TWI391375B - Diamine, liquid crystal aligning agent, liquid crystal alignment layer, and liquid crystal display device - Google Patents

Description

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

This invention relates to a novel diamine and a polyamic acid obtained using the same, further to the use of the polyaminic acid. In addition, the term "liquid crystal aligning agent" in the present invention means a polymer-containing composition used to form a liquid crystal alignment film.

The liquid crystal display element is mostly used for a display portion of a mobile phone, a notebook personal computer or a desktop personal computer screen, and a view finder and a projection display for a video camera. Among various display devices such as (projection display), it has recently been used in television. Moreover, the liquid crystal display element is also used as an optoelectronic related element such as an optical printer head, an optical Fourier transform element, a light valve, or the like. The liquid crystal display element of the prior art is mainly a display element using a nematic liquid crystal, and is practically used: 1) a twisted nematic (TN) type liquid crystal display element which is twisted by 90 degrees, and 2) normally twisted. A super twisted nematic (STN) type liquid crystal display element of 180 degrees or more, 3) a thin film transistor (TFT) type liquid crystal display element using a thin film transistor, or the like.

However, these liquid crystal display elements have the following disadvantages: they can be appropriately recognized The angle of view of the image is narrow, and a decrease in brightness or contrast and a halftone brightness inversion occur when viewed from an oblique direction. In recent years, the problem of the viewing angle has been further improved by the following techniques: 1) a TN-TFT type liquid crystal display element using an optical compensation film, and 2) a vertical alignment (VA) type liquid crystal display using a vertical alignment and an optical compensation film. Element, 3) Multi-Horizon Vertical Alignment (MVA) type liquid crystal display element for vertical alignment and protrusion structure, or 4) In-Plane Switching (IPS) of transverse electric field mode Liquid crystal display device, 5) Electrostatically Controlled Birefringence (ECB) type liquid crystal display device, 6) Optically Compensated Bend (Optically Compenated Bend, or Optically Self-Compensated Birefringence, OCB) type liquid crystal display device, etc. Make these components practical.

The development of the liquid crystal display device technology can be achieved not only by improving the driving method or the element structure of the liquid crystal display elements, but also by improving the constituent elements used in the display elements. Among the constituent components used in the display element, in particular, the liquid crystal alignment film is one of important factors relating to the display quality of the liquid crystal display element, and as the display element is made higher in quality, the role of the liquid crystal alignment film is becoming more and more important.

The liquid crystal alignment film is prepared from a liquid crystal alignment agent. Currently, the liquid crystal alignment agent which is mainly used is a solution in which polylysine or soluble polyimine is dissolved in an organic solvent. After applying such a solution onto a substrate, a film is formed by heating or the like to form a polyimide film. Also studied various liquid crystal alignment agents other than poly-proline, but in terms of heat resistance, Chemical resistance (liquid crystal resistance), coating properties, liquid crystal alignment properties, electrical properties, optical properties, display properties, and the like are hardly practical.

In order to improve the display quality of a liquid crystal display (LCD), the characteristics required for the liquid crystal alignment film must be high in voltage holding ratio (VHR). In an active matrix type LCD, for example, if the voltage holding ratio is low, the voltage associated with the liquid crystal during the frame period is lowered, resulting in a change in luminance, and no normal tone is formed. Especially recently, LCDs have been used for television applications, and the degradation of VHR over time has become important. In order to produce a large screen and display a clear LCD, an aligning film in which the brightness of the backlight becomes high and the VHR does not deteriorate due to light or heat is sought.

Next, the important characteristics required for the alignment film include a small residual charge (direct current (DC)). The residual DC refers to the electric charge accumulated between the electrodes as the LCD is driven. This phenomenon applies an excessive voltage to the electrode. For example, after the voltage is cut off, the so-called "afterimage" remains after the display image does not disappear. "." Recently, it has been reported that a liquid crystal alignment film having a small residual DC can be produced by using a diamine having a nitrogen atom (Patent Documents 1, 2, and 3) as one of methods for reducing residual DC.

[Previous Technical Literature]

[Patent Document 1] International Publication No. 2004-053583

[Patent Document 2] International Publication No. 2004-021076

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-104633

However, with the development of high performance of liquid crystal display elements, there is a need for an alignment film which can further reduce residual DC, which is difficult only by the previously proposed technique. Fully meet the required characteristics.

An object of the present invention is to develop a polylysine which can achieve many characteristics (high voltage holding ratio, small residual DC, high liquid crystal alignment, high rubbing resistance, etc.) required for a liquid crystal alignment film.

In order to solve the above problems, the inventors of the present invention have made an effort to introduce a 1-phenylfluorene structure into a diamine which is a raw material of polylysine, and to have an alignment film composed of the polymer. In the liquid crystal display device, the residual DC is lowered while maintaining a high voltage holding ratio. Further, it has been found that the diamine of the present invention and the polyaminic acid or polyimine using the diamine of the present invention have high solubility with respect to a solvent which is usually used, thereby completing the present invention.

The diamine of the present invention is represented by the following item [1].

[1] A diamine represented by the formula (1):

Wherein Y is a single bond or a linear alkyl group having a carbon number of 1 to 9; any -CH ₂ - of the alkyl group may be -O-, -N(CH ₃ )-, 1,4-phenylene , 1,4-cyclohexylene or piperazine-1,4-diyl substituted; n is 0 or 1; and a hydrogen of a benzene ring to which an amine group is bonded may be substituted by -OH. Here, when Y is an alkylene group and n is 0, there is no case where -CH ₂ - having an amine group bonded thereto is substituted by -O- or -N(CH ₃ )-.

The diamine of the present invention can be easily synthesized without using a special reaction apparatus, and the liquid crystal alignment agent of the present invention is soluble in a solvent which is usually used in the art, and does not precipitate upon storage. Further, according to the present invention, it is possible to provide a liquid crystal display element having a high voltage holding ratio and a small residual DC.

The above described features and advantages of the present invention will be more apparent from the following description.

First, the terms used in the present invention will be described. The diamine represented by the formula (1) is sometimes referred to as a diamine (1). Diamines sometimes represented by other formulas are also represented by the same abbreviations. For the compound other than the diamine, for example, the tetracarboxylic dianhydride represented by the formula (A) may be abbreviated as the acid anhydride (A). The term "arbitrary" as used in the description of chemical formula means "not only the position can be freely chosen, but the quantity can also be freely selected." For example, the expression "any A can be replaced by B, C, D or E" has not only the meaning that one A can be replaced by B, C, D or E, and any of a plurality of A can be B, C, D and E. The meaning of any of the substitutions also has the meaning that at least two of A substituted by B, A substituted by C, A substituted by D, and A substituted by E exist. When any -CH ₂ - may be substituted by -O-, substitutions resulting in the formation of a bonding group -OO- are not included.

The substituent having an undefined bonding position with respect to the carbon constituting the ring means that the bonding position is free in the range of no chemical problem. The use of the same symbols in a plurality of formulae means that the groups have the same defined range, but it is not meant that all of the formulae must be the same group at the same time. Can be phase in multiple formulas The same group may also be a different group in different formulas.

The present invention is constituted by the above item [1] and the following items [2] to [11].

[2] The diamine according to [1], wherein the benzene ring to which the amine group is bonded is a benzene ring having no -OH as a substituent.

[3] The diamine according to [1], wherein the benzene ring to which the amine group is bonded is a benzene ring having a substituent -OH with respect to an ortho position of the amine group.

[4] The diamine according to [1], wherein Y is a single bond or a 1,4-phenylene group, and n is 0.

[5] The diamine according to [1], wherein Y is a single bond, or any -CH ₂ - may be substituted by -O- or -N(CH ₃ )-, and has a linear chain of 1 to 9 carbon atoms. An alkyl group; and n is 1.

