KR20170097552A - Liquid crystal aligning agents for forming liquid crystal alignment films, liquid crystal alignment films and liquid crystal display devices using the same - Google Patents

Abstract

The present invention relates to a liquid crystal alignment agent containing at least one polymer selected from a polyamic acid obtained by making tetracarboxylic acid dianhydride react with a diamine compound and derivatives of the polyamic acid, and at least one among compounds represented by formula (1). A liquid crystal alignment film which has a high film hardness, is not cut well, and has good liquid crystal aligning properties can be formed by using the liquid crystal alignment agent of the present invention. In formula (1), R^1 is a monovalent organic group having any one among the structures of AA, BB, CC, and DD, which are directly connected to N or connected to N by interposing linking groups between the structures and N in *. Further, R^2 and R^3 are each independently a monovalent organic group having any one among the structures of EE, FF, GG, HH and II, which are directly connected to N or connected to N by interposing the linking groups between the structures and N in *.

Description

TECHNICAL FIELD [0001] The present invention relates to a liquid crystal alignment material for forming a liquid crystal alignment layer, a liquid crystal alignment layer, and a liquid crystal display device using the same. BACKGROUND OF THE INVENTION [0002]

The present invention relates to a liquid crystal aligning agent containing a polyamic acid or a derivative thereof and a specific compound, a liquid crystal alignment film formed using the liquid crystal aligning agent, and a liquid crystal display element having the liquid crystal alignment film.

Various display devices such as a PC monitor, a liquid crystal television, a viewfinder of a video camera, a projection display, and the like, and optoelectronics related devices such as an optical printer head, a light Fourier transform device, and a light valve, In the liquid crystal display element being formed, a display element using nematic liquid crystal is the mainstream. As a display method of a nematic liquid crystal display device, TN (Twisted Nematic) mode and STN (Super Twisted Nematic) mode are well known. In recent years, in order to improve narrowness of the viewing angle, which is one of the problems of these modes, a TN type liquid crystal display device using an optical compensation film, an MVA (Multi-domain Vertical Alignment) mode using a combination of vertical and projection structures, An In-Plane Switching (IPS) mode, an FFS (Fringe Field Switching) mode, and the like have been proposed and put into practical use.

The development of the technology of the liquid crystal display element is achieved not only by improving the driving method and device structure thereof but also by improving the constituent members used in the element. Among the constituent members used in the liquid crystal display element, in particular, the liquid crystal alignment film is one of important materials related to the display quality, and it has become important to improve the performance of the alignment film with the improvement of the quality of the liquid crystal display element.

The liquid crystal alignment film is formed of a liquid crystal aligning agent. At present, the liquid crystal aligning agent mainly used is a solution (varnish) in which a polyamic acid, a polyamic acid ester, or a polyimide is dissolved in an organic solvent. This solution is applied to a substrate, and then the film is formed by means such as heating to form a polyimide-based liquid crystal alignment film. After the film formation, an orientation treatment suitable for the above-described display mode is carried out if necessary.

Industrially, a rubbing method which is simple and capable of high-speed processing at a large area is widely used as an orientation treatment method. The rubbing process is a process of rubbing the surface of the liquid crystal alignment film in one direction using a fabric obtained by planting fibers such as nylon, rayon, and polyester, thereby making it possible to obtain uniform orientation of the liquid crystal molecules. However, problems such as rubbing by rubbing and generation of static electricity have been pointed out, and development of an orientation treatment method in place of the rubbing method has been actively conducted recently.

What is attracting attention as an orientation treatment method instead of the rubbing method is an optical alignment treatment method in which light is irradiated to perform orientation treatment. Many optical alignment methods such as photo decomposition method, photoisomerization method, optical dimerization method and photo-crosslinking method have been proposed in the photo-alignment treatment method (for example, see Non-Patent Document 1, Patent Document 1 and Patent Document 2). Since the photo alignment method has higher alignment uniformity than the rubbing method and is a non-contact alignment treatment method, it is possible to reduce the cause of occurrence of defective display of liquid crystal display elements such as oscillation and static electricity without causing scratches on the film .

Up to now, a photo alignment layer having a photoreactive group causing photoisomerization or optical dimerization in a polyamic acid structure has been studied (see, for example, Patent Documents 1 to 6). In particular, by applying the photoisomerization technique described in Patent Documents 4 to 6, a liquid crystal alignment film having high anchoring energy, good orientation, and excellent electrical characteristics such as voltage retention rate was obtained. However, when such a photo alignment film is applied to an actual liquid crystal display device, there is a problem that the alignment film is peeled off, and foreign matter generated lowers the display quality of the liquid crystal display element.

In order to improve the defects, a method of improving the film hardness of an alignment film by adding a crosslinking agent to the liquid crystal aligning agent is known (see, for example, Patent Documents 7 to 9). However, when such a crosslinking agent is added, the film hardness is improved but the alignment property of the liquid crystal is largely lowered, and in the case of the FFS mode liquid crystal display element, a residual image is generated after long-term driving. In addition, there are some crosslinking agents in which the alignment property of the liquid crystal is not deteriorated. However, such a crosslinking agent has insufficient film hardness, and the liquid crystal alignment film is cut off when the panel is used, and display defects are caused.

Japanese Patent Application Laid-Open No. 9-297313 Japanese Patent Application Laid-Open No. 10-251646 Japanese Patent Application Laid-Open No. 2005-275364 Japanese Unexamined Patent Application Publication No. 2010-049230 Japanese Patent Application Laid-Open No. 2010-197999 International Publication No. 2013-157463 Japanese Unexamined Patent Publication No. 9-146100 Japanese Laid-Open Patent Publication No. 10-333153 Japanese Patent Application Laid-Open No. 2007-139949

 Liquid Crystal, Vol. 3, No. 4, 262, 1999

As described above, it is possible to increase the film hardness of an alignment film by adding a compound having two or more crosslinkable groups such as a glycidyl group to the liquid crystal aligning agent. However, since it reacts directly with the carboxylic acid of the polyamic acid, when the number of the crosslinking sites is two or more, it becomes a rigid structure and the flexibility is deteriorated, which causes a problem of greatly lowering the liquid crystal alignability. Particularly, when the device is used in a transverse electric field type device, deterioration of the afterimage characteristic due to the orientation defect is caused and the solution has become urgent. Disclosed is a liquid crystal aligning agent capable of forming a liquid crystal alignment film having a high film hardness, a good shrinkage and a good alignment property of a liquid crystal, and a liquid crystal aligning element having a liquid crystal alignment film formed by the liquid crystal aligning agent. .

As a result of intensive studies, the inventors of the present invention have found that a liquid crystal alignment film having a high film hardness, good shrinkage, and good liquid crystal alignability can be obtained by using a liquid crystal aligning agent containing a compound represented by formula (1) Thereby completing the present invention.

The present invention is as follows.

[1] a liquid crystal aligning agent containing at least one polymer selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound and at least one compound represented by the following formula (1);

In the formula (1), R ¹ is a monovalent organic group having any one of the following structures connected directly to N via a linking group in *

And R < ² > and R < ³ > are each independently a monovalent organic group having any one of the following structures connected directly to N via a linker or a linker.

[2] The liquid crystal aligning agent according to item [1], wherein the compound represented by formula (1) is at least one compound represented by formula (1-1) to formula (1-4);

In the formula (1-3), R is -CH ₃ or -CH ₂ CH ₃ .

[3] the tetracarboxylic acid dianhydride contains at least one selected from the group of compounds represented by the following formulas (AN-I) to (AN-VII);

A diamine having no side chain represented by the following formulas (DI-1) to (DI-16), a dihydrazide having no side chain represented by the following formulas (DIH-1) to (DIH- , And a diamine having a side chain represented by the following formulas (DI-31) to (DI-35);

Formula (AN-I), (AN -IV) and in (AN-V), X is independently a single bond or -CH ₂ - and;

In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF _{3) 2} - and;

In the formulas (AN-II) to (AN-IV), Y is independently selected from the group consisting of the following trivalent groups, the bonding hand is connected to any carbon, and at least one hydrogen May be substituted with methyl, ethyl or phenyl;

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, May be substituted with methyl, ethyl or phenyl, the bonding hands attached to the ring may be connected to any carbon constituting the ring, and the two bonding hands may be connected to the same carbon;

In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl and Ph represents phenyl;

In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO- and r is independently 0 or 1;

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen of the phenylene may be replaced by -OH;

Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONCH 3 -, -CONH-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m -, -O- (CH ₂ ) _m -O-, -N (-CH ₃ ) - (CH ₂ ) _k -N (-CH ₃ ) -, - (OC ₂ H ₄ ) _m -O-, _{2 -C (CF 3) 2 -CH} 2 -O-, -O-CO- (CH 2) m -CO-O-, -CO-O- (CH 2) m -O-CO-, - (CH _{2) m -NH- (CH 2)} m -, -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH-, -CO-C ₃ H ₆ -, and _{(NH-C 3 H 6)} n -CO-, or _{-S- (CH 2) m -S-,} m is independently an integer of from 1 to 12, k is an integer from 1 to 5 , n is 1 or 2;

In the formula (DI-4), s is independently an integer of 0 to 2;

In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, -NH- or alkylene having 1 to 10 carbon atoms;

Formula (DI-2) ~ formula (DI-7) cyclohexane ring and benzene, at least one hydrogen is -F, -Cl, alkyl, -OCH _3, -OH, -CF of 1 to 3 carbon atoms in the ring _3, (DI-4-a) in which at least one hydrogen of the benzene ring is replaced by -O-, -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl. ) To the formula (DI-4-e);

A group in which the bonding position is not fixed to the carbon atom constituting the ring in the above formula represents an arbitrary bonding position in the ring;

The bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² ;

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;

In formula (DI-11), r is 0 or 1;

In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;

In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego ;

In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl of 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, An integer of 4;

In formula (DI-15), ring C is a monocyclic ring containing a heteroatom;

In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, r is 0 or 1;

A group in which the bonding position is not fixed to the carbon atom constituting the ring in the above formula represents an arbitrary bonding position in the ring;

In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is at any position;

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or -C (CF _{3) 2} - and;

In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, at least one hydrogen of which rings may be substituted by methyl, ethyl, or phenyl;

In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of these rings may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -;

In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonding to the ring is at any position;

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} - and m' is an integer of 1 to 12;

R ²⁵ is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a), wherein at least one hydrogen may be substituted with -F, And at least one -CH ₂ - may be substituted with -O-, -CH═CH- or -C≡C-, and the hydrogen of the phenyl may be substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, and the bonding position of -NH ₂ bonded to the benzene ring may be any position in the ring And,

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are linking groups and independently represent a single bond or alkylene having 1 to 12 carbon atoms, and one or more -CH ₂ - -O-, -COO-, -OCO-, -CONH-, -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine- Naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, and at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ is -F or two being in the coupler may be substituted with -CH _3, s, t and u are independently an integer of 0 to 2, their sum is in the range of 0 to 5, and, s, t or u is 2 when the work, each of the brackets May be the same or different and the two rings may be the same or different and R ²⁶ is a hydrogen, -F, -OH, alkoxy of 1 to 30 carbon atoms alkyl, fluorine-substituted alkyl having 1 to 30 carbon atoms, having 1 to 30 carbon atoms _{of, -CN, -OCH 2 F, -OCHF} 2, or -OCF _3, and , At least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b)

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms;

At least one hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl;

A group in which the bonding position is not fixed to any carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;

In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring represents any bonding position in the ring;

In formula (DI-34) and formula (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms and G ³² is a single bond or alkyl having 1 to 3 carbon atoms R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH = CH- or -C≡C-, and R ³² Is alkyl of 6 to 22 carbon atoms, R ³³ is hydrogen or alkyl of 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1, and -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

(4) A tetracarboxylic acid dianhydride represented by the following formula (AN-1-1), (AN-1-2), (AN- AN-4-27, AN-4-27, AN-4-29, AN-4-27, AN-4-27, AN- AN-5-2, AN-10-1, AN-11-3, AN-16, and AN- -1), at least one selected from the formulas (AN-16-3) and (AN-16-4);

(DI-3-1), DI-2-1, DI-4-1, DI-4-2, (DI-5-15), the formula (DI-5-1), the formula (DI-5-5) ), DI-5-17, DI-5-28, DI-5-30, DI-6-7, DI-7-3, (DIH-2-1) selected from the group consisting of a compound represented by the formula (DI-13-1), a formula (DI-13-1), a formula A liquid crystal aligning agent according to item [3];

In the formulas (AN-1-2) and (AN-4-17), m is independently an integer of 1 to 12.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is independently an integer of 1 to 12;

In the formula (DI-5-30), k is an integer of 1 to 5; And

In the formula (DI-7-3), each n is independently 1 or 2.

[5] The method according to any one of [1] to [4], wherein the polyamic acid and the derivative thereof are the polymer (a) obtained by reacting at least one of tetracarboxylic acid dianhydride and diamine with a compound having a photoreactive structure. Wherein the liquid crystal aligning agent is a liquid crystal aligning agent.

[6] The liquid crystal aligning agent according to [5], wherein the photoreactive structure is at least one selected from the group consisting of structures represented by the following formulas (P-1) to (P-7).

In the formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

(7) The compound having a photoreactive structure is represented by the following formula (II-1), formula (II-2), formula (III-1), formula At least one tetracarboxylic acid dianhydride or diamine compound selected from the group consisting of compounds represented by formulas (V-1) to (V-2), (V-1) to (V- The liquid crystal aligning agent according to [6], wherein the liquid crystal aligning agent is the liquid crystal aligning agent.

In the formulas (V-2), R ⁶ is independently a group in which the bonding position is not fixed to any carbon atom constituting the ring, and the bonding position in the ring is arbitrary. It is _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently an integer from 0 to 2, and formula (V-3) in the ring a and ring B are each independently a single ring-shaped And R ¹¹ is at least one selected from the group consisting of a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N (CH ₃ ) CO- and, R ¹² is C 1 -C 20 linear alkylene, -COO-, -OCO-, -NHCO-, or -N (CH ₃₎ in the CO- and, for R ¹¹ and R ^12, straight-chain alkylene , One or two of -CH ₂ - of -O- may be substituted with -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH, and b to e are independent A is an integer of 0-4.

[8] The liquid crystal aligning agent according to the item [7], wherein the diamine compound having a photoreactive structure is represented by the following formula (PDI-7).

In the formula (PDI-7), R ⁵¹ are each independently _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, s are each independently an integer of 0 to 2.

[9] A process for producing a polymer comprising reacting at least one polymer (b) selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride having no photoreactive structure and a diamine having no photoreactive structure together with the polymer (a) The liquid crystal aligning agent according to any one of [5] to [8], further containing the liquid crystal aligning agent.

[10] A process for producing a polymer (b), wherein the tetracarboxylic acid dianhydride used in the synthesis of the polymer (b) is at least one selected from the group consisting of the following formulas (AN-1-1) (AN-4-17), (AN-4-21), (AN-4-27), and (AN-4-29), AN-4-30, AN-5-1, AN-7-2, AN-10-1 and AN-11 -3), at least one selected from the formulas (AN-16-1), (AN-16-3) and (AN-16-4);

(DI-3-1), DI-2-1, DI-4-1, DI-4-2, (DI-5-15), the formula (DI-5-1), the formula (DI-5-5) ), DI-5-17, DI-5-28, DI-5-30, DI-6-7, DI-7-3, (DIH-2-1) selected from the group consisting of a compound represented by the formula (DI-13-1), a formula (DI-13-1), a formula A liquid crystal aligning agent according to the item [9];

In the formulas (AN-1-2) and (AN-4-17), m is independently an integer of 1 to 12.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is independently an integer of 1 to 12;

In the formula (DI-5-30), k is an integer of 1 to 5; And

 In the formula (DI-7-3), each n is independently 1 or 2.

[1] to [6], further comprising at least one compound selected from the group consisting of an oxazine compound, an oxazoline compound, an epoxy compound other than the compound represented by the formula (1), and a compound comprising a silane coupling agent. 10], wherein the liquid crystal aligning agent is a liquid crystal aligning agent.

[12] A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of [1] to [11].

[13] A liquid crystal alignment film for a transverse electric field driven liquid crystal display element formed by the liquid crystal aligning agent according to any one of [1] to [11].

[14] A liquid crystal display element having the liquid crystal alignment film according to [12] or [13].

When a liquid crystal aligning agent containing the formula (1) of the present invention is used, a liquid crystal alignment film having a high film hardness and good liquid crystal alignability can be obtained. By using this liquid crystal alignment film, it is possible to obtain a liquid crystal display device excellent in display characteristics without defective spotting due to a foreign substance.

≪ Compound represented by formula (1) >

The present invention is a liquid crystal aligning agent containing at least one polymer selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride and a diamine and at least one compound represented by the following formula (1) .

In the formula (1), R ¹ is a monovalent organic group having any one of the following structures connected directly to N via a linking group in *

And R < ² > and R < ³ > are each independently a monovalent organic group having any one of the following structures connected directly to N via a linker or a linker.

The compound represented by the formula (1) can be specifically represented by the following formulas (1-1) to (1-4).

When the compound represented by the formula (1) is used in a liquid crystal aligning agent for rubbing, the addition amount of the compound represented by the formula (1) 0.1% by weight or more. On the other hand, in order to prevent orientation defects accompanying deterioration of the orientation property of the liquid crystal alignment film, the addition amount is preferably 10% by weight or less. When it is used for a liquid crystal aligning agent for rubbing, the addition amount is more preferably 0.3 to 3% by weight. When used in a liquid crystal aligning agent for optical alignment, it is preferably 0.1% by weight or more based on the total weight of the polyamic acid or its derivative in order to obtain an effect of preventing the screen shaving due to a decrease in film hardness. On the other hand, in order to prevent orientation defects accompanying deterioration of the orientation property of the liquid crystal alignment film, the addition amount is preferably 30% by weight or less. In the case of being used for a liquid crystal aligning agent for photo-alignment, the addition amount is more preferably 5 to 20% by weight.

Among the compounds represented by the formula (1), it is preferable to use the compounds represented by the formulas (1-1) to (1-4) in order to obtain a liquid crystal alignment film having a high liquid crystal orientation and a high film hardness, 1-1) is more preferably used.

