KR102262893B1 - Photosensitive diamines, liquid crystal aligning agents and liquid crystal display devices - Google Patents

Abstract

식(1)에 있어서, 환 A, 환 B는, 단환식 탄화수소, 축합 다환식 탄화수소 또는 복소환이며; R¹은, 탄소수 2∼20의 직쇄 알킬렌, -COO-, -OCO-, -NHCO-, 또는 -N(CH₃)CO-이며; R²는, 탄소수 2∼20의 직쇄 알킬렌, -COO-, -OCO-, -CONH-, 또는 -CON(CH₃)-이며; R^a∼R^d는, 각각 독립적으로, -F, -CH₃, -OCH₃, -CF₃, 또는 -OH; a∼d는 0∼4의 정수이다.The liquid crystal aligning agent containing the polyamic acid obtained by making the diamine component containing the photosensitive diamine represented by Formula (1) of this invention react with tetracarboxylic dianhydride, or its derivative(s) has high transmittance|permeability and forms a liquid crystal aligning film with high orientation can do.

In formula (1), ring A and ring B are monocyclic hydrocarbon, condensed polycyclic hydrocarbon, or heterocyclic ring; R ¹ is linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, or -N(CH ₃ )CO-; R ² is a linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-; R ^a to ^{R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH; a to d are integers from 0 to 4.

Description

A photosensitive diamine, a liquid crystal aligning agent, and a liquid crystal display element {PHOTOSENSITIVE DIAMINES, LIQUID CRYSTAL ALIGNING AGENTS AND LIQUID CRYSTAL DISPLAY DEVICES}

The present invention relates to a novel photosensitive diamine, a polyamic acid obtained using the same or a derivative thereof, and also to a use thereof. And the term "liquid crystal aligning agent" in this invention means the polymer containing composition used in order to form a liquid crystal aligning film.

Various display devices such as PC monitors, liquid crystal TVs, video camera viewfinders, and projection displays, as well as optoelectronic related elements such as optical printer heads, optical Fourier transform elements, and light valves, etc. As for the liquid crystal display elements commercialized and generally distributed, the display element using a nematic liquid crystal has comprised the mainstream. As a display method of a nematic liquid crystal display element, TN (Twisted Nematic) mode and STN (Super Twisted Nematic) mode are well known. Recently, in order to improve the narrow viewing angle, which is one of the problems of these modes, a TN-type liquid crystal display device using an optical compensation film, a multi-domain vertical alignment (MVA) mode using a technology of vertical alignment and a protrusion structure together , or a transverse electric field type IPS (In-Plane Switching) mode and FFS (Fringe Field Switching) mode have been proposed and put to practical use.

Technological development of liquid crystal display elements has been achieved not only by improvement of these driving methods and element structures, but also by improvement of constituent members used in elements. Among the constituent members used in a liquid crystal display element, a liquid crystal aligning film in particular is one of the important materials related to display quality, and improving the performance of an aligning film is important with quality improvement of a liquid crystal display element.

A liquid crystal aligning film is formed with a liquid crystal aligning agent. Currently, the liquid crystal aligning agent mainly used is the solution (varnish) which melt|dissolved the polyamic acid or a soluble polyimide in the organic solvent. After apply|coating this solution to a board|substrate, it forms into a film by means, such as a heating, and forms a polyimide-type liquid crystal aligning film.

Industrially, a rubbing method that is simple and capable of high-speed processing of a large area is widely used as an orientation treatment method. The rubbing method is a treatment in which the surface of the liquid crystal aligning film is rubbed in one direction using a fabric implanted with fibers such as nylon, rayon, and polyester, and thereby, a constant alignment of the liquid crystal molecules can be obtained. However, problems such as oscillation and generation of static electricity by the rubbing method are pointed out, and development of an orientation treatment method instead of the rubbing method is actively being made.

It is the photo-alignment processing method which orientation-processes by irradiating light to be attracting attention as an orientation treatment method which will replace the rubbing method. Many orientation mechanisms, such as a photolysis method, a photoisomerization method, a photodimerization method, and a photocrosslinking method, are proposed for the photo-alignment processing method (for example, refer nonpatent literature 1, patent documents 1 and 2). The photo-alignment method has higher uniformity of alignment than the rubbing method, and since it is a non-contact alignment treatment method, the film is not damaged, and causes such as oscillation and static electricity that cause display defects in liquid crystal display elements can be reduced. have. However, with respect to the rubbing method, the anchoring energy is small and the orientation is low. Since this causes a decrease in the response speed of the liquid crystal molecules and burn-in, improvement has been desired.

In order to overcome the drawbacks of such a photo-alignment treatment method, we have studied a photo-alignment film having a photo-reactive group causing photo-isomerization or photo-dimerization in the polyamic acid structure (see, for example, Patent Documents 3 to 7). After apply|coating the liquid crystal aligning agent which consists of a polyamic acid which has liquid crystallinity or its derivative(s) to a board|substrate, and light-irradiating and baking after that, anchoring energy is large, orientation is favorable, and the photo-alignment film with good electrical characteristics, such as voltage retention. can get However, since the photoreactive group absorbs light, there is a problem in that the transmittance is lowered, and further higher orientation is required, so there is still room for improvement.

Japanese Patent Application Publication No. Hei 9-297313 Japanese Patent Application Publication No. Hei 10-251646 Japanese Patent Application Publication No. 2005-275364 Japanese Patent Application Publication No. 2007-248637 Japanese Patent Application Publication No. 2009-069493 Japanese Patent Application Publication No. 2010-049230 Japanese Patent Application Publication No. 2010-197999

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

An object of the present invention is to provide a liquid crystal aligning agent with high transmittance and high orientation. The subject of this invention is also providing the oriented film using this liquid crystal aligning agent, and providing the liquid crystal display element using this aligning film.

The present inventors developed the photosensitive diamine represented by Formula (1). By using the liquid crystal aligning agent containing the polyamic acid which used the said diamine as a raw material, or its derivative(s), it discovered that the liquid crystal aligning film with high transmittance|permeability and orientation could be obtained, and completed this invention.

This invention consists of the following structures.

[1] The photosensitive diamine represented by Formula (1).

In formula (1), ring A and ring B are each independently at least one selected from a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, and a heterocycle;

R ¹ is linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, or -N(CH ₃ )CO-;

R ² is a linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-;

In R ¹ and R ² _{, one or two of —CH 2} — of the straight-chain alkylene may be substituted with —O—;

R ^{a -R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH;

a to d are each independently an integer of 0 to 4;

Incidentally, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary.

[2] The photosensitive diamine according to the item [1], which is represented by the formula (2).

In Formula (2), R<^1> is a C2-C20 linear alkylene, -COO-, -OCO-, -NHCO-, or -N(CH ₃ )CO-;

R ² is a linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-;

In R ¹ and R ² _{, one or two of —CH 2} — of the straight-chain alkylene may be substituted with —O—;

R ^{a -R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH;

a to d are each independently an integer of 0 to 4;

Incidentally, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary.

[3] The photosensitive diamine according to the item [1] or the item [2], which is represented by the formula (3).

In Formula (3), R<^1> is a C2-C20 linear alkylene, -COO-, -OCO-, -NHCO-, or -N(CH ₃ )CO-;

R ² is a linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-;

R ^{a -R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ , or -OH; And,

a to d are each independently an integer of 0 to 4; And,

A group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary.

[4] The photosensitive diamine according to any one of [1] to [3], wherein the photosensitive diamine is represented by any one of formulas (1-1) to (1-5).

[5] A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one photosensitive diamine according to any one of [1] to [4] with tetracarboxylic dianhydride.

[6] In addition to the photosensitive diamine represented by formula (1), the following formulas (DI-1) to formula (DI-16), formula (DIH-1) to formula (DIH-3), and formula (DI-31) The polyamic acid according to item [5] or a derivative thereof, obtained by reacting a diamine containing at least one selected from the group consisting of to formula (DI-35) with tetracarboxylic dianhydride.

In formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted with -NH- or -O-, m is an integer of 1 to 12, and alkyl at least one hydrogen of ren may be substituted with -OH;

In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, -SS -, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -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 -(NH-C ₃ H ₆ ) _n -CO-, or -S-(CH ₂ ) _m' -S-, and m' is independently an integer of 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 formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF _{3 )} ) ₂ -, or alkylene having 1 to 10 carbon atoms;

In formulas (DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or may be substituted with benzyl, and in formula (DI-4), the following formulas (DI-4-a) to formulas (DI-4-e) may be substituted;

The 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, and the bonding position _{of -NH 2} ^{to the cyclohexane ring or the benzene ring is that of G 21} or G ²² . any position except the binding site;

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

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

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

In the formula (DI-14), ring B is monocyclic heteroaromatic, and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, alkenyl having 2 to 6 carbon atoms. , alkynyl having 1 to 6 carbon atoms, q is independently an integer from 0 to 4;

In the formula (DI-15), ring C is a monocyclic ring containing a hetero atom;

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;

In formulas (DI-13) to (DI-16), the 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 formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;

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

In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen in the ring may be substituted with methyl, ethyl, or phenyl, Y is a single bond, carbon number 1-20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;

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

In 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' -, m' is an integer of 1 to 12, and R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or the following formula ( DI-31-a), wherein in this alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - is -O-, -CH=CH- or -C may be substituted with ≡C-, hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or alkyl having a carbon number of 3 to 30 carbon atoms, 3 to 30 may be substituted with the alkoxy of, and the hydrogen of this cyclohexyl may be substituted with alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and _{the bonding position of -NH 2 to} the benzene ring is arbitrary in the ring. indicates the location of

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more —CH ₂ — of the alkylene is -O-, -COO-, -OCO-, -CONH-, -CH=CH- may be substituted, and Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenyl Lene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene- 2,7-diyl or anthracene-9,10-diyl, wherein in 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 from 0 to 2, the sum of which is 1 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, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF _{3 and 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 the formula (DI-31-b), R27 and R28 are independently alkyl having 2 to 3 carbon atoms, and v is an integer of 1 to 6;

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen , alkyl having 1 to 20 carbon atoms, or alkenyl having 2 to 20 carbon atoms;

One hydrogen of the benzene ring in formula (DI-33) may be substituted with C1-C20 alkyl or phenyl, and,

In the formulas (DI-32) and (DI-33), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary;

In formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, G ³² is a single bond or alkylene having 1 to 3 carbon atoms;

R ³¹ is hydrogen or an alkyl having 1 to 20 carbon atoms, at least one of -CH ₂ - of the alkyl may be substituted with -O-, -CH=CH- or -C≡C-, and R ³² is a carbon number 6 to 22 alkyl, R ³³ is hydrogen or alkyl having 1 to 22 carbon atoms, ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, r is 0 or 1, and benzene _{-NH 2} bonded to a ring indicates that the bonding position in the ring is arbitrary.

[7] In addition to the photosensitive diamine of formula (1), the following formulas (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5- 12), formula (DI-5-13), formula (DI-5-24), formula (DI-5-28) to formula (DI-5-30), formula (DI-6-7), formula ( Item [6], obtained by reacting a mixture of diamines comprising at least one selected from DI-7-3), formula (DI-11-2), and formula (DI-13-1) with tetracarboxylic dianhydride The polyamic acid or its derivatives as described in.

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

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

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

[8] The polyamic acid according to any one of [5] to [7] or a derivative thereof obtained by reacting a mixture of a diamine containing at least one of the photosensitive diamines other than the formula (1) with tetracarboxylic dianhydride. .

[9] The polya according to item [8], wherein the photosensitive diamine other than the formula (1) is at least one selected from the group consisting of azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. Mixed acid or a derivative thereof.

[10] The photosensitive diamine other than the formula (1) is at least one compound selected from the group consisting of the following formulas (PDI-1) to (PDI-12), the item according to the item [8] or [9]. polyamic acid or a derivative thereof.

In the formula (PDI-7), R ⁵¹ is independently -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer from 0 to 2, and, in formula (PDI-12) wherein R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine.

[11] The polyamic acid or derivative thereof according to any one of [8] to [10], wherein the photosensitive diamine other than the formula (1) is a compound represented by the following formula (PDI-7).

In the formula (PDI-7), R ⁵¹ is independently -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer of 0 to 2 independently.

[12] according to any one of [5] to [11], wherein the tetracarboxylic dianhydride is at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII) described polyamic acids or derivatives thereof.

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

In formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or - C(CF ₃ ) ₂ -;

In formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups,

at least one hydrogen of these groups may be substituted with methyl, ethyl or phenyl;

In formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a fused polycyclic hydrocarbon group having 6 to 30 carbon atoms, and at least one of these groups hydrogen may be substituted with methyl, ethyl or phenyl, the bond on the ring may be connected to any carbon constituting the ring, and two bonds 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, Ph represents phenyl;

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

[13] The tetracarboxylic dianhydride is a formula (AN-1-1), a formula (AN-1-2), a formula (AN-1-13), a formula (AN-2-1), a formula (AN -3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29) , Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10), Formula (AN-11-3), Formula (AN-16- 3) and the polyamic acid or derivative thereof according to item [12], which is a tetracarboxylic dianhydride comprising at least one selected from formula (AN-16-4).

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

[14] A liquid crystal aligning agent containing the polyamic acid according to any one of [5] to [13] or a derivative thereof.

[15] The liquid crystal aligning agent containing the polyamic acid or its derivative(s) in any one of [7]-[13], and another polyamic acid or its derivative(s).

[16] Other polyamic acids or derivatives thereof are the formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI) described in the item [6]. The liquid crystal aligning agent according to [15], which is a polyamic acid obtained by reacting at least one diamine selected from the group consisting of -31) to tetracarboxylic dianhydride with a formula (DI-35) or a derivative thereof.

[17] Other polyamic acids or derivatives thereof include the following formulas (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5- 13), formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13-1), formula (DI-16-1), and formula The liquid crystal aligning agent according to [16], which is a polyamic acid obtained by reacting at least one diamine selected from (DIH-2-1) with tetracarboxylic dianhydride, or a derivative thereof.

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

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

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

[18] at least one tetracarboxylic dianhydride selected from the group of tetracarboxylic dianhydrides represented by the formulas (AN-I) to (AN-VII) described in [12], wherein the other polyamic acid or its derivative is The liquid crystal aligning agent in any one of [15]-[17] which is a polyamic acid obtained by making diamine react, or its derivative(s).

[19] Other polyamic acids or derivatives thereof include the following formulas (AN-1-1), formula (AN-1-2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4- 29), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula (AN-11-3), formula (AN-) 16-3) and the liquid crystal aligning agent according to [18], which is a polyamic acid obtained by making at least 1 tetracarboxylic dianhydride and diamine selected from Formula (AN-16-4) react, or its derivative(s).

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

[20] further containing at least one selected from the group consisting of an alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound, [14] to The liquid crystal aligning agent in any one of [19].

[21] The liquid crystal aligning agent according to any one of [14] to [20], wherein the liquid crystal aligning agent is for photo alignment.

[22] The liquid crystal aligning agent according to any one of [14] to [21], wherein the liquid crystal aligning agent is for a liquid crystal display element of a transverse electric field system.

[23] The liquid crystal aligning film formed with the liquid crystal aligning agent in any one of [14]-[22].

[24] A liquid crystal display device having the liquid crystal aligning film according to [23].

The photo-alignment film containing the polymer obtained using the photosensitive diamine compound of this invention as a raw material is excellent in orientation, and there is very little coloring. The liquid crystal display element provided with these alignment films has favorable display performance, and the electrical characteristic is also favorable. Moreover, the alignment film obtained from the alignment agent prepared by blending the above-mentioned polymer with the polymer for a base is excellent in alignment property, and coloring decreases, and there is also no fall in the sensitivity with respect to light. By using this alignment film, the liquid crystal display element which has favorable display characteristics and favorable electrical characteristics can be provided.

The terms used in the present invention will be described. The compound represented by formula (I-1) is sometimes described as compound (I-1). The compound represented by another formula may be abbreviated similarly in some cases. "Arbitrary" used when defining a chemical structural formula shows that it is arbitrary about not only a position but a number. In the chemical structural formula, a group surrounding a letter (eg, A) in a circle or hexagon means that it is a group of a ring structure (ring A).

The photosensitive diamine of this invention is demonstrated. Hereinafter, "photosensitive diamine" may be simply described as "diamine" in the specification.

The photosensitive diamine of this invention is represented by following formula (1).

In formula (1), ring A and ring B are each independently at least one selected from a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon, and a heterocyclic aromatic group, and R ¹ is a straight-chain alkylene having 2 to 20 carbon atoms. , -COO-, -OCO-, -NHCO-, or -N(CH ₃ )CO-, and R ² is a linear alkylene having 2 to 20 carbon atoms, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-. In R ¹ and R ² , at least one -CH ₂ - of the straight-chain alkylene may be substituted with -O-. R ^a to ^{R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and a to d are each independently any one of 0 to 4. A group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary.

As described above, the diamine of the present invention is an azo group-containing diamine having a four ring structure and a spacer group of a straight chain alkylene having 2 to 20 carbon atoms, an ester group, an amide group or an N-methylamide group between the ring and the ring. A polyamic acid or a derivative thereof obtained by reacting an azobenzene-containing diamine having two rings, such as 4,4'-diaminoazobenzene, with tetracarboxylic dianhydride has a long conjugated system through an azo group. to absorb When it uses as a liquid crystal aligning film, the transmittance|permeability becomes low and the display quality of a liquid crystal display element is reduced. On the other hand, the polyamic acid or a derivative thereof obtained by reacting the diamine of the present invention with tetracarboxylic dianhydride has a spacer group represented by ^{R 1} and R ^{2 compared to the above-described polyamic acid or a derivative thereof, so the conjugated system is} Since it becomes short and the absorption wavelength shifts to the short wavelength side, the fall of the transmittance|permeability can be suppressed. Moreover, since it becomes a more flexible structure, it becomes easy to show liquid crystallinity, and can improve orientation.

The diamine compound represented by Formula (1) WHEREIN: The diamine compound represented by Formula (2) from the ease of acquisition of a raw material is preferable.

In the formula (2), R ¹ is an alkylene, -COO-, -OCO-, -NHCO-, or -N (CH ₃₎ CO- straight chain having a carbon number of 2~20, R ² has a carbon number of 2 -20 straight-chain alkylene, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-. In R ¹ and R ² _{, one or two of —CH 2} — of the straight-chain alkylene may be substituted with —O—. R ^a to ^{R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and a to d are each independently any one of 0 to 4. The amino group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary.

Among Formula (2), when it attaches importance to improving the orientation of a liquid crystal, the diamine compound represented by Formula (3) whose bonding position of an amino group is a para position is preferable.

In the formula (3), R ¹ is an alkylene, -COO-, -OCO-, -NHCO-, or -N (CH ₃₎ CO- straight chain having a carbon number of 2~20, R ² has a carbon number of 2 -20 straight-chain alkylene, -COO-, -OCO-, -CONH-, or -CON(CH ₃ )-. R ^a to ^{R d} are each independently -F, -CH ₃ , -OCH ₃ , -CF ₃ or -OH, and a to d are each independently any one of 0 to 4.

The diamine of Formula (3) can be synthesize|combined by the following route, for example.

The compound represented by (c) can be obtained by protecting a diamine (a) and a diamine (b) with a trifluoroacetyl group, for example, one amino group, and reacting sodium peroxoborate tetrahydrate and boric acid. Next, by making potassium carbonate act, the trifluoroacetyl group is deprotected, and the diamine represented by Formula (3) of this invention can be obtained. As the protecting group, in addition to the trifluoroacetyl group, an acetyl group and tert-butoxycarbonyl group are useful, and synthesis methods for these protection and deprotection are described in many publications on organic synthesis.

