KR100776526B1 - Polyamide compounds and liquid crystal aligning agents containing the same - Google Patents

Abstract

SUMMARY OF THE INVENTION An object of the present invention is a poly for liquid crystal aligning agent which can be improved so that various characteristics such as electrical characteristics such as voltage retention and image sticking at initial tilt angle or orientation and residual charge desired in a liquid crystal aligning agent are comprehensive and balanced. It is to provide an amide compound. The compound is a polyamide compound of formula (1) wherein R ² is selected from an organic moiety group having side chain groups of 3 or more carbon atoms.

Formula 1

In Formula 1 above,

R ¹ is a dicarboxylic acid divalent organic residue,

R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms,

R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ ,

n is a natural number.

Polyamide, liquid crystal aligning agent, voltage retention, residual charge, afterimage, initial tilt angle.

Description

Polyamide compounds and liquid crystal aligning agents containing the same             

The present invention relates to a novel polyamide compound, and more particularly, to a polyamide compound that is excellent in electrical characteristics (voltage retention, residual charge, afterimage) when used as a liquid crystal aligning agent, and capable of imparting an appropriate initial tilt angle. It is about.

The polyamide compound of the present invention is preferably used in combination with other polymer components, for example, polyamic acid or soluble polyimide, to further improve the above-described characteristics according to the liquid crystal aligning agent and to use in the field of electronic materials other than the liquid crystal aligning agent. For example, it can apply also to an insulating film, a protective film, etc.

A liquid crystal display device is to use the current nematic liquid crystal, for example, the liquid crystal molecules 90 ^o twist TN liquid crystal device, typically 180 ^o or more twist STN liquid crystal device, a so-called TFT-type LCD using a thin film transistor The device is mainstream. In addition, the transverse electric field type IPS type liquid crystal display element etc. which improved visual characteristics are currently utilized, and the display element by various methods is utilized. The development of the liquid crystal display device is being developed not only by the development of these methods but also by the active improvement of its peripheral materials for improving the characteristics of the liquid crystal display device. One of the peripheral materials is a liquid crystal aligning agent, which is one of important factors depending on the display quality of the liquid crystal display device, but its role is further increased as the quality of the display device is required.

Currently, the liquid crystal aligning agent mainly used is polyimide-type aligning agents, such as polyamic acid and soluble polyimide, which imidate and use polyamic acid. According to the prior literature, various polymeric alignment agents have been studied in addition to the above, but all are insufficient in practical terms in terms of heat resistance, chemical resistance (liquid crystal) properties, coating properties, electrical properties, display properties, or orientation stability of liquid crystal molecules, and are not practically used.

In addition to polyimide-based alignment agents, polyamides in which hydrogen atoms of polyamides and amide bonds (CONH) of polyamides are substituted with other groups have been studied, but these have problems in orientation, electrical properties of liquid crystal elements, and the like. Moreover, although the liquid crystal aligning agent which uses the polymeric material which mix | blended or block-copolymerized several polymeric materials, there exists a difficulty in residual image, residual charge, retention rate, etc., at present.

Thus, the conventional liquid crystal aligning agent is not able to satisfy the required characteristic comprehensively and in balance.

The object of the present invention is to solve the above-mentioned drawbacks of the prior art, and in particular to achieve a comprehensive and balanced improvement in the initial tilt angle or orientation desired in the liquid crystal aligning agent and electrical properties such as residual charge, voltage retention, and afterimage. It is providing the polyamide compound for liquid crystal aligning agents which can be obtained.

The above problem will be described in more detail. Liquid crystal display devices have started to be used in various fields, but with this, the required characteristics are becoming higher.

As such a request for the orientation of the liquid crystal represented by the initial inclination angle of the liquid crystal, the demand for the electrical characteristics of the liquid crystal element such as the current consumption value, the voltage retention, the residual charge, or the reliability for the long-term use of these characteristics, and also the liquid crystal display. The demand for display quality, such as an afterimage phenomenon of a device, display unevenness, etc. are mentioned.

Among these requirements, the initial inclination angle of the liquid crystal will be described first. The initial inclination angle varies depending on the driving method of the liquid crystal display element. For example, an initial tilt angle of about 1 to 6 degrees is required in a TN type liquid crystal display device or a TFT type liquid crystal display device in which a liquid crystal is twisted at 90 degrees, and about 3 to 8 degrees in an STN type liquid crystal display device having a large twist angle. Initial tilt angle of is required. However, these required values of the initial tilt angle vary somewhat depending on the application, and in recent years, the STN type liquid crystal display device may require 2 to 3 degrees or 8 degrees or more. On the other hand, in the IPS-type device, because the liquid crystal molecule moves in the horizontal direction with respect to the substrate it is not necessary to increase the initial inclination angle of the initial inclination angle is preferably generally is about 1 ^o.

In addition, not only the initial tilt angle but also characteristics related to the orientation of the liquid crystal, such as alignment uniformity, orientation stability, or anchoring energy of the liquid crystal-alignment layer interface, are also importantly related to the performance of the liquid crystal device. In addition, in the manufacturing process of the liquid crystal display device, a process machine having these characteristics is also important, and when the initial tilt angle or the orientation of the liquid crystal changes depending on the drying conditions of the solvent after coating of the alignment agent or annealing treatment conditions after the liquid crystal injection. There is a big problem.

As for the low voltage type used in the STN type liquid crystal display device, especially in the field of portable devices, its driving voltage is low, so the demand for improvement of the consumption current value is important. In other words, when the current consumption value of the liquid crystal element is increased, the voltage according to the liquid crystal is relatively lowered, and thus the tendency of the low voltage is further strengthened. Therefore, starting of the liquid crystal molecules is insufficient, and contrast is lowered.

In addition, in the low-voltage type liquid crystal display device, the change (reliability) of the current consumption value that occurs during long-term use of the liquid crystal display device is also important. In the STN type display device, since the display is turned on and off with a slight potential difference, when the current consumption value of the device changes, the voltage applied to the liquid crystal also changes and normal driving cannot be performed. In extreme cases, even a long time of driving does not display an image of the liquid crystal display device at all.

On the other hand, regarding the TFT type liquid crystal display device, the demand for voltage retention and residual charge is particularly important. If the voltage holding ratio is low, the voltage due to the liquid crystal decreases during the field period, resulting in a problem of lowering the contrast. When the residual charge is large, even after the voltage is turned off, the charge remains as it is, and the phase to be erased remains as an afterimage. In the TFT type liquid crystal display device, such an afterimage phenomenon is one of very important problems.

In addition, recently, liquid crystals having a large dielectric anisotropy have been used as the liquid crystal driving voltage has been lowered, but there is a problem of minute Vth unevenness occurring in the display surface. In particular, when water washing to remove the debris generated when the alignment film is subjected to friction treatment is performed, a phenomenon in which the washed water remains as Vth nonuniformity (washing nonuniformity) occurs, which is a big problem.

In order to achieve the above object, the present invention has the following configuration.

(1) The polyamide compound of formula 1, wherein R ² is selected from the group of organic residues having side chain groups having 3 or more carbon atoms of formulas 2-1 to 2-4.

In Formula 1 above,

R ¹ is a dicarboxylic acid divalent organic residue,

R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms,

R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ ,

n is a natural number.

In the above formula 2-1 to 2-4,

R ⁵ , R ¹⁶ and R ¹⁷ are hydrogen or an alkyl group having 1 to 12 carbon atoms,

Y is a single bond or CH ₂ ,

Ring A is a benzene ring or a cyclohexane ring,

Z is a single bond, CH ₂ , CH ₂ CH ₂ or oxygen,

r is 0 to 3,

s is 0 to 5,

t is an integer of 0 to 3, respectively, and when t is 2 or 3, each Z may be the same or different from each other,

Hydrogen of any benzene ring or cyclohexane ring may be substituted with a lower alkyl group, provided that any ring in the steroid backbone in Formulas 2-2 and 2-3 may be reduced, enlarged or ring-opened, may be a bicyclo ring, and optionally The unsaturated bond at the position may be increased or decreased, and the hydrogen atom or alkyl group at any position may be substituted with any monovalent organic group.

(2) The polyamide compound of formula 1, wherein R ² is an organic moiety having a side chain group of 3 or more carbon atoms in formula (3).

Formula 1

In Formula 1 above,

R ¹ is a dicarboxylic acid divalent organic residue,

R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms,

R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ ,

n is a natural number.

