JP2001064384A - Polyamide compound and liquid crystal alignment agent containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a liquid crystal alignment agent improved in characteristics such as pretilt angle, aligning properties, residual electric charge, and voltage retention by using a polyamide compound containing organic residues each having a side chain having at least a specified number of carbon atoms. SOLUTION: An N-substituted polyamide represented by formula I (wherein R2 is an organic residue having a side chain having at least three carbon atoms and is represented by formula II, III, or the like) is used. The polyamide is dissolved in an aprotic solvent (e.g. N-methyl-2-pyrrolidone) to give a varnish composition with a concentration of 0.1-40 wt.%, which is applied to a substrate and dried at 150-300 deg.C to form an aligned liquid crystal film. In the formulas, R1 is a dicarboxylic acid-derived divalent organic residue; R3 and R4 are each H or a monovalent organic group provided the monovalent organic group accounts for at least 30 mol% of the sum of R3 and R4; R5 is H or a 1-12C alkyl; Y is a single bond or CH2; ring A is a benzene ring, or the like; Z is a single bond, CH2, or the like; (r) is 0-3; (s) is 0-5; (t) is 0-3; X1 is a single bond, CH2, or the like; R6 and R7 are each H, a 1-12C alkyl or a perfluoroalkyl; and (u) is 0-3.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a novel polyamide compound, and more particularly to a novel polyamide compound which, when used as a liquid crystal aligning agent, has excellent electrical characteristics (voltage holding ratio, residual charge, burn-in) and an appropriate pretilt angle. It relates to polyamide compounds which can be provided. The polyamide compound of the present invention is preferably used in combination with another polymer component, for example, polyamic acid or soluble polyimide, thereby further improving the above-mentioned properties relating to the liquid crystal aligning agent, and applications in the field of electronic materials other than the liquid crystal aligning agent. For example, it can be applied to an insulating film, a protective film, and the like.

[0002]

2. Description of the Related Art At present, a liquid crystal display element using a nematic liquid crystal is mainly used. For example, a TN type liquid crystal element in which liquid crystal molecules are twisted by 90 °, usually an S liquid crystal element having a twist of 180 ° or more
Various types of display elements such as a TN type liquid crystal element, a so-called TFT type liquid crystal element using a thin film transistor, and a lateral electric field type IPS type liquid crystal element having improved viewing angle characteristics have been put into practical use. The development of liquid crystal display devices is not only simply progressing in these systems, but also the improvements in peripheral materials are being actively made to improve the characteristics of liquid crystal display devices. One of the peripheral materials is a liquid crystal aligning agent, which is one of the important factors relating to the display quality of the liquid crystal display element. Has become.

At present, liquid crystal aligning agents mainly used are polyimide-based aligning agents such as polyamic acid and soluble polyimide which are used by imidizing polyamic acid. According to the prior literature, various other polymer-based alignment agents have been studied, but all of them are heat-resistant and chemical-resistant (liquid crystal).
The properties, applicability, electrical properties, display characteristics, alignment stability of liquid crystal molecules, etc. are insufficient, and they have hardly been put to practical use. In addition to the polyimide-based aligning agent, polyamides and polyamides in which the hydrogen atom of the amide bond (CONH) of the polyamide is replaced with another group have been studied, but they have problems in alignment properties and electric characteristics of liquid crystal elements. In addition, there are liquid crystal aligning agents using a polymer material obtained by blending a plurality of polymer materials or by block copolymerization. However, at present, there are difficulties in image sticking, residual charge, retention, and the like. As described above, the conventional liquid crystal aligning agent cannot satisfy the required characteristics comprehensively and in a well-balanced manner.

[0004]

SUMMARY OF THE INVENTION An object of the present invention is to solve the above-mentioned drawbacks of the prior art, and in particular, to pre-tilt angle and orientation desired for a liquid crystal aligning agent, and to obtain electric charge such as residual charge, voltage holding ratio and image sticking. It is an object of the present invention to provide a polyamide compound for a liquid crystal aligning agent capable of achieving an overall and well-balanced improvement in various properties such as a mechanical property.

As a further extension of the above-mentioned problems, liquid crystal display elements have been used in various fields, and accordingly, the required characteristics are becoming higher. These requirements include requirements for the orientation of the liquid crystal represented by the pretilt angle of the liquid crystal, requirements for the electrical characteristics of the liquid crystal element such as current consumption, voltage holding ratio, residual charge, and reliability of these characteristics in long-term use. Request for
Further, there is a demand for display quality such as an afterimage phenomenon of a liquid crystal display element and display unevenness. Among these required characteristics, the pretilt angle of the liquid crystal will be described first. The pretilt angle differs depending on the driving method of the liquid crystal element. For example, a TN type liquid crystal display element or a TFT type liquid crystal display element in which the liquid crystal is twisted 90 degrees is about 1 to 6 degrees, and an STN type liquid crystal display element having a large twist angle is 3 to 6 degrees.
A pretilt angle of about 8 degrees is required. However,
The required value of the pretilt angle slightly varies depending on the application, and recently, a STN type liquid crystal display element may be required to have an angle of 2 to 3 degrees or 8 degrees or more. On the other hand, in the IPS type device, since the liquid crystal molecules move in the horizontal direction with respect to the substrate, it is not necessary to increase the pretilt angle, and the pretilt angle only needs to be about 1 °. In addition, not only the pretilt angle, but also the properties related to the alignment property of the liquid crystal, such as alignment uniformity, alignment stability, and anchoring energy at the liquid crystal-alignment film interface, greatly affect the performance of the liquid crystal element. is important. Furthermore, the process margin of these characteristics in the manufacturing process of the liquid crystal display element is also important, and the pretilt angle and the alignment of the liquid crystal change depending on the drying conditions of the solvent after the application of the alignment agent or the annealing treatment conditions after the injection of the liquid crystal. This is a big problem.

[0006] With respect to STN-type liquid crystal display elements, particularly those of low voltage type used in the field of portable equipment, the driving voltage of the liquid crystal display element is low, so that a demand for improvement in current consumption is important. That is, when the current consumption value of the liquid crystal element increases, the voltage applied to the liquid crystal relatively decreases and the low voltage tendency further increases, so that the rising of the liquid crystal molecules becomes insufficient and the contrast decreases.
Further, in a low-voltage type liquid crystal display device, a change (reliability) in a current consumption value occurring during long-term use of the liquid crystal display device is also important. In the case of STN type display element, display ON-
Since the OFF is performed with a slight potential difference, if the current consumption value of the element changes, the voltage applied to the liquid crystal also changes, and normal driving cannot be performed. In an extreme case, a phenomenon in which an image on the liquid crystal display element is not displayed at all may occur due to long-time driving.

On the other hand, regarding a TFT type liquid crystal display element,
Particularly, the requirements for the voltage holding ratio and the residual charge are important.
If the voltage holding ratio is low, the voltage applied to the liquid crystal during the field period decreases, causing a problem that the contrast decreases. If the residual charge is large, the charge remains as it is even if the voltage is turned off after the voltage is applied, and an image to be erased remains as an afterimage. In the TFT type liquid crystal display device, this afterimage phenomenon is one of quite important problems.

Further, in recent years, a liquid crystal having a large dielectric anisotropy has been used as the driving voltage of the liquid crystal has been lowered, and as a result, minute Vth unevenness generated in the surface of the display is regarded as a problem. Is to be done. In particular, when water washing is performed to remove shavings generated when the alignment film is rubbed, a phenomenon in which traces of water washing remain as Vth unevenness (water washing unevenness) occurs, which is a serious problem.