Also about the diamines of Formulas (1) and (2), by making one of the phenylenes of the said diamine (a) and diamine (b) as the said ring A, and also making the bonding position of an amine into an arbitrary position, similarly can be synthesized.

As the diamine of the present invention, if necessary, those purified by various purification methods such as recrystallization and column chromatography can also be used. And the diamine of this invention can be used for various polyimide coating agents, a polyimide resin molded article, a film, a fiber, etc. other than the liquid crystal aligning agent use.

As an example of the diamine represented by Formula (1), the compound represented by a following formula is mentioned.

In the said diamine, the diamine represented by Formula (1-1) - Formula (1-9) is preferable when an anchoring energy is high, ie, when it attaches importance to improving the alignment property of a liquid crystal more, and improving the transmittance|permeability In the case of importance, the diamine of the present invention of formulas (1-10) to (1-12) is used in order to obtain an orientation film with less coloring, and in order to obtain an orientation agent with higher solubility in a solvent, formula (1) -13) and by using the diamine of the present invention of formula (1-14), an alignment film capable of achieving desired properties can be obtained. Further, as in Formulas (1-1) to (1-4) and (1-7) to (1-18), R ¹ and R ² in Formula (1) represent a main chain composed of an even number of atoms. By using the diamine of this invention, the polyamic acid of this invention and its derivative(s) which show liquid crystallinity in a wider temperature range can be adjusted.

From the viewpoint of suppressing the ease of synthesis and coloring, formulas (1-1) to (1-5), (1-8), (1-12), (1-13), and formulas (1- 15) and Formulas (1-19) to (1-22) are preferable, and Formula (1-1) is particularly preferable.

The polyamic acid of this invention and its derivative(s) are demonstrated.

The polyamic acid and its derivatives of the present invention are reaction products of tetracarboxylic dianhydride and diamine containing diamine represented by formula (1). The derivative of the polyamic acid is a component that dissolves in a solvent when it is made into a liquid crystal aligning agent to be described later containing a solvent, and when the liquid crystal aligning agent is made into a liquid crystal aligning film, a liquid crystal aligning film containing polyimide as a main component can be formed is an ingredient in Such polyamic acid derivatives include, for example, soluble polyimide, polyamic acid ester, and polyamic acid amide. More specifically, 1) polyimide in which all amino and carboxyl of polyamic acid are dehydrated and ring-closed; 2 ) Partial polyimide by dehydration and ring closure reaction, 3) polyamic acid ester in which carboxyl of polyamic acid is converted to ester, 4) tetracarboxylic acid dianhydride by replacing a part of acid dianhydride contained in the compound with organic dicarboxylic acid The obtained polyamic acid-polyamide copolymer and further 5) polyamideimide obtained by dehydration ring closure reaction of a part or all of the said polyamic acid-polyamide copolymer are mentioned. One type of compound may be sufficient as the said polyamic acid and its derivative(s), and 2 or more types may be sufficient as it. In addition, the polyamic acid and its derivatives may be compounds having a structure of a reaction product of tetracarboxylic dianhydride and diamine, and using other raw materials, a reaction product by reaction other than the reaction between tetracarboxylic dianhydride and diamine may contain.

The tetracarboxylic dianhydride used to prepare the polyamic acid and derivatives thereof of the present invention will be described.

The tetracarboxylic dianhydride used in the present invention can be selected from known tetracarboxylic dianhydrides without limitation. Such tetracarboxylic dianhydride is an aromatic system (including a heteroaromatic ring system) in which dicarboxylic acid anhydride is directly bonded to an aromatic ring, and an aliphatic system (heterocyclic system) in which dicarboxylic acid anhydride is not directly bonded to an aromatic ring. included) may belong to either group.

Preferred examples of such a tetracarboxylic dianhydride include tetracarboxylic dianhydrides represented by formulas (AN-I) to (AN-VII) in terms of ease of raw material availability, ease of polymer polymerization, and electrical properties of the film. can

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

In formulas (AN-III) to (AN-V), 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, and at least one of these groups Hydrogen may be substituted with methyl, ethyl or phenyl, and a bond attached to the ring may be connected to any carbon constituting the ring, and two bonds 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.

More specifically, tetracarboxylic dianhydride represented by the formulas of the following formulas (AN-1) to (AN-16-14) is exemplified.

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 one 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 cannot be a single bond. And, R ¹¹ is hydrogen or —CH ₃ . Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formula.

In a formula (AN-1-2) and a formula (AN-1-14), m is an integer of 1-12.

In formula (AN-2), R ¹² is independently hydrogen, -CH ₃ , -CH ₂ CH ₃ , or phenyl. Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formula.

In formula (AN-3), ring A ¹¹ is a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formula.

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 divalent group represented by the following formula (G13-1), and m is an integer of 1 to 12.

In the formula (G13-1), G ^13a and G ^13b each independently represent a single bond or a divalent group represented by -O- or -NHCO-. As for phenylene, 1, 4- phenylene and 1, 3- phenylene are preferable.

Ring A ¹¹ is each independently a cyclohexane ring or a benzene ring. G ¹³ may be bonded to any position of ring A ^{11 .} Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formula.

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

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 dianhydride represented by the formula (AN-5) include compounds represented by the following formula.

In 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 dianhydride represented by the formula (AN-6) include compounds represented by the following formula.

In formula (AN-7), X ¹¹ is a single bond or -CH ₂ -. Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formula.

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 dianhydride represented by the formula (AN-8) include compounds represented by the following formula.

In formula (AN-9), r is each independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formula.

Formula (AN-10) is the following tetracarboxylic dianhydride.

In formula (AN-11), ring A ¹¹ is independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-11) include compounds represented by the following formula.

In formula (AN-12), ring A ¹¹ is each independently a cyclohexane ring or a benzene ring. Examples of the tetracarboxylic dianhydride represented by the formula (AN-12) include compounds represented by the following formula.

In the formula (AN-13), X ¹³ represents alkylene having 2 to 6 carbon atoms, and Ph represents phenyl. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formula.

In formula (AN-14), G ¹⁴ is independently -O-, -COO- or -OCO-, and r is independently 0 or 1. Examples of the tetracarboxylic dianhydride represented by the formula (AN-14) include compounds represented by the following formula.

In formula (AN-15), w is an integer of 1-10. Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formula.

Examples of the tetracarboxylic dianhydride other than the above include the following compounds.

In the above acid dianhydride, preferred materials for improving each property will be described. When it attaches importance to improving the orientation of a liquid crystal, the compound represented by a formula (AN-1), a formula (AN-3), and a formula (AN-4) is preferable, Formula (AN-1-2), Compounds represented by formulas (AN-1-13), (AN-3-2), (AN-4-17) and (AN-4-29) are particularly preferred, and among these, compounds represented by formula (AN- In 1-2), the time of m=4 or 8 is preferable, in Formula (AN-4-17), m=4 or 8 is preferable, and m=8 is especially preferable.

When attaching importance to improving the transmittance|permeability of a liquid crystal display element, a formula (AN-1-1), a formula (AN-1-2), a formula (AN-2-1), a formula (AN-) among the said acid dianhydrides 3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula ( AN-16-3) and compounds represented by formula (AN-16-4) are preferable, and among these, in formula (AN-1-2), when m = 4 or 8 is preferable, and formula (AN In -4-17), m=4 or 8 is preferable, and m=8 is especially preferable.

When attaching importance to improving the VHR of a liquid crystal display element, a formula (AN-1-1), a formula (AN-1-2), a formula (AN-2-1), a formula (AN-) among the said acid dianhydrides 3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-3), and formula The compound represented by (AN-16-4) is preferable, among them, in formula (AN-1-2), when m = 4 or 8, in formula (AN-4-17), m = 4, or 8 is preferred, and m = 8 is particularly preferred.

It is effective as one of the methods of preventing burn-in to improve the relaxation rate of the residual electric charge (residual DC) in an alignment film by reducing the volume resistance value of a liquid crystal aligning film. When this purpose is emphasized, among the above acid dianhydrides, formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29), and The compound represented by formula (AN-11-3) is preferable.

In this invention, the photosensitive diamine of Formula (1) and another photosensitive material can be used together, It can select from well-known photosensitive tetracarboxylic dianhydride without restrict|limiting. Examples of the photosensitive tetracarboxylic dianhydride include the following formulas (PAN-1) and (PAN-8).

The diamine and dihydrazide used for preparing the polyamic acid and its derivatives of the present invention will be described. In producing the polyamic acid or its derivative of the present invention, it can be selected from known diamines and dihydrazides without limitation.

Diamine can be divided into two types according to the structure. That is, when the skeleton connecting two amino groups is regarded as the main chain, it is a group branching from the main chain, i.e., a diamine having a side chain group and a diamine having no side chain group. This side chain group is a group having the effect of increasing the pretilt angle. The side chain group having such an effect needs to be a group having 3 or more carbon atoms, and 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 groups having a steroid skeleton. As a group having one or more rings, a group in which a ring at the terminal has any one of alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, and alkoxyalkyl having 2 or more carbon atoms as a substituent has an effect as a side chain group. In the following description, the diamine which has such a side chain group may be called a side chain type diamine. And the diamine which does not have such a side chain group may be called non-branched type diamine.

By properly separating and using the non-branched diamine and the branched diamine, it is possible to respond to the pretilt angle required for each. It is preferable to use together side chain type diamine to such an extent that the characteristic of this invention is not impaired. In addition, it is preferable to select and use the branched diamine and the non-branched diamine for the purpose of improving vertical alignment, voltage retention, burn-in characteristics, and alignment with respect to the liquid crystal.

Non-branched diamine is demonstrated. Examples of the diamine having no existing side chain 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 in the alkylene may be substituted with -OH. In formulas (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, -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 -(NH-C ₃ H ₆ ) _n -CO-, or -S-(CH ₂ ) _m' -S-, and m' is independently an integer of 1 to 12, k is an integer of 1-5, and n is 1 or 2. In formula (DI-4), s is an integer of 0-2 independently. In formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF _{3 )} ) ₂ -, or alkylene having 1 to 10 carbon atoms. At least one hydrogen of the cyclohexane ring and the benzene ring in formulas (DI-2) to (DI-7) is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or may be substituted with benzyl, and in the formula (DI-4), the following formulas (DI-4-a) to (DI -4-e) may be substituted. The 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 addition, the bonding position _{of -NH 2} to the cyclohexane ring or the benzene ring is any position except for the bonding position of ^{G 21} or G ^{22 .}

In 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 formulas (DI-8) to (DI-11), the bonding position of _{-NH 2 bonded to the ring is any position.}

In formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, G ²³ is independently alkylene having 1 to 6 carbon atoms, phenylene or alkyl-substituted phenylene, w is an integer from 1 to 10; In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, or -Cl, p is independently an integer from 0 to 3, q is an integer from 0 to 4 to be. In the formula (DI-14), ring B is a monocyclic heterocyclic aromatic group, R ²⁴ is hydrogen, -F, -Cl, alkyl of 1 to 6 carbon atoms, alkoxy, vinyl, alkynyl, q is independently It is an integer from 0 to 4. In formula (DI-15), ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the 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. Incidentally, the 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 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) are exemplified as the diamine having no side chain in the formulas (DI-1) to (DI-16).

The example of the diamine represented by Formula (DI-1) is shown below.

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

The example of the diamine represented by a formula (DI-2) - a formula (DI-3) is shown below.

The example of the diamine represented by a formula (DI-4) is shown below.

The example of the diamine represented by a formula (DI-5) is shown below.

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

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

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

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

In formulas (DI-5-35) to (DI-5-37) and (DI-5-39), m is an integer of 1 to 12, and formulas (DI-5-38) and formulas ( In DI-5-39), k is an integer of 1-5, and in Formula (DI-5-40), n is an integer of 1 or 2.

The example of the diamine represented by Formula (DI-6) is shown below.

The example of the diamine represented by a formula (DI-7) is 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.

The example of the diamine represented by a formula (DI-8) is shown below.

The example of the diamine represented by a formula (DI-9) is shown below.

The example of the diamine represented by a formula (DI-10) is shown below.

The example of the diamine represented by Formula (DI-11) is shown below.

The example of the diamine represented by a formula (DI-12) is shown below.

The example of the diamine represented by a formula (DI-13) is shown below.

The example of the diamine represented by Formula (DI-14) is shown below.

The example of the diamine represented by a formula (DI-15) is shown below.

The example of the diamine represented by Formula (DI-16) is shown below.

Dihydrazide is demonstrated. As the known dihydrazide having no side chain, the following formulas (DIH-1) to (DIH-3) are exemplified.

In formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -.

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

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

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

Such non-branched diamines and hydrazides have an effect of improving electrical properties, such as reducing the ion density of the liquid crystal display device. When a non-branched diamine and/or hydrazide is used as a diamine used to prepare a polyamic acid or a derivative thereof used in the liquid crystal aligning agent of the present invention, the ratio of the diamine and dihydrazide to the total amount It is preferable to set it as 0-90 mol%, and it is more preferable to set it as 0-50 mol%.

The branched diamine is demonstrated. As a side chain group of a side chain type diamine, the following groups are mentioned.

First, as a side chain group, alkyl, alkyloxy, alkyloxyalkyl, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, alkylaminocarbonyl, alkenyl, alkenyloxy, alkenylcarbonyl, alkenylcarbonyloxy , alkenyloxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl and the like. Alkyl, alkenyl, and alkynyl in these groups are all groups of 3 or more carbon atoms. However, in the case of alkyloxyalkyl, the whole group may have 3 or more carbon atoms. These groups may be linear or branched.

Next, phenyl, phenylalkyl, phenylalkyloxy, phenyloxy, phenylcarbonyl, phenylcarbonyloxy; Phenyloxycarbonyl, phenylaminocarbonyl, phenylcyclohexyloxy, cycloalkyl having 3 or more carbon atoms, cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenyl oxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkyl, bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenyloxycarbonyl, and a group having a ring structure such as cyclohexylbis(phenyl)oxycarbonyl.

In addition, as a group having two or more benzene rings, a group having two or more cyclohexane rings, or 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 has as a substituent an alkyl having 1 or more carbon atoms, a fluorine-substituted alkyl having 1 or more carbon atoms, alkoxy having 1 or more carbon atoms, or an alkoxyalkyl having 2 or more carbon atoms. An aggregator is an example. It is effective as an airway side chain group having a steroid skeleton.

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

In 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 single bonds, -O-, -COO-, -OCO-, -CH ₂ O-, and alkylene having 1 to 3 carbon atoms, and particularly preferred examples are single bonds, -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, and _{-F, -CH 3, -OCH 3,} -OCH 2 F, -OCHF 2, -OCF 3, may be substituted with alkyl or alkoxy having a carbon number of 3 to 30 carbon atoms of 3 to 30, the The hydrogen of cyclohexyl may be substituted with C3-C30 alkyl or C3-C30 alkoxy. _{Although the bonding position of -NH2 couple|} bonded with a benzene ring shows that it is an arbitrary position in the ring, it is preferable that the bonding position is meta or para. That is, when ^{the binding position of the group "R 25} -G ²⁶ -" is the 1st position, it is preferable that the two bonding positions are the 3rd position and the 5th position, or the 2nd position and the 5th position.

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, and these are independently a single bond or an alkylene having 1 to 12 carbon atoms, and one or more —CH ₂ — of the alkylene is It may be substituted by -O-, -COO-, -OCO-, -CONH-, and -CH=CH-. Ring B ²¹ , Ring B ²² , Ring B ²³ and Ring B ²⁴ are independently 1,4-phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2 , 5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene-2,7-diyl or anthracene-9,10-diyl, and ring B ²¹ , ring B ²² , ring B ²³ and In ring B ²⁴ , at least one hydrogen _{may be substituted with -F or -CH 3} , s, t and u are independently integers from 0 to 2, the sum of which is 1 to 5, and s, t or when 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, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF _{3 and 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbons, and v is an integer of 1 to 6; Preferred examples of R ²⁶ are alkyl having 1 to 30 carbons and alkoxy having 1 to 30 carbons.

In formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is 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 in the benzene ring in the formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms. Incidentally, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary. It is preferable that one of the two groups "-phenylene-G30-O-" in the formula (DI-32) is bonded to the 3-position of the steroid nucleus, and the other is bonded to the 6-position of the steroid nucleus. . It is preferable that the bonding position of two groups "-phenylene-G30-O-" to the benzene ring in formula (DI-33) is a meta position or a para position with respect to the bonding position of a steroid nucleus, respectively. In formulas (DI-32) and (DI-33), -NH ₂ bonded to a benzene ring indicates that the bonding position in the ring is arbitrary.

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, and G ³² is a single bond or alkylene having 1 to 3 carbon atoms. R ³¹ is hydrogen or an 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. _{In addition, -NH 2} bonded to the benzene ring indicates that the bonding position in the ring is arbitrary, but it is preferably a meta position or a para position with respect to the bonding position of ^{G 31 independently.}

Specific examples of the branched diamine are exemplified below. Examples of the diamine having a side chain 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 the formulas (DI-31-1) to (DI-31-11), R ³⁴ is alkyl having 1 to 30 carbon atoms or alkoxy having 1 to 30 carbon atoms, preferably alkyl having 5 to 25 carbon atoms or 5 carbon atoms. to 25 alkoxy. R ³⁵ is alkyl having 1 to 30 carbons or alkoxy having 1 to 30 carbons, preferably alkyl having 3 to 25 carbons or alkoxy having 3 to 25 carbons.

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

In the formulas (DI-31-18) to (DI-31-43), R ³⁸ is alkyl having 1 to 20 carbon atoms or alkoxy having 1 to 20 carbon atoms, preferably alkyl having 3 to 20 carbon atoms or 3 carbon atoms. -20 alkoxy. R ³⁹ is hydrogen, -F, alkyl of 1 to 30 carbon atoms, an alkoxy _{group, -CN, -OCH 2 F, -OCHF} 2 or -OCF ₃ group of 1 to 30 carbon atoms, and preferably having a carbon number of 3 to 25 alkyl, or It is an alkoxy 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.

In formulas (DI-34-1) to (DI-34-12), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbon atoms, preferably hydrogen or alkyl having 1 to 10 carbon atoms, and R ⁴¹ is hydrogen or alkyl having 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 alkyl having 6 to 30 carbon atoms, and R ⁴¹ is hydrogen or alkyl having 1 to 12 carbon atoms.

As the diamine in the present invention, formula (DI-1-1) to formula (DI-16-1), formula (DIH-1-1) to formula (DIH-3-6) and formula (DI-31-1) ) to diamines other than the diamines represented by formulas (DI-35-3) can also be used. Examples of such diamines include compounds represented by the following formulas (DI-36-1) to (DI-36-13).

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

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

When attaching importance to improving the orientation of a liquid crystal more, a formula (DI-1-3), a formula (DI-5-1), a formula (DI-5-5), a formula among the said diamine and dihydrazide (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-29), formula (DI-6-7), formula (DI-7- 3) and it is preferable to use the diamine represented by the formula (DI-11-2), and among these, in the formula (DI-5-1), m = 2, 4 or 6 is preferable, and m = 4 is particularly preferred, in the formula (DI-5-12), m = 2 to 6 is preferred, m = 5 is particularly preferred, and in the formula (DI-5-13), m = 1 or 2 is preferred, and m = 1 is particularly preferred.

When it is important to improve the transmittance, among the above diamines and dihydrazides, formulas (DI-1-3), formula (DI-2-1), formula (DI-5-1), formula (DI-) It is preferable to use the diamine represented by 5-5), a formula (DI-5-24), and a formula (DI-7-3), and the diamine represented by a formula (DI-2-1) is especially preferable. . In the formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and in the formula (DI-7-3), m = 2, or 3, n = 1, or 2 is preferred, m = 1 is particularly preferred.