In Formula 3 above,

X ¹ is a single bond, CH ₂ or CH ₂ CH ₂ ,

R ⁶ and R ⁷ are each independently hydrogen or an alkyl group or perfluoroalkyl group having 1 to 12 carbon atoms, at least one of which is an alkyl group or perfluoroalkyl group having 3 or more carbon atoms,

u is 0 to 3, and when u is 2 or 3, each X ¹ may be the same or different from each other,

The hydrogen of any benzene ring may be substituted with a lower alkyl group.

(3) The polyamide compound of formula (1) wherein R ² is an organic moiety having a side chain group of 3 or more carbon atoms in formula (4).

Formula 1

In Formula 1 above

R ¹ is a dicarboxylic acid divalent organic residue,

R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms,

R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ ,

n is a natural number.

In Formula 4 above,                 

X ² and X ³ are each independently a single bond, O, COO, OCO, NH, CONH or (CH ₂ ) _n ,

R ⁸ and R ⁹ are each independently a divalent group containing 1 to 3 single bonds or aromatic rings and / or alicyclic rings,

R ¹⁰ is hydrogen, F, a hydrocarbon group, a fluorinated hydrocarbon group, an alkoxy group, a cyano group or an OH group,

n is an integer from 1 to 5,

Provided that the group -X ² -R ⁸ -X ³ -R ⁹ -R ¹⁰ is not a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group or a trifluoromethyl group.

(4) The polyamide compound of formula (1), wherein R ² is an organic moiety having a side chain group of 3 or more carbon atoms of formula (5).

Formula 1

In Formula 1 above,

R ¹ is a dicarboxylic acid divalent organic residue,

R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms,

R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ ,

n is a natural number.

In Formula 5 above,

A ₁ is a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent two or more arbitrary methylene groups of the alkyl group may be substituted with an oxygen atom,

A ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms, one of the alkylene groups or two or more non-adjacent arbitrary methylene groups may be substituted with an oxygen atom,

m is 0 to 3,                 

p is 1-5.

(5) R ³ and R ⁴ are independently of each other hydrogen or a monovalent organic group having 5 or less carbon atoms, and the content of the monovalent organic group is 50 mol% or more of the total amount of R ³ and R ⁴ ( The polyamide compound of formula (1) according to any one of items 1) to (4).

(6) R ³ and R ⁴ are each independently a monovalent organic group selected from hydrogen, an alkyl group having 5 or less carbon atoms, or an oxygen-containing alkyl group, and the content of the monovalent organic group is 70 mol% of the total amount of R ³ and R ⁴ . The polyamide compound of the formula (1) according to any one of items (1) to (5), characterized in that the above.

(7) The liquid crystal aligning agent containing the polyamide compound in any one of item (1) -item (6).

Best Mode for Carrying Out the Invention
The polyamide compound of the present invention has R ² selected from the group of organic residues having side chain groups having 3 or more carbon atoms in the substantially N-substituted polyamide of formula 1 (hereinafter sometimes simply referred to as N-substituted polyamide). There is a main feature to being limited to something specific.

Suitable examples of R ² in accordance with the above limitations may be organic residues of formulas 2-1 to 2-4, formula 3, formula 4 and formula 5.

In addition to the above limitation of R ² , the polyamide compound of the present invention is R ³ and R ⁴ independently of each other hydrogen or a monovalent organic group having 5 or less carbon atoms, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ . Is more preferably at least 50 mol%, preferably at least 70 mol%. In addition, R <^3> and R <^4> are monovalent organic groups each substituted with the hydrogen atom of an amide bond (CONH) part.

By using the polyamide compound of this invention of such a structure as a component of a liquid crystal aligning agent, the objective of this invention, ie, the general characteristics, such as the initial tilt angle and orientation required for a liquid crystal aligning agent, and electrical characteristics, such as residual charge, voltage retention, an afterimage, etc. It is possible to achieve a comprehensive and balanced improvement.

It is known that the object of the present invention is achieved to some extent by introducing side chain groups of 3 or more carbon atoms into at least one group of R ¹ to R ⁴ in the polyamide compound of formula (1). As said introduction method, for example, the method (1st method) performed with respect to R <^3> or R <^4> , the method previously performed with respect to a dicarboxylic acid (2nd method), or the method previously performed with respect to a diamine (3rd method) ).

Among these introduction methods, the third method is most preferable because the limitation of R ² can be easily performed as described above. However, the first method is not preferable because the monovalent organic group generally increases to 6 or more carbon atoms with the introduction of the side chain group, and it is easy to impair the orientation of the liquid crystal. In addition, the second method alone is sufficient to achieve the object of the present invention. Since it is not necessarily sufficient, when following this method, it is preferable to carry out in combination with a 3rd method.

The dicarboxylic acids providing R ¹ in the polyamide compound represented by the general formula (1) of the present invention may be any group of an aromatic system (including a heterocyclic system), an alicyclic system (including a heterocyclic system), or an aliphatic system (acyclic). Although it may belong to, it is preferable to have a ring structure in the double point in that it maintains the orientation of liquid crystal molecules satisfactorily.

Therefore, when using an alicyclic aliphatic type, it is preferable to use it in combination with an alicyclic type and / or aromatic type, and also the usage-amount shall be in the range which does not adversely affect orientation. In addition, R ¹ is preferably a structure containing no oxygen or sulfur such as ester groups or ether groups, which tends to cause deterioration of the electrical properties of the liquid crystal device. It doesn't matter.

As dicarboxylic acid which provides such R <^1> , the thing described next is mentioned concretely.

Malonic acid, oxalic acid, dimethylmalonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 3 Aliphatic dicarboxylic acids such as, 3-diethyl succinic acid, azelaic acid, sebacic acid and suberic acid;                 

1,1-cyclopropanedicarboxylic acid, 1,2-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, 1,2-cyclobutanedicarboxylic acid, 1,3-cyclobutanedicarboxylic acid, 3,4-di Phenyl-1,2-cyclobutanedicarboxylic acid, 2,4-diphenyl-1,3-cyclobutanedicarboxylic acid, 3,4-bis (2-hydroxyphenyl) -1,2-cyclobutanedicarboxylic acid, 2 , 4-bis (2-hydroxyphenyl) -1,3-cyclobutanedicarboxylic acid, 1-cyclobutene-1,2-dicarboxylic acid, 1-cyclobutene-3,4-dicarboxylic acid, 1,1-cyclo Pentanedicarboxylic acid, 1,2-cyclopentanedicarboxylic acid, 1,3-cyclopentanedicarboxylic acid, 1,1-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1 , 4-cyclohexanedicarboxylic acid, 1,4- (2-norbornene) dicarboxylic acid, norbornene-2,3-dicarboxylic acid, bicyclo [2.2.2] octane-1,4-dicarboxylic acid, non Cyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-di Bovine-1,4-bicyclo [2.2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro [3.3] Alicyclic dicarboxylic acids such as heptanedicarboxylic acid, 1,3-adamantane 2-acetic acid and camphoric acid;

o-phthalic acid, isophthalic acid, terephthalic acid, 5-methylisophthalic acid, 5-tert-butylisophthalic acid, 5-aminoisophthalic acid, 5-hydroxyisophthalic acid, 2,5-dimethylterephthalic acid, tetramethylterephthalic acid, 1, 4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 1,4-anthraquinonedicarboxylic acid, 2,5 -Biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 "-terphenyldicarboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4 ' -Diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid, 4,4'-diphenyletherdicarboxylic acid, 4,4'-bibenzyl Dicarboxylic acid, 4,4'-stilbendicarboxylic acid, 4,4'-tolandicarboxylic acid,

4,4'-carbonyl-dibenzoic acid, 4,4'-sulfonyl-dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylenediacetic acid, 3,3'-p-phenylenedipropionic acid, 4- Carboxycinnamic acid, p-phenylenediacrylic acid, 3,3 '-[4,4'-(methylenedi-p-phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p -Phenylene)] dipropionic acid, 4,4 '-[4,4'-(oxydi-p-phenylene)] dibutyric acid, (isopropylidenedi-p-phenylenedioxy) dibutyric acid, bis (p -Carboxyphenyl) dimethylsilane, 1,5- (9-oxofluorene) dicarboxylic acid, 3,4-furandicarboxylic acid, 4,5-thiazoledicarboxylic acid, 2-phenyl-4,5-thiazoledicarboxylic acid, 1 , 2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 2 Aromatic dicarboxylic acids such as, 5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid and 3,6-pyridinedicarboxylic acid. Carboxylic Acid Dihal Id may be a type of.

The above-mentioned dicarboxylic acid or its acid dihalide (hereinafter sometimes referred to as dicarboxylic acids) is particularly preferable in that dicarboxylic acids capable of providing a polyamide having a linear structure maintain the orientation of liquid crystal molecules.