<Liquid Crystal Aligner>

The liquid crystal aligning agent of the present invention comprises at least one polymer selected from the group consisting of a polyamic acid and a derivative thereof, which is a reaction product of at least one selected from a tetracarboxylic acid dianhydride and a derivative thereof and a diamine, ). &Lt; / RTI &gt; The derivative of polyamic acid is a component which is dissolved in a solvent when it is a liquid crystal aligning agent to be described later containing a solvent and is a component capable of forming a liquid crystal alignment film having polyimide as a main component when the liquid crystal aligning agent is used as a liquid crystal alignment film . Examples of such derivatives of polyamic acid include soluble polyimides, polyamic acid esters, and polyamic acid amides, and more specifically, 1) polyimides obtained by subjecting all amino groups of polyamic acid to a dehydration ring- , 2) partial polyimide partially dehydrated and cyclized, 3) polyamic acid ester converted into carboxyl ester of polyamic acid, 4) part of acid dianhydride contained in tetracarboxylic acid dianhydride compound, A polyamic acid-polyamide copolymer obtained by reacting a polyamic acid-polyamide copolymer with an acid; and 5) a polyamideimide obtained by subjecting a part or all of the polyamic acid-polyamide copolymer to a dehydration ring-closure reaction. The polyamic acid and the derivative thereof may be one kind of polymer or two or more kinds. The polyamic acid and the derivative thereof may be a polymer having a structure of the reaction product of a tetracarboxylic acid dianhydride and a diamine and may be obtained by a reaction other than the reaction of a tetracarboxylic acid dianhydride with a diamine The reaction product may be contained.

The polyamic acid ester may be synthesized by reacting the above-mentioned polyamic acid with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, etc., or a method in which a tetracarboxylic acid diester or tetracarboxylic acid diester dichloride derived from an acid dianhydride and a diamine In the presence of a base. The tetracarboxylic acid diester derived from the acid dianhydride can be obtained, for example, by ring opening by reacting the acid dianhydride with the alcohol of the second equivalent, and the tetracarboxylic acid diester dichloride is obtained by reacting the tetracarboxylic acid diester with 2 equivalents With a chlorinating agent such as thionyl chloride. In addition, the polyamic acid ester may have only an amic acid ester structure, or may be a partial esterified product in which an amic acid structure and an amic ester structure coexist.

The tetracarboxylic acid dianhydride used for producing the polyamic acid and derivatives thereof contained in the liquid crystal aligning agent of the present invention will be described. The tetracarboxylic acid dianhydride used in the present invention is not limited to the known tetracarboxylic dianhydrides and can be selected. Such a tetracarboxylic acid dianhydride is an aromatic (including a complex aromatic ring system) in which a dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic system in which a dicarboxylic acid anhydride is not directly bonded to the aromatic ring (Including a heterocyclic ring system). The tetracarboxylic acid dianhydride may be prepared by reacting one compound with diamine or by mixing two or more compounds with diamine. In the present specification, the term &quot; tetracarboxylic dianhydride &quot; refers not only to one compound but also to a mixture of two or more compounds.

The tetracarboxylic acid dianhydride can be roughly divided into a tetracarboxylic acid dianhydride having a photoreactive structure and a tetracarboxylic acid dianhydride having no photoreactive structure.

Preferable examples of the tetracarboxylic acid dianhydride having no photoreactive structure include those represented by formulas (AN-I) to (AN-VII) in view of easiness of obtaining raw materials, ease of polymer polymerization, And tetracarboxylic acid dianhydrides.

In the formula (AN-I), (AN -IV) and (AN-V), X represents a single bond or -CH ₂ independently is. In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF ₃ ) ₂ -. In the formulas (AN-II) to (AN-IV), Y is independently selected from the group consisting of the following trivalent groups, the bonding hand is connected to any carbon, and at least one hydrogen May be substituted with methyl, ethyl or phenyl.

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, May be substituted with methyl, ethyl or phenyl and the bonding hands attached to the ring may be connected to any carbon constituting the ring and two bonding hands may be connected to the same carbon. In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl and Ph represents phenyl. In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1.

More specifically, the tetracarboxylic acid dianhydride represented by the following formulas (AN-1) and (AN-3) to (AN-16-15) may be mentioned.

[Tetracarboxylic acid dianhydride represented by the formula (AN-1)] [

In formula (AN-1), G ¹¹ is a single bond, alkylene having 1 to 12 carbon atoms, 1,4-phenylene, or 1,4-cyclohexylene. X ¹¹ is independently a single bond or -CH ₂ -. G ¹² is independently any of the following trivalent groups.

When G ¹² is > CH-, the hydrogen of > CH- may be substituted with -CH ₃ . When G ¹² is> N-, G ¹¹ is not a single bond and -CH ₂ -, and X ¹¹ is not a single bond. And R ¹¹ is hydrogen or -CH _3.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-1) include compounds represented by the following formulas.

In the formulas (AN-1-2) and (AN-1-14), m is an integer of 1 to 12.

[Tetracarboxylic acid dianhydride represented by the formula (AN-3)

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-3) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-4)

In formula (AN-4), G ¹³ is a single bond, - (CH ₂ ) _m -, -O-, -S-, -C (CH ₃ ) ₂ -, -SO ₂ -, -CO-, C (CF ₃ ) ₂ -, or a bivalent group represented by the following formula (G13-1), and m is an integer of 1 to 12. Ring A ¹¹ is, each independently, a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of the ring A ¹¹ .

In the formula (G13-1), G ^13a and ^13b G is a bivalent group represented by a single bond, -O- or -NHCO-, each independently. Phenylene is preferably 1,4-phenylene and 1,3-phenylene.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-4) include the compounds represented by the following formulas.

In the formula (AN-4-17), m is an integer of 1 to 12.

[Tetracarboxylic acid dianhydride represented by the formula (AN-5)] [

In formula (AN-5), R ¹¹ is hydrogen or -CH ₃ . R ¹¹ in which the bonding position is not fixed to the carbon atom constituting the benzene ring indicates that the bonding position in the benzene ring is arbitrary.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-5) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-6)] [

In the formula (AN-6), X ¹¹ is independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH = CH-. n is 1 or 2;

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-6) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-7)] [

In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-7) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-8)

In formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl, and ring A ¹² is a cyclohexane ring or a cyclohexene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-8) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-9)] [

In formula (AN-9), r is each independently 0 or 1.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-9) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-10-1) and the formula (AN-10-2)

[Tetracarboxylic acid dianhydride represented by the formula (AN-11)] [

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-11) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-12)

In the formula (AN-12), each of the rings A ¹¹ is independently a cyclohexane ring or a benzene ring.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-12) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-13)] [

In the formula (AN-13), X ¹³ represents alkylene having 2 to 6 carbon atoms, and Ph represents phenyl.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-13) include compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-14)

In the formula ^(AN-14), G 14 are independently -O-, -COO- or -OCO-, r is independently 0 or 1;

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-14) include the compounds represented by the following formulas.

[Tetracarboxylic acid dianhydride represented by the formula (AN-15)] [

In the formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic acid dianhydride represented by the formula (AN-15) include the compounds represented by the following formulas.

As the tetracarboxylic acid dianhydride other than the above, the following compounds may be mentioned.

Preferable materials for improving the respective properties of the tetracarboxylic acid dianhydride having no photoreactive structure will be described.

(AN-1), (AN-3) and (AN-4) are preferable, and the compounds represented by formulas (AN-1-2), (AN- 1-13), (AN-3-2), (AN-4-5), (AN-4-17) and (AN-4-29) are more preferable. In the formula (AN-1-2), m = 4 or 8 is preferable. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

(AN-1-1), (AN-1-2), (AN-3-1), (AN-2-1) and AN-4-17), AN-4-30, AN-5-1, AN-7-2, AN-10-1, AN- -16-4) is preferable. In the formula (AN-1-2), m = 4 or 8 is preferable. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

(AN-1-1), (AN-1-2), (AN-3-1), (AN-3-1) and AN-4-17), AN-4-30, AN-7-2, AN-10-1, AN-16-1, AN- -16-4) is preferable, and in the formula (AN-1-2), m = 4 or 8 is preferable. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

It is effective to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film as one of methods for preventing burn-in. (AN-1-13), (AN-3-2), (AN-4-21), and (AN-4-29) among the above tetracarboxylic acid dianhydrides, , And (AN-11-3) are preferable.

The diamines and dihydrazides used for producing the polyamic acid and derivatives thereof contained in the liquid crystal aligning agent of the present invention will be described. The diamines and dihydrazides used in the present invention can be selected without limitation in known diamines and dihydrazides. The diamine may be prepared by reacting one compound with a tetracarboxylic acid dianhydride, or by mixing two or more compounds with a tetracarboxylic acid dianhydride. In the present specification, the term &quot; diamine &quot; refers not only to one compound, but also to a mixture of two or more compounds. In the present specification, it is assumed that dihydrazide is also treated as &quot; diamine &quot;.

Like the diamine tetracarboxylic acid dianhydride, it can be roughly divided into a diamine having a photoreactive structure and a diamine having no photoreactive structure. The diamine having no photoreactive structure can be divided into two types according to its structure. That is, when a skeleton connecting two amino groups is considered as a skeleton, it is a skeleton branched from the main chain, that is, a diamine having a side chain and a diamine having no side chain. This side wrench is a unit having an effect of increasing the pretilt angle. The side chain having such an effect needs to be a group having 3 or more carbon atoms. Specific examples thereof include alkyl having 3 or more carbon atoms, alkoxy having 3 or more carbon atoms, alkoxyalkyl having 3 or more carbon atoms, and a group having a steroid skeleton. A group having at least one ring and having a ring at the terminal thereof has any one of an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as substituents. In the following description, the diamine having such a side chain is sometimes referred to as a side chain diamine. The diamine having no such side chain is sometimes referred to as a side chain type diamine.

By suitably separating the non-side chain diamine and the side chain diamine, it is possible to cope with the required pretilt angle. The side chain type diamine is preferably used in combination so as not to impair the characteristics of the present invention. Further, it is preferable to select and use the side chain type diamine and the side chain type diamine for the purpose of improving the vertical alignment property, the voltage holding ratio, the burning property and the orientation property of the liquid crystal.

The non-chain type diamine will be described. Examples of the diamines which do not have a side chain already known include diamines of the following formulas (DI-1) to (DI-16).

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen of the phenylene may be substituted with -OH. Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONCH 3 -, -CONH-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m -, _{-O- (CH 2) m -O-,} -N (CH 3) - (CH 2) k -N (CH 3) -, - (OC 2 H 4) m -O-, -O-CH 2 - _{C (CF 3) 2 -CH 2} -O-, -O-CO- (CH 2) m -CO-O-, -CO-O- (CH 2) m -O-CO-, - (CH 2) _{m -NH- (CH 2) m -} , -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH-, -CO-C 3 H ₆ and _{(NH-C 3 H 6)} n -CO-, or _{-S- (CH 2) m -S-,} m is independently an integer of from 1 to 12, k is independently an integer from 1-5 and , and n is 1 or 2. In the formula (DI-4), s is independently an integer of 0 to 2. In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, -NH-, or an alkylene having 1 to 10 carbon atoms. Formula (DI-2) ~ formula (DI-7) of the cyclohexane ring and has at least one hydrogen of the benzene ring, -F, -Cl, C 1 -C 3 alkylene group, -OCH _3, -OH, -CF of _{3, -CO 2 H, -CONH 2} , -NHC 6 H 5, and be substituted by phenyl or benzyl, and the formula (DI-4) in cyclohexane ring and at least one hydrogen of the benzene ring to the formula ( May be substituted with one group selected from the group of groups represented by the formulas DI-4-a to Formula (DI-4-e). A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. The bonding position of -NH ₂ to the cyclohexane ring or benzene ring is any position other than the bonding position of G ²¹ or G ²² .

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ .

In formula (DI-11), r is 0 or 1. In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at an arbitrary position.

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10; In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 to be. In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl of 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, Lt; / RTI &gt; In formula (DI-15), ring C is a monocyclic ring containing a heteroatom. In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, and r is 0 or 1. A group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is any position.

Specific examples of the following formulas (DI-1-1) to (DI-16-1) may be mentioned as the diamines having no side chains of the formulas (DI-1) to (DI-16).

Examples of the diamine represented by the formula (DI-1) are shown below.

In the formulas (DI-1-7) and (DI-1-8), k is independently an integer of 1 to 3.

Examples of the diamines represented by the formulas (DI-2) and (DI-3) are shown below.

Examples of the diamine represented by the formula (DI-4) are shown below.

Examples of diamines represented by the formula (DI-5) are shown below.

In the formula (DI-5-1), m is an integer of 1 to 12.

In the formulas (DI-5-1), (DI-5-12) and (DI-5-13), m is an integer of 1 to 12.

In the formula (DI-5-16), v is an integer of 1 to 6.

In the formula (DI-5-30), k is an integer of 1 to 5.

In the formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is independently an integer of 1 to 12, In the formula (DI-5-39), k is independently an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2.

Examples of diamines represented by the formula (DI-6) are shown below.

Examples of diamines represented by the formula (DI-7) are shown below.

In the formulas (DI-7-3) and (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2.

In the formula (DI-7-12), m is an integer of 1 to 12.

Examples of diamines represented by the formula (DI-8) are shown below.

Examples of the diamine represented by the formula (DI-9) are shown below.

Examples of diamines represented by the formula (DI-10) are shown below.

Examples of the diamine represented by the formula (DI-11) are shown below.

Examples of diamines represented by the formula (DI-12) are shown below.

Examples of diamines represented by the formula (DI-13) are shown below.

Examples of diamines represented by the formula (DI-14) are shown below.

Examples of the diamine represented by the formula (DI-15) are shown below.

Examples of diamines represented by the formula (DI-16) are shown below.

Describe Dehydrazide. Dihydroidazides having no known side chain include the following formulas (DIH-1) to (DIH-3).

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or - (CF ₃ ) ₂ -. In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of these rings may be substituted by methyl, ethyl, or phenyl. In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of these rings may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -. In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is arbitrary.

Examples of the formulas (DIH-1) to (DIH-3) are shown below.

In the formula (DIH-1-2), m is an integer of 1 to 12.

Such non-chain type diamine and hydrazide have the effect of improving the electric characteristics such as lowering the ion density of the liquid crystal display element. When a side chain type diamine and / or a hydrazide is used as a diamine to be used for producing a liquid crystal aligning agent comprising a polyamic acid, a polyamic acid ester or a polyimide used in the liquid crystal aligning agent of the present invention, The proportion of the total amount of the droplets is preferably 0 to 90 mol%, more preferably 0 to 50 mol%.

The side chain type diamine will be described. As the side chain group of the side chain type diamine, the following groups may be mentioned.

As the side chain, it is preferable to firstly substitute alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy , Alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like. The alkyl, alkenyl and alkynyl in these groups are all three or more carbon atoms. However, in alkyloxyalkyl, the number of carbon atoms in the whole group may be 3 or more. These groups may be linear or branched.

Subsequently, it is preferable that the ring at the terminal is substituted with at least one substituent selected from the group consisting of phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy , Phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl of 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexyl (Cyclohexyl) phenyloxy, bis (cyclohexyl) oxy, bis (cyclohexyl) alkyl, bis (cyclohexyl) , And cyclohexyl bis (phenyl) oxycarbonyl, and the like.

A group having two or more benzene rings, a group having two or more cyclohexane rings, or a group having two or more rings composed of a benzene ring and a cyclohexane ring, the bonding group is independently a single bond, -O-, -COO- , -OCO-, -CONH- or alkylene having 1 to 3 carbon atoms, and the ring at the terminal is substituted with a substituent such as alkyl having 1 or more carbon atoms, fluorine-substituted alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, or alkoxyalkyl having 2 or more carbon atoms And a grouper. It is effective as a prayer side instrument with a steroid skeleton.

Examples of the diamine having a side chain include compounds represented by the following formulas (DI-31) to (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} -, and m' is an integer of 1 to 12. Preferred examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, particularly preferred examples are a single bond, -O-, -COO -, -OCO-, -CH ₂ O-, -CH ₂ - and -CH ₂ CH ₂ -. R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - may be substituted with -O-, -CH = CH-, or -C≡C-. Hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or may be substituted by alkoxy of 3 to 30 carbon atoms or alkyl of 3 to 30 carbon atoms. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, but the bonding position is preferably meta or para. That is, when the bonding position of the group &quot; R ²⁵ -G ²⁶ - &quot; is taken as 1 position, it is preferable that the two bonding positions are 3 position and 5 position or 2 position and 5 position.

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are linking groups and independently represent a single bond or alkylene having 1 to 12 carbon atoms, and one or more -CH ₂ - -O-, -COO-, -OCO-, -CONH- or -CH = CH-. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently selected from the group consisting of 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, Diyl, piperidine-1,4-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted with -F or -CH ₃ , s, t and u are independently integers of 0 to 2, Is 0 to 5, and when s, t or u is 2, the two bonding groups in each parenthesis may be the same or different and the two rings may be the same or different. R ²⁶ is hydrogen, -F, -OH, C 1 -C 30 alkyl, C 1 -C 30 fluorine-substituted alkyl, _{alkoxy, -CN, -OCH 2 F, -OCHF} 2, or -OCF of 1 to 30 carbon atoms in the ₃ And at least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b).

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are alkyl having 1 to 30 carbon atoms and alkoxy having 1 to 30 carbon atoms.

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in formulas (DI-32) and (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl. A group in which the bonding position is not fixed to any carbon atom constituting the ring indicates that the bonding position in the ring is arbitrary. Formula (DI-32) 2 group of from the "- phenylene -G ³⁰ -O-" is one of bonded to the 3-position of the steroid nucleus, and the other one is preferably bonded to the 6-position of the steroid nucleus . Equation 2 groups in (DI-33) "- phenylene -G ³⁰ -O-" binding site on the benzene ring is, for the engaged position of the steroid nucleus, preferably in the meta-position or para-position, respectively . In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary.

In formula (DI-34) and formula (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms and G ³² is a single bond or alkyl having 1 to 3 carbon atoms It's Len. R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH = CH- or -C≡C-. R ³² is alkyl having 6 to 22 carbon atoms, and R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. And -NH ₂ bonded to the benzene ring represents any bonding position in the ring, it is preferable that the bonding position of G ³¹ is independently a meta position or a para position with respect to the bonding position of G ³¹ .

Specific examples of the side chain type diamine are illustrated below. Examples of the diamines having side chains of the formulas (DI-31) to (DI-35) include compounds represented by the following formulas (DI-31-1) to (DI-35-3).

Examples of the compound represented by the formula (DI-31) are shown below.

In formulas (DI-31-1) to (DI-31-11), R ³⁴ is independently alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms or Alkoxy of 5 to 25 carbon atoms. R ³⁵ is independently an alkyl having 1 to 30 carbon atoms or an alkoxy having 1 to 30 carbon atoms, preferably an alkyl having 3 to 25 carbon atoms or an alkoxy having 3 to 25 carbon atoms.

In the formulas (DI-31-12) to (DI-31-17), R ³⁶ is independently an alkyl having 4 to 30 carbon atoms, preferably an alkyl having 6 to 25 carbon atoms. R ³⁷ is independently an alkyl having 6 to 30 carbon atoms, preferably an alkyl having 8 to 25 carbon atoms.