When attaching importance to improving the VHR of a liquid crystal display element, a formula (DI-2-1), a formula (DI-4-1), a formula (DI-4-2), among the said diamine and dihydrazide, diamines represented by formula (DI-4-10), formula (DI-4-15), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1) It is preferable to use, and the diamines represented by a formula (DI-2-1), a formula (DI-5-1), and a formula (DI-13-1) are especially preferable. Among them, in the formula (DI-5-1), m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

It is effective as one of the methods of preventing burn-in to improve the relaxation rate of the residual electric charge (residual DC) in an alignment film by reducing the volume resistance value of a liquid crystal aligning film. When this objective is important, among the said diamine and dihydrazide, a formula (DI-4-1), a formula (DI-4-2), a formula (DI-4-10), a formula (DI-4- 15), represented by formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), and formula (DI-16-1) It is preferable to use the diamine used, and the diamine represented by a formula (DI-4-1), a formula (DI-5-1), and a formula (DI-5-13) is especially preferable. Among these, in the formula (DI-5-1), m = 2, 4 or 6 is preferable, m = 4 is particularly preferable, and in the formula (DI-5-12), m = 2 to 6 are preferable. and m = 5 is particularly preferable, in the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is particularly preferable.

In this invention, the photosensitive diamine of Formula (1) and another photosensitive material can be used together, It can select from well-known photosensitive diamine without restrict|limiting. For example, it can be selected from an azobenzene derivative, a stilbene derivative, an acetylene derivative, a coumarin derivative, a cinnamic acid derivative, and a benzophenone derivative. As such a photosensitive diamine compound, the following formulas (PDI-1) - a formula (PDI-12) are mentioned.

In the formula (PDI-7), R ⁵¹ is independently -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer from 0 to 2, and, in formula (PDI-12) wherein R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine.

Formula (PDI-7) is preferable if it emphasizes improving the orientation of a liquid crystal more among said other photosensitive diamines. In the aspect of using together the photosensitive diamine of Formula (1) of this invention, and the said other photosensitive diamine compound, when the improvement of orientation and the transmittance|permeability are considered, the ratio of photosensitive diamine (1)/other photosensitive diamine is 100/0 (mol%) to 50/50 (mol%) are preferable, and 100/0 (mol%) to 80/20 (mol%) are more preferable. Moreover, in order to improve various characteristics mentioned above, such as an electrical characteristic and an afterimage characteristic, you may use together 2 or more of other photosensitive diamines.

Each diamine WHEREIN: In the range of 40 mol% or less of the ratio of the monoamine with respect to the diamine, a part of diamine may be substituted by the monoamine. Such substitution can cause termination of the polymerization reaction at the time of producing a polyamic acid, and can suppress further progress of the polymerization reaction. Therefore, by such substitution, the molecular weight of the polymer (polyamic acid or its derivative|guide_body) obtained can be controlled easily, for example, the application|coating characteristic of a liquid crystal aligning agent can be improved without the effect of this invention being impaired. . The number of diamines substituted with monoamine may be 1 type, or 2 or more types may be sufficient as long as the effect of this invention is not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, and n-nonylamine. , n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n- octadecylamine, and n-eicosylamine.

The polyamic acid or derivative thereof of the present invention may further contain a monoisocyanate compound in the monomer. By including the monoisocyanate compound in the monomer, the terminal of the obtained polyamic acid or a derivative thereof is modified, and the molecular weight is controlled. By using this terminal modification type polyamic acid or its derivative(s), for example, the application|coating characteristic of a liquid crystal aligning agent can be improved without the effect of this invention being impaired. It is preferable from the above-mentioned viewpoint that content of the monoisocyanate compound in a monomer is 1-10 mol% with respect to the total amount of diamine and tetracarboxylic dianhydride in a monomer. Examples of the mono isocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyamic acid and its derivative(s) of this invention are obtained by making the mixture of the said acid anhydride and diamine react in a solvent. In this synthesis reaction, special conditions other than selection of a raw material are not required, The conditions in normal polyamic-acid synthesis|combination can be applied as it is. The solvent to be used will be described later.

The liquid crystal aligning agent of this invention may contain other components other than a polyamic acid or its derivative(s) further. The number of other components may be 1 type or 2 or more types may be sufficient as them. As another component, there exist other polymers, compounds, etc. which are mentioned later, for example.

The liquid crystal aligning agent of this invention may contain other polymers other than the polyamic acid of this invention or its derivative(s) further. Examples of other polymers are polymers other than polyamic acid or derivatives thereof obtained by reacting tetracarboxylic dianhydride with diamine containing diamine of the present invention, and polyamic acid obtained by reacting with diamine containing no diamine of Formula (1); Derivatives thereof (hereinafter referred to as “other polyamic acids or derivatives thereof”), polyesters, polyamides, polysiloxanes, cellulose derivatives, polyacetals, polystyrene derivatives, poly(styrenephenylmaleimide) derivatives, poly(meth)acrylates etc. It may be 1 type, or 2 or more types may be sufficient In these, other polyamic acid or its derivative(s), and polysiloxane are preferable, and other polyamic acid or its derivative(s) are more preferable.

In the alignment agent blended with the polyamic acid or its derivative of the present invention and another polyamic acid or its derivative, the structure or molecular weight of each polymer is controlled, and as will be described later, by applying to a substrate and performing preliminary drying. , It is possible to separate the polyamic acid or its derivative component [A] of the present invention as an upper layer, and other polyamic acid or its derivative component [B] as a lower layer. This can be controlled by utilizing 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 layer separation can be confirmed that the surface energy of the formed alignment film is equal to or close to the surface energy of the film formed by the liquid crystal aligning agent containing only the [A] component.

As tetracarboxylic dianhydride used for synthesizing other polyamic acids or derivatives thereof, known tetracarboxylic dianhydrides as tetracarboxylic dianhydrides used for synthesizing polyamic acid or a derivative thereof, which is an essential component of the liquid crystal aligning agent of the present invention It can be selected without limitation from water, and the same ones as those exemplified above can be exemplified.

Among them, in the above-mentioned acid dianhydride, when it is important to improve the layer separation properties, the formulas (AN-3-2), (AN-1-13), and (AN-4-30) are preferable. Do.

When attaching importance to improving the transmittance|permeability of a liquid crystal display element, a formula (AN-1-1), a formula (AN-1-2), a formula (AN-2-1), a formula (AN -3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10), formula Compounds represented by (AN-16-3) and formula (AN-16-4) are preferable, and among these, in formula (AN-1-2), when m = 4 or 8 is preferable, and formula ( In AN-4-17), m=4 or 8 is preferable, and m=8 is especially preferable.

When attaching importance to improving the VHR of a liquid crystal display element, Formula (AN-2-1), Formula (AN-7-2), Formula (AN-10), Formula (AN-16) among the above-mentioned acid dianhydrides -3) and the compound represented by formula (AN-16-4) are preferable, and especially, in formula (AN-1-2), the time of m=4 or 8 is preferable.

It is effective as one of the methods of preventing burn-in to improve the relaxation rate of the residual electric charge (residual DC) in an alignment film by reducing the volume resistance value of a liquid crystal aligning film. When this purpose is emphasized, among the above-mentioned acid dianhydrides, formula (AN-1-13), formula (AN-3-2), formula (AN-4-21), formula (AN-4-29), and a compound represented by the formula (AN-11-3).

The tetracarboxylic dianhydride used for synthesizing other polyamic acids or derivatives thereof preferably contains 10 mol% or more of aromatic tetracarboxylic dianhydride, based on the total tetracarboxylic dianhydride, and preferably contains 30% or more. more preferably.

Examples of the diamine and hydrazide used for synthesizing other polyamic acids or derivatives thereof include those exemplified above as other diamines usable for synthesizing polyamic acid or derivatives thereof, which are essential components of the liquid crystal aligning agent of the present invention. The same can be given as an example.

Among them, when it is important to further improve the layer separation properties, that is, the alignment property of the liquid crystal, among the diamine and dihydrazide, formula (DI-4-1), formula (DI-4-2), formula ( Diamines and hydras represented by DI-4-10), formula (DI-5-1), formula (DI-5-9), formula (DI-5-28), and formula (DIH-2-1) It is preferable to use a zid, and among these, in formula (DI-5-1), m = 1, 2, or 4 is preferable, and m = 1 or 2 is especially preferable.

When it is important to improve the transmittance, among the diamines and dihydrazides, formulas (DI-1-2), formulas (DI-2-1), formulas (DI-5-1), and formulas (DI) It is preferable to use the diamine represented by -7-3), and the diamine represented by a formula (DI-2-1) is especially preferable. In the formula (DI-5-1), m = 1, 2, or 4 is preferable, m = 1 or 2 is particularly preferable, and in the formula (AN-7-3), m = 2, or 3, n=1, or 2 is preferred, and m=1 is particularly preferred.

When attaching importance to improving the VHR of a liquid crystal display element, a formula (DI-2-1), a formula (DI-4-1), a formula (DI-4-2), among the said diamine and dihydrazide, Diamines represented by formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula (DI-13-1) It is preferable to use, and the diamines represented by a formula (DI-2-1), a formula (DI-5-1), and a formula (DI-13-1) are especially preferable. Among them, in the formula (DI-5-1), m = 1 or 2 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable.

It is effective as one of the methods of preventing burn-in to improve the relaxation rate of the residual electric charge (residual DC) in an alignment film by reducing the volume resistance value of a liquid crystal aligning film. When this purpose is emphasized, among the above diamines and dihydrazides, formula (DI-4-1), formula (DI-4-2), formula (DI-4-10), formula (DI-4- 15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula ( It is preferable to use diamines represented by DI-5-30) and formula (DI-16-1), formula (DI-4-1), formula (DI-5-1), and formula (DI- 5-12) is particularly preferred. Among them, in the formula (DI-5-1), m = 1 or 2 is preferable, in the formula (DI-5-12), m = 2 to 6 are preferable, and m = 5 is particularly preferable. , In the formula (DI-5-13), m = 1 or 2 is preferred, m = 1 is particularly preferred, and in the formula (DI-5-30), k = 2 is particularly preferred.

It is preferable to contain 30 mol% or more of aromatic diamine with respect to all the diamines, and, as for the diamine used in order to synthesize|combine another polyamic acid or its derivative(s), it is more preferable to contain 50% or more.

Another polyamic acid or its derivative(s) can each be synthesize|combined according to what described below as a synthesis|combining method of the polyamic acid which is an essential component of the liquid crystal aligning agent of this invention, or its derivative(s).

As the ratio of component [A] to the total amount of the polyamic acid or its derivative (component [A] above) and other polyamic acids or derivatives thereof (component [B] above) of the present invention, 10% by weight to 100% by weight preferred, more preferably 20% by weight to 100% by weight.

Examples of the polysiloxane include Japanese Patent Application Laid-Open No. 2009-036966, Japanese Patent Application Laid-Open No. 2010-185001, Japanese Patent Application Laid-Open No. 2011-102963, Japanese Patent Application Laid-Open No. 2011-253175, Japanese Patent Application Laid-Open No. 2012-159825, International Publication 2008/044644, 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 Publication 2012/165354 and the like may also contain polysiloxanes.

<Alkenyl-substituted nadimide compound>

For example, the liquid crystal aligning agent of this invention may contain the alkenyl-substituted nadimide compound further for the purpose of stabilizing the electrical characteristic of a liquid crystal display element for a long period of time. An alkenyl-substituted nadimide compound may be used individually by 1 type, and may use 2 or more types together. The content of the alkenyl-substituted nadimide compound is preferably from 1 to 100% by weight, more preferably from 1 to 70% by weight, and further from 1 to 50% by weight relative to the polyamic acid or its derivative for the above purpose. desirable.

Hereinafter, the nadimide compound will be described in detail. It is preferable that the alkenyl-substituted nadimide compound is a compound which can be melt|dissolved in the solvent which melt|dissolves the polyamic acid or its derivative(s) used by this invention. As an example of such an alkenyl-substituted nadimide compound, the compound represented by a following formula (NA) is mentioned.

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 or benzyl having 6 to 12 carbons, n is 1 or 2.

In the formula (NA), when n=1, W is alkyl having 1 to 12 carbon atoms, alkenyl having 2 to 6 carbon atoms, cycloalkyl having 5 to 8 carbon atoms, aryl having 6 to 12 carbon atoms, benzyl, -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H, wherein Z ¹ , Z ² and Z ³ are independently alkylene having 2 to 6 carbon atoms, r is 0 or 1, and k is an integer of 1 to 30), -(Z ⁴ ) _r -BZ ⁵ -H (where Z ⁴ and Z ⁵ are independently alkylene having 1 to 4 carbon atoms or cycloalkylene having 5 to 8 carbon atoms) , B is phenylene, and r is 0 or 1), -BTBH, wherein B is phenylene, and T is -CH ₂ -, -C(CH ₃ ) ₂ - , -O-, -CO-, -S-, or -SO ₂ -), or a group in which 1 to 3 hydrogens of these groups are substituted with -OH.

In this case, preferred W is alkyl having 1 to 8 carbons, alkenyl having 3 to 4 carbons, cyclohexyl, phenyl, benzyl, poly(ethyleneoxy)ethyl having 4 to 10 carbons, phenyloxyphenyl, phenylmethylphenyl, phenyliso 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 alkylene having 2 to 20 carbon atoms, cycloalkylene having 5 to 8 carbon atoms, arylene having 6 to 12 carbon atoms, -Z ¹ -O-(Z ² O ) _k -Z ³ -, wherein ^{the meanings of Z 1 to Z 3} and k are as described above, -Z ⁴ -BZ ⁵ -, wherein the meanings of ^{Z 4} , Z ^{5 and B are} as described above), -B-(OB) _r -T-(BO) _r -B- (wherein B is phenylene and T is alkylene having 1 to 3 carbon atoms, -O- or -SO ₂ -, and the meaning of r is as described above), or a group in which 1 to 3 hydrogens of these groups are substituted with -OH.

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

Such an alkenyl-substituted nadimide compound is obtained by synthesizing, for example, as described in Japanese Patent 2729565, an alkenyl-substituted nadic anhydride derivative and a diamine at a temperature of 80 to 220°C for 0.5 to 20 hours. A compound or a commercially available compound can be used. As a specific example of an alkenyl-substituted nadimide compound, the compound shown below is mentioned.

N-methylallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-methylallylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide , N-methylmethallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-methylmethallylmethylbicyclo[2.2.1]hepto-5-ene-2,3-di Carboxyimide, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide;

N-(2-Ethylhexyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-allyl-allylbicyclo[2.2.1]hepto-5- N-2,3-dicarboxyimide, N-allyl-allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-allyl-methallylbicyclo[2.2.1]hepto -5-ene-2,3-dicarboxyimide, N-isopropenyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-allyl (methyl )bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-isopropenyl-methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide; N-Cyclohexyl-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-cyclohexyl-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2 ,3-dicarboxyimide, N-cyclohexyl-methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-phenyl-allylbicyclo[2.2.1]hepto-5- ene-2,3-dicarboxyimide;

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

N-(2,2-Dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2,2-dimethyl-3-hyde Roxypropyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide, N-(2,3-dihydroxypropyl)-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyi Mead, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide;

N-(4-hydroxyphenyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(4-hydroxyphenyl)-allyl(methyl)bicyclo[2.2 .1]hepto-5-ene-2,3-dicarboxyimide, N-(4-hydroxyphenyl)-methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N -(4-hydroxyphenyl)-methallylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1 ]hepto-5-ene-2,3-dicarboxyimide, N-(3-hydroxyphenyl)-allyl (methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide; N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-{2-(2-hydroxyethoxy)ethyl}-allylbi cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide;

N-{2-(2-hydroxyethoxy)ethyl}-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-{2-(2-hydr Roxyethoxy)ethyl}-methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-{2-(2-hydroxyethoxy)ethyl}-methallylmethylbicyclo [2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2.1]hepto -5-ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl(methyl)bicyclo[2.2.1]hepto-5- ene-2,3-dicarboxyimide, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methallylbicyclo[2.2.1]hepto-5-ene-2,3- Dicarboxyimide, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-{4-( 4-Hydroxyphenylisopropylidene)phenyl}-allyl(methyl)bicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, N-{4-(4-hydroxyphenylisopropyl lidene)phenyl}-methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide, and oligomers thereof;

N,N'-ethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N '-Trimethylenebis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-hexamethylenebis(allylbicyclo[2.2.1]hepto-5- ene-2,3-dicarboxyimide), N,N'-hexamethylenebis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-dode Camethylenebis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylenebis(allylmethylbicyclo[2.2.1]hepto-5- ene-2,3-dicarboxyimide), N,N'-cyclohexylenebis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-cyclo hexylenebis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide);

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

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

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

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

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

1,4-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)-2,5-dihydroxybenzene, N,N'-p-(2-hydro Roxy)xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-(2-hydroxy)xylylene-bis( Allylmethylcyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis(allylbicyclo[2.2.1] hepto-5-ene-2,3-dicarboxyimide), N,N'-m-(2-hydroxy)xylylene-bis(methallylbicyclo[2.2.1]hepto-5-ene-2, 3-dicarboxyimide), N,N'-p-(2,3-dihydroxy)xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide ),

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

The alkenyl-substituted nadimide 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, preferred compounds are shown below. N,N'-ethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(allylmethylbicyclo[2.2.1] Hepto-5-ene-2,3-dicarboxyimide), N,N'-ethylene-bis(methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N '-Trimethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide), N,N'-hexamethylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N '-dodecamethylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1 ]hepto-5-ene-2,3-dicarboxyimide), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-cyclohexylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide),

N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-phenylene-bis(allylmethyl ratio Cyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m-phenylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3 -dicarboxyimide), N,N'-m-phenylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-{(1 -Methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-xylylene-bis( Allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene -2,3-dicarboxyimide), N,N'-m-xylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), N,N'-m -xylene-bis(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hepto) -5-ene-2,3-dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hepto-5-ene-2,3) -dicarboxyimide)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methallylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenoxy}phenyl ]propane, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hepto- 5-ene-2,3-dicarboxyimide)phenyl}methane.

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

More preferable alkenyl-substituted nadimide compounds are shown below.

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

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

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

And as a particularly preferable alkenyl-substituted nadimide compound, bis{4-(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide)phenyl represented by the following formula (NA-1) } methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide) represented by the formula (NA-2), and the formula N,N'-hexamethylenebis(allylbicyclo[2.2.1]hepto-5-ene-2,3-dicarboxyimide) represented by (NA-3) is exemplified.

<Compound having a radically polymerizable unsaturated double bond>

For example, the liquid crystal aligning agent of this invention may contain the compound which has a radically polymerizable unsaturated double bond further for the purpose of stabilizing the electrical characteristic of a liquid crystal display element for a long period of time. One type of compound may be sufficient as the compound which has a radically polymerizable unsaturated double bond, and 2 or more types of compounds may be sufficient as it. In addition, the alkenyl-substituted nadimide compound is not contained in the compound which has a radically polymerizable unsaturated double bond. 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, more preferably 1 to 50% by weight relative to the polyamic acid or its derivative for the above purpose. It is more preferable that

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl-substituted nadimide compound reduces the ion density of the liquid crystal display device, suppresses an increase in ion density over time, and suppresses the generation of an afterimage. For this purpose, the compound/alkenyl-substituted nadimide compound having a radically polymerizable unsaturated double bond is preferably 0.1 to 10, more preferably 0.5 to 5, by weight.

Hereinafter, the compound having a radically polymerizable unsaturated double bond will be described in detail. Examples of the compound having a radical polymerizable unsaturated double bond include (meth)acrylic acid derivatives such as (meth)acrylic acid ester and (meth)acrylic acid amide, and bismaleimide. It is more preferable that the compound which has a radically polymerizable unsaturated double bond is a (meth)acrylic acid derivative which has two or more radically polymerizable unsaturated double bonds.

