydroxide solution or a potassium hydroxide aqueous solution (Schottten-Baumann reaction) in an inert state may also be mentioned.

When the condensation reaction is carried out in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt can be used. Acid salt, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, O-(benzotriazol-1-yl)-N,N,N ',N'-tetramethylurea salt tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea salt hexafluorophosphate, 2,3-dihydro-2-thione-3-benzoxazolyl)sulfonic acid diphenyl, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl a condensing agent such as 4-methoxymorpholine chloride n-hydrate.

Further, in the method of using the above condensing agent, by adding Lewis acid as an additive, the reaction can be carried out efficiently. As the Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of addition of Lewis acid is preferably 0.1 to 1.0 times the molar amount of C ₁ .

With respect to the linking group represented by C ₁ and C ₂ in the general formula [2], a divalent organic group represented by the following formula [6] is preferable as the structure of C ₁ and C ₂ .

[化38]

-S ₃ -R ₂ -S ₄ -R ₃ -[6]

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

[39]

The diamine of the formula [4-c] can be synthesized according to the method in which the above-mentioned cyclized portion faces the side chain.

[化40]

The synthesis of the diamine of the formula [4-i] and the formula [4-h] can be carried out according to the method in which the cyclized moiety is oriented toward the diamine side, and the synthesis method can be a method other than the above, without special limited.

When an olefin structure is introduced into a diamine, the same effect can be obtained by any of the E (trans) and Z (cis) structural isomers. When the E body is synthesized, it can be synthesized using fumaric acid, and the Z body can be synthesized by using maleic acid. The synthesis method of the E body can be a method of synthesizing by the isomerization reaction of the Z body, which is more excellent in selectivity than the synthesis method via fumaric acid, and can be synthesized in a good yield, so regardless of the E body, Z The method of using maleic acid is preferred.

For the diamine synthesis examples of the formula [4-i] and the formula [4-h], although there is a step of forming an ether bond, the ether bond may be an alkyl halide or an aryl halide with an alcohol. In the solvent of the reaction, a Williamson ether synthesis method in which the reaction is carried out in the presence of a base is obtained. A method such as using a palladium catalyst or the like, a method of using copper as a catalyst, or the like can be obtained. The preferred means can be selected by the matrix of the reaction. The Williamson ether synthesis method is preferred in view of the post-reaction treatment or cost level. The base to be used is not particularly limited, and an inorganic base such as sodium hydride, potassium hydride, potassium carbonate, sodium hydroxide, sodium alkoxide or potassium alkoxide or triethylamine, trimethylamine, tributylamine or trioctylamine can be used. An organic base such as an amine.

By synthesizing the dinitrobenzene derivative [8] by the above-described synthesis method or the like, the nitro group can be converted into an amine group by a general reduction reaction to obtain the desired diamine. The method for reducing the dinitro compound is not particularly limited, and generally, palladium-carbon, platinum oxide, Raney nickel, platinum rhodium, ruthenium-alumina, platinum sulfide carbon or the like can be used as a catalyst, in ethyl acetate. A method of reducing by a hydrogen, a hydrazine, a hydrogen chloride or the like in a solvent such as toluene, tetrahydrofuran, dioxane or alcohol. A high temperature autoclave or the like can be used as necessary. On the other hand, when p-palladium carbon, platinum carbon or the like is used in the structure containing an unsaturated bond, it is feared that the unsaturated bond site is reduced and becomes a saturated bond. Therefore, as a preferable condition, reduced iron, tin, and chlorination are used. The reduction conditions of the transition metal such as tin as a catalyst are preferred.

[化41]

<Polymer of the invention>

The polymer in the present invention refers to a polyimide precursor, a polyimine obtained by imidization of the polyimide precursor, and a polyamine. Here, the term "polyimine precursor" refers to polyamic acid and polyphthalate. The diamine of the present invention can be reacted with a tetracarboxylic acid, a tetracarboxylic acid dihalide, a tetracarboxylic dianhydride or the like, a tetracarboxylic acid or a derivative thereof to obtain a polylysine having a specific structure in a side chain. Further, a polyglycolate can be obtained by a reaction of a tetracarboxylic acid diester dichloride with a diamine or by reacting a tetracarboxylic acid diester with a diamine in the presence of a suitable condensing agent and a base. Further, the polylysine is subjected to dehydration ring closure, or the polyphthalate is heated at a high temperature to promote dealcoholization, and after ring closure, a polyimine having a specific structure in a side chain can be obtained.

<Polyuric acid, and polyamidomate>

The polyproline of the present invention can be obtained by a reaction of a diamine component containing a diamine represented by the formula [1] with a tetracarboxylic dianhydride. Further, the polyphthalate of the present invention is a reaction of a diamine component containing a diamine represented by the formula [1] with a tetracarboxylic acid diester dichloride in the presence of a base, or a tetracarboxylic acid diester and two The amine is obtained by reacting in the presence of a suitable condensing agent and a base. The polyimide of the present invention is obtained by subjecting the polylysine to dehydration ring closure or by heating and ring-closing the polyphthalate. The polyamic acid, polyphthalate, and polyimine can be used as a polymer for obtaining a liquid crystal alignment film.

The content of the diamine represented by the formula [1] is not limited as long as a diamine component (hereinafter also referred to as a diamine component) of polyglycine is obtained by a reaction with the above tetracarboxylic dianhydride. In the liquid crystal alignment film of the present invention obtained by using the above polyamine or polyimine, the content ratio of the diamine represented by the formula [1] in the diamine component increases, and the tilt angle of the liquid crystal increases.

For the purpose of increasing the tilt angle of the liquid crystal, it is preferred that 1 mol% or more of the diamine component is a diamine represented by the formula [1]. The preferred content of the side chain structure or the liquid crystal orientation mode of the formula [1] is different, so that the preferred content cannot be set, but for the TN mode, the OCB mode, etc., since it is necessary to add a horizontal orientation regulating force, it is used for polymerization. The content ratio of the diamine represented by the formula [1] in the diamine component is preferably from 1 to 50 mol%, particularly preferably from 5 to 30 mol%.

In order to orient the liquid crystal to be vertical, 100 mol% of the diamine component may be a diamine represented by the formula [1]. The diamine of the formula [1] can greatly reduce the polymerization viscosity of the polymer, and the viscosity of the liquid crystal aligning agent is lowered. Therefore, the content of the film is preferably 30 to 70 mol% for stencil printing or the like.

In the case where the diamine component of the formula (1) is used in an amount of less than 100 mol%, the specific diamine other than the diamine represented by the formula (1) (hereinafter also referred to as another diamine) is specifically as follows. Show.

Examples of the alicyclic diamines include 1,4-diaminocyclohexane, 1,3-diaminocyclohexane, 4,4'-diaminodicyclohexylmethane, and 4, 4'-Diamino-3,3'-dimethyldicyclohexylamine, isophorone diamine, and the like.

Examples of the aromatic diamines include o-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 2,4-diaminotoluene, 2,5-di Aminotoluene, 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'-dimethylbiphenylmethyl, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylmethane, 3,4 '-Diaminodiphenylmethane, 4,4'-diamino-3,3'-dimethyldiphenylmethane, 2,2'-diaminopurine, 4,4'-diamino Indole, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfide, 4,4'-diamine Diphenylanthracene, 3,3'-diaminodiphenylanthracene, 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)biphenylmethyl, 2,2-bis[(4-aminophenoxy)- Propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, Bis[4-(3-aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene, 1,1-bis(4-aminophenyl) ring Hexane, α,α'-bis(4-aminophenyl)-1,4-diisopropylbenzene, 9,9-bis(4-aminophenyl)anthracene, 2,2-bis(3) -aminophenyl)hexafluoropropane, 2,2-bis(4-aminophenyl)hexafluoropropane, 4,4'-diaminodiphenylamine, 2,4-diaminodiphenyl Amine, 1,8-diaminonaphthyl, 1,5-diaminonaphthyl, 1,5-diaminoguanidine, 1,3-diaminopurine, 1,6-diaminoguanidine, 1,8-Diaminoguanidine, 2,7-diaminoguanidine, 1,3-bis(4-aminophenyl)tetramethyldioxane, benzidine, 2,2'-dimethyl Benzidine, 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)decane, 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)decane, 1,10-bis ( 4-aminophenoxy)decane, bis(4-aminophenyl)propane-1,3-dicarboxylate, bis(4-aminophenyl)butane-1,4-dicarboxylate, Bis(4-aminophenyl)pentane-1,5-diester, bis(4-aminophenyl)hexane-1,6-diester, bis(4-aminophenyl)g Alkane-1,7-diester, bis(4-aminophenyl)octane-1,8-diester, bis(4-aminophenyl)decane-1,9-diester, Bis(4-aminophenyl)decane-1,10-diester, 1,3-bis[4-(4-aminophenoxy)phenoxy]propane, 1,4-bis[4 -(4-Aminophenoxy)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]decane, 1,10-bis[4-(4-amino) Phenoxy)phenoxy]nonane and the like.

Examples of the aromatic-aliphatic diamine include 3-aminobenzylamine, 4-aminobenzylamine, 3-amino-N-methylbenzylamine, and 4-amino group. -N-methylbenzylamine, 3-aminophenethylamine, 4-aminophenethylamine, 3-amino-N-methylphenethylamine, 4-amino-N-methyl Phenylethylamine, 3-(3-aminopropyl)aniline, 4-(3-aminopropyl)aniline, 3-(3-methylaminopropyl)aniline, 4-(3-methyl Aminopropyl)aniline, 3-(4-aminobutyl)aniline, 4-(4-aminobutyl)aniline, 3-(4-methylaminobutyl)aniline, 4-(4 -Methylaminobutyl)aniline, 3-(5-aminopentyl)aniline, 4-(5-aminopentyl)aniline, 3-(5-aminoaminopentyl)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 the heterocyclic diamines include 2,6-diaminopyridine, 2,4-diaminopyridine, 2,4-diamino-1,3,5-triazine, 2. 7-Diaminodibenzofuran, 3,6-diaminocarbazole, 2,4-diamino-6-isopropyl-1,3,5-triazine, 2,5-bis (4 -aminophenyl)-1,3,4-oxadiazole and the like.

Examples of the aliphatic diamines include 1,2-diaminoethane, 1,3-diaminopropane, 1,4-diaminobutane, and 1,5-diaminopentane. 1,6-Diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane , 1,3-diamino-2,2-dimethylpropane, 1,6-diamino-2,5-dimethylhexane, 1,7-diamino-2,5-dimethyl Heptane, 1,7-diamino-4,4-dimethylheptane, 1,7-diamino-3-methylheptane, 1,9-diamino-5-methylheptane Alkane, 1,12-diaminododecane, 1,18-diaminooctadecane, 1,2-bis(3-aminopropoxy)ethane, and the like.

It can be used in combination as a diamine compound having an alkyl group, a fluorine-containing alkyl group, an aromatic ring, an aliphatic ring, a heterocyclic ring or a large cyclic substituent formed therefrom. Specific examples thereof include diamines represented by the following formulas [DA1] to [DA26].

[化42]

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

[化43]

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

[化44]

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

[化45]

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

[Chem. 46]

(S ₈ represents -COO-, -OCO-, -CONH-, -NHCO-, -COOCH ₂ -, -CH ₂ OCO-, -CH ₂ O-, -OCH ₂ -, -CH ₂ -, -O- Or -NH-, R ₉ represents a fluoro group, a cyano group, a trifluoromethyl group, a nitro group, an azo group, a decyl group, an ethyl group, an ethoxy group or a hydroxy group)

[化47]

[48]

(R ₁₀ represents an alkyl group having 3 to 12 carbon atoms, and 1,4-cyclohexyl cis-trans isomerism is each a trans form)

[化49]

[化50]

[化51]

In the case of directional treatment by light, it is preferred to use a diamine of the general formula [1] and a diamine of the above [DA-1] to [DA-26] in combination to obtain a more stable tilt angle. Preferred diamines which can be used in combination are preferably the formula [DA-10] to [DA-26], and more preferably a diamine of [DA-10] to [DA-16]. The content of the diamine is not particularly limited, and is preferably 5 to 50 mol% of the diamine component, and preferably 5 to 30 mol% from the viewpoint of printability.

Further, the following diamines may also be used in combination.

[化52]

(m represents an integer of 0 to 3, and in the formula [DA-34], n represents an integer of 1 to 5).

By containing a diamine such as the formula [DA-27] or the formula [DA-28], the voltage holding property as a liquid crystal alignment film can be improved, and the diamine of the formula [DA-29] to [DA-34] can be electrochemically accumulated. The reduction is effective.

Further, as shown by the following formula [DA-35], a diamine siloxane or the like may be mentioned as another diamine.

[化53]

(m is an integer from 1 to 10).

The other diamine compound may be used in combination with one or two or more types in combination with characteristics such as liquid crystal orientation, voltage retention characteristics, and storage charge when used as a liquid crystal alignment film.

The tetracarboxylic dianhydride which reacts with the diamine component when the polyglycolic acid of the present invention is obtained is not particularly limited. This specific example is given below.

Examples of the tetracarboxylic dianhydride having an alicyclic structure or an aliphatic structure include 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 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-cyclobutane tetracarboxylic dianhydride, 1,2,3,4-cyclopentane tetracarboxylic dianhydride, 2,3,4,5-tetrahydrofuran tetracarboxylic dianhydride, 1, 2,4,5-cyclohexanetetracarboxylic dianhydride, 3,4-dicarboxy-1-cyclohexyl succinic dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1 -naphthyl succinic dianhydride, 1,2,3,4-butane tetracarboxylic dianhydride, bicyclo[3,3,0]octane-2,4,6,8-tetracarboxylic dianhydride, 3 , 3',4,4'-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, cis-3,7-dibutylcyclooctane-1,5-di Alkene-1,2,5,6-tetracarboxylic dianhydride, tricyclo[4.2.1.0 ^2,5 ]decane-3,4,7,8-tetracarboxylic acid-3,4:7,8-di Anhydride, 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-tetrahydronaphthyl-1,2-dicarboxylic anhydride.