In formulas (DI-31-18) to (DI-31-43), R ³⁸ is independently alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, preferably alkyl having 3 to 20 carbon atoms or Alkoxy of 3 to 20 carbon atoms. R ³⁹ is independently hydrogen, -F, C 1 -C 30 alkyl, C 1 -C 30 alkoxy, -CN, -OCH ₂ and F, -OCHF ₂ or -OCF _3, preferably from 3 to 25 carbon atoms in the alkyl , Or an alkoxy group having 3 to 25 carbon atoms. And G ³³ is alkylene having 1 to 20 carbon atoms.

Examples of the compound represented by the formula (DI-32) are shown below.

Examples of the compound represented by the formula (DI-33) are shown below.

Examples of the compound represented by the formula (DI-34) are shown below.

Formula (DI-34-1) ~ formula (DI-34-14), R ⁴⁰ is independently hydrogen or alkyl having 1 to 20 carbon atoms, preferably hydrogen or alkyl of 1 to 10 carbon atoms, and R ⁴¹ in the Is independently hydrogen or alkyl of 1 to 12 carbon atoms.

Examples of the compound represented by the formula (DI-35) are shown below.

In formulas (DI-35-1) to (DI-35-3), R ³⁷ is independently an alkyl having 6 to 30 carbon atoms and R ⁴¹ is independently hydrogen or alkyl having 1 to 12 carbon atoms.

(DI-1-1) to (DI-16-1), DIH-1-1 to DIH-3-6, and DI- -1) to (DI-35-3) may also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

In the formulas (DI-36-1) to (DI-36-8), each of R ⁴² independently represents an alkyl group having 3 to 30 carbon atoms.

In formula (DI-36-9) to formula (DI-36-11), e is an integer of 2 to 10, and in formula (DI-36-12), R ⁴³ is each independently hydrogen, -NHBoc and -N (Boc) _2, at least one of R ⁴³ is -NHBoc or -N (Boc) _2, in formula (DI-36-13), R ⁴⁴ is -NHBoc or -N (Boc) _2, and , And m is an integer of 1 to 12. Wherein Boc is a t-butoxycarbonyl group.

Preferable materials for improving the properties of the diamine and the dihydrazide will be described.

(DI-1-3), (DI-4-1), (DI-5-1) and (DI-5-2) among the above diamines and dihydrazides, (DI-5-5), the formula (DI-5-9), the formula (DI-5-12), the formula -7), the compound represented by formula (DI-7-3), and the compound represented by formula (DI-11-2). The diamine represented by the formula (DI-4-1), the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13) Do. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 1 is more preferable.

(DI-3-1), the formula (DI-2-1), the formula (DI-5-1) and the formula (DI-2-1) among the above diamines and dihydrazides, The compound represented by the formula (DI-5-1), the compound represented by the formula (DI-5-1), the compound represented by the formula (DI-5-17) and the compound represented by the formula (DI-7-3) In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 1 is more preferable.

(DI-2-1), formula (DI-4-1) and formula (DI-4-2) among the diamines and dihydrazides described above are of importance in improving the VHR of the liquid crystal display element. (DI-5-28), the formula (DI-5-30), the formula (DI- (DI-5-1), (DI-13-1) and (DI-31-56) , And a compound represented by the formula (DI-31-56) are more preferable. In the formula (DI-5-1), m = 1 is preferable. In the formula (DI-5-30), k = 2 is preferable.

It is effective to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film as one of methods for preventing burn-in. (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-2) (DI-5-1), DI-5-12, DI-5-13, DI-5-28 and DI-16-1 Compounds represented by formulas (DI-4-1), (DI-5-1) and (DI-5-13) are more preferable. In the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is more preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable.

In each of the diamines, a part of the diamine may be substituted with a monoamine in the range that the ratio of the monoamine to the diamine is 40 mol% or less. Such substitution can cause termination of the polymerization reaction at the time of producing the polyamic acid, and can further suppress the progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the obtained polymer (polyamic acid, polyamic acid ester or polyimide) can be easily controlled, and for example, the effect of the present invention is not impaired and the coating property of the liquid crystal aligning agent Can be improved. The diamine substituted with a monoamine may be used in one kind or in two or more types unless the effect of the present invention is impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, Octadecylamine, and n-eicosylamine.

The polyamic acid and the derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer. By incorporating the monoisocyanate compound into the monomer, the terminal of the resulting polyamic acid or its derivative is modified to control the molecular weight. By using the polyamic acid of the terminal modification type or a derivative thereof, for example, the effect of the present invention is not impaired and the coating property of the liquid crystal aligning agent can be improved. The content of the monoisocyanate compound in the monomer is preferably from 1 to 10 mol% based on the total amount of the diamine and the tetracarboxylic acid dianhydride in the monomer from the viewpoint of the above. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

In the present invention, polyamic acid having a photoreactive structure and derivatives thereof can be preferably used. The photoreactive structure includes, for example, a photo-isomerization structure that causes isomerization by ultraviolet irradiation, a photodegradation structure that causes decomposition, and a photo-dimerization structure that causes dimerization.

The polyamic acid having a photoreactive structure and derivatives thereof are referred to as polymer (a). In the polymer (a), a diamine having a photoreactive structure or a tetracarboxylic acid dianhydride having a photoreactive structure and derivatives thereof can be used as a raw material, and a diamine having a photoreactive structure and a tetracarboxylic acid having a photoreactive structure Acid dianhydrides and derivatives thereof may be used in combination. Examples of the photoreactive structure include structures represented by the following formulas (P-1) to (P-7).

In the formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group.

Examples of the compound having a photoreactive structure that causes photodegradation represented by the formula (P-1) include compounds represented by the following formulas (PA-1) to (PA-6).

In formulas (PA-3) to (PA-6), R ⁶² is independently an alkyl group having 1 to 5 carbon atoms.

Among the compounds represented by the formula (P-1), the above formulas (PA-1), (PA-2) and (PA-5) are preferably used.

The compounds represented by the formulas (PA-1) to (PA-6) can be used in combination with a liquid crystal aligning agent based on photoisomerization, a liquid crystal aligning agent based on optical dimerization, When used as a material for a liquid crystal aligning agent, it is used as a tetracarboxylic acid dianhydride having no photoreactive structure.

Examples of the compound having a photoreactive structure represented by the formulas (P-2) to (P-4) include tetracarboxylic acid dianhydrides and diamine compounds represented by the following formulas (II-1) to (VI- .

In the formulas (V-2), R ⁶ is independently a group in which the bonding position is not fixed to any carbon atom constituting the ring, and the bonding position in the ring is arbitrary. It is _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently an integer from 0 to 2, in the formula (V-3), ring a and ring B are each independently a monocyclic hydrocarbon , Condensed polycyclic hydrocarbon and heterocyclic ring, and R ¹¹ is a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N (CH ₃ ) CO- , R ¹² is a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N (CH ₃ ) CO-, and in R ¹¹ and R ¹² , And one or two of -CH ₂ - may be replaced by -O-, R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH, and b ~ E are each independently It is an integer from 0 to 4.

The compounds represented by the above formulas (V-1), (V-2) and (VI-2) are particularly preferably used in view of their photosensitivity. In the formulas (V-2) and (VI-2), a compound in which the bonding position of the amino group is para-position and a compound in which a = 0 in the formula (V-2) Can be used.

Acid dianhydrides or diamines having a structure capable of causing optical isomerization by ultraviolet irradiation represented by the following formulas (II-1) to (VI-2) .

When a compound containing a structure capable of causing isomerization by irradiation with ultraviolet rays is used as the compound of the formulas (VI-1-1) to (V-3-8), a liquid crystal aligning agent for photo- . V-2-1, V-2-1, V-2-4 to V-2-11 and V-3-1 to V- -8) having a structure capable of causing isomerization by irradiation with ultraviolet rays, it is possible to obtain a liquid crystal aligning agent for optical alignment capable of more evenly orienting the liquid crystal molecules. When the compound containing a structure capable of causing isomerization by UV irradiation is used as the compound of the formula (V-2-4) to the compound of the formula (V-3-8), a liquid crystal aligning agent for photo- Can be obtained.

Among them, a compound represented by the formula (V-2-1) can be more preferably used since it exhibits greater anisotropy when the liquid crystal alignment film is formed.

Examples of the compound having a photoreactive structure represented by the formulas (P-5) to (P-7) include diamine compounds represented by the following formulas (PDI-9) to (PDI-13).

In formula (PDI-12), R ⁵⁴ is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen of alkyl or alkoxy may be substituted with fluorine.

The above formulas (PDI-9) and (PDI-11) can be preferably used.

In the case of using a tetracarboxylic acid dianhydride having no photoreactive structure (non-photosensitive) and a (photosensitive) tetracarboxylic acid dianhydride having a photoreactive structure, the sensitivity of the liquid crystal alignment film to light is prevented from being lowered , The amount of the photosensitive tetracarboxylic acid dianhydride is preferably from 0 to 70 mol%, more preferably from 0 to 70 mol%, based on the total amount of the tetracarboxylic acid dianhydride used as a raw material in the production of the polyamic acid and the derivative thereof of the present invention. And particularly preferably 50 mol%. Further, two or more photosensitive tetracarboxylic acid dianhydrides may be used in combination in order to improve the aforementioned characteristics such as sensitivity to light, electric characteristics, residual image characteristics and the like.

In the case of using the (photosensitive) diamine having no photoreactive structure (non-photosensitive) and the (photosensitive) diamine having a photoreactive structure in combination, in order to prevent the sensitivity of the orientation film to a decrease in sensitivity, the polyamic acid and its derivative Is preferably 20 to 100 mol%, and particularly preferably 50 to 100 mol%, based on the total amount of the diamine used as a raw material in the production of the photosensitive layer. Further, two or more photosensitive diamines may be used in combination in order to improve the above-mentioned various characteristics such as sensitivity to light, residual image characteristics and the like. As described above, the embodiment of the present invention includes a case in which the total amount of the tetracarboxylic acid dianhydride is occupied by the non-photosensitive tetracarboxylic acid dianhydride. However, even in this case, at least 20 mol% of the total amount of the diamine is the photosensitive diamine .

Sensitive tetracarboxylic acid dianhydride and photosensitive diamine may be used in combination in order to improve the above-mentioned various properties such as sensitivity to light, residual image characteristics, etc., and two or more of them may be used in combination.

The polyamic acid and the derivative thereof of the present invention are obtained by reacting a mixture of the tetracarboxylic acid dianhydride and a diamine in a solvent. In this synthesis reaction, special conditions other than the selection of the raw materials are not required, and the conditions for conventional synthesis of polyamic acid can be applied as they are. The solvent to be used will be described later.

The polymer contained in the liquid crystal aligning agent of the present invention may be one, or two or more may be blended. An embodiment of blending two or more polymers includes a polymer (a) obtained by reacting at least one polymer, at least one of a tetracarboxylic acid dianhydride and a diamine with a raw monomer having a photoreactive structure, and the other polymer At least one polymer (b) selected from polyamic acid and derivatives thereof obtained by reacting at least one tetracarboxylic acid dianhydride having no photoreactive structure and diamine having no photoreactive structure. The polymer (a) has a photo-reactive structure isomerized, decomposed or dimerized by irradiation with an energy ray such as ultraviolet ray to change its structure and accordingly has a capability of aligning liquid crystal molecules in contact with the polymer film in a specific direction . Such polymers may be used in blends with other polymers that do not contain a photoreactive structure.

The liquid crystal aligning agent of the present invention may further contain components other than the polyamic acid or the derivative thereof. The other components may be one kind or two kinds or more. As other components, for example, other polymers and compounds described later can be mentioned.

When a plurality of polymers are blended and used in the liquid crystal aligning agent of the present invention, the structure and the molecular weight of each polymer are controlled, and the liquid crystal aligning agent is applied to the substrate as described later and pre-dried, The polymer (a) having the photo-alignment function can be separated into the upper layer of the coating film and the other polymer (b) into the lower layer of the coating film. This can be controlled by using a phenomenon in which a polymer having a small surface energy is separated into an upper layer and a polymer having a large surface energy is separated into a lower layer in a mixed polymer. Confirmation of the layer separation can be confirmed by the fact that the surface energy of the formed alignment film is equal to or close to the surface energy of the alignment film formed by the liquid crystal aligning agent containing only the polymer (a).

As a tetracarboxylic acid dianhydride used for synthesizing the above polymer (b), there can be used a tetracarboxylic acid dianhydride which is known as a tetracarboxylic acid dianhydride used for synthesizing a polyamic acid or its derivative which is an essential component of the liquid crystal aligning agent of the present invention Tetracarboxylic acid dianhydride, and the same ones as those exemplified above.

(AN-3-2), the formula (AN-1-13), and the formula (AN-4-30) in the case where the improvement of the layer separability is emphasized in the tetracarboxylic acid dianhydride, ) Is preferable.

(AN-1-1), (AN-1-2), (PA-1), and (AN- AN-4-17, AN-4-30, AN-5-1, AN-7-2, AN-10-1, Compounds represented by formulas (AN-10-2), (AN-16-3), and (AN-16-4) are preferred. In the formula (AN-1-2), m = 4 or 8 is preferable. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

(PA-1), the formula (AN-4-17), the formula (AN-7-2) and the formula (AN- (AN-10-1), formula (AN-10-2), formula (AN-16-1), formula (AN-16-3) and formula (AN-16-4). In the formulas (AN-1-2) and (AN-4-17), m = 4 or 8 is preferable.

It is effective to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film as one of the methods for preventing burn-in. (AN-1-13), (AN-3-2), (AN-4-21), and (AN-4), among the above tetracarboxylic acid dianhydrides, -29), and formula (AN-11-3) are preferable.

The tetracarboxylic acid dianhydride used for synthesizing the polymer (b) preferably contains an aromatic tetracarboxylic acid dianhydride in an amount of 10 mol% or more, more preferably 30 mol% or more, Or more.

The diamine and hydrazide used for synthesizing the polymer (b) are the same as those exemplified above as other diamines that can be used for synthesizing the polyamic acid or its derivative, which is an essential component of the liquid crystal aligning agent of the present invention .

When it is desired to further improve the layer separability, that is, the alignment property of the liquid crystal, among the above diamines and dihydrazides, a compound represented by formula (DI-4-1), formula (DI-4-2) (DI-4-10), the compound represented by the formula (DI-5-1), the compound represented by the formula (DI-5-9), the compound represented by the formula (DI-5-28) desirable. In the formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is more preferable.

(DI-2-1), (DI-2-1), (DI-5-1), and (DI-5-1) among the diamines and dihydrazides described above, DI-7-3), and diamines represented by the formula (DI-2-1) are more preferable. In the formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 1 or 2 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 1 is more preferable.

(DI-2-1), formula (DI-4-1) and formula (DI-4-2) among the diamines and dihydrazides described above are of importance in improving the VHR of the liquid crystal display element. , DI-5-15, DI-5-28, DI-5-30, DI-13-1 and DI- 31-56) is preferably used. Diamines represented by the formulas (DI-2-1), (DI-5-1), (DI-13-1) and (DI-36-14) are more preferable. In the formula (DI-5-1), m = 1 or 2 is preferable. In the formula (DI-5-30), k = 2 is preferable.

It is effective to improve the relaxation speed of the residual charge (residual DC) in the alignment film by lowering the volume resistance value of the liquid crystal alignment film as one of the methods for preventing burn-in. (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-2) 5-15), the formula (DI-5-1), the formula (DI-5-9), the formula (DI-5-1), and the compound represented by the formula (DI-16-1) are preferably used, 5-12) is more preferable. In the formula (DI-5-1), m = 1 or 2 is preferable. In the formula (DI-5-12), m = 2 to 6 is preferable, and m = 5 is more preferable. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-5-30), k = 2 is preferable.

The diamine used for synthesizing the polymer (b) preferably contains an aromatic diamine in an amount of 30 mol% or more, more preferably 50 mol% or more, based on the total diamine.

In the liquid crystal aligning agent of the present invention, the proportion of the polymer (a) relative to the total amount of the polymer (a) and the polymer (b) is preferably 10% by weight to 100% by weight, more preferably 20% Is more preferable.

The liquid crystal aligning agent of the present invention may further contain components other than the polyamic acid or the derivative thereof of the present invention. The other components may be one kind or two kinds or more. As other components, for example, other polymers and compounds described later can be mentioned.

Examples of other polymers include polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly (styrene-phenylmaleimide) derivatives, and poly (meth) acrylates. One kind may be used, or two or more kinds may be used. Of these, other polyamic acid or derivatives thereof and polysiloxane are preferable, and other polyamic acids or derivatives thereof are more preferable.

As the polysiloxane, there may be mentioned, for example, Japanese Patent Application Laid-Open Nos. 2009-036966, 2010-185001, 2011-102963, Japanese Laid-Open Patent Publication No. 2011-253175, Japanese Laid-Open Patent Publication No. 2012-159825, , International Publication 2009/148099, International Publication 2010/074261, International Publication 2010/074264, International Publication 2010/126108, International Publication 2011/068123, International Publication 2011/068127, International Publication 2011/068128, International Publication 2012/115157, International &Lt; RTI ID = 0.0 &gt; 2012/165354, &lt; / RTI &gt;

The liquid crystal aligning agent of the present invention may further contain an additive other than the compound represented by the formula (1). Examples of the additive other than the compound represented by the formula (1) include an alkenyl-substituted nordium compound, an oxazine compound, an oxazoline compound, an epoxy compound other than the compound represented by the formula (1), a polyamic acid and a derivative thereof Polymer compounds, and other low-molecular compounds, and they can be selected depending on the purpose.

&Lt; Alkenyl-substituted nadimide compound &

The liquid crystal aligning agent of the present invention may further contain an alkenyl-substituted nadimide compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The alkenyl-substituted nadimide compound may be used alone or in combination of two or more. The content of the alkenyl-substituted nadimide compound is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight based on the polyamic acid or the derivative thereof for the above- More preferable.

The nadimide compound will be specifically described below.

The alkenyl-substituted nadimide compound is preferably a compound capable of dissolving in the solvent for dissolving the polyamic acid or the derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadimide compound include compounds represented by the following formula (NA).

In formula (NA), L ¹ and L ² are independently hydrogen, alkyl having 1 to 12 carbons, alkenyl having 3 to 6 carbons, cycloalkyl having 5 to 8 carbons, aryl having 6 to 12 carbons or benzyl, n is 1 or 2;

In the formula (NA), when n = 1 il, W is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, having a carbon number of 5-8 of the cycloalkyl, aryl, benzyl having a carbon number of 6 ~ 12, -Z ¹ of - (O) _r - (Z ² O) _k -Z ³ -H, wherein Z ¹ , Z ² and Z ³ are independently alkylene of 2 to 6 carbon atoms, r is 0 or 1, (Z ⁴ ) _r -BZ ⁵ -H (wherein Z ⁴ and Z ⁵ are each independently an alkylene group having 1 to 4 carbon atoms or a cycloalkylene group having 5 to 8 carbon atoms, , B is phenylene, and r is the group, -BTBH (wherein, B is phenylene, and T is _{-CH 2 -, -C (CH 3} ) represented by a 0 or a 1) ₂ -, -O- , -CO-, -S-, or -SO ₂ -), or a group in which one to three hydrogens of these groups are substituted with -OH.