Among them, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, pyridinedicarboxylic acid, naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4 "-terphenyldi Carboxylic acid, 4,4'-diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid and 4 , 4'-diphenyletherdicarboxylic acid or acid dihalide thereof and the like are preferably used.

In addition, one part of these dicarboxylic acids can be used together with the siloxane dicarboxylic acid of formula (6) or acid dichloride thereof for the purpose of increasing the adhesiveness to the substrate.

In Formula 6 above

R ¹¹ and R ¹² are selected from methyl group, ethyl group, phenyl group and cyclohexyl group,

v, w and x are 1-5.

Moreover, the compound of following formula (7) or (8) is mentioned as an example of the dicarboxylic acid which provides R <^1> which introduce | transduced C3 or more side chain group in order to enlarge the initial tilt angle of a liquid crystal molecule.

In Formula 7 above                 

X ⁴ is a single bond, O, COO, NH, alkylene having 1 to 6 carbon atoms, OCO, NHCO, CONH, S or CH ₂ ,

R ¹³ is a steroid group which may have a hydrocarbon group or a perfluoroalkyl group or a substituent having 3 to 20 carbon atoms, and as the steroid skeleton, cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergostere Reel, Estoryl, 11α-Hydroxymethylsteryl, 11α-Progesteryl, Lanosteryl, Meratranyl, Methyltestorosteryl, Noresterosteryl, Pregnnonyl, β-Sitosteryl, Stigma Steril, testosteryl or cholesterol acetate, and the like.

In Formula 8 above,

R ¹⁴ and R ¹⁵ are each independently an alkyl group having 1 to 12 carbon atoms, but their total carbon number is 4 or more.

The dicarboxylic acids according to the present invention are not limited to these, and needless to say that various embodiments exist in addition to the scope within which the object of the present invention is achieved. In addition, these dicarboxylic acids can be used individually or in combination of 2 or more types.

The diamine compound which gives R <^2> is then to any group of an aromatic system (including a heterocyclic system), an alicyclic system (including a heterocyclic system), or an aliphatic system (acyclic) as in the case of dicarboxylic acids. Although it may belong, it is preferable to have a ring structure among these in the point which maintains the orientation of liquid crystal molecule favorably.

As described above, R ² preferably has a structure containing no oxygen or sulfur, such as ester groups or ether groups, which tend to cause deterioration of the electrical properties of the liquid crystal device. However, even if such a structure has such a structure, these properties are not affected. No problem.

Since the polyamide compound of this invention needs to have a function which gives an initial tilt angle to a liquid crystal, it is necessary for at least the component of R <^1> to have a C3 or more side chain group in the component of R <^2> . As for the electrons, that is, to introduce the side chain a group having a carbon number of 3 or more in the dicarboxylic acid R ¹ may Referring now to as been described.

The diamine compound providing R ² may be a diamine compound having no side chain when R ¹ is a dicarboxylic acid having a side chain group having 3 or more carbon atoms, but in this case, it is more preferable to use a diamine compound having a side chain group having 3 or more carbon atoms. On the other hand, when the dicarboxylic acid which has a C3 or more side chain group is not used for the component of R <^1>, the diamine compound which has a C3 or more side chain group is essential.

Examples of the side chain group of the diamine compound include an aliphatic hydrocarbon group having 3 or more carbon atoms, a hydrocarbon group containing an alicyclic structure, a hydrocarbon group containing an aromatic group, a group having a siloxane group, a group having a steroid skeleton, or a group in which these are used in combination. In addition, when said side chain group is cyclic structures, such as a cyclohexane group, its carbon number shall be shown based on the carbon number which comprises a ring.

The side chain group may be a part of the hydrocarbon constituting it is substituted with another atom such as oxygen, but preferably contains no oxygen atom-containing group such as O, CO or COO, sulfur-containing group such as S or SO ₂ desirable. However, when the side chain group is a hydrocarbon group containing an alicyclic structure or a hydrocarbon group containing an aromatic group, these may have a substituent such as an alkyl group, an alkoxy group, a halogen or an OH group.

As a diamine compound which has a C3 or more side chain group, the diamine compound whose R <^2> is any one of the organic residues of the said Formula (2-1)-2-4, (3), (4) or (5) is mentioned.

In Formulas 2-2 to 2-3, as the steroid skeleton, cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estryl, 11α-hydroxymethylsteryl, 11α Progesteryl, lanosteryl, meratranyl, methyltestosterolyl, noretysteryl, pregnnonyl, β-sitosteryl, stigmasteryl, testosteryl or cholesterol acetate have.

As a specific example of such a diamine compound, the following are mentioned as a compound of General formula 2-1-2-4.

If Z is oxygen, r is 0 and t is 1:

1,1-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-methylcyclohexane, 1,1-bis [ 4- (4-aminophenoxy) phenyl] -4-ethylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-propylcyclohexane, 1,1-bis [ 4- (4-aminophenoxy) phenyl] -4-n-butylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- n-pentylcyclohexane, 1,1- Bis [4- (4-aminophenoxy) phenyl] -4-n-hexylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-heptylcyclohexane, 1, 1-bis [4- (4-aminophenoxy) phenyl] -4-n-octylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-nonylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-decylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-undecyl Cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-dodecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- n-tride Silcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-tetradecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4 -n-pentadecylcyclohexane;

If r and t are 0:

1,1-bis (4-aminophenyl) cyclohexane, 1,1-bis (4-aminophenyl) -4-methylcyclohexane, 1,1-bis (4-aminophenyl) -4-ethylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-propylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-butylcyclohexane, 1,1-bis (4-aminophenyl ) -4-n-pentylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-hexyl cyclohexane, 1,1-bis (4-aminophenyl) -4-n-heptylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-octylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-nonylcyclohexane, 1,1-bis (4-aminophenyl ) -4-n-decylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-undecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-dodecylcyclo Hexane, 1,1-bis (4-aminophenyl) -4-n-tridecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-tetradecylcyclohexane, 1,1-bis ( 4-aminophenyl) -4-n-pentadecylcyclohexane;

When A is a cyclohexyl group, r is 1 and s and t are 0:

1,1-bis (4-aminophenyl) -4-cyclohexylcyclohexane, 1,1-bis (4-aminophenyl) -4- (4-methyl-trans-cyclohexyl) cyclohexane, 1,1- Bis (4-aminophenyl) -4- (4-ethyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-propyl-trans-cyclohexyl) cyclo Hexane, 1,1-bis (4-aminophenyl) -4- (4-n-butyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n- Pentyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-hexyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-heptyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-octyl-trans-cyclohexyl) cyclohexane, 1,1 -Bis (4-aminophenyl) -4- (4-n-nonyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-decyl-trans-cyclo Hexyl) cyclohexane, 1 , 1-bis (4-aminophenyl) -4- (4-n-undecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-dodecyl -Trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-tridecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-tetradecyl-trans-cyclohexyl) cyclohexane, 1,1-bis (4-aminophenyl) -4- (4-n-pentadecyl-trans-cyclohexyl) cyclohexane;

When A is a cyclohexyl group, Z is oxygen, r is 1, s is 0 and t is 1:

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (cyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4- Methylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-ethylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy Phenyl] -4- (4-propylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-butylcyclohexyl) cyclohexane, 1,1 -Bis [4- (4-aminophenoxy) phenyl] -4- (4-pentylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4- Hexylcyclohexyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-heptylcyclohexylcyclohexane, 1,1-bis [4- (4-aminophenoxy ) Phenyl] -4- (4-octylcyclohexyl) cyclohexane;

When A is a cyclohexyl group, Y is CH ₂ , r and s are 1 and t is 0:

1,1-bis (4-aminophenyl) -4- (cyclohexylmethyl) cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-methylcyclohexyl) methyl] cyclohexane, 1 , 1-bis (4-aminophenyl] -4-[(4-ethylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-propylcyclohexyl) methyl] Cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-butylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-pentylcyclo Hexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-hexylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl] -4-[( 4-heptylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl] -4-[(4-octylcyclohexyl) methyl] cyclohexane;

When A is a phenyl group, Y is CH ₂ and Z is oxygen and r, s and t are 1:

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (phenylmethyl) cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4 -Methylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1-bis [4- (4 -Aminophenoxy) phenyl] -4-[(4-propylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-butylphenyl) methyl ] Cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy ) Phenyl] -4-[(4-hexylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-[(4-octylphenyl) methyl] cyclohexane;

