TW201620958A - Liquid crystal aligning agent for forming liquid crystal alignment film for photoalignment, liquid crystal alignment film, and liquid crystal display device using the same - Google Patents

Abstract

The present relates to a liquid crystal aligning agent for photoalignment, containing at least one polymer selected from the group of a polyamic acid obtained by allowing at least one selected from tetracarboxylic acid dianhydride and a derivative thereof to react with diamine, a polyamic acid ester obtained therefrom, and polyimide obtained by imidizing the materials, in which at least one raw material monomer of the polymer has photoisomerization structure, and the raw material monomer of the polymer contains at least one of compounds represented by formula (1) below. A liquid crystal display device in which no reduction of display quality is caused even if exposed to intense light for a long period of time can be provided by using a liquid crystal alignment film formed using the liquid crystal aligning agent for photoalignment according to the invention.

Description

Liquid crystal alignment agent for forming a liquid alignment film for photoalignment, liquid crystal alignment film, and liquid crystal display element using the same

The present invention relates to a liquid alignment alignment agent for photoalignment and a photo alignment film and a liquid crystal display device using the same.

Various personal display devices such as monitors for personal computers, LCD TVs, viewfinders for cameras, projection displays, optical optics, optical Fourier transform components, optical valves, and other optoelectronics related components The mainstream of liquid crystal display elements that have been commercialized and generally circulated today are display elements using nematic liquid crystals. The display mode of the nematic liquid crystal display element is widely known as a twisted nematic (TN) mode or a super twisted nematic (STN) mode. In recent years, in order to improve the problem of one of these modes, that is, the viewing angle is narrow, a multi-domain vertical alignment (MVA) using a TN type liquid crystal display element using an optical compensation film and using a technique of vertical alignment and protrusion structures has been proposed. In-Plane Switching (IPS) mode or Fringe Field Switching (FFS) mode, such as mode or transverse electric field mode, has been put into practical use.

The development of the technology of the liquid crystal display element is realized not only by the improvement of these driving methods or the structure of the elements, but also by the improvement of the constituent members used in the elements. Among the constituent members used in the liquid crystal display device, in particular, the liquid crystal alignment film is one of important materials related to display quality, and as the liquid crystal display element is made higher in quality, it is important to improve the performance of the alignment film.

The liquid crystal alignment film is formed of a liquid crystal alignment agent. At present, a liquid crystal alignment agent mainly used is a solution (varnish) obtained by dissolving polylysine or soluble polyimine in an organic solvent. After the solution is applied onto a substrate, film formation is carried out by heating or the like to form a polyimide film. After film formation, an alignment process suitable for the display mode is performed as needed.

A rubbing method which can easily perform large-area high-speed processing in an industrial manner is widely used as an alignment treatment method. In the rubbing method, a cloth to which a fiber such as nylon, rayon, or polyester is grafted is used, and the surface of the liquid crystal alignment film is rubbed in one direction, whereby uniform alignment of liquid crystal molecules can be obtained. However, in order to point out problems such as dust generation and static electricity generated by the friction method, an alignment treatment method in place of the friction method has been actively developed in recent years.

As an alignment treatment method instead of the rubbing method, attention has been paid to an optical alignment treatment method in which light is irradiated and an alignment treatment is performed. In the photo-alignment processing method, a large number of alignment mechanisms such as a photo-decomposition method, a photo-isomerization method, a photodimerization method, and a photo-crosslinking method are proposed (for example, refer to Non-Patent Document 1, Patent Document 1 and Patent Document 2). Since the alignment of the photo-alignment method is higher than that of the rubbing method, and it is a non-contact alignment treatment method, there is an advantage that the liquid crystal display element can be reduced in display or the like without causing damage to the film.

In the past, a photo-alignment film having a photoreactive group such as photoisomerization or photodimerization has been studied in the structure of poly-proline (see, for example, Patent Documents 1 to 7). In the photoisomerization technique described in Patent Document 3 to Patent Document 5, the optical alignment film has a large anchoring property, a good alignment property, and a good electrical property such as a voltage holding ratio. However, evaluation and research on the reduction of residual voltage (Direct Current (DC)) which is one of the characteristics required for the liquid crystal alignment film are not sufficient. The residual DC is the voltage remaining when the voltage is restored to 0 V after the voltage is applied by applying a voltage. It is known that when a liquid crystal display element is displayed with an arbitrary image for a long period of time, when the image is changed to another image, the previous image remains as an afterimage, and the display quality is deteriorated. However, it is known that the residual DC is suppressed. By accumulating and shortening the relaxation time, the afterimage can be suppressed (for example, refer to Patent Document 7).

In recent years, in the liquid crystal display device, in consideration of improvement in display quality or for outdoor use, there is also a use in which the brightness of a backlight serving as a light source is increased as compared with the prior art, and it is required to display quality even when exposed to intense light for a long period of time. Liquid crystal display elements that do not drop. Even with the above technology, it is difficult to provide a liquid alignment agent for photoalignment that satisfies the above requirements. [Prior Art Literature]

[Patent Document 1] Japanese Patent Laid-Open No. Hei 9-297313 [Patent Document 2] Japanese Patent Laid-Open No. Hei 10-251646 [Patent Document 3] Japanese Patent Laid-Open No. Hei No. 2005-275364 [Patent Document 4] Japanese Patent [Patent Document 5] Japanese Patent Laid-Open No. 2009-069493 [Patent Document 6] Japanese Patent Laid-Open No. 2008-233713 [Patent Document 7] International Publication No. 2013/157463 [Non-Patent Document] [Non- Patent Document 1] Liquid Crystal, Vol. 3, No. 4, Page 262, 1999

[Problems to be solved by the invention]

An object of the present invention is to provide a liquid crystal display element which does not deteriorate in display quality even when exposed to intense light for a long period of time, and further provides a liquid crystal alignment agent and a liquid crystal alignment film which can provide such a display element. [Technical means to solve the problem]

As a result of diligent research, it was confirmed that the display element having a deteriorated display quality due to long-term use has a low voltage holding ratio after being used for a long period of time. Further, it has been found that by using the diamine represented by the formula (1) of the present invention as a raw material for the liquid alignment alignment agent for light alignment, the voltage retention ratio does not decrease even when used for a long period of time, thereby providing a long-term exposure to intense light. A liquid crystal display element in which the quality is not lowered is displayed, and a liquid crystal alignment agent and a liquid crystal alignment film capable of providing such a display element can be provided. The present invention includes the following constitutions.

[1] A liquid alignment alignment agent for photoalignment comprising at least one selected from the group consisting of polylysine, polylysine, and polyamidene obtained by ruthenium imidization thereof The polyamic acid, the polyamidomate, and the polyimine obtained by ruthenium imidization thereof are obtained by reacting at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof with a diamine. Obtaining, wherein at least one of the raw material monomers of the polymer has a photoisomerization structure, and the raw material monomer of the polymer comprises at least one of the compounds represented by the following formula (1); In the formula (1), R ^a is hydrogen or a methyl group; R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; and the tetracarboxylic acid The derivative of dianhydride means a tetracarboxylic acid diester or a tetracarboxylic acid diester dichloride.