[6] A poly-proline, which is a composition comprising at least one of the diamines according to [1], or at least one of the diamines as described in the item [1] and at least one other diamine. An amine mixture is obtained by reacting with at least one tetracarboxylic anhydride.

[7] The polyamic acid according to [6], wherein at least one of the tetracarboxylic anhydrides is a tetracarboxylic anhydride selected from the compounds represented by the formulae (A1) to (A63).

[8] A polyimine obtained by dehydrating and dehydrating a polyamic acid according to the item [6].

[9] A solution comprising at least one polymer selected from the group consisting of polylysine as described in item [6] and polyamidene according to item [8].

[10] A liquid crystal alignment agent comprising the polymer solution according to [9].

[11] A liquid crystal display element comprising the liquid crystal alignment film obtained by the liquid crystal alignment agent according to [10].

The diamine of the present invention is represented by the formula (1).

In the formula (1), Y is a single bond or a linear alkylene group having a carbon number of 1 to 9. Further, any -CH ₂ - of the alkylene group may be -O-, -N(CH ₃ )-, 1,4-phenylene (1,4-phenylene), 1,4-cyclohexylene (1, 4-cyclohexylene) or piperazine-1,4-diyl (piperazine-1,4-diyl) substitution. Preferred examples of Y are a single bond, a 1,4-phenylene group, a piperazine-1,4-diyl group, and an arbitrary -CH ₂ - may be substituted by -O- or -N(CH ₃ )-. ~9 linear alkyl group. A more preferred example of Y is a 1,4-phenylene group and any -CH ₂ -a straight-chain alkylene group having a carbon number of 1 to 9 which may be substituted by -O- or -N(CH ₃ )-. n is 0 or 1. However, when Y is the above alkyl group and n is 0, there is no case where -CH ₂ - having an amine group bonded thereto is substituted by -O- or -N(CH ₃ )-. Further, one hydrogen of the benzene ring to which an amine group is bonded may be substituted by -OH. When the benzene ring has a substituent -OH, its position relative to the bond position of the amine group is an ortho position, preferably an ortho position.

The polylysine obtained by reacting the diamine (1) with the tetracarboxylic dianhydride has high solubility in a solvent, and can prevent precipitation of the polymer when it is stored in a refrigerator or the like. When the composition of the raw material other than the diamine (1) is expected to become a poorly soluble polyamine, it is preferred to use an asymmetric diamine (1) wherein n is 0, since solubility can be improved. Further, in the case where a polyimine having a solubility lower than polyglycolic acid is used in the alignment agent, it is also preferred to use a diamine (1) wherein n in the formula (1) is 0.

Further, in order to obtain an alignment film having a large alignment regulating force, Y is preferably a linear alkylene group having a carbon number of 1 to 9, more preferably a linear alkylene group having a carbon number of 2 to 9. The alkylene group in this case is -CH ₂ - an alkylene group which is not substituted by another group.

The effect of reducing the residual DC by the alignment film obtained from the polyamic acid using the diamine of the present invention is remarkably large. Therefore, by using a known other diamine having a particularly large alignment regulating force as shown below and a diamine (1), it is possible to obtain an alignment film having a large alignment resistance to liquid crystal and a low residual DC.

In order to prepare the electrical properties of the alignment film to a desired value, any -CH ₂ - in the linear alkyl group of Y may be substituted by -O- or N(CH ₃ )-. At this time, from the viewpoint of easiness of obtaining the raw material, it is preferred that -CH ₂ - adjacent to the anthracene ring is substituted by -O- or N(CH ₃ )-, and from the viewpoint of stability of the compound, preferably -O- Not adjacent to N(CH ₃ )-.

Specific examples of the diamine (1) are shown below.

The diamine (1) wherein Y is a single bond and n is 0 can be synthesized by the route shown below.

In Scheme 1, a commercially available 5-amino hydrazine or 6-amino hydrazine represented by (S1-1) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain A compound represented by (S1-2). Then, the diamine represented by the formula (1) can be synthesized by reducing the nitro group by hydrogen-catalyzed reduction of the compound represented by (S1-2).

When Y is a compound having a linear alkyl group having 1 to 9 carbon atoms and n is 1, it can be synthesized by the route shown below.

In the above Scheme 2, the two represented by (S2-1) are obtained according to the method described in Tetrahedron Letters 41 (11), 1811-1814 (2000). An amine (wherein Y is a single bond or a linear alkyl group having a carbon number of 1 to 9) is reacted with triethanolammonium chloride to obtain a compound represented by (S2-2). Then, the compound represented by the above (S2-2) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S2-3). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S2-3), whereby the diamine represented by the formula (1) can be synthesized.

When Y is a compound having a linear alkyl group having 2 to 9 carbon atoms and n is 0, it can be synthesized by the route shown below.

In the above Scheme 3, the compound represented by (S3-1) and the amino acetylide (where Y' is a single bond or carbon according to the method described in Tetrahedron Letters 34 (40), 6403-6406 (1993) The linear alkyl group having a number of 1 to 7 is reacted to obtain a compound represented by (S3-2). Then, the compound represented by the above (S3-2) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S3-3). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S3-3), whereby the diamine represented by the formula (1) can be synthesized.

A compound in which Y is a methylene group having a carbon number of 1 and n is 0 can be synthesized by the route shown below.

In the above Scheme 4, a commercially available 5-(aminomethyl)anthracene or 6-(aminomethyl)anthracene represented by (S4-1) is used in the presence of a base such as sodium hydride. - Fluoronitrobenzene is reacted to obtain a compound represented by (S4-2). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S4-2), whereby the diamine represented by the formula (1) can be synthesized.

When Y is a compound in which 1,4-phenylene group and n is 0, it can be synthesized by the route shown below.

In the above Scheme 5, commercially available 5-bromoindole or 6-bromoindole represented by (S5-1) and commercially available 4-aminophenylboronic acid are coupled by using a palladium catalyst. The compound represented by (S5-2) is obtained by the reaction. Then, the compound represented by the above (S5-2) is reacted with 4-fluoronitrobenzene in the presence of a base such as sodium hydride to obtain a compound represented by (S5-3). Then, the nitro group is reduced by hydrogen-catalyzed reduction of the compound represented by (S5-3), whereby the diamine represented by the formula (1) can be synthesized.

Next, the polyproline of the present invention will be specifically described. A solution containing polylysine, partially sulfiliated polylysine, or a mixture of these is obtained by reacting the diamine (1) with a tetracarboxylic dianhydride in a solvent. These solutions are sometimes referred to as varnish in the following description. Further, a polyamidene-containing varnish is obtained by subjecting the polyamic acid contained in the varnish, the partially ruthenized polylysine, or a mixture thereof to a ring-opening by a dehydration reaction. In the present invention, the diamine (1) may be used singly or in combination of two or more kinds of diamines (1). Further, the diamine represented by the formula (1) may be used in combination with other known diamines. In the following description, polylysine, or partially ruthenized polylysine, or a mixture of such glycosides, and polyamido acids, or partially ruthenium The polyamidiamine obtained by dehydrating and ring-opening polylysine or a mixture thereof is collectively referred to as a polymer.

The molecular weight of the polymer of the present invention is, based on the weight average molecular weight measured by a gel permeation chromatography (GPC) method, preferably from 1,000 to 500,000, more preferably from 10,000 to 250,000. The reason for this is that if the weight average molecular weight is 10,000 or more, the sublimation of the polymer is suppressed in the substrate calcination step in forming the alignment film, and if the weight average molecular weight is 250,000 or less, the solubility in the solvent can be prevented from being lowered. The analysis of the polymer portion when the alignment agent is applied to the substrate is suppressed.

In the present invention, the reason for the tetracarboxylic dianhydride is not particularly limited, and specific examples of the preferred tetracarboxylic dianhydride which are suitably used are shown below.

