KR20100026112A - Liquid crystal aligning agent, liquid crystal aligning film and liquid crystal display device - Google Patents

Abstract

PURPOSE: A liquid crystal display device is provided to ensure high ion density and to be applied to various driving methods. CONSTITUTION: A liquid crystal alignment agent comprises polyamic acids that are reaction products of tetracarboxylic dianhydride and diamine, or their mixture. The diamines are represented by chemical formulas (1) ~ (8). In chemical formulas, X is oxygen atom or NR^6, wherein R^6 represents hydrogen atom, C1-30 alkyl group or phenyl group; R^1, R^4, and R^5 represent an aromatic group or heterocyclic group containing monocycle or plural polycycles; and R^2 and R^3 represent an aromatic group or containing monocycle or plural polycycles, plural polycycle group or alicyclic group, a group in which an alkylene group is bonded with ring groups, or alkylene group.

Description

Liquid crystal aligning agent, liquid crystal aligning film, and liquid crystal display element {LIQUID CRYSTAL ALIGNING AGENT, LIQUID CRYSTAL ALIGNING FILM AND LIQUID CRYSTAL DISPLAY DEVICE}

The present invention provides a liquid crystal aligning agent containing a polyamic acid obtained by reacting a diamine containing a benzoxazole or a benzoimidazole skeleton with a tetracarboxylic dianhydride or a derivative thereof, a liquid crystal aligning film obtained from the liquid crystal aligning agent, and the liquid crystal aligning film. The branch relates to a liquid crystal display element.

Liquid crystal display devices are used in various liquid crystal display devices such as monitors of notebook computers and desktop computers, viewfinders of video cameras, projection displays, and the like, and have recently been used in televisions. Liquid crystal display elements are also used in optoelectronics-related elements such as optical printer heads, optical Fourier transform elements, and light valves.

Although various elements are known as the liquid crystal display element, the development of the technology of the liquid crystal display element is achieved not only by the driving method of the liquid crystal display element and the structure improvement of the liquid crystal display element but also by the improvement of the structural member used for a liquid crystal display element. . A liquid crystal display element usually has a liquid crystal aligning film for orientating the liquid crystal composition in a liquid crystal layer in a specific direction. The liquid crystal aligning film is one of important factors related to the display quality of the liquid crystal display element, and the role of the liquid crystal aligning film is becoming increasingly important as the quality of the liquid crystal display element is improved.

A liquid crystal aligning film is prepared from a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution which melt | dissolved polyamic acid or soluble polyimide in the organic solvent. A liquid crystal aligning film is formed by apply | coating such a solution to a board | substrate, and forming into a film by means, such as a heating.

Ion density is mentioned as an important characteristic calculated | required by the liquid crystal aligning film in order to improve the display quality of a liquid crystal display element. If the ion density is high, the voltage applied to the liquid crystal during the frame period is lowered, and as a result, the luminance is lowered, which may cause a problem in normal gradation display.

As an attempt to solve the above problem, for example, a polyamic acid composition containing two or more polyamic acids having different physical properties in order to form a liquid crystal alignment film is known (see Patent Documents 1 and 2, for example).

These prior arts leave room for new investigation in the electrical properties of the liquid crystal aligning film required for the liquid crystal aligning agent which forms the present liquid crystal aligning film which requires a new improvement, and the material for obtaining desired electrical properties.

On the other hand, as a polyamic acid, the polyamic acid containing bisbenzoimidazole and various aromatic acid dianhydrides is known (refer nonpatent literature 1). However, the use as a liquid crystal aligning agent was not examined.

Moreover, the polyimide resin and polyimide varnish containing the diamine and acid anhydride which have a benzoazole structure are known (for example, refer patent document 3). However, the use as a liquid crystal aligning agent was not examined similarly.

[Patent Document 1] Japanese Patent Application Laid-Open No. 11-193345

[Patent Document 2] Japanese Patent Application Laid-Open No. 11-193347

[Patent Document 3] WO 2008/047591 Brochure

[Non-Patent Document 1] Journal of Materials Chemistry, 2002, Vol. 12, Page 3551-3559

This invention provides the liquid crystal display element in which the expression of a desired ion density is achieved, the liquid crystal aligning film which achieves expression of a desired ion density in this liquid crystal display element, and the liquid crystal aligning agent which can form the same.

MEANS TO SOLVE THE PROBLEM When this invention uses the composition containing the polyamic acid which uses the aromatic diamine which has a benzoxazole or a benzoimidazole skeleton as a raw material, or its derivative for a liquid crystal aligning agent, the liquid crystal display element which has the liquid crystal aligning film formed by this has favorable ion density. It was found that can have, to complete the present invention.

The present invention consists of the following configurations.

[1] A liquid crystal aligning agent containing a polyamic acid or a derivative thereof that is a reaction product of tetracarboxylic dianhydride and diamine.

The said diamine is a liquid crystal aligning agent containing the diamine represented by the following general formula (1)-(8).

(In general formulas (1) to (8), X represents an oxygen atom or NR ⁶ (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a phenyl group), and R ¹ , R ⁴ , R ⁵ Each independently represents an aromatic ring group or a heterocyclic group consisting of a monocyclic ring or a plurality of rings, and R ² , R ³ each independently represents an aromatic ring group, a heterocyclic group or an alicyclic group consisting of a monocyclic ring or a plurality of rings, Alkylene group bound or alkylene group)

[2] The liquid crystal aligning agent according to [1], wherein the diamine is an oxazole represented by the following General Formulas (O) -1 to (O) -6.

(In General Formulas (O) -1 to (O) -6, n independently represents an integer of 0 to 8, and m represents an integer of 1 to 8).

[3] The liquid crystal aligning agent according to [1], wherein the diamine is imidazole represented by the following General Formulas (I) -1 to (I) -6.

(In General Formulas (I) -1 to (I) -6, n independently represents an integer of 0 to 8, and m represents an integer of 1 to 8).

[4] The liquid crystal aligning agent according to [2], wherein the diamine is an aromatic oxazole represented by the following General Formula (O) -2 or an alkyloxazole represented by the following General Formula (O) -3.

(In general formula (O) -3, m represents an integer of 1-8.)

[5] The liquid crystal aligning agent according to [3], wherein the diamine is an aromatic imidazole represented by the following General Formula (I) -2 or an alkylimidazole represented by the following General Formula (I) -3.

(In general formula (I) -3, m represents the integer of 1-8.)

[6] The liquid crystal according to any one of [1] to [5], wherein the diamine further includes a diamine having the side chain structure represented by the following General Formulas (VIII) and (X) to (XIII). Aligning agent.

In formula (VIII), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) m- (m represents an integer of 1 to 6). ), R ¹ represents a group having a steroid skeleton, a group represented by the following general formula (IX), and when the position of the two amino groups bonded to the benzene ring is para, further includes alkyl having 1 to 30 carbon atoms. and, when the said position is meta further comprising a phenyl or alkyl of 1 to 30 carbon atoms, in the alkyl, arbitrary -CH ₂ - is independently selected from _{-CF 2 -, - CHF-, -O-} ( stage , Discontinuous), -CH = CH- or -C≡C-, -CH ₃ can be substituted with -CH ₂ F, -CHF ₂ or -CF ₃ , the hydrogen of the phenyl is independent a, which may be substituted with _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2 or -OCF _3.

In formula (IX), A ⁴ and A ⁵ are each independently a single bond, -O- (but not discontinuous), -COO-, -OCO-, -CONH-, -CH = CH- or 1 carbon atom. To -12 alkylene, R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl represents a, R ⁴ is -H, -F, alkoxy, -CN fluorine substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF ₂ or -OCF ₃ And a and b each represent an integer of 0 to 4, c, d and e each represent an integer of 0 to 3, f and g each independently represent an integer of 0 to 2, and c + d + e ≧ 1. .

In formulas (X) and (XI), R ⁵ independently represents —H or —CH ₃ , R ⁶ represents —H, or alkyl or alkenyl of 1 to 20 carbon atoms, and A ⁶ independently represents A bond, -C (= 0)-or -CH _2- , and in general formula (XI), R ⁷ and R ⁸ each independently represent alkyl or phenyl having 1 to 20 carbon atoms.

In formulas (XII) and (XIII), A ⁷ independently represents —O— or alkylene having 1 to 6 carbon atoms, and in formula (XII), R ⁹ represents —H or alkyl having 1 to 30 carbon atoms. represents, any -CH ₂ in the alkyl from 2 to 30 carbon atoms of the alkyl- is -O- and may be substituted with (but not continuously), -CH = CH- or -C≡C-, a ⁸ is a single A bond or alkylene having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexylene, h represents 0 or 1, and in formula (XIII), R ¹⁰ represents C6-C22 alkyl is shown, R <^11> represents C1-C22 alkyl.

[7] The diamine having the side chain structure is represented by the following general formulas (VIII-2), (VIII-4) to (VIII-6), (XII-2), (XII-4), and (XII-6). It is at least one chosen from the compound shown, The liquid crystal aligning agent as described in [6] characterized by the above-mentioned.

In said general formula, R <^23> , R <^29> and R <^30> represent C1-C30 alkyl or C1-C30 alkoxy, respectively.

[8] The diamine further comprises a diamine having no side chain structure represented by the following general formulas (I) to (VII) and (XV), wherein the diamine further comprises any of [1] to [7]. Liquid crystal aligning agent.

In formula (I), X represents-(CH ₂ ) _m- (m represents an integer of 1 to 6), and in formulas (III) and (V) to (VII), Y is independently, Single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -NH-, -N (CH ₃ )-(CH ₂ ) _m -N (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- (CH ₂ ) _m -S- (m represents an integer of 1 to 6), in formula (V), Z represents a single bond or none, and in formula (XV), R ³³ and R ³⁴ are each Independently alkyl or phenyl having 1 to 3 carbon atoms, A ³ independently represents methylene, phenylene or alkyl substituted phenylene, l represents an integer of 1 to 6, m represents an integer of 1 to 10 In the formulas (II) to (VII), hydrogen bonded to a cyclohexane ring or a benzene ring is independently -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, Or it may be substituted with -PO ₃ H _{2 It} is bonded to the benzene ring in the general formula (IV) Hydrogen present may be substituted with benzyl.

[9] The diamine having no side chain structure is represented by the following structural formulas (IV-1), (IV-2), (IV-15) to (IV-17), (V-1) to (V-13), ( V-33), (V-35) to (V-37), (VII-2), and at least one selected from the compounds represented by (XV-1), the liquid crystal aligning as described in [8] characterized by the above-mentioned. My.