[2] The liquid alignment alignment agent according to [1], which comprises: having at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine having photoisomerism At least one of a polymer obtained by reacting a compound having a chemical structure and a diamine containing at least one of the compounds represented by the formula (1); or comprising: a component selected from the group consisting of tetracarboxylic dianhydride and its derivative And at least one of a polymer obtained by reacting a raw material monomer of a compound having a photoisomerization structure of at least one of a group consisting of a diamine; and a tetracarboxylic dianhydride, a derivative thereof, and a diamine Any one of the polymers obtained by reacting a raw material monomer having at least one of the compounds represented by the formula (1) without a photoisomerization structure and having a diamine.

[3] The liquid alignment alignment agent according to [2], which comprises: having at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine having photoisomerism At least one of a compound obtained by reacting a compound having a chemical structure and a diamine containing at least one of the compounds represented by the formula (1); and other polymers used in combination with the polymer; The other polymer is a polymer obtained by reacting a raw material monomer having no photoisomerization structure in any of tetracarboxylic dianhydride, a derivative thereof, and a diamine.

[4] The liquid alignment alignment agent according to [2], which comprises: having at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine having photoisomerism At least one of a compound obtained by reacting a compound having a chemical structure and a diamine containing at least one of the compounds represented by the formula (1); and other polymers used in combination with the polymer; and other polymerization The product is obtained by reacting a raw material monomer having at least one of a compound represented by the formula (1) and a diamine containing a tetracarboxylic dianhydride, a derivative thereof, and a diamine without a photoisomerization structure. Polymer.

[5] The liquid alignment alignment agent according to [1], which comprises: at least one of the group consisting of a group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine having light At least one of a polymer obtained by reacting a raw material monomer of a compound of an isomerized structure; and any one of a tetracarboxylic dianhydride, a derivative thereof, and a diamine having no photoisomerization structure, and The amine contains at least one of a polymer obtained by reacting a raw material monomer of at least one of the compounds represented by the formula (1).

The liquid crystal alignment agent for photoalignment according to any one of the above aspects, wherein the diamine represented by the formula (1) is selected from the group consisting of the formula (1-1) At least one of the group consisting of an amine and a diamine represented by the formula (1-2): In the formulae (1-1) and (1-2), R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms.

The liquid crystal alignment agent for photoalignment according to any one of the above aspects, wherein the diamine represented by the formula (1) is selected from the following formula (1-1-1) ～Formula (1-1-6), Formula (1-1-17), Formula (1-1-18), Formula (1-2-1) to Formula (1-2-6), Formula (1- At least one of the group consisting of 2-17) and the diamine represented by the formula (1-2-18): .

The liquid crystal alignment agent for photoalignment according to any one of the above aspects, wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is a formula (II) to At least one of the compounds represented by (VI): In the formulae (II) to (V), R ² and R ³ are a monovalent organic group having -NH ₂ or a monovalent organic group having -CO-O-CO-, and in the formula (IV), R ⁴ is a divalent organic group, in the formula (VI), R ⁵ is -NH ₂ or an aromatic ring having -CO-O-CO- of.

[9] The liquid alignment alignment agent according to [8], wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is selected from the group consisting of Formula (II-1) and Formula (II-2). Formula (III-1), Formula (III-2), Formula (IV-1), Formula (IV-2), Formula (V-1) to Formula (V-3), Formula (VI-1), And at least one of the group of compounds represented by the formula (VI-2): In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a is an integer of 0 to 2; in the formula (V-3), ring A and ring B are each independently selected from a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon and at least one heterocyclic ring, R ¹¹ is a linear-chain carbon number of the alkylene group having 1 to 20, -COO -, - OCO -, - NHCO -, - CONH -, - N (CH 3) CO-, or -CON(CH ₃ )-, R ¹² is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ )CO-, or In -CON(CH ₃ )-, R ¹¹ and R ¹² , one or two of -CH ₂ - of the linear alkyl group may be substituted by -O-, and R ⁷ to R ¹⁰ are independently -F, -CH, respectively. ₃ , -OCH ₃ , -CF ₃ , or -OH, and b to e are each independently an integer of 0 to 4.

[10] The liquid alignment alignment agent according to any one of [1], wherein the tetracarboxylic dianhydride having no photoisomerization structure is selected from the group consisting of the following formula (AN- I) to at least one of the group of tetracarboxylic dianhydrides represented by the formula (AN-VII): In the formula (AN-I), the formula (AN-IV) and the formula (AN-V), X is independently a single bond or -CH ₂ -; in the formula (AN-II), G is a single bond, and the carbon number is 1 ～20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; formula (AN-II)～ In the formula (AN-IV), Y is independently one selected from the group of trivalent groups described below, At least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; in the formula (AN-III) to the formula (AN-V), the ring A ¹⁰ is a group of a monocyclic hydrocarbon having a carbon number of 3 to 10. Or a group of a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms, wherein at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and a bond bonded to the ring may be bonded to any carbon constituting the ring, Two bonding bonds may be bonded to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group, in the formula (AN-VII) , G ^{10 is} independently -O-, -COO- or -OCO-; and r is independently 0 or 1.

[11] The liquid alignment alignment agent according to [10], wherein the tetracarboxylic dianhydride having no photoisomerization structure is selected from the group consisting of the following formula (AN-1-1), and the 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), in the formula (AN-10-1), the formula (AN-11-3), the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4) At least one of: In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12.