These tetracarboxylic dianhydrides may be used singly or in combination of two or more. Among these tetracarboxylic dianhydrides, particularly preferred examples are an acid anhydride (A1), an acid anhydride (A2), and an acid anhydride (A20), which can provide a higher voltage holding ratio by using at least one of these tetracarboxylic dianhydrides. Liquid crystal display element.

In the preparation of the polymer of the present invention, the diamine represented by the formula (1) and the known diamine not represented by the formula (1) can be used in combination within a range not impairing the effects of the present invention. In this case, in order to maximize the effect of the present invention, when the total amount of the diamine is set to 100 mol%, the content of the diamine represented by the formula (1) is 0.5 mol%. Percentage of 95 moles, preferably from 5 mole percent to 90 mole percent.

A preferred example of a known diamine is selected from the formula (II) shown below. A diamine in the compound group represented by the formula (VIII). At least one of these diamines may be used in combination with the diamine (1). Further, a diamine not represented by the formula (II) to the formula (VIII) may be used in combination.

H ₂ N-(CH ₂ ) _m -NH ₂ (II)

In the formulae (II) to (VIII), m is an integer of 1 to 12, and G ^{1 is} independently a single bond, -O-, -S-, -SS-, -SO ₂ -, -CO-, -CONH -, -NHCO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -(CH ₂ ) _k -, -O-(CH ₂ ) _k -O-, or -S-(CH ₂ ) _k -S-, -N(CH ₃ )-(CH ₂ ) _k -N(CH ₃ )-, and k is an integer from 1 to 12; G ^{2 is} independently a single bond, -O-, -S- , -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having a carbon number of 1 to 3; and any hydrogen of the cyclohexane ring and the benzene ring may be fluorine or -CH ₃ replaced. In the formula (III), it is preferred that the two amine groups are not bonded to the same carbon atom. The amine group in the formula (IV) is preferably not bonded to a carbon atom to which G ¹ is bonded.

Specific examples of the diamine (II) to the diamine (IV) are shown below.

Specific examples of the diamine (V) are shown below.

Specific examples of the diamine (VI) are shown below.

Specific examples of the diamine (VII) are shown below.

Specific examples of the diamine (VIII) are shown below.

The diamine (II) to diamine (VIII) can be adjusted to have a pretilt angle of 0° to 3° by combining at least one of these diamines with the diamine (1) of the present invention. Therefore, it is suitable as an aligning film raw material for IPS.

In order to obtain an alignment film for IPS having a higher voltage holding ratio, it is preferred to use a diamine (VI-1) or a diamine (VI-2) in combination.

In order to obtain an alignment film having a lower residual DC, it is preferred to use a diamine (VI-14), a diamine (VI-15) or a diamine (VI-22) in combination, and it is particularly preferred to use a diamine (VI-). 22) Combined use.

In order to obtain an alignment film which improves the black display property of the liquid crystal display element, it is preferred to use a diamine represented by a diamine (VI-10) or a diamine (VIII-3) in combination.

As another well-known diamine, a diamine which has a side chain structure is mentioned. An example of a known diamine having a side chain structure is the following diamine (IX) to diamine. (XII). At least one of these diamines may be used in combination with the diamine (1). At least one of the diamine (II) to the diamine (VIII) and at least one of the diamines (IX) to diamines (XII) may be used in combination with the diamine (1). Further, in the present invention, in addition to the diamine (II) to diamine (XII), a diamine other than these diamines may be used.

In the formula (IX), G ³ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or -(CH ₂ ) _k -, and k is an integer of 1 to 12. R ¹ is an alkyl group having 3 to 20 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (IX-S). In the alkyl group, any hydrogen may be substituted by fluorine, and any -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen of the phenyl group may be substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ or -OCF ₃ . The bonding position of the amine group to the benzene ring is arbitrary, but it is preferred that the bonding position relationship of the two amine groups is meta or para. That is, when the bonding position of the group "R ¹ -G ³ -" is 1 position, it is preferred that the two amine groups are bonded to the 3 position and the 5 position, or the 2 position and the 5 position, respectively.

In the formula (IX-S), R ⁵ is hydrogen, fluorine, an alkyl group having 1 to 20 carbon atoms, a fluorine-substituted alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , G ⁷ , G ⁸ and G ⁹ are bonding groups, and these are independently a single bond, -O-, -COO-, -OCO-, -CONH-, -CH=CH- or an alkylene group having a carbon number of 1 to 12, A ² , A ³ and A ⁴ are a ring, and the respective are 1,4-phenylene, 1,4-stretch Cyclohexyl, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7 -diyl or fluoren-9,10-diyl, in any ring, any hydrogen may be substituted by fluorine or -CH ₃ ; b, c and d are independently an integer of 0 to 2, and the total of these is 1 to 5 When b, c or d is 2, the two bonding groups may be the same or different, and the two rings may be the same or different.

In the formula (X) and the formula (XI), R ^{2 is} independently hydrogen or methyl. R ^{3 is} independently hydrogen, an alkyl group having 1 to 20 carbon atoms, or an alkenyl group having 2 to 20 carbon atoms. G ^{4 is} independently a single bond, -CO- or -CH ₂ -. One hydrogen of the benzene ring in the formula (XII) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group.

In the formula (X), it is preferred that one of the two groups "NH ₂ -phenylene-G ⁴ -O-" is bonded to the 3 position of the steroid nucleus, and the other is bonded to the 6 position of the steroid nucleus. The bonding position of the two groups "NH ₂ -phenylene-G ⁴ -O-" to the benzene ring in the formula (XI) is preferably a meta or para position with respect to the bonding position of the steroid nucleus. In the formula (XI) and the formula (XII), the bonding position of the amine group to the benzene ring is preferably a meta or para position with respect to the bonding position of G ⁴ .

In the formula (XII), R ⁴ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and any -CH ₂ - in the alkyl group having 2 to 20 carbon atoms in the alkyl group may be -O-, -CH= CH- or -C≡C- substituted. G ⁵ is -O- or an alkylene group having a carbon number of 1 to 6. A ¹ is a 1,4-phenylene group or a 1,4-cyclohexylene group, and G ⁶ is a single bond or an alkylene group having a carbon number of 1 to 3, and a is 0 or 1. The bonding position of the amine group to the benzene ring is preferably a meta or para position with respect to the bonding position of G ⁵ .

Specific examples of the diamine (IX) are shown below.

Specific examples of the diamine (X) are shown below.

Specific examples of the diamine (XI) are shown below.

Specific examples of the diamine (XII) are shown below.

Diamine (IX-1) to diamine (IX-4), diamine (IX-25) to diamine (IX-28), and diamine (XII-1) to diamine (XII-6), By using at least one of these diamines in combination with the diamine (1) of the present invention, the pretilt angle of the liquid crystal molecules is adjusted to 3 to 15°, and thus it is suitable as an alignment film raw material for TN, STN, and OCB. .

Higher voltage retention, suppressing residual DC to lower, regardless of The conditions of the alignment film forming step can stably impart a desired pretilt angle to the liquid crystal molecules, and the raw material of the alignment film for TN, STN, and OCB is preferably a diamine (IX-2) or a diamine (XII-). 1), at least one of the diamine (XII-4) and the diamine (XII-6) is used in combination with the diamine (1).

Diamine (IX-7), diamine (IX-8), diamine (IX-13) to diamine (IX-16), diamine (IX-29) to diamine (IX-33), diamine (X-1)~diamine (X-4), diamine (XI-1)~diamine (XI-4), and diamine (XII-7)~diamine (XII-11) Since at least one of these diamines is used in combination with the diamine (1) to adjust the pretilt angle of the liquid crystal molecules to 90°, it is suitable as an alignment film raw material for VA.