[10] The liquid crystal aligning agent according to any one of [1] to [9], wherein the tetracarboxylic dianhydride contains an aromatic tetracarboxylic dianhydride.

[11] The liquid crystal alignment according to [10], wherein the aromatic tetracarboxylic dianhydride is at least one of compounds represented by the following structural formulas (1), (2), (5) to (7) and (14). My.

[12] The liquid crystal aligning agent according to [11], wherein the aromatic tetracarboxylic dianhydride is a compound represented by the structural formula (1).

[13] The liquid crystal aligning agent according to any one of [1] to [12], wherein the tetracarboxylic dianhydride includes one or both of an alicyclic tetracarboxylic dianhydride and an aliphatic tetracarboxylic dianhydride.

[14] A compound in which the alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride are represented by the following structural formulas (19), (23), (25), (35) to (39), (44) and (49) It is at least one of, The liquid crystal aligning agent as described in [13].

[15] The liquid crystal aligning agent according to [14], wherein the alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride are compounds represented by the structural formula (19).

[16] A liquid crystal aligning agent containing the polyamic acid or its derivatives A and B, wherein the polyamic acid or its derivative A contains a diamine having the side chain structure in the diamine, and the polyamic acid or its derivative A and The liquid crystal aligning agent in any one of [6]-[15] containing the diamine represented by general formula (1)-(8) in one or both of the diamine of B.

[17] [1] to [16, further comprising at least one selected from an alkenyl substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. ] Liquid crystal aligning agent in any one of.

[18] A liquid crystal aligning film formed by heating a coating film of the liquid crystal aligning agent according to any one of [1] to [17].

[19] a pair of substrates, a liquid crystal molecule containing liquid crystal molecules, an electrode for applying a voltage to the liquid crystal layer formed between the pair of substrates, and a liquid crystal alignment film for orienting the liquid crystal molecules in a predetermined direction A liquid crystal display element, wherein said liquid crystal aligning film is a liquid crystal aligning film as described in [18].

According to the present invention, a liquid crystal display device having a high ion density and applicable to various driving methods can be provided.

Best Mode for Carrying Out the Invention

The liquid crystal aligning agent of this invention contains the polyamic acid or its derivative which is a reaction product of tetracarboxylic dianhydride and diamine. The derivative of the polyamic acid is a component that dissolves in the solvent when the liquid crystal aligning agent described later containing a solvent is used, and when the liquid crystal aligning agent is used as the liquid crystal aligning film described later, a liquid crystal aligning film containing polyimide as a main component can be formed. Ingredient. Examples of such polyamic acid derivatives include soluble polyimides, polyamic acid esters, polyamic acid amides, and the like, and more specifically, 1) polyimide in which all amino and carboxyl of the polyamic acid are subjected to dehydration ring closure. 2) Partially polyimide partially dehydrated and closed, 3) Polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) Substitution of organic dicarboxylic acid with a part of acid 2 anhydride included in tetracarboxylic dianhydride compound The polyamic acid-polyamide copolymer obtained by making it react, and the polyamideimide which carried out the dehydration ring-closure reaction of part or all of 5) said polyamic acid-polyamide copolymer are mentioned. The said polyamic acid or its derivative (s) may be 1 type, or 2 or more types may be sufficient as it.

The said diamine contains the diamine represented by following General formula (1)-(8). The diamine used in the present invention may be one kind of compound or two or more kinds of compounds.

In General Formulas (1) to (8), X represents an oxygen atom or NR ⁶ (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a phenyl group), and R ¹ , R ⁴ , and R ⁵ represent Each independently represents an aromatic ring group or a heterocyclic group composed of a monocyclic or plural ring, and R ² and R ³ each independently represent an aromatic ring group, a heterocyclic group or an alicyclic group composed of a monocyclic or plural ring, The group which the alkylene couple | bonded or the alkylene group is shown.

In said general formula (1)-(8), when X is an oxygen atom, it is preferable that oxazole is represented and the said diamine is an oxazole represented with the following general formula (O) -1-(O) -6.

In said general formula (O) -1-(O) -6, n represents the integer of 0-8 independently, and m represents the integer of 1-8.

It is more preferable that they are the aromatic oxazole represented by (O) -2 or the alkyloxazole represented by (O) -3 among the said oxazoles.

In the formulas (1) to (8), X represents imidazole in the case of NR ⁶ (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a phenyl group), and the diamine represents the following general formula It is preferable that it is the imidazole represented by Formula (I) -1-(I) -6.

In said general formula (I) -1-(I) -6, n represents the integer of 0-8 independently, and m represents the integer of 1-8.

It is more preferable that they are the aromatic imidazole represented by (I) -2 or the alkyl imidazole represented by (I) -3 among the said imidazole.

In this invention, the following compounds are mentioned as diamine represented by General formula (1)-(8), for example.

Particularly preferably used among the diamines are compounds represented by (o-9), (o-10), (o-22), (i-5) to (i-10), and (i-22). .

In order to express desired ion density in a liquid crystal display element, and to realize long-term stability, the diamine represented by the said General Formula (1)-(8) is used for the diamine which comprises the polyamic acid of the liquid crystal aligning agent of this invention. Therefore, it is preferable to be contained 20-100% in molar ratio, and it is more preferable to contain 35-100%.

The diamine represented by the said General Formula (1)-(8) can be manufactured by a well-known method. As such a manufacturing method, for example, as described in Non Patent Literature 1, phthalic anhydride is reacted with 1,2-phenylenediamine under a nitrogen atmosphere, and the reactant is dissolved in concentrated sulfuric acid and mixed with fuming nitric acid. The method of reducing the nitro group of the obtained compound with an amino group on normal reducing conditions using reducing agents, such as tin and hydrochloric acid, is mentioned.

The said diamine may contain only the diamine represented by the said General Formula (1)-(8), and may also contain other diamine further. As another diamine, the diamine which has a side chain structure, and the diamine which does not have a side chain structure is mentioned, for example. Such other diamines may be one kind of compound or two or more kinds of compounds.

The diamine which has the said side chain structure means the diamine which has a substituent (side chain) which can express the desired pretilt angle branched from a main chain, when the substituent which connects two amino groups is made into a main chain. Although the side chain in the diamine which has a side chain structure should just be selected suitably according to the pretilt angle requested | required, for example, a C3 or more group is mentioned to the said side chain. As a diamine which has the said side chain structure, the compound represented by the following general formula (VIII) and (X)-(XIII) is mentioned.

In formula (VIII), A ³ represents a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) m- (m represents an integer of 1 to 6). ), R ¹ represents a group having a steroid skeleton, a group represented by the following general formula (IX), and when the position of the two amino groups bonded to the benzene ring is para, further includes alkyl having 1 to 30 carbon atoms. and, when the said position is meta further comprising a phenyl or alkyl of 1 to 30 carbon atoms, in the alkyl, arbitrary -CH ₂ - is independently selected from _{-CF 2 -, - CHF-, -O-} ( stage , Discontinuous), -CH = CH- or -C≡C-, -CH ₃ can be substituted with -CH ₂ F, -CHF ₂ or -CF ₃ , the hydrogen of the phenyl is independent a, which may be substituted with _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2 or -OCF _3.

In formula (IX), A ⁴ and A ⁵ are each independently a single bond, -O- (but not discontinuous), -COO-, -OCO-, -CONH-, -CH = CH- or 1 carbon atom. To -12 alkylene, R ² and R ³ each independently represent -F or -CH ₃ , and ring S independently represents 1,4-phenylene, 1,4-cyclohexylene, 1,3 -Dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl represents a, R ⁴ is -H, -F, alkoxy, -CN fluorine substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF ₂ or -OCF ₃ And a and b each represent an integer of 0 to 4, c, d and e each represent an integer of 0 to 3, f and g each independently represent an integer of 0 to 2, and c + d + e ≧ 1. .

In formulas (X) and (XI), R ⁵ independently represents —H or —CH ₃ , R ⁶ represents —H, or alkyl or alkenyl of 1 to 20 carbon atoms, and A ⁶ independently represents A bond, -C (= 0)-or -CH _2- , and in general formula (XI), R ⁷ and R ⁸ each independently represent alkyl or phenyl having 1 to 20 carbon atoms.

In formulas (XII) and (XIII), A ⁷ independently represents —O— or alkylene having 1 to 6 carbon atoms, and in formula (XII), R ⁹ represents —H or alkyl having 1 to 30 carbon atoms. represents, any -CH ₂ in the alkyl from 2 to 30 carbon atoms of the alkyl- is -O- and may be substituted with (but not continuously), -CH = CH- or -C≡C-, a ⁸ is a single A bond or alkylene having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexylene, h represents 0 or 1, and in formula (XIII), R ¹⁰ represents C6-C22 alkyl is shown, R <^11> represents C1-C22 alkyl.

As diamine represented by general formula (VIII), the diamine represented by the following general formula (VIII-1)-(VIII-37) and structural formula (VIII-38)-(VIII-43) is mentioned, for example.

In general formulas (VIII-1) to (VIII-11), R ²³ preferably represents alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and alkyl having 5 to 25 carbon atoms or alkoxy having 5 to 25 carbon atoms. More preferably. In addition, R ²⁴ preferably represents alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, more preferably alkyl having 3 to 25 carbon atoms or alkoxy having 3 to 25 carbon atoms.

In general formulas (VIII-12) to (VIII-15), R ²⁵ preferably represents alkyl having 4 to 30 carbon atoms, and more preferably represents alkyl having 6 to ²⁵ carbon atoms. In General Formulas (VIII-16) and (VIII-17), R ²⁶ preferably represents alkyl having 6 to 30 carbon atoms, and more preferably represents alkyl having 8 to 25 carbon atoms.

In General Formulas (VIII-18) to (VIII-37), R ²⁷ preferably represents alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 25 carbon atoms or 3 to 25 carbon atoms. It is more preferable to represent alkoxy. In addition, R ²⁸ is -H, -F, more preferably represents an _{alkoxy, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ of alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, and a carbon number of 3 to 25 It is more preferable to represent alkyl or alkoxy having 3 to 25 carbon atoms.

Among them, diamines represented by general formulas (VIII-1) to (VIII-11) are preferred, and diamines represented by general formulas (VIII-2) and (VIII-4) to (VIII-6) are more preferred. Do.