[12] The liquid alignment alignment agent for photoalignment according to any one of [1], wherein the diamine having no photoisomerization structure is selected from the following formula (DI-1). At least one of the group consisting of the formula (DI-16), the formula (DIH-1) to the formula (DIH-3), and the formula (DI-31) to the formula (DI-35): In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group may be -OH substituents; in formula (DI-3) and formula (DI-5) ~ of formula (DI-7), G ²¹ are each 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 An integer of 1 to 5, n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; in the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single a bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having a carbon number of 1 to 10; In DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or benzyl substitution, Further, in the formula (DI-4), at least one hydrogen of the benzene ring may be substituted with one selected from the group consisting of a group represented by the following formula (DI-4-a) to formula (DI-4-e) ; In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; the bond site is not fixed at the carbon atom constituting the ring, and is represented on the ring. bonding position is arbitrary, -NH ₂ bonding position on the cyclohexane ring or benzene ring is bonded to any position other than G ²¹ or G ²² in position; In formula (DI-11), r is 0 or 1; of formula (DI-8) ~ of formula (DI-11) in bonded on the ring -NH ₂ bonding positions to an arbitrary position; In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. The substituted phenyl group, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, q is an integer of 0 to 4; in the formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, and the carbon number is 1. An alkyl group of ～6, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 1 to 6 carbon atoms, and q independently an integer of 0 to 4; In 15), ring C is a monocyclic ring containing a hetero atom; in the formula (DI-16), G ²⁴ is a single bond, an alkylene group having a carbon number of 2 to 6 or a 1,4-phenylene group, and r is 0. Or 1; in the formula (DI-13) to the formula (DI-16), the group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position on the ring is arbitrary; In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group 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 of the ring may be a methyl group, an ethyl group, or a phenyl group. In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the ring may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond and a carbon number. Is an alkyl group of 1 to 20, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; (DIH-2 And in the formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary 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, R ²⁵ is alkyl having 3 to 30, a phenyl group having a steroid skeleton, or by the a group represented by the formula (DI-31-a) wherein at least one hydrogen of the alkyl group may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡C - Substituting, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or a carbon number of 3 to 30 The alkoxy group is substituted, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. 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 group having 1 to 12 carbon atoms, and more than one alkyl group of the alkylene group -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- In the diyl, naphthalene-2,7-diyl or inden-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , s, t, and u are independent integers of 0 to 2, and their total is 1 to 5. 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 different. R ²⁶ may be the same or different, and R ²⁶ is hydrogen, -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. , -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be represented by the following formula (DI-31-b) Bivalent base substitution, In formula (DI-31-b), R 27 and R ²⁸ are independently alkyl having 1 to 3, v is an integer of 1 to 6; Of formula (DI-32) and formula (DI-33) in, G ³⁰ are each independently a single bond, CO- or -CH ₂ -, R ²⁹ is independently hydrogen or -CH _3, R ³⁰ is hydrogen, a carbon number of 1 An alkyl group of -20 or an alkenyl group having 2 to 20 carbon atoms; a hydrogen of the benzene ring of the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the formula (DI- 32) and in the formula (DI-33), a group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. And R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-, and R ³² is a carbon number Is an alkyl group of 6 to 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1, and The -NH ₂ bonded to the benzene ring indicates that the bonding position on the ring is arbitrary.

[13] The liquid alignment alignment agent according to [12], wherein the diamine having no photoisomerization structure is selected from the group consisting of the following formula (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-5-17), formula (DI-5-28) , formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI- At least one of the group consisting of: 16-1), (DI-31-44), and (DIH-2-1): In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; 5-30), k is an integer from 1 to 5; and in the formula (DI-7-3), n is 1 or 2; .

[14] The liquid alignment alignment agent according to any one of [1] to [13] further comprising a radically polymerizable unsaturated double selected from the group consisting of an alkenyl group substituted with a nadic ylidene compound. At least one of a group of compounds of a bond, a oxazine compound, an oxazoline compound, and an epoxy compound.

[15] The liquid alignment alignment agent for light alignment according to any one of [1] to [14], which is used for the manufacture of a lateral electric field type liquid crystal display element.

[16] A liquid crystal alignment film which is formed by the liquid alignment alignment agent for photoalignment according to any one of [1] to [15].

[17] A liquid crystal display element comprising the liquid crystal alignment film according to [16].

[18] A transverse electric field type liquid crystal display element comprising the liquid crystal alignment film according to [16]. [Effects of the Invention]

The liquid crystal display element having the liquid alignment alignment film formed by the liquid alignment alignment agent of the present invention does not decrease in voltage holding ratio even when used for a long period of time, and can be maintained high even when exposed to intense light. Display quality.

<Liquid alignment agent for light alignment>

The liquid alignment alignment agent for photoalignment according to the present invention contains at least one polymer selected from the group consisting of polylysine, polylysine, and polyamidene obtained by ruthenium imidization thereof. The polyamidamine obtained by the ruthenium imidization and the ruthenium imidization thereof is a reaction product of at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine. It is characterized in that at least one of the raw material monomers of the polymer has a photoisomerization structure, and the diamine contains at least one of the compounds represented by the following formula (1). The polylysine, the poly phthalate, and the polyimine obtained by ruthenium imidation thereof are components dissolved in a solvent when a liquid crystal alignment agent to be described later containing a solvent is prepared, and When the liquid crystal alignment agent is formed into a liquid crystal alignment film to be described later, it is possible to form a component of a liquid crystal alignment film containing polyilylimine as a main component. Polyammonium esters can be synthesized by a method of synthesizing the polylysine with a hydroxyl group-containing compound, a halide, an epoxy group-containing compound, or the like, or by subjecting an acid dianhydride to A method of synthesizing a derivatized tetracarboxylic acid diester or tetracarboxylic acid diester dichloride with a diamine. The tetracarboxylic acid diester derived from an acid dianhydride can be obtained, for example, by reacting an acid dianhydride with 2 equivalents of an alcohol and ring-opening, and the tetracarboxylic acid diester dichloride can be obtained by making a tetracarboxylic acid diester and 2 equivalents of chlorine. It is obtained by reacting a chemical (for example, sulfoxide, etc.). Further, the polyglycolate may have only a phthalate structure, or may be a partial ester compound in which a valeric acid structure and a phthalate structure coexist. The liquid-aligning agent for photoalignment of the present invention may contain one of the above-mentioned poly-proline, a polyphthalate, and a polyimine obtained by ruthenium imidation thereof, or two or more kinds thereof. The definitions of R ^a and R ^b in the formula (1) are as described above.

The liquid alignment alignment agent for photoalignment according to the present invention comprises: at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine having a photoisomerization structure, and the diamine contains the formula (1) at least one of a polymer obtained by reacting a raw material monomer of at least one of the compounds represented; or a mixture comprising: a group selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine At least one of the polymers obtained by reacting at least one raw material monomer having a photoisomerization structure; and having no photoisomerization structure for any of the tetracarboxylic dianhydride and its derivative, and the diamine And the diamine contains at least one of a polymer obtained by reacting a raw material monomer of at least one of the compounds represented by the formula (1). <Photoreactive structure>

In the present invention, the photoreactive structure means a photoisomerization structure which causes isomerization by ultraviolet irradiation. A raw material monomer having a structure which causes isomerization by ultraviolet irradiation can be suitably used.

The monomer having the photoisomerization structure may, for example, be a tetracarboxylic dianhydride having a photoisomerization structure or a diamine having a photoisomerization structure, and is preferably selected from the following formulas having good photosensitivity ( At least one of the group of the compounds represented by the formula (VI) and the compound represented by the formula (V) is more preferably a compound represented by the formula (V). In the formulae (II) to (V), R ² and R ³ are a monovalent organic group having -NH ₂ or a monovalent organic group having -CO-O-CO-, and in the formula (IV), R ⁴ is In the divalent organic group, in the formula (VI), R ⁵ is an aromatic ring having -NH ₂ or -CO-O-CO-.

The photoisomerization structure may be incorporated into either the main chain or the side chain of the poly-proline or the derivative thereof of the present invention, and may be suitably used for a liquid crystal in a transverse electric field mode by being incorporated into the main chain. Display component.

As the material having the photoisomerization structure, a compound selected from the following formula (II-1), formula (II-2), formula (III-1), formula (III-2), and formula (( At least one of the group of compounds represented by IV-1), formula (IV-2), formula (V-1) to formula (V-3), formula (VI-1), and formula (VI-2) One.