In this case, preferable W is an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 3 to 4 carbon atoms, cyclohexyl, phenyl, benzyl, poly (ethyleneoxy) ethyl having 4 to 10 carbon atoms, phenyloxyphenyl, phenylmethylphenyl, Propylidenephenyl, and groups in which one or two hydrogens of these groups are substituted with -OH.

In the formula (NA), when n = 2, W is an alkylene having 2 to 20 carbon atoms, a cycloalkylene having 5 to 8 carbon atoms, an arylene having 6 to 12 carbon atoms, -Z ¹ -O- (Z ² O ) _k -Z ³ - (wherein, Z ¹ ~ Z ^3, and the definition of k is a group represented by as defined above), -Z ⁴ -BZ ⁵ - (wherein, Z ^4, Z ⁵ and B are defined in the -B- (OB) _r -T- (BO) _r -B- wherein B is phenylene, T is alkylene having 1 to 3 carbon atoms, -O- or -SO ₂ -, and the definition of r is as defined above), or a group in which one to three hydrogens of these groups are substituted with -OH.

In this case, preferable W is an alkylene group having 2 to 12 carbon atoms, cyclohexylene, phenylene, tolylene, xylylene, -C ₃ H ₆ -O- (Z ² -O) _n -OC ₃ H ₆ - , Z ² is alkylene having 2 to 6 carbon atoms and n is 1 or 2, -BTB- (wherein B is phenylene and T is -CH ₂ -, -O- or -SO ₂ -), -BOBC ₃ H ₆ -BOB- (wherein B is phenylene), and groups in which one or two hydrogens of these groups are substituted with -OH.

Such an alkenyl-substituted nadimide compound is obtained by synthesizing an alkenyl-substituted nadic anhydride derivative and diamine at a temperature of 80 to 220 ° C for 0.5 to 20 hours as described in, for example, Japanese Patent No. 2729565 A compound or a commercially available compound can be used. Specific examples of the alkenyl-substituted nadimide compound include the following compounds.

2,1-hept-5-ene-2,3-dicarboxyimide, N-methyl-allylbicyclo [2.2.1] 2.2.1] hept-5-ene-2,3-dicarboxyimide, N-methyl-methallylmethylbicyclo [2.2.1] hept- , 3-dicarboxyimide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

2.2.1] hept-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo [2.2.1] hepto-5- N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-allyl- 2,1-hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl ) Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-isopropenyl-methallylbicyclo [2.2.1] N-cyclohexyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl (methyl) bicyclo [2.2.1] hept- , 3-dicarboxyimide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo [2.2.1] Ene-2,3-dicarboxyimide,

N-phenyl-allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-benzyl-allylbicyclo [2.2.1] hepto- Benzyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N-benzyl-allylmethylbicyclo [2.2.1] hept- 2,3-dicarboxyimide, N- (2-hydroxyethyl) - allylbicyclo [2.2.1] hept-5- 2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2-hydroxyethyl) -malilylbicyclo [2.2.1] hept- , 3-dicarboxyimide,

(2,2-dimethyl-3-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (2,3-dihydroxypropyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxy-1-propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (4-hydroxycyclohexyl) (Methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

(4-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- 2,1-hept-5-ene-2,3-dicarboxyimide, N- (4-hydroxyphenyl) methallylbicyclo [2.2.1] hept- - (4-hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allylbicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboxyimide, N- (3-hydroxyphenyl) -allyl (methyl) bicyclo [2.2.1] (P-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide,

N- {2- (2-hydroxyethoxy) ethyl} -allyl (methyl) bicyclo [2.2.1] hepto-5- Ethyl} - methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {2- (2-hydroxyethoxy) ethyl} [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- [2- {2- (2- hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.1] -2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -allyl (methyl) bicyclo [2.2.1] 2,3-dicarboxyimide, N- [2- {2- (2-hydroxyethoxy) ethoxy} ethyl] -malilylicyclo [2.2.1] hept- Dicarboximide, N- {4- (4-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {4- (Methyl) bicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide, N- {4- Phenyl} -methallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide, and their oligomers,

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Bis {3 '- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} ethane, 1,2- Bis [3 '- (methallylbicyclo [2.2.1] hept-5-en-2-yl) , 3-dicarboxyimide) propoxy} ethane, bis [2 '- (3' - (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} , Bis [2 '- {3' - (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} ethyl] ether, (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} butane, 1,4-bis {3 ' - ene-2,3-dicarboxyimide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- Xylylene-bis (allylmethylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide),

Bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2- Phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide Phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- Phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- 2,1-hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 .1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone,

Bis [4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, 1,6-bis (allylbicyclo [2.2.1] hepto- -2,3-dicarboxyimide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide) 1,3-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -5-hydroxy-cyclohexane, 1,5-bis { 3'- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) propoxy} -3-hydroxy-pentane, 1,4- ] Hept-5-ene-2,3-dicarboxyimide) -2-hydroxy-benzene,

Di-hydroxy-benzene, N, N'-p- (2- (4-hydroxyphenyl) N'-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Methylcyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-m- (2-hydroxy) xylylene- bis (allylbicyclo [2.2.1] N'-m- (2-hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-di Carboxyimide), N, N'-p- (2,3-dihydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

Phenoxy} phenyl] propane, bis {4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -2- - (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -2-hydroxyphenyl} methane, bis {3- Phenyl] ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) - Phenyl} sulfone, 1,1,1-tri {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)} phenoxymethylpropane, N , N ', N "-tri (ethylene methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) isocyanurate, and oligomers thereof.

The alkenyl-substituted nordium compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene-phenylene group.

Among the alkenyl-substituted nadimide compounds, preferable compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide)

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- 2,2-bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) -5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, Phenoxy} phenyl] propane, 2,2-bis [4- {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Phenyl] propane, bis {4- (allylbicyclo [2.2.1] hepto-5- (methallylbicyclo [2.2.1] hept- -2,3-dicarboxyimide) phenyl} methane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane.

Bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane, bis {4- Phenyl} methane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- 2,1-hept-5-ene-2,3-dicarboxyimide) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] Dicarboxyimide) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} sulfone, bis {4- (allylmethylbicyclo [2.2 Phenyl] sulfone, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} Sulfone.

More preferred alkenyl substituted nadimide compounds are shown below.

N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 2,3-dicarboxyimide), N, N'-ethylene-bis (metallylbicyclo [2.2.1] hept- (Allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'-hexamethylene-bis N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Dodecamethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- ] Hept-5-ene-2,3-dicarboxyimide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] N, N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide).

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Cyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- (Dicarboxyimide), N, N'-m-phenylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- -Methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- Bis (cyclohexyl [2.2.1] hept-5-ene-2,3-dicarboxyimide), N, N'- , 3-dicarboxyimide), N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hepto-5- Xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide).

Bis [4- {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, 2,2- Phenyl] propane, 2,2-bis [4- {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) 1] hept-5-ene-2,3-dicarboxyimide) phenoxy} phenyl] propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide ) Phenyl} methane, bis {4- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) Phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl} methane .

Particularly preferred alkenyl-substituted nadimide compounds include bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) phenyl } Methane, N, N'-m-xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxyimide) represented by the formula (NA- -3), and N, N'-hexamethylene-bis (allylbicyclo [2.2.1] hepto-5-ene-2,3-dicarboxyimide).

<Compound Having Radically Polymerizable Unsaturated Double Bond>

The liquid crystal aligning agent of the present invention may further contain a compound having a radically polymerizable unsaturated double bond for the purpose of stabilizing the electric characteristics of the liquid crystal display element for a long term. The compound having a radically polymerizable unsaturated double bond may be a single compound or two or more compounds. The compound having a radically polymerizable unsaturated double bond does not contain an alkenyl-substituted nadimide compound. The content of the compound having a radically polymerizable unsaturated double bond is preferably 1 to 100% by weight, more preferably 1 to 70% by weight, and more preferably 1 to 50% by weight, based on the polyamic acid or the derivative thereof, %.

Further, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound is such that the ion density of the liquid crystal display element is reduced, the increase of the ion density over time is suppressed, , The compound having a radical polymerizable unsaturated double bond / alkenyl-substituted nadimide compound is preferably in a weight ratio of 0.1 to 10, more preferably 0.5 to 5.

Hereinafter, the compound having a radically polymerizable unsaturated double bond will be specifically described.

Examples of the compound having a radical polymerizable unsaturated double bond include (meth) acrylic acid derivatives such as (meth) acrylic acid ester, (meth) acrylamide, and bismaleimide. The compound having a radically polymerizable unsaturated double bond is more preferably a (meth) acrylic acid derivative having two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth) acrylic esters include, for example, cyclohexyl (meth) acrylate, 2-methylcyclohexyl (meth) acrylate, dicyclopentanyl (meth) acrylate, dicyclopentanyloxyethyl (Meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate.

Specific examples of the bifunctional (meth) acrylic acid ester include ethylenebisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200 manufactured by Toa Synthetic Chemical Industry Co., Ltd., KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684 manufactured by Osaka Organic Chemical Industry Co., Ltd., V260, V312 and V335HP manufactured by Kyowa Chemical Industry Co., Ltd., and Light Acrylate BA -4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of trifunctional or more polyfunctional (meth) acrylic acid esters include 4,4'-methylene bis (N, N-dihydroxyethylene acrylate aniline), Aro, a product of Toagosei Chemical Industry Co., KAYARADDPCA-20, KAYARADDPCA-20 manufactured by NIPPON KAYAKU CO., LTD., Which are products of Nikon M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M- 30, KAYARADDPCA-60, KAYARADDPCA-120, and VGPT, a product of Osaka Organic Chemical Industry Co., Ltd.

Specific examples of the (meth) acrylic acid amide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-propyl acrylamide, N-propyl methacrylamide, N-cyclopropyl acrylamide, Tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethylacrylamide, N-ethylacrylamide, N-ethylmethacrylamide, N-methylacrylamide, N, N-diethylacrylamide, N-methyl-N-propyl acrylamide, N-methyl- N, N'-ethylenebisacrylamide, N, N'-dihydroxyethylenebisacrylamide, N- (4-hydroxyphenyl) methacryloyl Amide, N-phenylmethacrylamide, N-butyl methacrylamide, N- (iso- (N, N-dimethylamino) ethyl] methacrylamide, N, N-dimethyl methacrylamide, N- [3- (dimethylamino) propyl] methacrylamide, (Methoxymethyl) methacrylamide, N- (hydroxymethyl) -2-methacrylamide, N-benzyl-2-methacrylamide, and N, N'-methylenebis methacrylamide .

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

Examples of the bismaleimide include BMI-70 and BMI-80 manufactured by K-I Hasegawa Co., Ltd. and BMI-1000, BMI-3000, BMI-4000 and BMI-5000 manufactured by Daika Chemical Industry Co., And BMI-7000.

&Lt;

The liquid crystal aligning agent of the present invention may further contain an oxazine compound in order to stabilize the electric characteristics of the liquid crystal display element in the long term. The oxazine compound may be a single compound or two or more compounds. The content of the oxazine compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and even more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof for the above purpose .

The oxazine photochemical compound will be specifically described below.

The oxazine compound is preferably an oxazine compound which is soluble in a solvent for dissolving polyamic acid or a derivative thereof and has ring-opening polymerizability.

The number of the oxazine structures in the oxazine photographic compound is not particularly limited.

Various structures are known in the structure of the jade photograph. In the present invention, the structure of the oxazine is not particularly limited, but the structure of the oxazine having an aromatic group containing a condensed polycyclic aromatic group such as benzooxazine or naphthoquinone is included in the oxazine structure of the oxazine compound. .

Examples of the oxazine photographic compound include compounds represented by the following formulas (OX-1) to (OX-6). In the following formulas, the bond indicated toward the center of the ring indicates that the bond is bonded to a carbon which constitutes a ring and is capable of bonding a substituent.

In the formula (OX-1) ~ formula ^(OX-3), L 3 and L ⁴ are in an organic group of 1 to 30 carbon atoms, formula (OX-1) ~ formula ^{(OX-6), L 5} ~ L ⁸ is in a hydrocarbon group having 1 to 6 carbon atoms or hydrogen, formula (OX-3), formula (OX-4) and formula (OX-6), Q ¹ represents a single bond, -O-, -S- _{, -SS-, -SO 2 -, -CO-} , -CONH-, -NHCO-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) v -, -O - (CH ₂ ) _v -O-, -S- (CH ₂ ) _v -S-, wherein v is an integer of 1 to 6, and in formula (OX-5) and formula (OX- ² is a single bond independently, -O-, -S-, -CO-, -C (CH 3) 2 -, -C (CF 3) 2 - or an alkylene group having a carbon number of 1 to 3, in the Q ² of the benzene ring, hydrogen bonded to the naphthalene ring is optionally independently substituted with _{-F, -CH 3, -OH, -COOH} , -SO 3 H, -PO 3 H 2.

The jade photographic compound contains an oligomer or polymer having an oxazine structure in its side chain, and an oligomer or polymer having an oxazine structure in its main chain.

As the oxazine compound represented by the formula (OX-1), for example, the following oxazine compounds can be mentioned.

In the formula (OX-1-2), L ³ is preferably an alkyl having 1 to 30 carbon atoms, more preferably an alkyl having 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-2) include the following oxazine compounds.

In the formula, L ³ is preferably alkyl of 1 to 30 carbon atoms, more preferably alkyl of 1 to 20 carbon atoms.

Examples of the oxazine compound represented by the formula (OX-3) include an oxazine compound represented by the following formula (OX-3-I).

Wherein L ³ and L ⁴ are each an organic group having 1 to 30 carbon atoms, L ⁵ to L ⁸ are hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, Q ¹ is a single bond, - _{CH 2 -, -C (CH 3} ) 2 -, -CO-, -O-, -SO 2 -, -C (CH 3) 2 -, or -C (CF _{3) 2} - a. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

In the formulas, L ³ and L ⁴ are preferably alkyl of 1 to 30 carbon atoms, more preferably alkyl of 1 to 20 carbon atoms.

As the oxazine compound represented by the formula (OX-4), for example, the following oxazine compounds can be mentioned.

As the oxazine compound represented by the formula (OX-5), for example, the following oxazine compounds can be mentioned.

As the oxazine photographic compound represented by the formula (OX-6), for example, the following oxazine photographic compounds may be mentioned.

Among them, more preferably, the compound represented by the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX- 3-5) (OX-5), the formula (OX-5-4), the formula (OX-3-9) (OX-6-2) to (OX-6-4).

The oxazine compound can be produced by the same method as described in International Publication Nos. 2004/009708, 11-12258 and 2004-352670.

The oxazine compound represented by the formula (OX-1) is obtained by reacting a phenol compound, a primary amine and an aldehyde (see WO 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting a primary amine with formaldehyde by a slow addition method and then adding a compound having a naphthol-based hydroxyl group to react it (see WO 2004/009708 ).

The oxazine compound represented by the formula (OX-3) is obtained by reacting 1 mole of a phenol compound, at least 2 moles of an aldehyde and 1 mole of a primary amine per one phenolic hydroxyl group in an organic solvent, In the presence of a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound (see WO 2004/009708 and JP-A 11-12258).

The oxazine compounds represented by the formulas (OX-4) to (OX-6) are obtained by reacting a plurality of benzene rings such as 4,4'-diaminodiphenylmethane and the like with an aldehyde having an organic group bonding them, And phenol are subjected to a dehydration condensation reaction in n-butyl alcohol at a temperature of 90 占 폚 or higher (see JP-A-2004-352670).

<Oxazoline compound>

The liquid crystal aligning agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electric characteristics of the liquid crystal display element in the long term. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be a single compound or two or more compounds. The content of the oxazoline compound is preferably 0.1 to 50% by weight, more preferably 1 to 40% by weight, and more preferably 1 to 20% by weight based on the polyamic acid or the derivative thereof for the above purposes. Or the content of the oxazoline compound is preferably from 0.1 to 40% by weight based on the polyamic acid or a derivative thereof when the oxazoline structure in the oxazoline compound is converted to oxazoline.

The oxazoline compound will be specifically described below.

The oxazoline compound may have one oxazoline structure or two or more oxazoline structures in one compound. The oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more oxazoline compounds. The oxazoline compound may be a polymer having an oxazoline 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 a side chain, or may be a copolymer of a monomer having an oxazoline structure in a 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 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 May be used.

The oxazoline structure is preferably a structure existing in an 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 with each other.

Examples of the oxazoline compound include 2,2'-bis (2-oxazoline), 1,2,4-tris- (2-oxazolyl-2) (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl ) Benzene, 2,2-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl Isopropylidenebis (4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis (4-phenyl- 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 Epocross (trade name, manufactured by Nippon Kogyo Co., Ltd.) are also exemplified. Among them, 1,3-bis (4,5-dihydro-2-oxazolyl) benzene is more preferable.

<Epoxy Compound>

The liquid crystal aligning agent of the present invention may further contain an epoxy compound other than the compound represented by formula (1) for the purpose of stabilizing the electric characteristics in the liquid crystal display element for a long term. The epoxy compound may be one kind of compound or two or more kinds of compounds. The content of the epoxy compound is preferably from 0.1 to 50% by weight, more preferably from 1 to 40% by weight, and still more preferably from 1 to 20% by weight, based on the polyamic acid or the derivative thereof for the above purposes.

The epoxy compounds other than the compound represented by the formula (1) will be specifically described below.

Examples of the epoxy compound include various compounds having one or more epoxy rings in the molecule. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, hexafluoropropylene oxide, cyclo (Nonafluoro-N-butyl) epoxides such as hexane oxide, 3- glycidoxypropyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, N-glycidylphthalimide, N, N-diglycidyl aniline, and 3- [2- (perfluorohexyl) ethoxy] -1, 2-ethylhexyl methacrylate, And 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, 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.

Examples of the compound having three epoxy rings in the molecule include 2- [4- (2,3-epoxypropoxy) phenyl] -2- [4- [1,1- 3-epoxypropoxy] phenyl]] ethyl] phenyl] propane (trade name: TEXMORE VG3101L, manufactured by Mitsui Chemicals).

Examples of the compound having four epoxy rings in the molecule include 1,3,5,6-tetraglycidyl-2,4-hexanediol, N, N, N ', N'-tetraglycidyl- (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl Methane, 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. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of other monomers copolymerizable with the monomer having an epoxy ring include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, butyl Butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy Ethyl (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide and N-phenylmaleimide .