Further, in addition to the tetracarboxylic dianhydride having the above alicyclic structure or aliphatic structure, when aromatic tetracarboxylic dianhydride is used, liquid crystal directionality can be improved and the storage charge of the unit cell can be reduced, which is preferable.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, and 2,2',3,3'-biphenyl. Tetracarboxylic dianhydride, 2,3,3',4-biphenyltetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3,3 ',4-benzophenonetetracarboxylic dianhydride, bis(3,4-dicarboxyphenyl)ether dianhydride, bis(3,4-dicarboxyphenyl)ruthenic anhydride, 1,2,5, 6-naphthyltetracarboxylic dianhydride, 2,3,6,7-naphthyltetracarboxylic dianhydride, and the like.

The tetracarboxylic dianhydride can be used in combination with a liquid crystal alignment film, a voltage holding property, a storage charge, and the like, and can be used in one type or two types or more.

The dialkyl tetracarboxylic acid to be reacted with the diamine component of the polyphthalate of the present invention is not particularly limited. Specific examples thereof will be given below.

Specific examples of the aliphatic tetracarboxylic acid diester include 1,2,3,4-cyclobutanetetracarboxylic acid dialkyl ester and 1,2-dimethyl-1,2,3,4-. Dialkyl cyclobutane tetracarboxylate, dialkyl 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylate, 1,2,3,4-tetramethyl- 1,2,3,4-cyclobutane tetracarboxylic acid dialkyl ester, 1,2,3,4-cyclopentane tetracarboxylic acid dialkyl ester, 2,3,4,5-tetrahydrofuran tetracarboxylic acid Dialkyl ester, 1,2,4,5-cyclohexanetetracarboxylic acid dialkyl ester, 3,4-dicarboxy-1-cyclohexyl succinic acid dialkyl ester, 3,4-dicarboxyl-1 , dialkyl 2,3,4-tetrahydro-1-naphthyl succinate, dialkyl 1,2,3,4-butanetetracarboxylate, bicyclo[3,3,0]octane- Dialkyl 2,4,6,8-tetracarboxylate, dialkyl 3,3',4,4'-dicyclohexyltetracarboxylate, 2,3,5-tricarboxycyclopentylacetic acid Alkyl ester, cis-3,7-dibutylcyclooctane-1,5-diene-1,2,5,6-tetracarboxylic acid dialkyl ester, tricyclo[4.2.1.0 ^2,5 ]壬Alkane-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, 2,3,4-tetrahydronaphthyl-1,2-dicarboxylic acid dialkyl Wait.

Examples of the aromatic tetracarboxylic acid dialkyl ester include dialkyl pyromellitate, 3,3',4,4'-biphenyltetracarboxylic acid dialkyl ester, and 2,2',3. , 3'-biphenyltetracarboxylic acid dialkyl ester, 2,3,3',4-biphenyltetracarboxylic acid dialkyl ester, 3,3',4,4'-benzophenone IV Dialkyl carboxylate, dialkyl 2,3,3',4-benzophenonetetracarboxylate, bis(3,4-dicarboxyphenyl)ether dialkyl ester, bis(3,4 - Dicarboxyphenyl) decyl dialkyl ester, 1,2,5,6-naphthyltetracarboxylic acid dialkyl ester, 2,3,6,7-naphthyltetracarboxylic acid dialkyl ester, and the like.

<Synthesis of Polyamide>

The dicarboxylic acid to be reacted with the diamine component of the polyamine of the present invention is not particularly limited. Specific examples of the aliphatic dicarboxylic acid as the dicarboxylic acid or a derivative thereof include malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, and viscous acid. Capric acid, 2-methyladipate, trimethyl adipate, pimelic acid, 2,2-dimethylglutaric acid, 3,3-diethyl succinic acid, sebacic acid, sebacic acid , suberic acid and so on.

Examples of the alicyclic dicarboxylic acid include 1,1-cyclopropane dicarboxylic acid, 1,2-cyclopropane dicarboxylic acid, 1,1-cyclobutane dicarboxylic acid, and 1,2-cyclobutane. Dicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-diphenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutane II Carboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic acid, 1,2-cyclopentane Carboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 - cyclohexanedicarboxylic acid, 1,4-(2-northene)dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxyl Acid, bicyclo[2.2.2]octane-2,3-dicarboxylic acid, 2,5-di-oxo-1,4-bicyclo[2.2.2]octanedicarboxylic acid, 1,3-adamantane Carboxylic acid, 4,8-di-oxo-1,3-adamantane dicarboxylic acid, 2,6-spiro[3.3]heptane dicarboxylic acid, 1,3-adamantane diacetic acid, camphoric acid, and the like.

Examples of the aromatic dicarboxylic acid include o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, and 5-amine. Isophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1,4-naphthyl dicarboxylic acid, 2,5-naphthyl Dicarboxylic acid, 2,6-naphthyl dicarboxylic acid, 2,7-naphthyl dicarboxylic acid, 1,4-nonanedicarboxylic acid, 1,4-nonanedicarboxylic acid, 2,5-biphenyl Dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-terminated phenyldicarboxylic acid, 4,4"-triphenyldicarboxylic acid, 4,4'-diphenylmethane Dicarboxylic acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 4,4' -diphenyl ether dicarboxylic acid, 4,4'-biphenylmethyldicarboxylic acid, 4,4'-nonanedicarboxylic acid, 4,4'-diphenylacetylene (tolane) dicarboxylic acid, 4,4 '-Carbonyl benzoic acid, 4,4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylene dipropylene Acid, 4-carboxycinnamic acid, p-phenylene diacrylate, 3,3'-[4,4'-(methyl-di-p-phenylene) Dipropionic acid, 4,4'-[4,4'-(oxydi-p-phenylene)]dipropionic acid, 4,4'-[4,4'-(oxydi-p- Phenyl)]dibutyric acid, (isopropylidenebis-p-phenylenedioxy)dibutyric acid, bis(p-carboxyphenyl)dimethylnonane, and the like.

Examples of the dicarboxylic acid containing a heterocyclic ring include 1,5-(9-side oxindole)dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, and 2-phenyl- 4,5-thiazoledicarboxylic acid, 1,2,5-thiadiazolyl-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3- Pyridine dicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, etc. .

The above various dicarboxylic acids may be those having an acid dihalide or an acid anhydride. When these dicarboxylic acids are particularly dicarboxylic acids which can impart a polyamine of a linear structure, it is preferable to maintain the directivity of liquid crystal molecules. They also use terephthalic acid, isophthalic acid, 1,4-cyclohexanedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-diphenylmethane dicarboxyl Acid, 4,4'-diphenylethane dicarboxylic acid, 4,4'-diphenylpropane dicarboxylic acid, 4,4'-diphenylhexafluoropropane dicarboxylic acid, 2,2-dual ( Phenyl)propane dicarboxylic acid, 4,4-triphenyldicarboxylic acid, 2,6-naphthyldicarboxylic acid, 2,5-pyridinedicarboxylic acid or the like acid dihalides are preferred. Although an isomer is present in these compounds, it may be a mixture containing them. Further, two or more kinds of compounds may be used in combination.

When the polyamine of the present invention is obtained by the reaction of a dicarboxylic acid and a diamine component, a known synthetic method can be used. It is generally a method of reacting a dicarboxylic acid and a diamine component in an organic solvent.

<Synthesis of polylysine>

A method of obtaining the polyglycine of the present invention by reacting a tetracarboxylic dianhydride with a diamine component can be carried out by a known method. A method of reacting a tetracarboxylic dianhydride with a diamine component in an organic solvent is generally employed. The reaction of the tetracarboxylic dianhydride with the diamine is relatively easy to carry out in an organic solvent, and has the advantage that no by-products are produced.

The organic solvent used for the reaction of the tetracarboxylic dianhydride and the diamine is not particularly limited as long as it can dissolve the produced polyamic acid. Specific examples thereof will be given below.

Examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, and N-methyl caprolactone. Amine, dimethyl hydrazine, tetramethyl urea, pyridine, dimethyl hydrazine, hexamethyl hydrazine, γ-butyrolactone, isopropanol, methoxymethylpentanol, dipentene, ethyl Amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, methyl serotonin, ethyl serotonin, methyl sarbuta acetate, ethylene Alcohol diethyl ether acetate, butyl carbitol, ethyl carbitol, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, propylene glycol, Propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary 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 single Propyl ether, 3-methyl-3-methoxybutyl acetate, Propylene glycol methyl ether, 3-methyl-3-methoxybutanol, diisopropyl ether, ethyl isobutyl ether, diisobutylene, pentyl acetate, butyl butyrate, butyl ether, Diisobutylketone, methylcyclohexene, propyl ether, dihexyl ether, dioxane, n-hexane, n-pentane, n-octane, diethyl ether, cyclohexanone, ethylene carbonate Ester, propylene carbonate, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxy Methyl propionate, methyl ethyl 3-ethoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid, 3-methoxypropionic acid, 3-methoxypropionic acid Propyl ester, butyl 3-methoxypropionate, diglyme, 4-hydroxy-4-methyl-2-pentanone, 3-methoxy-N,N-dimethylpropane decylamine 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, and the like. These can be used alone or in combination. Further, even if it is a solvent which does not dissolve polylysine, it may be mixed and used in the above solvent in the range which does not precipitate the polyamic acid produced.

Further, since the water in the organic solvent hinders the polymerization reaction and becomes a cause of the polyamic acid produced by the hydrolysis, it is preferred that the organic solvent be dried as described above.

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 an organic solvent is stirred, and the tetracarboxylic dianhydride is directly or dispersed or dissolved in an organic solvent and then added. Conversely, a method of adding a diamine component to a solution in which a tetracarboxylic dianhydride is dispersed or dissolved in an organic solvent, a method of mutually adding a tetracarboxylic dianhydride and a diamine component, or the like may be used. Further, when the tetracarboxylic dianhydride or the diamine component is formed of a plurality of compounds, the reaction may be carried out in a state of being mixed in advance, or the reaction may be carried out in a separate order, and the low molecular weight bodies of the respective reactions may be subjected to a mixing reaction. After that, it is a high molecular weight body.

The polymerization temperature at this time may be any temperature of from -20 to 150 ° C, but is preferably in the range of from -5 to 100 ° C. Further, the reaction can be carried out at any concentration. However, when the concentration is too low, the obtaining of a polymer having a high molecular weight becomes difficult. When the concentration is too high, the viscosity of the reaction liquid is too high, and it is difficult to uniformly stir, so tetracarboxylic acid The total concentration in the reaction solution of the dianhydride and the diamine component is preferably from 1 to 50% by mass, preferably from 5 to 30% by mass. The initial stage of the reaction is carried out at a high concentration, and thereafter an organic solvent can be added.

In the polymerization reaction of polyglycolic acid, the ratio of the total number of moles of the tetracarboxylic dianhydride to the total number of moles of the diamine component is preferably from 0.8 to 1.2, more preferably from 0.9 to 1.1. As in the case of the general polycondensation reaction, the closer the molar ratio is to 1.0, the larger the molecular weight of the produced polylysine.

<Synthesis of Polyimine>

The polyimine of the present invention is a polyimine obtained by subjecting the polyamic acid to dehydration ring closure, and can be used as a polymer for obtaining a liquid crystal alignment film.

With regard to the polyimine of the present invention, the dehydration ring closure ratio of the proline group (the imidization ratio) does not need to be 100%, and can be arbitrarily adjusted for the purpose or purpose.

Examples of the method for carrying out hydrazine imidization of polylysine include a thermal hydrazylation method in which a solution of poly-proline acid is directly heated, and a catalyst catalyzed by adding a catalyst to a solution of poly-proline. Amination method.

The temperature at which the polyaminic acid is thermally imidized in the solution is 100 to 400 ° C, preferably 120 to 250 ° C, and the water formed by the ruthenium imidization reaction is excluded from the system. It is better to carry on one side.

The catalyst of ruthenium amide is imidized by adding a basic catalyst and an acid anhydride to a solution of polyglycine, and stirring is carried out at -20 to 250 ° C, preferably at 0 to 180 ° C. The amount of the basic catalyst is 0.5 to 30 moles, preferably 2 to 20 moles, and the amount of the acid anhydride is 1 to 50 moles, preferably 3 to the amidate group. 30 moles. Examples of the basic catalyst include pyridine, triethylamine, trimethylamine, tributylamine, and trioctylamine. Among them, pyridine is also preferred because it has a basicity suitable for the reaction. Examples of the acid anhydride include acetic anhydride, trimellitic anhydride, and pyromellitic dianhydride. Among them, purification after the completion of the reaction in the case of using acetic anhydride is preferred, and it is preferred. The imidization ratio of the imidization by the catalyst oxime can be controlled by adjusting the amount of the catalyst, the reaction temperature, the reaction time, and the like.

<Synthesis of polyamidomate>

As a method of synthesizing a polyphthalate, a reaction of a tetracarboxylic acid diester dichloride and a diamine, or a reaction of a tetracarboxylic acid diester and a diamine in the presence of a suitable condensing agent and a base may be mentioned or A method of prepolymerizing polylysine and esterifying a carboxylic acid in valeric acid by a polymer reaction.