In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary, and in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a is an integer of 0 to 2. In the formula (V-3), ring A and ring B are independently selected from monocyclic hydrocarbons and condensed polycyclic hydrocarbons. And at least one of the heterocyclic rings, R ¹¹ is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ )CO-, or -CON(CH ₃ )-, R ¹² is a linear alkyl group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ )CO-, or -CON(CH ₃ )-, R ¹¹ and R ¹² , one or two of -CH ₂ - of the linear alkyl group may be substituted by -O-, and R ⁷ to R ¹⁰ are independently -F, -CH, respectively. ₃ , -OCH ₃ , -CF ₃ or -OH, and b to e are each independently an integer of 0 to 4.

From the viewpoint of the photosensitivity, the compounds represented by the above formula (V-1), formula (V-2) and formula (VI-2) can be used particularly suitably. From the viewpoint of the above-mentioned alignment, a compound in which the bonding position of the amine group in the formula (V-2) and the formula (VI-2) is para-position, and a in the formula (V-2) can be more suitably used. Compound with =0.

The acid dianhydride or diamine having a structure which can be isomerized by ultraviolet irradiation, which is represented by the formula (II-1) to the formula (VI-2), can have the following formula (II-1-1) to formula (VI). -2-3) Specifically indicated.

Among these, by formulating the formula (VI-1-1) to the formula (V-3-8) as a compound containing a structure capable of isomerization by ultraviolet irradiation, it is possible to obtain light having higher sensitivity to ultraviolet irradiation. A liquid crystal alignment agent for alignment. By formula (VI-1-1), formula (V-2-1), formula (V-2-4) to formula (V-2-11), and formula (V-3-1) to formula (V) -3-8) A compound containing a structure capable of isomerization by ultraviolet irradiation, and a liquid alignment agent for photoalignment which can align liquid crystal molecules more uniformly can be obtained. By formulating the formula (V-2-4) to the formula (V-3-8) as a compound containing a structure capable of isomerization by ultraviolet irradiation, it is possible to obtain a further reduction in coloring of the formed alignment film. A liquid crystal alignment agent for light alignment.

In the case where a tetracarboxylic dianhydride having no photoreactive structure (non-photosensitive) and a tetracarboxylic dianhydride having a photoreactive structure (photosensitive property) are used in combination, in order to prevent a decrease in sensitivity of the alignment film to light The photosensitive tetracarboxylic dianhydride is preferably 0 mol% (% by mole) to 70 mol based on the total amount of the tetracarboxylic dianhydride used as the raw material used in the production of the poly-proline or the derivative thereof of the present invention. %, particularly preferably from 0 mol% to 50 mol%. Further, in order to improve various characteristics such as sensitivity to light, electrical characteristics, and afterimage characteristics, two or more kinds of photosensitive tetracarboxylic dianhydrides may be used in combination.

In the case where a diamine having no photoreactive structure (non-photosensitive) and a diamine having a photoreactive structure (photosensitive) are used in combination, in order to prevent a decrease in sensitivity of the alignment film to light, as a manufacturing cost The total amount of the diamine of the raw material used in the polyglycine or the derivative thereof of the invention is preferably 20 mol% to 100 mol%, particularly preferably 50 mol% to 100 mol%, based on the photosensitive diamine. Further, in order to improve various characteristics such as sensitivity to light and afterimage characteristics, two or more kinds of photosensitive diamines may be used in combination. As described above, in the aspect of the present invention, the case where the non-photosensitive tetracarboxylic dianhydride occupies the total amount of the tetracarboxylic dianhydride is contained, and even in the case, the minimum amount of the diamine is required to be 20 mol. % is a photosensitive diamine.

In order to improve various characteristics such as sensitivity to light and afterimage characteristics, a photosensitive tetracarboxylic dianhydride and a photosensitive diamine may be used in combination, or two or more kinds may be used in combination.

The diamine represented by the formula (1) of the present invention will be described. In the diamine represented by the formula (1), R ^a is hydrogen or a methyl group, and R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. The position of substitution in the benzene ring of the two amine groups is not particularly limited, and is preferably 3, 5 or 2 with respect to the substitution position of the guanamine group in order to provide a liquid crystal alignment agent in which liquid crystal molecules are more closely arranged. 5 digits. The diamine represented by the formula (1) is classified into ^a diamine represented by the formula (1-1) wherein R ^a is hydrogen and a diamine represented by the formula (1-2) wherein R ^a is a methyl group. In the formulae (1-1) and (1-2), R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. In the case where a liquid crystal alignment agent having a higher solubility in a solvent is required, it is preferred to use a diamine of the formula (1-1). Further, in the case where a liquid crystal alignment film having higher reliability is required, it is preferred to use a compound in which R ^b is hydrogen or -OH in the formulae (1-1) and (1-2). Specific examples of the diamine represented by the formula (1-1) are the compounds represented by the following formulas (1-1-1) to (1-1-28). Specific examples of the diamine represented by the formula (1-2) are the compounds represented by the following formulas (1-2-1) to (1-2-28).

The diamine represented by the formula (1-1-1) to the formula (1-1-4), the formula (1-2-1), and the formula (1-2-2) can be used as the liquid crystal constituting the present invention. One of the raw materials of the polymer of the alignment agent is used to obtain a liquid crystal alignment film having high liquid crystal alignment properties which does not deteriorate even when the display quality is used for a long period of time.

By using the diamine represented by the formula (1-2-1) to the formula (1-2-6) as one of the raw materials of the polymer constituting the liquid crystal alignment agent of the present invention, even if the formula (1) is used in combination Other diamines other than diamine can also inhibit gelation during polymer synthesis. The reason is considered to be that the hydrogen of the guanamine group is substituted by a methyl group, so that the interaction between molecules formed by hydrogen bonding disappears.

The non-photosensitive tetracarboxylic dianhydride containing the liquid-aligning liquid-aligning agent selected from the group consisting of polyphthalic acid, polyphthalate, and polyimine is described.

The non-photosensitive tetracarboxylic dianhydride used in the present invention can be selected from known non-photosensitive tetracarboxylic dianhydrides without limitation. The non-photosensitive tetracarboxylic dianhydride may be an aromatic system (including a heteroaromatic ring system) in which a dicarboxylic anhydride is directly bonded to an aromatic ring, and an aliphatic group in which a dicarboxylic anhydride is not directly bonded to an aromatic ring. A tetracarboxylic dianhydride in any group of heterocyclic lines.

A suitable example of such a non-photosensitive tetracarboxylic dianhydride is a formula (AN-I) from the viewpoints of easiness of obtaining a raw material, easiness in polymerization of a polymer, and electrical properties of a film. - Tetracarboxylic dianhydride represented by the formula (AN-VII).

In the formula (AN-I), the formula (AN-IV), and the formula (AN-V), X is independently a single bond or -CH ₂ -. In the formula (AN-II), G is a single bond, an alkylene group having 1 to 20 carbon atoms, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, Or -C(CF ₃ ) ₂ -. In the formula (AN-II) to the formula (AN-IV), Y is independently one selected from the group of trivalent groups described below, and the bond is bonded to any carbon, and at least one hydrogen of the group may be Substituted by ethyl, ethyl or phenyl.