Specific examples of the (meth)acrylic acid ester include, for example, (meth)acrylic acid cyclohexyl, (meth)acrylic acid-2-methylcyclohexyl, (meth)acrylic acid dicyclopentanyl, (meth)acrylic acid dicyclopentanyloxyethyl, (meth)acrylic acid dicyclopentanyloxyethyl ) acrylic acid isoboronyl, (meth)acrylic acid phenyl, (meth)acrylic acid benzyl, (meth)acrylic acid-2-hydroxyethyl, and (meth)acrylic acid-2-hydroxypropyl.

Specific examples of the bifunctional (meth)acrylic acid ester include, for example, ethylene bisacrylate, Aronix M-210, Aronix M-240 and Aronix M-6200 manufactured by Toa Synthetic Chemical Industries, Ltd., Nippon Gunpowder ( KAYARADHDDA, KAYARADHX-220, KAYARADR-604 and KAYARADR-684 manufactured by Osaka Organic Chemical Co., Ltd., V260, V312 and V335HP manufactured by Osaka Organic Chemical Co., Ltd., and light acrylate BA-, manufactured by Kyoeisha Oil and Chemical Industry Co., Ltd. 4EA, light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth)acrylic acid ester include, for example, 4,4'-methylenebis(N,N-dihydroxyethyleneacrylate aniline), Aronix manufactured by Toa Synthetic Chemical Industry Co., Ltd. M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, KAYARADTMPTA, KAYARADDPCA-20, KAYARADDPCA-30 manufactured by Nippon Explosives Co., Ltd. , 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, for example, N-isopropylacrylamide, N-isopropylmethacrylamide, Nn-propylacrylamide, Nn-propylmethacrylamide, N-cyclopropylacrylamide, N -Cyclopropylmethacrylamide, N-ethoxyethylacrylamide, N-ethoxyethylmethacrylamide, N-tetrahydrofurfurylacrylamide, N-tetrahydrofurfurylmethacrylamide, N-ethylacrylamide, N -Ethyl-N-methylacrylamide, N,N-diethylacrylamide, N-methyl-Nn-propylacrylamide, N-methyl-N-isopropylacrylamide, N-acryloylpiperidine, N-acrylamide Roylpyrrolidine, N,N'-methylenebisacrylamide, N,N'-ethylenebisacrylamide, N,N'-dihydroxyethylenebisacrylamide, N-(4-hydroxyphenyl)methacrylamide , N-phenylmethacrylamide, N-butylmethacrylamide, N-(iso-butoxymethyl)methacrylamide, N-[2-(N,N-dimethylamino)ethyl]methacrylamide, N,N -Dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-(methoxymethyl)methacrylamide, N-(hydroxymethyl)-2-methacrylamide, N-benzyl- 2-methacrylamide, and N,N'-methylenebismethacrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylenebisacrylamide, ethylenebisacrylate, and 4,4'-methylenebis(N,N-di hydroxyethylene acrylate aniline) is particularly preferred.

As the bismaleimide, for example, BMI-70 and BMI-80 manufactured by K-I Chemicals Co., Ltd., and BMI-1000, BMI-3000, BMI-4000, BMI manufactured by Daiwa Chemical Industries, Ltd. -5000 and BMI-7000.

<Oxazine compound>

For example, the liquid crystal aligning agent of this invention may contain the oxazine compound further from the objective of stabilizing the electrical characteristic in a liquid crystal display element for a long period of time. One type of compound may be sufficient as an oxazine compound, and 2 or more types of compounds may be sufficient as it. It is preferable that content of an oxazine compound is 0.1 to 50 weight% with respect to a polyamic acid or its derivative(s) for the said objective, It is more preferable that it is 1 to 40 weight%, It is more preferable that it is 1 to 20 weight%.

Hereinafter, the oxazine compound will be described in detail.

It is preferable that an oxazine compound is an oxazine compound which can melt|dissolve in the solvent which dissolves a polyamic acid or its derivative(s), and has ring-opening polymerizability.

In addition, the number of oxazine structures in an oxazine compound is not specifically limited.

Various structures are known for the structure of oxazine. In the present invention, the structure of the oxazine is not particularly limited. Examples of the structure of the oxazine in the oxazine compound include the structure of an oxazine having an aromatic group containing a condensed polycyclic aromatic group, such as benzoxazine or naphthooxazine. can

Examples of the oxazine compound include compounds represented by the following formulas (OX-1) to (OX-6). And in the following formula, the bond indicated toward the center of the ring indicates that it is bonded to any one carbon constituting the ring and capable of bonding to a substituent.

In formulas (OX-1) to (OX-3), L ³ and L ⁴ are organic groups having 1 to 30 carbon atoms, and in formulas (OX-1) to (OX-6), L ⁵ to L ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms, and in formulas (OX-3), (OX-4) and (OX-6), Q ¹ is 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-, where v is an integer of 1 to 6, and in Formulas (OX-5) and (OX-6), Q ² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, or alkylene having 1 to 3 carbon atoms, and in Q ² The hydrogen couple|bonded with the benzene ring and the naphthalene ring may be independently _{substituted with -F, -CH 3} , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ .

Moreover, the oligomer and polymer which have an oxazine structure in a side chain, and the oligomer and polymer which have an oxazine structure in a main chain are contained in an oxazine compound.

Examples of the oxazine compound represented by the formula (OX-1) include the following oxazine compounds.

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

In the formula (OX-3-I), L ³ and L ⁴ are 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 -. Examples of the oxazine compound represented by the formula (OX-3-I) include the following oxazine compounds.

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

Examples of the oxazine compound represented by the formula (OX-4) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-5) include the following oxazine compounds.

Examples of the oxazine compound represented by the formula (OX-6) include the following oxazine compounds.

Among these, more preferably, a formula (OX-2-1), a formula (OX-3-1), a formula (OX-3-3), a formula (OX-3-5), a formula (OX-3- 7), formula (OX-3-9), formula (OX-4-1) to formula (OX-4-6), formula (OX-5-3), formula (OX-5-4), and formula The oxazine compounds represented by the formulas (OX-6-2) to (OX-6-4) are exemplified.

The oxazine compound can be prepared by the same method as described in International Publication No. 2004/009708, Japanese Patent Application Laid-Open No. Hei 11-12258, and Japanese Patent Application Laid-Open No. 2004-352670.

The oxazine compound represented by Formula (OX-1) is obtained by making a phenol compound, a primary amine, and an aldehyde react (refer international publication 2004/009708).

The oxazine compound represented by the formula (OX-2) is obtained by reacting by a method of gradually adding a primary amine to formaldehyde, and then adding a compound having a naphthol-based hydroxyl group to the reaction (see International Publication 2004/009708) .

The oxazine compound represented by the formula (OX-3) contains 1 mole of a phenol compound in an organic solvent, at least 2 moles or more of an aldehyde per 1 mole of the phenolic hydroxyl group, and 1 mole of a primary amine, a secondary aliphatic amine; It is obtained by reacting in the presence of a tertiary aliphatic amine or an alkaline nitrogen-containing heterocyclic compound (see International Publication 2004/009708 and Japanese Patent Application Laid-Open No. Hei 11-12258).

The oxazine compounds represented by formulas (OX-4) to (OX-6) are aldehydes such as diamine and formalin having a plurality of benzene rings and organic groups bonding them, such as 4,4'-diaminodiphenylmethane , and phenol are obtained by dehydration condensation reaction in n-butyl alcohol at a temperature of 90°C or higher (refer to Japanese Patent Application Laid-Open No. 2004-352670).

<Oxazoline compound>

For example, the liquid crystal aligning agent of this invention may contain the oxazoline compound further from the objective of stabilizing the electrical characteristic in a liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. One type of compound may be sufficient as an oxazoline compound, and 2 or more types of compounds may be sufficient as it. It is preferable that content of an oxazoline compound is 0.1 to 50 weight% with respect to a polyamic acid or its derivative(s) for the said objective, It is more preferable that it is 1 to 40 weight%, It is more preferable that it is 1 to 20 weight%. Alternatively, the content of the oxazoline compound, when the oxazoline structure in the oxazoline compound is converted into oxazoline, is more preferably 0.1 to 40% by weight relative to the polyamic acid or its derivative for the above purpose.

Hereinafter, the oxazoline compound will be described in detail.

The oxazoline compound may have one type of oxazoline structure in one compound, and may have it 2 or more types. Moreover, although an oxazoline compound should just have one oxazoline structure in one compound, it is preferable to have two or more. Moreover, the polymer which has an oxazoline ring structure in a side chain may be sufficient as an oxazoline compound, and a copolymer may be sufficient as it. The polymer having an oxazoline structure in the side chain may be a homopolymer of a monomer having an oxazoline structure in the side chain, or may be a copolymer of a monomer having an oxazoline structure in the side chain and a monomer not having an 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 two or more monomers having an oxazoline structure in the side chain and a monomer having no oxazoline structure A copolymer may be sufficient.

It is preferable that an oxazoline structure is a structure which exists in an oxazoline compound so that the carbonyl group of a polyamic acid may react with one or both of oxygen and nitrogen in an oxazoline structure.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2-ylmethylene. 2-phenyl-4H-oxazol-5-one, 1,4-bis (4,5-dihydro-2-oxazolyl) benzene, 1,3-bis (4,5-dihydro-2-oxazolyl) ) Benzene, 2,3-bis (4-isopropenyl-2-oxazolin-2-yl) butane, 2,2'-bis-4-benzyl-2-oxazoline, 2,6-bis (isopropyl) -2-oxazolin-2-yl)pyridine, 2,2'-isopropylidenebis(4-tert-butyl-2-oxazoline), 2,2'-isopropylidenebis(4-phenyl-2- oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline). In addition to these, polymers and oligomers having oxazolyl such as Epocross (trade name, manufactured by Nippon Catalyst Co., Ltd.) are also exemplified. Of these, more preferably, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is exemplified.

<Epoxy compound>

For example, the liquid crystal aligning agent of this invention may contain an epoxy compound further for the purpose of stabilizing the electrical characteristic in a liquid crystal display element for a long period of time. One type of compound may be sufficient as an epoxy compound, and 2 or more types of compounds may be sufficient as it. It is preferable that content of an epoxy compound is 0.1 to 50 weight% with respect to a polyamic acid or its derivative(s) for the said objective, It is more preferable that it is 1 to 40 weight%, It is more preferable that it is 1 to 20 weight%.

Hereinafter, the epoxy compound will be described in detail.

As an epoxy compound, the various compound which has one or two or more epoxy rings in a molecule|numerator is mentioned. Examples of the compound having one epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethylpropylene oxide, styrene oxide, hexafluoropropylene oxide Cid, cyclohexeneoxide, 3-glycidoxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, N-glycidylphthalimide, (nonafluoro-N -Butyl)epoxide, perfluoroethylglycidylether, epichlorohydrin, epibromohydrin, N,N-diglycidylaniline, and 3-[2-(perfluorohexyl)ethoxy] -1,2-epoxypropane.

Examples of the compound having two epoxy rings in the molecule include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, 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'-epoxycyclohexenecarboxylate 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-bis[4-([2, 3-epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Tecmore VG3101L", manufactured by Mitsui Chemicals Co., Ltd.).

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- m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane , and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxysilane.

In addition to the above, examples of the compound having an epoxy ring in the molecule include oligomers and polymers having an epoxy ring. Examples of the monomer having an epoxy ring include glycidyl (meth) acrylate, 3,4-epoxycyclohexyl (meth) acrylate, and methyl glycidyl (meth) acrylate.

As another monomer copolymerized with a monomer having an epoxy ring, for example, (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl ( meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl)methyl(meth)acrylate, N-cyclohexylmaleimide and N-phenylmaleimide.

As a preferable specific example of the polymer of the monomer which has an epoxy ring, polyglycidyl methacrylate etc. are mentioned. Moreover, as a preferable specific example of the copolymer of the monomer which has an epoxy ring, and another monomer, 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-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N' ,N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Tekmore VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, Particular preference is given to N-phenylmaleimide-glycidylmethacrylate copolymer, and 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane.

More systematically, as the epoxy compound, for example, glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidylamide, glycidyl isocyanurate, chain aliphatic epoxy compound, and a cyclic aliphatic epoxy compound. In addition, 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, glycidylamine, epoxy group-containing acrylic resin, glycidylamide, glycidyl isocyanurate, chain aliphatic epoxy compound, and cyclic fat There are foot type epoxy compounds.

As glycidyl ether, for example, a bisphenol A epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a bisphenol type epoxy compound, a hydrogenated bisphenol A type epoxy compound, a hydrogenated bisphenol F type epoxy compound, a hydrogenation Bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, phenol novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolak type epoxy compound , Brominated cresol novolak epoxy compound, bisphenol A novolak epoxy compound, naphthalene skeleton-containing epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadienephenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compounds, polysulfide-type diglycidyl ether compounds, and biphenol-type epoxy compounds.

As glycidyl ester, there exist a diglycidyl ester compound and a glycidyl ester epoxy compound, for example.

As glycidylamine, there exist a polyglycidylamine compound and a glycidylamine type epoxy resin, for example.

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

As glycidylamide, there exists a glycidylamide type epoxy compound, for example.

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

As a cyclic aliphatic epoxy compound, there exists a compound containing an epoxy group obtained by oxidizing the carbon-carbon double bond of a cycloalkene compound, for example.

Examples of the bisphenol A epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, jER1010 (all manufactured by Mitsubishi Chemical Co., Ltd.), Epottoto YD-128 (manufactured by Toto Chemical Co., Ltd.), DER -331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Epicro 840, Epicro 850, Epicro 1050 (all manufactured by DIC Corporation), Epomic R-140, Epomic R-301 , and Epomic R-304 (all manufactured by Mitsui Chemicals).

Examples of the bisphenol F-type epoxy compound include jER806, jER807, jER4004P (all manufactured by Mitsubishi Chemical Co., Ltd.), EPOTTO YDF-170, EPOTTO YDF-175S, and EPOTTO YDF-2001 (all Toto). There are DER-354 (manufactured by Dow Chemical Co., Ltd.), Epicro 830, and Epicro 835 (all manufactured by DIC Corporation).

As a bisphenol-type epoxy compound, there exists an epoxide of 2, 2-bis (4-hydroxyphenyl) -1,1,1,3,3,3-hexafluoropropane, for example.

Examples of the hydrogenated bisphenol-A epoxy compound include Santoto ST-3000 (manufactured by Toto Chemical Co., Ltd.), Rika Resin HBE-100 (manufactured by Nippon Ewha Co., Ltd.), and Denacol EX-252 (Nagase). Chemtex Co., Ltd.).

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

Examples of the brominated bisphenol-A epoxy compound include jER5050, jER5051 (all manufactured by Mitsubishi Chemical Co., Ltd.), Epottoto YDB-360, Epottoto YDB-400 (all manufactured by Toto Chemicals, Ltd.), DER -530, DER-538 (all manufactured by The Dow Chemical Company), Epicro 152, and Epicro 153 (all manufactured by DIC Corporation).

As a phenol novolak-type epoxy compound, for example, jER152, jER154 (all are manufactured by Mitsubishi Chemical Corporation), YDPN-638 (all are manufactured by Toto Chemical Company), DEN431, DEN438 (all are manufactured by The Dow Chemical Company), Epicro N -770 (manufactured by DIC Co., Ltd.), EPPN-201, and EPPN-202 (all manufactured by Nippon Explosives Co., Ltd.).

As a cresol novolak-type epoxy compound, for example, jER180S75 (manufactured by Mitsubishi Chemical Co., Ltd.), YDCN-701, YDCN-702 (all manufactured by Toto Chemical Co., Ltd.), Epiqro N-665, Epiqro N-695 (all of them) DIC Corporation), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (all manufactured by Nippon Explosives Co., Ltd.).

Examples of the bisphenol A novolak-type epoxy compound include jER157S70 (manufactured by Mitsubishi Chemical Co., Ltd.) and Epicro N-880 (manufactured by DIC Corporation).

Examples of the naphthalene skeleton-containing epoxy compound include Epicro HP-4032, Epicro HP-4700, Epicro HP-4770 (all manufactured by DIC Corporation), and NC-7000 (manufactured by Nippon Kayaku Co., Ltd.).

As the aromatic polyglycidyl ether compound, for example, hydroquinone diglycidyl ether (formula EP-1), catechol diglycidyl ether (formula EP-2), resorcinol diglycidyl ether ( Formula EP-3), 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4-([2,3-epoxypropoxy]phenyl) ]ethyl]phenyl]propane (formula EP-4 below), tris(4-glycidyloxyphenyl)methane (formula EP-5 below), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 ( The Dow Chemical Company), Denacol EX-201 (manufactured by Nagase Chemtex Co., Ltd.), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Explosives Co., Ltd.), Tecmore VG3101L (Mitsui) Chemical Co., Ltd.), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

Examples of the dicyclopentadienephenol type epoxy compound include TACTIX-556 (manufactured by The Dow Chemical Company) and Epicro HP-7200 (manufactured by DIC Corporation).

Examples of the alicyclic diglycidyl ether compound include a cyclohexanedimethanol diglycidyl ether compound and Rika Resin DME-100 (manufactured by Nippon Ewha Co., Ltd.).

As an aliphatic polyglycidyl ether compound, For example, ethylene glycol diglycidyl ether (the following formula EP-8), diethylene glycol diglycidyl ether (the following formula EP-9), polyethyleneglycol diglycidyl Ether, propylene glycol diglycidyl ether (the following formula EP-10), tripropylene glycol diglycidyl ether (the following formula EP-11), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether (Formula EP-12 below), 1,4-butanediol diglycidyl ether (Formula EP-13), 1,6-hexanediol diglycidyl ether (Formula EP-14 below), dibromoneopentyl glycol diglycidyl ether (formula EP-15), denacol EX-810, denacol EX-851, denacol EX-8301, denacol EX-911, denacol EX-920, denacol EX-931, Denacol EX-211, Denacol EX-212, Denacol EX-313 (all manufactured by Nagase Chemtex Co., Ltd.), DD-503 (manufactured by ADEKA Co., Ltd.), Rika Resin W-100 (New Nippon Ewha Co., Ltd.) ), 1,3,5,6-tetraglycidyl-2,4-hexanediol (Formula EP-16 below), glycerin polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether cidyl ether, pentaerythritol polyglycidyl ether, denacol EX-313, denacol EX-611, denacol EX-321, and denacol EX-411 (all manufactured by Nagase Chemtex Co., Ltd.).

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both manufactured by Toraythiochol Co., Ltd.).