Specifically, the tetracarboxylic acid diester dichloride and the diamine can be carried out in the presence of a base and an organic solvent at -20 to 150 ° C, preferably at 0 to 50 ° C for 30 minutes to 24 hours, more preferably It is synthesized by reaction for 1 to 4 hours.

As the base, pyridine, triethylamine, 4-dimethylaminopyridine or the like can be used, but pyridine is preferred for the reaction to be stable. The amount of the base to be added is preferably from 2 to 4 times the mole of the tetracarboxylic acid diester dichloride from the viewpoint of easily removing the amount and easily obtaining a high molecular weight body.

When the condensation polymerization is carried out in the presence of a condensing agent, triphenylphosphite, dicyclohexylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide salt can be used. Acid salt, N,N'-carbonyldiimidazole, dimethoxy-1,3,5-triazinylmethylmorpholine, O-(benzotriazol-1-yl)-N,N,N ',N'-tetramethylurea salt tetrafluoroborate, O-(benzotriazol-1-yl)-N,N,N',N'-tetramethylurea salt hexafluorophosphate, 2,3-dihydro-2-thione-3-benzoxazolyl)sulfonic acid diphenyl, 4-(4,6-dimethoxy-1,3,5-triazin-2-yl a condensing agent such as 4-methoxymorpholine chloride n-hydrate.

Further, in the method of using the above condensing agent, by adding Lewis acid as an additive, the reaction can be carried out efficiently. As the Lewis acid, lithium halide such as lithium chloride or lithium bromide is preferred. The amount of the 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 in the polymerization of the above polyamic acid can be used. From the viewpoint of the solubility of the monomer and the polymer, N-methyl-2-pyrrolidone and γ-butyrolactone can be used. It is preferable to use one type or a mixture of two or more types. The concentration of the polymer at the time of the synthesis is preferably from 1 to 30% by mass, and preferably from 5 to 20% by mass, from the viewpoint that the polymer is not easily precipitated and a high molecular weight body is easily obtained. Further, in order to prevent hydrolysis of the tetracarboxylic acid diester dichloride, it is preferred that the solvent used for the synthesis of the polyglycolate is dehydrated as much as possible, and the reaction is carried out in a nitrogen atmosphere to prevent the incorporation of outside air.

<Recycling of Polymers>

When the produced polymer is recovered from a reaction solution such as polyglycolic acid, polyphthalate or polyimine, it is preferred to introduce the reaction solution into a weak solvent to precipitate it. Examples of the weak solvent used for precipitation include methanol, acetone, hexane, ethylene glycol dibutyl ether, heptane, methyl ethyl ketone, methyl isobutyl ketone, ethanol, toluene, benzene, water, and the like. The polymer precipitated in a weak solvent is recovered by filtration, and dried under normal pressure or reduced pressure at room temperature or under heating. Further, when the precipitate-recovered polymer is redissolved in an organic solvent, and the operation of reprecipitation and recovery is repeated 2 to 10 times, impurities in the polymer can be reduced. Examples of the weak solvent in this case include alcohols, ketones, and hydrocarbons. When three or more types of weak solvents selected from the group are used, the purification efficiency can be further improved.

The molecular weight of the polymer contained in the liquid crystal aligning agent of the present invention is determined by GPC (Gel Permeation Chromatography) method in consideration of the obtained coating film strength, workability at the time of formation of a coating film, and uniformity of a coating film. The weight average molecular weight is preferably 5,000 to 1,000,000, preferably 10,000 to 150,000.

<Liquid directional treatment agent>

The liquid crystal aligning agent of the present invention is a coating liquid when a liquid crystal alignment film is formed, and is a solution in which a resin component when a resin film is to be formed is dissolved in an organic solvent. The resin component contains at least one polymer selected from the above-described polymers of the present invention. The content of the liquid crystal aligning agent in the resin component is preferably from 1 to 20% by mass, preferably from 3 to 15% by mass, particularly preferably from 3 to 10% by mass.

The resin component may be the polymer of the present invention, and other polymers may be mixed. In this case, the content of the other polymer in the resin component is preferably 0.5 to 15% by mass, preferably 1 to 10% by mass.

The other polymer, for example, a polyamine component obtained by reacting a diamine compound other than a specific diamine compound, or the like, may be mentioned as a diamine component which reacts with a tetracarboxylic dianhydride component.

The organic solvent used in the liquid crystal aligning agent of the present invention is not particularly limited as long as it is an organic solvent capable of dissolving the resin component. Specific examples thereof will be given below.

Examples thereof include N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, N-methylcaprolactam, 2-pyrrolidone, and N-B. Pyrrolidone, N-vinylpyrrolidone, dimethyl hydrazine, tetramethylurea, pyridine, dimethyl hydrazine, hexamethylarylene, γ-butyrolactone, 3-methoxy-N,N-dimethyl Propane amide, 3-ethoxy-N,N-dimethylpropane decylamine, 3-butoxy-N,N-dimethylpropane decylamine, 1,3-dimethyl-imidazolidinone Ethyl amyl ketone, methyl decyl ketone, methyl ethyl ketone, methyl isoamyl ketone, methyl isopropanone, cyclohexanone, ethylene carbonate, propylene carbonate, diglyme , 4-hydroxy-4-methyl-2-pentanone, and the like. These can be used alone or in combination.

The liquid crystal aligning agent of the present invention may contain components other than the above. In this example, a compound having a uniformity in film thickness when applying a liquid crystal alignment treatment agent or a solvent multi-substance which improves surface smoothness, and the like, and a compound which improves the adhesion between the liquid crystal alignment film and the substrate are used.

Specific examples of the solvent (weak solvent) for improving film thickness uniformity or surface smoothness include the following.

For example, isopropyl alcohol, methoxymethylpentanol, methyl sarbuta, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, methyl stilbene acetate, ethylene glycol diethyl ether Acid ester, butyl carbitol, ethyl carbitol, ethyl carbitol acetate, ethylene glycol, ethylene glycol monoacetate, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl Ether, propylene glycol, propylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol-tertiary 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, pentyl acetate, butyl butyrate, butyl ether, diisobutyl ketone, methyl cyclohexene, propyl ether, dihexyl ether, 1-hexanol, N-hexane, n-pentane, n-octane, two Ethyl ether, methyl lactate, ethyl lactate, methyl acetate, ethyl acetate, n-butyl acetate, propylene glycol monoethyl ether, methyl pyruvate, ethyl pyruvate, 3-methoxypropionic acid Ester, 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-1-monoethyl ether-2-acetate, dipropylene glycol, 2 -(2-ethoxypropoxy)propanol, methyl lactate, ethyl lactate, n-propyl lactate, n-butyl lactate, isoamyl lactate, etc. .

These weak solvents can be used in one type or in a mixture of plural types. When the solvent is used, the solvent contained in the liquid crystal aligning agent is preferably from 5 to 80% by mass, preferably from 20 to 60% by mass.

Examples of the compound for improving the uniformity of the film thickness or the surface smoothness include a fluorine-based surfactant, a polyfluorene-based surfactant, and a nonionic surfactant.

More specifically, for example, Eftop EF301, EF303, EF352 (manufactured by TOHKEM PRODUCTS CORP), Megafac F171, F173, R-30 (manufactured by Dainippon Ink Co., Ltd.), Fluorad FC430, FC431 (manufactured by Sumitomo 3M Co., Ltd.), Asahiguard AG710, and Surflon S -382, SC101, SC102, SC103, SC104, SC105, SC106 (made by Asahi Glass Co., Ltd.). The use ratio of the surfactant is preferably 0.01 to 2 parts by mass, more preferably 0.01 to 1 part by mass, per 100 parts by mass of the resin component contained in the liquid crystal alignment treatment agent.

Specific examples of the compound which improves the adhesion between the liquid crystal alignment film and the substrate include the following functional decane-containing compound, epoxy group-containing compound, and the like.

Examples thereof include 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 2-aminopropyltrimethoxydecane, and 2-aminopropyltriethoxydecane. N-(2-Aminoethyl)-3-aminopropyltrimethoxydecane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane, 3-anthracene Ureapropyltrimethoxydecane, 3-guanidinopropyltriethoxydecane, N-ethoxycarbonyl-3-aminopropyltrimethoxydecane, N-ethoxycarbonyl-3-aminopropyl Triethoxy decane, N-triethoxymercaptopropyltriethylamine, N-trimethoxydecylpropyltriethylamine, 10-trimethoxydecyl-1, 4,7-triazadecane, 10-triethoxyindolyl-1,4,7-triazadecane, 9-trimethoxyindolyl-3,6-diazaindolyl acetic acid Ester, 9-triethoxyindolyl-3,6-diazaindolyl acetate, N-benzyl-3-aminopropyltrimethoxydecane, N-benzyl-3-amine Propyl triethoxy decane, N-phenyl-3-aminopropyl trimethoxy decane, N-phenyl-3-aminopropyl triethoxy decane, N-bis (oxyethyl) )-3-aminopropyltrimethoxydecane, N-bis(oxyethyl)-3- Aminopropyltriethoxydecane, ethylene glycol propylene oxide ether, polyethylene glycol propylene oxide ether, propylene glycol propylene oxide ether, tripropylene glycol propylene oxide ether, polypropylene glycol propylene oxide ether, neopentyl Alcohol propylene oxide, 1,6-hexanediol propylene oxide ether, glycerin propylene oxide ether, 2,2-dibromoneopentyl glycol propylene oxide ether, 1,3,5,6-tetrapropylene oxide Base-2,4-hexanediol, N,N,N',N',-tetrapropene oxide-m-xylenediamine, 1,3-bis(N,N-propylene oxide aminomethyl) Cyclohexane, N, N, N', N', - propylene oxide-4, 4'-diaminodiphenylmethane, and the like.

In addition to further improving the adhesion between the substrate and the film, it is preferable to contain an additive such as the following phenolic resin for the purpose of preventing deterioration of electrical characteristics due to the backlight. Specifically, the phenolic plastic additive is shown below.

[54]

When a compound which improves the adhesion to the substrate is used, the amount of use is preferably from 0.1 to 30 parts by mass, preferably from 1 to 20 parts by mass, per 100 parts by mass of the resin component. When the amount of use is less than 0.1 part by mass, the effect of improving the adhesion cannot be expected. When the amount is more than 30 parts by mass, the orientation of the liquid crystal may be deteriorated.

In addition to the above, the liquid crystal aligning agent of the present invention may be added to improve the electrical properties such as the dielectric constant and the conductivity of the liquid crystal alignment film in the range which does not impair the effects of the present invention. A cross-linking compound or the like for the purpose of film hardness or density in the case of a dielectric material, a conductive material, or even a liquid crystal alignment film.

<Liquid crystal alignment film and liquid crystal display element>

After the liquid crystal alignment treatment agent of the present invention is applied onto a substrate and fired, it is subjected to orientation treatment by rubbing treatment, light irradiation, or the like, or used as a liquid crystal alignment film without orientation treatment in a vertical alignment application or the like. In this case, the substrate to be used is not particularly limited as long as it is a substrate having high transparency, and a plastic substrate such as a glass substrate, an acrylic substrate, or a polycarbonate substrate can be used. Moreover, when a substrate formed of an ITO electrode or the like at the time of liquid crystal driving is used, it is preferable that the process can be simplified. Further, in the reflective liquid crystal display device, a single-sided substrate may be used, and an opaque material such as a germanium wafer may be used. In this case, a material that reflects light such as aluminum may be used as the electrode.

The coating method of the liquid crystal alignment treatment agent is not particularly limited, but generally, methods such as screen printing, offset printing, stencil printing, and jet printing are industrially performed. Other coating methods are carried out by mixing purposes such as dipping, roll coating, slit coating, and spin coater.

The liquid crystal alignment agent is applied onto a substrate and then fired by heating means such as a hot plate at 50 to 300 ° C, preferably 80 to 250 ° C, to evaporate the solvent to form a coating film. When the thickness of the coating film formed after firing is too thick, it is disadvantageous in terms of the power consumption of the liquid crystal display element. When the thickness is too thin, the reliability of the liquid crystal display element may be lowered, so it is preferably 5 to 300 nm. More preferably, it is 10 to 100 nm. When the liquid crystal is oriented horizontally or obliquely, the coating film after firing is subjected to rubbing or polarized ultraviolet irradiation or the like.

In the liquid crystal display device of the present invention, a substrate having a liquid crystal alignment film is obtained from the liquid crystal alignment treatment agent of the present invention by the above-described method, and a unit cell is produced by a known method as a liquid crystal display element.

To cite one example of cell fabrication, prepare a pair of substrates formed by a liquid crystal alignment film, and walk a spacer on a liquid crystal alignment film of a single-sided substrate so that the liquid crystal alignment film surface becomes inside and the substrate on the other surface is bonded. A method of sealing the liquid crystal after pressure-injection, or a method of laminating the liquid crystal on the surface of the liquid crystal alignment film of the spacer, and then sealing the substrate to seal it may be exemplified. The thickness of the spacer at this time is preferably from 1 to 30 μm, more preferably from 2 to 10 μm.

[Examples]

Hereinafter, the present invention will be described in more detail by way of Examples and Comparative Examples. However, the present invention is not limited thereto.

<Example 1> Synthesis of 2-(t-butoxycarbonylamino)-4-octylamine phenyl 3,5-diaminobenzoate (HC-01)

[化55]

Step 1 Synthesis of 4-octylamine-2-nitrophenol

[化56]

To a 500 mL (ml) 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. After cooling, the inside of the system was brought to 0 ° C, and 16.3 g (103 mmol) of n-octyl chloride was added thereto, followed by stirring at room temperature. After the completion of the reaction, 50 mL of pure water was added and stirred, and after the reaction was completed, ethyl acetate was added thereto, and the organic layer was separated, and the organic layer was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The obtained solid was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7 (volume ratio, the same below)) to obtain 27.0 g (yield: 94%) as a pale yellow solid.