In the formula (AN-III) to the formula (AN-V), the ring A ¹⁰ is a group of a monocyclic hydrocarbon having 3 to 10 carbon atoms or a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms. At least one of the hydrogens may be substituted by a methyl group, an ethyl group or a phenyl group, and the bonding bond attached to the ring may be bonded to any carbon constituting the ring, and the two bonding bonds may be bonded to the same carbon. In the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group. In the 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 following formula (AN-1) to formula (AN-16-14) can be mentioned. [Tetracarboxylic dianhydride represented by the formula (AN-1)] In the formula (AN-1), G ¹¹ is a single bond, an alkylene group having 1 to 12 carbon atoms, a 1,4-phenylene group, or a 1,4-cyclohexylene group. X ¹¹ is independently a single bond or -CH ₂ -. G ^{12 is} independently any of the following trivalent groups. When G ¹² is >CH-, the hydrogen of >CH- can be substituted by -CH ₃ . When G ¹² is >N-, G ^{11 is} not a single bond and -CH ₂ -, and X ^{11 is} not a single bond. Moreover, R ¹¹ is hydrogen or -CH ₃ .

Examples of the tetracarboxylic dianhydride represented by the formula (AN-1) include compounds represented by the following formulas. In the formula (AN-1-2) and the formula (AN-1-14), m is an integer of 1 to 12. [Tetracarboxylic dianhydride represented by the formula (AN-2)] In the formula (AN-2), R ^{12 is} independently hydrogen, -CH ₃ , -CH ₂ CH ₃ or a phenyl group.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-2) include compounds represented by the following formulas. [Tetracarboxylic dianhydride represented by the formula (AN-3)] Of formula (AN-3), ring A ¹¹ is a benzene ring or a cyclohexane ring.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-3) include compounds represented by the following formulas. [Tetracarboxylic dianhydride represented by the formula (AN-4)] In the 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. Ring A ^{11 is} independently a cyclohexane ring or a benzene ring. G ¹³ can be bonded to any position of the ring A ¹¹ . In the formula (G13-1), G ^13a and G ^13b are each independently a single bond, -O- or a divalent group represented by -NHCO-. The phenyl group is preferably a 1,4-phenylene group and a 1,3-phenylene group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-4) include compounds represented by the following formulas. In the formula (AN-4-17), m is an integer of 1 to 12. [Tetracarboxylic dianhydride represented by the formula (AN-5)] In the 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 formulas. [Tetracarboxylic dianhydride represented by the formula (AN-6)] In the formula (AN-6), X ^{11 is} independently a single bond or -CH ₂ -. X ¹² is -CH ₂ -, -CH ₂ CH ₂ - or -CH=CH-. n is 1 or 2.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-6) include compounds represented by the following formulas. [Tetracarboxylic dianhydride represented by the formula (AN-7)] In the formula (AN-7), X ¹¹ is a single bond or -CH ₂ -.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-7) include compounds represented by the following formulas. [Tetracarboxylic dianhydride represented by the formula (AN-8)] In the formula (AN-8), X ¹¹ is a single bond or -CH ₂ -. R ¹² is hydrogen, -CH ₃ , -CH ₂ CH ₃ or a phenyl group, 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 formulas. [Tetracarboxylic dianhydride represented by the formula (AN-9)] In the formula (AN-9), r is independently 0 or 1.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-9) include compounds represented by the following formulas. [Tetracarboxylic acid dianhydride represented by the formula (AN-10-1) and the formula (AN-10-2)] [Tetracarboxylic dianhydride represented by the formula (AN-11)] In the formula (AN-11), the 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 formulas. [Tetracarboxylic dianhydride represented by the formula (AN-12)] In the formula (AN-12), the ring A ^{11 is} 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 formulas. [Tetracarboxylic dianhydride represented by formula (AN-13)] In the formula (AN-13), X ¹³ is an alkylene group having 2 to 6 carbon atoms, and Ph represents a phenyl group. Examples of the tetracarboxylic dianhydride represented by the formula (AN-13) include compounds represented by the following formulas. [Tetracarboxylic dianhydride represented by the formula (AN-14)] In the 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 formulas. [Tetracarboxylic dianhydride represented by the formula (AN-15)] In the formula (AN-15), w is an integer of 1 to 10.

Examples of the tetracarboxylic dianhydride represented by the formula (AN-15) include compounds represented by the following formulas. Examples of the tetracarboxylic dianhydride other than the above include the following compounds. A suitable material for improving each characteristic of the acid dianhydride will be described.

In the acid dianhydride used for the polymer using a monomer having a photoisomerization structure, when it is important to improve the alignment of the liquid crystal, it is preferable to have the formula (AN-1), the formula (AN-3), and The compound represented by the formula (AN-4) is more preferably represented by the formula (AN-1-2), the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-5), A compound represented by the formula (AN-4-17) and the formula (AN-4-29). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When it is important to increase the transmittance of the liquid crystal display device, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), and the formula. (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10) A compound represented by the formula (AN-16-3) and the formula (AN-16-4). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

When it is important to increase the voltage holding ratio (VHR) of the liquid crystal display element, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), and the formula (AN). AN-2-1), formula (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), A compound represented by the formula (AN-16-1), the formula (AN-16-3), and the formula (AN-16-4). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

As one of the methods for preventing burn marks, it is effective to lower the volume resistance value of the liquid crystal alignment film to increase the relaxation rate of residual electric charge (residual DC) in the alignment film. In the case of paying attention to the object, the acid dianhydride preferably has the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), and the formula (AN-4- 29), and a compound represented by the formula (AN-11-3).

In an acid dianhydride used for a polymer which does not use a monomer having a photoisomerization structure, in order to improve the alignment of the liquid crystal, it is preferred to have the formula (AN-1), the formula (AN-3), The compound represented by the formula (AN-4) is more preferably of the formula (AN-1-1), the formula (AN-1-2), the formula (AN-1-13), and the formula (AN-2-1). A compound represented by the formula (AN-3-2), the formula (AN-4-17), and the formula (AN-4-29). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferred.

When it is important to increase the transmittance of the liquid crystal display device, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), and the formula. (AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-5-1), formula (AN-7-2), formula (AN-10) A compound represented by the formula (AN-16-3) and the formula (AN-16-4). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

In the case where the VHR of the liquid crystal display element is emphasized, the acid dianhydride preferably has the formula (AN-1-1), the formula (AN-1-2), the formula (AN-2-1), and the formula (AN). AN-3-1), formula (AN-4-17), formula (AN-4-30), formula (AN-7-2), formula (AN-10), formula (AN-16-1), A compound represented by the formula (AN-16-3) and the formula (AN-16-4). In the formula (AN-1-2), m = 4 or 8 is preferred. In the formula (AN-4-17), m = 4 or 8 is preferable, and m = 8 is more preferable.