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

As the diglycidyl ester compound, for example, diglycidyl terephthalate (formula EP-17 below), diglycidyl phthalate (formula EP-18 below), bis(2-methyloxiranylmethyl)phthalate ( Formula EP-19), diglycidyl hexahydrophthalate (Formula EP-20), a compound represented by Formula EP-21, a compound represented by Formula EP-22, and Formula EP-23 There are compounds that are

Examples of the glycidyl ester epoxy compound include jER871, jER872 (all manufactured by Mitsubishi Chemical Co., Ltd.), Epiqro 200, Epicro 400 (all manufactured by DIC Corporation), denacol EX-711, and denacol There is EX-721 (all manufactured by Nagase Chemtex Co., Ltd.).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (Formula EP-24 below), N,N-diglycidyl-o-toluidine (Formula EP-25 below), N ,N-diglycidyl-m-toluidine (formula EP-26 below), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27 below), 3-(N ,N-diglycidyl)aminopropyltrimethoxysilane (formula EP-28 below), N,N,O-triglycidyl-p-aminophenol (formula EP-29 below), N,N,O- Triglycidyl-m-aminophenol (formula EP-30), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (formula EP-31), N ,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-32), 1,3-bis(N,N -diglycidylaminomethyl)cyclohexane (TETRAD-C (manufactured by Mitsubishi Gas Chemical Co., Ltd.), the following formula EP-33), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (Formula EP-34 below), 1,3-bis(N,N-diglycidylamino)cyclohexane (Formula EP-35 below), 1,4-bis(N,N-diglycidylamino) Cyclohexane (formula EP-36 below), 1,3-bis(N,N-diglycidylamino)benzene (formula EP-37 below), 1,4-bis(N,N-diglycidylamino) ) benzene (following formula EP-38), 2,6-bis(N,N-diglycidylaminomethyl)bicyclo[2.2.1]heptane (following formula EP-39), N,N,N', N'-tetraglycidyl-4,4'-diaminodicyclohexylmethane (formula EP-40), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl) -4,4'-diaminophenyl (following formula EP-41), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl ether (following formula EP-42); 1,3,5-tris(4-(N,N-diglycidyl)aminophenoxy)benzene (formula EP-43 below), 2,4,4'-tris(N,N-diglycidyl) Amino) diphenyl ether (following formula EP-44), tris (4-(N,N-diglycidyl) aminophenyl) methane (following formula EP-45), 3,4,3',4'-tetra kiss (N,N-diglycidylamino)biphenyl (formula EP -46), 4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (the following formula EP-47), and a compound represented by the following formula EP-48.

As a homopolymer of the monomer which has oxiranyl, there exists polyglycidyl methacrylate, for example. As the copolymer of the monomer having oxiranyl, for example, N-phenylmaleimide-glycidylmethacrylate copolymer, N-cyclohexylmaleimide-glycidylmethacrylate copolymer, benzylmethacrylate- Glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxeta nyl)methylmethacrylate-glycidylmethacrylate copolymer, and styrene-glycidylmethacrylate copolymer.

Examples of the oxiranyl-containing monomer 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, iso-butyl (meth) acrylate, tert-butyl (meth) acrylate, cyclohexyl (meth) acrylate, benzyl (meth) acrylate, 2-hydroxyethyl (meth) acrylic Late, 2-hydroxypropyl (meth) acrylate, styrene, methylstyrene, chloromethylstyrene, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, N-cyclohexylmaleimide, and N- phenylmaleimide.

As glycidyl isocyanurate, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (below Formula EP-50), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (the following formula EP-51 ), and a glycidyl isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Epolide PB3600 (manufactured by Daicel Corporation).

Examples of the cyclic aliphatic epoxy compound include 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (Celoxide 2021, manufactured by Daicel Corporation), the following formula EP-52 ), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3',4'-epoxycyclohexylcarboxylate (following formula EP-53), 2,3-epoxycyclopentane-2' ,3'-epoxycyclopentane ether (following formula EP-54), ε-caprolactone-modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexane carboxylate, 1,2:8,9 -diepoxylimonene (Celoxide 3000 (manufactured by Daicel Co., Ltd.), the following formula EP-55), a compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all of The Ciba- Geigy Chemical Corp. (available from Huntsman Japan Co., Ltd.), EHPD-3150 (manufactured by Daicel Corporation), and a cyclic aliphatic epoxy resin.

The epoxy compound is preferably at least one of a polyglycidyl amine compound, a bisphenol A novolak type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic type epoxy compound, N,N,N',N'-tetra Glycidyl-m-xylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4'-dia minodiphenylmethane, trade name "Tecmore VG3101L", 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate, N-phenylmaleimide-glycidylmethacrylate copolymer, At least one of N,N,O-triglycidyl-p-amino phenol, bisphenol A novolak-type epoxy compound, and cresol novolac-type epoxy compound is preferable.

Moreover, for example, the liquid crystal aligning agent of this invention may contain various additives further. Various additives include, for example, high molecular weight compounds other than polyamic acid and derivatives thereof, and low molecular weight compounds, which can be selected and used according to the respective purpose.

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

In addition, as the said low molecular weight compound, for example, 1) a surfactant for this purpose when an improvement in applicability is desired, 2) an antistatic agent when an antistatic improvement is required, 3) When an improvement of adhesiveness with a board|substrate is desired, A silane coupling agent or a titanium-based coupling agent, and 4) an imidation catalyst when imidation is carried out at a low temperature.

As the silane coupling agent, for example, vinyltrimethoxysilane, vinyltriethoxysilane, N-(2-aminoethyl)-3-aminopropylmethyldimethoxysilane, N-(2-aminoethyl)-3- Aminopropylmethyltrimethoxysilane, paraaminophenyltrimethoxysilane, paraaminophenyltriethoxysilane, metaaminophenyltrimethoxysilane, metaaminophenyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3 -Aminopropyltriethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-chloropropylmethyldimethoxysilane, 3-chloropropyltrimethoxysilane, 3- Methacryloxypropyltrimethoxysilane, 3-mercaptopropyltrimethoxysilane, N-(1,3-dimethylbutylidene)-3-(triethoxysilyl)-1-propylamine, and N,N '-bis[3-(trimethoxysilyl)propyl]ethylene diamine. A preferred silane coupling agent is 3-amino propyltriethoxysilane.

Examples of the imidization catalyst 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; Pyridine, methyl substituted pyridine, hydroxy substituted pyridine, quinoline, methyl substituted quinoline, hydroxy substituted quinoline, isoquinoline, methyl substituted isoquinoline, hydroxy substituted isoquinoline, imidazole, methyl substituted imidazole, hydroxy substituted imidazole, etc. of cyclic amines. The imidization catalyst is one or more selected from N,N-dimethylaniline, o-, m-, p-hydroxyaniline, o-, m-, p-hydroxypyridine, and isoquinoline. desirable.

The addition amount of a silane coupling agent is 0 to 20 weight% of the total weight of a polyamic acid or its derivative(s) normally, and it is preferable that it is 0.1 to 10 weight%.

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

Although the addition amount of another additive changes with the use, it is 0-100 weight% of the total weight of a polyamic acid or its derivative(s) normally, and it is preferable that it is 0.1-50 weight%.

The polyamic acid or its derivative of this invention can be manufactured by the method similar to the well-known polyamic acid or its derivative(s) used for formation of the film|membrane of a polyimide. It is preferable that the total amount of the tetracarboxylic dianhydride charged is approximately equal to the total number of moles of diamine (a molar ratio of about 0.9 to 1.1).

It is a weight average molecular weight (Mw) of polystyrene conversion, and, as for the molecular weight of the polyamic acid of this invention or its derivative(s), it is preferable that it is 7,000-500,000, and it is more preferable that it is 10,000-200,000. The molecular weight of the said polyamic acid or its derivative(s) can be measured and calculated|required by gel permeation chromatography (GPC) method.

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

Moreover, for example, the liquid crystal aligning agent of this invention may contain the solvent further from a viewpoint of the applicability|paintability of a liquid crystal aligning agent, and adjustment of the density|concentration of the said polyamic acid or its derivative(s). The solvent can be applied without particular limitation as long as it has the ability to dissolve the polymer component. The solvent includes a wide range of solvents commonly used in the production process and use of polymer components such as polyamic acid and soluble polyimide, and may be appropriately selected according to the purpose of use. The number of said solvents may be one, or 2 or more types of mixed solvent may be sufficient as them.

As a solvent, the solvent-friendly agent of the said polyamic acid or its derivative(s), and the other solvent aiming at the improvement of applicability|paintability are mentioned.

Examples of the aprotic polar organic solvent that is a good solvent for 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 γ-butyrolactone.

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

Among these, the solvent is N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol It is especially preferable that they are monomethyl ether and dipropylene glycol monomethyl ether.

It is preferable that the density|concentration of the polyamic acid in the aligning agent of this invention is 0.1 to 40 weight%. When apply|coating this aligning agent to a board|substrate, operation which dilutes the polyamic acid contained with a solvent beforehand may be necessary for film thickness adjustment.

The solid content concentration in the aligning agent of this invention is not specifically limited, What is necessary is just to select the optimal value suitable for the following various application|coating methods. Usually, in order to suppress nonuniformity, pinholes, etc. at the time of application|coating, with respect to the weight of varnish, Preferably it is 0.1 to 30 weight%, More preferably, it is 1 to 10 weight%.

The viscosity of the liquid crystal aligning agent of this invention differs in the preferable range with the method of apply|coating, the density|concentration of a polyamic acid or its derivative(s), the kind of polyamic acid or its derivative(s) used, and the kind and ratio of a solvent. For example, in the case of application by a printing press, it is 5 to 100 mPa·s (more preferably 10 to 80 mPa·s). When it is smaller than 5 mPa*s, it becomes difficult to obtain a sufficient film thickness, and when it exceeds 100 mPa*s, printing nonuniformity may become large. In the case of application by spin coating, 5 to 200 mPa·s (more preferably 10 to 100 mPa·s) is suitable. When applying using an inkjet coating device, 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 viscometer, for example, using a rotational viscometer (TVE-20L type, manufactured by Toki Industries, Ltd.) (measurement temperature: 25°C).

The liquid crystal aligning film of this invention is demonstrated in detail. The liquid crystal aligning film of this invention is a film|membrane formed by heating the coating film of the liquid crystal aligning agent of this invention mentioned above. The liquid crystal aligning film of this invention can be obtained with the normal method of producing a liquid crystal aligning film from a liquid crystal aligning agent. For example, the liquid crystal aligning film of this invention can be obtained by passing the process of forming the coating film of the liquid crystal aligning agent of this invention, the process of heat-drying, and the process of heating and baking. About the liquid crystal aligning film of this invention, so that it may mention later, as needed, the film|membrane obtained through a heat-drying process and a heat-firing process can be rubbed, and anisotropy can also be provided. Alternatively, anisotropy may be imparted by irradiating light after the coating film step or heat drying step, or irradiating light after the heat firing step as needed. Moreover, it can be used also as a liquid crystal aligning film for VA which did not perform a rubbing process.

A coating film can be formed by apply|coating the liquid crystal aligning agent of this invention to the board|substrate in a liquid crystal display element similarly to preparation of a normal liquid crystal aligning film. As the substrate, an electrode such as ITO (Indium Tin Oxide), IZO (In ₂ O ₃ -ZnO), IGZO (In-Ga-ZnO ₄ ) electrode, or a glass substrate on which a color filter can be installed can be exemplified. .

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

As for the said heat-drying process, the method of heat-processing in oven or infrared furnace, the method of heat-processing on a hotplate, etc. are generally known. The heat drying step is preferably performed at a temperature within the range where the solvent can be evaporated, and more preferably performed at a relatively low temperature with respect to the temperature in the heat firing step. Specifically, it is preferable that heat-drying temperature is the range of 30 degreeC - 150 degreeC, Furthermore, it is the range of 50 degreeC - 120 degreeC.

The said heat-firing process can be performed under the conditions required for the said polyamic acid or its derivative(s) to make|form a dehydration and ring closure reaction. As for the baking of the said coating film, the method of heat-processing in oven or infrared furnace, the method of heat-processing on a hot plate, etc. are generally known. These methods are similarly applicable in the present invention. Generally, it is preferable to carry out at a temperature of about 100-300 degreeC for 1 minute to 3 hours, 120-280 degreeC is more preferable, 150-250 degreeC is still more preferable.

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

The liquid crystal aligning film of this invention using the rubbing method, the process of apply|coating the liquid crystal aligning agent of this invention to a board|substrate, the process of heat-drying the board|substrate to which the aligning agent was apply|coated, the process of heat-firing the film, and rubbing the film|membrane It can be formed through a process.

A rubbing process can be performed similarly to the rubbing process for the orientation process of a normal liquid crystal aligning film, and what is necessary is just the conditions which can obtain sufficient retardation in the liquid crystal aligning film of this invention. Preferred conditions are a hair press-in amount of 0.2 to 0.8 mm, a stage moving speed of 5 to 250 mm/sec, and a roller rotation speed of 500 to 2,000 rpm.

The formation method of the liquid crystal aligning film of this invention by the photo-alignment method is demonstrated in detail. The liquid crystal aligning film of this invention using the photo-alignment method can provide anisotropy to a coating film by irradiating the linearly polarized light or unpolarized light of a radiation, after heat-drying a coating film, and can form it by heating and baking the film. Alternatively, the coating film can be formed by irradiating linearly polarized light or unpolarized light of a radiation after drying and heating the coating film. From the point of orientation, it is preferable to perform the irradiation process of a radiation before a heat-firing process.

Moreover, in order to raise the liquid-crystal orientation ability of a liquid crystal aligning film, you may irradiate the linearly polarized light or unpolarized light of a radiation, heating a coating film. Irradiation of radiation can also be performed in the process of heat-drying a coating film, or the process of heating and baking, and can also perform it between a heat-drying process and a heat-firing process. It is preferable that the heat-drying temperature in the said process is the range of 30 degreeC - 150 degreeC, Furthermore, it is preferable that it is the range of 50 degreeC - 120 degreeC. Moreover, it is preferable that the heat-firing temperature in the said process is the range of 30 degreeC - 300 degreeC, Furthermore, it is preferable that it is the range of 50 degreeC - 250 degreeC.

As the radiation, for example, although ultraviolet rays or visible rays containing light having a wavelength of 150 to 800 nm can be used, ultraviolet rays containing light having a wavelength of 300 to 400 nm are preferable. It is also possible to use linearly polarized light or unpolarized light. Although these lights will not be specifically limited if it is light which can provide liquid-crystal orientation ability to the said coating film, Linearly polarized light is preferable with respect to a liquid crystal to express strong orientation regulating force.

The liquid crystal aligning film of this invention can show high liquid-crystal orientation ability also in low energy light irradiation. Dose of the linearly polarized light in the irradiation step is preferably 0.05~20 J / cm ^2, and more preferably 0.5~10 J / cm ^2. Moreover, it is preferable that it is 200-400 nm, and, as for the wavelength of linearly polarized light, it is more preferable that it is 300-400 nm. Although the irradiation angle with respect to the film surface of linearly polarized light is not specifically limited, When it wants to express strong orientation regulating force with respect to a liquid crystal, it is preferable from a viewpoint of shortening an orientation treatment time that it is perpendicular|vertical as much as possible with respect to the film surface. Moreover, the liquid crystal aligning film of this invention can orientate a liquid crystal in the direction perpendicular|vertical with respect to the polarization direction of linearly polarized light by irradiating linearly polarized light.

When the pretilt angle is to be expressed, the light irradiated to the film may be linearly polarized light or unpolarized light as described above. If the pre-tilt is desired to express the amount of irradiation light irradiated to each of the membrane should preferably be 0.05~20 J / cm ^2, and 0.5~10 J / cm ² is particularly preferred, the wavelength of 250~400 ㎚ It is preferable, and 300-380 nm is especially preferable. Although the irradiation angle with respect to the said film|membrane surface of the light irradiated to the said film|membrane is not specifically limited when it intends to express a pretilt angle, It is preferable that it is 30 degrees - 60 degrees from a viewpoint of shortening of orientation treatment time.

Examples of light sources used in the process of irradiating linearly polarized or unpolarized radiation include ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, deep UV lamps, halogen lamps, metal halide lamps, high power metal halide lamps, xenon lamps, mercury Xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, LED lamps, sodium lamps, microwave-excited electrodeless lamps, etc. can be used without limitation.

The liquid crystal aligning film of this invention is preferably obtained by the method further including the process other than the process mentioned above. For example, in the liquid crystal aligning film of the present invention, the step of cleaning the film after firing or irradiation with a cleaning solution is not essential, but a cleaning step may be provided depending on other steps.

Examples of the cleaning method with the cleaning liquid include brushing, jet spraying, steam cleaning, or ultrasonic cleaning. These methods may be performed independently and may be used together. As the cleaning solution, pure water or various alcohols such as methyl alcohol, ethyl alcohol and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene and xylene, halogen-based solvents such as methylene chloride, and ketones such as acetone and methyl ethyl ketone can be used. However, it is not limited to these. Of course, these cleaning liquids are sufficiently purified and contain few impurities. Such a washing|cleaning method is applicable also to the said washing|cleaning process in formation of the liquid crystal aligning film of this invention.

In order to improve the liquid-crystal orientation ability of the liquid crystal aligning film of this invention, before and after a heat baking process, before and after a rubbing process, or before and after irradiation of polarized or unpolarized radiation, annealing treatment by heat or light can be used. In the annealing treatment, the annealing temperature is 30 to 180 deg. C, preferably 50 to 150 deg. C, and the time is preferably 1 minute to 2 hours. In addition, a UV lamp, a fluorescent lamp, an LED lamp, etc. are mentioned as annealing light used for annealing process. It is preferable that the irradiation amount of light is 0.3-10 J/cm<^2>.

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

The liquid crystal aligning film of this invention has especially large orientation anisotropy, It is characterized by the above-mentioned. The magnitude of such anisotropy can be evaluated by a method using polarized IR described in Japanese Patent Application Laid-Open No. 2005-275364 or the like. In addition, as shown in the following examples, the evaluation can also be performed by a method using ellipsommetry. In detail, the retardation value of a liquid crystal aligning film can be measured with a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of orientation of the polymer main chain. That is, what has a large retardation value has a large orientation degree, and when it uses as a liquid crystal aligning film, it is considered that the orientation film which has greater anisotropy has a large orientation regulating force with respect to a liquid crystal composition.

The liquid crystal aligning film of this invention has little coloring and is characterized by the high transmittance|permeability. The transmittance can be evaluated using an ultraviolet-visible spectroscopic altimeter. In order to exhibit favorable display characteristics, it is preferable that the transmittance|permeability calculated from the average value of the absorbance of 380 nm - 780 nm is 85 % or more, and it is more preferable that it is 87 % or more.

The liquid crystal aligning film of this invention can be used suitably for the liquid crystal display element of a transverse electric field system. When using for the liquid crystal display element of a transverse electric field system, the black display level in a dark state becomes high, and contrast improves, so that a Pt angle is small and liquid-crystal orientation ability is high. The Pt angle is preferably 0.1° or less.

The alignment film of the present invention can be used for alignment control of an optical compensator and other liquid crystal materials other than the alignment use of the liquid crystal composition for liquid crystal displays. In addition, since the alignment layer of the present invention has a large anisotropy, it can be used alone for an optical compensator.

The liquid crystal display element of this invention is demonstrated in detail.

The present invention relates to a pair of substrates disposed to face each other, electrodes formed on one or both of the opposing surfaces of each of the pair of substrates, and a liquid crystal formed on each of the opposing surfaces of the pair of substrates. In a liquid crystal display device having an alignment layer and a liquid crystal layer formed between the pair of substrates, the liquid crystal display device is an alignment layer of the present invention, wherein the liquid crystal alignment layer is an alignment layer.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Such an electrode includes, for example, ITO or a metal vapor deposition film. Moreover, the electrode may be formed in the whole surface of one side of a board|substrate, and may be formed in the desired shape patterned, for example. The desired shape of the electrode includes, for example, a comb shape or a zigzag structure. An electrode may be formed in one of a pair of board|substrates, and may be formed in both board|substrates. The form of electrode formation differs depending on the type of liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, the electrode is disposed on one side of the pair of substrates, and in the case of other liquid crystal display elements, the Electrodes are disposed on both sides of the pair of substrates. The liquid crystal alignment layer is formed on the substrate or the electrode.

The liquid crystal layer is formed in such a way that the liquid crystal composition is sandwiched by the pair of substrates in which the surface on which the liquid crystal aligning film is formed is opposed. In the formation of the liquid crystal layer, a spacer, such as fine particles or a resin sheet, interposed between the pair of substrates to form an appropriate space can be used as needed.