Step 2 Synthesis of 4-octylamine-2-aminophenol

[化57]

Add 15.0 g (53.5 mmol) of N-(3-nitro-4-hydroxyphenyl)octylamine, 40 mL of ethanol, and 1.0 g of 5% palladium carbon in a 500 mL four-neck flask under a hydrogen atmosphere at room temperature. Stir. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to give a white solid (13.0 g, yield 97%).

Step 3 Synthesis of 4-octylamine-2-t-butoxycarbonylaminophenol

[化58]

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

Step 4 Synthesis of 2-(t-butoxycarbonylamino)-4-octylamine phenyl 3,5-dinitrobenzoate

[化59]

To a 300 mL four-necked flask were added HC-03-17.0 g (20.0 mmol), tetrahydrofuran 80 mL, and pyridine 1.6 g (20.0 mmol). After cooling, the temperature in the system was changed to 0 ° C, and 5.5 g (20.0 mmol) of 3,5-dinitrobenzimidyl chloride was added thereto, and the mixture was stirred at room temperature. After the completion of the reaction, a 10% by mass aqueous potassium carbonate solution was added to make a pH of 8 to 9. Ethyl acetate was added and the organic layer was separated, and the organic layer was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:1), and recrystallised from ethyl acetate and n-hexane (1:9) to give a pale yellow solid 5.9 g. (Yield 54%).

Step 5 Synthesis of HC-01

[60]

2-(T-butoxycarbonylamino-4-octylamine phenyl) 3,5-dinitrobenzoate 5.9 g (10.8 mmol), tetrahydrofuran 150 mL, and 5 were added to a 500 mL four-neck flask. % palladium/carbon 0.6 g, stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to give 5.2 g (yield: 99%) as a gray solid. The ¹ H-NMR results of the obtained individuals are shown below. From this result, it was confirmed that the target substance was HC-01.

Further, the identification of the compound in the examples of the present invention was carried out by ¹ H-NMR (NMR of ¹ H, model of Varian Co., Ltd.: 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-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzimidamide (HC-02)

[化61]

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

[化62]

25.0 g (163 mmol) of 3,4-diaminonitrobenzene, 250 mL of tetrahydrofuran, and 35.6 g (163 mmol) of di-t-butyl dicarbonate were placed in a 300 mL four-necked flask, and refluxed for 4 hours under a nitrogen atmosphere. Stir. After the completion of the reaction, the solvent was removed in a rotary distiller, and the obtained solid was washed with methanol, and recrystallized from a mixed solvent of ethyl acetate and n-hexane (5:5) to give a yellow solid (33.8 g). %).

Step 2 Synthesis of N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminobenzene

[化63]

In a 300 mL four-necked flask, 18.3 g (95.0 mmol) of 4-pentylbenzoic acid, 150 mL of tetrahydrofuran, and 20 mL of dimethylformamide were added, and the system was cooled to 0 ° C, and 14.1 g (119 mmol) of hydrazine chloride was added. After returning to room temperature, stirring was carried out for 2 hours to prepare a 4-pentylbenzoic acid chloride solution. On the other hand, in a 500 mL four-necked flask, 20.0 g (79.0 mmol) of 3-t-butoxycarbonylamino-4-aminonitrobenzene, 100 mL of tetrahydrofuran, and 7.5 g of pyridine (95.0 mmol) were added, and the system was cooled. The inside was changed to 0 ° C, and the previously prepared 4-pentylbenzoic acid chloride solution was slowly dropped, and stirred at room temperature. After the completion of the reaction, the solvent was removed by a rotary distiller, and ethyl acetate was added thereto, and a 10% by mass aqueous sodium hydrogencarbonate solution was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed with methanol and then recrystallized from ethyl acetate and n-hexane (2:8) to afford 24.7 g (yield: 73%).

Step 3 Synthesis of N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminoaniline

[化64]

20.0 g (46.8 mmol) of N-4-(4-pentyl benzhydrylamino)-3-t-butoxycarbonylamino nitrobenzene, 200 mL of tetrahydrofuran, and 10% were added to a 500 mL four-neck flask. Palladium carbon 2.0 g was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, the palladium carbon was removed by filtration, the solvent was distilled off using a rotary distiller, re-dissolved in acetone, activated carbon was added and temporarily stirred at room temperature, and then activated carbon was filtered, and acetone was distilled off to be vacuum dried. Thereafter, 17.7 g (yield 95%) of a pale yellowish green glassy solid was obtained.

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

[化65]

Add 10.0 g (25.2 mmol) of N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminoaniline in a 300 mL four-necked flask, 150 mL of tetrahydrofuran, and dimethylformamidine. 20 mL of amine and 2.4 g of pyridine (30.2 mmol). After cooling, the temperature in the system was changed to 0 ° C, and 5.8 g (25.2 mmol) of 3,5-dinitrobenzimidyl chloride was added thereto, and the mixture was stirred at room temperature. After the completion of the reaction, the solvent was removed by a rotary distiller, and ethyl acetate was added thereto, and a 10% by mass aqueous sodium hydrogencarbonate solution was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed with methanol, and then recrystallized from ethyl acetate and n-hexane (3:7) to yield 11.8 g (yield: 79%).

Step 5 Synthesis of HC-02

[化66]

To a 300 mL four-necked flask was added N-4-(4-pentyl benzhydrylamino)-3-t-butoxycarbonylaminophenyl 3,5-dinitrobenzamide 10.0 g ( 16.9 mmol), tetrahydrofuran 100 mL, and 10% palladium carbon 1.0 g were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7), and further washed with n-hexane to obtain 8.6 g (yield: 96%) as a white solid. The ¹ H-NMR results of the solid obtained for the objective are shown below. From this result, the HC-02 of the target was confirmed.

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-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzamide (HC-03)

[67]

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

[化68]

2.10 g (19.4 mmol) of 2,4-dinitrobenzoic acid, 150 mL of dichloromethane, and 20 mL of dimethylformamide were added to a 300 mL four-necked flask, and the system was cooled to 0 ° C. 2.26 g (19.4 mmol) of hydrazine chloride was added to the room temperature and stirred for 2 hours to prepare a 2,4-dinitrobenzoic acid chloride solution. The other side was charged with 4-(4-pentyl benzhydrylamino)-3-t-butoxycarbonylaminoaniline 7.00 g (17.6 mmol), tetrahydrofuran 100 mL, and pyridine 2.09 g in a 500 mL four-neck flask. 26.4 mmol), cooling to 0 ° C in the system, the previously prepared 2,4-dinitrobenzoic acid chloride solution was slowly dropped, and stirred at 40 ° C under a nitrogen atmosphere. After the completion of the reaction, the solvent was removed by a rotary distiller, ethyl acetate was added thereto, and the mixture was washed with a 10% by mass aqueous sodium hydrogencarbonate solution, water, and brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed with methanol, and recrystallized from a mixed solvent of dichloroethane and n-hexane (2:8) to yield 6.56 g (yield: 63%) of pale yellow solid.

Step 2 Synthesis of N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzimidamide

[化69]

Add N-4-(4-pentyl benzhydrylamino)-3-tert-butoxycarbonylaminophenyl 2,4-dinitrobenzamide 6.00g in a 300 mL four-necked flask ( 10.2 mmol), 100 mL of tetrahydrofuran, and 0.60 g of 10% palladium carbon were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed with a mixed solvent of methanol and 2-propanol, and then recrystallized from a mixed solvent of ethyl acetate and n-hexane (2:8) to obtain a pale yellow solid of 4.88 g (yield 90). %). The results of ¹ H-NMR of the substance obtained for the objective are shown below. From this result, the HC-02 of the target was confirmed.

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-pentylbenzylidenyloxy)-3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide (HC-04)

[化70]

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

[71]

2-amino-4-nitrophenol 12.3 g (79.8 mmol), tetrahydrofuran 250 mL, di-tert-butyl dicarbonate 14.2 g (87.9 mol), and 4-dimethylamino group were added to a 300 mL four-neck flask. Pyridine 2.00 g (7.98 mol) was stirred at room temperature. After the completion of the reaction, ethyl acetate was added, and the mixture was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was purified by silica gel column chromatography (ethyl acetate:hexane = 1:1), and recrystallized from ethyl acetate and n-hexane (1:9) to give a pale yellow solid. g (yield 73%).

Step 2 Synthesis of 4-(4-pentyl benzhydryloxy)-3-tert-butoxycarbonylamino nitrobenzene

[化72]

6.4 g (32.8 mol) of 4-pentylbenzoic acid and 60 mL of tetrahydrofuran were added to a 200 mL four-necked flask, and the system was cooled to 0 ° C, and 4.3 g (35.3 mol) of hydrazine chloride was added thereto, and the mixture was returned to room temperature. After stirring for 1 hour, a 4-pentylbenzoic acid chloride solution was prepared. On the other hand, in a 500 mL four-necked flask, 6.3 g (25.2 mmol) of 2-t-butoxycarbonylamino-4-nitrophenol, 60 mL of tetrahydrofuran, and 4.0 g of pyridine (50.4 mmol) were added, and the system was cooled to 0. The previously prepared 4-pentyl benzoic acid chloride solution was slowly added dropwise at ° C, and stirred at room temperature. After the completion of the reaction, a 10% by mass aqueous potassium carbonate solution was added to adjust the pH to 8 to 9. Ethyl acetate was added, the organic layer was separated, and the organic layer was washed with water and brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (7:3) to yield 6.9 g (yield: 64%).

Step 3 Synthesis of 4-(4-pentylbenzylidenyloxy)-3-tert-butoxycarbonylaminoaniline

[化73]

8.8 g (20.5 mol) of 4-(4-pentyl benzhydryloxy)-3-t-butoxycarbonylamino nitrobenzene 2, tetrahydrofuran 100 mL, and 5% were placed in a 300 mL four-neck flask. Palladium carbon 0.9 g was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (7:3) to yield 6.8 g (yield: 84%) of white solid.

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

[化74]

6.8 g (17.1 mmol) of 4-(4-pentylbenzylideneoxy)-3-t-butoxycarbonylaminoaniline, 100 mL of tetrahydrofuran, and 1.5 g of pyridine (18.8 mmol) were added to a 300 mL four-neck flask. ). The mixture was cooled to 0 ° C, and 4.6 g (20.0 mol) of 3,5-dinitrobenzhydryl chloride was added thereto, and the mixture was stirred at room temperature. After the completion of the reaction, a 10% by mass aqueous potassium carbonate solution was added to adjust the pH to 8 to 9. Ethyl acetate was added, the organic layer was separated, and the organic layer was washed with water and brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7) to yield 11.0 g (yield: 99%) of pale yellow solid.

Step 5

Synthesis of HC-04

[化75]

Into a 300 mL four-necked flask was added N-4-(4-pentyl benzhydryloxy)-3-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzamide 11.0 g ( 18.6 mmol), 100 mL of tetrahydrofuran, and 1.0 g of 5% palladium carbon were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to give 9.7 g (yield 98%) as a gray solid. The results of ¹ H-NMR of the substance obtained for the objective are shown below. From this result, the HC-04 of the target was confirmed.

¹ H NMR (400 MHz, [D ₆ ]-DMSO): δ 9.99 (s, 1H), 8.88 (s, 1H), 7.99-8.01 (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-t-butoxycarbonylaminophenyl 3,5-diaminobenzoic acid ester (HC-05)

[化76]

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

[化77]

6.2 g (50.3 mmol) of 6-amino-m-cresol, 150 mL of tetrahydrofuran, and 14.2 g (55.3 mmol) of di-t-butyl dicarbonate were placed in a 300 mL four-neck flask, and stirred at room temperature. After the completion of the reaction, ethyl acetate was added, and the mixture was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, and magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distillation apparatus to obtain 11.2 g (yield: 99%) of white solid.

Step 2 3-methyl-6-tert-butoxycarbonylaminophenyl 3,5-dinitrobenzoate

[化78]

To a 300 mL four-necked flask was added 11.3 g (50.2 mmol) of 6-t-butoxycarbonylamino-m-cresol, 200 mL of tetrahydrofuran, and 4.0 g (50.2 mmol) of pyridine. After cooling, the inside of the system was brought to 0 ° C, and 11.5 g (50.2 mmol) of 3,5-dinitrobenzimidyl chloride was added thereto, and the mixture was stirred at room temperature. After the 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. Next, the solid was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to obtain 20.2 g (yield: 97%) as a yellow solid.

Step 3 Synthesis of HC-05

[化79]

To a 300 mL four-necked flask was added 3-methyl-6-t-butoxycarbonylaminophenyl 3,5-dinitrobenzoate 10.0 g (24.0 mmol), tetrahydrofuran 100 mL, and 5% palladium/ 1.0 g of carbon was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to give 8.7 g (yield: 99%) as a gray solid. The results of ¹ H-NMR of the substance obtained for the objective are shown below. From this result, the HC-05 of the target was confirmed.