[0009]

In order to achieve the above object, the present invention comprises the following. (1) Equation (1)

[0010]

Embedded image

(Wherein, R ¹ represents a divalent organic residue derived from a dicarboxylic acid, and R ² represents a divalent organic residue derived from a diamine. At least one of them represents a side having 3 or more carbon atoms.) A divalent organic residue having a chain group, wherein R ³ and R ⁴ independently represent hydrogen or a monovalent organic group, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ is 30 mol% or more based on, n is a natural number. in the polyamide compound represented by), R ² is formula (2-1) to (2-4)

[0012]

Embedded image

(Wherein, 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 represents a benzene ring or a cyclohexane ring, Z represents a single bond, CH ₂ , CH ₂ CH ₂ or oxygen, and r represents 0 to
3, s is a positive number from 0 to 5 and t is a positive number from 0 to 3, respectively.
When t is 2 to 3, each Z may be the same or different. Further, hydrogen on any benzene ring or cyclohexane ring may be substituted with a lower alkyl group.
However, any ring in the steroid skeleton in formulas (2-2) and (2-3) may be contracted, expanded or cleaved, or may be a bicyclo ring, and the unsaturated bond at any position may be May be increased or decreased,
A hydrogen atom or an alkyl group at an arbitrary position may be substituted with an arbitrary monovalent organic group. ) A polyamide compound selected from the group of organic residues having a side chain group having 3 or more carbon atoms represented by: (2) Equation (1)

[0014]

Embedded image

(In the formula, R ¹ represents a divalent organic residue derived from a dicarboxylic acid, and R ² represents a divalent organic residue derived from a diamine. At least one of them represents a side having 3 or more carbon atoms. A divalent organic residue having a chain group, wherein R ³ and R ⁴ independently represent hydrogen or a monovalent organic group, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ is 30 mol% or more based on, n represents the polyamide compound represented by a natural number.), R ² is formula (3)

[0016]

Embedded image

(Wherein X ¹ is a single bond, CH ₂ or CH ₂
CH ₂ and R ⁶ and R ⁷ each independently represent hydrogen or an alkyl group having 1 to 12 carbon atoms or a perfluoroalkyl group, at least one of which represents an alkyl group having 3 or more carbon atoms or a perfluoroalkyl group; -Represents a fluoroalkyl group, and u is 0 to 3. When u is 2 to 3, each X ¹ may be the same or different. Further, hydrogen on any benzene ring may be substituted with a lower alkyl group. A) a polyamide compound having an organic residue having a side chain group having 3 or more carbon atoms represented by (3) Equation (1)

[0018]

Embedded image

(In the formula, R ¹ represents a divalent organic residue derived from a dicarboxylic acid, and R ² represents a divalent organic residue derived from a diamine. At least one of them represents a side having 3 or more carbon atoms. A divalent organic residue having a chain group, wherein R ³ and R ⁴ independently represent hydrogen or a monovalent organic group, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ is 30 mol% or more based on, n represents the polyamide compound represented by a natural number.), R ² is formula (4)

[0020]

Embedded image

(Wherein X ² and X ³ are each independently a single bond, O, COO, OCO, NH, CONH or (CH
₂ ) represents _n , R ⁸ and R ⁹ each independently represent a single bond or a divalent group containing 1 to 3 aromatic rings and / or alicyclic rings, and R ¹⁰ represents hydrogen, F, A hydrogen group, a fluorohydrocarbon group, an alkoxy group, a cyano group or an OH group,
Is a positive number from 1 to 5. However, group ^{-X 2 -R 8 -X 3 -R 9} -
R ¹⁰ is not any of a hydrogen atom, an alkyl group having 1 to 8 carbon atoms, an alkoxy group, and a trifluoromethyl group. A) a polyamide compound having an organic residue having a side chain group having 3 or more carbon atoms represented by (4) Equation (1)

[0022]

Embedded image

(Wherein, R ¹ represents a divalent organic residue derived from a dicarboxylic acid, and R ² represents a divalent organic residue derived from a diamine. At least one of them represents a side having 3 or more carbon atoms.) A divalent organic residue having a chain group, wherein R ³ and R ⁴ independently represent hydrogen or a monovalent organic group, and the content of the monovalent organic group is the total amount of R ³ and R ⁴ is 30 mol% or more based on, n represents the polyamide compound represented by a natural number.), R ² is formula (5)

[0024]

Embedded image

(Where A₁Is a hydrogen atom or carbon number 1
To 12 straight-chain or branched alkyl groups;
One or two or more non-adjacent ones in the alkyl group
May be substituted with an oxygen atom;_Two
Represents a single bond or an alkylene group having 1 to 5 carbon atoms;
One or more than two non-adjacent alkylene groups
Any methylene group may be substituted with an oxygen atom,
m is 0 to 3, and n is 1 to 5. ) Charcoal
It is an organic residue having a side chain group with a prime number of 3 or more
Polyamide compound to be used. (5) Smell of the polyamide compound represented by the formula (1)
And R^ThreeAnd R^FourAre independently hydrogen or 5 carbon atoms or less
Wherein the content of the monovalent organic group is R ^ThreeWhen
R^FourIs at least 50 mol% based on the total amount of
(1) The polyamide according to any one of (1) to (4),
Compound. (6) In the polyamide compound represented by the formula (1)
And R^ThreeAnd R^FourAre independently hydrogen or 5 carbon atoms or less
From each alkyl or oxygen-containing alkyl group
Represents a selected monovalent organic group, and the content of the monovalent organic group is
R^ThreeAnd R^FourAt least 70 mol% based on the total amount of
Poria according to any one of (1) to (5), wherein
Mid compound. (7) Poria according to any one of (1) to (6)
A liquid crystal aligning agent containing a amide compound.

[0026]

BEST MODE FOR CARRYING OUT THE INVENTION The polyamide compound of the present invention is a substantially N-substituted polyamide represented by the formula (1) (hereinafter sometimes simply referred to as an N-substituted polyamide) having 3 or more carbon atoms. The main feature is that R ² selected from the group of organic residues having a side chain group is limited to specific ones. As preferred examples of R ^{2 according to} the above limitation, organic residues represented by the above formulas (2-1) to (2-4), formulas (3), (4) and (5) are shown. Can be. In the polyamide compound of the present invention, in addition to the above-mentioned limitation of R ² , R ³ and R ⁴ independently represent hydrogen or a monovalent organic group having 5 or less carbon atoms, and the content of the monovalent organic group is R ³ More preferably, it is 50 mol% or more, preferably 70 mol% or more based on the total amount of R ⁴ and R ⁴ . Note that the above R
³ and R ⁴ each represent a monovalent organic group which replaces a hydrogen atom in the amide bond (CONH).

By using the polyamide compound of the present invention having such a structure as a component of a liquid crystal aligning agent, the objects of the present invention, namely, the pretilt angle and alignment desired for the liquid crystal aligning agent, residual charge, voltage holding ratio, image sticking, and the like. It is possible to achieve the improvement of various characteristics such as electric characteristics comprehensively and in a well-balanced manner.