In the diamine represented by the general formula (X), in general formula (X), one of the two "NH ₂ -Ph-A ⁶ -O-" is bonded to the 3 position of the steroid skeleton, the other 6 It is preferred to be bound to the body. Moreover, it is preferable that two amino groups are respectively couple | bonded with the phenyl ring carbon, and are couple | bonded with meta or para with respect to the bonding position of A <^6> .

As diamine represented by general formula (X), the diamine represented by the following structural formula (X-1) (X-4)-is mentioned, for example.

In the diamine represented by the general formula (XI), in the general formula (XI), two "NH _2- (R ^6- ) Ph-A ⁶ -O-" are each bonded to a carbon of a phenyl ring, but are preferable. Preferably, it is bound to carbon of meta or para to the carbon to which the steroid backbone is bound. Moreover, although two amino groups are each couple | bonded with the phenyl ring carbon, it is preferable that they are couple | bonded with meta or para with respect to A <^6> .

As a diamine represented by general formula (XI), the diamine represented by the following structural formula (XI-1) (XI-8)-is mentioned, for example.

In the diamine represented by general formula (XII), in the general formula (XII), the two amino groups are each bonded to the carbon of the phenyl ring, but are preferably bonded to meta or para to A ⁷ .

As diamine represented by general formula (XII), the diamine represented by the following general formula (XII-1) (XII-8)-is mentioned, for example.

In general formulas (XII-1) to (XII-3), R ^{29 preferably} represents -H, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 30 carbon atoms or 3 to 30 carbon atoms. It is more preferable to represent 30 alkoxy. In formulas (XII-4) to (XII-8), R ³⁰ preferably represents -H, alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, and alkyl having 3 to 30 carbon atoms or carbon atoms. It is more preferable to represent 3-30 alkoxy.

In the diamine represented by general formula (XIII), in the general formula (XIII), the two amino groups are each bonded to the carbon of the phenyl ring, but are preferably bonded to meta or para to A ⁷ .

As diamine represented by general formula (XIII), the diamine represented by the following general formula (XIII-1) (XIII-3)-is mentioned, for example.

In general formulas (XIII-1) to (XIII-3), R ³¹ preferably represents alkyl having 6 to 22 carbon atoms, and more preferably represents alkyl having 6 to 20 carbon atoms. R ³² preferably represents -H or alkyl having 1 to 22 carbon atoms, and more preferably represents alkyl having 1 to 10 carbon atoms.

The diamine having the side chain structure is selected from compounds represented by general formulas (VIII-2), (VIII-4) to (VIII-6), (XII-2), (XII-4) and (XII-6). It is preferable that it is at least one.

The diamine having the side chain structure is preferably contained in a molar ratio of 1 to 90% in the diamine constituting the polyamic acid in the liquid crystal aligning agent of the present invention in order to express a desired pretilt angle in the liquid crystal display device. It is more preferable to contain 5 to 70%.

The diamine which does not have the said side chain structure means the diamine which does not have a substituent (side chain) which can express the desired pretilt angle branched from a main chain, when the substituent which connects two amino groups is made into a main chain. As a diamine which does not have the said side chain structure, the compound represented by the following general formula (I)-(VII) and (XV) is mentioned.

(In general formula (I), X represents-(CH ₂ ) _m- (m represents an integer of 1 to 6), and in general formulas (III) and (V) to (VII), Y independently , Single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -NH-, -N (CH ₃ )-(CH ₂ ) _m- N (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- ( CH ₂ ) _m -S- (m represents an integer of 1 to 6), in formula (V), Z represents a single bond or none, and in formula (XV), R ³³ and R ³⁴ are Each independently represent alkyl or phenyl having 1 to 3 carbon atoms, A ³ independently represents methylene, phenylene or alkyl substituted phenylene, l represents an integer of 1 to 6, and m represents an integer of 1 to 10; In the formulas (II) to (VII), hydrogen bonded to a cyclohexane ring or a benzene ring is independently -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, or may be substituted with -PO ₃ H _2, being bonded to the benzene ring in the general formula (IV) Hydrogen which may be substituted by benzyl.

As diamine represented by general formula (I), the diamine represented by following structural formula (I-1)-(I-3) is mentioned, for example.

As diamine represented by general formula (II), the diamine represented by the following structural formula (II-1) and (II-2) is mentioned, for example.

As diamine represented by general formula (III), the diamine represented by the following structural formula (III-1) (III-3)-is mentioned, for example.

As diamine represented by general formula (IV), the diamine represented by the following structural formula (IV-1) (IV-17) is mentioned, for example.

As diamine represented by general formula (V), the diamine represented by the following structural formula (V-1) (V-37) is mentioned, for example.

As diamine represented by general formula (VI), the diamine represented by the following structural formula (VI-1) (VI-6)-is mentioned, for example.

As diamine represented by general formula (VII), the diamine represented by the following structural formula (VII-1) (VII-16)-is mentioned, for example.

As a diamine represented by general formula (XV), the compound represented by the following structural formula (XV-1) is mentioned, for example.

In these, the diamine which does not have the said side chain structure is a structural formula (IV-1)-(IV-5), (IV-15)-(IV-17), (V-1)-(V-13), ( V-26), (V-27), (V-31), (V-33), (V-35)-(V-37), (VI-1), (VI-2), (VI- 6), diamines represented by (VII-1) to (VII-5) and (XV-1) are preferable, and the structural formulas (IV-1), (IV-2), and (IV-15) to (IV-) 17), and diamines represented by (V-1) to (V-13), (V-33), (V-35) to (V-37), (VII-2) and (XV-1). desirable.

The diamine which does not have the said side chain structure contains 1 to 98% by molar ratio in the diamine which comprises a polyamic acid in the liquid crystal aligning agent of this invention, in order to express desired electrical characteristics, such as ion density, in a liquid crystal display element. Preferably, it is more preferable to contain 10 to 95%.

Diamines other than the diamine represented by general formula (I)-(VIII) and (X)-(XIII) which were mentioned above can be used for the diamine in this invention. As such other diamine, the naphthalene type diamine which has a naphthalene structure, the fluorene type diamine which has a fluorene structure, and the diamine which has a side chain structure other than general formula (VIII)-(XII) are mentioned, for example. have.

As other diamine, the compound represented by following General formula (1 ')-(8') is mentioned, for example.

In General Formulas (1 ') to (8'), R ³⁵ and R ³⁶ each independently represent an alkyl group having 3 to 30 carbon atoms.

Diamine other than the above can be used in the range which does not impair the effect of this invention in the diamine which comprises the polyamic acid in the liquid crystal aligning agent of this invention.

As for the said diamine, in the range of 40 mol% or less of the ratio of the monoamine with respect to the diamine, a part of diamine may be substituted by monoamine. By substituting in this way, the termination of the polymerization reaction at the time of producing a polyamic acid can be caused and the progress of further polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the polymer (polyamic acid or derivative thereof) obtained can be easily controlled, and for example, the coating property of the liquid crystal aligning agent can be improved without impairing the effect of the present invention. have. The diamine substituted by monoamine may be one kind or two or more kinds if the effect of the present invention is not impaired. As said monoamine, it is aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, for example. , n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n- Octadecylamine, and n-eicosylamine.

The tetracarboxylic dianhydride used in the present invention may be one kind of compound or two or more kinds of compounds. As said tetracarboxylic acid, aromatic tetracarboxylic dianhydride, alicyclic tetracarboxylic dianhydride, and aliphatic tetracarboxylic dianhydride are mentioned.

The aromatic tetracarboxylic dianhydride is a compound in which at least one of two acid anhydrides is an acid anhydride by two carboxy bonds to an aromatic compound. As said aromatic tetracarboxylic dianhydride, the compound represented by following structural formula (1)-(18) is mentioned, for example.

It is preferable that the aromatic tetracarboxylic dianhydride is a compound represented by the structural formulas (1), (2), (5) to (7) and (14), and more preferably a compound represented by the structural formula (1). Do.

The alicyclic tetracarboxylic acid dianhydride is a compound in which at least one of the two acid anhydrides is an acid anhydride by two carboxy bonds to the alicyclic compound. As said alicyclic tetracarboxylic dianhydride, the compound represented, for example by following structural formula (19)-(22), (24)-(44) and (49)-(65) is mentioned.

The alicyclic tetracarboxylic acid dianhydride is preferably a compound represented by the structural formulas (19), (25), (35) to (37), (39), (44) and (49), and the structural formula (19) It is more preferable that it is a compound represented by).

The aliphatic tetracarboxylic dianhydride is a compound having two acid anhydrides by two carboxy bonds to an aliphatic compound. As said aliphatic tetracarboxylic dianhydride, the compound represented by following structural formula (23), (45)-(48), (66), and (67) is mentioned, for example.

It is preferable that the said aliphatic tetracarboxylic dianhydride is a compound represented by the said Formula (23).

Tetracarboxylic dianhydride other than tetracarboxylic dianhydride represented by Structural Formulas (1) to (67) can also be used for the tetracarboxylic dianhydride. As other tetracarboxylic dianhydride, the tetracarboxylic dianhydride which has a side chain structure is mentioned, for example. By using tetracarboxylic dianhydride which has a side chain structure, the pretilt angle in a liquid crystal display element can be enlarged.

As tetracarboxylic dianhydride which has a side chain structure, the compound which has a steroid skeleton represented by following structural formula (68) and (69) is mentioned, for example.

The kind and compounding quantity of the said tetracarboxylic dianhydride can be used arbitrarily in the range in which the effect of this invention is achieved.

The said tetracarboxylic dianhydride can also replace one part with carboxylic acid dianhydride. By substituting in this way, since the termination of the polymerization reaction at the time of producing a polyamic acid can be caused, the progress of further polymerization reaction can be suppressed. Therefore, by substituting in this way, the molecular weight of the polymer (polyamic acid or its derivative) obtained can be easily controlled, for example, the coating characteristic of a liquid crystal aligning agent can be improved, without impairing the effect of this invention. . The ratio of the carboxylic acid anhydride to the tetracarboxylic dianhydride may be in a range which does not impair the effects of the present invention. The tetracarboxylic dianhydride substituted with carboxylic anhydride may be one kind or two or more kinds, provided that the effects of the present invention are not impaired. Examples of the carboxylic acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decylsuccinic anhydride, n-dodecylsuccinic anhydride, n-tetradecylsuccinic anhydride, n-hexadecylsuccinic anhydride, and cycloanhydride. Hexane anhydride is mentioned.