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-pentylbenzylidenylamino)-2-tert-butoxycarbonylamino 3,5-diaminobenzoate (HC-06)

[化80]

Step 1 Synthesis of 4-(4-pentyl benzhydrylamino)-2-nitrophenol

[化81]

12.5 g (64.9 mmol) of 4-pentylbenzoic acid, 100 mL of tetrahydrofuran, and 20 mL of DMF (N,N-dimethylformamide) were added to a 200 mL four-necked flask, and the system was cooled to 0 ° C, and chlorination was added. 7.80 g (65.5 mol) of anthraquinone was stirred at 60 ° C for 2 hours to prepare a 4-pentylbenzoic acid chloride solution. On the other hand, in a 300 mL four-necked flask, 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, and the system was cooled to 0 ° C, which was previously prepared. The 4-pentyl benzoic acid chloride solution was slowly added, and after returning to room temperature, it was stirred for 1 day under a nitrogen atmosphere. After the completion of the reaction, the solvent was distilled off in a distiller, ethyl acetate and 50 mL of pure water were added and stirred, and the organic layer was separated, and the organic layer was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was purified by column chromatography (mixed solvent of ethyl acetate and n-hexane (8:2), and then washed again with a mixture solvent of ethyl acetate and n-hexane (2:8). After that, 15.6 g of a yellow solid was obtained (yield: 73%).

Step 2 Synthesis of 4-(4-pentyl benzhydrylamino)-2-aminophenol

[化82]

In a 200 mL four-necked flask, 10.0 g (30.5 mol) of 4-(4-pentyl benzhydrylamino)-2-nitrophenol, 100 mL of tetrahydrofuran, and 1.0 g of 10% palladium carbon were added under a hydrogen atmosphere. Stir at room temperature. After the completion of the reaction, the palladium carbon was removed by filtration, the solvent was distilled off using a rotary distiller, re-dissolved with acetone, and activated carbon was added and stirred. Thereafter, activated carbon was removed by filtration, and the filtrate was distilled off using a rotary distiller to obtain 8.4 g (yield: 93%) of a pale brown confectionery solid.

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

[化83]

4-(4-pentyl benzhydrylamino)-2-aminophenol 6.0 g (20.1 mmol), tetrahydrofuran 100 mL, di-tert-butyl dicarbonate 4.4 g (20.1 mmol) in a 200 mL four-neck flask And 0.16 g (2.01 mmol) of pyridine were stirred at room temperature. After the completion of the reaction, the solvent was distilled off by a rotary distiller, and ethyl acetate was added thereto, followed by washing with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7) to afford 5.8 g (yield: 72%) as white solid.

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

[化84]

To a 200 mL four-necked flask was added 5.00 g (12.5 mmol) of 4-pentyl benzhydrylamino-2-butoxycarbonylaminophenol, 80 mL of tetrahydrofuran, and 0.99 g (12.5 mmol) of pyridine. After cooling, the inside of the system was brought to 0 ° C, and 2.9 g (12.5 mmol) of 3,5-dinitrobenzhydryl chloride was added thereto, and the mixture was stirred at room temperature. After the completion of the reaction, ethyl acetate was added, and washed with a 10% by mass aqueous sodium hydrogencarbonate solution, water, and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was subjected to dispersion washing with a mixed solvent of methanol and 2-propanol (3:7), and recrystallization was carried out using a mixed solvent of ethyl acetate and n-hexane (2:8) to obtain a pale yellow solid (5.09 g). Yield 90%).

Step 5 Synthesis of HC-06

[化85]

In 100mL four-necked flask was added 4- (4-benzoyl-pentyl-ylamino) _- 2-tert-butoxy-carbonyl group of 3,5-dinitrobenzoyl ester 4.52g (7.59 mmol), 50 mL of 1,4-dioxane and 0.45 g of 10% palladium carbon were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of dichloroethane and n-hexane (5:5) to give 3.62 g (yield: 90%) as a pale gray solid. The ¹ H-NMR results of the obtained material are shown below. From this result, the HC-07 of the target substance was confirmed.

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- 1.56 (m, 2H), 1.46 (s, 9H), 1.37-1.16 (m, 4H), 0.88-0.84 (t, 3H)

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

[化86]

Step 1 Synthesis of [4-(4-pentylbenzylidenylamino)-3-(t-butoxycarbonylamino)phenyl](2,4-dinitrophenyl)acetamide

[化87]

In 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, and the system was cooled to 0 ° C, and slowly added to B. Dichloromethane 1.6g (12.3 mmol) was returned to room temperature and stirred for 2 hours to prepare a 2,4-dinitrophenylacetic acid chloride solution. On the other hand, in a 200 mL four-necked flask, 4.5 g (11.2 mmol) of N-4-(4-pentyl benzhydrylamino)-3-t-butoxycarbonylaminoaniline and 50 mL of dichloromethane were added. Further, 1.1 g (13.4 mmol) of pyridine was cooled to 0 ° C in the system, and the previously prepared 2,4-dinitrobenzoic acid chloride solution was slowly dropped, and stirred at room temperature under a nitrogen atmosphere. After the completion of the reaction, the solvent was removed by a rotary distiller, and ethyl acetate was added thereto, and washed with a 10% by mass aqueous sodium hydrogencarbonate solution, water, and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed with methanol, and then recrystallized from ethyl acetate and n-hexane (2:8) to give 5.2 g (yield: 77%).

Step 2 Synthesis of HC-07

[化88]

Add N-[4-(4-pentyl benzhydrylamino)-3-(t-butoxycarbonylamino)phenyl](2,4-dinitrophenyl) in a 100 mL four-neck flask 4.5 g (7.43 mmol) of acetamide, 50 mL of 1,4-dioxane, and 0.45 g of platinum oxide were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, platinum oxide was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (5:5) to give 3.6 g (yield: 89%) as a pale brown solid. The ¹ H-NMR results of the obtained material are shown below. From this result, the HC-07 of the target substance was confirmed.

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. (m, 4H), 0.89-0.85 (t, 3H)

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

[化89]

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

[化90]

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

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

[化91]

25.0 g (126 mmol) of 3,5-dinitrobenzyl alcohol, 300 mL of chloroform, and 19.1 g (189 mmol) of triethylamine were placed in a 500 mL four-necked flask, and the system was cooled to 0 ° C under a nitrogen atmosphere. Maleic anhydride (14.8 g, 151 mmol) was stirred for 2 hours, and after returning to room temperature, the reaction was carried out for 6 hours. After the completion of the reaction, the mixture was cooled again to 10 ° C, and 200 mL of a 10% by mass aqueous sodium hydrogencarbonate solution was added thereto, and the mixture was stirred for 1 hour, and then the aqueous layer was separated, and the aqueous layer was washed with dichloroethane, cooled again to 10 ° C, and added to a mass of 10 The aqueous solution of hydrochloric acid was adjusted to a pH of 4 to 5 to precipitate a white solid. After the obtained solid was dissolved in ethyl acetate and extracted, the ethyl acetate layer was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was washed and washed with ethanol, and then recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7) to obtain 32.1 g (yield: 86%) of white solid.

Step 3 Synthesis of (Z)-3,5-Dinitrobenzyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutan-2-enoate

[化92]

Add 10.00 g (33.7 mmol) of 2-butenedioic acid (2Z)-, 3,5-dinitrobenzyl ester, 200 mL of THF, 1.71 g (16.9 mmol) of triethylamine, and 4 in a 300 mL four-neck flask. -(4,6-dimethoxy-1,3,5-triazin-2-yl)4-methoxymorpholine chloride n-hydrate (DMT-MM) 13.99 g (50.6 mmol), After stirring at room temperature for 30 minutes, 7.67 g (36.8 mmol) of 2-(t-butoxycarbonylamino)aniline was slowly added, and the reaction was carried out at room temperature for 6 hours under a nitrogen atmosphere.

After the completion of the reaction, the reaction solution was concentrated in a rotary distiller, and 200 ml of ethyl acetate was added thereto. After stirring at 50 ° C for 1 hour, the insoluble matter was filtered, and washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from methanol to give a pale yellow solid, 14.59 (yield: 89%).

Step 4 Synthesis of HC-08

[化93]

(Z)-3,5-Dinitrobenzyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutan-2- in a 300 mL four-neck flask 10.0 g (20.6 mmol) of enoate, 11.5 g (200 mmol) of reduced iron, 107 g of 10% by mass aqueous ammonium chloride solution (200 mmol of ammonium chloride), and 150 mL of toluene, under a nitrogen atmosphere at a mechanical stirrer at 70 The reaction was carried out while stirring at ° C for 1 day. After the completion of the reaction, ethyl acetate was added, and the iron was filtered, and the organic layer of the filtrate was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and activated carbon was added to the organic layer and stirred for a while. Thereafter, the activated carbon was removed by filtration, and the solvent was distilled off in a rotary distiller. Purification was carried out by column chromatography (mixed solvent of ethyl acetate and dichloroethane (3:7)), and dried under reduced pressure to give 8.0 g (yield: 91%) as a pale yellow glassy solid.

The ¹ H-NMR results of the obtained material are shown below. From this result, the HC-08 of the target was confirmed.

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-(t-butoxycarbonylamino)phenylamino)-4-oxobutan-2-enoate (HC-09) and 2-(2,4-diaminophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutyrate Synthesis of (HC-10)

[化94]

[化95]

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

[化96]

Add 13.6 g (134 mmol) of triethylamine, 50 mL of ethylene glycol, and 150 mL of tetrahydrofuran in a 300 mL four-neck flask, cool to 10 ° C under nitrogen, and add 25.0 g of 2,4-dinitrofluorobenzene (134 mmol). ), heating at 60 ° C and carrying out the reaction for 16 hours. After the completion of the reaction, the solvent was removed by a rotary distiller, ethyl acetate was added, and the mixture was washed with water and brine, and dried over magnesium sulfate. Thereafter, magnesium sulfate was removed by filtration, and the solvent was distilled off in a rotary distiller. Recrystallization was carried out by a mixed solvent of methanol and 2-propanol (3:7), and the mixture was washed with n-hexane to obtain 26.0 g (yield: 85%) of white solid.

Step 2 (1) Synthesis of 2-butenedioic acid (2E)-,2-(2,4-dinitrophenoxy)ethanol ester (method of isomerization by maleic anhydride)

[化97]

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

Step 2 (2) Synthesis of 2-butenedioic acid (2E)-,2-(2,4-dinitrophenoxy)ethanolate

[化98]

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

Step 3 (E)-(2,4-Dinitrophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutan-2-enoate Synthesis

[化99]

Add 2-0.0-(2E)-, 2-(2,4-dinitrophenoxy)ethanol ester 10.0 g (30.7 mmol), chloroform 100 mL, and DMF 30 mL to a 200 mL four-neck flask, followed by nitrogen. Under the environment, 4,3 g (33.8 mmol) of ethylene dichloride was slowly added at 0 ° C, and the mixture was returned to room temperature and stirred for 2 hours. Next, 9.6 g (46.1 mmol) of 2-(t-butoxycarbonylamino)aniline was added, and the reaction was carried out at room temperature for 24 hours under a nitrogen atmosphere. After the completion of the reaction, ethyl acetate was added and the organic layer was separated, and the organic layer was washed with water, 10% by mass aqueous hydrochloric acid, 10% by mass aqueous sodium hydrogen carbonate, water, and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7), and washed with ethanol to give 12.1 g (yield: 76%) of pale yellow solid.

Step 4 Synthesis of HC-09

[化100]

(E)-(2,4-Dinitrophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-side oxygen was added to a 200 mL four-neck flask Butyl-2-enoate 5.0 g (9.68 mmol), reduced iron 5.4 g (96.8 mmol), 10% by mass aqueous ammonium chloride solution 51.8 g (ammonium chloride 96.8 mmol), and toluene 70 mL, with a mechanical stirrer in nitrogen In the environment, the reaction was carried out while stirring at 70 ° C for 1 day. After the completion of the reaction, ethyl acetate was added, and the iron was filtered, and the organic layer of the filtrate was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, activated carbon was added to the organic layer, and stirred for a while. Thereafter, the activated carbon was removed by filtration, and the solvent was distilled off in a rotary distiller. Purification was carried out by column chromatography (mixed solvent of ethyl acetate and dichloroethane (5:5)), and dried under reduced pressure to give 3.5 g (yield: 80%) of pale yellow glassy solid.

The ¹ H-NMR results of the obtained material are shown below. From this result, the HC-09 of the target was confirmed.

¹ H NMR (400 MHz, CDCl ₃ ): 58.80 (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

[化101]

Add (E)-(2,4-dinitrophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-side oxygen to a 300 mL four-neck flask 5.0 g (9.68 mmol) of but-2-enoate, 50 mL of tetrahydrofuran, and 0.50 g of 10% palladium carbon were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and then the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (2:8) to yield 4.40 g (yield: 90%) of white solid.

The ¹ H-NMR results of the obtained material are shown below. From this result, the HC-09 of the target was confirmed.

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 compounds used in the present specification are abbreviated as follows.