As one of the methods for preventing burn marks, it is effective to lower the volume resistance value of the liquid crystal alignment film to increase the relaxation rate of residual electric charge (residual DC) in the alignment film. In the case of paying attention to the object, the acid dianhydride preferably has the formula (AN-1-13), the formula (AN-3-2), the formula (AN-4-21), and the formula (AN-4- 29), and a compound represented by the formula (AN-11-3).

Non-photosensitive other than the diamine represented by the formula (1) for use in the photo-alignment liquid crystal alignment agent containing at least one selected from the group consisting of polyphthalic acid, polyphthalate, and polyimine. The description will be made of a diamine and a non-photosensitive dioxime. When the liquid alignment alignment agent for photoalignment of the present invention is produced, it can be selected from known non-photosensitive diamines and non-photosensitive diterpenes without limitation.

Diamines can be classified into two types depending on their structures. That is, a diamine having a side chain group and a diamine having no side chain group, the side chain group being a group branched from the main chain when the skeleton linking the two amine groups is regarded as a main chain. The side chain group is a group having an effect of increasing the pretilt angle. The side chain group having such an effect is required to have a carbon number of 3 or more. Specific examples thereof include an alkyl group having 3 or more carbon atoms, an alkoxy group having 3 or more carbon atoms, and a carbon number of 3 or more. An alkoxyalkyl group and a group having a steroid skeleton. Any one having one or more rings and having a ring having a carbon number of 1 or more, an alkoxy group having 1 or more carbon atoms, and an alkoxyalkyl group having 2 or more carbon atoms as a substituent The base also has an effect as a side chain group. In the following description, a diamine having such a side chain group may be referred to as a side chain type diamine. Further, a diamine having no such a side chain group is sometimes referred to as a non-side chain type diamine.

By suitably separating the non-side chain type diamine from the side chain type diamine, it is possible to correspond to the respective pretilt angles required. The side chain type diamine is preferably used in combination to the extent that the characteristics of the present invention are not impaired. In addition, it is preferable to use a side chain type diamine and a non-side chain type diamine for the purpose of improving the vertical alignment property, the voltage holding ratio, the burn-in property, and the alignment property of the liquid crystal.

The non-side chain type diamine is described. Examples of the known diamine having no side chain include the following diamines of the formula (DI-1) to the formula (DI-16).

In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group is extended. Can be replaced by -OH. In the formula (DI-3) and the formula (DI-5) to the formula (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-, m is independently an integer of 1 to 12, k is an integer of 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 formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having a carbon number of 1 to 10. At least one hydrogen of the cyclohexane ring and the benzene ring in the formula (DI-2) to the formula (DI-7) may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl or benzyl substitution, further, in formula (DI-4), at least one hydrogen of the cyclohexane ring and the benzene ring may be selected One of the groups of the groups represented by the following formulas (DI-4-a) to (DI-4-e) is substituted. The group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. Further, the bonding position of -NH ₂ on the cyclohexane ring or the benzene ring is any position other than the bonding position of G ²¹ or G ²² . In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ . In the formula (DI-11), r is 0 or 1. Of formula (DI-8) - in the formula (DI-11), bonded on the ring -NH ₂ bonding positions to an arbitrary position.

In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. Substituted phenyl, w is an integer from 1 to 10. In the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, and q is 0 to 4 The integer. In the formula (DI-14), the ring B is a monocyclic heterocyclic aromatic group, and R ²⁴ is hydrogen, -F, -Cl, an alkyl group having 1 to 6 carbon atoms, an alkoxy group, a vinyl group, or an alkyne group. Base, q is independently an integer from 0 to 4. In the formula (DI-15), the ring C is a heterocyclic aromatic group or a heterocyclic aliphatic group. In the formula (DI-16), G ²⁴ is a single bond, an alkylene group having 2 to 6 carbon atoms or a 1,4-phenylene group, and r is 0 or 1. Further, the group in which the bonding position is not fixed to the carbon atom constituting the ring indicates that the bonding position on the ring is arbitrary. In the formula (DI-13) to the formula (DI-16), the bonding position of -NH ₂ bonded to the ring is an arbitrary position.

Specific examples of the diamine having no side chain of the formula (DI-1) to the formula (DI-16) include the following formula (DI-1-1) to formula (DI-16-1). An example of the diamine represented by the formula (DI-1) is shown below. In the formula (DI-1-7) and the formula (DI-1-8), k is independently an integer of 1 to 3. Examples of the diamine represented by the formula (DI-2) to the formula (DI-3) are shown below. An example of the diamine represented by the formula (DI-4) is shown below. An example of the diamine represented by the formula (DI-5) is shown below. In the formula (DI-5-1), m is an integer of 1 to 12. In the formula (DI-5-12) and the formula (DI-5-13), m is an integer of from 1 to 12. In the formula (DI-5-16), v is an integer of 1 to 6. In the formula (DI-5-30), k is an integer of 1 to 5.

In the formula (DI-5-35) to the formula (DI-5-37) and the formula (DI-5-39), m is an integer of 1 to 12, and the formula (DI-5-38) and the formula (DI- In 5-39), k is an integer of 1 to 5, and in the formula (DI-5-40), n is an integer of 1 or 2. An example of the diamine represented by the formula (DI-6) is shown below. An example of the diamine represented by the formula (DI-7) is shown below. In the formula (DI-7-3) and the formula (DI-7-4), m is an integer of 1 to 12, and n is independently 1 or 2. In the formula (DI-7-12), m is an integer of 1 to 12. An example of the diamine represented by the formula (DI-8) is shown below. An example of the diamine represented by the formula (DI-9) is shown below. An example of the diamine represented by the formula (DI-10) is shown below. An example of the diamine represented by the formula (DI-11) is shown below. An example of the diamine represented by the formula (DI-12) is shown below. An example of the diamine represented by the formula (DI-13) is shown below. An example of the diamine represented by the formula (DI-14) is shown below. An example of the diamine represented by the formula (DI-15) is shown below. An example of the diamine represented by the formula (DI-16) is shown below. Explain the second. Examples of the known diterpenes having no side chain include the following formula (DIH-1) to formula (DIH-3).

Of formula (DIH-1) in, G ²⁵ is a single bond, an alkylene group having a carbon number of 1 to 20, -CO -, - O -, - S -, - SO 2 -, - C (CH 3) 2 - , or -C(CF ₃ ) ₂ -. In the formula (DIH-2), the ring D is a cyclohexane ring, a benzene ring or a naphthalene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group. In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond, and the carbon number is 1-20. Alkyl, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -. In the formula (DIH-2) and the formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary position. Examples of the formula (DIH-1) to the formula (DIH-3) are shown below. In the formula (DIH-1-2), m is an integer of 1 to 12.

Such a non-side chain type diamine and diterpene have an effect of improving electrical characteristics such as a decrease in ion density of a liquid crystal display element. Use of a non-side chain type diamine and/or dipthylene as a liquid alignment for photoalignment for producing a polyglycolic acid, polyphthalate or polyimine used in the liquid crystal alignment agent of the present invention In the case of the diamine of the agent, the proportion of the total amount of the diamine and the dioxane is preferably from 0 mol% to 90 mol%, more preferably from 0 mol% to 50 mol%.