In the tetracarboxylic dianhydride, a portion of the tetracarboxylic dianhydride may be substituted with dicarboxylic acid in a range of 10 mol% or less of dicarboxylic acid to tetracarboxylic dianhydride. The tetracarboxylic dianhydride substituted with dicarboxylic acid may be one kind or two or more kinds, provided that the effects of the present invention are not impaired.

The polyamic acid or its derivative may further contain a monoisocyanate compound in the monomer. By including a monoisocyanate compound in a monomer, the terminal of the obtained polyamic acid or its derivative is modified, and molecular weight is adjusted. By using this terminal-modified polyamic acid or its derivative, the coating characteristic of a liquid crystal aligning agent can be improved, for example, without impairing the effect of this invention. The content of the monoisocyanate compound in the monomer is more preferably 1 to 10 mol% based on the total amount of the diamine and tetracarboxylic dianhydride in the monomer, from the above viewpoints. As said monoisocyanate compound, phenyl isocyanate and naphthyl isocyanate are mentioned, for example.

The polyamic acid or derivatives thereof can be produced in the same manner as the known polyamic acid or derivatives thereof used for forming a film of polyimide except for using diamines represented by the general formulas (1) to (8). The total amount of the tetracarboxylic acid dianhydride is preferably approximately equal to the total mole number of the diamine (molar ratio of 0.9 to 1.1).

As for the molecular weight of the said polyamic acid or its derivative, it is preferable that it is 10,000-500,000, and, as for polystyrene conversion weight average molecular weight (Mw), it is more preferable that it is 20,000-200,000. The molecular weight of the polyamic acid or its derivatives can be determined from the measurement by gel permeation chromatography (GPC) method.

The polyamic acid or derivatives thereof can be confirmed by analyzing the solids obtained by precipitation with a large amount of poor solvent by IR and NMR. In addition, the monomer used can be confirmed by analyzing the extract by the organic solvent of the decomposition product of the said polyamic acid or its derivative by strong alkali aqueous solution, such as KOH and NaOH, by GC, HPLC, or GC-MS.

The liquid crystal aligning agent of this invention may further contain other components other than the said polyamic acid or its derivative (s). Another component may be 1 type, or 2 or more types.

For example, the liquid crystal aligning agent of this invention may further contain an alkenyl substituted nadiimide compound in order to stabilize the electrical characteristic of a liquid crystal display element for a long term. The alkenyl substituted nadiimide compound may be one kind of compound or two or more kinds of compounds. It is preferable that it is 0.01-1.00 by weight ratio with respect to the polyamic acid or its derivative in a liquid crystal aligning agent, as for content of the said alkenyl substituted nadiimide compound from a viewpoint, It is more preferable that it is 0.01-0.70, It is more preferable that it is 0.01-0.50 desirable.

It is preferable that the said alkenyl substituted nadiimide compound is a compound which can be dissolved in the solvent which melt | dissolves the polyamic acid or its derivative (s) used by this invention. As an example of such an alkenyl substituted nadiimide compound, the compound represented by the following general formula (Ina) is mentioned.

In formula (Ina), L ¹ and L ² each independently represent hydrogen, alkyl having 1 to 12 carbon atoms, alkenyl having 3 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl or benzyl, and n is 1 Or 2 is represented.

When n = 1, W is alkyl having 1 to 12 carbons, alkenyl having 2 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -Z ^1- (O) _q- ( Z ² O) _r -Z ³ -H (Z ¹ , Z ² and Z ³ independently represent alkylene having 2 to 6 carbon atoms, q represents 0 or 1, and r represents an integer of 1 to 30 Group represented by,-(Z ⁴ ) _s -BZ ⁵ -H (Z ⁴ and Z ⁵ independently represent alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms, B is phenylene And s represents 0 or 1, -BTBH (B represents phenylene, and T represents -CH _2- , -C (CH ₃ ) _2- , -O-, -CO -, -S- or SO ₂ -are represented) or a group in which 1 to 3 hydrogens of these groups are substituted with hydroxyl groups.

At this time, preferred W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbon atoms, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbon atoms, phenyloxyphenyl, phenylmethylphenyl and phenylisopropyl. Lidenephenyl and a group in which one or two hydrogens of these groups are substituted with hydroxyl groups.

When n = 2 In one general formula (Ina), W is arylene, -O- -Z ¹ (Z ² O of the cycloalkylene, 6 to 12 carbon atoms in the alkylene group, having a carbon number of 5 to 8 of 2 to 20 carbon atoms ) a group represented by _r -Z ^3- (Z ^{1 to} Z ³ , and r is as described above), -Z ⁴ -BZ ⁵ -((Z ⁴ , Z ⁵ and B are as described above) ), -B- (OB) _s -T- (BO) _s -B- (B represents phenylene, T represents alkylene having 1 to 3 carbon atoms, -O- or -SO _2- And s represents 0 or 1), or a group in which 1 to 3 hydrogens of these groups are substituted with hydroxyl groups.

In this case, preferred W is C2-C12 alkylene, cyclohexylene, phenylene, tolylene, xylene, -C ₃ H ₆ -O- (Z ² -O) _r -OC ₃ H _6- (Z ² is A group represented by alkylene having 2 to 6 carbon atoms, r represents 1 or 2, -BTB- (B represents phenylene, and T represents -CH _2- , -O- or -SO _2- ; Group represented by), -BOBC ₃ H ₆ -BOB- (where B represents phenylene), and a group in which one or two hydrogens of these groups are substituted with hydroxyl groups.

Such alkenyl-substituted nadiimide compounds are synthesized by, for example, maintaining an alkenyl-substituted nadic acid anhydride derivative and a diamine at a temperature of 80 to 220 ° C. for 0.5 to 20 hours, as described in, for example, Japanese Patent No. 2729565. The compound obtained by this and the compound commercially available can be used. As a specific example of an alkenyl substituted nadiimide compound, the compound shown below is mentioned.

N-methyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-di Carboxylimide, N-methyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-methyl-methylmethylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (2-ethylhexyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide, N-allyl-allylmethylbicyclo [2.2.1] hepto-5-en-2,3-dicarboxyimide, N-allyl-metharylbicyclo [2.2.1] hepto -5-ene-2,3-dicarboxyimide, N-isopropenyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl ) Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide, N-cyclohexyl-metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide, N-benzyl-allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N-benzyl-metharylbicyclo [2.2.1] hepto-5-ene- 2,3-dicarboxyimide, N- (2-hydroxyethyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl)- Allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl) -metharylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide,

N- (2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,2-dimethyl-3-hydrate Oxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyl Mead, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxycyclohexyl) -allyl (Methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- (4-hydroxyphenyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N -(4-hydroxyphenyl) -metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxy ethoxy) ethyl} -allyl Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboximide, N- {2- (2-hydroxy Hydroxyethoxy) ethyl} -metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} -metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] hepto -5-ene-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -metharylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- ( 4-hydroxyphenylisopropylidene) phenyl} -allyl (methyl) bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, N- {4- (4-hydroxyphenylisoph Phil den) phenyl} meth rilbi [2.2.1] hept-5-ene-2,3-dicarboxyimide, and oligomers thereof,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

1,2-bis {3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3'-(allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2-bis {3 '-(metharylbicyclo [2.2.1] hepto-5-ene-2 , 3-dicarboxyimide) propoxy} ethane, bis [2 '-{3'-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether , Bis [2 '-{3'-(allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, 1,4-bis {3'- (Allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hepto-5 -En-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylbi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene-bis (Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metharylbicyclo [ 2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxylate Mid) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metharylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfone,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, 1,6-bis (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) -3-hydroxy-hexane, 1,12-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -3,6- Dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane, 1,5-bis { 3 '-(allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2,5-dihydroxy-benzene, N, N'-p- (2- Hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p- (2-hydroxy) xylene-bis (allylmethylcyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p- (2,3-dihydroxy) xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenoxy} phenyl] propane, bis {4 -(Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide) -4-hydroxy-phenyl} ether, bis {3- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)- 5-hydroxy-phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane, N , N ', N "-tri (ethylenemetharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) isocyanurate, oligomers thereof and the like.

In addition, the alkenyl substituted nadiimide compound used for this invention may be a compound represented by the following structural formula containing an asymmetric alkylene phenylene group.

Preferred compounds are shown below in the alkenyl-substituted nadiimide compounds.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylbi Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene-bis (Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), 2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene -2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4 -{4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-di Carboxyimide) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane,

Bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metharylmethylbicyclo [2.2.1] hepto-5- En-2,3-dicarboxyimide) phenyl} methane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- ( Allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3- Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulphone, bis {4- (allylmethylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenyl} sulfon, bis {4- (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} Sulfone.

Moreover, a preferable alkenyl substituted nadiimide compound is shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (allylmethylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N, N'-ethylene-bis (metharylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Trimethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto- 5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-Dodecamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1 ] Hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-phenylene-bis (allylmethyl ratio Cyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3 -Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N '-{(1 -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allyl Bicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-p-xylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2, 3-dicarboxyimide), N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide), N, N'-m-xylene- Bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

2,2-bis [4- {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- { 4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2-bis [4- {4- (metharylbicyclo [2.2 .1] hepto-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metharylbicyclo [2.2.1] Hepto-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- (metharylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) phenyl} methane .

And bis {4- (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by the structural formula (Ina-1) shown below as an especially preferable alkenyl substituted nadiimide compound Phenyl} methane, N, N'-m-xylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by structural formula (Ina-2), and structural formula ( N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) represented by Ina-3) is mentioned.

 For example, the liquid crystal aligning agent of this invention may further contain the compound which has a radically polymerizable unsaturated double bond in order to maintain the electrical characteristic of a liquid crystal display element for a long time stably. The compound having a radically polymerizable unsaturated double bond may be one kind of compound or two or more kinds of compounds. In addition, the alkenyl substituted nadiimide compound is not included in the compound having the radically polymerizable unsaturated double bond. It is preferable that it is 0.01-1.00 by weight ratio with respect to a polyamic acid or its derivative | guide_body, as for content of the compound which has the said radically polymerizable unsaturated double bond, it is more preferable that it is 0.01-0.70, and it is more preferable that it is 0.01-0.50. Do.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadiimide compound is to reduce the ion density of the liquid crystal display device, to suppress the increase of the ion density over time, and to suppress the afterimage. It is preferable that it is 0.1-10 by weight ratio, and it is more preferable that it is 0.5-5.