<tetracarboxylic dianhydride>

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

PMDA: pyromellitic dianhydride

CBDE: 1,2,3,4-cyclobutane tetracarboxylic acid dimethyl ester

[化102]

<Diamine>

p-PDA: p-phenylenediamine

3-ABA: 3-aminobenzylamine

2,4-DAA: N,N-dipropylpropylamino 2,4-diaminobenzene

C14DAB: 4-tetradecyloxy-1,3-diamine benzene

C16DAB: 4-hexadecyloxy-1,3-diamine benzene

CAB-2: N-(4-(trans-4-n-heptylcyclohexyl)benzylidene)amino 2,4-diaminobenzene

PCH-7AB: N-(4-(trans-4-n-heptylcyclohexyl)phenoxy) 2,4-diamine benzene

m-TDA: m-tolyl 3,5-diaminobenzoate

HC-01: 2-(Tertibutoxycarbonylamino)-4-octylamine phenyl 3,5-diaminobenzoate

HC-02: N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide

HC-03: N-4-(4-pentylbenzylidenylamino)-3-tert-butoxycarbonylaminophenyl 2,4-diaminobenzamide

HC-04: N-4-(4-pentyl benzhydryloxy)-3-tert-butoxycarbonylaminophenyl 3,5-diaminobenzamide

HC-05: 2-methyl-6-t-butoxycarbonylaminophenyl 3,5-diaminobenzoate

HC-06: 4-(4-pentyl benzhydrylamino)-2-tert-butoxycarbonylamino 3,5-diaminobenzoate

HC-07: [4-(4-pentyl benzhydrylamino)-2-(t-butoxycarbonylamino)phenyl]2-(2,4-diaminophenyl)acetamidine amine

HC-08: (Z)-3,5-dinitrobenzyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobut-2-enoate

HC-09: (E)-(2,4-diaminophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutane-2 -enoate

HC-10: 2-(2,4-Diaminophenoxy)ethyl 4-(2-(t-butoxycarbonylamino)phenylamino)-4-oxobutyrate

HC-11: 4-(trans-4-pentylcyclohexanecarboxyamino)-3-(t-butoxycarbonylamino)phenyl 3,5-diaminobenzamide

HC-12: 4-[4-(trans-4-pentylcyclohexyl)benzamide]-3-(t-butoxycarbonylamino)phenyl 3,5-diaminobenzamide

[化103]

[化104]

[化105]

<condenser>

DMT-MM: 4-(4,6-dimethoxy-1,3,5-triazin-2-yl)4-methoxymorpholine chloride n-hydrate

<organic solvent>

NMP: N-methyl-2-pyrrolidone

γ-BL: γ-butyrolactone

BC: ethylene glycol dibutyl ether

DPM: dipropylene glycol monomethyl ether

<Measurement of molecular weight>

The molecular weight of the polymer obtained by the polymerization reaction is measured by a GPC (normal temperature gel permeation chromatography) apparatus, and the calculated value is calculated as a conversion value of polyethylene glycol and polyethylene oxide. Average molecular weight and weight average molecular weight.

GPC device: manufactured by Shodex (GPC-101)

Pipe column: made by Shodex company (inline of KD803, KD805)

Column temperature: 50 ° C

Dissolution: N,N-dimethylformamide (as additive, lithium bromide-hydrate (LiBr‧H2O) 30 mmol/L, phosphoric acid ‧ anhydrous crystal (o-phosphoric acid) 30 mmol/L, tetrahydrofuran (THF) ) is 10mL/L)

Flow rate: 1.0 mL / min

A standard sample for the calibration curve was prepared: TSK standard polyethylene oxide (molecular weight of about 900,000, 150,000, 100,000, 30,000) manufactured by Tosho Co., Ltd., and polyethylene glycol (molecular weight of about 12,000, 4,000, 1,000) manufactured by Polymer Laboratories.

<Measurement of yttrium imidation rate>

The oxime imidization ratio of the polyimine in the synthesis example was measured as follows. 20 mg of polyimine powder was placed in an NMR sample tube (NMR standard sampling tube manufactured by Kusano Scientific Co., Ltd.), and 0.53 mL of dimethylated dimethyl hydrazine (DMSO-d6, 0.05% by mass TMS mixture) was added, in ultrasonic waves. Make it completely soluble. The proton NMR at 500 MHz of this solution was measured by an NMR measuring instrument (JNW-ECA500) manufactured by JEOL DATUM. The ruthenium imidization ratio is determined by a proton derived from a structure which does not change before and after the imidization, and the peak integral value of the proton and the NH group derived from proline which is present in the vicinity of 9.5 to 10.0 ppm are used. The proton peak integral value is obtained by the following equation.

醯 imidization rate (%) = (1-α‧x/y) × 100

For the above formula, x represents the proton peak integral value of the NH group derived from proline, y represents the peak integral value of the reference proton, and α represents the proline acid when the polyproline (0% imidization ratio is 0%) The ratio of the number of reference protons corresponding to one NH matrix.

<The production of unit cell>

For the liquid crystal alignment treatment agents prepared in the examples and the comparative examples, a unit cell was produced as follows.

The liquid crystal alignment treatment agent was spin-coated on a glass substrate with a transparent electrode, dried on a hot plate at 80 ° C for 70 seconds, and then fired on a hot plate at 210 ° C for 10 minutes to form a film thickness of 100 nm. Coating film. For the rubbed liquid crystal aligning treatment, the coating film surface was rubbed with a rubbing device having a roll diameter of 120 mm, and rubbed under the conditions of a roll rotation speed of 1000 rpm, a roll speed of 50 mm/sec, and a pushing amount of 0.3 mm to obtain a coating. A substrate having a liquid crystal alignment film. The liquid crystal alignment treatment by light was carried out by irradiating a linearly polarized UV light (UV wavelength: 313 nm, 500 mJ equivalent) on the coating film surface at a tilt of 40° with respect to the normal of the plate.

Two sheets of the substrate with the liquid crystal alignment film subjected to the liquid crystal alignment treatment were prepared, and a spacer of 6 μm was spread on the surface of the liquid crystal alignment film, and then the sealing agent was applied thereon to bond the other substrate to the liquid crystal. Oriented film surface, the rubbing direction is straight (twisted nematic cell) or the direction of polarization of the paste-forming synthesis and irradiation is parallel (vertical orientation mode), and the hollow cell is made by hardening the sealant. In the cell, a liquid crystal MLC-2003 (manufactured by Mok Corporation) was injected into the twisted nematic cell by a vacuum injection method, and liquid crystal MLC-6608 (manufactured by Mok Corporation) was injected in a vertical alignment mode to block the injection. A twisted nematic cell is obtained after the inlet.

The physical property measurement and the characteristic evaluation method of each of the produced unit cells are as follows.

Further, Tables 2 to 4 show the results of the compositions of the liquid crystal aligning agents of Examples 1 to 9 and Comparative Examples 1 to 3, the physical properties of each of the liquid crystal alignment films, and the evaluation of characteristics.

<Friction tolerance evaluation>

When the substrate having the liquid crystal alignment film was produced by the method described in the above-mentioned <Cell Cell Production>, the amount of the rubbing condition was changed to 0.5 mm, and the liquid crystal alignment film for the evaluation of the friction resistance was produced. A confocal laser microscope was observed and the following evaluation was performed.

○: No shaving or frictional damage was observed.

△: A shaving or a rubbing injury was observed.

×: Film peeling or scratching was visually observed.

<Measurement of the tilt angle>

The twisted nematic cell or the antiparallel cell produced by the method described in the above-mentioned "cell preparation" was heated at 105 ° C for 5 minutes, and then the tilt angle was measured. The tilt angle was measured by "Axo Scan" manufactured by Axo Metrix Co., Ltd. using a Mueller Matrix method.

<Measurement of Voltage Retention Rate (VHR) and Backlite aging Resistance>

The voltage holding ratio in the initial state of the unit cell produced by the method described in the above-mentioned "cell fabrication" and the backlight aging (the cell is mounted on the backlight for the LCD panel and driven by AC10V in 2 weeks) Determination of voltage retention. The voltage holding ratio was measured by applying a voltage of 4 V for 60 μs at a temperature of 90 ° C, and measuring the voltage after 16.67 ms, and calculating the voltage holding degree as the voltage holding ratio. Further, the voltage holding ratio measuring device (VHR-1) manufactured by TOYO Corporation was used for the measurement of the voltage holding ratio.

(Embodiment 10)

In a 50 mL four-necked flask, 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 as a diamine component, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-1) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-1) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-1) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-1. The polyamic acid had a number average molecular weight of 14,300 and a weight average molecular weight of 41,200.

(Example 11)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.80 g (1.5 mmol) of HC-02, and 28.6 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-2) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-2) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-2) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-2. The polyamic acid had a number average molecular weight of 12,300 and a weight average molecular weight of 26,700.

(Embodiment 12)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.80 g (1.5 mmol) of HC-03, and 28.6 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-3) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-3) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-3) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-3. The polyamine had a number average molecular weight of 9,800 and a weight average molecular weight of 26,900.

(Example 13)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.80 g (1.5 mmol) of HC-04, and 28.6 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-4) concentration of 15% by mass.

30 g of this polyaminic acid (PAA-4) solution was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-4) of 6 mass% and an NMP of 74. A solution of mass % and BC of 20% by mass was used to obtain a liquid crystal aligning agent-4. The polyamic acid had a number average molecular weight of 11,300 and a weight average molecular weight of 25,800.

(Example 14)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.54 g (1.5 mmol) of HC-05, and 27.1 g of NMP were placed, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-5) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-5) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-5) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-5. The polyamic acid had a number average molecular weight of 12,600 and a weight average molecular weight of 30,200.

(Example 15)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.80 g (1.5 mmol) of HC-06, and 28.6 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-6) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-6) was transferred to a 100 mL Erlenmeyer flask, and NMP 30.0 g and BC 15.0 g were added and diluted to obtain a polyamine acid (PAA-6) of 6 mass% and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-6. The polyamic acid had a number average molecular weight of 12,700 and a weight average molecular weight of 27,700.

(Embodiment 16)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.82 g (1.5 mmol) of HC-07, and 28.7 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-7) concentration of 15% by mass.

30 g of the solution of the polyaminic acid (PAA-7) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-7) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-7. The polyamine has a number average molecular weight of 10,200 and a weight average molecular weight of 26,500.

(Example 17)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.71 g (1.5 mmol) of HC-10, and 28.1 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmoj) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-8) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-8) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-8) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-8. The polyamine had a number average molecular weight of 9,900 and a weight average molecular weight of 23,500.

(Embodiment 18)

2.00 g (5.60 mmol) of HC-05 and 17.5 g of NMP as a diamine component were placed in a 50 mL four-necked flask, and the mixture was cooled to about 10 °C. Next, CBDA (1.08 g, 5.49 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-9) concentration of 15% by mass.

15 g of the solution of the polyamic acid (PAA-9) was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.5 g of BC were added and diluted to obtain a polyamine acid (PAA-9) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-9. The polyamic acid had a number average molecular weight of 21,200 and a weight average molecular weight of 50,900.

(Embodiment 19)

2.00 g (4.70 mol) of HC-08, PCH-7AB 0.45 g (1.17 mmol) and NM 20.3 g as a diamine component were placed in a 50 mL four-necked flask, and the mixture was cooled to about 10 °C. Next, 1.13 g (5.81 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-10) concentration of 15% by mass.

20 g of the solution of the polyamic acid (PAA-10) was transferred to a 100 mL Erlenmeyer flask, and 20.0 g of NMP and 10.0 g of BC were added and diluted to obtain a polyglycine (PAA-10) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-10. The polyamine had a number average molecular weight of 13,300 and a weight average molecular weight of 428,00.

(Embodiment 20)

2.00 g (4.38 mol) of HC-09, PCH-7AB 0.45 g (1.10 mmol) and NMP 19.7 g as a diamine component were placed in a 50 mL four-necked flask, and the mixture was cooled to about 10 °C. Next, CBDA 1.06 g (5.43 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-11) concentration of 15% by mass.

20 g of the solution of the polyaminic acid (PAA-11) was transferred to a 100 mL Erlenmeyer flask, and 20.0 g of NMP and 10.0 g of BC were added and diluted to obtain a polyglycine (PAA-11) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-11. The polyamine has a number average molecular weight of 10,700 and a weight average molecular weight of 35,300.

(Example 21)

To a 100 mL four-necked flask were added 3-ABA 0.307 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), 1.00 g (1.89 mol) of HC-02, and NMP 12.3 g as a diamine component. , cooled to about 10 ° C. Next, PMDA 0.412 g (1.89 mmol) was added, and the mixture was returned to room temperature, and allowed to react for 1 hour under a nitrogen atmosphere. Further, CBDA 0.964 g (4.91 mmol) was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a polyglycine (PAA-12) concentration of 20% by mass.

To 15.0 g of a solution of polyaminic acid (PAA-12), 22.5 g of NMP was added and diluted, and then 1.96 g of acetic anhydride and 0.84 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After the reaction solution was cooled to room temperature, it was slowly poured while stirring at 150 mL of methanol cooled at about 10 ° C to precipitate a solid. The precipitated solid was collected, washed with a total of two times of 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a tan powder of polyimine (SPI-1). The polyimine had a number average molecular weight of 11,200 and a weight average molecular weight of 30,800. Further, the hydrazine imidation ratio was 89%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-1), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-1) of 5% by mass and a γ-BL of 65 mass. Liquid crystal aligning agent -12 having a %, BC of 15% by mass and a DPM of 15% by mass.

(Example 22)

To a 100 mL four-necked flask, 3-ABA 0.307 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), 1.00 g (1.89 mol) of HC-03, and NMP 12.3 g were added as a diamine component. , cooled to about 10 ° C. Next, PMDA 0.412 g (1.89 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, CBDA 0.964 g (4.91 mmol) was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a polyglycine (PAA-13) concentration of 20% by mass.

To 15.0 g of a polyaminic acid (PAA-13) solution, 22.5 g of NMP was added and diluted, and then 1.96 g of acetic anhydride and 0.84 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 150 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, and further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain an orange powder of polyimine (SPI-2). The polyimine had a number average molecular weight of 9,800 and a weight average molecular weight of 23,500. The yield of hydrazine was 89%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-2), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-2) of 5% by mass and a γ-BL of 65 mass. Liquid crystal aligning agent-13 having a %, BC of 15% by mass and a DPM of 15% by mass.