In the polyamide compound represented by the formula (1), the object of the present invention is achieved to some extent by introducing a side chain group having 3 or more carbon atoms into at least one of R ^{1 to} R ^4. It is known. Examples of the introduction method include a method performed on R ³ or R ⁴ (first method), a method previously performed on dicarboxylic acid (second method), and a method previously performed on diamine (third method). Can be mentioned. Among these methods of introduction, most preferred since the third method can easily perform limitation of R ² as described above. However, the first method is not preferable because the monovalent organic group generally increases to one having 6 or more carbon atoms with the introduction of the side chain group, and the orientation of the liquid crystal is easily deteriorated. Since it is not always sufficient to achieve the object of the present invention by using only this method, it is preferable to use this method in combination with the third method.

In the polyamide compound represented by the formula (1) of the present invention, the dicarboxylic acids giving R ¹ may be aromatic (including heterocyclic), alicyclic (including heterocyclic) or aliphatic. The compound may belong to any group of group (non-cyclic) group, and among them, a compound having a ring structure is preferable from the viewpoint of maintaining good alignment of liquid crystal molecules. Therefore, when a non-cyclic aliphatic system is used, it is converted to an alicyclic system and / or
Alternatively, it is preferable to use the compound in combination with an aromatic compound, and the amount of the compound should be within a range that does not adversely affect the orientation. Further, R ¹ preferably has a structure that does not contain oxygen or sulfur, such as an ester group or an ether group, which is likely to cause a reduction in the electrical properties of the liquid crystal element. There is no problem unless the characteristics are affected.

Specific examples of the dicarboxylic acids giving R ¹ include the following.
Malonic acid, oxalic acid, dimethyl malonic acid, succinic acid, fumaric acid, glutaric acid, adipic acid, muconic acid, 2-methyladipic acid, trimethyladipic acid, pimelic acid, 2,2
-Aliphatic dicarboxylic acids such as dimethylglutaric acid, 3,3-diethylsuccinic 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-diphenyl-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, -Cyclobutene-3,4-dicarboxylic acid, 1,1-cyclopentanedicarboxylic 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, bicyclo [2.2.2] octane-2,3-dicarboxylic acid, 2,5-dioxo- 1,4-bicyclo [2.
2.2] octanedicarboxylic acid, 1,3-adamantanedicarboxylic acid, 4,8-dioxo-1,3-adamantanedicarboxylic acid, 2,6-spiro [3.3] heptanedicarboxylic acid, 1,3-adamantanedicarboxylic acid Alicyclic dicarboxylic acids such as 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, tetramethyl Terephthalic acid, 1,4-naphthalenedicarboxylic acid, 2,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid,
1,4-anthracene dicarboxylic acid, 1,4-anthraquinone dicarboxylic acid, 2,5-biphenyl dicarboxylic acid, 4,4′-biphenyl dicarboxylic acid, 1,5-biphenylenedicarboxylic acid, 4,4 ″ -tert-phenyl dicarboxylic acid Acid, 4,4′-diphenylmethanedicarboxylic acid,
4,4'-diphenylethanedicarboxylic acid, 4,4'-
Diphenylpropane dicarboxylic acid, 4,4′-diphenylhexafluoropropane dicarboxylic acid, 4,4′-diphenyl ether dicarboxylic acid, 4,4′-bibenzyl dicarboxylic acid, 4,4′-stilbene dicarboxylic acid,
4,4′-trandicarboxylic acid,

4,4'-carbonyldibenzoic acid, 4,
4'-sulfonyl dibenzoic acid, 4,4'-dithiodibenzoic acid, p-phenylene diacetic 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-
Thiazole dicarboxylic acid, 1,2,5-thiadiazole-3,4-dicarboxylic acid, 1,2,5-oxadiazole-3,4-dicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid Acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,
Examples thereof include aromatic dicarboxylic acids such as 4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, and 3,6-pyridinedicarboxylic acid, and these dicarboxylic acids may be in the form of an acid dihalide. . The above dicarboxylic acid or its acid dihalide (hereinafter sometimes referred to as dicarboxylic acids) is preferably a dicarboxylic acid capable of giving a polyamide having a linear structure, from the viewpoint of maintaining the orientation of liquid crystal molecules. .

Among these, 1,4-cyclohexanedicarboxylic acid, terephthalic acid, isophthalic acid, pyridinedicarboxylic acid, naphthalenedicarboxylic acid, 1,4-anthracenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4 " -Tert-phenyldicarboxylic acid, 4,4 '
-Diphenylmethanedicarboxylic acid, 4,4'-diphenylethanedicarboxylic acid, 4,4'-diphenylpropanedicarboxylic acid, 4,4'-diphenylhexafluoropropanedicarboxylic acid and 4,4'-diphenyletherdicarboxylic acid, or their acids Dihalide and the like are preferably used.

Further, a part of these dicarboxylic acids may be used together with a siloxane dicarboxylic acid represented by the formula (6) or an acid dichloride thereof in order to enhance the adhesion to the substrate.

[0036]

Embedded image

Wherein R ¹¹ and R ¹² are selected from a methyl group, an ethyl group, a phenyl group and a cyclohexyl group;
v, w, and x are 1 to 5. )

Further, as examples of dicarboxylic acids giving R ¹ into which a side chain group having 3 or more carbon atoms has been introduced in order to increase the pretilt angle of liquid crystal molecules, those represented by the formula (7) or (8) are exemplified. Can be shown.

[0039]

Embedded image

(Wherein X ⁴ is a single bond, O, COO, N
H, alkylene having 1 to 6 carbon atoms, OCO, NHCO, C
ONH, S or CH ₂ , R ¹³ represents a hydrocarbon group having 3 to 20 carbon atoms or a perfluoroalkyl group or a steroid group which may have a substituent, and cholesteryl, androsteryl, β Cholesteryl, epiandrosteryl, erygosteryl, estolyl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, melatranil, methyltestosterosteryl, noretisteryl, pregnenonyl, β-
Sitosteryl, stigmasteryl, testosteryl, cholesterol acetate and the like can be mentioned. )

[0041]

Embedded image

(In the formula, R ¹⁴ and R ¹⁵ each independently represent an alkyl group having 1 to 12 carbon atoms, and the total number of carbon atoms is 4 or more.) The dicarboxylic acids according to the present invention include It is needless to say that the present invention is not limited to this, and various other embodiments exist within a range in which the object of the present invention is achieved. These dicarboxylic acids can be used alone or in combination of two or more.

Next, as in the case of the dicarboxylic acids, the diamine compound giving R ² may be an aromatic (including a heterocyclic system), an alicyclic (including a heterocyclic system) or an aliphatic (non-heterocyclic) system. Ring) may belong to any group,
Among them, those having a ring structure are preferable from the viewpoint of maintaining good alignment of liquid crystal molecules. R ² preferably has a structure that does not contain oxygen or sulfur such as an ester group or an ether group which is likely to cause a decrease in the electrical properties of the liquid crystal element, as described above. There is no problem unless these properties are affected.

Since the polyamide compound of the present invention needs to have a function of giving a pretilt angle to the liquid crystal, it is necessary that at least the R ¹ component or the R ² component has a side chain group having 3 or more carbon atoms. It is. The former, that is, the case where a side chain group having 3 or more carbon atoms is introduced into R ¹ derived from dicarboxylic acids, may be referred to as it is.