As a compound which has the said radically polymerizable unsaturated double bond, (meth) acrylic acid derivatives, such as (meth) acrylic acid ester and (meth) acrylic acid amide, and bismaleimide are mentioned. It is more preferable that the compound which has the said radically polymerizable unsaturated double bond is a (meth) acrylic acid derivative which has 2 or more of radically polymerizable unsaturated double bonds.

As a specific example of (meth) acrylic acid ester, (meth) acrylic-acid cyclohexyl, (meth) acrylic-acid 2-methylcyclohexyl, (meth) acrylic-acid dicyclopentanyl, (meth) acrylic-acid dicyclopentanyloxyethyl, (meth) Isoboroyl acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate. (Meth) acrylic acid 2-hydroxyethyl and (meth) acrylic acid 2-hydroxypropyl are mentioned.

As a specific example of a bifunctional (meth) acrylic acid ester, For example, ethylene bisacrylate, Aronix M-210, Aronix M-240, and Aronix M-6200 which are products of Tokyo Chemical Industry Co., Ltd., Japan, Japan. (株) KAYARAD HDDA, KAYARAD HX-220, KAYARAD R-604 and KAYARAD R-684, V260, V312 and V335HP, which are manufactured by Daiichi Chemical Engineering Co., Ltd., and Light Acrylate, which is a product of KSARA Chemical Co., Ltd. BA-4EA, light acrylate BP-4PA and light acrylate BP-2PA.

As a specific example of a trifunctional or more than trifunctional (meth) acrylic acid ester, For example, 4,4'- methylenebis (N, N- dihydroxy ethylene acrylate aniline), anaronics M-400, anaronics M- 405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARAD TMPTA, KAYARAD DPCA-20, KAYARAD DPCA-30, KAYARAD DPCA-60, KAYARAD DPCA-120, and The VGPT which is a large product made from a chemical industry.

As a specific example of a (meth) acrylic-acid amide derivative, N-isopropyl acrylamide, N-isopropyl methacrylamide, Nn-propyl acrylamide, Nn-propyl methacrylamide, N-cyclopropyl acrylamide, N, for example -Cyclopropyl methacrylamide, N-ethoxyethylacrylamide, N-ethoxyethyl methacrylamide, N-tetrahydroprpracrylamide, N-tetrahydroprrylmethacrylamide, N-ethylacrylamide, N -Ethyl-N-methylacrylamide, N, N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acrylic Loylpyrrolidine, N, N'-methylenebisacrylamide, N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacrylamide , N-phenyl methacrylamide, N-butyl methacrylamide, N- (iso-butoxy Methyl) methacrylamide, N- [2- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethylmethacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, N -(Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebismethacrylamide.

Among the (meth) acrylic acid derivatives, N, N'-methylenebisacrylamide, N, N'-dihydroxyethylene-bisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis (N, N-- Dihydroxyethylene acrylate aniline) is particularly preferred.

As the bismaleimide, for example, BMI-70 and BMI-80, which are manufactured by KAI Chemical Co., Ltd., BMI-1000, BMI-3000, BMI-4000, BMI-5000, and BMI-, which are manufactured by Daiwa Chemical Industries Co., Ltd. 7000 may be mentioned.

For example, the liquid crystal aligning agent of this invention may further contain an oxazine compound in order to stabilize the electrical property in a liquid crystal display element for a long term. The oxazine compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of the said oxazine compound is 0.1-50 weight% with respect to the said polyamic acid or its derivative from the said viewpoint, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight% .

The oxazine compound is soluble in a solvent in which a polyamic acid or a derivative thereof is dissolved, and an oxazine compound having ring-opening polymerizability is preferable.

In addition, the number of the oxazine structure in the said oxazine compound is not specifically limited.

There are many known structures of oxazines. Although the structure of an oxazine is not specifically limited in this invention, As an oxazine structure in the said oxazine compound, the structure of the oxazine which has aromatic groups containing condensed polycyclic aromatic groups, such as benzoxazine and naphthoxazine, Can be mentioned.

As said oxazine compound, the compound represented by the following general formula (a)-(f) is mentioned, for example. In addition, in the following general formula, the bond shown toward the center of a ring shows that it is couple | bonded with any one carbon which can comprise a ring and the bond of a substituent is possible.

In said general formula (a)-(c), R <^1> and R <^2> represents a C1-C30 organic group. In said general formula (a)-(f), R <^3> -R <^6> represents hydrogen or a C1-C6 hydrocarbon group. In addition, in the general formulas (c), (d) and (f), X is a single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO -, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, -S- (CH ₂ ) _m -S Indicates-. Here, m is an integer of 1-6. In formulas (e) and (f), Y is independently a single bond, -O-, -S-, -CO-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -or C1-C3 alkylene is shown. Hydrogen bonded to the benzene ring and the naphthalene ring in Y may be independently substituted with -F, -CH ₃ , -OH, -COOH, -SO ₃ H, or -PO ₃ H ₂ .

The said oxazine compound contains the oligomer and polymer which have an oxazine structure in a side chain, and the oligomer and polymer which have an oxazine structure in a main chain.

As an oxazine compound represented by general formula (a), the following oxazine compound is mentioned, for example.

In formula, R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxazine compound represented by general formula (b), the following oxazine compound is mentioned, for example.

In formula, R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxazine compound represented by general formula (c), the oxazine compound represented with the following general formula (I) is mentioned.

In the general formula (I), R ¹ and R ² are an organic group having 1 to 30 carbon atoms, R ³ to R ⁶ are hydrogen or a hydrocarbon group having 1 to ⁶ carbon atoms, X is a single bond, -CH _2- , -C (CH ₃ ) _2- , -CO-, -O-, -SO ₂ -or -C (CF ₃ ) _2- . As an oxazine compound represented by said general formula (I), the following oxazine compound is mentioned, for example.

In formula, R <^1> has preferable C1-C30 alkyl, and its C1-C20 alkyl is more preferable.

As an oxazine compound represented by general formula (d), the following oxazine compound is mentioned, for example.

As an oxazine compound represented by general formula (e), the following oxazine compound is mentioned, for example.

As an oxazine compound represented by general formula (f), the following oxazine compound is mentioned, for example.

Among these, More preferably, Formula (b-1), Formula (c-1), Formula (c-3), Formula (c-5), Formula (c-7), Formula (c-9), And oxazine compounds represented by formulas (d-1) to (d-6), (e-3), (e-4) and (f-2) to (f-4). have.

The said oxazine compound can be manufactured by the method similar to the method of international publication 2004/009708 pamphlet, Unexamined-Japanese-Patent No. 11-12258, and Unexamined-Japanese-Patent No. 2004-352670.

For example, the oxazine compound represented by the general formula (a) is obtained by reacting a phenol compound, a primary amine, and an aldehyde (see International Publication 2004/009708 pamphlet).

In addition, the oxazine compound represented by General formula (b) is obtained by making the primary amine react with the method of gradually adding formaldehyde, and then adding and reacting the compound which has a naphthol-type hydroxyl group (international publication 2004/009708). Pamphlet).

In addition, the oxazine compound represented by the general formula (c) is composed of 1 mole of phenolic compounds in an organic solvent, at least 2 moles or more of aldehydes per mole of this phenolic hydroxyl group, and 1 mole of the highest amines. Obtained by reacting in the presence of an amine or alkaline nitrogen-containing heterocyclic compound (see International Publication 2004/009708 pamphlet and Japanese Patent Laid-Open No. 11-12258).

In addition, the oxazine compound represented by general formula (d)-(f) contains benzene rings, such as 4,4'- diamino diphenylmethane, aldehydes, such as diamine and formalin, which have these organic groups which couple these, and phenol. and dehydration condensation reaction in the n-butanol at the temperature of 90 degreeC or more (see Unexamined-Japanese-Patent No. 2004-352670).

For example, the liquid crystal aligning agent of this invention may further contain an oxazoline compound in order to stabilize the electrical characteristic in a liquid crystal display element for a long term. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of the said oxazoline compound is 0.1-50 weight% with respect to the said polyamic acid or its derivatives, It is more preferable that it is 1-40 weight%, It is preferable that it is 1-20 weight%. Or it is preferable from the said viewpoint that content of the said oxazoline compound is 0.1-40 weight% with respect to the said polyamic acid or its derivative, when converting the oxazoline structure in an oxazoline compound into oxazoline.

The oxazoline compound may have only one type of oxazoline structure in one compound, or may have two or more types. Although the said oxazoline compound may have one said oxazoline structure in one compound, it is preferable to have two or more. The oxazoline compound may be a polymer having an oxazoline ring structure in the side chain, or may be a copolymer. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or may be a copolymer of a monomer having an oxazoline structure in the side chain and a monomer having no oxazoline structure. The copolymer having an oxazoline structure in the side chain may be a copolymer of two or more kinds of monomers having an oxazoline structure in the side chain, or may be a copolymer of two or more monomers having an oxazoline structure in the side chain and a monomer having no oxazoline structure. It may be a copolymer.

The oxazoline structure is preferably a structure present in the oxazoline compound so that one or both of oxygen and nitrogen in the oxazoline structure and the carbonyl group of the polyamic acid can react.

As said oxazoline compound, 2,2'-bis (2-oxazoline), 1,2, 4- tris (2-oxazolinyl-2) -benzene, 4-furan-2-ylmethylene- is mentioned, for example. 2-phenyl-4H-oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl ) Benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl) 2-oxazolin-2-yl) pyridine, 2,2'-isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl-2- Oxazoline), 2,2'-methylenebis (4-tert-butyl-2-oxazoline), and 2,2'-methylenebis (4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having an oxazolyl such as epochrose (trade name, manufactured by Nippon Kogyo Co., Ltd.) may also be mentioned.

For example, the liquid crystal aligning agent of this invention may contain an epoxy compound further in order to stabilize the electrical characteristic in a liquid crystal display element for a long term. The epoxy compound may be one kind of compound or two or more kinds of compounds. It is preferable that content of the said epoxy compound is 0.1-50 weight% with respect to the said polyamic acid or its derivative from the said viewpoint, It is more preferable that it is 1-40 weight%, It is more preferable that it is 1-20 weight% .