When A is a phenyl group, Y is CH ₂ , r and s are 1 and t is O:

1,1-bis (4-aminophenyl) -4- (phenylmethyl) cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-methylphenyl) methyl] cyclohexane, 1,1- Bis (4-aminophenyl) -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-propylphenyl) methyl] cyclohexane, 1, 1-bis (4-aminophenyl) -4-[(4-butylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-pentylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-hexylphenyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-heptylphenyl) methyl] cyclo Hexane, 1,1-bis (4-aminophenyl) -4-[(4-octylphenyl) methyl] cyclohexane;

When A is a phenyl group, Y is CH ₂ , Z is CH ₂ and r, s and t are 1:

1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- (phenylmethyl) cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4 -[(4-methylphenyl) methyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-[(4-ethylphenyl) methyl] cyclohexane, 1,1- Bis [4-[(4-aminophenyl) methyl] phenyl] -4-[(4-propylphenyl) methyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl]- 4-[(4-butylphenyl) methyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-[(4-pentylphenyl) methyl] cyclohexane, 1, 1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-[(4-hexylphenyl) methyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl ] -4-[(4-heptylphenyl) methyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-[(4-octylphenyl) methyl] cyclohexane;

If Z is CH ₂ , r is O and t is 1:

1,1-bis [4-[(4-aminophenyl) methyl] phenyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-methylcyclohexane, 1, 1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-ethylcyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-propylcyclohexane , 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-butylcyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-pentyl Cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-hexylcyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4 -Heptylcyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-octylcyclohexane;

When A is a cyclohexyl group, Y is CH ₂ , Z is CH ₂ , r and t are 1 and s is 2:

1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (cyclohexylethylcyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl ] -4- [2- (4-methyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4- Ethyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4-propyl-trans-cyclohexyl) ethyl] cyclo Hexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4-butyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4- [(4-aminophenyl) methyl] phenyl] -4- [2- (4-pentyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl ] -4- [2- (4-amyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4- Hexyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4-heptyl-t Lance-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4-octyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4- [2- (4-nonyl-trans-cyclohexyl) ethyl] cyclohexane, 1,1-bis [4- [( 4-aminophenyl) methyl] phenyl] -4- [2- (4-dodecyl-trans-cyclohexyl) ethyl] cyclohexane.

In these diamine compounds, when r is 0 and R ⁵ is hydrogen or a short chain alkyl group, the initial inclination angle is small, and when r is 1 to 5 (2 to 6 in the side chain ring), the initial inclination angle is large even if R ⁵ is hydrogen. .

If the initial angle of inclination is small, and accordingly the IPS devices, if the initial angle of inclination of about 3 to 8 ^o, it is appropriate for the TN type TFT element. In the case of the STN element, a larger initial tilt angle may be required, but in this case, a component having a long side chain group may be used.

Next, about the general formula (3), the diamine compounds described below are mentioned.

If X ¹ is CH ₂ and u is 1:

2,2-bis [4-[(4-aminophenyl) methyl] phenyl] pentane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] hexane, 2,2-bis [4- [(4-aminophenyl) methyl] phenyl] heptane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] octane, 2,2-bis [4-[(4-aminophenyl) methyl ] Phenyl] nonane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] decane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] undecane, 2, 2-bis [4-[(4-aminophenyl) methyl] phenyl] dodecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] tridecane, 2,2-bis [4- [(4-aminophenyl) methyl] phenyl] tetedecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] pentadecane, 2,2-bis [4-[(4-aminophenyl ) Methyl] phenyl] hexadecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] heptadecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] octa Decane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] nonadecan, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluoropentane, 2, 2-bis [4-[(4-aminophenyl) methyl] phenyl] purple Fluorohexane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluoroheptane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluoro Octane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorononane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorodecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorodecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorododecane, 2, 2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorotridecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl) perfluorotetedecane, 2,2 -Bis [4-[(4-aminophenyl) methyl] phenyl] perfluoropentadecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorohexadecane, 2,2 -Bis [4-[(4-aminophenyl) methyl] phenyl] perfluoroheptadecane, 2,2-bis [4-[(4-aminophenyl) methyl] phenyl] perfluorooctadecane, 2,2 -Bis [4-[(4-aminophenyl) methyl] phenyl) perfluorononadecane.

In addition, although the above was described about the example of a 2, 2-bis system compound, 1, 1-bis system, 3, 3-bis system, 4, 4-bis system, or 5, according to carbon number of R <^6> and R <^7> , Needless to say, the same can be said about the 5-bis compound.

Next, about the general formula (4), the diamine compounds described below are mentioned.

4- [3- (4-biphenyloxy) propoxy] -1,3-diamine, 4- [8- (4-biphenyloxy) octyloxy] -1,3-diaminobenzene, 4- [3 -(4-cyanobiphenyl-4'-oxy) propoxy] -1,3-diaminobenzene, 4- [12- (4-cyanobiphenyl-4'-oxy) dodecyloxy] -1,3 -Diaminobenzene, 4- [6- (4-methoxybiphenyl-4'-oxy) hexyloxy] -1,3-diaminobenzene, 4- [3- (4-fluorobiphenyl-4 ' -Oxy) propoxy] -1,3-diaminobenzene, 2,4-diaminobenzoic acid dodecyl, 2,4-diaminobenzoic acid octyl, 1,5-diamino-2-octyloxycarbonylaminobenzene and Diamine compound which has a substituent of each steroid type described in description of General formula 2-2 and 2-3.

Furthermore, 1,4-diamino-3- [4- (4-alkylcyclohexyl) cyclohexyloxy] benzene, 1,4-diamino-3- [4- (4-alkylphenyl) cyclohexyloxy ] Diamine compound in which steroid type side chain is provided in benzene, 1,4-diamino-3-((4-alkylterphenyl) oxy) benzene, 2-alkyloxy-1,4-diaminobenzene, and phenylenediamine Etc. can be mentioned.

Subsequently, the diamine compound described next about Formula (5) is mentioned.

1-cyclohexyl-4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-methylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1- ( 4-propylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-pentylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1 -(4-octylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-decylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane , 1- (4-dodecylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl) cyclohexane, 1-cyclohexyl-4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1 -(4-methylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-propylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane , 1- (4-pentylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-octylcycle Lohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- (4-decylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane, 1- ( 4-dodecylcyclohexyl) -4- (3-aminobenzyl-2-aminophenyl) cyclohexane.

The foregoing merely describes specific examples of the diamine compound represented by the formulas (2-1 to 2-4), (3), (4) or (5). The diamine compound which concerns on this invention is not limited to these, Needless to say that various aspects exist besides the range in which the objective of this invention is achieved. In addition, these diamine compounds can be used individually or in combination of 2 or more.

Among the above-mentioned embodiments, diamine compounds having side chain groups having 3 or more carbon atoms (hereinafter, first diamine) capable of increasing the initial tilt angle of the liquid crystal molecules as mentioned in Formulas 2-1 to 2-4, Formula 3, Formula 4 or Formula 5 It may be called a compound) and the diamine compound without a side chain (it may be called a 2nd diamine compound below) may be used together.

As a 2nd diamine compound, the aromatic diamine compound, alicyclic diamine compound, or aliphatic diamine compound enumerated next is mentioned, for example.

Aromatic Diamine Compounds:

p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-xylenediamine, m-xylylenediamine, p-xylylenediamine, m-xylylenediamine, 2,4-diamino Toluene, 2,6-diaminotoluene, 2,3,5,6-tetramethyl-p-phenylenediamine, 2,5-dimethyl-p-phenylenediamine, 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,3'-diaminodiphenylethane, 4,4'-diaminodiphenylethane, 1,3-bis (4-aminophenyl) propane, 2,2- Bis (4-aminophenyl) propane, 2,2-bis (3-aminophenyl) propane, 2,2-bis (4-aminophenyl) perfluoropropane, 2,2-bis (3-aminophenyl) purple Luoropropane, bis (4-amino-3-methylphenyl) methane, bis (4-amino-2-methylphenyl) methane, 1,2-bis (4-amino-3-methylphenyl) ethane, 1,3-bis ( 4-amino-3-methylphenyl) propane, 1,2-bis (4-amino-2-methylphenyl) ethane, 1,3-bis (4-amino-2-methylphenyl) propane, 1,4-bis [(4 -Aminophenyl) methyl] benzene, 1,4-bis [(3- Minophenyl) methyl] benzene, 1,4-bis [(4-aminophenyl) ethyl] benzene, 1,4-bis [(3-aminophenyl) ethyl] benzene, 1,4-bis [(4-amino- 3-methyl-phenyl) methyl] benzene, 1,4-bis [(4-amino-3-methyl-phenyl) ethyl] benzene, bis [(4- (4-aminophenylmethyl) phenyl] methane, bis [( 4- (4-aminophenylmethyl) phenyl] ethane, bis [(4- (3-aminophenylmethyl) phenyl] methane, bis [(4- (3-aminophenylmethyl) phenyl] ethane, 2,2'- Bis [(4- (4-aminophenylmethyl) phenyl] propane, 2,2'-bis [(4- (3-aminophenylmethyl) phenyl] propane, 2,2'-bis [(4- (3- Aminophenylmethyl) phenyl] perfluoropropane, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 2,2-bis (4-aminophenoxy ) Propane, bis [4- (4-aminophenoxy) phenyl] methane, 2,2-bis [4- (4-aminophenoxy) phenyl] ethane, 1,1-bis [4- (4-aminophenoxy C) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 1,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2- Bis [4- (2-aminophenoxy) phenyl] perfluoropropane, 2,2-bis [4- (3-aminophenoxy) phenyl] perfluoropropane, 2,2-bis [4- (4 -Aminophenoxy) phenyl] perfluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] butane, 4,4'-diaminobiphenyl, 3,3'-dimethylbenzidine, 3 , 3'-dimethoxybenzidine, 1,4-bis (4-aminophenyl) benzene, 4,4'-bis (4-aminophenyl) biphenyl, 4,4'-diaminoterphenyl, 3,3 ' -Dimethyl-4,4'-diaminobiphenyl, 1,3-bis [4- (4-aminophenoxy) phenyl] benzene, 1,4-bis [4- (4-aminophenoxy) phenyl] benzene , 4,4-bis [4- (4-aminophenoxy) phenyl] biphenyl, 1,2-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,3-bis [4- ( 4-aminophenoxy) phenyl] cyclohexane, 1,4-bis [4- (4-aminophenoxy) phenyl] cyclohexane, 1,5-diaminonaphthalene, 2,6-diaminonaphthalene, 2,7 -Diaminofluorene, 9,9-bis (4-aminophenyl) fluorene, 9,9-bis (4-aminophenyl) -10-anthracene , 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 4,4'-diaminobenzanilide, 3,3 ' -Diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,3'-diaminodiphenylbenzophenone, 4,4'-bis (4-aminophenoxy ) Diphenyl ketone, 3,3'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, 3,3'-diaminodi Phenylsulfone, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 3,3'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether , 3,4'-diaminodiphenyl ether, bis (4-aminophenyl) diethylsilane, bis (4-aminophenyl) diphenylsilane, bis (4-aminophenyl) ethylphosphine oxide, 2,2- Bis [4- (3-carbamoyl-4-aminophenoxy) phenyl] perfluoropropane, 2,2-bis- (3-sulfamoyl-4-aminophenyl) perfluoropropane, 2,2-ratio -(3-carboxy-4-aminophenyl) perfluoropropane, 2,2-bis [4- (3-sulfamoyl-4-aminophenoxy) phenyl] perfluoropropane, 2,2-bis [4 -(3-carboxy-4-aminophenoxy) phenyl] perfluoropropane, 1,3-bis [2- (4- (4-aminophenoxy) phenyl) perfluoroisopropyl] benzene, 2,4 -Bis (β-amino-t-butyl) toluene, bis (p-β-methyl-aminopentyl) benzene, bisp- (1,1-dimethyl-5-aminopentyl) benzene, bis (p-β-amino -t-butylphenyl) ether, bis (4-aminobenzyloxy) methane, bis (4-aminobenzyloxy) ethane, bis (4-aminobenzyloxy) propane, bis (4-aminobenzyloxy) cyclohexane, 2 , 3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyridine, diaminopyrimidine, diaminopiperazine, bis (4-aminophenyl) -N -Butylamine, N, N-bis- (4-aminophenyl) -N-methylamine, N- (3-aminophenyl) -4-aminobenzamide and the like;

Alicyclic Diamine Compounds:

1,4-diaminocyclohexane, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, isophoronediamine, norbornanediamine, 4,4'-diaminodi Cyclohexyl methane, bis (2-methyl-4-aminocyclohexyl) methane, tetrahydrodicyclopentadienylenediamine, hexahydro-4,7-methanoindanylenedimethylenediamine, tricyclo [6.2.1.02,7] -Undecylenedimethyldiamine, 4,4'-methylenebis (cyclohexylamine), 2,5-bis (aminomethyl) -bicycloheptane, 2,6-bisaminomethylbicycloheptane, 2,3-diamino Bicyclo [2,2,1] heptane, 2,5-diaminobicyclo [2,2,1] heptane, 2,6-diaminobicyclo [2,2,1] heptane, 2,7-dia Minobicyclo [2,2,1] heptane, 2,3-diamino-7-azabicyclo [2,2,1] heptane, 2,5-diamino-7-azabicyclo [2,2,1] Heptane, 2,6-diamino-7-azabicyclo [2,2,1] heptane, 2,3-diamino-7-thiabi Iclo [2,2,1] heptane, 2,5-diamino-7-thiabicyclo [2,2,1] heptane, 2,6-diamino-7-thiabicyclo [2,2,1 ] Heptane, 2,3-diaminobicyclo [2,2,2] octane, 2,5-diaminobicyclo [2,2,2] octane, 2,6-diaminobicyclo [2,2, 2] octane, 2,5-diaminobicyclo [2,2,2] octane-7-ene, 2,5-diamino-7-azabicyclo [2,2,2] octane, 2,5-dia Mino-7-oxabicyclo [2,2,2] octane, 2,5-diamino-7-thiabicyclo [2,2,2] octane, 2,6-diaminobicyclo [3,2, 1] octane, 2,6-diaminoazabicyclo [3,2,1] octane, 2,6-diaminooxabicyclo [3,2,1] octane, 2,6-diaminothiabicyclo [3 , 2,1] octane, 2,6-diaminobicyclo [3,2,2] nonane, 2,6-diaminobicyclo [3,2,2] nonan-8-ene, 2,6-dia Mino-8-azabicyclo [3,2,2] nonane, 2,6-diamino-8-oxabicyclo [3,2,2] nonane, 2,6-diamino-8-thiabicyclo [3 , 2,2] nonane and the like;

Aliphatic Diamine Compounds:

Oxygen atoms in ethylenediamine, trimethylenediamine, propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine and alkylene groups Diamine compounds, such as alkylenediamine which has.

The above-mentioned 2nd diamine compound is not limited to these, Needless to say that various aspects exist besides the range in which the objective of this invention is achieved. In addition, these diamine compounds can be used individually or in combination of 2 or more types. The aliphatic diamine compound in a large amount of these second diamine compounds adversely affects the orientation of the liquid crystal molecules, so the amount of the aliphatic diamine compound should be within a range to avoid such adverse effects. Moreover, in order to avoid the fall of the electrical property of a liquid crystal element, the thing of the structure which does not contain oxygen-containing groups, such as an ester group and an ether group, and a sulfur-containing group also in a 2nd diamine compound is preferable.

The ratio of the first diamine compound to the second diamine compound in the diamine compound providing R ² is not the same depending on the type and initial tilt angle required, but is generally represented by the first diamine compound / second diamine compound (mol%). In this case, 100/0 to 1/99, preferably 100/0 to 10/90, more preferably 100/0 to 20 / 8O are suitable.

Subsequently, in the N-substituted polyamide of the present invention of Formula 1, R ³ and R ⁴ are independently of each other hydrogen or a monovalent organic group having 5 or less carbon atoms as previously described, and the content of the monovalent organic group is R ³ and R ^4. 50 mol% or more, preferably 70 mol% or more of the total amount of is suitable, but these can use several kinds together.

The polyamide obtained by introducing the monovalent organic group particularly remarkably improves its electrical properties when used as a liquid crystal aligning agent. In addition, when the said monovalent organic group has many carbon atoms (high flexibility), liquid crystal aligning property may deteriorate extremely, and a C5 or less organic group, especially a C5 or less alkyl group or an oxygen containing alkyl group is preferable.

R ³ and R ⁴ may be an organic group having an unsaturated bond or a cyclo ring, an organic group having an aromatic ring, an organic group having a steroid skeleton, or an organic group having halogen, nitrogen, silicon or phosphorus, if there is no problem in liquid crystal alignment. none. In addition, these organic groups may have a substituent in the structure.

Specific examples of the monovalent organic group for providing such R ³ or R ⁴ include those described below.