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. It is preferable to use a diamine compound having a side chain group in combination. On the other hand, in the case of not using the dicarboxylic acids having a side chain group having 3 or more carbon atoms in components of R ¹ include diamine compounds having 3 or more side groups carbon is essential. The side chain group of the diamine compound has 3 carbon atoms.
The above-mentioned aliphatic hydrocarbon group, a hydrocarbon group containing an alicyclic structure, a hydrocarbon group containing an aromatic, a group having a siloxane group, a group having a steroid skeleton, or a group in which these are used in combination it can. When the side chain group is a cyclic structure such as a cyclohexane group, the number of carbon atoms is represented based on the number of carbon atoms constituting the ring. The side-chain group may be one in which a part of the hydrocarbon constituting the side-chain group is replaced by another atom such as oxygen.
Or an oxygen-containing group such as COO, S, or S
It is preferable that it does not contain a sulfur atom-containing group such as O ₂ . 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. Good.

As such a diamine compound having a side chain group having 3 or more carbon atoms, R ² has the formula (2-1) to
Examples of the diamine compound include any of the organic residues represented by (2-4), Formula (3), Formula (4) or Formula (5). The steroid skeleton in the above formulas (2-2) to (2-3) includes cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, ergosteryl, estolyl, 11α-hydroxymethylsteryl, 11α-progesteryl, lanosteryl, and melatranil. , Methyltestrosteryl, noretisteryl,
Pregnenonyl, β-sitosteryl, stigmasteryl, testosteryl, cholesterol acetate and the like can be mentioned.

As specific examples of such a diamine compound, those represented by formulas (2-1) to (2-4) include the following. When Z = oxygen, r = 0 and t = 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-tridecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-tetradecylcyclohexane, 1,1-bis [4- (4-aminophenoxy) phenyl] -4-n-pentadecylcyclohexane,

When r and t = 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-hexylcyclohexane, 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-bis (4-aminophenyl) -4-n-undecylcyclohexane, 1,1-bis (4-aminophenyl)
-4-n-dodecylcyclohexane, 1,1-bis (4
-Aminophenyl) -4-n-tridecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-tetradecylcyclohexane, 1,1-bis (4-aminophenyl) -4-n-penta Decylcyclohexane,

A = cyclohexyl group, r = 1, s, t =
When it is 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) cyclohexane, 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-cyclohexyl) 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,

A = cyclohexyl group, Z = oxygen, r =
1, s = 0 and t = 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-heptylcyclohexyl) cyclohexane, 1,
1-bis [4- (4-aminophenoxy) phenyl]-
4- (4-octylcyclohexyl) cyclohexane,

A = cyclohexyl group, Y = CH ₂ , r,
When s = 1 and t = 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-bis (4-aminophenyl) -4-[(4-butylcyclohexyl) methyl] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-pentylcyclohexyl) methyl] cyclohexane, 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,

A = phenyl group, Y = CH ₂ , Z = oxygen,
When r, s, t = 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,

A = phenyl group, Y = CH ₂ , r, s =
1, when t = 0: 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] cyclohexane, 1,1-bis (4-aminophenyl) -4-[(4-octylphenyl) methyl] cyclohexane,

A = phenyl group, Y = CH ₂ , Z is CH ₂ ,
When r, s, t = 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,

When Z = CH ₂ , r = 0, t = 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-pentylcyclohexane, 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.

A = cyclohexyl group, Y = CH ₂ , Z =
CH ₂ , r, t = 1, s = 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] cyclohexane, 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-trans-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, r is 0
In the case where R ⁵ is hydrogen or a short-chain alkyl group, the pretilt angle is small, and r is 1 to 5 (the side chain ring is 2 to 5).
In the case of 6), even if R ⁵ is hydrogen, the pretilt angle becomes large. When the pretilt angle is small, it is suitable for the IPS element, and when the pretilt angle is about 3 to 8 °, TN
It is suitable for a type TFT element. In the case of the STN element, an even larger pretilt angle may be required. In this case, a component having a long side chain group may be used.

Next, the compounds represented by the formula (3) include the following diamine compounds. When X ¹ = CH ₂ and u = 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} tetradecane, 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} octadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} nonadecane,

2,2-bis {4-[(4-aminophenyl) methyl] phenyl} perfluoropentane, 2,2
-Bis {4-[(4-aminophenyl) methyl] phenyl} perfluorohexane, 2,2-bis {4-[(4
-Aminophenyl) methyl] phenyl} per-fluoroheptane, 2,2-bis {4-[(4-aminophenyl)
Methyl] phenyl {perfluorooctane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl}
Perfluorononane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} per-fluorodecane,
2,2-bis {4-[(4-aminophenyl) methyl]
Phenyl perfluoroundecane, 2,2-bis4
-[(4-aminophenyl) methyl] phenyl} per-fluorododecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} per-fluorotridecane,
2,2-bis {4-[(4-aminophenyl) methyl]
Phenyl perfluorotetradecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl perfluoropentadecane, 2,2-bis {4-[(4-
Aminophenyl) methyl] phenyl} per-fluorohexadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} per-fluoroheptadecane,
2,2-bis {4-[(4-aminophenyl) methyl]
Phenyl @ per-fluorooctadecane, 2,2-bis {4-[(4-aminophenyl) methyl] phenyl} per-fluorononadecane. Although the examples of 2,2-bis compounds have been described above, 1,1-bis, 3,3-bis, 4,4-bis, and 5,6-bis compounds may be used depending on the number of carbon atoms of R ⁶ and R ⁷ . It goes without saying that a 5-bis compound can be similarly shown.

Next, the compounds represented by the formula (4) include the following diamine compounds. 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, dodecyl 2,4-diaminobenzoate, octyl 2,4-diaminobenzoate, 1,5-diamino-2-octyloxycarbonylaminobenzene, and the formula ( 2-
2) Diamine compounds having various steroidal substituents described in the description of (2-3).

Further, 1,4-diamino-3- [4-
(4-alkylcyclohexyl) cyclohexyloxy] benzene, 1,4-diamino-3- [4- (4-alkylphenyl) cyclohexyloxy] benzene,
1,4-diamino-3-((4-alkylta-phenyl) oxy) benzene, 2-alkyloxy-1,4-
Examples thereof include diaminobenzene, and diamine compounds having a steroidal side chain provided on phenylenediamine.

Next, the compounds represented by the formula (5) include the following diamine compounds. 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- Kurohekishiru-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-octylcyclohexyl) -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 above expressions have been described by formulas (2-1) to (2-)
These are merely specific examples of the diamine compound represented by 4), (3), (4) or (5). The diamine compound according to the present invention is not limited to these, and it goes without saying that various other embodiments exist within a range in which the object of the present invention is achieved. These diamine compounds can be used alone or in combination of two or more.

In the above embodiments, the formulas (2-1) to (2-
4), (3), a diamine compound having a side chain group having 3 or more carbon atoms capable of increasing the pretilt angle of a liquid crystal molecule as mentioned in (4) or (5) (hereinafter, a first diamine compound) ) And a diamine compound having no side chain (hereinafter sometimes referred to as a second diamine compound). Examples of the second diamine compound include an aromatic diamine compound, an alicyclic diamine compound and an aliphatic diamine compound described below.