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. As a compound which has one epoxy ring in a molecule | numerator, for example, phenyl glycidyl ether, butyl glycidyl ether, 3,3,3- trifluoromethyl propylene oxide, styrene oxide, hexafluoro propylene oxide , Cyclohexene oxide, N-glycidyl phthalimide, (nonnafluoro-N-butyl) epoxide, perfluoroethylglycidyl ether, epichlorohydrin, epibromohydrin, N, N- Diglycidyl aniline and 3- [2- (perfluorohexyl) ethoxy] -1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, and polypropylene glycol. Diglycidyl ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerin diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate and 3- (N, N- diglycidyl) aminopropyltrimethoxysilane are mentioned.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1-bis [4-([2, 3-epoxy propoxy] phenyl] ethyl] phenyl] propane (the brand name "Texmore VG3101L", the product made by Sansei Chemical Co., Ltd.) is mentioned.

As a compound which has four epoxy rings in a molecule | numerator, for example, 1,3,5,6- tetraglycidyl-2,4-hexanediol, N, N, N ', N'- tetraglycidyl-m Xylenediamine, 1,3-bis (N, N- diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, And 3- (N-allyl-N-glycidyl) aminopropyltrimethoxysilane.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. As a monomer which has an epoxy ring, glycidyl (meth) acrylate, 3, 4- epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate are mentioned, for example.

As another monomer copolymerizing with the monomer which has an epoxy ring, for example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, iso-butyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( Meta) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

Polyglycidyl methacrylate etc. are mentioned as a preferable specific example of the polymer of the monomer which has an epoxy ring. Moreover, as a preferable specific example of the copolymer of the monomer which has an epoxy ring, and another monomer, N-phenyl maleimide- glycidyl methacrylate copolymer, N-cyclohexyl maleimide- glycidyl methacrylate copolymer, Benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl 3-oxetanyl) methyl methacrylate-glycidyl methacrylate copolymer and a styrene-glycidyl methacrylate copolymer are mentioned.

Among these examples, N, N, N ', N'-tetraglycidyl-m-xylenediamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N' , N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Texmore VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate and Particular preference is given to N-phenylmaleimide-glycidyl methacrylate copolymers.

For example, the liquid crystal aligning agent of this invention may further contain various additives. As various additives, a high molecular compound other than a polyamic acid and its derivatives, and a low molecular compound are mentioned, for example, It can select and use according to each objective.

For example, the said high molecular compound can mention the high molecular compound soluble in an organic solvent. It is preferable to add such a high molecular compound to the liquid crystal aligning agent of this invention from a viewpoint of controlling the electrical characteristics and orientation of the liquid crystal aligning film formed. Examples of the polymer compound include polyamide, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, silicone-modified polyurethane, and silicone-modified polyester.

As the low molecular weight compound, for example, 1) a surfactant according to this purpose for improving the coating property, 2) an antistatic agent for improving the antistatic property, and 3) a silane for improving the adhesion and rubbing resistance with the substrate. An imidation catalyst is mentioned when a coupling agent, a titanium type coupling agent, and 4) imidation advances at low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, and N- (2-aminoethyl) -3- Aminopropylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-gridsideoxypropyltrimethoxysilane, 3-gridsideoxypropylmethyldimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-chloro Propylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3 -(Triethoxysilyl) -1-propylamine, and N, N'-bis [3- (trimethoxysilyl) propyl] ethylene And diamines.

As said imidation catalyst, For example, aliphatic amines, such as trimethylamine, triethylamine, tripropylamine, and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline, hydroxy substituted aniline; pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, And cyclic amines such as isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole. It is preferable that the said imidation catalyst is 1 type, or 2 or more types chosen from N, N- dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. Do.

The amount of the silane coupling agent added is usually 0 to 10% by weight of the total weight of the polyamic acid or its derivatives, and preferably 0.1 to 3% by weight.

The addition amount of an imidation catalyst is 0.01 to 5 equivalents with respect to the carbonyl group of polyamic acid or its derivative (s) normally, and it is preferable that it is 0.05 to 3 equivalents.

Although the addition amount of other additives changes with the use, it is 0-30 weight% of the total weight of a polyamic acid or its derivative normally, and it is preferable that it is 0.1-10 weight%.

For example, the liquid crystal aligning agent of this invention is a range which does not impair the effect of this invention (preferably within 20 weight% of the said polyamic acid or its derivative), and is an acrylic acid polymer, an acrylate polymer, and tetra It may further contain other polymer components, such as polyamideimide which is a reaction product of carboxylic dianhydride, dicarboxylic acid, or derivatives thereof, and diamine.

For example, the liquid crystal aligning agent of this invention may contain a solvent further for adjustment of the coating property of a liquid crystal aligning agent, and the density | concentration of the said polyamic acid or its derivative (s). The solvent may be applied without particular limitation as long as it has a solvent capable of dissolving the polymer component. The said solvent contains the solvent normally used by the manufacturing process of a polymeric component, such as a polyamic acid and a soluble polyimide, and a use, and can be suitably selected according to a use purpose. The solvent may be one kind or a mixed solvent of two or more kinds.

As said solvent, the solvent of the said polyamic acid or its derivative (s), and the other solvent for the purpose of improving applicability | paintability are mentioned.

Examples of the aprotic polar organic solvent that is a solvent for the polyamic acid or its derivatives include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, And lactones such as N-dimethylacetamide, dimethyl sulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and γ-butyrolactone.

Examples of other solvents for the purpose of improving the coating properties include ethylene glycol monoalkyl ethers such as alkyl lactate, 3-methyl-3-methoxybutanol, tetralin, isophorone and ethylene glycol monobutyl ether, and diethylene glycol. Propylene glycol monoalkyl ethers such as diethylene glycol monoalkyl ethers such as monoethyl ether, ethylene glycol monoalkyl or phenyl acetate, triethylene glycol monoalkyl ether, propylene glycol monomethyl ether, and propylene glycol monobutyl ether, diethyl malonic acid Ester compounds, such as dipropylene glycol monoalkyl ether, such as malonic acid dialkyl and dipropylene glycol monomethyl ether, and these acetates, are mentioned.

Among them, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol mono Methyl ether and dipropylene glycol monomethyl ether are particularly preferred.

In this invention, although the density | concentration of the polymer component containing the said polyamic acid or its derivative in a liquid crystal aligning agent is not specifically limited, 0.1-40 weight% is preferable. When apply | coating the said liquid crystal aligning agent to a board | substrate, the operation which dilutes the polymer component contained for the film thickness adjustment with a solvent beforehand may be needed. At this time, in order to adjust the viscosity of a liquid crystal aligning agent to the viscosity suitable for easily mixing a solvent with respect to a liquid crystal aligning agent, it is preferable that the density | concentration of the said polymeric component is 40 weight% or less.

In addition, the density | concentration of the said polymer component in a liquid crystal aligning agent may be adjusted with the coating method of a liquid crystal aligning agent. When the coating method of a liquid crystal aligning agent is a spinner method or the printing method, in order to maintain a film thickness favorably, the density | concentration of the said polymer component is usually made into 10 weight% or less in many cases. In other coating methods, for example, the dipping method and the inkjet method, the concentration may be further lowered. On the other hand, when the density | concentration of the said polymer component is 0.1 weight% or more, the film thickness of the liquid crystal aligning film obtained will be easily optimized. Therefore, the density | concentration of the said polymeric component is 0.1 weight% or more, Preferably it is 0.5-10 weight% in normal spinner method, printing method, etc. However, it can also be used in lower concentration according to the coating method of a liquid crystal aligning agent.

And when using for manufacture of a liquid crystal aligning film, the viscosity of the liquid crystal aligning agent of this invention can be determined according to the means or method of forming the film of this liquid crystal aligning agent. For example, when forming the film of a liquid crystal aligning agent using a printing machine, it is preferable that it is 5 mPa * s or more in order to acquire sufficient film thickness, and it is preferable that it is 100 mPa * s or less in order to suppress printing nonuniformity, More preferably, Is 10 to 80 mPa · s. When apply | coating a liquid crystal aligning agent and forming a film | membrane of a liquid crystal aligning agent by spin coating, it is preferable that it is 5-200 mPa * s from a similar viewpoint, More preferably, it is 10-100 mPa * s. The viscosity of a liquid crystal aligning agent can be made small by curing by dilution with a solvent, and stirring.

The liquid crystal aligning agent of this invention may contain one type of polyamic acid or its derivative (s), and may be what is called a polymer blend form in which 2 or more types of polyamic acid or its derivative (s) are mixed. In the liquid crystal aligning agent in the form of a polymer blend, as a liquid crystal aligning agent containing a polyamic acid or its derivatives A and B, a polyamic acid or its derivative A contains the diamine which has the said side chain structure in diamine, and also polyamic acid or The liquid crystal aligning agent containing the diamine represented by the said General formula (1)-(8) to one or both of the diamine of the derivatives A and B is mentioned.

Polyamic acid or its derivative A is a polyamic acid or its derivative containing the diamine which has the said side chain structure. Polyamic acid or its derivative B is a polyamic acid or its derivative containing diamine except the diamine which has a side chain structure. The diamines represented by the general formulas (1) to (8) may be included in at least one kind of polyamic acid or derivatives thereof mixed in a polymer blend, or may be included in both of the polyamic acid or derivatives A and B thereof, and the polymer It may also be included in all polyamic acids or derivatives thereof that are blended under the brand.

The liquid crystal aligning film of this invention is a film | membrane formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal aligning film of this invention can be obtained according to the normal method of manufacturing a liquid crystal aligning film from a liquid crystal aligning agent, For example, the liquid crystal aligning film of this invention is a process of forming the coating film of the liquid crystal aligning agent of this invention, and It can obtain by the process of baking. About the liquid crystal aligning film of this invention, you may rub the film obtained by the said baking process as needed.

The said coating film can be formed by apply | coating the liquid crystal aligning agent of this invention to the board | substrate in a liquid crystal display element similarly to manufacture of a normal liquid crystal aligning film. Examples of the substrate include glass substrates on which electrodes such as indium tin oxide (ITO) electrodes, color filters, and the like may be provided.

As a method of apply | coating a liquid crystal aligning agent to a board | substrate, the spinner method, the printing method, the dipping method, the dropping method, the inkjet method, etc. are generally known. These methods can be similarly applied in the present invention.

Firing of the coating film can be carried out under the conditions necessary for the polyamic acid or its derivative to undergo a dehydration / closing reaction. Baking of the coating film is generally known as a method of heat treatment in an oven or infrared, a method of heat treatment on a hot plate, and the like. These methods can be similarly applied in the present invention. Generally, it is preferable to carry out for 1 minute-3 hours at the temperature of about 150-300 degreeC.