Methyl, ethyl, n-propyl, n-butyl, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, n-undecyl, n-dodecyl, n-tridecyl , n-tetradecyl, n-pentadecyl, n-hexadecyl, n-heptadecyl, n-octadecyl, n-nonadecyl, n-eicosyl, isopropyl, isobutyl, secondary-butyl, tertiary- Butyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, isohexyl, 1-ethylpentyl, 2-ethylpentyl, 3-ethylpentyl Linear or branched alkyl groups such as 4-ethylpentyl, 2,4-dimethylhexyl, 2,3,5-triethylheptyl, vinyl, ethynyl, 1-propenyl, 2-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-penten-4-ynyl, 2-nonyl-2-butenyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl , Cyclopropylmethyl, cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, bicyclohexylmethyl, 2-cycle Penten-1-yl, 2,4-cyclopentadiene-1-yl, such as an unsaturated bond or an organic group having a bicyclo ring;

Phenyl, 2,6-dimethylphenyl, 2,6-diisopropylphenyl, biphenyl, triphenyl, terphenyl, benzyl, biphenylmethyl, triphenylmethyl, terphenylmethyl, 4-methylbenzyl, 4- (3 An organic group having an aromatic ring such as tert-butyl) benzyl, α-methylbenzyl, 1-naphthyl, 2-naphthyl, 9-anthrylmethyl, 5-phenyl-2,4-pentadiinyl;

Cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estoryl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, meratranyl, methyl Organic groups having a steroid skeleton such as testosterone, noretysteryl, pregnnonyl, β-sitosteryl, stigmasteril, testosteryl, and cholesterol esters;

Methoxy, ethoxy, propyloxy, butyloxy, pentyloxy, hexyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxypentyl, methoxyhexyl, ethoxymethyl, ethoxyethyl , Ethoxypropyl, ethoxybutyl, ethoxypentyl, ethoxyhexyl, hexyloxymethyl, hexyloxyethyl, hexyloxypropyl, hexyloxybutyl, hexyloxypentyl, hexyloxyhexyl, phenoxy, benzyloxy, 4-meth Oxybenzyl, biphenyloxy, naphthyloxy, phenoxymethyl, benzyloxymethyl, biphenyloxymethyl, naphthyloxymethyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxy Oxyhexyl, furfuryl, (3-furyl) methyl, oxiranylmethyl, 2-methyloxyranylmethyl, 2-oxetanylmethyl, 3-oxetanylmethyl, oxoranylmethyl, dioxoranylmethyl, formyl Oxygen-containing organic groups such as acetyl, benzoyl, methoxycarbonyl and phenylmethoxycarbonyl;

Trifluoromethyl, perfluoroethyl, n-perfluoropropyl, n-perfluorobutyl, n-perfluoropentyl, n-perfluorohexyl, n-perfluoroheptyl, n-perfluoro Octyl, n-perfluorononyl, n-perfluorodecyl, n-perfluorodecyl, n-perfluorododecyl, n-perfluorotridecyl, n-perfluorotetradecyl, n-purple Luoropentadecyl, n-perfluorohexadecyl, n-perfluoroheptadecyl, n-perfluorooctadecyl, n-perfluorononadecyl, n-perfluoroicosyl, 4-trifluoromethyl Halogen-containing organic groups such as benzyl;

Aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl, aminoheptyl, aminooctyl, aminononyl, aminodecyl, aminoundecyl, aminododecyl, aminotridecyl, aminotetradecyl, aminopentadecyl , Aminohexadecyl, amino heptadecyl, aminooctadecyl, aminononadecyl, aminoeicosyl, 2-aminoisopropyl, 3-aminoisobutyl, 2-pyridylmethyl, 3-pyridylmethyl, 4-pyridylmethyl , 2,2,6,6-tetramethyl-4-piperidinyl, 1,2,2,6,6-pentamethyl-4-piperidinyl, 2,2,6,6-tetramethyl-1- (2-propenyl) -4-piperidinyl, 1-methyl-2,5-dioxo-3-pyrrolidinyl, (1,2,3,6-tetrahydro-1,3-dimethyl-2, 6-dioxo-7H-purin-7-yl) methyl, cyano, cyanomethyl, cyanoethyl, cyanopropyl, cyanophenyl, cyanobiphenyl, cyanoterphenyl, cyanobenzyl, cyanophenyl Methyl, cyanobiphenylmethyl, cyanoterphenylme Trimethylsilyl, triethylsilyl, triphenylsilyl, trimethylsilyl 4-benzyl, dimethoxy phosphinylmethyl methyl, diethoxy methyl phosphonic nitrogen, such as sulfinyl, silicon or phosphorus-containing organic.

Among these, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, secondary-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, vinyl, ethynyl, 1-propenyl, 2-propenyl, isopropenyl, 2-butenyl, 1,3-butadienyl, 2-pentenyl, 2-penten-4-ynyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclo Propylmethyl, cyclobutylmethyl, 2-cyclopenten-1-yl, 2,4-cyclopentadien-1-yl, trifluoromethyl, perfluoroethyl, methoxy, ethoxy, propyloxy, butyloxy, Pentyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl, ethoxypropyl, hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl , Furfuryl, (3-furyl) methyl, oxiranylmethyl, 2-methyloxyranylmethyl, 2-oxetanylmethyl, 3-oxetanylmethyl, oxoranylmethyl, dioxo Carbonyl-methyl, formate wheat, one having a carbon number of 5 or less, such as acetyl is used as the organic groups are preferred.

The monovalent organic group which provides R <^3> and R <^4> which concerns on this invention is not limited to these, Needless to say that various aspects exist besides the range in which the objective of this invention is achieved. In addition, these monovalent organic groups can be used individually or in combination of 2 or more.

The N substituted polyamides of the present invention can be obtained by either of the two methods described below. One method is a method of polymerizing a diamine compound having a dicarboxylic acid and a hydrogen atom of an amino group (NH ₂ ) previously substituted with R ³ and / or R ⁴ (hereinafter sometimes referred to as a pre-substitution method). Is a method in which a hydrogen atom of an amide bond (CONH) of a polyamide obtained by polymerizing a diamine compound with a dicarboxylic acid is replaced with R ³ and / or R ⁴ (hereinafter sometimes referred to as post-substitution method). . Any of the above-mentioned methods can be applied, but since the latter is excellent in reactivity, the molecular weight of the resulting polymer is increased, and thus, when the liquid crystal aligning film is used, the film is reduced in a friction process that has good mechanical properties of the film itself and imparts orientation. It is preferable because defects such as disorientation can be avoided. Further, the substitution rate of the organic group in the N substituted polyamide is 50% or more, preferably 70% or more, more preferably 9% or more.

The substituted diamine compound according to the pre-substitution method is a known organic synthesis method, for example, diamine and aldehydes such as propylaldehyde or benzaldehyde or ketones such as methyl ethyl ketone or cyclohexanone to reduce the double bond of the imine obtained by dehydration condensation A method of reducing the carbonyl group of the amide obtained by reacting diamine with acid halides such as acetyl chloride or benzoic acid chloride with lithium aluminum hydride, and the like, and n-methylaniline, N, N-diphenylamine or n- N-substituted anilines, such as methyl-3-aminotoluene, and formaldehyde are easily obtained by referring to a method of reacting N, N'-substituted diaminodiphenylmethanes in the presence of an acid catalyst and the like.

In the post-substitution method, polyamide dissolved in a solvent such as dimethyl sulfoxide, n-methylpyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide is used for sodium hydride, potassium hydride, sodium hydroxide, It is carried out by reacting with a halide such as R ³ -X or R ⁴ -X in the presence of a base such as potassium hydroxide or triethylamine, but when the reactivity is low, H of the amide bond portion is replaced with sodium hydride or butyllithium. It is preferable to remove in advance by acting and to react with the above-mentioned halide long after.

In preparing the N-substituted polyamide, in any case, the N-substituted diamine compound (in the case of pre-substitution method) or the diamine compound (in the case of post-substitution method) must be reacted with dicarboxylic acids. If necessary, condensing agents such as (PhO) ₃ P, (PhO) PCl ₂ , PhPOCl _2, or (C ₃ H ₇ ) ₃ P (O) O, pyridine, dimethylsulfoxide, N-methyl, if necessary It can carry out by making it react in 20-300 degreeC in presence of solvent, such as a pyrrolidone, N, N- dimethylformamide, or N, N- dimethylacetamide.

When the reactivity is low, dicarboxylic acid dihalide may be used in place of dicarboxylic acid, or N, N'-diacetyldiamine or N, N'-bis (trimethylsilyl) diamine may be used in place of diamines.