Aromatic diamine compounds: p-phenylenediamine, m-phenylenediamine, o-phenylenediamine, p-xylenediamine, m-xylenediamine,
p-xylylenediamine, m-xylylenediamine,
2,4-diaminotoluene, 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) per-fluoropropane,
2,2-bis (3-aminophenyl) per-fluoropropane, 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-aminophenyl) 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) 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] per-fluoropropane,
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'-diaminota-phenyl, 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′-diaminodiphenyl sulfide,
4'-diaminodiphenyl sulfide, bis [4- (4
-Aminophenoxy) phenyl] sulfide, 3,3 '
-Diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone, bis [4- (4-aminophenoxy) phenyl] sulfone, 3,3'-diaminodiphenylether, 4,4'-diaminodiphenylether,
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] per-fluoropropane, 2,2-bis- (3-sulfamoyl-4-aminophenyl) per-fluoropropane, 2,2-bis- (3
-Carboxy-4-aminophenyl) per-fluoropropane, 2,2-bis [4- (3-sulfamoyl-4-
Aminophenoxy) phenyl] perfluoropropane,
2,2-bis [4- (3-carboxy-4-aminophenoxy) phenyl] per-fluoropropane, 1,3-bis [2- {4- (4-aminophenoxy) phenyl} per-fluoroisopropyl] benzene , 2,4-bis (β
-Amino-t-butyl) toluene, bis (p-β-methyl-γ-aminopentyl) benzene, bis p- (1,1
-Dimethyl-5-aminopentyl) benzene, bis (p
-Β-amino-t-butylphenyl) ether, bis (4-aminobenzoyloxy) methane, bis (4-aminobenzoloxy) ethane, bis (4-aminobenzoloxy) propane, bis (4 -Aminobenzoyloxy)
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'-diaminodicyclohexylmethane, bis (2-methyl-4-aminocyclohexyl) methane, tetrahydrodicyclopentadienylenediamine, hexahydro-
4,7-methanoindanylene dimethylene diamine, tricyclo [6.2.1.0,7] -undecylene dimethyl diamine, 4,4'-methylene bis (cyclohexylamine), 2,5-bis (aminomethyl) -bicyclo Heptane, 2,6-bisaminomethyl-bicycloheptane,
2,3-diaminobicyclo [2,2,1] heptane,
2,5-diaminobicyclo [2,2,1] heptane,
2,6-diaminobicyclo [2,2,1] heptane,
2,7-diaminobicyclo [2,2,1] heptane,
2,3-diamino-7-azabicyclo [2,2,1] heptane, 2,5-diamino-7-azabicyclo [2,2
2,1] heptane, 2,6-diamino-7-azabicyclo [2,2,1] heptane, 2,3-diamino-7-thiabicyclo [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-diamino-7-oxabicyclo [2,2,2] octane, 2,5-diamino-7-thiabicyclo [2,2 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-diamino-8-azabicyclo [3,2
2] nonane, 2,6-diamino-8-oxabicyclo [3,2,2] nonane, 2,6-diamino-8-thiabicyclo [3,2,2] nonane,

Aliphatic diamine compounds: ethylenediamine, trimethylenediamine, propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 4,4-diaminoheptamethylenediamine, And diamine compounds such as alkylenediamines having an oxygen atom in the alkylene group.

The above-mentioned second diamine compound is not limited to these, and it goes without saying that various other embodiments exist within a range in which the object of the present invention is achieved. Also,
These diamine compounds can be used alone or in combination of two or more. Of these second diamine compounds, the use of an aliphatic diamine compound in a large amount adversely affects the orientation of liquid crystal molecules. Therefore, the amount of the aliphatic diamine compound used should be within a range that can avoid such adverse effects.
Also, in order to avoid a decrease in the electrical properties of the liquid crystal element, the second
The diamine compound also preferably has a structure that does not contain an oxygen-containing group such as an ester group or an ether group or a sulfur-containing group.

In the diamine compound giving R ² , the ratio between the first diamine compound and the second diamine compound is not uniform depending on the type and the required pretilt angle, but generally the first diamine compound / second diamine compound (mol%) ), 100/0 to 1/99, preferably 100/0 to 10/90, more preferably 10/0 to 10/90.
0/0 to 20/80 are suitable.

Next, in the N-substituted polyamide of the present invention represented by the formula (1), R ³ and R ⁴ independently represent hydrogen or a monovalent organic group having 5 or less carbon atoms as described above. The content of the monovalent organic group is 5 based on the total amount of R ³ and R ^4.
0 mol% or more, preferably 70 mol% or more is suitable,
A plurality of them may be used in combination. By introducing the monovalent organic group, the obtained polyamide has remarkably improved electric properties especially when used as a liquid crystal aligning agent. When the monovalent organic group has a large number of carbon atoms (having a high flexibility), it may extremely deteriorate the liquid crystal alignment. Therefore, the organic group having 5 or less carbon atoms, particularly 5 or less carbon atoms. Is preferably an alkyl group or an oxygen-containing alkyl group. 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, a halogen, nitrogen, silicon or phosphorus-containing organic group if there is no problem in liquid crystal alignment. And so on. Further, these organic groups may have a substituent in the structure.

Specific examples of the monovalent organic group giving R ³ or R ⁴ include the following. 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, sec-butyl, tert-butyl, isopentyl, neopentyl, tert-pentyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, Isohexyl, 1
Linear or branched alkyl groups such as -ethylpentyl, 2-ethylpentyl, 3-ethylpentyl, 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, bicyclohexyl An organic group having an unsaturated bond or a cyclo ring such as methyl, 2-cyclopenten-1-yl and 2,4-cyclopentadien-1-yl;

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

Cholesteryl, androsteryl, β-cholesteryl, epiandrosteryl, erygosteryl,
Estoril, 11α-hydroxymethylsteryl, 11
an organic group having a steroid skeleton such as α-progesteryl, lanosteryl, melatranil, methyltestosteryl, norethisteryl, pregnenonyl, β-sitosteryl, stigmasteryl, testosteryl, and cholesterol acetate;

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-methoxybenzyl, biphenyloxy, naphthyloxy,

Phenoxymethyl, benzyloxymethyl, biphenyloxymethyl, naphthyloxymethyl,
Hydroxymethyl, hydroxyethyl, hydroxypropyl, hydroxybutyl, hydroxypentyl, hydroxyhexyl, furfuryl, (3-furyl) methyl, oxiranylmethyl, 2-methyloxiranylmethyl,
Oxygen-containing organic groups such as -oxetanylmethyl, 3-oxetanylmethyl, oxolanylmethyl, dioxolanylmethyl, formyl, acetyl, benzoyl, methoxycarbonyl, phenylmethoxycarbonyl,

Trifluoromethyl, perfluoroethyl, n-perfluoropropyl, n-perfluorobutyl, n-perfluoropentyl, n-perfluorohexyl, n-perfluoroheptyl, n-perfluorooctyl, n-per Fluorononyl, n-perfluorodecyl, n-perfluoroundecyl, n-perfluorododecyl, n-perfluorotridecyl, n-perfluorotetradecyl, n-perfluoropentadecyl, n
A halogen-containing organic group such as -perfluorohexadecyl, n-perfluoroheptadecyl, n-perfluorooctadecyl, n-perfluorononadecyl, n-perfluoroeicosyl, 4-trifluoromethylbenzyl,

Aminomethyl, aminoethyl, aminopropyl, aminobutyl, aminopentyl, aminohexyl, aminoheptyl, aminooctyl, aminononyl,
Aminodecyl, aminoundecyl, aminododecyl, aminotridecyl, aminotetradecyl, aminopentadecyl, aminohexadecyl, aminoheptadecyl, 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, 2,2,2 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-7
H-purin-7-yl) methyl, cyano, cyanomethyl, cyanoethyl, cyanopropyl, cyanophenyl,
Cyanobiphenyl, cyanoterphenyl, cyanobenzyl, cyanophenylmethyl, cyanobiphenylmethyl,
Organic groups containing nitrogen, silicon or phosphorus, such as cyanoterphenylmethyl, trimethylsilyl, triethylsilyl, triphenylsilyl, 4-trimethylsilylbenzyl, dimethoxyphosphinylmethyl, diethoxyphosphinylmethyl and the like.