The liquid crystal composition is not particularly limited, and various liquid crystal compositions having positive or negative dielectric anisotropy can be used. Preferred liquid crystal compositions having positive dielectric anisotropy include Japanese Patent 3086228, Japanese Patent 2635435, Japanese Patent Application Publication No. Hei 5-501735, Japanese Patent Application Laid-Open No. Hei 8-157826, Japanese Patent Application Laid-Open No. Hei 8-231960, Japanese Patent Application Publication No. Hei 8-231960 Application Publication No. Hei 9-241644 (EP885272A1), Japanese Patent Application Publication No. Hei 9-302346 (EP806466A1), Japanese Patent Application Publication No. Hei 8-199168 (EP722998A1), Japanese Patent Application Publication No. Hei 9-235552, Japanese Patent Application Publication No. Hei 9-255956, Japanese Patent Application Publication No. Hei 9-241643 (EP885271A1), Japanese Patent Application Publication No. Hei 10-204016 (EP844229A1), Japanese Patent Application Publication No. Hei 10-204436, Japanese Patent Application Publication No. Hei 10 -231482, Japanese Patent Application Laid-Open No. 2000-087040, Japanese Patent Application Laid-Open No. 2001-48822 and the like are exemplified liquid crystal compositions.

One or more optically active compounds may be added to the liquid crystal composition having positive or negative dielectric anisotropy.

A liquid crystal composition having a negative dielectric anisotropy will be described. As a liquid crystal composition of negative dielectric anisotropy, for example, there is 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 a first component.

Here, R ^1a and R ^2a are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine. is; Ring A ² and Ring B ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2 -Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl, or 7,8-difluorochroman-2,6-diyl; , 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-phenylene, 2,3-di fluoro-6-methyl-1,4-phenylene, or 7,8-difluorochroman-2,6-diyl; Z ¹ is independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, or -CF ₂ O-; j is 1, 2, or 3.

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

Here, R ^1a and R ^2a are independently alkyl having 1 to 12 carbons, alkoxy having 1 to 12 carbons, alkenyl having 2 to 12 carbons, or alkenyl having 2 to 12 carbons in which at least one hydrogen is substituted with fluorine. to be. Preferred R ^1a and R ^2a are alkyl having 1 to 12 carbon atoms to increase stability against ultraviolet rays or heat, or alkoxy having 1 to 12 carbon atoms to increase the absolute value of dielectric anisotropy.

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

Preferred alkoxy is methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy, or heptyloxy. In order to lower the viscosity, more preferable alkoxy is methoxy or ethoxy.

Preferred alkenyls are vinyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pen tenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. More preferred alkenyl is vinyl, 1-propenyl, 3-butenyl, or 3-pentenyl to lower the viscosity. The preferred configuration of -CH=CH- in these alkenyls depends on the position of the double bond. Trans is preferable for alkenyls such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl and 3-hexenyl for reasons of lowering the viscosity. For alkenyls such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferred. In these alkenyls, straight-chain alkenyls are more preferable than branched ones.

Preferred examples of alkenyl in which at least one hydrogen is substituted with fluorine are 2,2-difluoro vinyl, 3,3-difluoro-2-propenyl, 4,4-difluoro-3-butenyl , 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.

Ring A ² and Ring B ² are independently 1,4-cyclohexylene, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2 -Fluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2-fluoro-3-chloro- 1,4-phenylene, 2,3-difluoro-6-methyl-1,4-phenylene, 2,6-naphthalenediyl, 7,8-difluorochroman-2,6-diyl; 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-phenylene, 2,3-difluoro rho-6-methyl-1,4-phenylene, 7,8-difluorochroman-2,6-diyl, and when j is 2 or 3, any two rings A ² may be the same and may be different. Preferred ring A ² and ring B ² are, respectively, 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl to increase dielectric anisotropy, and 1,4 to decrease viscosity. -Cyclohexylene.

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. Preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each 1,4-cyclohexylene in order to reduce the viscosity.

Z ¹ and Z ² are independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, -CF ₂ O-, and when j is 2 or 3, any two Z ¹ may be the same or different, and when k is 2 or 3, any two Z ² may be the same or different, preferably Z ¹ and Z ² _{are —CH 2} to increase the dielectric anisotropy It is O- and is a single bond to lower the viscosity.

Z ¹¹ and Z ¹² are independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, or -COO-. Preferred Z ¹¹ and Z ¹² _{are —CH 2} O— to increase the dielectric anisotropy, and a single bond to decrease the viscosity.

j is 1, 2, or 3. Preferred j is 1 for lowering the lower limit temperature and 2 for increasing the upper limit temperature.

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

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

Moreover, for example, the liquid crystal composition used for the element of this invention may add an additive further from a viewpoint of improving orientation, for example. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, defoamers, polymerization initiators, polymerization inhibitors, and the like.

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

The photopolymerizable monomer or oligomer is preferably 0.01 wt% or more in order to exhibit the effect of determining the inclination direction of the liquid crystal after polymerization. Moreover, in order to make the orientation effect of the polymer after polymerization appropriate, or in order to avoid that unreacted monomer or oligomer elutes to a liquid crystal after ultraviolet irradiation, it is preferable that it is 30 weight% or less.

An optically active compound is incorporated into the composition for the purpose of inducing the helical structure of the liquid crystal to impart a twist angle. An example of such a compound is a compound (PAC-1-4) from a compound (PAC-1-1). A preferred proportion of the optically active compound is 5% by weight or less. A more preferred proportion is in the range from 0.01% to 2% by weight.

In order to prevent a decrease in resistivity due to heating in the atmosphere, or to maintain a large voltage retention rate not only at room temperature but also at high temperatures after the device is used for a long time, an antioxidant is mixed with the liquid crystal composition.

Preferred examples of the antioxidant are compounds (AO-1) and the like in which w is an integer of 1 to 10. In compound (AO-1), preferable w is 1, 3, 5, 7, or 9. More preferred w is 1 or 7. Since the compound (AO-1) in which w is 1 is highly volatile, it is effective in preventing a decrease in specific resistance due to heating in the air. Since the compound (AO-1) in which w is 7 has low volatility, it is effective for maintaining a large voltage retention not only at room temperature but also at high temperature after the device is used for a long time. The preferable ratio of antioxidant is 50 ppm or more in order to acquire the effect, and in order not to reduce an upper limit temperature, or to not raise a lower limit temperature, it is 600 ppm or less. A more preferable ratio is in the range of 100 ppm to 300 ppm.

Preferred examples of the ultraviolet absorber include benzophenone derivatives, benzoate derivatives, and triazole derivatives. Light stabilizers such as sterically hindered amines are also preferred. The preferable ratio in these water absorbents and stabilizers is 50 ppm or more in order to acquire the effect, and in order not to reduce an upper limit temperature, or to not raise a lower limit temperature, it is 10000 ppm or less. A more preferred ratio is in the range from 100 ppm to 10000 ppm.

A dichroic dye such as an azo dye, an anthraquinone dye, etc. is mixed with the composition in order to be suitable for a GH (guest host) mode device. A preferable proportion of the dye is in the range of 0.01% by weight to 10% by weight.

In order to prevent foaming, an antifoaming agent such as dimethyl silicone oil or methylphenyl silicone oil is 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 display defects. A more preferable ratio is in the range of 1 ppm to 500 ppm.

Polymerizable compounds may be incorporated into the composition for adaptation to devices in polymer sustained alignment (PSA) mode. Preferred 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), and vinyl ketone. Particularly preferred examples are derivatives of acrylates or methacrylates. Examples of such a compound are compound (PM-2-9) from compound (PM-2-1). A preferable proportion of the polymerizable compound is about 0.05 wt% or more to obtain the effect, and about 10 wt% or less for preventing display defects. More preferred proportions range from about 0.1% to about 2% by weight.

wherein R ^3a , R ^4a , R ^5a , and R ^6a are independently acryloyl or methacryroyl, R ^7a and R ^8a are independently hydrogen, halogen, or alkyl having 1 to 10 carbon atoms; 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.

As a substance necessary to easily generate radicals or ions and to initiate a chain polymerization reaction, a polymerization initiator may be mixed. For example, photoinitiators Irgacure651 (registered trademark), Irgacure184 (registered trademark), or Darocure1173 (registered trademark) (Ciba Japan K.K.) are suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1 wt% to 5 wt%. Particularly preferably, the photopolymerization initiator is included in the range of 1 wt% to 3 wt%.

In the radical polymerization system, a polymerization inhibitor can be mixed for the purpose of rapidly reacting with a radical generated from a polymerization initiator or a monomer to be converted into a stable radical or a neutral compound, and as a result, to stop the polymerization reaction. Polymerization inhibitors are classified into several structurally. One is a radical that is itself stable, such as tri-p-nitrophenylmethyl, di-p-fluorophenylamine, etc., and the other is that it easily reacts with radicals present in the polymerization system to change into a stable radical. , typically nitro, nitriso, amino, polyhydroxy compounds, and the like. Examples of the latter include hydroquinone and dimethoxybenzene. The preferable ratio of a polymerization inhibitor is 5 ppm or more in order to acquire the effect, and 1000 ppm or less in order to prevent display defect. A more preferable ratio is in the range of 5 ppm to 500 ppm.

By using the liquid crystal composition which has negative dielectric anisotropy for the liquid crystal display element of this invention, it is excellent in an afterimage characteristic, and the liquid crystal display element with favorable orientation stability can be provided.

[Example]

Hereinafter, the present invention will be described by way of Examples. In addition, the evaluation method and compound used in the Example are as follows.

<Evaluation method>

1. Viscosity

Using a viscometer (manufactured by Toki Industrial Co., Ltd., TV-22), it was measured at 25°C.

2. Weight average molecular weight (Mw)

The weight average molecular weight of a polyamic acid was measured by the GPC method using the 2695 separation module 2414 differential refractometer (made by Waters), and was calculated|required by polystyrene conversion. The obtained polyamic acid was diluted with a phosphoric acid-DMF mixed solution (phosphoric acid/DMF=0.6/100: weight ratio) so that the polyamic acid concentration might be about 2% by weight. As the column, HSPgel RT MB-M (manufactured by Waters) was used, and the mixed solution was used as a developing agent, and measurement was performed at a column temperature of 50° C. and a flow rate of 0.40 mL/min. As standard polystyrene, TSK standard polystyrene manufactured by Tosoh Co., Ltd. was used.

3. Measurement of retardation and film thickness of alignment film

It calculated|required using the spectroscopic ellipsometer M-2000U (made by J. A. Woollam Co. Inc.). In the case of this embodiment, the retardation value of the film increases in proportion to the orientation degree of the polymer main chain. That is, a thing having a large retardation value has a large degree of orientation.

4. Transmittance

The transmittance|permeability of the board|substrate with a liquid crystal aligning film mentioned later was measured, and the average value of the absorbance of 380 nm - 780 nm was computed. An ultraviolet visible spectrophotometer V-660 (manufactured by Japan Spectroscopy Co., Ltd.) was used as the ultraviolet visible spectrophotometer.

5. Pre-tilt angle measurement

It was measured based on the crystal rotation method.

6. Voltage retention

It was carried out by the method described in "Mizushima et al., the 14th Liquid Crystal Discussion Preliminary Collection p78 (1988)". The measurement was performed by applying a rectangular wave with a wavelength height of ±5 V to the cell. The measurement was performed at 60 degreeC. This value is an index indicating how much the applied voltage is maintained after the frame period, and if this value is 100%, it indicates that all charges are maintained.

8. Measurement of the amount of ions in liquid crystal (ion density)

Applied Physics, Vol. 65, No. 10, 1065 (1996) was measured using a liquid crystal physical property measurement system type 6254 manufactured by Toyo Technica. A triangular wave with a frequency of 0.01 Hz was used, and measurements were made at a voltage range of ±10 V and a temperature of 60° C. (the area of the electrode was 1 cm ² ). When the ion density is large, problems such as burn-in due to ionic impurities are likely to occur. That is, the ion density is a physical property value used as an index for predicting the occurrence of burn-in.

<Tetracarboxylic dianhydride>

Acid dianhydride (AN-1-1): 1,2,3,4-butanetetracarboxylic dianhydride

Acid dianhydride (AN-1-2, m=8): 3,3'-(octane-1,8-diyl)bis(dihydrofuran-2,5-dione)

Acid dianhydride (AN-1-13): ethylenediamine tetraacetic dianhydride

Acid dianhydride (AN-2-1): 1,2,3,4,-cyclobutanetetracarboxylic dianhydride

Acid dianhydride (AN-3-1): 1,2,4,5-cyclohexanetetracarboxylic acid dianhydride

Acid dianhydride (AN-3-2): pyromellitic acid dianhydride

Acid dianhydride (AN-4-5): 3,3',4,4'-biphenyltetracarboxylic dianhydride

Acid dianhydride (AN-4-17, m = 4): 1,4-bis (3,4-dicarboxylic acid phenyl) butane dianhydride

Acid dianhydride (AN-4-17, m = 8): 1,8-bis (3,4-dicarboxylic acid phenyl) octane dianhydride

Acid dianhydride (AN-4-21): 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride

Acid dianhydride (AN-4-29): 5,5'-p-phenylenebis (isobenzofuran-1,3-dione)

Acid dianhydride (AN-4-30): N,N'-(1,4-phenylene)bis(1,3-dioxooctahydroisobenzofuran-5-carboxyamide)

Acid dianhydride (AN-7-2): 2,3,5-tricarboxycyclopentylacetic acid dianhydride

Acid dianhydride (AN-10): bicyclo [3.3.0] octane-2,4,6,8-tetracarboxylic dianhydride

<Diamine and dihydrazide>

Diamine (1-1): the diamine compound obtained in the synthesis route of Example 1

Diamine (1-2): the diamine compound obtained in the synthesis route of Example 2

Diamine (1-4): the diamine compound obtained in the synthesis route of Example 3

Diamine (1-5): the diamine compound obtained in the synthesis route of Example 373

Diamine (1-8): a diamine compound obtained according to the synthesis route of Example 1

Diamine (1-12): a diamine compound obtained according to the synthesis route of Example 1

Diamine (1-13): a diamine compound obtained according to the synthesis route of Example 1

Diamine (1-19): the diamine compound obtained in the synthesis route of Example 374

Diamine (DI-1-3): 1,6-diaminohexane

Diamine (DI-2-1): 1,4-cyclohexanediamine

Diamine (DI-4-1): 1,4-phenylenediamine

Diamine (DI-5-1, m = 1): 4,4'-diaminodiphenylmethane

Diamine (DI-5-1, m=2): 4,4'-diaminodiphenylethane

Diamine (DI-5-1, m=4): 4,4'-diaminodiphenylbutane

Diamine (DI-5-9): 4,4'-diaminodiphenyl ether

Diamine (DI-5-12, m=5): 1,5-bis(4-aminophenoxy)pentane

Diamine (DI-5-28): 4,4'-diaminodiphenylamine

Diamine (DI-5-30, k=2): N,N'-bis(4-aminophenyl)-N,N'-dimethylethylene diamine

Diamine (DI-6-7): 4,4'-p-phenylenedianiline

Diamine (DI-7-3, m=3, n=1): 1,3-bis(4-(4-aminophenyl)methyl)phenyl)propane

Diamine (DI-13-1): 4,4'-N,N'-bis(4-aminophenyl)piperazine

Diamine (DI-16-1): 1-(4-aminophenyl)-1H-indol-5-amine

Dihydrazide (DHI-2-1): Terephthalic acid dihydrazide

Diamine (PDI-7-a): 4,4'-diaminoazobenzene

Diamine (PDI-8-a): 4,4'-bis[(4-aminophenyl)methyl]azobenzene

<solvent>

N-methyl-2-pyrrolidone: NMP

Butyl Cellosolve (ethylene glycol monobutyl ether): BC

<Additives>

Additive (Ad1): 1,3-bis (4,5-dihydrooxazolyl) benzene

Additive (Ad2): N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane

Additive (Ad3): 3-Aminopropyltriethoxysilane

[Example 1] Synthesis of compound (1-1)

<Step 1; Protection of the amino group>

1,2-bis(4-aminophenyl)ethane (25.0 g, 117.8 mmol), 4-dimethylaminopyridine (2.9 g, 23.5) in a 500 mL three-necked flask equipped with a thermometer, a nitrogen inlet tube and a dropping funnel mmol) and triethylamine (17.9 g, 176.6 mmol) were added, and 250 mL of dichloromethane was added thereto. The solution was cooled to 0°C. To this, trifluoroacetic anhydride (37.1 g, 176.6 mmol) was added dropwise while maintaining the solution at 0°C. Then, the solution was stirred under a nitrogen atmosphere for 6 hours while maintaining the temperature at 0°C. The reaction solution was put into 250 mL of water, and the organic layer was washed 3 times with pure water. After drying the organic layer with magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized with a mixed solvent of toluene/ethanol = 10/1 to obtain 1-(4-N-trifluoroacetylphenyl)-2-(4-aminophenyl)ethane (amount 33.4 g) , yield 92%).

<Second step; Synthesis of azo compounds>

1-(4-N-trifluoroacetylphenyl)-2-(4-aminophenyl)ethane (30 g, 97.3 mmol) obtained in the first step in a 500 mL 3-neck flask equipped with a reflux tube and a thermometer , sodium peroxoborate tetrahydrate (20.0 g, 131.3 mmol) and boric acid (5.1 g, 84.7 mmol) were added, and 300 mL of acetic acid was added. Sodium peroxoborate tetrahydrate (7.7 g, 48.7 mmol) was added to what was heat-stirred at 60 degreeC for 1 hour, and it heat-stirred for 6 hours further. The reaction solution was put into 600 mL of pure water, and the precipitate was collected by filtration. The obtained precipitate was washed 3 times with pure water, and the obtained crystals were vacuum dried at 60°C for 8 hours to obtain 4,4'-bis(2-(4-N-trifluoroacetylphenyl)ethyl)azobenzene (amount 25.3). g, yield 85%).

<3rd step; Deprotection>

In a three-necked flask equipped with a thermometer and a reflux tube, 4,4'-bis(2-(4-N-trifluoroacetylphenyl)ethyl)azobenzene (25.0 g, 40.8 mmol) obtained in the second step and carbonic acid Potassium (13.5 g, 98.0 mmol) was added, methanol 200 mL, tetrahydrofuran 25 mL, and pure water 10 mL were added. After heating and stirring at 60° C. for 12 hours, the reaction solution was added to 300 mL pure water, and ethyl acetate 500 mL After drying the organic layer with magnesium sulfate, the solvent is distilled off under reduced pressure to obtain crude crystals.Crude crystals are recrystallized with a mixed solvent of toluene/ethanol = 1/1 (volume ratio), and 4,4' -bis(2-(4-aminophenyl)ethyl)azobenzene was obtained (amount 15.5 g, yield 90%).

[Example 2] Synthesis of compound (1-2)

<Step 1; Esterification>

Azobenzene-4,4'-dicarbonyldichloride (25.0 g, 81.4 mmol) and triethylamine (19.8 g, 195.4 mmol) were placed in a three-necked flask equipped with a thermometer and a dropping funnel, and 150 mL of dichloromethane was added. While maintaining this solution at 5° C. or lower, a solution obtained by dissolving 4-(N-tert-butoxycarbonylamino)phenol (34.5 g, 179.1 mmol) in dichloromethane (100 mL) was added dropwise thereto, and room temperature The temperature was raised to , and stirred for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed three times with pure water (300 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain azobenzene-4,4'-bis(4-(N-tert-butoxycarbonylamino)phenyl)dibenzoate (amount 44.6 g, yield 84%).