The side chain type diamine is described. Examples of the side chain group of the side chain type diamine include the following groups.

The side chain group may, first, be an alkyl group, an alkoxy group, an alkoxyalkyl group, an alkylcarbonyl group, an alkylcarbonyloxy group, an alkoxycarbonyl group, an alkylaminocarbonyl group, an alkenyl group, an alkenyloxy group, or the like. Alkenylcarbonyl, alkenylcarbonyloxy, alkenoxycarbonyl, alkenylaminocarbonyl, alkynyl, alkynyloxy, alkynylcarbonyl, alkynylcarbonyloxy, alkynyloxycarbonyl, alkynylaminocarbonyl, and the like. The alkyl group, the alkenyl group and the alkynyl group in these groups are each a group having a carbon number of 3 or more. However, in the alkoxyalkyl group, the carbon number of the entire group may be 3 or more. These groups may be linear or branched.

Next, the terminal ring has an alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms as a substituent, and examples thereof include a phenyl group and a benzene group. An alkyl group, a phenyl alkoxy group, a phenoxy group, a phenylcarbonyl group, a phenylcarbonyloxy group, a phenoxycarbonyl group, a phenylaminocarbonyl group, a phenylcyclohexyloxy group, a cycloalkane having a carbon number of 3 or more , cyclohexylalkyl, cyclohexyloxy, cyclohexyloxycarbonyl, cyclohexylphenyl, cyclohexylphenylalkyl, cyclohexylphenoxy, bis(cyclohexyl)oxy, bis(cyclohexyl)alkane , bis(cyclohexyl)phenyl, bis(cyclohexyl)phenylalkyl, bis(cyclohexyl)oxycarbonyl, bis(cyclohexyl)phenoxycarbonyl, and cyclohexylbis(phenyl)oxycarbonyl The base of the isocyclic structure.

Further, examples thereof include a ring group having two or more benzene rings, a group having two or more cyclohexane rings, or two or more rings including a benzene ring and a cyclohexane ring. And the bonding group is independently a single bond, -O-, -COO-, -OCO-, -CONH- or an alkylene group having a carbon number of 1 to 3, and the terminal ring has an alkyl group having 1 or more carbon atoms, A fluorine-substituted alkyl group having 1 or more carbon atoms, an alkoxy group having 1 or more carbon atoms, or an alkoxyalkyl group having 2 or more carbon atoms is used as a substituent. A group having a steroid skeleton is also effective as a side chain group.

The diamine having a side chain includes a compound represented by the following formula (DI-31) to formula (DI-35).

In the formula (DI-31), G ²⁶ is a single bond, -O-, -COO-, -OCO-, -CO-, -CONH-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O- -OCF ₂ - or -(CH ₂ ) _m' -, m' is an integer from 1 to 12. Preferable examples of G ²⁶ are a single bond, -O-, -COO-, -OCO-, -CH ₂ O-, and an alkylene group having 1 to 3 carbon atoms, and particularly preferred examples are a single bond, -O -, - COO -, - OCO -, - CH 2 O -, - CH 2 - and -CH ₂ CH ₂ -. R ²⁵ is an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the following formula (DI-31-a). In the alkyl group, at least one hydrogen may be substituted by -F, and at least one -CH ₂ - may be substituted by -O-, -CH=CH- or -C≡C-. The hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or an alkoxy group having 3 to 30 carbon atoms. Replace. The bonding position of -NH ₂ bonded to the benzene ring indicates an arbitrary position in the ring, and the bonding position is preferably a meta or para position. That is, when the bonding position of the base "R ²⁵ -G ²⁶ -" is set to 1 bit, the two bonding positions are preferably 3 bits and 5 bits, or 2 bits and 5 bits.

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 group having a carbon number of 1 to 12, and more than one of the alkyl groups CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -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 fluoren-9,10-diyl, ring B ²¹ , ring B ²² In the ring B ²³ and the ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , and s, t and u are independently an integer of 0 to 2, and their total is 1 to 5, when s, t or u is At 2 o'clock, the two bonding groups in each bracket can be the same or different, and the two rings can be the same or different. R ²⁶ is hydrogen, -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group 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 each} independently an alkyl group having 1 to 3 carbon atoms, and v is an integer of 1 to 6. Preferable examples of R ²⁶ are an alkyl group having 1 to 30 carbon atoms and an alkoxy group having 1 to 30 carbon atoms.

In the formula (DI-32) and the formula (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, and the carbon number is 1. An alkyl group of -20 or an alkenyl group having 2 to 20 carbon atoms. At least one hydrogen of the benzene ring in the formula (DI-33) may be substituted with an alkyl group having 1 to 20 carbon atoms or a phenyl group. Further, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position in the ring is arbitrary. Preferably, one of the two base "-phenyl-G ³⁰ -O-" in the formula (DI-32) is bonded to the 3-position of the steroid core, and the other is bonded to the 6-position of the steroid core. The bonding position of the two base "-phenyl-G ³⁰ -O-" in the formula (DI-33) on the benzene ring is preferably a meta position or a para position relative to the steroid nucleus. In the formula (DI-32) and the formula (DI-33), -NH ₂ bonded to the benzene ring means that the bonding position in the ring is arbitrary.

In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O-, -NH-, or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or a carbon number of 1 to 3 alkyl groups. R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-. R ³² is an alkyl group having 6 to 22 carbon atoms, and R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms. Ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1. Moreover, -NH ₂ bonded to the benzene ring means that the bonding position on the ring is arbitrary, but is preferably independent and the bonding position with respect to G ³¹ is meta or para.

Specific examples of the side chain type diamine are exemplified below. The diamine having a side chain of the formula (DI-31) to the formula (DI-35) is represented by the following formula (DI-31-1) to formula (DI-35-3). Compound. An example of the compound represented by the formula (DI-31) is shown below.

In the formula (DI-31-1) to the formula (DI-31-11), R ³⁴ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, preferably 5 to 25 carbon atoms. The alkyl group or alkoxy group having a carbon number of 5 to 25. R ³⁵ is an alkyl group having 1 to 30 carbon atoms or an alkoxy group having 1 to 30 carbon atoms, and preferably an alkyl group having 3 to 25 carbon atoms or an alkoxy group having 3 to 25 carbon atoms.

In formula (DI-31-12) ~ of formula (DI-31-17), R ³⁶ is alkyl having 4 to 30 carbon atoms is preferably an alkyl group having 6 to 25. R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and preferably an alkyl group having 8 to 25 carbon atoms.