Of these, methyl, ethyl, n-propyl, n-butyl, n-pentyl, isopropyl, isobutyl, sec-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, cyclopropylmethyl, 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-methyloxiranylmethyl, −
Monovalent organic groups having 5 or less carbon atoms such as oxetanylmethyl, 3-oxetanylmethyl, oxolanylmethyl, dioxolanylmethyl, formyl, and acetyl are preferably used. The monovalent organic group providing R ³ and R ^{4 according} to the present invention is not limited to these, and it goes without saying that there are various other embodiments within a range in which the object of the present invention is achieved. These monovalent organic groups can be used alone or in combination of two or more.

The N-substituted polyamide of the present invention can be obtained by one of the following two methods. One of them is a method in which a dicarboxylic acid is polymerized with a diamine compound in which a hydrogen atom of an amino group (NH ₂ ) has been previously substituted with R ³ and / or R ⁴ (hereinafter sometimes referred to as a pre-substitution method). The other is a method in which a diamine compound and a dicarboxylic acid are polymerized and a hydrogen atom of an amide bond (CONH) of the polyamide thus obtained is substituted with R ³ and / or R ⁴ (hereinafter referred to as a post-substitution method). May be called). Although any of the above methods can be applied, the latter is more excellent in reactivity and thus increases the molecular weight of the produced polymer. Therefore, when a liquid crystal alignment film is used, the film itself has good mechanical properties and imparts orientation. This is preferable because defects such as abrasion of the film and disturbance of the orientation in the rubbing step can be avoided.
The substitution rate of the organic group in the N-substituted polyamide is 5
0% or more, preferably 70% or more, more preferably 9% or more.
0% or more is suitable. If the substitution rate is less than 50%, it is difficult to obtain an effect in terms of electric characteristics of the liquid crystal display device.

The substituted diamine compound according to the pre-substitution method is
A known organic synthesis method, for example, a method of reducing a double bond of an imine obtained by dehydration-condensation of a diamine with an aldehyde such as propyl aldehyde or benzaldehyde or a ketone such as methyl ethyl ketone or cyclohexanone, diamine and acetyl chloride or benzoic acid A method of reducing the carbonyl group of an amide obtained by reacting an acid halide such as chloride with lithium aluminum hydride or the like; It can be easily obtained by reacting a substituted aniline with formaldehyde in the presence of an acid catalyst to obtain an N, N′-substituted diaminodiphenylmethane.

On the other hand, in the post-substitution method, a polyamide dissolved in a solvent such as dimethyl sulfoxide, N-methylpyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide is treated with sodium hydride, potassium hydride, R ³ -X or R ⁴ -X in the presence of a base such as sodium oxide, potassium hydroxide or triethylamine
Is carried out by reacting with a halide such as
When the reactivity is low, it is preferable that H in the amide bond is extracted in advance by the action of sodium hydride, butyllithium, or the like, and then reacted with the above halide.

In producing the N-substituted polyamide, the N-substituted diamine compound (in the case of the pre-substitution method) or the diamine compound (in the case of the post-substitution method)
And dicarboxylic acids must be reacted with each other. In this reaction, each of the above-mentioned components is optionally used as (PhO) ₃ P,
(PhO) PCl ₂ , PhPOCl ₂ or (C ₃ H ₇ )
_In the presence of a condensing agent such as ₃ P (O) O, pyridine and, if necessary, a solvent such as dimethylsulfoxide, N-methylpyrrolidone, N, N-dimethylformamide or N, N-dimethylacetamide, in the range of 20 to 300 ° C. It can be performed by reacting. When the reactivity is low, dicarboxylic acid dihalide may be used instead of dicarboxylic acid, or N, N'-diacetyldiamine or N, N'-bis (trimethylsilyl) diamine may be used instead of diamines. .

The liquid crystal aligning agent of the present invention contains the above-mentioned N-substituted polyamide as an essential component. However, there is no problem if used in combination with other polymer components as long as the effects of the present invention are not impaired. In particular, further improvement in properties may be achieved by using in combination with another polymer component. In this case, a polymer component that can be used in combination with the N-substituted polyamide of the present invention is generally used as a liquid crystal aligning agent. Polyamic acid, soluble polyimide,
Materials such as polyamide can be mentioned.

The liquid crystal aligning agent of the present invention is generally obtained as a varnish composition in which the above-mentioned N-substituted polyamide is dissolved in a solvent so that a liquid crystal aligning film can be formed on a substrate. In the varnish composition, the concentration of the polymer component is from 0.1 to
40% by weight is suitable. When the varnish composition is applied to a substrate, an operation of diluting a polymer component contained in the composition with a solvent in advance to adjust the film thickness may be required. If the content is more than 10% by weight, the viscosity of the composition becomes too high, and even if a solvent is added, the mixing with the composition becomes poor, and adverse effects such as the inability to obtain a desired dilution may occur, which is not preferable. In the case of the spinner method or the printing method, in order to keep the film thickness good, the content is usually set to 10% by weight or less. In other coating methods, for example, a dipping method, the concentration may be even lower than 10% by weight. On the other hand, if the concentration of the polymer component is less than 0.1% by weight, a problem that the thickness of the obtained liquid crystal alignment film becomes too thin tends to occur. Therefore, the concentration of the polymer component is 0.1% by weight or more, preferably about 0.5 to 10 in a usual spinner method or printing method. However, depending on the method of applying the varnish, a more dilute concentration may be used.

In the above varnish composition, the solvent used together with the polymer component can be applied without any particular limitation as long as the solvent has the ability to dissolve the polymer component. Such solvents include a wide range of solvents that are commonly used in the production process and applications of N-substituted polyamides, polyamic acids, and soluble polyimides, and are appropriately selected according to the purpose of use. Examples of these solvents include N-substituted polyamides, polyamic acids, and aprotic polar organic solvents that are lipophilic to soluble polyimides, such as N-methyl-2-pyrrolidone, dimethylimidozolidinone, N-methylcaprolactam,
N-methylpropionamide, N, N-dimethylacetamide, dimethylsulfoxide, N, N dimethylformamide, N, N-diethylformamide, diethylacetamide, γ-butyllactone, etc. Solvents such as alkyl lactate, 3-
Methyl-3-methoxybutanol, tetralin, isophorone, ethylene glycol monoalkyl ether such as ethylene glycol monobutyl ether, diethylene glycol monoalkyl ether such as diethylene glycol monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene Examples thereof include propylene glycol monoalkyl ethers such as glycol monobutyl ether, dialkyl malonates such as diethyl malonate, dipropylene glycol monoalkyl ethers such as dipropylene glycol monomethyl ether, and ester compounds such as acetates thereof.