Although the liquid crystal aligning agent of this invention contains N substituted polyamide as an essential component, it does not cause any problem even if it uses together with another polymer component, unless the effect of this invention is impaired. In particular, by using in combination with other polymer components, further improvement of properties is achieved. In this case, as the polymer component that can be used in combination with the N-substituted polyamide of the present invention, polyamic acid and soluble polyimide generally used as a liquid crystal aligning agent And materials such as polyamide.

Since the liquid crystal aligning agent of this invention makes it possible to form a liquid crystal aligning film on a board | substrate, it is common to provide it as the varnish composition of the state which dissolved N substituted polyamide in the solvent.

The concentration of the polymer component in the varnish composition is preferably from 0.1 to 40% by weight. When the varnish composition is applied to the substrate, an operation of diluting the containing polymer component in the composition with a solvent may be required in advance to adjust the film thickness. However, if the concentration of the polymer component exceeds 40% by weight, the viscosity of the composition is too high. It is not preferable because it may cause a bad effect such as poor mixing with the composition and dilution as desired even if the solvent is added.

In the case of the spinner method or the printing method, in order to maintain a good film thickness, it may be set as the concentration normally lower than 10 weight%. On the other hand, when the density | concentration of a polymer component is less than 0.1 weight%, it becomes easy to produce the problem that the film thickness of the liquid crystal aligning film obtained becomes too thin. Therefore, the concentration of the polymer component is suitably 0.1% by weight or more, and preferably about 0.5 to 10% by weight in the usual spinner method, printing method and the like. However, depending on the method of applying the varnish, it can be used at a thinner concentration. The solvent used with the polymer component in the varnish composition described above may be applied without particular limitation as long as it is a solvent having the ability to dissolve the polymer component. Such solvents include a wide range of solvents commonly used in the manufacturing process or use of N-substituted polyamide, polyamic acid, soluble polyimide, and are appropriately selected depending on the intended use.

Examples of these solvents include aprotic polar organic solvents, such as N-methyl-2-pyrrolidone, dimethylimidazolidinone, and N-, which are aprotic solvents for N-substituted polyamides, polyamic acids, and soluble polyimides. Methyl caprolactam, N-methylpropionamide, N, N-dimethylacetamide, dimethylsulfooxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide or γ-butyrolactone ; In addition, other solvents for the purpose of improving the coating properties, for example, ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monobutyl ether, di Diethylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monoalkyl ethers such as propylene glycol monobutyl ether, malonic acid dialkyl such as diethyl malonate And ester compound systems such as dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether or acetates thereof.

The varnish composition thus obtained is mainly suitable for the formation of the liquid crystal alignment film for TFTs, but from the viewpoint of providing an appropriate initial inclination, the liquid crystal for conventional TN devices, STN devices, ferroelectric liquid crystals or antiferroelectric liquid crystal devices It is also useful when forming an alignment film, and since it is excellent in electrical characteristics as a liquid crystal display element, it can be used also for a protective film, an insulating film, etc.

When forming a liquid crystal aligning film, it carries out by the process of apply | coating a varnish composition on a board | substrate, the following drying process, and the process of heat processing required for dehydration and ring-closure reaction.

Spinner methods, printing methods, immersion methods or dropping methods and the like are generally known as the coating step method, but these methods can be similarly applied to the present invention. In addition, as a process method for carrying out the heat treatment required for the drying process and the dehydration and ring-closure reaction, a method of heat treatment in an oven or an infrared furnace or a heat treatment on a heating plate is generally known, but these methods are also the same in the present invention. Can be applied.

It is preferable to perform a drying process at the comparatively low temperature within the range which a solvent can evaporate, and heat processing process is generally performed at the temperature of about 150-300 degreeC.

The varnish composition may contain various additives as necessary. For example, when an applicability is desired, a surfactant according to this purpose, an antistatic agent when an antistatic improvement is required, and a silane coupling agent or a titanium-based coupling agent are added when an adhesiveness with a substrate is desired. can do.

EXAMPLES Next, an Example is described and this invention is not limited at all by these Examples. In addition, in the present Example, although the case where N-substituted polyamide and polyamic acid are used in combination for the purpose of further improving the characteristic, N-substituted polyamide is used alone unless the effect of the present invention is impaired. It doesn't matter at all.

In each example, the raw material ingredients used are indicated according to the abbreviation of the following item 1, and the amounts, ratios, and concentrations of each ingredient are based on weight unless otherwise specified. In addition, the synthesis of the polymer component according to the method of the next item 2, the combination of the varnish for forming the alignment film is according to the method of the next item 3, the preparation of the cell for the alignment film evaluation is according to the method of the next item 4, the liquid crystal cell The evaluation of each shall be carried out in accordance with the method of the next section 5.

1. used raw material

Dicarboxylic acid component

Terephthalic Acid: TPE

1,4-cyclohexanedicarboxylic acid: DCCh

Side chain free diamine compound component

4,4'-diaminodiphenylmethane: DPM                 

4,4'-diaminodiphenylethane: DPEt

Diamine compound component which has a C3 or more side chain group

1,1-bis [4-[(4-aminophenyl) methyl] phenyl] cyclohexane: ChB1B

1,1-bis [4-[(4-aminophenyl) methyl] phenyl] -4-butylcyclohexane: 4ChB1B

1,1-bis [4- (4-aminophenoxy) phenyl] -4- (4-pentylcyclohexyl)

Cyclohexane: 5ChChBOB

1- (4-pentylcyclohexyl) -4- (4-aminobenzyl-2-aminophenyl)

Cyclohexane: 5ChChDPM

Tetracarboxylic dianhydride component

Pyromellitic dianhydride: PMDA

Cyclobutanetetracarboxylic dianhydride: CBDA solvent component

N-methyl-2-pyrrolidone: NMP

Butyl Cellosolve: BC

2. Polymer synthesis

1) Synthesis of Polyamide

Into a 500 ml four-necked flask equipped with a thermometer, agitator, raw material inlet, and nitrogen gas inlet, 3.2156 g of TPA, l.9185 g of DPM, and 4.8655 g of 4ChB1B were added thereto, followed by addition of 8.63 g of dehydrated NMP and 9.33 g of pyridine. It is done. 12.01 g of triphenyl phosphite, 4 g of lithium chloride, and 12 g of calcium chloride were sequentially added thereto, followed by 2 at 100 to 140 ° C.

React for hours. The obtained reaction solution is reprecipitated with methanol and pure water and then dried under reduced pressure to give 10 g of polyamide (PA1). Other polyamides are also synthesized by the same synthetic method. The composition of the synthesized polyamide is shown in Table 1.

2) Synthesis of N Substituted Polyamide

Into a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 5.026 g of polyamide (PA1) and 26.39 g of dehydrated NMP were added. After stirring at room temperature for a while, 0.934 g of sodium hydride was added again to 40 Continue stirring for minutes. To this solution was added 3.037 g of methyl iodide and reacted again for 1 hour. The obtained reaction solution is reprecipitated in the same manner as the polyamide (PA1) described above, followed by drying under reduced pressure to obtain an N substituted polyamide (NPA1). Other N substituted polyamides are also synthesized by the same synthesis method. The composition of the synthesized polyamide is shown in Table 2. In addition, NPA8-11 of Table 2 synthesize | combines using ethyl bromide, n-heptyl bromide, benzyl bromide, and anthryl methyl bromide instead of methyl iodide, respectively. Table 2 also shows the weight average molecular weight of the obtained polymer.

Note: (a), (b), (c), (d), (e), (f), (g) and (h) in the table are TPA, ChDC, DPM, DPEt, ChBIB, 4ChBIB, 5ChChBOB, respectively. And 5 ChChDPM.

3) Synthesis of Polyamic Acid

Into a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 4.8908 g of DPM and 90.Og of dehydrated NMP were added and stirred and dissolved under a dry nitrogen stream. While maintaining the temperature of the reaction system at 5 to 70 ° C., 2.6902 g of PMDA and 2.4190 g of CBDA were sequentially added to react for 5 to 30 hours, and then BC 10 O.Og was added to give a polymer concentration of 5% polyamic acid (PA Synthesize acid 1). When temperature rises by reaction temperature during reaction of a raw material, reaction temperature is suppressed to about 70 degreeC or less and made to react. In addition, the weight average molecular weight of the obtained polymer is 75000.