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Specific examples of preferred copolymers of monomers having an epoxy ring and other monomers include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-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 styrene-glycidyl methacrylate copolymer.

Among these examples, N, N, N ', N'-tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenyl methane, trade name "Texmore VG3101L", 3,4-epoxycyclohexenylmethyl-3', 4'-epoxycyclohexene carboxylate , N-phenylmaleimide-glycidyl methacrylate copolymer, and 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are particularly preferable.

More systematically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, Epoxy compounds, and cyclic aliphatic epoxy compounds. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidyl amine, epoxy group-containing acrylic resin, glycidyl amide, glycidyl isocyanurate, chain type aliphatic epoxy compound, Type aliphatic epoxy compounds.

Examples of the glycidyl ether include bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, bisphenol type epoxy compounds, hydrogenated bisphenol-A type epoxy compounds, hydrogenated bisphenol-F type epoxy compounds, Hydrogenated bisphenol-type epoxy compound, hydrogenated bisphenol-type epoxy compound, hydrogenated bisphenol-type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolac type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy A cresol novolak type epoxy compound, a brominated cresol novolak type epoxy compound, a bisphenol A novolak type epoxy compound, a naphthalene skeleton containing epoxy compound, an aromatic polyglycidyl ether compound, a dicyclopentadiene phenol type epoxy compound, an alicyclic diglycidyl ether compound, Aliphatic polyglycidyl ether compounds, polysulfides Type diglycidyl there may be mentioned ether compound, and biphenol type epoxy compound.

Examples of glycidyl esters include diglycidyl ester compounds and glycidyl ester epoxy compounds.

Examples of glycidyl amines include polyglycidyl amine compounds and glycidyl amine type epoxy resins.

Examples of the epoxy group-containing acrylic compound include homopolymers and copolymers of monomers having oxiranyl.

As the glycidyl amide, for example, a glycidyl amide type epoxy compound can be mentioned.

Examples of the chain type aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of an alkene compound.

Examples of the cyclic aliphatic epoxy compound include compounds containing an epoxy group obtained by oxidizing a carbon-carbon double bond of a cycloalkene compound.

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007 and jER1010 (all trade names, manufactured by Mitsubishi Chemical Corporation) , DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epiclon 840, Epiclon 850, Epiclon 1050 (Trade name, manufactured by Mitsui Chemicals, Inc.) can be mentioned.

Examples of the bisphenol F type epoxy compounds include jER806, jER807, and jER4004P (all trade names, manufactured by Mitsubishi Chemical Corporation), Epitoto YDF-170, Eptoto YDF-175S and Eptoto YDF- DER-354 (trade name, manufactured by Dow Chemical Company), Epiclon 830, and Epiclon 835 (all trade names, manufactured by DIC Corporation).

Examples of the bisphenol-type epoxy compounds include epoxy compounds of 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of the hydrogenated bisphenol-A type epoxy compound include SANTOTO ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), Ricare resin HBE-100 (trade name, manufactured by Shin-Nippon Chemical Co., Ltd.) -252 (trade name, manufactured by Nagase Chemtex Co., Ltd.).

Examples of the hydrogenated bisphenol type epoxy compound include epoxides of hydrogenated 2,2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane.

Examples of the brominated bisphenol-A type epoxy compound include jER5050, jER5051 (all trade names, manufactured by Mitsubishi Chemical Corporation), Ecototo YDB-360 and Ecototo YDB-400 (all trade names, DER-530, DER-538 (all trade names, manufactured by The Dow Chemical Company), Epiclon 152, and Epiclone 153 (all trade names, manufactured by DIC Corporation).

Examples of the phenol novolak type epoxy compound include jER152, jER154 (all trade names, manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Toto Hossei Co., Ltd.), DEN431 and DEN438 Epiclon N-770 (trade name, manufactured by DIC Corporation), EPPN-201, and EPPN-202 (all trade names, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the cresol novolak epoxy compounds include epoxy resins such as jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701 and YDCN-702 EOCN-1025, and EOCN-1027 (all trade names, manufactured by Nippon Kayaku Co., Ltd.) were charged into a reactor equipped with a stirrer, .

Examples of the bisphenol A novolak epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation) and Epiclon N-880 (trade name, manufactured by DIC Corporation).

Examples of the naphthalene skeleton-containing epoxy compound include Epikron HP-4032, Epikron HP-4700, Epikron HP-4770 (all trade names, manufactured by DIC Corporation), and NC-7000 (trade name, ).

Examples of the aromatic polyglycidyl ether compounds include hydroquinone diglycidyl ether (the following formula EP-1), catechol diglycidyl ether (the following formula EP-2), resorcinol diglycidyl ether ( Bis [4 - ([2,3-epoxypropoxy] phenyl) -2- [4- [ ] Ethyl] phenyl] propane (the following formula EP-4), tris (4-glycidyloxyphenyl) methane (the following formula EP-5), jER1031S, jER1032H60 (all trade names, manufactured by Mitsubishi Chemical Corporation) DPPN-501H, DPPN-501H, and NC6000 (all trade names, manufactured by Nippon Yakitori Co., Ltd.), DPPN- , Texomor VG3101L (trade name, manufactured by Mitsui Chemicals), a compound represented by the following formula EP-6, and a compound represented by the following formula: EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include TACTIX-556 (trade name, manufactured by The Dow Chemical Company) and EPICROON HP-7200 (trade name, manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include cyclohexanedimethanol diglycidyl ether compounds and ricerazine DME-100 (trade name, manufactured by Shin-Nippon Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethylene glycol diglycidyl Ether, propylene glycol diglycidyl ether (following formula EP-10), tripropylene glycol diglycidyl ether (following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether 1,4-butanediol diglycidyl ether (following formula EP-13), 1,6-hexanediol diglycidyl ether (following formula EP-14), dibromonopentyl Denacol EX-910, Denacol EX-830, Denacol EX-911, Denacol EX-920, Denacol EX-931, (Trade name, manufactured by Nagase Chemtex Co., Ltd.), DD-503 (trade name, manufactured by ADEKA), Rica resin W-100 (trade name, , Shin Nihon Tetraglycidyl-2,4-hexanediol (the following formula: EP-16), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylol Denacol EX-311, Denacol EX-611, Denacol EX-321, and Denacol EX-411 (all trade names, available from Nagase Chemtex Co., Ltd.) ).

Examples of the polysulfide diglycidyl ether compound include FLDP-50 and FLDP-60 (both trade names, manufactured by Toray Industries, Inc.).

Examples of the biphenol type epoxy compound include YX-4000, YL-6121H (all trade names, manufactured by Mitsubishi Chemical Corporation), NC-3000P and NC-3000S (all trade names, .

Examples of the diglycidyl ester compound include diglycidyl terephthalate (the following formula EP-17), diglycidyl phthalate (the following formula EP-18), bis (2-methyloxiranylmethyl) phthalate A compound represented by the following formula: EP-21, a compound represented by the following formula: EP-22, and a compound represented by the following formula: .

Examples of the glycidyl ester epoxy compounds include jER871, jER872 (all trade names, manufactured by Mitsubishi Chemical Corporation), Epiclon 200, Epiclone 400 (all trade names, manufactured by DIC Corporation), Denacol EX-711 , And Denacol EX-721 (both trade names, manufactured by Nagase Chemtex Co., Ltd.).

Examples of the polyglycidylamine compounds include N, N-diglycidyl aniline (formula EP-24), N, N-diglycidyl-o-toluidine (formula EP- , N-diglycidyl-m-toluidine (following formula EP-26), N, N-diglycidyl-2,4,6-tribromoaniline , N, N, O-triglycidyl-p-aminophenol (formula EP-29), aminopropyltrimethoxysilane (formula EP- N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane (the following formula EP-31), N , N, N ', N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (trade name, manufactured by Mitsubishi Gas Chemical Co., N-diglycidylaminomethyl) cyclohexane (TETRAD-C (trade name, manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33) ) Cyclohexane (the following formula EP-34), 1,3-bis (N, N-diglycidylamino) cyclohex (N, N-diglycidylamino) cyclohexane (the following formula EP-36), 1,3-bis (N, N-diglycidylamino) Benzene (the following formula EP-37), 1,4-bis (N, N-diglycidylamino) benzene (the following formula EP-38), 2,6- ) N, N, N ', N'-tetraglycidyl-4,4'-diaminodicyclohexyl methane (formula EP-40) N, N ', N', N'-tetramethylbiphenyl (formula EP-41), 2,2'-dimethyl- -Tetraglycidyl-4,4'-diaminodiphenyl ether (EP-42), 1,3,5-tris (4- (N, N-diglycidyl) aminophenoxy) benzene (Represented by the following formula EP-43), 2,4,4'-tris (N, N-diglycidylamino) diphenyl ether (N, N-diglycidylamino) biphenyl (formula EP-46), 3,4, 4,3'4'-tetrakis , 3 ', 4'-tetrakis (N, N-diglycidylamino) diphenyl Terminus (the following formula EP-47), the following formula to the compound and represented by the EP-48 and compounds represented by the formula EP-49.

The homopolymer of the oxiranyl-containing monomer includes, for example, polyglycidyl methacrylate. Examples of the copolymer of the monomer having oxiranyl include N-phenylmaleimide-glycidyl methacrylate copolymer, N-cyclohexylmaleimide-glycidyl methacrylate copolymer, benzyl methacrylate-gly Methyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl ) Methyl methacrylate-glycidyl methacrylate copolymer, and styrene-glycidyl methacrylate copolymer.

Examples of the monomer having oxiranyl include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

Examples of the monomer other than the oxiranyl-containing monomer in the copolymer of the oxiranyl-containing monomer include (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (Meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, cyclohexyl Acrylate, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl) methyl (meth) acrylate, N-cyclohexylmaleimide, and N-phenylmaleimide.

Examples of the glycidyl isocyanurate include 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) 5-allyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H) -thione (EP- ), And glycidyl isocyanurate type epoxy resin.

Examples of the chain type aliphatic epoxy compound include epoxidized polybutadiene and Epolide PB3600 (trade name, manufactured by Daicel Co., Ltd.).

Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celloxide 2021 (manufactured by Daicel), EP -52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3 ', 4'-epoxycyclohexylcarboxylate (the following formula EP- Epoxycyclohexylmethyl-3 ', 4'-epoxycyclohexanecarboxylate, 1,2: 8', 3'-epoxycyclopentane ether (following formula EP-54), epsilon -caprolactone- , 9-diepoxy limonene (Celloxide 3000 (trade name, manufactured by Daicel), the following formula EP-55), a compound represented by the following formula EP-56, CY-175, CY-177 and CY- (Trade name, available from The Ciba-Geigy Chemical Corp. (available from Huntsman Japan)), EHPD-3150 (trade name, manufactured by Daicel Co.), and cyclic aliphatic epoxy resins have.

The epoxy compound is preferably at least one of a polyglycidylamine compound, a bisphenol A novolak type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic epoxy compound. N, N, N ' Tetraglycidyl-m-xylene diamine, 1,3-bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ' - diaminodiphenylmethane, trade name "Texmore VG3101L", 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate, N-phenylmaleimide-glycidyl methacrylate copolymer And at least one of N, N, O-triglycidyl-p-aminophenol, bisphenol A novolak type epoxy compound, and cresol novolak type epoxy compound.

For example, the liquid crystal aligning agent of the present invention may further contain various additives. Examples of various additives include polymer compounds other than polyamic acid and derivatives thereof, and low molecular weight compounds, and they can be selected depending on the purpose.

Examples of the polymer compound include a polymer compound soluble in an organic solvent. The addition of such a polymer compound to the liquid crystal aligning agent of the present invention is preferable from the viewpoint of controlling the electric characteristics and orientation of the liquid crystal alignment film to be formed. Examples of the polymer compound include polyamides, polyurethanes, polyureas, polyesters, polyepoxides, polyester polyols, silicone modified polyurethanes, and silicone modified polyesters.

Examples of the above-mentioned low-molecular compounds include: 1) a surfactant for this purpose when it is desired to improve the coating property; 2) an antistatic agent when it is necessary to improve the antistatic property; and 3) A silane coupling agent or a titanium-based coupling agent; and 4) an imidization catalyst when imidization proceeds at a low temperature.

Examples of the silane coupling agent include vinyltrimethoxysilane, vinyltriethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, N- (2-aminoethyl) -3- Aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, p-aminophenyltrimethoxysilane, p-aminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metamaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3 -Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-propylamine, N'-bis [3- (trimethoxysilyl) propyl] ethylenediamine. A preferred silane coupling agent is 3-aminopropyltriethoxysilane.

Examples of imidization catalysts include aliphatic amines such as trimethylamine, triethylamine, tripropylamine and tributylamine; Aromatic amines such as N, N-dimethylaniline, N, N-diethylaniline, methyl substituted aniline, and hydroxy substituted aniline; Substituted substituted isoquinoline, substituted isoquinoline, substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, and the like can be used. Examples of the substituted pyrrolidine derivative include pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, Of cyclic amines. The imidation catalyst may be one or more selected from N, N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline desirable.

The addition amount of the silane coupling agent is usually 0 to 20% by weight, preferably 0.1 to 10% by weight, based on the total weight of the polyamic acid or the derivative thereof.

The addition amount of the imidation catalyst is usually 0.01 to 5 equivalents, preferably 0.05 to 3 equivalents, relative to the carbonyl group of the polyamic acid or its derivative.

The amount of other additives to be added varies depending on the use, but is usually 0 to 100% by weight and preferably 0.1 to 50% by weight based on the total weight of the polyamic acid or its derivative.

The polyamic acid or a derivative thereof of the present invention can be produced in the same manner as the known polyamic acid or derivative thereof used for forming a film of polyimide. The total amount of the tetracarboxylic acid dianhydride to be injected is preferably approximately equal to the total number of moles of diamine (molar ratio of about 0.9 to 1.1).

The molecular weight of the polyamic acid or its derivative of the present invention is preferably 7,000 to 500,000, more preferably 10,000 to 200,000, in terms of weight average molecular weight (Mw) in terms of polystyrene. The molecular weight of the polyamic acid or its derivative can be determined by measurement by gel permeation chromatography (GPC).

The polyamic acid or its derivative of the present invention can be confirmed by analyzing a solid component obtained by precipitation with a large amount of a poor solvent by IR or NMR. Also, the monomer used can be identified by analyzing an extract of the decomposition product of the polyamic acid or its derivative by an aqueous solution of a strong alkali such as KOH or NaOH with an organic solvent by GC, HPLC or GC-MS.

In addition, for example, the liquid crystal aligning agent of the present invention may further contain a solvent in view of the coating property of the liquid crystal aligning agent and the adjustment of the concentration of the polyamic acid or its derivative. The solvent is not particularly limited as long as it is a solvent capable of dissolving a polymer component. The solvent widely includes a solvent commonly used in the production process or application of a polymer component such as polyamic acid and soluble polyimide, and may be appropriately selected depending on the purpose of use. The solvent may be one kind or two or more kinds of mixed solvents.

Examples of the solvent include a hydrophilic solvent for the polyamic acid or a derivative thereof, and other solvents for improving the applicability.

Examples of the aprotic polar organic solvent which is a hydrophilic solvent for the polyamic acid or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, N-methylcaprolactam, N-methylpropionamide, N, N And lactones such as dimethylacetamide, dimethylsulfoxide, N, N-dimethylformamide, N, N-diethylformamide, diethylacetamide and? -Butyrolactone.

It is preferable to use at least one solvent selected from the group consisting of other solvents, especially alcohols, ethers and ketones, for the purpose of improving the coating properties.

Examples of the alcohol include butyl cellosolve (ethylene glycol monobutyl ether), ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether Ether, 1-butoxy-2-propanol, 2- (2-methoxypropoxy) propanol, ethyl lactate, methyl lactate, propyl lactate and butyl lactate.

Examples of the ether include alkylene glycol dialkyl ethers such as ethylene glycol dimethyl ether and ethylene glycol diethyl ether; diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol butyl methyl ether Dialkylene glycol monoalkyl ethers such as diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, dipropylene glycol monomethyl ether and dipropylene glycol monoethyl ether; ethylene glycol monoalkyl ethers such as ethylene glycol monoalkyl ether propylene glycol monoethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, diethylene glycol monobutyl ether Acetai , Alkylene glycol alkyl ether acetates such as propylene glycol monomethyl ether acetate, propylene glycol monopropyl ether acetate and propylene glycol monobutyl ether acetate: propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, propylene glycol Propylene glycol monoalkyl ether propionate such as monopropyl ether ether propionate and propylene glycol monobutyl ether propionate; and cyclic ether such as tetrahydrofuran.

Examples of the ketone include methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, 4-hydroxy-4-methyl-2-pentanone, methyl isoamyl ketone, diisobutyl ketone, methyl- Phonate, and the like.

Among them, the solvent is preferably selected from the group consisting of N-methyl-2-pyrrolidone, dimethylimidazolidinone,? -Butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, Particularly preferred are monomethyl ether, dipropylene glycol monomethyl ether, diethylene glycol diethyl ether and 1-butoxy-2-propanol.

The concentration of the polyamic acid or its derivative in the alignment agent of the present invention is preferably 0.1 to 40% by weight. When this alignment agent is applied to the substrate, it may be necessary to dilute the polyamic acid contained in advance with a solvent in order to adjust the film thickness.

The solid content concentration in the alignment agent of the present invention is not particularly limited, and the optimum value may be selected in accordance with the following various application methods. The amount is preferably 0.1 to 30% by weight, more preferably 1 to 10% by weight based on the weight of the varnish in order to suppress unevenness and pinholes at the time of coating.

The viscosity of the liquid crystal aligning agent of the present invention differs depending on the method of application, the concentration of the polyamic acid or its derivative, the type of the polyamic acid or derivative thereof to be used, and the type and ratio of the solvent. For example, it is 5 to 100 mPa · s (more preferably 10 to 80 mPa · s) in the case of application by a printing machine. If it is smaller than 5 mPa · s, it is difficult to obtain a sufficient film thickness. If it exceeds 100 mPa · s, printing unevenness may become large. In the case of coating by spin coating, 5 to 200 mPa · s (more preferably 10 to 100 mPa · s) is suitable. In the case of coating using an inkjet coating apparatus, 5 to 50 mPa · s (more preferably 5 to 20 mPa · s) is suitable. The viscosity of the liquid crystal aligning agent is measured by a rotational viscosity measurement method and measured (measured temperature: 25 ° C) using, for example, a rotational viscometer (TVE-20L type manufactured by Toray Industries).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the above-mentioned liquid crystal aligning agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a conventional method for producing a liquid crystal alignment film with a liquid crystal aligning agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal aligning agent of the present invention, a step of heating and drying, and a step of heating and firing. In the liquid crystal alignment film of the present invention, anisotropy may be imparted to the liquid crystal alignment film by rubbing the film obtained through the heating and drying process and the heating and firing process as described later, if necessary. Alternatively, if necessary, anisotropy may be imparted by irradiating light after the coating film process, the heating and drying process, or after the heating and baking process. It may also be used as a VA liquid crystal alignment film without rubbing treatment.