The varnish composition thus obtained is
It is mainly suitable for forming a liquid crystal alignment film for a TFT, but can provide an appropriate pretilt, so that it can be used for a normal TN element, an STN element, a ferroelectric liquid crystal, or an antiferroelectric liquid crystal element. It is useful for forming a liquid crystal alignment film, and furthermore has excellent electric characteristics as a liquid crystal display element, so that it can be used for a protective film, an insulating film and the like. In the case of forming a liquid crystal alignment film, a step of applying a varnish composition onto a substrate, a subsequent drying step, and a step of performing a heat treatment necessary for a dehydration / ring closure reaction are performed. As a method of the coating step, a spinner method, a printing method, a dipping method, a dropping method, and the like are generally known, and these methods can be similarly applied to the present invention. Further, as a method of a drying step and a step of performing a heat treatment required for a dehydration / ring closure reaction, a method of performing a heat treatment in an oven or an infrared furnace, a method of performing a heat treatment on a hot plate, and the like are generally known. , These methods are equally applicable in the present invention.

The drying step is preferably performed at a relatively low temperature within a range in which the solvent can be evaporated, and the heat treatment step is generally preferably performed at a temperature of about 150 to 300 ° C.

The varnish composition can contain various additives as required. For example, if it is desired to improve coatability, a surfactant for such purpose is used, an antistatic agent is required when antistatic improvement is required, and a silane cup is used if improved adhesion to the substrate is desired. A ring agent or a titanium-based coupling agent may be blended.

[0096]

EXAMPLES Examples are shown below, but the present invention is not limited to these examples. Further, in the present embodiment, an example in which an N-substituted polyamide and a polyamic acid are used in combination for the purpose of further improving the properties is described. There is no problem with using it. In each of the examples, the raw material components used are indicated by the abbreviations in the following item 1, and the amounts, proportions or concentrations of the respective components are based on weight unless otherwise specified. The synthesis of the polymer component is the second
According to the method described in the section, the varnish for forming the alignment film is prepared in the third step.
According to the method described in Section 4, the production of the alignment film evaluation cell was performed by the method described in Section 4, and the evaluation of the liquid crystal cell was performed by the method described in Section 5.

1. Raw materials used Dicarboxylic acid component Terephthalic acid: TPE 1,4-cyclohexanedigarbonic acid: DCCh Diamine compound component having no side chain 4,4′-diaminodiphenylmethane: DPM 4,4′-diaminodiphenylethane: DPEt C3 or more Diamine compound component having a 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 cyclobutane tetracarboxylic acid dianhydride: CBDA solvent component N- methyl-2-pyrrolidone: NMP Butyl cellosolve: BC

2. Polymer synthesis 1) Synthesis of polyamide TPA was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet.
2156g, DPM 1.9185g, 4ChB1B
4.8655 g was added, and 8.63 g of dehydrated NMP and 9.33 g of pyridine were added thereto to obtain a homogeneous solution. Then 12.01 g of triphenyl phosphite, 4 g of lithium chloride,
After adding calcium chloride 12g sequentially, 100-14
The reaction was performed at 0 ° C. for 2 hours. The obtained reaction solution was treated with methanol.
After reprecipitation with pure water and pure water, 10 g of polyamide (PA1) was obtained. Other polyamides were synthesized in the same manner. Table 1 shows the composition of the synthesized polyamide.

[0099]

[Table 1]

2) Synthesis of N-substituted polyamide Polyamide (P) was placed in a 200 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet.
A1) Put 5.026 g and 26.39 g of dehydrated NMP,
After stirring at room temperature for a while, 0.934 g of sodium hydride was added, and stirring was further continued for 40 minutes. 3.037 g of methyl iodide was added to this solution, and the mixture was further reacted for 1 hour. The obtained reaction solution was reprecipitated in the same manner as the above-mentioned polyamide (PA1), and then dried under reduced pressure to obtain an N-substituted polyamide (NPA1). Other N-substituted polyamides were synthesized in the same manner. Table 2 shows the composition of the synthesized polyamide. In addition, NPA8-11 of Table 2
Are ethyl bromide and n-bromide instead of methyl iodide
Synthesis was carried out using heptyl, benzyl bromide and anthrylmethyl bromide. Table 2 also shows the weight average molecular weight of the obtained polymer.

[0101]

[Table 2]

3) Synthesis of polyamic acid DPM was placed in a 500 ml four-necked flask equipped with a thermometer, a stirrer, a raw material charging port and a nitrogen gas inlet.
8908 g and 90.0 g of dehydrated NMP were added, and the mixture was stirred and dissolved under a stream of dry nitrogen. While maintaining the temperature of the reaction system at 5 to 70 ° C., 2.6902 g of PMDA and 2.419 of CBDA
0 g was added in order and reacted for 5 to 30 hours.
By adding 00.0 g, a polyamic acid (PA acid 1) having a polymer concentration of 5% was synthesized. In the case where the temperature rises due to the reaction temperature during the reaction of the raw materials, the reaction was carried out while keeping the reaction temperature at about 70 ° C. or lower. The weight average molecular weight of the obtained polymer was 75,000.

3. Preparation of varnish for forming alignment film To 18.0 g of varnish made of polyamic acid having a polymer concentration of 5% obtained in the synthesis example of polyamic acid, 0.10 g of N-substituted polyamide obtained in synthesis example of N-substituted polyamide was added and dissolved. After that, the resultant was diluted with a diluting solvent to a polymer concentration of 3% to obtain a varnish for forming an alignment film.

4. Preparation of Cell for Evaluating Alignment Film 1) Preparation of Cell for Evaluating Residual Charge and Voltage Holding Each varnish for application was coated on a glass substrate with a transparent electrode ITO using a spinner, and was reserved at 80 ° C. for about 5 minutes. After firing, heat treatment was performed at 250 ° C. for 30 minutes to form an alignment film. The substrate surface after the formation of the alignment film is subjected to an alignment treatment by rubbing with a rubbing device, and then a 7μ gap material is sprayed on the substrate surface. Sealing was carried out with a curing agent to produce an anti-parallel cell having a gap of 7 μm. In this cell, a liquid crystal composition comprising the following components (NI
(Point: 81.3 ° C., birefringence: 0.092), the inlet is sealed with a photocuring agent, UV irradiation is applied to cure the liquid crystal injection hole, and then heated at 110 ° C. for 30 minutes. The cell was subjected to the treatment to evaluate the residual charge and the voltage holding ratio.

[0105]

Embedded image

2) Preparation of Pretilt Angle Measurement Cell A 20 μm cell thickness was prepared in the same manner as in the above-described production of the residual charge and voltage holding ratio evaluation cell except that a 20 μm gap material was used instead of the 7 μm gap. Was prepared, a liquid crystal composition was injected, and the subsequent processing was performed to obtain a pretilt measurement cell.

5. Evaluation of liquid crystal cell 1) Measurement method of residual charge The measurement of the residual charge is described in, for example, Miyake et al., IEICE Technical Report
91-111 p19 "by measuring the hysteresis voltage by an existing method. The measurement was performed by superimposing a 50 mV, 1 kHz alternating current and a 0.0036 Hz direct current triangular wave on the liquid crystal cell.

2) Method for Measuring Voltage Holding Ratio The voltage holding ratio was measured by an existing method described in, for example, “Mizushima et al., Proceedings of the 14th Liquid Crystal Symposium, p. 78”. The measurement conditions were as follows: gate width 69 μs, frequency 6
At 0 Hz, the wave height is ± 4.5 V, and the measurement temperature is 60 ° C.

3) Method of Measuring Pretilt Angle The pretilt angle of the liquid crystal was measured by a crystal rotation method.