3.Combination of varnish for formation of alignment film

0.10 g of N-substituted polyamide obtained in Synthesis of N-substituted polyamide was added to 18.0 g of a varnish consisting of polyamic acid having a polymer concentration of 5% obtained in Synthesis Example of polyamic acid, and then diluted with a diluted solvent. It is set as the polymer concentration of 3%, and it is set as the varnish for oriented film formation.

4. Fabrication of cell for evaluation of alignment film

1) Fabrication of Residual Charge and Voltage Retention Rate Cell

Each coating varnish was applied on a glass substrate with a transparent electrode ITO with a spinner, prebaked at 80 ° C. for about 5 minutes, and then heated at 250 ° C. for 30 minutes to form an alignment film. After the alignment film is formed, the substrate surface is oriented by friction with a friction device, and then a substance giving a gap of 7 mu is spread thereon, and the peripheral portion from which the liquid crystal injection hole is removed with the alignment film forming surface inward is sealed with an epoxy curing agent to form a gap of 7 mu m. Create a non-parallel cell.

A liquid crystal composition (NI point: 81.3 ° C., birefringence: 0.092) consisting of the following components was injected into such a cell, the injection hole was sealed with a photocuring agent, UV irradiated to cure the liquid crystal injection hole, and then heated at 110 ° C. for 30 minutes. The treatment is performed to obtain a cell for evaluating residual charge and voltage retention.

2) Fabrication of initial tilt angle measuring cell

A non-parallel cell having a cell thickness of 20 μ, preparation of a liquid crystal composition, and the same as in the case of manufacturing a cell for evaluating the residual charge and voltage retention except for using a 20 μ gap-forming material in place of the 7 μ gap-providing material, Subsequent processing is performed to obtain an initial tilt measurement cell.

5.Evaluation of Liquid Crystal Cells

1) Method of measuring residual charge

The measurement of the residual charge is performed by measuring the magnetic hysteresis voltage by the conventional method described in "Miyake et al., Shingaku bubble EID 91-111 p19", for example. Moreover, it measures by superposing a triangular wave of 50 mV, alternating current of 1 kHZ, and direct current of frequency 0.0036HZ in a liquid crystal cell.

2) Measurement method of voltage retention

The measurement of voltage retention is measured by the existing method described, for example in "The 14th liquid crystal debate notice p78 of Mizushima et al.". The measurement conditions are gate width 69μs, frequency 60HZ, wave height 4.5V and measurement temperature 60 ℃.

3) Measuring method of initial tilt angle

The initial tilt angle of the liquid crystal is measured by the crystal rotation method.                 

4) Evaluation method of orientation

The evaluation of the orientation is performed by observing a cell used when measuring the initial tilt angle under a polarizing microscope to determine the presence or absence of a domain.

Examples 1-11

0.10 g of N-substituted polyamides dissolved in 18.0 g of a varnish consisting of a polyamic acid (PA acid 1) having a polymer concentration of 5% were dissolved except for NPA1 to NPA 11 described in the column of the synthesis example of Table 2, respectively. In the same manner as in Item 3, the varnish for forming the alignment film (liquid crystal aligning agent) is combined to determine the residual charge, the voltage retention, the initial tilt angle, and the orientation for each varnish. The results are as described in Table 3.

From Table 3, the liquid crystal aligning agent of Examples 1-11 using the N substituted polyamide of this invention synthesize | combined each characteristic including the electrical characteristics, such as residual charge and voltage retention, or orientation characteristics, such as initial inclination angle and orientation. Interpretation is balanced and excellent.

As described above, according to the present invention, the poly for liquid crystal aligning agent can be improved while the overall characteristics such as the initial tilt angle or orientation desired for the liquid crystal aligning agent and electrical properties such as residual charge, voltage retention, and afterimage are comprehensive and balanced. Amide compounds can be provided.

Moreover, the liquid crystal aligning agent containing the said polyamide compound is used suitably especially for TFT elements (TN type | mold TFT, IPS element), and it is excellent in an electrical property, and can also arbitrarily adjust the initial tilt angle, STN element, ferroelectric liquid crystal Since it can also be used for antiferroelectric liquid crystal elements, it can be used as a protective film or an insulating film.

Claims (9)

A polyamide compound of formula (I) wherein at least one of R ² is selected from an organic moiety group having side chain groups of 3 or more carbon atoms of formulas 2-1 to 2-4. Formula 1

In Formula 1 above, R ¹ is a dicarboxylic acid divalent organic residue, R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ , n is a natural number. Formula 2-1

Formula 2-2

Formula 2-3

Formula 2-4

In the above formula 2-1 to 2-4, R ⁵ , R ¹⁶ and R ¹⁷ are hydrogen or an alkyl group having 1 to 12 carbon atoms, Y is a single bond or CH ₂ , Ring A is a benzene ring or a cyclohexane ring, Z is a single bond, CH ₂ , CH ₂ CH ₂ or oxygen, r is 0 to 3, s is 0 to 5, t is an integer of 0 to 3, respectively, and when t is 2 or 3, each Z may be the same or different from each other, Hydrogen of any benzene ring or cyclohexane ring may be substituted with a lower alkyl group, provided that any ring in the steroid backbone in Formulas 2-2 and 2-3 may be reduced, enlarged or ring-opened, may be a bicyclo ring, and optionally The unsaturated bond at the position may be increased or decreased, and the hydrogen atom or alkyl group at any position may be substituted with any monovalent organic group. The polyamide compound of formula 1, wherein at least one of R ² is an organic moiety having a side chain group of 3 or more carbon atoms of formula (3). Formula 1

In Formula 1 above, R ¹ is a dicarboxylic acid divalent organic residue, R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ , n is a natural number. Formula 3

In Formula 3 above, X ¹ is a single bond, CH ₂ or CH ₂ CH ₂ , R ⁶ and R ⁷ are each independently hydrogen or an alkyl group or perfluoroalkyl group having 1 to 12 carbon atoms, at least one of which is an alkyl group or perfluoroalkyl group having 3 or more carbon atoms, u is 0 to 3, and when u is 2 or 3, each X ¹ may be the same or different from each other, The hydrogen of any benzene ring may be substituted with a lower alkyl group. The polyamide compound of formula 1, wherein at least one of R ² is an organic moiety having a side chain group having 3 or more carbon atoms of formula (4). Formula 1

In Formula 1 above R ¹ is a dicarboxylic acid divalent organic residue, R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ , n is a natural number. Formula 4

In Formula 4 above, X ² and X ³ are each independently a single bond, O, COO, OCO, NH, CONH or (CH ₂ ) _n , R ⁸ and R ⁹ are each independently a single bond or a divalent group containing 1 to 3 groups selected from the group consisting of an aromatic ring, an alicyclic ring, and a combination thereof, R ¹⁰ is hydrogen, F, a hydrocarbon group, a fluorinated hydrocarbon group, an alkoxy group, a cyano group or an OH group, n is an integer from 1 to 5, Provided that the group -X ² -R ⁸ -X ³ -R ⁹ -R ¹⁰ is not a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group or a trifluoromethyl group. The polyamide compound of formula 1, wherein at least one of R ² is an organic moiety having a side chain group of 3 or more carbon atoms of formula (5). Formula 1

In Formula 1 above, R ¹ is a dicarboxylic acid divalent organic residue, R ² is a diamine divalent organic residue, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, R ³ and R ⁴ are each independently hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more of the total amount of R ³ and R ⁴ , n is a natural number. Formula 5

In Formula 5 above, A ₁ is a hydrogen atom or a straight or branched chain alkyl group having 1 to 12 carbon atoms, and one or more non-adjacent two or more arbitrary methylene groups in the alkyl group may be substituted with an oxygen atom, A ₂ is a single bond or an alkylene group having 1 to 5 carbon atoms, one of the alkylene groups or two or more non-adjacent arbitrary methylene groups may be substituted with an oxygen atom, m is 0 to 3, p is 1-5. The compound according to any one of claims 1 to 4, wherein R ³ and R ⁴ are independently of each other hydrogen or a monovalent organic group having 5 or less carbon atoms, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ . Polyamide compound of Formula 1, characterized in that more than 50 mol% of. The monovalent organic group according to any one of claims 1 to 4, wherein R ³ and R ⁴ are independently of each other hydrogen, an alkyl group having 5 or less carbon atoms, or an oxygen-containing alkyl group, and the content of the monovalent organic group is A polyamide compound of formula 1, characterized in that at least 70 mol% of the total amount of R ³ and R ⁴ . The liquid crystal aligning agent containing the polyamide compound in any one of Claims 1-4. Liquid crystal aligning agent containing the polyamide compound of Claim 5. Liquid crystal aligning agent containing the polyamide compound of Claim 6.