The said rubbing process can be performed similarly to the rubbing process for orientation processing of a normal liquid crystal aligning film, and should just be a condition which can obtain sufficient retardation in the liquid crystal aligning film of this invention. Particularly preferred conditions are 0.2 to 0.8 mm of hair pressing force, stage movement speed of 5 to 250 mm / sec, and roller rotation speed of 500 to 2,000 rpm. As an orientation processing method of a liquid crystal aligning film, the photo-alignment method, the transfer method, etc. are generally known besides the rubbing method. In the range from which the effect of this invention is acquired, these other orientation processing methods can be used together in the said rubbing process.

The liquid crystal aligning film of this invention is obtained preferably by the method of including the other process other than the said process further. As such another process, the process of drying the said coating film, the process of washing the film before and behind a rubbing process with a washing | cleaning liquid, etc. are mentioned.

As for the drying step, a method of heat treatment in an oven or an infrared furnace, a method of heat treatment on a hot plate, and the like are generally known as in the firing step. These methods can be similarly applied to the drying step. It is preferable to perform a drying process at the temperature within the range which can evaporate a solvent, and it is more preferable to carry out at relatively low temperature with respect to the temperature in the said baking process.

As a washing | cleaning method by the washing | cleaning liquid of the liquid crystal aligning film before and behind an orientation treatment, brushing, jet spray, steam washing | cleaning, ultrasonic washing | cleaning, etc. are mentioned. These methods may be used alone or in combination. Pure water or various alcohols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, ketones such as acetone and methyl ethyl ketone can be used as the washing liquid. However, it is not limited to these. Of course, these washing | cleaning liquids are used with few impurities refine | purified fully. Such a cleaning method can also be applied to the above-mentioned cleaning process in formation of the liquid crystal aligning film of this invention.

Although the film thickness of the liquid crystal aligning film of this invention is not specifically limited, It is preferable that it is 10-300 nm, and it is more preferable that it is 30-150 nm. The film thickness of the liquid crystal aligning film of this invention can be measured by well-known film thickness measuring devices, such as a stepmeter and an ellipsometer.

The liquid crystal display device of the present invention contains a pair of substrates, liquid crystal molecules, an electrode for applying a voltage to the liquid crystal layer and the liquid crystal layer formed between the pair of substrates, and the liquid crystal molecules in a predetermined direction. It has a liquid crystal aligning film to orientate. The liquid crystal aligning film of this invention mentioned above is used for the said liquid crystal aligning film.

The glass substrate mentioned above by the liquid crystal aligning film of this invention can be used for the said board | substrate, and the ITO electrode formed in the glass substrate as mentioned above by the liquid crystal aligning film of this invention can be used for the said electrode.

The said liquid crystal layer is formed of the liquid crystal composition by which the surface in which the liquid crystal aligning film in one board | substrate of the said pair of board | substrates is formed is sealed by the clearance gap between a pair of board | substrates which oppose toward the other board | substrate.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. As preferred liquid crystal compositions having a positive dielectric anisotropy, Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. 5-501735, Japanese Patent Laid-Open No. 8-157826, Japanese Patent Laid-Open No. 8-231960, Japanese Patent Laid-Open No. 9 -241644 (EP885272A1 specification), JP-A 9-302346 (EP806466A1 specification), JP-A 8-199168 (EP722998A1 specification), JP-A 9-235552, JP-A 9-255956, JP Japanese Patent Application Laid-Open No. 9-241643 (EP885271A1 specification), Japanese Patent Application Laid-Open No. 10-204016 (EP844229A1 specification), Japanese Patent Application Laid-Open No. 10-204436, Japanese Patent Application Laid-Open No. 10-231482, Japanese Patent Application Laid-Open No. 2000-087040, Japanese Patent Application Laid-Open No. 2001-48822 The liquid crystal composition disclosed by etc. is mentioned.

As preferred liquid crystal compositions having negative dielectric anisotropy, Japanese Patent Application Laid-Open Nos. 57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, JP-A-8-104869, Japanese Patent Laid-Open No. 10-168076, Japanese Patent Laid-Open No. 10-168453, Japanese Patent Laid-Open No. 10-236989, Japanese Patent Laid-Open No. 10-236990, Japanese Patent Laid-Open No. 10-236992, Japanese Patent Laid-Open No. 10-236993 10-236994, Japanese Patent Laid-Open No. 10-237000, Japanese Patent Laid-Open No. 10-237004, Japanese Patent Laid-Open No. 10-237024, Japanese Patent Laid-Open No. 10-237035, Japanese Patent Laid-Open No. 10-237075 237076, JP 10-237448 (EP967261A1 specification), JP 10-287874, JP 10-287875, JP 10-291945, JP 11-029581, JP Liquid crystal disclosed in Japanese Patent Application Laid-Open No. 11-080049, Japanese Patent Application Laid-Open No. 2000-256307, Japanese Patent Application Laid-Open 2001-019965, Japanese Patent Application Laid-Open 2001-072626, Japanese Patent Application Laid-Open No. 2001-192657 It may be the holy.

You may add and use 1 or more types of optically active compounds to the liquid crystal composition which is said dielectric anisotropy positive or negative.

The liquid crystal display element of this invention forms the liquid crystal aligning film of this invention in at least one of a pair of board | substrates, and opposes the obtained pair of board | substrates through a spacer in an inner direction through a liquid crystal aligning film, and a liquid crystal in the clearance gap formed between board | substrates. It is obtained by sealing a composition and forming a liquid crystal layer. The manufacturing of the liquid crystal display element of this invention may also include new processes, such as attaching a polarizing film to a board | substrate as needed.

The liquid crystal display element of this invention can form the liquid crystal display element for various electric field systems. In such a liquid crystal display device for an electric field system, the liquid crystal display device for a transverse electric field system in which the electrode applies a voltage to the liquid crystal layer in a horizontal direction with respect to the surface of the substrate, or in a direction perpendicular to the surface of the substrate. The liquid crystal display element for the longitudinal electric field system in which an electrode applies a voltage to the said liquid crystal layer is mentioned.

Since the liquid crystal display device for the transverse electric field system does not have to express a relatively large pretilt angle, a polyamic acid or derivative thereof having no side chain structure, such as a polyamic acid or derivative thereof obtained from a diamine containing no diamine having a side chain structure, may be used. The liquid crystal aligning film formed from the liquid crystal aligning agent of this invention containing is used suitably for the liquid crystal display element for a transverse electric field system.

Since the liquid crystal display element for a conventional electric field system requires expression of a comparatively large pretilt angle, it contains polyamic acid which has a side chain structure, or its derivative | guide_body, such as a polyamic acid obtained from the diamine containing the diamine which has a side chain structure, or its derivative (s). The liquid crystal aligning film formed from the liquid crystal aligning agent of this invention mentioned above is used suitably for the liquid crystal display element for a full-field system.

Thus, the liquid crystal aligning film manufactured using the liquid crystal aligning agent of this invention as a raw material can be applied to the liquid crystal display element of various display drive systems by selecting the polymer which is the raw material suitably.

The liquid crystal display element of this invention may further have elements other than the component mentioned above. As such other components, components commonly used in liquid crystal display elements such as polarizing plates (polarizing films), wave plates, light scattering films, and driving circuits may be mounted on the liquid crystal display elements of the present invention.

EXAMPLE

Hereinafter, although an Example demonstrates this invention, this invention is not limited to these Examples. The compound used in the Example is as follows.

<Tetracarboxylic acid dianhydride>

Compound (1): pyromellitic dianhydride: PMDA

Compound (19): Cyclobutanetetracarboxylic dianhydride: CBDA

<Diamine>

Compound: 1,2-bis (5-aminobenzooxazole) ethane: ABO (n = 2)

Compound: 1,2-bis (5-aminobenzooxazole) octane: ABO (n = 8)

Compound: o-bis (5-aminobenzooxazole) benzene: o-BO

Compound: m-bis (5-aminobenzooxazole) benzene: m-BO

Compound: p-bis (5-aminobenzoimidazole) benzene: p-BI

Compound: o-bis (5-aminobenzoimidazole) benzene: o-BI

Compound: m-bis (5-aminobenzoimidazole) benzene: m-BI

Compound: 4,4'-diaminodiphenylmethane: DDM

Compound: 4,4'-diaminodiphenyl ether: ODA

<Solvent>

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

<1. Synthesis of Polyamic Acid>

Synthesis Example 1

To a 100 mL four-necked flask equipped with a thermometer, a stirrer, a raw material inlet, and a nitrogen gas inlet, 1.723 g of Compound ABO (n = 2) and 20.0 g of dehydrated NMP were added and stirred under a dry nitrogen stream. Subsequently, Compound (1): 1.277 g of PMDA and 20.0 g of dehydrated NMP were added thereto and allowed to react for 24 hours under a room temperature environment. When reaction temperature rises during reaction, reaction temperature was suppressed to 40 degrees C or less and made to react. BCg was added to the obtained solution and the polyamic-acid solution of 6.0 weight% was obtained. Let this polyamic acid be PA1. The weight average molecular weight of PA1 was 27,500.

The weight average molecular weight of the polyamic acid is diluted with the obtained polyamic acid in a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) so that the polyamic acid concentration is about 1% by weight, and the 2695 Separation Module 2414 Differential Refractometer ( (Manufactured by Waters), the mixture solution was measured by GPC method as a developing agent and determined in terms of polystyrene. The column was HSPgel RT MB-M (manufactured by Waters), and was measured under the condition of a column temperature of 40 ° C. and a flow rate of 0.35 mL / min.

Synthesis Examples 2-14

As shown in Table 1, except having changed tetracarboxylic dianhydride and diamine, the polyamic-acid solution (PA2)-(PA14) was prepared according to the synthesis example 1. The results are shown in Table 1, including Synthesis Example 1.

TABLE 1

<2. Manufacturing of Liquid Crystal Display Elements>

Example 1

The polyamic acid solution having a concentration of 6.0% by weight synthesized in Synthesis Example 1 was added with a mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4.5% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was manufactured as follows.

<Method of Manufacturing Liquid Crystal Display Element>

The liquid crystal aligning agent was apply | coated to the two glass substrates with an ITO electrode with the spinner, and the film | membrane with a film thickness of 70 nm was formed. After coating and heating at 80 degreeC for about 5 minutes, it heat-processed at 210 degreeC for 20 minutes, and formed the liquid crystal aligning film. Next, the surface of the board | substrate with which the liquid crystal aligning film was formed was rubbed by the rubbing device, and the orientation process was carried out. Thereafter, the liquid crystal alignment film was ultrasonically cleaned in ultrapure water for 5 minutes and then dried at 120 ° C. for 30 minutes in an oven.