4) Method for Evaluating Orientation The orientation was evaluated by observing the cell used for measuring the pretilt angle under a polarizing microscope and determining the presence or absence of a domain.

Examples 1 to 11 In addition to 18.0 g of a varnish made of a polyamic acid (PA acid 1) having a polymer concentration of 5%, 0.10 g of an N-substituted polyamide dissolved therein are shown in Table 2 in the column of synthesis examples. NPA1
A varnish for forming an alignment film (liquid crystal aligning agent) was prepared in the same manner as in the above-mentioned item 3 except that the varnish was changed to 11, and the residual charge, the voltage holding ratio, the pretilt angle, and the orientation were determined for each varnish. The results were as shown in Table 3.

[0112]

[Table 3]

Table 3 shows that the liquid crystal aligning agents of Examples 1 to 11 using the N-substituted polyamide of the present invention included electric characteristics such as residual charge and voltage holding ratio, and alignment characteristics such as pretilt angle and alignment. It can be seen that each characteristic is well-balanced and excellent when viewed comprehensively.

[0114]

As described above, according to the present invention, it is possible to comprehensively improve various characteristics such as a pretilt angle and orientation desired for a liquid crystal aligning agent, and electric characteristics such as residual charge, voltage holding ratio and image sticking. A polyamide compound for a liquid crystal alignment agent that can be achieved in a well-balanced manner can be provided. The liquid crystal aligning agent containing the polyamide compound is particularly preferably used for a TFT device (TN type TFT, IPS device),
Furthermore, since it has excellent electrical characteristics and can adjust the pretilt angle arbitrarily, it can be used for STN devices, ferroelectric liquid crystals, and antiferroelectric liquid crystal devices, and can also be used as a protective film or an insulating film.

 ──────────────────────────────────────────────────続 き Continued on the front page F-term (reference) 2H090 HB09Y HB10Y HC05 KA05 KA08 KA14 KA15 MA10 MB01 4J001 DA01 DB01 DC01 DC14 DC15 DD01 DD06 DD08 DD14 EB05 EB06 EB07 EB08 EB09 EB14 EB15 EB16 EB30 EB35 EB35 EB35 EB35 EB34 EB35 EB60 EC04 EC05 EC06 EC07 EC08 EC09 EC14 EC16 EC36 EC44 EC45 EC46 EC47 EC48 EC55 EC56 EC66 EC74 EC75 GA13 JA07 JB11 JB36 JB38

Claims (7)

[Claims] (1) Formula (1) (Wherein, R ¹ is a divalent organic residue derived from dicarboxylic acids,
R ² represents a divalent organic residue derived from a diamine, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, and R ³ and R ⁴ are mutually independent. Represents hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more based on the total amount of R ³ and R ⁴ , and n is a natural number. In the polyamide compound represented by
R ² is represented by formulas (2-1) to (2-4) (In each formula, R ⁵ , R ¹⁶ , and R ¹⁷ are hydrogen or C 1 to C 12
Y is a single bond or CH ₂ , ring A is a benzene ring or cyclohexane ring, Z is a single bond, CH ₂ , C ₂
H ₂ CH ₂ or oxygen, r is 0 to 3, s is 0 to 5,
t is a positive number from 0 to 3, respectively. When t is from 2 to 3, each Z may be the same or different. Also,
Hydrogen on any benzene or cyclohexane ring may be substituted with a lower alkyl group. However, the expression (2-
2), any ring in the steroid skeleton in the formula (2-3) may be contracted, expanded or cleaved, may be a bicyclo ring, and may have an unsaturated bond at any position increased or decreased. And a hydrogen atom or an alkyl group at any position may be substituted with any monovalent organic group. ) A polyamide compound selected from the group of organic residues having a side chain group having 3 or more carbon atoms represented by: (2) Formula (1) (Wherein, R ¹ is a divalent organic residue derived from dicarboxylic acids,
R ² represents a divalent organic residue derived from a diamine, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, and R ³ and R ⁴ are mutually independent. Represents hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more based on the total amount of R ³ and R ⁴ , and n is a natural number. In the polyamide compound represented by
R ² is represented by the formula (3) (Wherein X ¹ represents a single bond, CH ₂ or CH ₂ CH ₂ ,
R ⁶ and R ⁷ are each independently hydrogen or C 1-12
Wherein at least one of them represents an alkyl group having 3 or more carbon atoms or a perfluoroalkyl group, and u represents 0 to
3, but when u is 2-3, each X ¹ may be the same or different. Further, hydrogen on any benzene ring may be substituted with a lower alkyl group. A) a polyamide compound having an organic residue having a side chain group having 3 or more carbon atoms represented by (3) Formula (1) (Wherein, R ¹ is a divalent organic residue derived from dicarboxylic acids,
R ² represents a divalent organic residue derived from a diamine, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, and R ³ and R ⁴ are mutually independent. Represents hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more based on the total amount of R ³ and R ⁴ , and n is a natural number. In the polyamide compound represented by
R ² is represented by the formula (4) (Wherein X ² and X ³ are each independently a single bond, O, CO
O, OCO, NH, CONH or (CH ₂ ) _n
R ⁸ and R ⁹ each independently represent a single bond or a divalent group containing 1 to 3 aromatic rings and / or alicyclic rings;
¹⁰ represents hydrogen, F, a hydrocarbon group, a fluorinated hydrocarbon group, an alkoxy group, a cyano group or an OH group, and n is a positive number of 1 to 5. However, 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. )
A polyamide compound characterized by being an organic residue having a side chain group having 3 or more carbon atoms represented by the following formula: 4. A compound of the formula (1) (Wherein, R ¹ is a divalent organic residue derived from dicarboxylic acids,
R ² represents a divalent organic residue derived from a diamine, at least one of which is a divalent organic residue having a side chain group having 3 or more carbon atoms, and R ³ and R ⁴ are mutually independent. Represents hydrogen or a monovalent organic group, and the content of the monovalent organic group is 30 mol% or more based on the total amount of R ³ and R ⁴ , and n is a natural number. In the polyamide compound represented by
R ² is represented by the formula (5) (In the formula, A ₁ represents a hydrogen atom or a linear or branched alkyl group having 1 to 12 carbon atoms, and one or two or more non-adjacent methylene groups in the alkyl group is an oxygen atom A ₂ represents a single bond or an alkylene group having 1 to 5 carbon atoms, and one or two or more non-adjacent methylene groups in the alkylene group are substituted with an oxygen atom. M is 0 to 3 and n is 1 to 5), which is an organic residue having a side chain group having 3 or more carbon atoms. 5. In the polyamide compound represented by the formula (1), R ³ and R ⁴ each independently represent hydrogen or a monovalent organic group having 5 or less carbon atoms, and the content of the monovalent organic group. Is R ³
The polyamide compound according to any one of claims 1 to ^{4, wherein} the amount is 50 mol% or more based on the total amount of R4 and R4. 6. In the polyamide compound represented by the formula (1), R ³ and R ⁴ are each independently hydrogen or a group having 5 carbon atoms.
The following monovalent organic groups selected from an alkyl group and an oxygen-containing alkyl group are shown, and the content of the monovalent organic group is 70 mol% or more based on the total amount of R ³ and R ^4. The polyamide compound according to any one of claims 1 to 5. 7. A liquid crystal aligning agent comprising the polyamide compound according to claim 1.