If the voltage retention ratio is higher, the residual DC can be suppressed to a lower level, and the alignment film material for the VA can be stably imparted to the liquid crystal molecules with a desired pretilt angle regardless of the conditions of the alignment film formation step. At least one of the diamine (IX-7), the diamine (IX-8), the diamine (IX-13), and the diamine (IX-14) is used in combination with the diamine (1).

Further, examples of the diamine which can be used in combination with the diamine of the present invention include a decane-based diamine containing a siloxane chain. The dioxane-based diamine is not particularly limited, and a diamine represented by the formula (S1) is preferably used.

Wherein R ^{6 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or a phenyl group substituted by an alkyl group. R ⁷ and R ^{8 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group. And f is an integer from 1 to 10. The amount of the naphthenice-based diamine used is not particularly limited as long as it does not impair the effects of the present invention.

The liquid crystal alignment agent of the present invention will be described. The liquid crystal alignment agent of the present invention is one or more polymer solutions containing a polymer selected from the present invention. Specific examples of the liquid crystal alignment agent of the present invention are obtained by reacting a diamine (1) with an acid dianhydride to obtain a polyaminic acid solution of the present invention, and removing a solvent from the polyamic acid solution. A polyphthalic acid solution obtained by dissolving a polymer of polylysine in a solvent, a mixture of these, and the like. The liquid crystal alignment agent of the present invention may be the reaction solution itself used in the preparation of the polymer of the present invention, or may be a solvent obtained by dissolving a solvent from the reaction solution in a solvent different from the solvent used in the reaction. a solution made in the middle.

The solvent to be used in the liquid crystal alignment agent of the present invention is not particularly limited, and examples thereof include N-methyl-2-pyrrolidone (NMP) and dimethylformamide (dimethyl). Formamide, DMF), dimethyl acetamide (DMAc), dimethyl sulfoxide (DMSO), ethylene glycol monobutylether (BC), ethylene glycol monoethyl ether, Γ-butyrolactone or the like. In the present invention, two or more kinds selected from the above solvents may be used in combination. Further, if the polymer of the present invention is soluble, a solvent other than the above may be used.

In the liquid crystal alignment agent of the present invention, in order to exhibit better characteristics as an alignment film, one or more selected from all of the well-known polymers may be further added. At this time, in order to exhibit the effects of the present invention, a preferred ratio of the polymer of the present invention in the total polymer is from 50% by weight to 100% by weight, and more preferably from 70% by weight to 100% by weight. ratio. Examples of such a polymer include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, hydrazine modified polyurethane, tamper-modified poly Ester and the like.

The proportion of the polymer contained in the liquid crystal alignment agent of the present invention is not particularly limited, and an optimum value can be selected in accordance with the procedure in the production of the liquid crystal display element. In general, in order to suppress unevenness or pinholes or the like at the time of coating the glass substrate, the above polymer ratio is preferably from 0.1% by weight to 30% by weight, and more preferably 1% by weight, based on the total weight of the liquid crystal alignment agent. ~10% by weight.

When an organic ruthenium compound is added to the liquid crystal alignment agent of the present invention, the adhesion and hardness of the alignment film to the glass substrate can be adjusted, and display defects due to the removal of the polyimide by rubbing or the like can be improved. The organic hydrazine compound to be added to the liquid crystal alignment agent of the present invention is not particularly limited, and for example, aminopropyltrimethoxydecane, aminopropyltriethoxydecane, vinyltrimethoxydecane, or the like is preferably added. N-(2-Aminoethyl)-3-aminopropylmethyldimethoxydecane, N-(2-aminoethyl)-3-aminopropyltrimethoxydecane, vinyl three Ethoxy decane, 3-methacryloxypropyltrimethoxydecane, 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2 - decane coupling agent such as (3,4-epoxycyclohexyl)ethyltrimethoxydecane, eucalyptus oil such as dimethyl polyoxane, polydimethyl siloxane or polydiphenyl fluorene; especially good The addition is the addition of aminopropyltriethoxydecane, 3-glycidoxypropylmethyldimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane.

The proportion of such an organic cerium compound added to the liquid crystal alignment agent, if There is no particular limitation on the range in which the display defects are improved without impairing the characteristics required for the alignment film. However, when a large amount of these organic ruthenium compounds are added, alignment of the liquid crystal occurs when the alignment film is formed. Therefore, the concentration of the organic cerium compound is preferably from 0.01% by weight to 50% by weight, more preferably from 0.1% by weight to 20% by weight based on the total mass of the polymer contained in the liquid crystal alignment agent.

Liquid crystal alignment agents which impart a desired pretilt angle can also be prepared by mixing different types of polymers. This is because when a plurality of polymers having different surface energies are mixed, when the polymers form a film, the polymer having a small surface energy tends to segregate toward the surface. By blending such a polymer, a pretilt angle can be imparted to the liquid crystal molecules on the surface of the alignment film, and a layer of a component exhibiting good liquid crystal alignment (referred to as polymer A) can be formed and formed on the coated substrate side. A layer of a component (polymer B) having good electrical properties. That is, an alignment film excellent in these two characteristics can be obtained. This method is disclosed in Japanese Laid-Open Patent Publication No. Hei 8-43831.

The polymer may also be blended in the liquid crystal alignment agent of the present invention. Since the polymer of the present invention forms an alignment film having excellent electrical properties, it is suitable as a component of the polymer B. Further, as described above, the polymer of the present invention can also be used as a component of the polymer A by combining the diamine of the present invention represented by the formula (1) with other diamines.

The mixing ratio of the polymer A to the polymer B can be arbitrarily selected from 1% by weight to 99% by weight, respectively. However, in order to exhibit good liquid crystal alignment characteristics and good electrical characteristics maintaining the pretilt angle, the ratio of the polymer A is based on the total weight of the polymer, preferably from 1 to 50% by weight. The weight percentage is more preferably from 5 weight percent to 30 weight percent.

The addition of a crosslinking agent which reacts with a carboxylic acid residue of polyproline to the liquid crystal alignment agent of the present invention is also important for preventing deterioration of characteristics with time or deterioration by environment. Examples of such a crosslinking agent include a polyfunctional epoxy resin, an isocyanate material, and the like described in JP-A No. 3049699, JP-A-2005-275360, and JP-A No. 10-212484. Further, the crosslinking agent itself reacts to form a polymer having a network structure and a material which enhances the strength of the polyaminic acid or polyimide film, and can also be used for the same purpose as described above. The polyfunctional vinyl ether, maleimide derivative, or diene described in JP-A-2004-341030, and the like. Propyl bisallyl nadiimide derivatives and the like. Further, the crosslinking agent used in the present invention may be a crosslinking agent other than these. When a crosslinking agent is used, in order to exhibit the effects of the present invention, the ratio of the crosslinking agent is preferably from 0.05 to 0.5, more preferably from 0.1 to 0.3, based on the weight ratio of the polymer of the present invention.

The viscosity of the liquid crystal alignment agent of the present invention is preferably 5 mPa, depending on the method of coating, the kind or concentration of the polymer, the kind of the solvent, and the like. s~100 mPa. s, more preferably 10 mPa. s~80mPa. s. In order to obtain a sufficient film thickness, it is more desirable to be greater than 5 mPa. The viscosity of s, in order not to produce uneven printing, ideally less than 100 mPa. s viscosity. Wherein, in the case of printing by the inkjet method, the viscosity is less than or equal to 5 mPa. The liquid crystal alignment agent of s can also be used.

Next, the liquid crystal display element of the present invention will be described. The invention The liquid crystal display element includes: (1) a pair of substrates disposed oppositely; (2) a liquid crystal alignment film formed on opposite faces of the pair of substrates; and (3) sandwiching between the pair of substrates Liquid crystal layer. An electrode may be disposed on both of the pair of substrates. However, in the case of the IPS type liquid crystal display device, an electrode (an electrode of a comb shape or a sawtooth structure) may be disposed on one of the pair of substrates.