The gap material of 7 micrometers was spread | spreaded on one glass substrate, and the surface which formed the liquid crystal aligning film was made to face in opposition so that rubbing direction might be parallel, and it sealed with epoxy hardening | curing agent, and produced the antiparallel cell of gap 7 micrometers. The liquid crystal composition shown below was injected to the said cell, and the injection hole was sealed with the photocuring agent. Subsequently, it heat-processed at 110 degreeC for 30 minutes, and manufactured the liquid crystal display element.

EXAMPLES 2-12

The polyamic-acid solution of the density | concentration 6.0 weight% synthesize | combined in the synthesis examples 2-12 was added the mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4.5-5.0 weight% to make the liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

[Comparative Examples 1 and 2]

The polyamic acid solution having a concentration of 6.0% by weight synthesized in Synthesis Examples 13 to 14 was added with a mixed solvent of NMP / BC = 1/1 (weight ratio), and the whole was diluted to 4.5% by weight to obtain a liquid crystal aligning agent. Using the obtained liquid crystal aligning agent, the liquid crystal display element was produced like Example 1.

<3.Evaluation of Electrical Characteristics>

About the liquid crystal display element manufactured in Examples 1-12 and Comparative Examples 1-2, the ion density was measured as follows.

1) Measurement of ion density

The ion density was measured using the liquid crystal physical property evaluation apparatus 6254 type made from Toyo Technica. Measurement conditions were waveform: triangle wave, frequency: 0.01 Hz, voltage: ± 10 V, and the measurement temperature was 60 ° C. The smaller this value, the better the electrical characteristics. The results are shown in Table 2.

TABLE 2

As shown in Table 2, the liquid crystal display element using the liquid crystal aligning film obtained from the liquid crystal aligning agent containing the polyamic acid containing ABO, ABI, BO, or BI in a monomer can obtain the effect that ion density is extremely low.

Claims (19)

In the liquid crystal aligning agent containing the polyamic acid or its derivative which is a reaction product of tetracarboxylic dianhydride and diamine, The said diamine is a liquid crystal aligning agent containing the diamine represented by the following general formula (1)-(8).

(In general formulas (1) to (8), X represents an oxygen atom or NR ⁶ (wherein R ⁶ represents a hydrogen atom, an alkyl group having 1 to 30 carbon atoms or a phenyl group), and R ¹ , R ⁴ , R ⁵ Each independently represents an aromatic ring group or a heterocyclic group consisting of a monocyclic ring or a plurality of rings, and R ² , R ³ each independently represents an aromatic ring group, a heterocyclic group or an alicyclic group consisting of a monocyclic ring or a plurality of rings, Alkylene group bound or alkylene group) The method of claim 1, Said diamine is oxazole represented with the following general formula (O) -1-(O) -6, The liquid crystal aligning agent characterized by the above-mentioned.

(In General Formulas (O) -1 to (O) -6, n independently represents an integer of 0 to 8, and m represents an integer of 1 to 8). The method of claim 1, Said diamine is imidazole represented by the following general formula (I) -1-(I) -6, The liquid crystal aligning agent characterized by the above-mentioned.

(In General Formulas (I) -1 to (I) -6, n independently represents an integer of 0 to 8, and m represents an integer of 1 to 8). The method of claim 2, Said diamine is aromatic oxazole represented by the following general formula (O) -2, or alkyloxazole represented by the following general formula (O) -3, The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (O) -3, m represents an integer of 1-8.) The method of claim 3, Said diamine is aromatic imidazole represented by the following general formula (I) -2, or alkylimidazole represented by the following general formula (I) -3, The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (I) -3, m represents the integer of 1-8.) The method according to any one of claims 1 to 5, Said diamine further contains the diamine which has a side chain structure represented by the following general formula (VIII) and (X)-(XIII), The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (VIII), A ³ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH- or-(CH ₂ ) m- (m is an integer of 1-6. R ¹ represents a group having a steroid skeleton and a group represented by the following general formula (IX), and when the position of the two amino groups bonded to the benzene ring is para, alkyl having 1 to 30 is further added. When the position is meta, further includes alkyl or phenyl having 1 to 30 carbon atoms, and in the alkyl, any -CH ₂ -is independently -CF _{2- ,} -CHF-, -O- ( Discontinuous), -CH = CH- or -C≡C-, and -CH ₃ can be substituted with -CH ₂ F, -CHF ₂ or -CF ₃ , the hydrogen of the phenyl independently, can be substituted with _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2 or -OCF ₃₎

(In formula (IX), A ⁴ and A ⁵ are each independently a single bond, -O- (but not discontinuous), -COO-, -OCO-, -CONH-, -CH = CH- or carbon number.) 1-12 alkylene, R ² and R ³ each independently represent -F or -CH ₃ , and Ring S is independently 1,4-phenylene, 1,4-cyclohexylene, 1, 3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10- represents a diyl, R ⁴ is -H, -F, alkoxy, -CN fluorine substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF ₂ or -OCF ₃ represents, a and b each represent an integer of 0 to 4, c, d and e each represent an integer of 0 to 3, f and g each independently represent an integer of 0 to 2, and c + d + e ≧ 1 being)

(In formulas (X) and (XI), R ⁵ independently represents -H or -CH ₃ , R ⁶ represents -H, or alkyl or alkenyl having 1 to 20 carbon atoms, and A ⁶ independently A single bond, -C (= 0)-or -CH _2- , and in formula (XI), R ⁷ and R ⁸ each independently represent alkyl or phenyl having 1 to 20 carbon atoms);

(In formula (XII) and (XIII), A ⁷ independently represents -O- or alkylene having 1 to 6 carbon atoms, and in formula (XII), R ⁹ represents -H or alkyl having 1 to 30 carbon atoms. any of the carbon atoms of 2 to 30 show, the alkyl -CH ₂ - is -O- and may be substituted with (but not continuously), -CH = CH- or -C≡C-, a ⁸ is A single bond or alkylene having 1 to 3 carbon atoms, ring T represents 1,4-phenylene or 1,4-cyclohexylene, h represents 0 or 1, and in formula (XIII), R ¹⁰ Represents alkyl having 6 to 22 carbon atoms, and R ¹¹ represents alkyl having 1 to 22 carbon atoms.) The method of claim 6, The diamine which has the said side chain structure is a compound represented by the following general formula (VIII-2), (VIII-4)-(VIII-6), (XII-2), (XII-4), and (XII-6) It is at least one selected from the liquid crystal aligning agent.

(In the general formula, R ²³ , R ²⁹ and R ³⁰ each represent alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms). The method according to any one of claims 1 to 7, The said diamine further contains the diamine which does not have a side chain structure represented by the following general formula (I)-(VII) and (XV), The liquid crystal aligning agent characterized by the above-mentioned.

(In general formula (I), X represents-(CH ₂ ) _m- (m represents an integer of 1 to 6), and in general formulas (III) and (V) to (VII), Y independently , Single bond, -O-, -S-, -SS-, -SO _2- , -CO-, -CONH-, -NHCO-, -NH-, -N (CH ₃ )-(CH ₂ ) _m- N (CH ₃ )-, -C (CH ₃ ) _2- , -C (CF ₃ ) ₂ -,-(CH ₂ ) _m- , -O- (CH ₂ ) _m -O-, or -S- ( CH ₂ ) _m -S- (m represents an integer of 1 to 6), in formula (V), Z represents a single bond or none, and in formula (XV), R ³³ and R ³⁴ are Each independently represent alkyl or phenyl having 1 to 3 carbon atoms, A ³ independently represents methylene, phenylene or alkyl substituted phenylene, l represents an integer of 1 to 6, and m represents an integer of 1 to 10; In the formulas (II) to (VII), hydrogen bonded to a cyclohexane ring or a benzene ring is independently -F, -CH ₃ , -CF ₃ , -OH, -COOH, -SO ₃ H, Or it may be substituted with -PO ₃ H _{2 It} is bonded to the benzene ring in the general formula (IV) Hydrogen may be substituted with benzyl) The method of claim 8, The diamine which does not have the said side chain structure has following structural formula (IV-1), (IV-2), (IV-15)-(IV-17), (V-1)-(V-13), (V-33 ), (V-35) to (V-37), (VII-2), and (XV-1). It is at least one selected from compounds represented by the liquid crystal aligning agent.

The method according to any one of claims 1 to 9, The said tetracarboxylic dianhydride contains aromatic tetracarboxylic dianhydride, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 10, The aromatic tetracarboxylic dianhydride is at least one of the compounds represented by the following structural formulas (1), (2), (5) to (7) and (14).

The method of claim 11, Said aromatic tetracarboxylic dianhydride is a compound represented by said structural formula (1), The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 1 to 12, Said tetracarboxylic dianhydride contains one or both of alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride, The liquid crystal aligning agent characterized by the above-mentioned. The method of claim 13, The alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride are at least one of compounds represented by the following structural formulas (19), (23), (25), (35) to (39), (44) and (49) It is a liquid crystal aligning agent characterized by the above-mentioned.

The method of claim 14, Said alicyclic tetracarboxylic dianhydride and aliphatic tetracarboxylic dianhydride are compounds represented by the said structural formula (19), The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 6 to 15, As a liquid crystal aligning agent containing the said polyamic acid or its derivatives A and B, Said polyamic acid or its derivative A contains the diamine which has the said side chain structure in the said diamine, and is represented by General formula (1)-(8) in one or both of the diamine of the said polyamic acid or its derivatives A and B Diamine is contained, The liquid crystal aligning agent characterized by the above-mentioned. The method according to any one of claims 1 to 16, A liquid crystal aligning agent, further comprising at least one selected from an alkenyl substituted nadiimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. The liquid crystal aligning film formed by heating the coating film of the liquid crystal aligning agent in any one of Claims 1-17. A liquid crystal display device comprising a pair of substrates, liquid crystal molecules, a liquid crystal layer formed between the pair of substrates, an electrode for applying a voltage to the liquid crystal layer, and a liquid crystal alignment film for orienting the liquid crystal molecules in a predetermined direction. To Said liquid crystal aligning film is liquid crystal aligning film of Claim 18, The liquid crystal display element characterized by the above-mentioned.