(Example 23)

To a 100 mL four-necked flask, 3-ABA 0.308 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), 1.00 g (0.89 mol) of HC-04, and NMP 12.3 g were added as a diamine component. , cooled to about 10 ° C. Next, PMDA 0.412 g (1.89 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, CBDA 0.964 g (4.91 mmol) was reacted at room temperature under a nitrogen atmosphere for 16 hours, and a solution of polyglycine (PAA-14) at a concentration of 20% by mass.

To 15.0 g of a solution of polyaminic acid (PAA-14), 22.5 g of NMP was added and diluted, and then 1.96 g of acetic anhydride and 0.84 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 150 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, and further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a tan powder of polyimine (SPI-3). The polyimine had a number average molecular weight of 11,800 and a weight average molecular weight of 25,100. Further, the sulfhydrylation rate was 88%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-3), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-3) of 5% by mass and a γ-BL of 65 mass. %, BC was 15% by mass, and DPM was 15% by mass of the liquid crystal aligning agent-14.

(Example 24)

3-ABA 0.308 g (2.52 mmol), 2,4-DAA 0.384 g (1.89 mmol), 1.00 g (0.89 mol) of HC-06, and NMP 12.3 g as a diamine component were placed in a 100 mL four-necked flask. , cooled to about 10 ° C. Next, PMDA 0.412 g (1.89 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, CBDA 0.964 g (4.91 mmol) was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a concentration of polyglycine (PAA-15) of 20% by mass.

To 15.0 g of a solution of polyaminic acid (PAA-15), 22.5 g of NMP was added and diluted, and then 1.96 g of acetic anhydride and 0.84 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 150 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, and further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a tan powder of polyimine (SPI-4). The polyimine had a number average molecular weight of 13,200 and a weight average molecular weight of 29,400. Further, the sulfhydrylation rate was 85%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-4), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-4) of 5% by mass and a γ-BL of 65 mass. Liquid crystal aligning agent -15 having a %, BC of 15% by mass and a DPM of 15% by mass.

(Embodiment 25)

3-ABA 0.298 g (2.44 mmol), 2,4-DAA 0.372 g (1.83 mmol), 1.00 g (0.83 mol) of HC-04, and NMP 12.0 g as a diamine component were placed in a 100 mL four-neck flask. , cooled to about 10 ° C. Next, PMDA 0.399 g (1.83 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, CBDA 0.933 g (4.76 mmol) was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a polyglycine (PAA-16) concentration of 20% by mass.

To 15.0 g of a solution of polyamic acid (PAA-16), 22.5 g of NMP was added and diluted, and then 1.94 g of acetic anhydride and 0.83 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 150 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, and further dispersed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a tan powder of polyimine (SPI-5). The polyimine had a number average molecular weight of 10,700 and a weight average molecular weight of 22,800. The yield of hydrazine was 87%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-5), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-5) of 5% by mass and a γ-BL of 65 mass. %, BC was 15% by mass, and DPM was 15% by mass of the liquid crystal aligning agent-16.

(Example 26)

2.78 g (9.12 mmol) of CBDE, 0.813 g (7.52 mmol) of p-PDA as a diamine component, 1.00 g (1.88 mmol) of HC-02, 30.7 g of NMP, and triethylamine 0.475 were added to a 100 mL four-necked flask. g (4.70 mmol), cooled to about 10 °C. Next, 7.80 g (28.2 mmol) of DMT-MM was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycolate (PAE-1) concentration of 12% by mass.

To the solution of the polyaminic acid (PAE-1), 34.9 g of NMP was added, and the mixture was poured while stirring to 500 mL of methanol at about 10 ° C to precipitate a solid. The precipitated solid was collected, and the mixture was washed twice with 300 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a white powder of polyamine (PAE-1). The polyperurethane had a number average molecular weight of 15,300 and a weight average molecular weight of 38,800.

18.0 g of γ-BL was added to 2.00 g of polyperurethane (PAE-1), and the mixture was stirred at room temperature for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Furthermore, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidene (PAE-1) of 5 mass% and a γ-BL of 65 mass. Liquid crystal aligning agent-17 having a %, BC of 15% by mass and a DPM of 15% by mass.

(Comparative Example 1)

To a 50 mL four-necked flask, 1.45 g (13.5 mol) of p-PDA as a diamine component, 0.52 g (1.50 mmol) of C16DAB, and 28.2 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-17) concentration of 15% by mass.

30 g of the solution of the poly-proline (PAA-17) was transferred to a 100 mL Erlenmeyer flask, and NMP 30.0 g and BC 15.0 g were added and diluted to obtain a polyamine acid (PAA-17) of 6 mass% and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-18. The polyamic acid had a number average molecular weight of 18,300 and a weight average molecular weight of 43,200.

(Comparative Example 2)

To a 50 mL four-necked flask, 1.45 g (13.5 mol) of p-PDA as a diamine component, 0.64 g (1.50 mmol) of CAB-2, and 28.2 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-18) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-18) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyglycine (PAA-18) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-19. The polyamic acid had a number average molecular weight of 97,00 and a weight average molecular weight of 19,200.

(Comparative Example 3)

MtDA 2.00 g (8.26 mmol) and NMP 20.3 as a diamine component were placed in a 50 mL four-necked flask, and cooled to about 10 °C. Next, 1.59 g (8.09 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-19) concentration of 15% by mass.

15 g of the solution of the polyamic acid (PAA-19) was transferred to a 50 mL Erlenmeyer flask, and 15.0 g of NMP and 7.5 g of BC were added and diluted to obtain a polyamine acid (PAA-19) of 6 mass% and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-20. The polyamine had a number average molecular weight of 22,000 and a weight average molecular weight of 49,600.

(Comparative Example 4)

3-ABA 0.508 g (4.16 mmol), 2,4-DAA 0.634 g (3.12 mmol), C14DAB 1.00 g (3.12 mmol), and NMP 17.7 g as a diamine component were placed in a 100 mL four-neck flask, and cooled to About 10 ° C. Next, PMDA 0.680 g (3.12 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, 1.59 g (8.11 mmol) of CBDA was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a polyamine acid (PAA-20) concentration of 20% by mass.

To 20.0 g of a solution of polyaminic acid (PAA-20), 30.0 g of NMP was added and diluted, and then 3.01 g of acetic anhydride and 1.29 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 200 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, washed with a total of two times of 150 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a tan powder of polyimine (SPI-6). The polyimine had a number average molecular weight of 10,700 and a weight average molecular weight of 22,800. Further, the sulfhydrylation rate was 88%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-6), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidimide (SPI-6) of 5% by mass and a γ-BL of 65. A solution having a mass %, a BC of 15% by mass, and a DPM of 15% by mass gave a liquid crystal aligning agent-21.

(Comparative Example 5)

3-ABA 0.386 g (3.16 mmol), 2,4-DAA 0.482 g (2.37 mmol), 1.00 g (2.37 mmol) of CAB-2, and NMP 14.4 g as a diamine component were added to a 100 mL four-neck flask. , cooled to about 10 ° C. Next, PMDA 0.517 g (2.37 mmol) was added, and the mixture was returned to room temperature, and the reaction was carried out for 1 hour under a nitrogen atmosphere. Further, 1.21 g (6.16 mmol) of CBDA was added, and the mixture was reacted at room temperature under a nitrogen atmosphere for 16 hours to obtain a solution having a polyglycine (PAA-21) concentration of 20% by mass.

To 15.0 g of a solution of polyaminic acid (PAA-21), 22.5 g of NMP was added and diluted, and then 2.10 g of acetic anhydride and 0.90 g of pyridine were added, and the reaction was carried out at 50 ° C for 3 hours. After cooling the reaction solution to room temperature, it was poured into 150 mL of methanol cooled to about 10 ° C, and the mixture was poured while stirring to precipitate a solid. The precipitated solid was collected, and further washed and washed twice with 100 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a yellow-orange powder of polyimine (SPI-7). The polyimine had a number average molecular weight of 9,900 and a weight average molecular weight of 28,800. Further, the hydrazine imidation ratio was 91%.

γ-BL 18.0 g was added to 2.00 g of polyimine (SPI-7), and the mixture was stirred at 50 ° C for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidene (SPI-7) of 5% by mass and a γ-BL of 65. A solution having a mass %, a BC of 15% by mass, and a DPM of 15% by mass gave a liquid crystal aligning agent-22.

(Comparative Example 6)

To a 50 mL four-necked flask, 1.00 g (9.28 mol) of m-PDA as a diamine component, 0.83 g (2.32 mmol) of PCH-7AB, and 23.3 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.23 g (11.4 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycine (PAA-22) concentration of 15% by mass.

20 g of the solution of the polyamic acid (PAA-22) was transferred to a 100 mL Erlenmeyer flask, and 20.0 g of NMP and 10.0 g of BC were added and diluted to obtain a polyglycine (PAA-22) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-23. The polyamic acid had a number average molecular weight of 16,300 and a weight average molecular weight of 40,200.

(Comparative Example 7)

CBDE 2.98 g (11.4 mmol), p-PDA 1.02 g (9.44 mmol) as a diamine component, CAB-21.00 g (2.36 mmol), NMP 36.6 g, and triethylamine 0.60 g were placed in a 100 mL four-necked flask. (5.90 mmol), cooled to about 10 °C. Next, 9.80 g (35.4 mmol) of DMT-MM was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyglycolate (PAE-2) concentration of 12% by mass.

To the solution of the polyaminic acid (PAE-2), 41.7 g of NMP was added, and the mixture was poured while stirring to 500 mL of methanol at about 10 ° C to precipitate a solid. The precipitated solid was collected, and the mixture was washed twice with 300 mL of methanol, and dried under reduced pressure at 100 ° C to obtain a pale pink powder of polyamine (PAE-2). The polyglycolate had a number average molecular weight of 13,200 and a weight average molecular weight of 35,700.

18.0 g of γ-BL was added to 2.00 g of polyperurethane (PAE-2), and the mixture was stirred at room temperature for 20 hours. At the end of the agitation, the polyimine was completely dissolved. Further, γ-BL 8.0 g, BC 6.0 g, and DPM 6.0 g were added to the solution, and the mixture was stirred at 50 ° C for 20 hours to obtain a polyamidene (PAE-2) of 5% by mass and a γ-BL of 65. A solution having a mass %, a BC of 15% by mass, and a DPM of 15% by mass gave a liquid crystal aligning agent-24.

When Comparative Examples 10 to 18 and Comparative Examples 1 and 2 were compared, it was found that the frictional resistance was improved in Examples 10 to 18, the VHR was high, and the backlight aging resistance was excellent.

When Example 17 was compared with Comparative Example 3, it was found that Comparative Example 3 (structure in which no cyclization reaction occurred) was smaller than the inclination angle of Example 17, and the improvement in friction resistance and aging resistance of VHR was also excellent.

When Examples 19 and 20 were compared with Comparative Example 6, it was found that the tilting expression was confirmed in Examples 19 and 20. The liquid crystal aligning agent was useful in the photo-alignment method.

When Comparative Examples 4 and 5 were compared with Comparative Examples 4 and 5, it was found that in Comparative Examples 4 and 5, when the liquid crystal alignment treatment agent was applied onto the substrate, pinholes or tilt unevenness were confirmed, but Example 21 was obtained. ～25 was excellent in printability, and such a defect was not confirmed, and the tilting performance was confirmed, and the effect of improving the backlight aging resistance of VHR was also confirmed. .

When Example 26 was compared with Comparative Example 7, it was found that Example 26 was excellent in printability, and the friction resistance and the backlight aging resistance of VHR were improved.

<Example 27> Synthesis of 4-(trans-4-pentylcyclohexanecarboxyamino)-3-(t-butoxycarbonylamino)phenyl 3,5-diaminobenzimidamide (HC-11) synthesis

[化106]

Step 1 Synthesis of 4-(trans-4-pentylcyclohexanecarboxyguanamine)-3-(t-butoxycarbonylamino)nitrobenzene

[107]

In a 100 mL eggplant-shaped flask with a tube, weighed 5.16 g (20.0 mmol) of trans-4-pentylcyclohexanecarboxylic acid, added 50 mL of THF and dissolved, and slowly dripped into the ice bath in the ice bath. 3.33 g (28.0 mmol) of a 50% by mass THF solution. Thereafter, the temperature was returned to room temperature, and the reaction was carried out for 2 hours to give a 4-pentylcyclohexanecarboxylic acid chloride.

On the other hand, 5.07 g (20.0 mmol) of 3-t-butoxycarbonylamino-4-aminonitrobenzene was weighed in a 200 mL four-necked flask, and 50.0 mL of THF and 4.05 g of triethylamine were added ( 40.0 mmol), the previously prepared 4-pentylcyclohexanecarboxylic acid chloride was dropped into the ice bath at 10 ° C or less under a nitrogen atmosphere. Thereafter, the temperature was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere.

After the completion of the reaction, ethyl acetate was added, and the mixture was washed in the order of 10% by mass aqueous sodium hydrogencarbonate solution, acetic acid water, purified water, and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (6:4) to give 5.31 g (yield: 61%) as a white solid.

Step 2 Synthesis of 4-(trans-4-pentylcyclohexanecarboxyguanamine)-3-(t-butoxycarbonylamino)aniline

[化108]

To a 100 mL four-necked flask was added 4-(trans-4-pentylcyclohexylcarboxyguanamine)-3-(t-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 were refluxed under a nitrogen atmosphere for 24 hours. After the completion of the reaction, 100 mL of ethyl acetate was added, and a 10% by mass aqueous sodium hydrogencarbonate solution was added thereto, 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. The anhydrous sodium sulfate was filtered and removed, and the solvent was removed by a rotary distillation apparatus to obtain 3.95 g (yield: 99%) as a yellow solid.