The liquid crystal alignment film is a liquid crystal alignment film formed by applying the liquid crystal alignment agent of the present invention to the substrate and heating it. Here, the film thickness of the liquid crystal alignment film is preferably from 10 nm to 300 nm, more preferably from 30 nm to 100 nm. Further, the liquid crystal alignment film is preferably subjected to rubbing treatment.

The pair of electrode-attached substrates disposed in the opposite direction are preferably transparent substrates (for example, glass substrates).

The liquid crystal layer sandwiched between the pair of substrates includes a liquid crystal composition. Here, the liquid crystal composition is not particularly limited, and any one of a liquid crystal composition having a positive dielectric anisotropy and a liquid crystal composition having a negative dielectric anisotropy can be used depending on the driving mode. An example of a preferred liquid crystal composition having a positive dielectric anisotropy is disclosed in Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, and Japanese Patent Laid-Open No. Hei 8-157826 Japanese Patent Laid-Open No. Hei 8-231960, Japanese Patent Laid-Open No. Hei 9-241644 (EP 885 272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), and Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1) Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japanese Patent Laid-Open No. Hei 9-241643 Japanese Patent Publication No. Hei 10-204016 (Japanese Laid-Open Patent Publication No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei No. Hei. Patent Publication No. 2001-48822 and the like.

The liquid crystal composition used in the VA liquid crystal display device can be various liquid crystal compositions having a negative dielectric anisotropy. Examples of the preferred liquid crystal composition are disclosed in Japanese Laid-Open Patent Publication No. SHO 57-114532, Japanese Patent Application Laid-Open No. Hei No. 2-4725, Japanese Patent Laid-Open No. Hei-4-224885, Japanese Patent Laid-Open No. Hei 8-104869, Japanese Patent Laid-Open No. Hei 10-168076, Japanese Patent Application Laid-Open No. Hei No. Hei No. Hei. Japanese Patent Laid-Open No. Hei 10-236992, Japanese Patent Laid-Open No. Hei 10-236993, Japanese Patent Laid-Open No. Hei 10-236994, Japanese Patent Laid-Open No. Hei No. Hei No. Hei 10--237000, and Japanese Patent Laid-Open No. Hei 10-237004 Japanese Patent Laid-Open No. Hei 10-237024, Japanese Patent Laid-Open No. Hei 10-237035, Japanese Patent Laid-Open No. Hei 10-237075, Japanese Patent Application Laid-Open No. Hei No. 10-237076, and Japanese Patent Laid-Open No. Hei 10-237448 Japanese Patent Laid-Open No. Hei 10-287874, Japanese Patent Laid-Open No. Hei 10-287875, Japanese Patent Laid-Open No. Hei 10-291945, and Japanese Patent Laid-Open No. Hei 11-029581 And Japanese Patent Laid-Open Publication No. 11-080049, Japanese Patent Laid-Open Publication No. 2000-256307, Japanese Patent Laid-Open Japanese Patent Publication No. 2001-072626, Japanese Patent Laid-Open No. 2001-192657, and the like.

For the liquid crystal composition having positive or negative dielectric anisotropy, one or more optically active compounds may be added.

The liquid crystal display element of the present invention may have other members. For example, in a color display TFT type liquid crystal element using a thin film transistor, a thin film transistor, an insulating film, a protective film, a signal electrode, a pixel electrode, or the like is formed on the first transparent substrate, and is blocked on the second transparent substrate. A black matrix, a color filter, a planarization film, and a pixel electrode of light outside the pixel region.

In the VA type liquid crystal display element, particularly the MVA type liquid crystal display element, minute protrusions called domains are formed on the first transparent substrate. Further, a spacer may be formed in order to form a cell gap between the substrates.

The liquid crystal display element of the present invention is produced by any method, and is produced, for example, by a method comprising the steps of: (1) a liquid crystal alignment agent coating step on the two transparent substrates; and (2) coating the liquid crystal. a drying step of the alignment agent; (3) for dehydrating the dried liquid crystal alignment agent. a heat treatment step of the ring-opening reaction; (4) an alignment treatment step of the obtained alignment film; (5) a liquid crystal sealing step of sealing the liquid crystal between the substrates after bonding the two substrates, or dropping the liquid crystal on one of the substrates The step of bonding another substrate to the top.

The coating method in the step of applying the liquid crystal alignment agent is generally known as a spinner method, a printing method, a dicing method, and a dropping method. Addition, inkjet (inkjet) method, and the like. These methods are also applicable to the present invention.

The above drying step and dehydration. The method of the heat treatment step necessary for the ring-opening reaction is generally known to be a heat treatment in an oven or an infrared furnace, a heat treatment on a hot plate, or the like. These methods are also applicable to the present invention. The drying step is preferably carried out at a lower temperature (50 ° C to 100 ° C) in the range in which the solvent can be evaporated. The heat treatment step is usually preferably carried out at a temperature of from about 150 ° C to about 300 ° C.

For the OCB type liquid crystal display element, the TN type liquid crystal display element, the STN type liquid crystal display element, and the IPS type liquid crystal display element, the alignment treatment is usually performed by rubbing treatment. Although the VA type liquid crystal display element is often not subjected to the rubbing treatment, it may be subjected to a rubbing treatment.

Next, an adhesive is applied to one of the substrates and bonded, and the liquid crystal is injected under reduced pressure. In the case of the drop addition method, the liquid crystal is dropped onto the substrate before bonding, and then the other substrate is bonded. The adhesive for bonding is cured by heat or ultraviolet rays to fabricate the liquid crystal display element of the present invention.

A polarizing plate (polarizing film), a wavelength plate, a light-scattering film, a driving circuit, and the like can be mounted in the liquid crystal display element of the present invention.

The liquid crystal display device of the present invention has a feature that the voltage holding ratio is high and the residual DC is low. The reason for this is that the liquid crystal alignment film of the liquid crystal display element of the present invention is formed of a liquid crystal alignment agent including a polylysine synthesized using a compound represented by a diamine (I) or a derivative of the polyaminic acid. . This is illustrated in the following examples.

[Examples]

The diamine of the present invention, the liquid crystal alignment agent obtained by using the diamine, and the liquid crystal display element will be described in detail in the following examples, but the present invention is not limited to these examples. In the examples, 1H-NMR measurement was carried out in deuterated dimethyl sulfoxide. The molecular weight was determined by using GPC, using polystyrene as a standard solution, and the solution being DMF. Further, in the following examples, the unit liter of the volume is represented by L. Therefore, mL means milliliters.

First, a method of evaluating a liquid crystal display element used in the examples will be described.

(1) Residual DC

After a DC voltage of 1 V was superimposed on a rectangular wave of 30 Hz and 3 V for 30 minutes, the flicker elimination voltage after 10 minutes was measured, and the absolute value of this value was taken as residual DC. The smaller the residual DC, the less the trace is, which is good.

(2) Voltage retention rate

According to the method described in "Water Margin, the 14th LCD Symposium Prep Draft p78". The measurement was performed by applying a rectangular wave having a gate width of 69 μs, a frequency of 0.3 Hz, and a pulse height of ±5.0 V to the cell. The measurement temperature was 60 °C.

(3) Pretilt angle

The pretilt angle was measured by a crystal rotation method. The wavelength of light used for the measurement was 589 nm.