The coating film can be formed by applying the liquid crystal aligning agent of the present invention to a substrate in a liquid crystal display element in the same manner as in the production of a conventional liquid crystal alignment film. Examples of the substrate include glass substrates on which electrodes such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ -ZnO), IGZO (In-Ga-ZnO ₄ ) electrodes and color filters may be formed.

As a method of applying a liquid crystal aligning agent to a substrate, a spinner method, a printing method, a dipping method, a dropping method, an ink jet method, and the like are generally known. These methods are equally applicable to the present invention.

The heating and drying process is generally known as a heating process in an oven or an infrared room, a heating process on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within a range in which evaporation of the solvent is possible, and more preferably at a relatively low temperature relative to the temperature in the heat-firing step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C.

The heating and firing step may be carried out under the conditions necessary for the polyamic acid or its derivative to exhibit a dehydration / ring-closing reaction. The firing of the coating film is generally known as a method of performing a heat treatment in an oven or an infrared ray, a method of performing heat treatment on a hot plate, and the like. These methods are equally applicable to the present invention. It is generally preferably carried out at a temperature of about 100 to 300 ° C for 1 minute to 3 hours, more preferably 120 to 280 ° C, even more preferably 150 to 250 ° C.

In the method of forming a liquid crystal alignment film of the present invention, a well-known forming method such as a rubbing method or a photo alignment method is preferably used as means for imparting anisotropy to the alignment film in order to orient the liquid crystal in one direction with respect to the horizontal and / Can be used.

The liquid crystal alignment film of the present invention using the rubbing method can be produced by a process comprising the steps of applying the liquid crystal aligning agent of the present invention to a substrate, heating and drying the substrate coated with the aligning agent, heating and firing the film, And can be formed through a process.

The rubbing treatment can be carried out in the same manner as the rubbing treatment for the ordinary alignment treatment of the liquid crystal alignment film, and only in the condition that satisfactory retardation can be obtained in the liquid crystal alignment film of the present invention. The preferable conditions are the indentation amount of the hair (foot) 0.2 to 0.8 mm, the stage moving speed 5 to 250 mm / sec, and the roller rotation speed 500 to 2,000 rpm.

A method of forming a liquid crystal alignment film of the present invention by a photo alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo alignment method can be formed by applying anisotropy to a coating film by irradiating linearly polarized light or unpolarized light of radiation after heating and drying the coating film and heating and firing the film. Or by heating and drying the coating film, heating and baking, and then irradiating linearly polarized light or unpolarized light of radiation. From the viewpoint of the orientation property, it is preferable that the step of irradiating the radiation is carried out before the heating and firing step.

Further, in order to enhance the liquid crystal aligning ability of the liquid crystal alignment film, it is also possible to irradiate linearly polarized light or unpolarized light of radiation while heating the coating film. The irradiation of the radiation may be performed by a step of heating and drying the coating film or a step of heating and firing, or between the heating and drying step and the heating and firing step. The heating and drying temperature in the process is preferably in the range of 30 ° C to 150 ° C, more preferably in the range of 50 ° C to 120 ° C. The heating and firing temperature in the process is preferably in the range of 30 ° C to 300 ° C, more preferably in the range of 50 ° C to 250 ° C.

As the radiation, ultraviolet rays or visible rays including light having a wavelength of, for example, 150 to 800 nm can be used, but ultraviolet rays containing light of 300 to 400 nm are preferable. In addition, linearly polarized light or unpolarized light can be used. The light is not particularly limited as long as it is a light capable of imparting liquid crystal aligning ability to the above coating film, but when it is intended to exhibit a strong alignment restricting force for liquid crystal, linearly polarized light is preferable.

The liquid crystal alignment film of the present invention can exhibit a high liquid crystal aligning ability even with light irradiation with low energy. The irradiation amount of linearly polarized light in the above-mentioned irradiation step is preferably 0.05 to 20 J / cm 2, more preferably 0.5 to 10 J / cm 2. The wavelength of the linearly polarized light is preferably 200 to 400 nm, more preferably 300 to 400 nm. The irradiation angle with respect to the film surface of the linearly polarized light is not particularly limited, but when it is intended to exhibit a strong alignment regulating force with respect to the liquid crystal, it is preferable from the viewpoint of shortening the orientation treatment time to be as perpendicular as possible to the film surface. The liquid crystal alignment film of the present invention can orient the liquid crystal in a direction perpendicular to the polarization direction of linearly polarized light by irradiating linearly polarized light.

In the case where a pretilt angle is intended to be expressed, light to be irradiated to the film may be linearly polarized light or unpolarized light as described above. The irradiation amount of the light irradiated to the film is preferably 0.05 to 20 J / cm 2, more preferably 0.5 to 10 J / cm 2, and the wavelength is preferably 250 to 400 nm , And particularly preferably from 300 to 380 nm. The angle of irradiation with respect to the film surface of the light irradiated to the film when the pretilt angle is intended to be developed is not particularly limited, but is preferably 30 to 60 degrees from the viewpoint of shortening the orientation treatment time.

Examples of the light source used in the step of irradiating linearly polarized light or unpolarized light of radiation include an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a Deep UV lamp, a halogen lamp, a metal halide lamp, a high power metal halide lamp, A xenon lamp, an excimer lamp, a KrF excimer laser, a fluorescent lamp, an LED lamp, a sodium lamp, and a microwave excitation non-electrode lamp.

The liquid crystal alignment film of the present invention is preferably obtained by a method further including a step other than the above-mentioned step. For example, the liquid crystal alignment film of the present invention does not require a step of cleaning the film after baking or irradiation with a cleaning liquid, but it is possible to form a cleaning step for other reasons.

Examples of the cleaning method using a cleaning liquid include brushing, jet spraying, steam cleaning, ultrasonic cleaning, and the like. These methods may be carried out alone or in combination. Examples of the cleaning liquid include pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone But are not limited to these. Needless to say, these cleaning liquids are used with a sufficiently small amount of purified impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

In order to enhance the liquid crystal alignment performance of the liquid crystal alignment film of the present invention, annealing treatment by heat or light can be used before, after, and after the heat firing step, before or after the rubbing step, or before or after irradiation with polarized or unpolarized light. In the annealing treatment, the annealing temperature is 30 to 180 占 폚, preferably 50 to 150 占 폚, and the time is preferably 1 minute to 2 hours. Examples of the annealing light used in the annealing process include a UV lamp, a fluorescent lamp, and an LED lamp. The irradiation amount of light is preferably 0.3 to 10 J / cm 2.

The thickness of the liquid crystal alignment film of the present invention is not particularly limited, but is preferably 10 to 300 nm, more preferably 30 to 150 nm. The film thickness of the liquid crystal alignment film of the present invention can be measured by a known film thickness measuring apparatus such as a stepped system or an ellipsometer.

The liquid crystal alignment film of the present invention is characterized by having anisotropy particularly in a large orientation. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in JP-A-2005-275364 or the like. It is also possible to evaluate by the method using ellipsometry as shown in the following examples. In detail, the retardation value of the liquid crystal alignment film can be measured by the spectroscopic ellipsometer. The retardation value of the film becomes larger in proportion to the degree of orientation of the polymer main chain. That is, having a large retardation value has a large degree of orientation, and when used as a liquid crystal alignment film, it is considered that an alignment film having a larger anisotropy has a large alignment restraining force for the liquid crystal composition.

The liquid crystal alignment film of the present invention can be preferably used for a liquid crystal display device of a transverse electric field system. When used in a liquid crystal display element of a transverse electric field system, the lower the Pt angle and the higher the liquid crystal aligning ability, the higher the black display level in the dark state, and the contrast is improved. The Pt angle is preferably 0.1 DEG or less.

The liquid crystal alignment film of the present invention can be used for alignment control of optical compensators and other liquid crystal materials in addition to the alignment of liquid crystal compositions for liquid crystal displays. Further, since the alignment film of the present invention has large anisotropy, it can be used solely for optical compensation material applications.

The liquid crystal display element of the present invention will be described in detail.

The present invention is a liquid crystal display device comprising: a pair of substrates disposed opposite to each other; an electrode formed on one or both sides of the opposing surfaces of the pair of substrates; And a liquid crystal layer formed between the pair of substrates, wherein the liquid crystal alignment film is an alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include a vapor-deposited film of ITO or a metal. The electrode may be formed on the entire surface of one surface of the substrate, or may be formed into a desired shape that is patterned, for example. The desired shape of the electrode is, for example, a comb-like or zigzag structure. The electrode may be formed on one of the pair of substrates, or may be formed on both of the substrates. For example, in the case of an IPS type liquid crystal display element, electrodes are disposed on one side of the pair of substrates, and in the case of other liquid crystal display elements, the pair of electrodes The electrodes are disposed on both sides of the substrate. And the liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in such a form that the liquid crystal composition is sandwiched by the pair of substrates on which the liquid crystal alignment film-formed side faces. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, which forms an appropriate gap between the pair of substrates can be used as needed.

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

There is no problem that one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy.

The liquid crystal composition having negative dielectric anisotropy will now be described. As the liquid crystal composition having a negative dielectric constant anisotropy, for example, a composition containing at least one liquid crystal compound selected from the group of liquid crystal compounds represented by the following formula (NL-1) as the first component may be mentioned.

Wherein R ^1a and R ^2a are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine , Ring A ² and ring B ² are independently selected from the group consisting of 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4- Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl or 7,8-difluorochroman- , Wherein at least one of ring A ² and ring B ² is 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro-1,4- Di-fluoro-chromene-2,6-diyl, and Z ¹ is independently a single bond, - (CH ₂ ) ₂ -, - CH ₂ O-, -COO-, or -CF ₂ O-, and j is 1, 2 or 3 And when j is 2 or 3, any two rings A ² may be the same or different and any two Z ^{1 s} may be the same or different.

Preferred ring A ² and ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl in order to increase the dielectric anisotropy, respectively, and 1,4- Cyclohexylene.

Preferred Z ¹ is -CH ₂ O- in order to increase the dielectric anisotropy and is a single bond to lower the viscosity.

The preferred j is 1 to lower the lower limit temperature and 2 to increase the upper limit temperature.

Specific examples of the liquid crystal compound of the formula (NL-1) include the compounds represented by the following formulas (NL-1-1) to (NL-1-32).

Wherein R ^1a and R ^2a are independently alkyl having 1 to 12 carbon atoms, alkoxy having 1 to 12 carbon atoms, alkenyl having 2 to 12 carbon atoms, or alkenyl having 2 to 12 carbon atoms in which at least one hydrogen is substituted with fluorine , Ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are independently 1,4-cyclohexylene or 1,4-phenylene, and Z ¹¹ and Z ¹² are independently a single bond , - (CH ₂ ) ₂ -, -CH ₂ O-, or -COO-.

Preferable R ^1a and R ^2a are alkyl having 1 to 12 carbon atoms in order to improve stability against ultraviolet rays or heat or alkoxy having 1 to 12 carbon atoms in order to increase absolute value of dielectric anisotropy.

Preferred alkyl is methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, or octyl. More preferred alkyl is ethyl, propyl, butyl, pentyl, or heptyl to lower the viscosity.

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. To lower the viscosity, the more preferred alkoxy is methoxy or ethoxy.

Preferred alkenyl are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, Decenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyls are vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl for lowering the viscosity. The preferred steric configuration of -CH = CH- in these alkenyls depends on the position of the double bond. In order to lower the viscosity, a trans is preferred for alkenyl such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl. In the case of alkenyl such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferable. In these alkenyl groups, straight-chain alkenyl groups are preferred over branches.

Preferred examples of the alkenyl in which at least one hydrogen is substituted with fluorine are 2,2-difluorovinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro- , 5,5-difluoro-4-pentenyl, and 6,6-difluoro-5-hexenyl. More preferred examples are 2,2-difluorovinyl, and 4,4-difluoro-3-butenyl for lowering the viscosity.

Preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene for lowering the viscosity.

Preferred Z ¹¹ and Z ¹² are -CH ₂ O- in order to increase the dielectric anisotropy and are single bonds in order to lower the viscosity.

The compound (NL-1-1), (NL-1-4), (NL-1-7), or (NL-1-7) is preferably used as the first component in the liquid crystal composition having negative dielectric anisotropy. -1-32).

As preferred examples of the liquid crystal composition having negative dielectric anisotropy, JP-A-57-114532, JP-A-2-4725, JP-A-4-224885, JP-A-8-40953, Japanese Patent Application Laid-Open Nos. 8-104869, 10-168076, 10-168453, 10-236989, 10-236990, 10 -236992, JP-A-10-236993, JP-A-10-236994, JP-A-10-237000, JP-A-10-237004, JP-A-10-237024, Japanese Patent Application Laid-Open Nos. 10-237035, 10-237075, 10-237076, 10-237448 (EP967261A1), 10-287874, 10-287874 10-287875, JP-A-10-291945, JP-A- Japanese Unexamined Patent Publication No. 11-029581, Japanese Unexamined Patent Application Publication No. 11-080049, Japanese Unexamined Patent Publication No. 2000-256307, Japanese Unexamined Patent Application Publication No. 2001-019965, Japanese Unexamined Patent Application Publication No. 2001-072626, Japanese Unexamined Patent Application Publication No. 2001-192657, 2010-037428, International Publication No. 2011/024666, International Publication No. 2010/072370, Japanese Laid-Open Patent Publication No. 2010-537010, Japanese Laid-Open Patent Publication No. 2012-077201, Japanese Laid-Open Patent Publication No. 2009-084362 and the like.

For example, the liquid crystal composition used in the device of the present invention may further contain an additive, for example, from the viewpoint of improving the orientation. Such additives include photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, colorants, antifoaming agents, polymerization initiators, polymerization inhibitors and the like.

The most preferable structure of the photopolymerizable monomer or oligomer for the purpose of improving the alignment property of the liquid crystal includes the structures of (PM-1-1) to (PM-1-6).

The photopolymerizable monomer or oligomer is preferably 0.01% by weight or more in order to exhibit the effect of determining the direction of the liquid crystal after polymerization. In order to make the orientation effect of the polymer after the polymerization proper, or to avoid elution of unreacted monomer or oligomer into the liquid crystal after ultraviolet irradiation, it is preferably 30% by weight or less.

An optically active compound is mixed into the composition for the purpose of imparting a helical structure of the liquid crystal and giving a twist angle. Examples of such compounds are compounds (PAC-1-1) to (PAC-1-4).

The preferred ratio of the optically active phosphorus compound is 5% by weight or less. A more preferable range is from 0.01 wt% to 2 wt%.

An antioxidant is mixed with the liquid crystal composition in order to prevent a decrease in resistivity due to heating in the air or to maintain a large voltage holding ratio at room temperature as well as at a high temperature after the device is used for a long time.

Preferable examples of the antioxidant include a compound (AO-1) wherein w is an integer of 1 to 10, and the like. In the compound (AO-1), a preferable w is 1, 3, 5, 7 or 9. More preferred w is 1 or 7. The compound (AO-1) wherein w is 1 is effective in preventing a decrease in resistivity due to heating in the atmosphere because of its high volatility. The compound (AO-1) with w = 7 is effective for maintaining a large voltage holding ratio at room temperature as well as at a high temperature after long use of the device because of low volatility. A preferable proportion of the antioxidant is not less than 50 ppm in order to obtain the effect and not more than 600 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferable range is from 100 ppm to 300 ppm.

Preferable examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, triazole derivatives and the like. Light stabilizers such as amines with steric hindrance are also preferred. A preferable ratio in these absorbents and stabilizers is not less than 50 ppm to obtain the effect, and not more than 10000 ppm so as not to lower the upper limit temperature or increase the lower limit temperature. A more preferable range is from 100 ppm to 10000 ppm.

Dichroic dyes such as azo dyes, anthraquinone dyes, and the like are mixed into the composition to suit the devices of the GH (Guest host) mode. A preferable proportion of the pigment is in the range of 0.01 wt% to 10 wt%.

In order to prevent foaming, antifoaming agents such as dimethyl silicone oil and methylphenyl silicone oil are mixed into the composition. A preferable proportion of the antifoaming agent is 1 ppm or more in order to obtain the effect and 1000 ppm or less in order to prevent defective display. A more preferable range is from 1 ppm to 500 ppm.

Polymerizable compounds can be incorporated into the compositions to suit the devices in the PSA (polymer sustained alignment) mode. Preferable examples of the polymerizable compound are compounds having a polymerizable group such as acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone and the like. A particularly preferred example is a derivative of acrylate or methacrylate. Examples of such compounds are compounds (PM-2-1) to (PM-2-9). A preferable proportion of the polymerizable compound is about 0.05% by weight or more for obtaining the effect and about 10% by weight or less for preventing defective display. A more preferred ratio is in the range of about 0.1 wt% to about 2 wt%.

Wherein R ^3a , R ^4a , R ^5a and R ^6a are independently acryloyl or methacryloyl, R ^7a and R ^8a are independently hydrogen, halogen, or alkyl of 1 to 10 carbon atoms, and Z ¹³ , Z ¹⁴ , Z ¹⁵ and Z ¹⁶ are independently a single bond or alkylene having 1 to 12 carbon atoms, and at least one -CH ₂ - may be substituted by -O- or -CH═CH-, and s, t And u are each independently 0, 1 or 2.

A polymerization initiator can be mixed as a substance necessary for easily generating a radical or an ion and initiating a chain polymerization reaction. Irgacure 651 (registered trademark), Irgacure 184 (registered trademark), or Darocure 1173 (registered trademark) (Ciba Japan K. K.), which are photo polymerization initiators, are suitable for radical polymerization. The polymerizable compound preferably contains the photopolymerization initiator in the range of 0.1 wt% to 5 wt%. Particularly preferably, the photopolymerization initiator is contained in the range of 1 wt% to 3 wt%.

In the radical polymerization system, the polymerization inhibitor can be mixed for the purpose of rapidly reacting with radicals generated from the polymerization initiator or the monomer and changing into a stable radical or a neutral compound, thereby stopping the polymerization reaction. Polymerization inhibitors are classified into several groups. One of them is a stable radical of itself such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine and the like, and the other one readily reacts with radicals present in the polymerization system to be converted into stable radicals, Nitro, nitrite, amino, and polyhydroxy compounds. Representative examples of the latter include hydroquinone, dimethoxybenzene and the like. A preferable proportion of the polymerization inhibitor is 5 ppm or more in order to obtain the effect and 1000 ppm or less in order to prevent defective display. A more preferable ratio is in the range of 5 ppm to 500 ppm.