Step 3 Synthesis of 4-(trans-4-pentylcyclohexanecarboxyguanamine)-3-(t-butoxycarbonylamino)phenyl 3,5-dinitrobenzamide

[化109]

4-(trans-4-pentylcyclohexanecarboxyguanamine)-3-(t-butoxycarbonylamino)phenylamine 4.79 g (11.9 mmol), tetrahydrofuran 80 mL, and pyridine 1.10 were added to a 200 mL four-neck flask. g (13.9 mmol), under nitrogen atmosphere, 10 ° C below the ice bath, slowly drip 3,5-dinitrobenzoic acid chloride 3.22 g (14.0 mmol) in 10% by mass THF solution, after returning to room temperature The reaction was carried out for 24 hours. After cooling, the inside of the system was brought to 0 ° C, and then 5.8 g (14.0 mmol) of 3,5-dinitrobenzhydryl chloride was added, and the mixture was stirred at room temperature. After the completion of the reaction, the solvent was removed by a rotary distiller, and ethyl acetate was added thereto, and a 10% by mass aqueous sodium carbonate solution was washed with water and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9) to give 5.26 g (yield: 74%) as pale yellow solid.

Step 4 Synthesis of HC-11

[110]

Add 4-(trans-4-pentylcyclohexanecarboxyguanamine)-3-(t-butoxycarbonylamino)phenyl 3,5-dinitrobenzamide 5.00 in a 300 mL four-neck flask g (8.37 mmol), tetrahydrofuran 30 mL, ethanol 30 mL, and 5% palladium carbon 0.50 g were stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9), and then washed with n-hexane to afford 4.20 g (yield: 93%) as a gray solid.

The ¹ H-NMR results of the obtained solid are shown below. From this result, the HC-10 of the target substance was confirmed.

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), 7.48-7.7 .46(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-(t-butoxycarbonylamino)phenyl 3,5-diaminobenzimidamide (HC Synthesis of -12)

[111]

Step 1 Synthesis of 4-[(trans-4-pentylcyclohexyl)benzamide]-3-tributoxycarbonylaminonitrobenzene

[化112]

In a 100 mL eggplant-shaped flask with a tube, weighed 5.07 g (22.0 mmol) of 4-(trans-4-pentylcyclohexyl)benzoic acid, added 50 mL of THF, and 1 mL of DMF, and slowly dripped in an ice bath. 3.33 g (28.0 mmol) of hydrazine chloride was returned to room temperature and reacted for 2 hours to give 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 in a 200 mL four-necked flask, and 50.0 mL of THF and 2.43 g (24.0 mmol) of triethylamine were added. The previously prepared 4-(trans-4-pentylcyclohexyl)benzoic acid chloride was dropped into the ice bath at 10 ° C or lower, and the mixture was returned to room temperature under nitrogen atmosphere for 24 hours.

After the completion of the reaction, ethyl acetate was added, and the mixture was washed with a 10% by mass aqueous sodium hydrogencarbonate solution, acetic acid water, pure water, and saturated brine. Thereafter, it was dried over magnesium sulfate, magnesium sulfate was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (3:7) to yield 6.03 g (yield: 60%) as a white solid.

Step 2 Synthesis of 4-[(trans-4-pentylcyclohexyl)benzamide]-3-(t-butoxycarbonylamino)aniline

[化113]

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

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

[化114]

4-[(trans-4-pentylcyclohexyl) benzhydryl decylamine]-3-(t-butoxycarbonylamino)phenylamine 5.94 g (12.4 mmol) and tetrahydrofuran 80 mL were added to a 200 mL four-neck flask. 1.10 g (13.9 mmol) of pyridine and a 10 mass% THF solution of 3.22 g (14.0 mmol) of 3,5-dinitrobenzoic acid chloride were slowly added dropwise under ice at 10 ° C in an ice bath. Thereafter, the temperature was returned to room temperature, and the reaction was carried out for 24 hours. After the completion of the reaction, the solvent was removed in a rotary distiller, and the residue was washed with methanol, and then recrystallized from a mixture solvent of ethyl acetate and n-hexane (1:9) to obtain 7.82 g of a pale yellow solid (yield 94%). ).

Step 4 Synthesis of HC-11

[化115]

4-[(trans-4-pentylcyclohexyl)benzamide)-3-(t-butoxycarbonylamino)phenyl 3,5-dinitrobenzoate in a 300 mL four-necked flask 6.00 g (8.9 mmol) of decylamine was dissolved in 60 mL of tetrahydrofuran, and 0.60 g of 5% palladium carbon was added thereto, and the mixture was stirred at room temperature under a hydrogen atmosphere. After the completion of the reaction, palladium carbon was removed by filtration, and the solvent was distilled off using a rotary distiller. The residue was recrystallized from a mixed solvent of ethyl acetate and n-hexane (1:9), and then washed with n-hexane to obtain 5.45 g (yield: 99%) as a gray solid.

The ¹ H-NMR results of the obtained solid are shown below. From this result, the HC-10 of the target substance was confirmed.

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. (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)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.81 g (1.5 mmol) of HC-11, and 28.6 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-23) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-23) was transferred to a 100 mL Erlenmeyer flask, and NMP 30.0 g and BC 15.0 g were added and diluted to obtain a polyglycine (PAA-23) of 6 mass% and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-25. The polyamic acid had a number average molecular weight of 10,100 and a weight average molecular weight of 22,500.

(Embodiment 30)

To a 50 mL four-necked flask, 1.46 g (13.5 mol) of p-PDA as a diamine component, 0.94 g (1.5 mmol) of HC-12, and 29.4 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.79 g (14.3 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-24) concentration of 15% by mass.

30 g of the solution of the polyamic acid (PAA-24) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-24) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent -26. The polyamic acid had a number average molecular weight of 13,700 and a weight average molecular weight of 28,200.

(Example 31)

To a 50 mL four-necked flask, 1.06 g (10.5 mol) of p-PDA as a diamine component, 2.48 g (4.5 mmol) of HC-11, and 36.4 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.88 g (14.7 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere, and the concentration of polyamine acid (PAA-25) was 15% by mass.

30 g of the solution of the polyamic acid (PAA-25) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-25) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-27. The polyamine had a number average molecular weight of 17,200 and a weight average molecular weight of 38,900.

(Example 32)

To a 50 mL four-necked flask, 1.06 g (10.5 mol) of p-PDA as a diamine component, 2.82 g (4.5 mmol) of HC-12, and 38.3 g of NMP were added, and the mixture was cooled to about 10 °C. Next, 2.88 g (14.7 mmol) of CBDA was added, and the mixture was returned to room temperature, and the reaction was carried out for 24 hours under a nitrogen atmosphere to obtain a solution having a polyamine acid (PAA-26) concentration of 15% by mass.

30 g of the solution of the polyaminic acid (PAA-26) was transferred to a 100 mL Erlenmeyer flask, and 30.0 g of NMP and 15.0 g of BC were added and diluted to obtain a polyamine acid (PAA-26) of 6 mass%, and NMP was A solution of 74% by mass and BC of 20% by mass was used to obtain a liquid crystal aligning agent-28. The polyamine had a number average molecular weight of 19,600 and a weight average molecular weight of 42,200.

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

<Side chain diamine solubility test>

As a test for comparing the solubility of the monomer, 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, and the dissolution was investigated. The test evaluation criteria are as follows

Dissolved: ○

By residue: ×

Industrial availability

The liquid crystal display element produced by using the liquid crystal alignment treatment agent of the present invention can be used as a TN liquid crystal display element, an STN liquid crystal display element, or a TFT liquid crystal display element, in addition to a high-definition liquid crystal television having high signal quality and large screen. A VA liquid crystal display element, an IPS liquid crystal display element, an OCB liquid crystal display element, etc. are useful.

The specification, the scope of the patent application, and the summary of the Japanese Patent Application No. 2010-150054, filed on Jun.

Claims (21)

A liquid crystal aligning agent characterized by comprising a polyimine precursor selected from the reaction of a diamine component containing a diamine of the following formula [1] and a tetracarboxylic dianhydride, and a precursor of the polyimine At least one polymer of a group of polyimine obtained by imidization of hydrazine; (wherein, X represents an organic group represented by the following formula [2], and Y ₁ and Y ₂ are independent, and represents a benzene ring or a cyclohexane ring; and p and q are independent, and represent an integer of 0 or 1, and S ₁ , S ₂ is independent and 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; and R ₁ represents hydrogen, a fluorine atom, and an alkyl group having 1 to 22 carbon atoms. a fluoroalkyl group or a steroid group having 1 to 22 carbon atoms; Wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents a thermal detachment group which changes -NHA to -NH ₂ by thermal post- detachment, and B ₁ represents a group selected from -CH _a divalent organic group of 2-, -O-, -NH-, and -S-; n represents 0 or 1; the bonding direction of X is not limited). The liquid crystal aligning agent of the first aspect of the invention, wherein the content of the diamine of the formula [1] in the diamine component is 5 to 95 mol%. The liquid crystal aligning agent of the first aspect or the second aspect of the invention, wherein the A of the above formula [2] is a heat-releasing group obtained by heating after detaching from 150 ° C to 300 ° C. The liquid crystal directional treatment agent according to claim 1 or 2, wherein A of the above formula [2] is a third-stage butoxycarbonyl group represented by the formula [3]; The liquid crystal aligning agent of Claim 1 or 2, wherein A of the above formula [2] is a benzyloxycarbonyl group, a 9-fluorenylmethyloxycarbonyl group, or an allyloxycarbonyl group. The liquid crystal aligning agent according to the first or second aspect of the invention, wherein C ₁ and C ₂ of the above formula [2] are a divalent organic group represented by the following formula [6]; [Chemical 4]-S ₃ -R ₂ -S ₄ -R ₃ -[6] (wherein, S ₃ and S ₄ are independent and represent a divalent linking group, and R ₂ and R ₃ are independent, and represent a single bond or a carbon number of 1 to 20 Valence hydrocarbon group). The liquid crystal aligning agent according to claim 1 or 2, wherein [-S ₄ -R ₃ -] of the above formula [6] is represented by the following formula [4], and C ₁ and C ₂ are Any structure having the formula [4]; (wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, and R ₁₀ represents a carbon number of 1~ a divalent hydrocarbon of 6; the structure of the olefin of the formula [4] may be either E or Z; the bond shown by a broken line is a benzene ring or a combination of C ₂ bonded to C _{1 of} the formula [2]. Carbonyl carbon). The liquid crystal aligning agent according to Item 1 or 2 of the patent application, wherein n=0 in the above formula [2]. A liquid crystal aligning agent according to claim 1 or 2, wherein in the above formula [2], C ₁ represents a single bond. The liquid crystal aligning agent according to claim 1 or 2, wherein in the above formula [2], B ₁ represents -O- or NH-. The liquid crystal aligning agent according to claim 7, wherein in the above formula [4], B ₂ represents -O- or NH-. The liquid crystal aligning agent according to claim 1 or 2, wherein the diamine represented by the above formula [1] is any one of the following formulas [1-a] to [1-k]; A liquid crystal aligning film characterized by using the liquid crystal aligning agent according to any one of claims 1 to 12. A liquid crystal alignment film which is a liquid crystal alignment film using the liquid crystal alignment treatment agent according to any one of the first to twelfth aspects of the invention, which is characterized in that the orientation treatment is performed by light irradiation. A liquid crystal display element characterized by comprising a liquid crystal alignment film according to item 13 or item 14 of the patent application. A diamine characterized by having a structure represented by the following formula [1], (wherein, X represents an organic group represented by the following formula [2], and Y ₁ and Y ₂ are independent, and represents a benzene ring or a cyclohexane ring; and p and q are independent, and represent an integer of 0 or 1, and S ₁ , S ₂ is independent and represents a single bond or a divalent linking group. When p=0, S ₁ is a single bond, when q=0, S ₂ is a single bond, and R ₁ represents hydrogen, a fluorine atom, and an alkyl group having 1 to 22 carbon atoms. a fluoroalkyl group or a steroid group having 1 to 22 carbon atoms; (wherein C ₁ and C ₂ are independent and represent a single bond or a divalent organic group, A represents an organic group obtained by thermal detachment, and B ₁ represents a group selected from -CH ₂ -, -O-, -NH- And the divalent organic group of -S-, n represents 0 or 1, and the bonding direction of X is not limited). For example, the diamine of the general item 16 is applied, wherein in the formula [2], A is a third-stage butoxycarbonyl group represented by the formula [3]; For example, in the formula [2], C ₁ and C ₂ are a divalent organic group represented by the following formula [6]; [Chemical 11]-S ₃ -R ₂ -S ₄ -R ₃ -[6] (wherein, S ₃ and S ₄ are independent and represent a divalent linking group, and R ₂ and R ₃ are independent, and represent a single bond or a divalent hydrocarbon group having 1 to 20 carbon atoms; ). The diamine of claim 16 or 17, wherein [-S ₄ -R ₃ -] of the above formula [6] is represented by the following formula [4], and any of C ₁ and C ₂ Is a structure having the formula [4]; (wherein B ₂ represents a divalent organic group selected from the group consisting of a single bond, a phenyl group, -CH ₂ -, -O-, -NH-, -NR ₁₀ -, and -S-, and R ₁₀ represents a carbon number of 1~ a divalent hydrocarbon of 6; the structure of the olefin of the formula [4] may be either E or Z; the bond shown by a broken line is a benzene ring or a combination of C ₂ bonded to C _{1 of} the formula [2]. Carbonyl carbon). a diamine characterized by any one of the following formulas [1-a] to [1-k]; A polyimine which is obtained by using a diamine of any one of the 16th to 20th aspects of the patent application as a raw material, a polyamine, or a polyamic acid. Amination of the resulting person.