<Second step; Deprotection>

Azobenzene-4,4'-bis(4-(N-tert-butoxycarbonylamino)phenyl)dibenzoate (44.0 g, 67.4 mm) obtained in the first step was placed in a three-necked flask equipped with a thermometer and a dropping funnel. ol), and dichloromethane (300 mL) was added. A mixed solution of 47% hydrobromic acid (25.5 g, 148.3 mmol) and acetic acid (75 mL) was added dropwise thereto while keeping the solution at 5°C or lower. The reaction solution was heated to room temperature and stirred for 6 hours. To this reaction solution, a saturated aqueous sodium hydrogencarbonate solution was added until the pH of the solution became 7 or higher. This solution was put into water (500 mL), dichloromethane was added 200 mL, extraction was performed, and the organic layer was washed 3 times with pure water (500 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystal was recrystallized with ethanol to obtain azobenzene-4,4'-bis(4-aminophenyl)dibenzoate (amount 23.8 g, yield 78%).

[Example 3] Synthesis of compound (1-4)

<Step 1; amidation>

Azobenzene-4,4'-dicarbonyldichloride (25.0 g, 81.4 mmol) and triethylamine (19.8 g, 195.4 mmol) were placed in a three-necked flask equipped with a thermometer and a dropping funnel, and 150 mL of dichloromethane was added. While maintaining this solution at 5°C or lower, a solution obtained by dissolving 4-(N-tert-butoxycarbonylamino)aniline (37.3 g, 179.1 mmol) in dichloromethane (100 mL) was added dropwise thereto, at room temperature. The temperature was raised to , and stirred for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed three times with pure water (300 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the following compound (amount 42.9 g, yield 81%).

<Second step; Deprotection>

In a three-necked flask equipped with a thermometer and a dropping funnel, the compound (40.0 g, 61.5 mmol) obtained in the first step was added, and dichloromethane (300 mL) was added thereto. A mixed solution of 47% hydrobromic acid (23.3 g, 135.2 mmol) and acetic acid (75 mL) was added dropwise thereto while keeping the solution at 5°C or lower. The reaction solution was heated to room temperature and stirred for 6 hours. To this reaction solution, a saturated aqueous sodium hydrogencarbonate solution was added until the pH of the solution became 7 or higher. This solution was put into water (500 mL), dichloromethane was added 200 mL, extraction was performed, and the organic layer was washed 3 times with pure water (500 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystal was recrystallized from ethanol to obtain compound (1-4) (amount 20.2 g, yield 73%).

[Example 4]

<Synthesis of polyamic acid>

In a three-neck flask equipped with a stirring blade and a thermometer, 2.5427 g of compound (1-1) synthesized in Example 1 and 2.4573 g of compound (AN-4-17) (m=8) were weighed and taken there. 65 g of N-methyl-2-pyrrolidone (NMP) was added thereto. It stirred at room temperature for 12 hours, ethylene glycol monobutyl ether (BC) 30g was added there, and it stirred for 2 hours further. The solution was heated at 60 degreeC until the viscosity of the solution became 35 m*Pa, the point reduction operation was performed, and the solution of 5 weight% of polyamic-acid density|concentrations was obtained. Let this solution be varnish A. The weight average molecular weight of the polyamic acid in this varnish was 72,000.

[Examples 5-20]

As shown in Table 1 below, according to the method described in Example 4, a varnish having a polyamic acid concentration of 5% by weight as a polymer for forming a photo-alignment film was obtained. The parentheses () indicate mol% when the total amount of the raw material is 100 mol%. In Examples 15 to 17, after the varnish was adjusted in the same manner as described above, the additives (Ad1) to (Ad3) were each added in a proportion of 10 parts by weight per 100 parts by weight of the polymer to make adjustments. Example 4 is also described again in the table.

[Table 1]

[Comparative Examples 1-3]

As shown in Table 2 below, according to the method described in Example 4, a varnish having a polyamic acid concentration of 5% by weight as a polymer for forming a photo-alignment film was obtained. The parentheses () indicate mol% when the total amount of the raw material is 100 mol%.

[Table 2]

[Example 21]

1.0 g of varnish A was weighed in a sample bottle, and NMP/BC = 1/1 (weight ratio) was added to make 1.67 g. On a transparent glass substrate, this about 3 weight% polyamic acid solution was dripped and it apply|coated by the spinner method (2,000 rpm, 15 second). After application, the substrate was heated at 80° C. for 3 minutes, the solvent was evaporated, and then, using Multilite ML-501C/B manufactured by Ushio Electric Co., Ltd., from the direction perpendicular to the substrate, ultraviolet rays were emitted through the polarizing plate. Linearly polarized light was irradiated. The exposure energy at this time was measured using a UV-integrated photometer UIT-150 (receiver: UVD-S365) manufactured by Ushio Electric Co., Ltd., and was 1.3±0.1 J/cm ^{2 at a wavelength of 365 nm.} , the exposure time was adjusted. The board|substrate after light irradiation was heat-processed for 15 minutes at 210 degreeC in oven, and the orientation film A with a film thickness of about 100 nm was obtained. JA Woollam Co. The retardation of the alignment layer A was determined using a spectroscopic ellipsometer M-2000U manufactured by Inc. In the case of this embodiment, the retardation value of the film increases in proportion to the orientation degree of the polymer main chain. That is, a thing having a large retardation value has a large degree of orientation. When the retardation of this alignment film A was measured, it was 19.2 nm. In addition, the UV-Vis spectrum of the alignment film A obtained was measured using a V-660 manufactured by Japan Spectroscopy, and the average value of transmittance at 380 to 780 nm was calculated as transmittance of the alignment film A, which was 92.5%. As a reference of the UV-Vis spectrum of the alignment film, a glass substrate on which the alignment film is not formed was used.

[Examples 22 to 34] and [Comparative Examples 4 to 6]

For the varnishes B to N and X to Z, alignment films B to I and X to Z were also formed in the same manner as in Example 21, and retardation and transmittance were measured in accordance with the method of Example 21. These results are shown in Tables 3 and 4. The results of Example 21 are also described again in Table 3.

[Table 3]

[Table 4]

In the alignment films A to N obtained from the varnishes A to N, it was found that all of the alignment films had large retardation and high transmittance. In the alignment film X obtained from the varnish X, although it had large retardation, it was visually observed that the transmittance|permeability was low and there was coloring in the film|membrane. In the alignment films obtained from the varnishes Y and Z, it was found that the retardation was small and the transmittance was also low.

[Example 35]

An alignment film A having a film thickness of about 100 nm was obtained in the same manner as in Example 21, except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. The two substrates on the ITO electrode on which the alignment film was formed were bonded to each other by providing a space for injecting the liquid crystal composition between the alignment films facing the surfaces on which the alignment film was formed. At this time, the polarization direction of the linearly polarized light irradiated to each alignment film was made to be parallel. The positive liquid crystal composition A shown below was inject|poured into this cell, and the liquid crystal cell A (liquid crystal display element) with a cell thickness of 7 micrometers was produced.

<Positive liquid crystal composition A>

Physical property value: NI 100.1°C; Δε 5.1; Δn 0.093; η 25.6 mPa s

When this liquid crystal cell A was observed visually, the so-called flow orientation, in which the liquid crystals were arranged radially from the injection port, was not observed at all. When the polarization microscope was made into a cross nicol state, and liquid crystal cell A was rotated, the clear light and dark state was observed. The pretilt angle (it may abbreviate as Pt angle hereafter) of this liquid crystal cell A was 0.0 degree. Moreover, VHR (voltage retention) and ion density were 99.0 % (30 Hz), 87.0 % (0.3 Hz), and 80 pC.

[Examples 36 to 48] and [Comparative Examples 7 to 9]

According to the method described in Example 35, liquid crystal cells B to N and X to Y were also produced for the varnishes B to N and X to Y, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Tables 5 and 6. Example 35 is also described again in Table 5.

[Table 5]

[Table 6]

In liquid crystal cells AN and X, a favorable orientation state is shown, Pt angle is 0.1 degrees or less, and favorable black display is shown. In addition, the electrical properties expressed by VHR and ion density were also good results. In the liquid crystal cells Y and Z, although the electrical property was favorable, the flow orientation of a liquid crystal was confirmed and it became the liquid crystal cell of a display defect.

<Polymer blending>

[Examples 49 to 58]

As shown in Table 7 below, according to the method described in Example 4, a varnish having a polyamic acid concentration of 5% by weight as a base polymer was obtained. The parentheses () indicate mol% when the total amount of the raw material is 100 mol%.

[Table 7]

[Example 59]

Weigh 0.2 g of varnish A and 0.8 g of varnish a in a sample bottle, add NMP/BC = 1/1 (weight ratio) to make 1.67 g, and photo-alignment film-forming polymer varnish: polymer varnish for base = 2:8 (weight ratio) ) of the polymer blended varnish Aa was obtained. On a transparent glass substrate, this about 3 weight% polyamic acid solution was dripped and it apply|coated by the spinner method (2,000 rpm, 15 second). After application, the substrate was heated at 80° C. for 3 minutes, the solvent was evaporated, and then, using Multilite ML-501C/B manufactured by Ushio Electric Co., Ltd., from a direction perpendicular to the substrate, ultraviolet rays were emitted through the polarizing plate. Linearly polarized light was irradiated. The exposure energy at this time was measured using a UV-integrated photometer UIT-150 (receiver: UVD-S365) manufactured by Ushio Electric Co., Ltd., and 1.3±0.1 J/cm ^{2 at a wavelength of 365 nm.} As much as possible, the exposure time was adjusted. The board|substrate after light irradiation was heat-processed in oven at 210 degreeC for 15 minutes, and the orientation film Aa of about 100 nm of film thickness was obtained. JA Woollam Co. The retardation of the alignment layer Aa was determined using a spectroscopic ellipsometer M-2000U manufactured by Inc. In the case of this embodiment, the retardation value of the film increases in proportion to the orientation degree of the polymer main chain. That is, a thing having a large retardation value has a large degree of orientation. When the retardation of this alignment film Aa was measured, it was 19.3 nm. In addition, the UV-Vis spectrum of the alignment film Aa obtained was measured using a V-660 manufactured by Japan Spectroscopy, and the average value of transmittance at 380 to 780 nm was calculated as transmittance of the alignment film Aa, and it was 95.5%. As a reference of the UV-Vis spectrum of the alignment film, a glass substrate on which no alignment film is formed was used.

[Examples 60 to 158] and [Comparative Examples 10 to 19]

With respect to varnishes B to N and X, polymer-blended varnishes Ab to Nj and Xa to Xj were obtained in the same manner as in Example 59. Next, according to Example 59, alignment films Ab to Nj and Xa to Xj were formed, and retardation and transmittance were measured. These results are shown in Tables 8-12. The results of Example 59 were also described again in Table 8. As described above, when varnish or an alignment layer is represented by a combination of uppercase letters and lowercase letters, uppercase letters indicate the type of the photo-alignment layer-forming polymer, and lowercase letters indicate the type of polymer for the base. The weight ratio of the two blended varnishes is: photo-alignment film-forming polymer varnish: polymer varnish for base = 2:8.

In Examples 129 to 158 shown in Tables 11 and 12, an additive (Ad1), an additive (Ad2), or an additive (Ad3) was added to the blended varnish. The amount of the additive added is 10 parts by weight based on 100 parts by weight of the total weight of the polymer after blending the polymer. In the table, the symbols of additives are written together with uppercase and lowercase letters of the alphabet within the frame.

[Table 8]

[Table 9]

[Table 10]

[Table 11]

[Table 12]

[Table 13]

In the varnishes A to N, an alignment film having a large retardation can be obtained even when polymer blending is performed, so that the sensitivity to light is not lowered. Further, it was found that an alignment film having a higher transmittance can be obtained by performing polymer blending. In the case of varnish X, although the sensitivity to light did not fall, even when polymer blending was performed, the transmittance|permeability was low as a result.

[Example 159]

An alignment film Aa having a film thickness of about 100 nm was obtained in the same manner as in Example 56, except that the glass substrate was replaced with a transparent glass substrate provided with an ITO electrode on one side. The two substrates on the ITO electrode on which the alignment film was formed were bonded to each other by providing a space for injecting the liquid crystal composition between the alignment films facing the surfaces on which the alignment film was formed. At this time, the polarization direction of the linearly polarized light irradiated to each alignment film was made to be parallel. The liquid crystal composition A mentioned above was inject|poured into these cells, and the liquid crystal cell Aa (liquid crystal display element) with a cell thickness of 7 micrometers was produced.

When this liquid crystal cell Aa was observed visually, the so-called flow orientation, in which liquid crystals were arranged radially from the injection port, was not observed at all. When the polarization microscope was made into a cross nicol state, and liquid crystal cell Aa was rotated, the clear light and dark state was observed. The pretilt angle of this liquid crystal cell A was 0.0 degree. In addition, VHR (voltage retention) and ion density were 99.2% (30 Hz), 87.3% (0.3 Hz), and 60 pC.

[Examples 160 to 258] and [Comparative Examples 20 to 29]

According to the method described in Example 159, liquid crystal cells Ab-Kj, Oa-Qj, and Xa-Xj were also prepared for the varnishes Ab-Kj, Oa-Qj, and Xa-Xj, and the orientation state, pretilt angle, VHR and ion density were measured. The measurement results are shown in Tables 14 to 19. Example 159 is also described again in Table 14.

[Table 14]

[Table 15]

[Table 16]

[Table 17]

[Table 18]

[Table 19]

All the produced liquid crystal cells show a favorable orientation state, are 0.1 degrees or less of Pt angles, and show favorable black display. In addition, the electrical properties expressed by VHR and ion density were also good results.

[Example 259]

Liquid crystal cell A' was produced by the method described in Example 32, except that the liquid crystal composition was replaced with the following negative liquid crystal composition B from the positive liquid crystal composition A. When this liquid crystal cell A' was observed visually, the so-called flow orientation, in which liquid crystals were arranged radially from the injection port, was not observed at all. When the polarization microscope was made into a cross nicol state, and liquid crystal cell A' was rotated, the clear light and dark state was observed. The pretilt angle of this liquid crystal cell A' was 0.0 degrees. Moreover, VHR (voltage retention) and ion density were 99.0 % (30 Hz), 87.0 % (0.3 Hz), and 80 pC.

<Negative liquid crystal composition B>

Physical property value: NI 75.7°C; Δε -4.1; Δn 0.101; η 14.5 mPa s

[Examples 260 to 272]

According to the method described in Example 259, liquid crystal cells B' to N' were also produced for varnishes B to N, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 20. Example 259 is also described again in Table 20.

[Table 20]

[Examples 273 to 372]

According to the method described in Example 259, liquid crystal cells Aa' to Kj' and Oa' to Qj' were also produced for the varnishes Aa to Kj and Oa to Qj, and the orientation state, pretilt angle, VHR, and ion density were measured. . The measurement results are shown in Tables 21 to 25.

[Table 21]

[Table 22]

[Table 23]

[Table 24]

[Table 25]

Even if the liquid crystal composition is replaced with the negative liquid crystal composition B from the positive liquid crystal composition A, it turns out that the liquid crystal display element provided with the alignment film which consists of this invention is excellent in a viewing characteristic and an electrical characteristic.

[Example 373] Synthesis of compound (1-5)

<Step 1; amidation>

Azobenzene-4,4'-dicarbonyldichloride (25.0 g, 81.4 mmol) was placed in a three-necked flask equipped with a thermometer and a dropping funnel, and 150 mL of dichloromethane was added. While maintaining this solution at 5° C. or lower, therein 4-nitro-N-methylaniline (27.3 g, 179.1 mmol) and triethylamine (19.8 g, 195.4 mmol) were dissolved in dichloromethane (100 mL). The solution was dripped, it heated up to room temperature, and stirred for 6 hours. The reaction solution was poured into water (250 mL), and the organic layer was washed three times with pure water (300 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain the following compound (amount 33.3 g, yield 76%).

<Second step; Reduction of nitro group>

In a 2 L eggplant-type flask, put the compound (30.0 g, 55.7 mmol) and sodium sulfate heptahydrate (80.3 g, 334.2 mmol) obtained in the first step, 750 mL of ethanol and 750 mL of pure water were added, and 8 hours heated to reflux. The reaction solution was poured into 1000 mL of ethyl acetate, and the organic layer was washed 3 times with pure water (1000 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The obtained crude crystal was recrystallized from ethanol to obtain compound (1-5) (amount 19.2 g, yield 72%).

[Example 374] Synthesis of compound (1-19)

<Step 1>

To a 1 L three-necked flask equipped with a thermometer and a dropping funnel, 1,4-dibromocyclohexane (25.0 g, 103.3 mmol), dichlorobistriphenylphosphinepalladium (II) (1.5 g, 2.1 mmol) ) and copper oxide (I) (0.8 g, 4.1 mmol) were added, and triethylamine (200 mL) and tetrahydrofuran (100 mL) were added thereto. While the solution was heated to reflux, a solution obtained by dissolving 4-ethynylaniline (11.5 g, 98.1 mmol) in 60 mL of tetrahydrofuran was added dropwise thereto, and after completion of the dropwise addition, the solution was further heated and refluxed under nitrogen atmosphere for 3 hours. . After standing to cool and removing insoluble substances by filtration, the liquid was poured into pure water (500 mL) and extracted with ethyl acetate (500 mL). The organic layer was washed 3 times with pure water (500 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were separated and purified by column chromatography (silica gel, eluent; toluene:methanol = 10:1 (volume ratio)) to obtain the following compound (amount; 16.2 g, yield; 63%).

<Step 2>

To a 1 L eggplant-type flask, the compound obtained in the first step (16.0 g, 57.5 mmol) and a hydrogenation catalyst BNA-5D (1.6 g) manufactured by N. E Chemcat were added. The mixture was stirred at room temperature in a hydrogen atmosphere for 18 hours, the catalyst was removed by filtration, and the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystal was recrystallized from a mixed solvent of ethanol:toluene = 1:3 to obtain the following compound (amount; 14.8 g, yield; 91%).

<Step 3>

In a 1 L eggplant-type flask, the compound obtained in step 2 (14.5 g, 51.4 mmol), benzophenoneimine (10.2 g, 56.5 mmol), [1,3-bis(2,6-diisopropylphenyl) ) Imidazole-2-ylidene] (3-chloro-pyridyl) palladium (II) dichloride (1.4 g, 2.1 mmol) and tert-butoxypotassium (8.7 g, 77.1 mmol) were added, and 1, 4-dioxane (100 mL) was added, and the mixture was stirred at 80° C. under a nitrogen atmosphere for 8 hours. After standing to cool and removing insoluble substances by filtration, the liquid was poured into pure water (500 mL) and extracted with ethyl acetate (500 mL). The organic layer was washed 3 times with pure water (500 mL). After drying the organic layer over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure to obtain crude crystals. The crude crystals were separated and purified by column chromatography (silica gel, eluent; toluene:methanol = 10:1 (volume ratio)) to obtain the following compound (amount; 16.1 g, yield; 82%).

<Step 4>

Compound (16.0 g, 41.8 mmol) in step 3, sodium peroxoborate tetrahydrate (8.6 g, 56.4 mmol) and boric acid (2.2 g, 36.4 mmol) in a 500 mL three-necked flask equipped with a reflux tube and thermometer ol), and 150 mL of acetic acid was added. Sodium peroxoborate tetrahydrate (3.2 g, 20.9 mmol) was added to what was heat-stirred at 60 degreeC for 1 hour, and it heat-stirred for 6 hours further. The reaction solution was put into 400 mL of pure water, and the precipitate was collected by filtration. The obtained precipitate was washed 3 times with pure water, and the obtained crystals were vacuum dried at 60° C. for 8 hours to obtain the following compound (amount 12.6 g, yield 79%).