[Example 1] <Synthesis of Diamine (1-1)>

To a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 11.4 g (0.46 mol) of 60% sodium hydride was added, and 100 mL of DMF was added. The solution was cooled to 5 ° C, and then a solution obtained by dissolving 30 g (0.23 mol) of commercially available 5-aminoindole in 200 mL of DMF was added dropwise thereto. The solution was then allowed to warm to room temperature and stirred under nitrogen for 1 hour. The solution was again cooled to 5 ° C, and a solution obtained by dissolving 39 g (0.28 mol) of 4-fluoronitrobenzene in 200 mL of DMF was added dropwise thereto. The solution was then warmed to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was subjected to extraction in a mixed solvent of 500 mL of ethyl acetate and 500 mL of pure water, and the organic layer was washed three times with 500 mL of pure water. The organic layer was dried over anhydrous sodium sulfate and dried over anhydrous sodium sulfate. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 5:1 (v/v)) to obtain N-(4-nitrophenyl)-5-aminoindole (yield was 35.0 g, yield 60%).

35.0 g (0.14 mol) of the obtained N-(4-nitrophenyl)-5-amino hydrazine, 3.5 g of palladium carbon powder was added to the autoclave reaction vessel (autoclave), and 350 was added. mL of ethanol and 35 mL of ethyl acetate. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3:1 (v/v)) to obtain diamine (1-1) (N-(4-aminophenyl)-5. -Aminoguanidine) (yield 28.8 g, yield 92%).

¹ H-NMR (ppm): 3.53 (-NH ₂ , br. s, 2H), 3.74 (-NH ₂ , br. s, 2H), 6.43 - 7.25 (arm.H, m, 9H).

[Embodiment 2] <Synthesis of diamine (1-2)>

A diamine (1-2) (N-(4-aminophenyl)-6-amine was obtained according to the method described in Example 1, except that 5-aminopurine was replaced by 6-aminopurine. Baseline).

¹ H-NMR (ppm): 3.52 (-NH ₂ , br. s, 2H), 3.75 (-NH ₂ , br. s, 2H), 5.85-8.18 (arm.H, m, 9H).

[Example 3] <Synthesis of diamine (1-5)>

50 g (0.25 mol) of 4,4'-diamine was added to a 1 L three-necked flask equipped with a stirrer, thermometer, cooler and nitrogen inlet according to the method described in Tetrahedron Letters 41, 1815-1818 (2000). Diphenylmethane, 18.6 g (0.10 mol) of triethanolamine hydrochloride, 11.3 g (0.05 mol) of tin (II) chloride dihydrate, 1.0 g (0.005 mol) of cerium (III) chloride Hydrate and 3.9 g (0.015 mol) of triphenylphosphine, 500 mL of dioxane and 50 mL of pure water. Make the system inside the nitrogen environment. Stir at 180 ° C for 20 hours. After standing to cool, the reaction solution was placed in 500 mL of 5% hydrochloric acid, and extracted with 500 mL of chloroform. The organic layer was washed three times with 500 mL of pure water, and then the organic layer was dried over anhydrous magnesium sulfate, and then evaporated over anhydrous magnesium sulfate. Then, it was separated and purified by column chromatography (ethyl acetate:hexane = 1:1 (v/v)) to obtain bis(5-fluorenyl)methane (yield: 7.3 g, yield 59%) .

1 L three port with mixer, thermometer and nitrogen inlet 1.3 g (0.056 mol) of 60% sodium hydride was added to the flask, and 10 mL of DMF was added. The solution was cooled to 5 ° C, and a solution obtained by dissolving 7 g (0.028 mol) of bis(5-fluorenyl)methane in 20 mL of DMF was added dropwise thereto. The solution was then allowed to warm to room temperature and stirred under nitrogen for 1 hour. The solution was again cooled to 5 ° C, and a solution obtained by dissolving 4.7 g (0.034) of 4-fluoronitrobenzene in 20 mL of DMF was added dropwise thereto. The solution was then warmed to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was subjected to extraction in a mixed solvent of 100 mL of ethyl acetate and 100 mL of pure water, and the organic layer was washed 3 times with 100 mL of pure water. The organic layer was dried over anhydrous sodium sulfate and dried over anhydrous sodium sulfate. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 5:1 (v/v)) to obtain bis(5-N-(4-nitrophenyl)indolyl) methane ( The yield was 9.3 g and the yield was 68%).

To the reaction tube for autoclaving, 9.0 g (0.018 mol) of the obtained bis(5-N-(4-nitrophenyl)indenyl)methane and 0.9 g of palladium carbon powder were added, and 100 mL was added. Ethanol and 10 mL of ethyl acetate. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3:1 (v/v)) to obtain a diamine (1-5) (bis(5-N-(4-aminobenzene) Base) mercapto) methane) (yield 7.1 g, yield 91%).

¹ H-NMR (ppm): 3.86 (-CH ₂ -, s, 2H), 4.1 (-NH ₂ , br. s, 4H), 6.52 - 8.72 (arm. H, m, 18H).

[Example 4] <Synthesis of diamine (1-9)>

A diamine (1-9) was obtained according to the method described in Example 3 except that 4,4'-diaminodiphenylmethane was replaced by 1,3-bis(4-aminophenyl)propane. 1,3-bis(5-N-(4-aminophenyl)indenyl)propane).

¹ H-NMR (ppm): 1.95 (-CH ₂ -, q, 2H), 2.62 (-CH ₂ -, t, 4H), 3.72 (-NH ₂ , br. s, 4H), 6.51 - 8.78 (arm) .H,m,18H).

[Example 5] <Synthesis of diamine (1-28)>

A diamine (1-28) was obtained according to the method described in Example 3 except that 4,4'-diaminodiphenylmethane was replaced by 4,4'-diaminodiphenyl ether (double ( 5-N-(4-Aminophenyl)indenyl)ether).

¹ H-NMR (ppm): 3.79 (-NH ₂ , br. s, 4H), 6.52-8.04 (arm.H, m, 18H).

[Embodiment 6] <Synthesis of diamine (1-31)>

Except that 4,4'-diaminodiphenylmethane was replaced by N,N'-dimethyl-N,N'-bis(4-aminophenyl)ethylenediamine, according to Example 3. The method of obtaining diamine (1-31) (N,N'-dimethyl-N,N'-bis(5-N-(4-aminophenyl)indenyl)ethylenediamine).

¹ H-NMR (ppm): 2.75 (>NCH ₃ , s, 4H), 3.58 (-CH ₂ -, s, 4H), 3.69 (-NH ₂ , br. s, 4H), 6.52-7.76 (arm. H, m, 18H).

[Embodiment 7] <Synthesis of diamine (1-35)>

To the mixer, thermometer, cooler and nitrogen inlet A 1 L three-necked flask was charged with 20 g (0.10 mol) of commercially available 5-bromoindole, 15.1 g (0.11 mol) of commercially available 4-aminophenylboronic acid, and 0.35 g (0.0005 mol) of bis(triphenyl). Phosphine) palladium (II) dichloride, 20.7 g (0.15 mol) potassium carbonate and 8.1 g (0.025 mol) of tetrabutylammonium bromide, 150 mL of ethanol, 75 mL of toluene and 100 mL of pure water . The mixture was heated to reflux for 3 hours under a nitrogen atmosphere. After standing to cool, the reaction solution was placed in water, extracted with 200 mL of toluene, and the organic layer was washed three times with 200 mL of pure water. After the organic layer was dried over anhydrous sodium sulfate, anhydrous sodium sulfate was removed, and the solvent was evaporated under reduced pressure to yield crude crystals. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 5:1 (v/v)) to obtain 5-(4-aminophenyl)indole (yield: 17.9 g, yield 86%).