By using a liquid crystal composition having negative dielectric anisotropy in the liquid crystal display element of the present invention, it is possible to provide a liquid crystal display element having excellent afterimage characteristics and good alignment stability.

Example

Hereinafter, the present invention will be described by way of examples. The evaluation methods and compounds used in the examples are as follows.

<Evaluation method>

1. Weight average molecular weight (Mw)

The weight average molecular weight of the polyamic acid was determined by the GPC method using a 2695 separation module 2414 differential refractometer (manufactured by Waters) and calculating the polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid / DMF = 0.6 / 100: weight ratio) such that the polyamic acid concentration was about 2% by weight. The column was subjected to measurement under the conditions of a column temperature of 50 캜 and a flow rate of 0.40 ml / min using HSPgel RT MB-M (manufactured by Waters) as the developing solution. Standard polystyrene was TSK standard polystyrene manufactured by Tosoh Corporation.

2. Pencil Hardness

Followed by JIS standard "JIS-K-5400, 8.4, pencil scratch test" method. The results were expressed as the hardness of the pencil core. If the pencil hardness is low, peeling or scraping easily occurs. If this value is larger than 2H, an alignment film which does not easily scrape off is obtained.

3. Rubbing resistance test

The rubbing resistance test was conducted using a rubbing treatment apparatus (manufactured by Iinuma Kogyo Co., Ltd.). The polyimide film applied to the glass substrate was subjected to rubbing treatment under the conditions of a fingertip penetration amount of the rubbing cloth (length of the fingernum of 1.9 mm: rayon) of 0.40 mm, a stage moving speed of 60 mm / sec and a roller rotation speed of 1000 rpm, Observation was carried out to confirm whether or not the polyimide film was cut. When the film was not cut, it was rated &amp; cir &amp;

4. Foreign matter test

The foreign substance test of the liquid crystal display element described later was carried out using FORCE MEASUREMENT, DS2-50N (manufactured by Imada Co., Ltd.). A force of 9.8 N was applied to the manufactured liquid crystal display element at 60 times / minute for 1 minute. The liquid crystal display element was observed with a microscope, and the presence or absence of a foreign substance was confirmed after pressing.

5. Contrast

The contrast of a liquid crystal device to be described later was evaluated using a luminance meter (YOKOGAWA 3298F). A liquid crystal display element was placed under a polarization microscope under a crossed Nicol state, and the minimum luminance was measured as black luminance. Next, an arbitrary square wave voltage was applied to the device, and the maximum luminance was measured as white luminance. The value of the white luminance / black luminance was taken as a contrast. The contrast is judged to be poor in less than 2500, good in 2500 or more, and best in 3000 or more.

6. AC afterimage measurement

The luminance-voltage characteristic (B-V characteristic) of the liquid crystal display element described later was measured. This is regarded as a luminance-voltage characteristic before the stress application: B (before). Next, an alternating current of 4.5 V and 60 Hz was applied to the device for 20 minutes, followed by a short circuit for 1 second, and the luminance-voltage characteristic (B-V characteristic) was measured again. This is regarded as a luminance-voltage characteristic after the application of the stress: B (after). Based on these values, the luminance change rate? B (%

B (%) = [B (after) - B (before)] / B (before) (Formula AC1)

Of the total population. These measurements were carried out with reference to International Publication No. 2000/43833. It can be said that the smaller the value of? B (%) at the voltage of 0.75 V, the more suppressed the occurrence of the AC afterimage, and preferably 3.0% or less.

&Lt; Tetracarboxylic acid dianhydride >

<Diamine>

<Solvent>

NMP: N-methyl-2-pyrrolidone

BC: butyl cellosolve (ethylene glycol monobutyl ether)

GBL:? -Butyrolactone

BP: 1-butoxy-2-propanol

EDM: diethylene glycol ethyl methyl ether

BDM: diethylene glycol butyl methyl ether

EDE: diethylene glycol diethyl ether

DIBK: Diisobutyl ketone

<Additives>

Ad1: N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Ad2: 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexene carboxylate (Celloxide 2021, manufactured by Daicel Co.)

Ad3: 1,4-butanediol diglycidyl ether

Ad4: 1,3,5-triglycidyl-1,3,5-triazine-2,4,6- (1H, 3H, 5H)

Ad5: 1,3-bis (4,5-dihydro-2-oxazolyl) benzene

A commercially available product (trade name: DA-MGIC; manufactured by Shikoku Chemical Industry Co., Ltd.) was directly used as the compound of the above formula (1-1). The compound of the formula (1-3) was synthesized in accordance with the method described in JP-A-2013-163654. The compound of the formula (1-4) was synthesized in accordance with the method described in JP-A-2013-151443.

[Synthesis Example] Synthesis of Compound of Formula (1-2)

12.8 g (49.7 mmol) of 1-allyl-3,5- (2-hydroxyethyl) isocyanurate, 20.0 g of toluene, and 20.0 g of para-toluenesulfonic acid were added to a 100 ml flask equipped with a thermometer and a condenser equipped with a water separator 0.2 g (1.0 mmol) of methoxyhydroquinone, 0.01 g (0.1 mmol) of methoxyhydroquinone and 7.8 g (109.4 mmol) of acrylic acid. The flask was immersed in an oil bath set at 110 DEG C, the reaction solution was heated and stirred, and the resulting water was reacted for 12 hours while removing moisture from the reaction system. The reaction solution was cooled to room temperature, and insolubles in the reaction solution were removed by filtration. The filtrate was washed twice with 20 g of a 10% aqueous solution of sodium hydrogencarbonate and then once with 20 g of water, and the solvent of the separated organic layer was distilled off under reduced pressure to obtain a solid. The obtained solid was purified by silica gel chromatography (ethyl acetate / hexane = 5/1, v / v) to obtain 9.4 g (yield: 1-allyl-3-5- (2- vinylcarbonyloxyethyl) isocyanurate Yield: 52%, purity: 97%).

365 mg (1.0 mmol) of 1-allyl-3,5- (2-vinylcarbonyloxyethyl) isocyanurate and 5.0 ml of dichloromethane were placed in a 50 ml flask equipped with a thermometer. 0.8 g (3.0 mmol) of 65% methachloro-benzoic acid was added under ice-cooling, and the mixture was stirred for 1 hour and then at room temperature for 9 hours. 10 ml of chloroform and 30 ml of a 10% sodium sulfite aqueous solution were added to the reaction solution and stirred, and the solvent of the separated organic layer was distilled off under reduced pressure. The resulting concentrate was purified by silica gel chromatography (ethyl acetate / hexane = 1/3, v / v) to obtain N, N'-bis (acrylate ethyl) -N "-glycidylisocyanuric acid 1-2) 301.3 mg (yield: 79%, purity: 99%).

[Example 1] Synthesis of varnish

0.9004 g of the compound represented by the formula (DI-4-1) and 1.6507 g of the compound represented by the formula (DI-5-1) (m = 1) were placed in a 100 ml three-necked flask equipped with a stirrer and a nitrogen- And 34.0 g of N-methyl-2-pyrrolidone (NMP) were added. The solution was ice-cooled to bring the liquid temperature to 5 占 폚 and then 1.6328 g of the compound represented by the formula (PA-1) and 1.8161 g of the compound represented by the formula (AN-3-2) were added and stirred at room temperature for 12 hours. 40.0 g of NMP and 20.0 g of butyl cellosolve (BC) were added thereto, and the solution was heated and stirred at 60 占 폚 until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, Varnish 1 having a molecular weight of approximately 63,000 and a resin content concentration of 6% by weight was obtained.

[Examples 2 to 31]

Varnish 2 to varnish 31 having a polymer solid content concentration of 6% by weight were prepared in accordance with Example 1, except that tetracarboxylic acid dianhydride and diamine were changed. The weight average molecular weights of the tetracarboxylic acid dianhydrides and diamines used and the polymer obtained are shown in Tables 1-1 to 1-3. Example 1 is also reproduced in Table 1-1.

[Table 1-1]

[Table 1-2]

[Table 1-3]

[Example 32]

&Lt; Preparation of liquid crystal aligning agent, rubbing resistance test >

10 g of varnish 1 was weighed and placed in a 50 ml eggplant type flask. To the 100 parts by weight of the polymer was added 0.5 part by weight of the compound represented by the formula (1-1), 7 g of N-methyl-2-pyrrolidone, And 3 g of butyl cellosolve were added and shaken for 2 hours to obtain a liquid crystal aligning agent RA-1 having a solid content of 3 wt%.

The resulting liquid crystal aligning agent RA-1 was applied to a substrate having a SiNx / ITO interdigital electrode attached thereto with a spinner, and on the opposite side, the alignment agent RA-1 was applied to a glass substrate (spacer height: 4 탆) The application condition was 2,300 rpm, 15 seconds. After the coating, the substrate was pre-baked at 80 캜 for about 5 minutes, and then baked at 200 캜 for 30 minutes to form a liquid crystal alignment film having a thickness of about 100 nm. The obtained polyimide film was rubbed with a rubbing treatment apparatus under the conditions of a film thickness of rubbed bubbles (rag) of 1.9 mm in length: 0.40 mm, a stage moving speed of 60 mm / sec and a roller rotation speed of 1000 rpm, As a result of observation, no shattering of the film was observed.

<Fabrication of FFS cell, confirmation of flow alignment, contrast and AC afterimage measurement>

The rubbed substrate was ultrasonically cleaned in ethanol for 5 minutes, then rinsed in ultrapure water, and then dried in an oven at 120 ° C for 30 minutes. The surfaces on which the alignment films of the two substrates on which the alignment films were formed were formed so as to face each other so that the rubbing directions were parallel to the respective alignment films and voids for injecting the liquid crystal composition were formed between the opposing alignment films, ), And an empty FFS cell having a cell thickness of 4 탆 was assembled. The positive-type liquid crystal composition A was vacuum-injected into the empty FFS cell thus manufactured, and the injection port was sealed with a photo-curing agent. Subsequently, heat treatment was performed at 110 占 폚 for 30 minutes to produce an FFS liquid crystal display element (FFS cell) 1-1.

&Lt; Positive type liquid crystal composition A >

Property Value: NI  100.1 C; Δε 5.1; ? N 0.093; ? 25.6 mPa 占 퐏.

As a result of confirming the orientation of the liquid crystal in the obtained liquid crystal display element, the orientation of the liquid crystal was not observed. As a result of measuring the contrast value, it was found to be 2800, and the result of measurement of the AC afterimage was 2.0%.

[Examples 33 to 66]

Rubbing resistance, contrast and AC afterimage were measured in accordance with Example 32 except that varnishes and additives to be used were changed. The measurement results are shown in Table 2-1 together with Example 32.

[Table 2-1]

[Comparative Examples 1 to 4]

Rubbing resistance, contrast and AC afterimage were measured in accordance with Example 32 except that the additives were changed. The measurement results are shown in Table 2-2.

[Table 2-2]

Comparing Examples 32 to 66 with Comparative Examples 1 to 4, it has been found that when the present invention is applied to an FFS liquid crystal display device, an FFS liquid crystal display device having good rubbing resistance and good contrast and AC afterimage characteristics can be obtained.

[Example 67]

2.0 g of the varnish 12 synthesized in Example 12 and 8.0 g of the varnish 23 synthesized in Example 23 were weighed and taken in a 50 ml eggplant type flask equipped with a stirrer and a nitrogen introducing tube, , 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added to 100 parts by weight of the polymer, and the mixture was stirred at room temperature for 1 hour to prepare an orientation agent RB-1 was obtained.

The obtained alignment agent RB-1 was applied to a glass substrate with a spinner. After the application, the substrate was heated at 80 占 폚 for 3 minutes to evaporate the solvent. Thereafter, using a Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd., a linear line of ultraviolet rays Polarized light was irradiated. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 1.3 ± 0.1 J / cm 2 at a wavelength of 365 nm Respectively. And baked at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the resulting substrate was measured and found to be 4H.

&Lt; Fabrication method of FFS cell, confirmation of flow orientation, confirmation of foreign matter generation, and measurement of residual image after AC &

The alignment agent RB-1 thus obtained was applied to a substrate to which a SiNx / ITO interdigital electrode was attached with a spinner, and on the opposite side, an orientation agent RB-1 was applied to a glass substrate (spacer height: 4 m) with a spacer. After the application, the substrate was heated at 80 占 폚 for 3 minutes to evaporate the solvent. Thereafter, using a Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd., a linear line of ultraviolet rays Polarized light was irradiated. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 1.3 ± 0.1 J / cm 2 at a wavelength of 365 nm Respectively. And baked at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The surfaces on which the alignment films of these two alignment film forming substrates were formed were opposed to each other so that the polarization directions of the linearly polarized light irradiated on the respective alignment films were parallel to each other and voids for injecting the liquid crystal composition were formed between the opposing alignment films, , And an empty FFS cell having a cell thickness of 4 탆 were assembled. The positive type liquid crystal composition was vacuum-injected into the manufactured empty FFS cell to produce an FFS liquid crystal display device. As a result of confirming the orientation of the liquid crystal in the obtained liquid crystal display element, the orientation of the liquid crystal was not observed. Subsequently, the liquid crystal display element after the foreign matter test was observed with a microscope, and as a result, the generation of foreign matter was not observed. As a result of measurement of the contrast value, it was found to be 3500, and the result of measurement of the AC residual image was 2.0%.

[Examples 68 to 96]

The pencil hardness, the foreign matter test, the contrast, and the after-image of the AC were measured in accordance with Example 67 except that the varnish to be used and the additive were changed. The measurement results are shown in Table 3-1 in addition to Example 67.

[Examples 97 to 98]

The varnish hardness, the foreign matter test, the contrast, and the after-effects of the AC after-image were measured in accordance with Example 67, except that the varnish to be used and the additive were changed and the heat treatment after the ultraviolet irradiation was performed at 110 캜 for 20 minutes and then at 220 캜 for 15 minutes. . The measurement results are shown in Table 3-1 in addition to Example 67.

[Example 99]

The varnish hardness, the foreign matter test, the contrast, and the after-effects of the AC after-image were measured in accordance with Example 67 except that the varnish to be used and the additives were changed and the heat treatment after the ultraviolet irradiation was performed at 180 캜 for 20 minutes and then at 220 캜 for 15 minutes. . The measurement results are shown in Table 3-1 in addition to Example 67.

[Table 3-1]

[Comparative Examples 5 to 8]

The pencil hardness, the foreign matter test, the contrast, and the after-image residuals were measured in accordance with Example 67 except that the varnish to be used and the additives were changed. The measurement results are shown in Table 3-2.

[Table 3-2]

Comparing Examples 67 to 99 and Comparative Examples 5 to 8, it was found that application of the present invention to an FFS liquid crystal display device can suppress generation of foreign matter, and can provide an FFS liquid crystal display device having excellent contrast and AC afterimage characteristics.

[Liquid crystal aligning agent for application by inkjet method]

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent suitable for application by the ink jet method, by appropriately selecting the solvent to be used.

[Example 100]

The varnish synthesized in Example 12 was poured into a large excess of methanol to precipitate the reaction product. The precipitate was washed with methanol and dried at 40 캜 for 15 hours under reduced pressure to obtain 3 g of polyamic acid (PAA-12). To the polyamic acid (PAA-12), 48.0 g of NMP, 12.0 g of? -Butyrolactone (GBL), 16.0 g of 1-butoxy-2-propanol (BP), 20.0 g of diethylene glycol ethyl methyl ether ), 3.0 g of diethylene glycol butyl methyl ether (BDM) and 3.0 g of diisobutyl ketone (DIBK) were added to the resulting mixture at a solid concentration of 3.0 wt% and a solvent composition of NMP / GBL / BP / EDM / BDM / (12-a) with DIBK = 48/12/16/15/3/3.

[Example 101]

Similarly, the varnish synthesized in Example 23 had a solid concentration of 3.0% by weight and a solvent composition of NMP / GBL / BP / EDM / BDM / DIBK = 48/12/16/15/3/3 (23-a) was prepared.

[Example 102]

2.0 g of the varnish (12-a) prepared in Example 100 and 8.0 g of the varnish (23-a) prepared in Example 101 were weighed and mixed with 100 parts by weight of the compound represented by the formula (1-1) 15 parts by weight of a liquid crystal aligning agent for coating with an ink jet method (RB (RB)) having a solid concentration of 3.0% by weight and a solvent composition of NMP / GBL / BP / EDM / BDM / DIBK = 48/12/16/15 / -38) was prepared.

[Example 103]

2.0 g of the varnish 15 synthesized in Example 15 and 8.0 g of the varnish 25 synthesized in Example 25 were weighed, and 15 parts by weight of the compound represented by the formula (1-1) was added to 100 parts by weight of the polymer, GBL: BC: BDM: EDE = 48: 13: 2) was added in an amount of 2.2 g, GBL of 1.4 g, BC of 1.0 g, BDM of 1.0 g and EDE of 2.8 g, (RB-39) for coating with an inkjet method was prepared.

[Example 104]

2.0 g of the varnish 12 synthesized in Example 12 and 8.0 g of the varnish 23 synthesized in Example 23 were weighed, and 15 parts by weight of the compound represented by the formula (1-1) was added to 100 parts by weight of the polymer, 2.2 g of GBL, 2.0 g of BC and 0.6 g of DIBK were added to the resulting mixture to obtain an inkjet recording head having a solid content concentration of 3.0% by weight and a solvent composition of NMP: GBL: BC: DIBK = 48: 26: 20: A liquid crystal aligning agent (RB-40) was prepared.

[Example 105]

A pencil hardness, a foreign matter test, a contrast test, and a gloss test were carried out in accordance with Example 67, except that a liquid crystal aligning agent (RB-38) for application of an inkjet method was applied to a glass substrate by an inkjet coating apparatus (DMP- 2831, AC residual image was measured. The liquid droplet gap and the cartridge application voltage were adjusted so that the film thickness of the liquid crystal alignment film was 100 nm.

[Examples 106 to 107]

The pencil hardness, the foreign matter test, the contrast, and the after-recorded image were measured in accordance with Example 105 except that the varnish used was changed. The measurement results are shown in Table 3-3 together with Example 102.

[Table 3-3]

It has been found that when the liquid crystal aligning agent of the present invention is applied to an FFS liquid crystal display element even when it is coated by an ink jet method, generation of foreign matter can be suppressed, and an FFS liquid crystal display element having excellent contrast and AC afterimage characteristics can be obtained.

[Example 108]

2.0 g of the varnish 15 synthesized in Example 15 and 8.0 g of the varnish 25 synthesized in Example 25 were weighed and taken in a 50 ml eggplant type flask equipped with a stirring blade and a nitrogen introduction tube, , 5.0 parts by weight based on 100 parts by weight of the polymer, 5 parts by weight of the compound of the additive (Ad5) based on 100 parts by weight of the polymer, 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve And the mixture was stirred at room temperature for 1 hour to obtain an orientation agent RB-41 having a resin concentration of 3% by weight.