<Step 5>

The compound (12.0 g, 15.8 mmol) obtained in step 4 was placed in a 500 mL eggplant-type flask, and 40 mL of 3N-hydrochloric acid and 120 mL of tetrahydrofuran were added thereto. It stirred at room temperature for 12 hours, and the solvent was distilled off under reduced pressure. Pure water (100 mL) was added thereto, and 20% aqueous sodium hydroxide solution was added until the solution reached a pH of 8. The precipitated crystals were taken, and the crude crystals were recrystallized from a mixed solvent of ethanol:toluene = 1:1 (volume ratio) to obtain the following compound (1-19) (amount; 5.5 g, yield; 80%).

[Examples 375 and 376]

As shown in Table 26 below, according to the method described in Example 4, a varnish having a polyamic acid concentration of 5% by weight as a polymer for forming a photo-alignment film was obtained. The parentheses () indicate mol% when the total amount of the raw material is 100 mol%.

[Table 26]

[Examples 377 and 378]

In the same manner as in Example 21, an alignment film R was formed using varnish R and an alignment film S was formed using varnish S, and retardation and transmittance were measured according to the method of Example 21. These results are shown in Table 27.

[Table 27]

It was found that both the alignment film R obtained from the varnish R and the alignment film S obtained from the varnish S had large retardation and high transmittance in all the alignment films.

[Examples 379 and 380]

According to the method described in Example 35, liquid crystal cell R was produced using varnish R and liquid crystal cell S was produced using varnish S, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 28.

[Table 28]

Liquid crystal cell R and liquid crystal cell S both show a favorable orientation state, and are 0.1 degrees or less of Pt angle, and show favorable black display. In addition, the electrical properties expressed by VHR and ion density were also good results.

[Examples 381 and 382]

Polymer blended varnish Rd was obtained in the same manner as in Example 59, except that varnish R was used instead of varnish A in Example 59 and varnish d was used instead of varnish a. Similarly, polymer-blended varnish Sh was obtained in the same manner as in Example 59, except that varnish S was used instead of varnish A in Example 59 and varnish h was used instead of varnish a. Next, according to Example 59, alignment films Rd and Sh were formed into a film, and retardation and transmittance were measured. These results are shown in Table 29. As described above, when varnish or an alignment layer is represented by a combination of uppercase letters and lowercase letters, uppercase letters indicate the type of polymer for forming the photo alignment layer, and lowercase letters indicate the type of polymer for the base. The weight ratio of the two blended varnishes is: the photo-alignment film-forming polymer varnish: the polymer varnish for base = 2:8.

[Table 29]

It can be seen that the varnishes R and S do not reduce the sensitivity to light since an alignment film having a large retardation can be obtained even by polymer blending.

[Examples 383 and 384]

According to the method described in Example 159, a liquid crystal cell Rd was produced using the varnish Rd and a liquid crystal cell Sh was produced using the varnish Sh, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 30.

[Table 30]

Liquid crystal cell Rd in which a liquid crystal aligning film was formed using varnish Rd and liquid crystal cell Sh in which a liquid crystal aligning film was formed using varnish Sh both show a favorable orientation state, Pt angle is 0.1 degrees or less, and shows favorable black display. In addition, the electrical properties expressed by VHR and ion density were also good results.

[Examples 385 and 386]

According to the method described in Example 259, a liquid crystal cell R' using varnish R and a liquid crystal cell S' using varnish S were produced, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 31.

[Table 31]

[Examples 387 and 388]

According to the method described in Example 259, a liquid crystal cell Rd' using varnish Rd and a liquid crystal cell Sh' using varnish Sh were prepared, and the orientation state, pretilt angle, VHR, and ion density were measured. The measurement results are shown in Table 32.

[Table 32]

It can be seen that even when the liquid crystal composition is replaced with the negative liquid crystal composition B from the positive liquid crystal composition A, the liquid crystal display devices produced using varnish R, varnish S, varnish Rd, and varnish Sh are excellent in viewing characteristics and electrical characteristics. .

By using the photo-aligning agent using the polyamic acid which used the diamine of this invention as a raw material, or its derivative(s), the sensitivity of the chemical change by light irradiation is favorable, and the alignment film with high transmittance|permeability and orientation can be obtained. By using this alignment film, a liquid crystal display element excellent in display characteristics and electrical characteristics can be obtained.

Claims (24)

A photosensitive diamine represented by the following formula (1):

In the formula (1), ring A and ring B are each independently 1,4-phenylene or cyclohexane-1,4-diyl;
R ¹ is straight-chain alkylene having 2 carbon atoms;
R ² is straight-chain alkylene having 2 carbon atoms. According to claim 1,
A photosensitive diamine represented by the following formula (1-1) or (1-19):

A polyamic acid or a derivative thereof obtained by reacting a diamine containing at least one photosensitive diamine according to claim 1 with tetracarboxylic dianhydride. 4. The method of claim 3,
In addition to the photosensitive diamine represented by the formula (1), the following formulas (DI-1) to (DI-16), (DIH-1) to (DIH-3), and (DI-31) to formulas Diamine containing at least one selected from the group consisting of (DI-35) and tetra containing at least one selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII) A polyamic acid or a derivative thereof obtained by reacting a carboxylic acid dianhydride:

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 in the alkylene may be substituted with -OH;
In the formulas (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, - SS-, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -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 -(NH-C ₃ H ₆ ) _n -CO-, or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12; , k is an integer from 1 to 5, and n is 1 or 2;
In the formula (DI-4), s is independently an integer of 0 to 2;
In the formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF) ₃ ) ₂ -, or alkylene having 1 to 10 carbon atoms;
In the formulas (DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH , -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or may be substituted with benzyl, and in the formula (DI-4), the following formula (DI-4-a) - may be substituted with formula (DI-4-e);
The 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, and the bonding position _{of -NH 2} ^{to the cyclohexane ring or the benzene ring is that of G 21} or G ²² . any position except the binding site;

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

In the 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 any position;}

In the formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene having 1 to 6 carbon atoms, phenylene or alkyl-substituted phenylene; , w is an integer from 1 to 10;
In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, or -Cl, p is independently an integer of 0 to 3, q is 0 to 4 is an integer;
In the formula (DI-14), ring B is a monocyclic heteroaromatic, and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, or alkyl having 2 to 6 carbon atoms. kenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer from 0 to 4;
In the formula (DI-15), ring C is a monocyclic ring containing a hetero atom;
In the 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;
In the formulas (DI-13) to (DI-16), the 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 formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen in the ring may be substituted with methyl, ethyl, or phenyl;
In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen in the ring may be substituted with methyl, ethyl, or phenyl, Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the above formulas (DIH-2) and (DIH-3), the bonding position of _{-CONHNH 2 bonded to the ring is 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' -, m' is an integer of 1 to 12, and R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or the following formula (DI-31-a), wherein in the alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - is -O-, -CH=CH- or - may be substituted with C≡C-, hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or alkyl having a carbon number of 3 to 30 carbon atoms, 3 to 30 may be substituted with alkoxy, and the hydrogen of this cyclohexyl may be substituted with alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and the bonding position of _{-NH 2 bonded to the benzene ring is in the ring} indicates an arbitrary position,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and at least one —CH ₂ — may be substituted with -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene -2,7-diyl or anthracene-9,10-diyl, and in 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 from 0 to 2,
The sum of s, t and u is 1 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. may be,
R ²⁶ is hydrogen, -F, -OH, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF _{3 and 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In the formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in the formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms,
And, in the formulas (DI-32) and (DI-33), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, G ³² is a single bond or alkylene having 1 to 3 carbon atoms; , R ³¹ is hydrogen or an alkyl having 1 to 20 carbon atoms, at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH=CH- or -C≡C-, and R ³² is alkyl having 6 to 22 carbon atoms, R ³³ is hydrogen or alkyl having 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 represents that the bonding position in the ring is arbitrary,

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;
In the formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups,

at least one hydrogen in the group may be substituted with methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), ring A ¹⁰ is a monocyclic hydrocarbon group having 3 to 10 carbon atoms or a fused polycyclic hydrocarbon group having 6 to 30 carbon atoms, and at least one of the groups hydrogen of may be substituted with methyl, ethyl or phenyl, the bond on the ring may be connected to any carbon constituting the ring, and two bonds 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, Ph represents phenyl,
In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1. 5. The method of claim 4,
In addition to the photosensitive diamine of formula (1), the following formulas (DI-1-3), formula (DI-2-1), formula (DI-4-1), formula (DI-4-2), formula (DI -4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-5), formula (DI-5-9), formula (DI-5-12) , Formula (DI-5-13), Formula (DI-5-24), Formula (DI-5-28) to (DI-5-30), Formula (DI-6-7), Formula (DI-7) -3), a mixture of a diamine containing at least one selected from formula (DI-11-2), and formula (DI-13-1), and formula (AN-1-1), formula (AN-1) -2), formula (AN-1-13), formula (AN-2-1), formula (AN-3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29), formula (AN-4-30), formula (AN-5-1), formula (AN-7- 2), formula (AN-10), formula (AN-11-3), formula (AN-16-3), and tetracarboxylic dianhydride containing at least one selected from formula (AN-16-4) A polyamic acid or a derivative thereof obtained by reacting:

In the above formulas (DI-5-1), (DI-5-12), (DI-5-13), and (DI-7-3), m is an integer of 1 to 12;
In the above formula (DI-5-30), k is an integer of 1 to 5;
And, in formula (DI-7-3), n is 1 or 2;

In the formulas (AN-1-2) and (AN-4-17), m is an integer of 1 to 12. 4. The method of claim 3,
A polyamic acid or a derivative thereof obtained by reacting a mixture of a diamine containing at least one of the photosensitive diamines other than the formula (1) with tetracarboxylic dianhydride. 7. The method of claim 6,
A polyamic acid or a derivative thereof, wherein the photosensitive diamine other than the formula (1) is at least one selected from the group consisting of azobenzene derivatives, stilbene derivatives, acetylene derivatives, coumarin derivatives, cinnamic acid derivatives, and benzophenone derivatives. 7. The method of claim 6,
A polyamic acid or a derivative thereof, wherein the photosensitive diamine other than the formula (1) is at least one compound selected from the group consisting of the following formulas (PDI-1) to (PDI-12):

In the formula (PDI-7), R ⁵¹ is independently _{-CH 3, -OCH 3, -CF 3} , or a -COOCH _3, s is an integer from 0 to 2, and, the formula (PDI-12 ), R ⁵² is alkyl or alkoxy having 1 to 10 carbon atoms, and at least one hydrogen may be substituted with fluorine. 7. The method of claim 6,
Polyamic acid or its derivative(s) whose photosensitive diamine other than said Formula (1) is a compound represented by following formula (PDI-7):

In the formula (PDI-7), R ⁵¹ is independently -CH _3, -OCH _3, and -CF _3, or -COOCH _3, s is an integer of 0 to 2 independently. The liquid crystal aligning agent containing the polyamic acid in any one of Claims 3-9, or its derivative(s). The liquid crystal aligning agent containing the polyamic acid in any one of Claims 5-9 or its derivative(s), and another polyamic acid or its derivative(s). 12. The method of claim 11,
Said other polyamic acid or its derivative|guide_body is following formula (DI-1) - formula (DI-16), said formula (DIH-1) - formula (DIH-3), and said formula (DI-31) - formula A liquid crystal aligning agent which is a polyamic acid obtained by reacting at least one diamine selected from the group consisting of (DI-35) and tetracarboxylic dianhydride, or a derivative thereof:

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 in the alkylene may be substituted with -OH;
In the formulas (DI-3) and (DI-5) to (DI-7), G ²¹ is independently a single bond, -NH-, -NCH ₃ -, -O-, -S-, - SS-, -SO ₂ -, -CO-, -COO-, -CONH-, -CONCH ₃ -, -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 -(NH-C ₃ H ₆ ) _n -CO-, or -S-(CH ₂ ) _m' -S-, m' is independently an integer from 1 to 12; , k is an integer from 1 to 5, and n is 1 or 2;
In the formula (DI-4), s is independently an integer of 0 to 2;
In the formulas (DI-6) and (DI-7), G ²² is independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF) ₃ ) ₂ -, or alkylene having 1 to 10 carbon atoms;
In the formulas (DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring is -F, -Cl, alkylene having 1 to 3 carbon atoms, -OCH ₃ , -OH , -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or may be substituted with benzyl, and in the formula (DI-4), the following formula (DI-4-a) - may be substituted with formula (DI-4-e);
The 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, and the bonding position _{of -NH 2} ^{to the cyclohexane ring or the benzene ring is that of G 21} or G ²² . any position except the binding site;

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

In the 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 any position;}

In the formula (DI-12), R ²¹ and R ²² are independently alkyl or phenyl having 1 to 3 carbon atoms, and G ²³ is independently alkylene having 1 to 6 carbon atoms, phenylene or alkyl-substituted phenylene; , w is an integer from 1 to 10;
In the formula (DI-13), R ²³ is independently alkyl having 1 to 5 carbon atoms, alkoxy having 1 to 5 carbon atoms, or -Cl, p is independently an integer of 0 to 3, q is 0 to 4 is an integer;
In the formula (DI-14), ring B is a monocyclic heteroaromatic, and R ²⁴ is hydrogen, -F, -Cl, alkyl having 1 to 6 carbon atoms, alkoxy having 1 to 6 carbon atoms, or alkyl having 2 to 6 carbon atoms. kenyl, alkynyl having 1 to 6 carbon atoms, q is independently an integer from 0 to 4;
In the formula (DI-15), ring C is a monocyclic ring containing a hetero atom;
In the 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;
In the formulas (DI-13) to (DI-16), the 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 formula (DIH-1), G ²⁵ is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the formula (DIH-2), ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen in the ring may be substituted with methyl, ethyl, or phenyl;
In the formula (DIH-3), each ring E is independently a cyclohexane ring or a benzene ring, at least one hydrogen in the ring may be substituted with methyl, ethyl, or phenyl, Y is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the above formulas (DIH-2) and (DIH-3), the bonding position of _{-CONHNH 2 bonded to the ring is 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' -, m' is an integer of 1 to 12, and R ²⁵ is alkyl having 3 to 30 carbon atoms, phenyl, a group having a steroid skeleton, or the following formula (DI-31-a), wherein in the alkyl, at least one hydrogen may be substituted with -F, and at least one -CH ₂ - is -O-, -CH=CH- or - may be substituted with C≡C-, hydrogen of the phenyl _{is, -F, -CH 3, -OCH 3} , -OCH 2 F, -OCHF 2, -OCF 3, or alkyl having a carbon number of 3 to 30 carbon atoms, 3 to 30 may be substituted with alkoxy, and the hydrogen of this cyclohexyl may be substituted with alkyl having 3 to 30 carbons or alkoxy having 3 to 30 carbons, and the bonding position of _{-NH 2 bonded to the benzene ring is in the ring} indicates an arbitrary position,

In the formula (DI-31-a), G ²⁷ , G ²⁸ and G ²⁹ are a bonding group, which are independently a single bond or an alkylene having 1 to 12 carbon atoms, and at least one —CH ₂ — may be substituted with -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ are independently 1,4- Phenylene, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5-diyl, naphthalene -2,7-diyl or anthracene-9,10-diyl, and in 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 from 0 to 2,
The sum of s, t and u is 1 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. may be,
R ²⁶ is hydrogen, -F, -OH, alkoxy, -CN of fluorine-substituted alkyl, of 1 to 30 carbon atoms in the alkyl, of 1 to 30 carbon atoms of 1 to 30 carbon atoms, -OCH ₂ F, -OCHF _2, or -OCF _{3 and 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 the formula (DI-31-b), R ²⁷ and R ²⁸ are independently alkyl having 1 to 3 carbon atoms, and v is an integer of 1 to 6;

In the formulas (DI-32) and (DI-33), G ³⁰ is independently a single bond, -CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH ₃ , R ³⁰ is hydrogen, alkyl having 1 to 20 carbons, or alkenyl having 2 to 20 carbons;
One hydrogen of the benzene ring in the formula (DI-33) may be substituted with alkyl or phenyl having 1 to 20 carbon atoms,
And, in the formulas (DI-32) and (DI-33), the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring indicates that the bonding position in the ring is arbitrary;

In the formulas (DI-34) and (DI-35), G ³¹ is independently -O- or alkylene having 1 to 6 carbon atoms, G ³² is a single bond or alkylene having 1 to 3 carbon atoms; , R ³¹ is hydrogen or an alkyl having 1 to 20 carbon atoms, at least one -CH ₂ - of the alkyl may be substituted with -O-, -CH=CH- or -C≡C-, and R ³² is alkyl having 6 to 22 carbon atoms, R ³³ is hydrogen or alkyl having 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 represents that the bonding position in the ring is arbitrary. 13. The method of claim 12,
Said other polyamic acid or its derivative(s) is a formula (DI-1-3), a formula (DI-2-1), a formula (DI-4-1), a formula (DI-4-2), a formula (DI -4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13) , formula (DI-5-28), formula (DI-5-30), formula (DI-7-3), formula (DI-13-1), formula (DI-16-1), and formula (DIH) A liquid crystal aligning agent which is a polyamic acid obtained by reacting at least one diamine selected from -2-1) with tetracarboxylic dianhydride or a derivative thereof:

In the above formulas (DI-5-1), (DI-5-12), (DI-5-13), and (DI-7-3), m is an integer of 1 to 12;
In the above formula (DI-5-30), k is an integer of 1 to 5;
And, in the formula (DI-7-3), n is 1 or 2. 12. The method of claim 11,
A polyamic acid obtained by reacting at least one tetracarboxylic dianhydride selected from the group of tetracarboxylic dianhydrides represented by the following formulas (AN-I) to (AN-VII) with diamine, wherein the other polyamic acids or derivatives thereof are polyamic acids or Liquid crystal aligning agents, which are derivatives thereof:

In the formulas (AN-I), (AN-IV) and (AN-V), X is independently a single bond or -CH ₂ -;
In the formula (AN-II), G is a single bond, alkylene having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -;
In the formulas (AN-II) to (AN-IV), Y is independently one selected from the group of the following trivalent groups,

at least one hydrogen in the group may be substituted with methyl, ethyl or phenyl;
In the formulas (AN-III) to (AN-V), 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, and at least one of the groups hydrogen of may be substituted with methyl, ethyl or phenyl, the bond on the ring may be connected to any carbon constituting the ring, and two bonds 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, Ph represents phenyl,
In the formula (AN-VII), G ¹⁰ is independently -O-, -COO- or -OCO-; and r is independently 0 or 1. 15. The method of claim 14,
Said other polyamic acid or its derivative|guide_body is a following formula (AN-1-1), a formula (AN-1-2), a formula (AN-1-13), a formula (AN-2-1), a formula (AN -3-1), formula (AN-3-2), formula (AN-4-5), formula (AN-4-17), formula (AN-4-21), formula (AN-4-29) , Formula (AN-4-30), Formula (AN-5-1), Formula (AN-7-2), Formula (AN-10), Formula (AN-11-3), Formula (AN-16- 3) and a polyamic acid obtained by reacting at least one tetracarboxylic dianhydride selected from formula (AN-16-4) with diamine, or a derivative thereof, a liquid crystal aligning agent:

In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12. 11. The method of claim 10,
A liquid crystal aligning agent further comprising at least one selected from the group consisting of an alkenyl-substituted nadimide compound, a compound having a radically polymerizable unsaturated double bond, an oxazine compound, an oxazoline compound, and an epoxy compound. 11. The method of claim 10,
The liquid crystal aligning agent is for optical alignment, a liquid crystal aligning agent. 11. The method of claim 10,
The liquid crystal aligning agent is for a liquid crystal display device of a transverse electric field system, a liquid crystal aligning agent. The liquid crystal aligning film formed with the liquid crystal aligning agent of Claim 10. The liquid crystal display device which has the liquid crystal aligning film of Claim 19. delete delete delete delete