To a 1 L three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 3.8 g (0.16 mol) of 60% sodium hydride was added, and 40 mL of DMF was added. The solution was cooled to 5 ° C, and a solution obtained by dissolving 16.7 g (0.08 mol) of 5-(4-aminophenyl) hydrazine in 200 mL of DMF was added dropwise thereto. The solution was then allowed to warm to room temperature and stirred under nitrogen for 1 hour. The solution was again cooled to 5 ° C, and a solution obtained by dissolving 14.1 g (0.10 mol) of 4-fluoronitrobenzene in 150 mL of DMF was added dropwise thereto. The solution was then warmed to room temperature and stirred under a nitrogen atmosphere for 12 hours. Thereafter, the reaction solution was subjected to extraction in a mixed solvent of 500 mL of ethyl acetate and 500 mL of pure water, and the organic layer was washed 3 times with 500 mL of pure water. The organic layer was dried over anhydrous sodium sulfate and dried over anhydrous sodium sulfate. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 5:1 (v/v)) to obtain N-(4-nitro Phenyl)-5-(4-aminophenyl)anthracene (yield 16.6 g, yield 63%).

To the reaction tube for autoclaving, 16.0 g (0.049 mol) of N-(4-nitrophenyl)-5-(4-aminophenyl)anthracene and 1.6 g of palladium carbon powder were added. 200 mL of ethanol and 20 mL of ethyl acetate. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (toluene: ethyl acetate = 3:1 (v/v)) to obtain diamine (1-35) (N-(4-aminophenyl)-5. -(4-Aminophenyl)indole) (yield 13.3 g, yield 91%).

¹ H-NMR (ppm): 3.53 (-NH ₂ , br. s, 2H), 3.74 (-NH ₂ , br. s, 2H), 6.42 - 8.18 (arm.H, m, 13H).

[Embodiment 8] <Preparation of polylysine>

To a 200 mL three-necked flask equipped with a thermometer, a stirrer, and a nitrogen inlet, 2.59 g of a diamine (1-1) was added and dissolved in 60 g of dehydrated NMP. While maintaining the solution at 5 ° C, 1.14 g of the compound (A14) and 1.27 g of the compound (A1) were added. Then, the solution was warmed to room temperature, and after reacting for 12 hours under a nitrogen atmosphere, 10 g of γ-butyrolactone and 25 g of BC were added, and the mixture was further stirred for 3 hours. In order to reduce the viscosity of the obtained solution, the solution was heated and stirred at 60 ° C until the viscosity of the solution reached 35 mPa. s, a solution having a polyamine concentration of 5 wt% was obtained. This solution was referred to as varnish A. The polyamine acid in the varnish A had a weight average molecular weight of 64,000.

[Examples 9 to 25, Comparative Examples 1 to 2, and Reference Example 1]

A diamine and a tetracarboxylic dianhydride were used in the same manner as shown in Table 1, and polyamic acid was produced in the same manner as in Example 8 to prepare a varnish B to U.

[Example 26] <Production of Measurement Unit for Electrical Characteristics>

The varnish A prepared in Example 8 was diluted with a mixed solvent of NMP/BC=6/4 (v/v), and the polyamine acid concentration was adjusted to 3 weight%, and this was made into a coating varnish.

This coating varnish was applied onto a glass substrate with an ITO electrode by a spinner method. The coating conditions were carried out at 2,000 rpm for 15 seconds. After coating, the substrate was heated to 80 ° C and preliminarily calcined for 5 minutes, and then heat-treated at 210 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 80 nm. The obtained alignment film is then subjected to a rubbing treatment. The rubbing treatment was carried out using a tanned rubbing cloth having a hair length of 1.9 mm, with a hair pressing amount of 0.40 mm, a platform moving speed of 60 mm/sec, and a roller rotation speed of 1,000 rpm.

The rubbed glass substrate was subjected to ultrasonic cleaning in ultrapure water for 5 minutes, and then dried in an oven at 120 ° C for 30 minutes. Spread a 7 μm gap agent on one substrate and clip the other substrate The interstices were overlapped and sealed with an epoxy hardener to form an antiparallel cell having a gap of 7 μm. Then, the liquid crystal composition A described below was injected into the unit as a liquid crystal material, and the injection port was sealed with a photo-curable resin. Then, the unit was heat-treated at 110 ° C for 30 minutes to obtain a voltage holding ratio, residual DC, and pretilt angle measuring unit.

<Liquid crystal composition A>

Using the fabricated cell, the voltage holding ratio, residual DC, and pretilt angle were measured by the above methods, and the results were 96.2%, 1.8 mV, and 1.7°, respectively.

[Examples 27 to 43 and Comparative Examples 3 to 4]

Using a varnish B to varnish T, a cell was produced according to the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured. The measurement results are shown in Table 2 (Example 26 is also disclosed again). Here, the alignment film formed using the varnish E, the varnish K, and the varnish Q is not subjected to rubbing treatment, and the liquid crystal material to be injected is a liquid crystal composition B instead of the liquid crystal composition A.

<Liquid crystal composition B>

[Embodiments 44 and 45] <Evaluation of electrical characteristics of blended alignment agent>

A varnish AU prepared by mixing varnish A and varnish U at a weight ratio of 8:2 was prepared. Using this varnish AU, a cell was produced according to the method described in Example 26. A varnish BU obtained by mixing varnish B and varnish U at a weight ratio of 8:2 was prepared, and the varnish BU was used to produce a unit in the same manner as varnish AU. The results obtained by measuring the voltage holding ratio, residual DC, and pretilt angle for these units are shown in Table 2.

[Examples 46 to 50, and Comparative Examples 5 to 6] <Confirmation of storage stability>

After preparing varnish A, varnish B, varnish F, varnish J, varnish AU, varnish S, and varnish T, it was stored at -20 ° C for 60 days, and using this storage varnish, a cell was fabricated according to the method described in Example 26, and the voltage was measured. Retention rate, residual DC, and pretilt angle. The measurement results are shown in Table 3.

[Example 51] <Preparation of polyimine]

100 g of varnish A was weighed into a 200 mL round bottom flask, and 9.5 g (0.09 mol) of acetic anhydride and 4.4 g (0.06 mol) of pyridine were added thereto, and the mixture was stirred at 120 ° C for 3 hours. The solution was then placed in 1000 mL of purified water to obtain 4.5 g of polyimine. The polyiminoimine had a weight average molecular weight of 49,000, and the polyamidimide had a ruthenium iodide ratio of 94% as determined by 1 H-NMR. 4 g of the obtained polyimine was dissolved in 76 g of a mixed solvent of NMP-GBL-BC (volume ratio 1:1:1) to obtain a varnish V having a polyimine concentration of 5%.

[Example 52]

Using a varnish V, a cell was produced according to the method described in Example 26, and the voltage holding ratio, residual DC, and pretilt angle were measured, and as a result, they were 95.9%, 4.2 mV, and 1.6°, respectively.

[Comparative Example 7]

In addition to the diamine (1-1) is replaced by Japanese Patent Laid-Open No. 10-104633 In addition to N,N'-bis(4-aminophenyl)-1,4-piperazine described in the publication, the varnish W was obtained according to the method described in Example 8.

100 g of varnish W was weighed in a 200 mL round bottom flask, and 8.2 g (0.08 mol) of acetic anhydride and 3.8 g (0.05 mol) of pyridine were added thereto, and heated to 120 ° C, and the precipitate was precipitated 1 hour after the start of heating. Precipitation, even if the temperature of the solution was raised to 180 ° C, the precipitate did not dissolve.

[Example 53] <Synthesis of Diamine (1-11)>

To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 29.0 g (102 mmol) of commercially available 5-iodonium and 17.0 g (122 mmol) of potassium carbonate were added, and 200 mL of DMF was added. A solution obtained by dissolving 17.3 g (122 mmol) of commercially available 4-fluoronitrobenzene in 100 mL of DMF was added thereto, and the mixture was stirred at 140 ° C for 2 hours under a nitrogen atmosphere. The reaction solution was then taken up in a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was separated by filtration, and the solvent was evaporated under reduced pressure to give crude crystals. The obtained crude crystals were recrystallized from toluene to obtain N-(4-nitrophenyl)-5-iodonium (yield: 33 g, yield: 83%).