The obtained alignment agent RB-41 was applied to a glass substrate with a spinner. After the application, the substrate was heated at 80 占 폚 for 3 minutes to evaporate the solvent. Thereafter, using a Multilight ML-501C / B manufactured by Ushio Electric Co., Ltd., a linear line of ultraviolet rays Polarized light was irradiated. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 1.3 ± 0.1 J / cm 2 at a wavelength of 365 nm Respectively. And baked at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The pencil hardness of the resulting substrate was measured and found to be 5H.

&Lt; Fabrication method of FFS cell, confirmation of flow orientation, confirmation of foreign matter generation, and measurement of residual image after AC &

The alignment agent RB-1 thus obtained was applied to a substrate to which a SiNx / ITO interdigital electrode was attached with a spinner, and on the opposite side, an orientation agent RB-41 was applied to a glass substrate (spacer height: 4 m) with a spacer. After the application, the substrate was heated at 80 占 폚 for 3 minutes, and the solvent was evaporated. Using a Multilight ML-501C / B manufactured by Ushio Electric Co., Polarized light was irradiated. The exposure energy at this time was measured by using UV ultraviolet light intensity meter UIT-150 (receiver: UVD-S365) manufactured by Ushio Inc., and the exposure time was set to 1.3 ± 0.1 J / cm 2 at a wavelength of 365 nm Respectively. And baked at 200 DEG C for 30 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The surfaces on which the alignment films of these two alignment film forming substrates were formed were opposed to each other so that the polarization directions of the linearly polarized light irradiated on the respective alignment films were parallel to each other and voids for injecting the liquid crystal composition were formed between the opposing alignment films, , And an empty FFS cell having a cell thickness of 4 탆 were assembled. The positive type liquid crystal composition was vacuum-injected into the manufactured empty FFS cell to produce an FFS liquid crystal display device. As a result of confirming the orientation of the liquid crystal in the obtained liquid crystal display element, the orientation of the liquid crystal was not observed. Subsequently, the liquid crystal display element after the foreign matter test was observed with a microscope, and as a result, the generation of foreign matter was not observed. As a result of measuring the contrast value, it was found to be 3300, and the result of measuring the after-image of AC was ΔB of 2.3%.

[Example 109]

The pencil hardness, the foreign matter test, the contrast, and the after-image residuals were measured in accordance with Example 108 except that the varnish to be used, the additive and the used amount were changed. The measurement results are shown in Table 4-1 in addition to Example 108.

[Table 4-1]

Comparing Examples 108 to 109 and Comparative Examples 5 to 8, it was found that application of the present invention to an FFS liquid crystal display device can suppress the generation of foreign matter and obtain an FFS liquid crystal display device having excellent contrast and AC afterimage characteristics.

[Liquid crystal aligning agent for application by inkjet method]

The liquid crystal aligning agent of the present invention is a liquid crystal aligning agent suitable for application by the ink jet method, by appropriately selecting the solvent to be used.

[Example 110]

2.0 g of the varnish 16 synthesized in Example 16 and 8.0 g of the varnish 26 synthesized in Example 26 were weighed and mixed with 5 parts by weight of the compound represented by the formula (1-1) per 100 parts by weight of the polymer, (Ad5) was added in an amount of 3 parts by weight based on 100 parts by weight of the polymer. The solid content concentration was 3.0% by weight and the solvent composition was NMP / GBL / BP / EDM / BDM / DIBK = 48/12/16/15/3 / (RB-43) for coating with an ink jet method was prepared.

[Example 111]

2.0 g of the varnish 17 synthesized in Example 17 and 8.0 g of the varnish 28 synthesized in Example 28 were weighed and added with 8 parts by weight of the compound represented by the formula (1-1) to 100 parts by weight of the polymer, (Ad1) was added in an amount of 2 parts by weight based on 100 parts by weight of the polymer, and 2.2 g of NMP, 2.6 g of GBL, 1.4 g of BC, 1.0 g of BDM and 2.8 g of EDE were added, (RB-44) for coating with an ink-jet method was prepared, in which the solvent composition was NMP: GBL: BC: BDM: EDE = 48: 13: 17: 5: 14.

[Example 112]

A pencil hardness, a foreign matter test, a contrast test, and a gloss test were carried out in the same manner as in Example 111, except that a liquid crystal aligning agent (RB-43) for application of an ink jet method was applied to a glass substrate by an inkjet coating apparatus (DMP- AC residual image was measured. The liquid droplet gap and the cartridge application voltage were adjusted so that the film thickness of the liquid crystal alignment film was 100 nm.

[Example 113]

The pencil hardness, foreign matter test, contrast, and after-image residuals were measured in accordance with Example 109 except that the aligning agent to be used was changed. The measurement results are shown in Table 4-2 in addition to Example 112.

[Table 4-2]

It has been found that when the liquid crystal aligning agent of the present invention is applied to an FFS liquid crystal display element even when it is coated by an ink jet method, generation of foreign matter can be suppressed, and an FFS liquid crystal display element having excellent contrast and AC afterimage characteristics can be obtained.

It was confirmed that the liquid crystal aligning agent of the present invention can form a liquid crystal alignment film exhibiting high film hardness and excellent liquid crystal alignability. It was confirmed that the liquid crystal display element having the liquid crystal alignment film formed of the liquid crystal aligning agent of the present invention had excellent characteristics such as that the foreign substances were not generated well during the operation of the touch panel and the high contrast was exhibited and the AC afterimage did not occur well. The liquid crystal aligning agent of the present invention can be suitably applied to a liquid crystal display device of the transverse electric field driving type in particular.

Claims (14)

A liquid crystal aligning agent containing at least one polymer selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride with a diamine compound and at least one compound represented by the following formula (1);

In the formula (1), R ¹ is a monovalent organic group having any one of the following structures connected directly to N via a linking group in *

And R &lt; ² &gt; and R &lt; ³ &gt; are each independently a monovalent organic group having any one of the following structures connected directly to N via a linker or a linker.

The method according to claim 1,
At least one compound represented by formula (1) represented by any one of formulas (1-1) to (1-4), liquid crystal aligning agent;

In the formula (1-3), R is -CH ₃ or -CH ₂ CH ₃ . 3. The method according to claim 1 or 2,
The tetracarboxylic acid dianhydride contains at least one selected from the group of compounds represented by the following formulas (AN-I) to (AN-VII);
A diamine having no side chain represented by the following formulas (DI-1) to (DI-16), a dihydrazide having no side chain represented by the following formulas (DIH-1) to (DIH- And a diamine having a side chain represented by the following formulas (DI-31) to (DI-35);

Formula (AN-I), (AN -IV) and in (AN-V), X is independently a single bond or -CH ₂ - and;
In the formula (AN-II), G represents a single bond, alkylene, -CO-, -O-, -S-, -SO 2 of carbon number 1 ~ 20 -, -C (CH 3) 2 -, or - C (CF _{3) 2} - and;
In the formulas (AN-II) to (AN-IV), Y is independently selected from the group consisting of the following trivalent groups, the bonding hand is connected to any carbon, and at least one hydrogen May be substituted with methyl, ethyl or phenyl;

In the formulas (AN-III) to (AN-V), the ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon group having 6 to 30 carbon atoms, May be substituted with methyl, ethyl or phenyl, the bonding hands attached to the ring may be connected to any carbon constituting the ring, and the two bonding hands may be connected to the same carbon;
In the formula (AN-VI), X ¹⁰ is alkylene having 2 to 6 carbon atoms, Me represents methyl and Ph represents phenyl;
In formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO- and r is independently 0 or 1;

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH-, -O-, m is an integer of 1 to 12, At least one hydrogen of the phenylene may be replaced by -OH;
Formula (DI-3) and formula (DI-5) ~ expression in (DI-7), G ²¹ represents a single bond _{independently, -NH-, -NCH 3 -, -O-} , -S-, -SS _{-, -SO 2 -, -CO-,} -COO-, -CONCH 3 -, -CONH-, -C (CH 3) 2 -, -C (CF 3) 2 -, - (CH 2) m -, -O- (CH ₂ ) _m -O-, -N (-CH ₃ ) - (CH ₂ ) _k -N (-CH ₃ ) -, - (OC ₂ H ₄ ) _m -O-, _{2 -C (CF 3) 2 -CH} 2 -O-, -O-CO- (CH 2) m -CO-O-, -CO-O- (CH 2) m -O-CO-, - (CH _{2) m -NH- (CH 2)} m -, -CO- (CH 2) k -NH- (CH 2) k -, - (NH- (CH 2) m) k -NH-, -CO-C ₃ H ₆ -, and _{(NH-C 3 H 6)} n -CO-, or _{-S- (CH 2) m -S-,} m is independently an integer of from 1 to 12, k is an integer from 1 to 5 , n is 1 or 2;
In the formula (DI-4), s is independently an integer of 0 to 2;
In formula (DI-6) and formula (DI-7), G ²² represents a single bond, -O-, -S-, -CO-, -C (CH 3) 2 independently -, -C (CF ₃ ) ₂ -, -NH- or alkylene having 1 to 10 carbon atoms;
Formula (DI-2) ~ formula (DI-7) cyclohexane ring and benzene, at least one hydrogen is -F, -Cl, alkyl, -OCH _3, -OH, -CF of 1 to 3 carbon atoms in the ring _3, (DI-4-a) in which at least one hydrogen of the benzene ring is replaced by -O-, -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl. ) To the formula (DI-4-e);
A group in which the bonding position is not fixed to the carbon atom constituting the ring in the above formula represents an arbitrary bonding position in the ring;
The bonding position of -NH ₂ to the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² ;

In the formulas (DI-4-a) and (DI-4-b), R ²⁰ is independently hydrogen or -CH ₃ ;

In formula (DI-11), r is 0 or 1;
In the formulas (DI-8) to (DI-11), the bonding position of -NH ₂ bonded to the ring is at any position;

In formula (DI-12), R ²¹ and R ²² are independently alkyl having 1 to 3 carbon atoms or phenyl, G ²³ is independently alkylene, phenylene or alkyl-substituted phenylene having 1 to 6 carbon atoms, w is an integer of 1 to 10;
In formula (DI-13), R ²³ is independently alkyl of 1 to 5 carbon atoms, alkoxy of 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is an integer of 0 to 4 ego ;
In formula (DI-14), ring B is monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, alkyl of 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, An integer of 4;
In formula (DI-15), ring C is a monocyclic ring containing a heteroatom;
In formula (DI-16), G ²⁴ is a single bond, alkylene having 2 to 6 carbon atoms or 1,4-phenylene, r is 0 or 1;
A group in which the bonding position is not fixed to the carbon atom constituting the ring in the above formula represents an arbitrary bonding position in the ring;
In the formulas (DI-13) to (DI-16), the bonding position of -NH ₂ bonded to the ring is at any position;

In the formula (DIH-1), G ²⁵ represents a single bond, alkylene, -CO-, -O- having a carbon number of _{1 ~ 20, -S-, -SO 2} -, -C (CH 3) 2 -, or -C (CF _{3) 2} - and;
In formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, at least one hydrogen of which rings may be substituted by methyl, ethyl, or phenyl;
In the formula (DIH-3), each of the rings E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of these rings may be substituted with methyl, ethyl or phenyl, Y is a single bond, -CO-, -O-, -S-, -SO ₂ -, -C (CH ₃ ) ₂ -, or -C (CF ₃ ) ₂ -;
In the formulas (DIH-2) and (DIH-3), the bonding position of -CONHNH ₂ bonding to the ring is at any position;

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O -, -OCF ₂ -, or - (CH ₂ ) _{m '} - and m' is an integer of 1 to 12;
R ²⁵ is an alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a), wherein at least one hydrogen may be substituted with -F, And at least one -CH ₂ - may be substituted with -O-, -CH═CH- or -C≡C-, and the hydrogen of the phenyl may be substituted with -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , alkyl having 3 to 30 carbon atoms or alkoxy having 3 to 30 carbon atoms, and the bonding position of -NH ₂ bonded to the benzene ring may be any position in the ring And,

In formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are linking groups and independently represent a single bond or alkylene having 1 to 12 carbon atoms, and one or more -CH ₂ - -O-, -COO-, -OCO-, -CONH-, -CH = CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, piperidine- Naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, and at least one hydrogen in ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ is -F or two being in the coupler may be substituted with -CH _3, s, t and u are independently an integer of 0 to 2, their sum is in the range of 0 to 5, and, s, t or u is 2 when the work, each of the brackets May be the same or different and the two rings may be the same or different and R ²⁶ is a hydrogen, -F, -OH, alkoxy of 1 to 30 carbon atoms alkyl, fluorine-substituted alkyl having 1 to 30 carbon atoms, having 1 to 30 carbon atoms _{of, -CN, -OCH 2 F, -OCHF} 2, or -OCF _3, and , At least one -CH ₂ - of the alkyl having 1 to 30 carbon atoms may be substituted with a divalent group represented by the following formula (DI-31-b)

In formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl of 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In formula (DI-32) and formula (DI-33), G ³⁰ are independently a single bond, -CO- or -CH ₂ -, and, R ²⁹ are independently hydrogen or -CH _3, R ³⁰ is hydrogen , Alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms;
At least one hydrogen of the benzene ring in formula (DI-33) may be substituted with alkyl having 1 to 20 carbon atoms or phenyl;
A group in which the bonding position is not fixed to any carbon atom constituting the ring in the above formula indicates that the bonding position in the ring is arbitrary;
In the formulas (DI-32) and (DI-33), -NH ₂ bonded to the benzene ring represents any bonding position in the ring;

In formula (DI-34) and formula (DI-35), G ³¹ is independently -O-, -NH- or alkylene having 1 to 6 carbon atoms and G ³² is a single bond or alkyl having 1 to 3 carbon atoms R ³¹ is hydrogen or alkyl having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH = CH- or -C≡C-, and R ³² Is alkyl of 6 to 22 carbon atoms, R ³³ is hydrogen or alkyl of 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1, and -NH ₂ bonded to the benzene ring indicates that the bonding position in the ring is arbitrary. The method of claim 3,
(AN-1-1), (AN-1-13), (PA-1) and (AN-3-1) ), AN-3-2, AN-4-5, AN-4-17, AN-4-21, AN-4-29, AN (AN-5-1), AN-7-2, AN-10-1, AN-11-3, AN-16-1, , The formula (AN-16-3), and the formula (AN-16-4);
(DI-3-1), DI-2-1, DI-4-1, DI-4-2, (DI-5-15), the formula (DI-5-1), the formula (DI-5-5) ), DI-5-17, DI-5-28, DI-5-30, DI-6-7, DI-7-3, (DIH-2-1) selected from the group consisting of a compound represented by the formula (DI-13-1), a formula (DI-13-1), a formula Personal, liquid crystal aligning agent;

In the formulas (AN-1-2) and (AN-4-17), m is independently an integer of 1 to 12.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is independently an integer of 1 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5; And
In the formula (DI-7-3), each n is independently 1 or 2. 5. The method according to any one of claims 1 to 4,
Wherein the polyamic acid and the derivative thereof is a polymer (a) obtained by reacting at least one of a tetracarboxylic acid dianhydride and a diamine with a compound having a photoreactive structure. 6. The method of claim 5,
The liquid crystal aligning agent is at least one selected from the group consisting of the structures represented by the following formulas (P-1) to (P-7).

In the formula (P-1), R ⁶¹ is independently a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a phenyl group. The method according to claim 6,
(IV-1), (IV-2), (III-1), , At least one tetracarboxylic acid dianhydride or diamine compound selected from the group consisting of formulas (V-1) to (V-3), and formulas (VI- Orientation agent.

In the formulas (V-2), R ⁶ is independently a group in which the bonding position is not fixed to any carbon atom constituting the ring, and the bonding position in the ring is arbitrary. It is _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, a is independently an integer from 0 to 2, and formula (V-3) in the ring a and ring B are each independently a single ring-shaped And R ¹¹ is at least one selected from the group consisting of a straight chain alkylene having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO- or -N (CH ₃ ) CO- and, R ¹² is C 1 -C 20 linear alkylene, -COO-, -OCO-, -NHCO-, or -N (CH ₃₎ in the CO- and, for R ¹¹ and R ^12, straight-chain alkylene , One or two of -CH ₂ - of -O- may be substituted with -O-, and R ⁷ to R ¹⁰ are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH, and b to e are independent A is an integer of 0-4. 8. The method of claim 7,
The liquid crystal aligning agent represented by the following formula (PDI-7) is a diamine compound having the photoreactive structure.

In the formula (PDI-7), R ⁵¹ are each independently _{-CH 3, -OCH 3, -CF 3} , or -COOCH _3, s are each independently an integer of 0 to 2. 9. The method according to any one of claims 5 to 8,
(B) selected from a polyamic acid and a derivative thereof obtained by reacting a tetracarboxylic acid dianhydride having no photoreactive structure and a diamine having no photoreactive structure, together with the polymer (a) A liquid crystal aligning agent. 10. The method of claim 9,
The tetracarboxylic acid dianhydride used in the synthesis of the polymer (b) is at least one selected from the group consisting of the following formulas (AN-1-1), (AN-1-2), (AN- ), AN-3-1, AN-3-2, AN-4-5, AN-4-17, AN-4-21, 4-29), AN-4-30, AN-5-1, AN-7-2, AN-10-1 and AN- , At least one selected from the formulas (AN-16-1), (AN-16-3) and (AN-16-4);
(DI-3-1), DI-2-1, DI-4-1, DI-4-2, (DI-5-15), the formula (DI-5-1), the formula (DI-5-5) ), DI-5-17, DI-5-28, DI-5-30, DI-6-7, DI-7-3, (DIH-2-1) selected from the group consisting of a compound represented by the formula (DI-13-1), a formula (DI-13-1), a formula Personal, liquid crystal aligning agent;

In the formulas (AN-1-2) and (AN-4-17), m is independently an integer of 1 to 12.

In the formulas (DI-5-1), (DI-5-12), (DI-5-13) and (DI-7-3), m is independently an integer of 1 to 12;
In the formula (DI-5-30), k is an integer of 1 to 5; And
In the formula (DI-7-3), each n is independently 1 or 2. 11. The method according to any one of claims 1 to 10,
Wherein the liquid crystal aligning agent further contains at least one member selected from the group consisting of an oxazine compound, an oxazine compound, an epoxy compound other than the compound represented by the formula (1), and a compound comprising a silane coupling agent. A liquid crystal alignment film formed by the liquid crystal aligning agent according to any one of claims 1 to 11. A liquid crystal alignment film for a liquid crystal display element of a transverse electric field driving type formed by the liquid crystal aligning agent according to any one of claims 1 to 11. 13. A liquid crystal display element having the liquid crystal alignment film according to claim 12 or claim 13.