Add 33 g (91 mmol) of N-(4-nitrophenyl)-5-iodonium, 3.2 g (4.6 mmol) to a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet. Bis(triphenylphosphine)palladium(II) chloride and 0.87 g (4.6 mmol) of copper (I) iodide were added to 300 mL of triethylamine. Then, 10.7 g (109 mmol) of a commercially available trimethyldecyl acetylene was added thereto, and the mixture was heated under reflux for 6 hours under a nitrogen atmosphere. then The reaction solution was poured into a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The magnesium sulfate was separated by filtration, and the solvent was evaporated under reduced pressure to give crude crystals of N-(4-nitrophenyl)-5-((trimethylsulfanyl)ethynyl)-indole (yield 27 g, The yield was 88%).

To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 27 g (81 mmol) of N-(4-nitrophenyl)-5-((trimethyldecyl)ethynyl) was added. - 吲哚, dissolved in 200 mL of tetrahydrofuran. Under a nitrogen atmosphere, the solution was cooled to -78 ° C in a dry ice-acetone bath while maintaining the liquid temperature at -78 ° C, and 85 mL of commercially available fluorinated tetrabutyl was added dropwise thereto. Base ammonium 1 mol/L solution. The solution was kept at -78 ° C, and after stirring for 2 hours, the reaction mixture was poured into a mixed solvent of 500 mL of ethyl acetate and 500 mL of purified water, and the organic layer was dried over anhydrous magnesium sulfate. The solvent was distilled off under reduced pressure to give N-(4-nitrophenyl)-5-ethynylindole (yield: 17 g, yield: 79%).

Add 17 g (65 mmol) of N-(4-nitrophenyl)-5-ethynylguanidine, 1.3 g (13 mmol) to a 500 mL three-necked flask equipped with a stirrer, thermometer, and air inlet. Copper (I) chloride and 2.5 g (21 mmol) of N,N'-tetramethylethylenediamine were added with 100 mL of ethylene glycol dimethyl ether. While using an air pump to feed air into the system, the air was stirred at room temperature for 24 hours. The reaction solution was filtered, and the obtained reaction product was washed once with 300 mL of aqueous ammonia, and washed twice with 300 mL of pure water to obtain 1,4-bis(5-(N-(4-nitrophenyl) )-mercapto))-1,3-butadiyne (yield 14 g, yield 82%)

To the reaction tube for autoclaving, 14.0 g (27 mmol) of the obtained 1,4-bis(5-(N-(4-nitrophenyl)-fluorenyl))-1,3-butyl was added. Diacetylene, 1.4 g of palladium carbon powder, 150 mL of ethanol and 150 mL of ethyl acetate were added. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. Then, the crude crystals were separated and purified by column chromatography (dichloromethane:methanol = 10:1 (v/v)), and recrystallized from ethanol to obtain 1,4-bis(5-(N-(4-) Aminophenyl)-indenyl)butane (yield 12 g, yield 91%).

1H-NMR (ppm): 1.74-1.76 (-CH ₂ -, m, 4H) 2.74-2.76 (-CH ₂ -, t, J = 6.4 Hz, 4H), 3.76 (-NH ₂ , br. s, 4H ), 6.52-7.45 (arm.H, 18H)

[Example 54] <Synthesis of diamine (1-37)>

To a 500 mL three-necked flask equipped with a stirrer, a thermometer, and a nitrogen inlet, 26.0 g (161 mmol) of commercially available 5-nitroguanidine and 27.0 g (194 mmol) of potassium carbonate were added, and 200 mL of DMF was added. A solution obtained by dissolving 38.0 g (242 mmol) of commercially available 5-fluoro-2-nitrophenol in 100 mL of DMF was added thereto, and the mixture was stirred at 140 ° C for 2 hours under a nitrogen atmosphere. Then, the reaction solution was placed in 1 L of pure water, and the obtained crystal was washed twice with 500 mL of pure water, twice with 500 mL of ethanol, and dried to obtain N-(3-hydroxy-4). -Nitrophenyl)-5-nitroindole (yield 45 g, yield 94%).

Add 45.0 g (150) to the reaction tube for autoclaving Methyl) N-(3-hydroxy-4-nitrophenyl)-5-nitroindole, 4.5 g of palladium carbon powder, 500 mL of ethanol was added. The system was stirred under a hydrogen atmosphere at a hydrogen pressure of 0.49 MPa for 12 hours at room temperature. Next, the palladium carbon powder was removed, and the obtained solution was concentrated to obtain a crude crystal. The crude crystals were recrystallized from ethanol/pure water = 1:1 (v/v) to obtain N-(4-amino-3-hydroxyphenyl)-5-aminoindole (yield 30 g, yield) The rate is 83%).

1H-NMR (ppm): 4.59 (-NH ₂ , br. s, 2H), 4.66 (-NH ₂ , br. s, 2H), 6.29-6.30 (=CH-, d, J = 3.0 Hz, 1H) , 6.53-7.13 (arm.H, m, 6H), 7.24-7.25 (=CH-, d, J=3.0 Hz, 1H)

As described above, the liquid crystal display device using the liquid crystal alignment agent of the present invention exhibits excellent characteristics such as high voltage holding ratio and small residual DC as compared with the conventional liquid crystal display element. Further, it is understood that the liquid crystal alignment agent of the present invention is excellent in storage stability and has high solubility in a solvent which is usually used.

Although the present invention has been disclosed in the above embodiments, it is not intended to limit the invention, and any one of ordinary skill in the art can make some modifications and refinements without departing from the spirit and scope of the invention. The scope of the invention is defined by the scope of the appended claims.

Claims (11)

A diamine represented by formula (1): Wherein Y is a single bond or a linear alkyl group having a carbon number of 1 to 9; any -CH ₂ - of the alkyl group may be -O-, -N(CH ₃ )-, 1,4-phenylene , 1,4-cyclohexylene or piperazine-1,4-diyl substituted; n is 0 or 1; and a hydrogen of a benzene ring to which an amine group is bonded may be substituted by -OH; wherein, when Y is a stretching When an alkyl group and n is 0, there is no case where -CH ₂ - having an amine group bonded thereto is substituted by -O- or -N(CH ₃ )-. The diamine according to claim 1, wherein the benzene ring to which an amine group is bonded is a benzene ring having no -OH as a substituent. The diamine according to claim 1, wherein the benzene ring to which the amine group is bonded is a benzene ring having a substituent -OH with respect to one of the ortho positions of the amine group. The diamine of claim 1, wherein Y is a single bond or 1,4-phenylene, and n is 0. The diamine according to claim 1, wherein Y is a single bond, or any -CH ₂ - may be substituted by -O- or -N(CH ₃ )-, and the linear alkylene having a carbon number of 1 to 9 Base; and n is 1. a poly-proline which is at least one of the first in the scope of the patent application The diamine described in the above, or a mixture of at least one diamine consisting of the diamine described in claim 1 and at least one other diamine, is obtained by reacting with at least one tetracarboxylic anhydride. The polyamic acid according to claim 6, wherein the at least one tetracarboxylic anhydride is a tetracarboxylic anhydride selected from the compounds represented by the formulae (A1) to (A63): A polyimine which is obtained by dehydrating and opening a polyamic acid as described in claim 6 of the patent application. A solution comprising at least one polymer selected from the group consisting of polylysine as described in claim 6 and polyamidiamine as described in claim 8 of the patent application. A liquid crystal alignment agent comprising a solution as described in claim 9 of the patent application. A liquid crystal display element comprising a liquid crystal alignment film obtained by the liquid crystal alignment agent according to claim 10 of the patent application.