In the formula (DI-31-18) to the formula (DI-31-43), R ³⁸ is an alkyl group having 1 to 20 carbon atoms or an alkoxy group having 1 to 20 carbon atoms, and preferably having 3 to 20 carbon atoms. The alkyl group or the alkoxy group having 3 to 20 carbon atoms. R ³⁹ is hydrogen, -F, an alkyl group having 1 to 30 carbon atoms, an alkoxy group having 1 to 30 carbon atoms, -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , preferably having a carbon number of 3 An alkyl group of ～25 or an alkoxy group having a carbon number of 3 to 25. Further, G ³³ is an alkylene group having 1 to 20 carbon atoms. An example of the compound represented by the formula (DI-32) is shown below. An example of the compound represented by the formula (DI-33) is shown below. An example of the compound represented by the formula (DI-34) is shown below. In formula (DI-34-1) ~ of formula (DI-34-14), R ⁴⁰ is hydrogen or alkyl having 1 to 20 carbon atoms, preferably hydrogen or alkyl having 1 to 10, and, R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms. An example of the compound represented by the formula (DI-35) is shown below. In the formula (DI-35-1) to the formula (DI-35-3), R ³⁷ is an alkyl group having 6 to 30 carbon atoms, and R ⁴¹ is hydrogen or an alkyl group having 1 to 12 carbon atoms.

As the diamine in the present invention, a formula (DI-1-1) to a formula (DI-16-1), a formula (DIH-1-1) to a formula (DIH-3-6), and a formula ( DI-31-1) to a diamine other than the diamine represented by the formula (DI-35-3). Examples of such a diamine include compounds represented by the following formula (DI-36-1) to formula (DI-36-13). In the formula (DI-36-1) to the formula (DI-36-8), R ⁴² each independently represents an alkyl group having 3 to 30 carbon atoms.

In the formula (DI-36-9) to the formula (DI-36-11), e is an integer of 2 to 10, and in the formula (DI-36-12), R ^{43 is} independently hydrogen, -NHBoc or -N ( Boc) ₂ , at least one of R ⁴³ is -NHBoc or -N(Boc) ₂ , in the formula (DI-36-13), R ⁴⁴ is -NHBoc or -N(Boc) ₂ , and m is 1 to 12 The integer. Here, Boc is a third butoxycarbonyl group. Suitable materials for improving the respective characteristics of the diamine and the dioxime will be described. In the diamine and the dioxime used for the polymer using the monomer having a photoisomerization structure, in the case where the orientation of the liquid crystal is further improved, the diamine and the dioxane are preferably used. Formula (DI-1-3), Formula (DI-5-1), Formula (DI-5-5), Formula (DI-5-9), Formula (DI-5-12), Formula (DI-5) -13), a diamine represented by the formula (DI-5-29), the formula (DI-6-7), the formula (DI-7-3), and the formula (DI-11-2). In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-5-12), m = 2 to 6, preferably m = 5. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-5-30), k = 2 is preferred. In the formula (DI-7-3), m = 2, 3 or 4, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

When it is important to increase the transmittance, it is preferable to use the formula (DI-1-3), the formula (DI-2-1), the formula (DI-5-1), and the diamine and the dioxime. The diamine represented by the formula (DI-5-5), the formula (DI-5-17), and the formula (DI-7-3) is more preferably a diamine represented by the formula (DI-2-1). In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

In the case where the VHR of the liquid crystal display element is emphasized, in the diamine and the dioxime, it is preferred to use the formula (DI-2-1), the formula (DI-4-1), and the formula (DI-4-2). ), formula (DI-4-10), formula (DI-4-15), formula (DI-5-1), formula (DI-5-28), formula (DI-5-30), and formula ( The diamine represented by DI-13-1) is more preferably a diamine represented by the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-13-1). In the formula (DI-5-1), m = 1 is preferred. In the formula (DI-5-30), k = 2 is preferred.

As one of the methods for preventing burn marks, it is effective to lower the volume resistance value of the liquid crystal alignment film to increase the relaxation rate of residual electric charge (residual DC) in the alignment film. In the case where the object is emphasized, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (II). DI-4-15), formula (DI-5-1), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28), formula (DI-7-12 And a diamine represented by the formula (DI-16-1), more preferably represented by the formula (DI-4-1), the formula (DI-5-1), and the formula (DI-5-13) Diamine. In the formula (DI-5-1), m = 2, 4 or 6, preferably m = 4. In the formula (DI-5-12), m = 2 to 6, preferably m = 5. In the formula (DI-5-13), m = 1 or 2 is preferable, and m = 1 is more preferable. In the formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 is more preferable.

In diamines and dioximes for polymers which do not use a monomer having a photoisomerization structure, the diamine and dioxime are emphasized in the case of further enhancing the layer separation property, that is, the alignment of the liquid crystal. In the crucible, it is preferred to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), the formula (DI-5-1), and the formula (DI-5-9). Diamine and dioxime represented by formula (DI-5-28) and formula (DIH-2-1). In the formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 1 or 2 is more preferable.

When it is important to increase the transmittance, it is preferable to use the formula (DI-1-2), the formula (DI-2-1), the formula (DI-5-1), and the diamine and the dioxime. The diamine represented by the formula (DI-7-3) is more preferably a diamine represented by the formula (DI-2-1). In the formula (DI-5-1), m = 1, 2 or 4 is preferable, and m = 1 or 2 is more preferable. In the formula (DI-7-3), m = 2 or 3, n = 1 or 2 is preferable, and m = 3 and n = 1 are more preferable.

In the case where the VHR of the liquid crystal display element is emphasized, in the diamine and the dioxime, it is preferred to use the formula (DI-2-1), the formula (DI-4-1), and the formula (DI-4-2). , represented by the formula (DI-4-15), the formula (DI-5-1), the formula (DI-5-28), the formula (DI-5-30), and the formula (DI-13-1) The diamine is particularly preferably a diamine represented by the formula (DI-2-1), the formula (DI-5-1), and the formula (DI-13-1). 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.

As one of the methods for preventing burn marks, it is effective to lower the volume resistance value of the liquid crystal alignment film to increase the relaxation rate of residual electric charge (residual DC) in the alignment film. In the case where the object is emphasized, it is preferable to use the formula (DI-4-1), the formula (DI-4-2), the formula (DI-4-10), and the formula (II). DI-4-15), formula (DI-5-1), formula (DI-5-9), formula (DI-5-12), formula (DI-5-13), formula (DI-5-28 a diamine represented by the formula (DI-5-30), the formula (DI-7-12), and the formula (DI-16-1), particularly preferably of the formula (DI-4-1), formula (DI) -5-1), and a diamine represented by the formula (DI-5-12). Wherein in the formula (DI-5-1), m = 1 or 2 is preferred, and in the formula (DI-5-12), preferably m = 2 to 6, particularly preferably m = 5, in the formula (DI-5) In -13), m = 1 or 2 is preferable, m = 1 is particularly preferable, and in the formula (DI-5-30), k = 2 is particularly preferable. In the formula (DI-7-12), m = 3 or 4 is preferable, and m = 4 is more preferable.

In each of the diamines, a part of the diamine may be substituted with a monoamine in a ratio of 40 mol% or less to the monoamine of the diamine. Such substitution can cause termination of the polymerization reaction when polyamic acid is formed, and further progress of the polymerization reaction can be suppressed. Therefore, by such substitution, the molecular weight of the obtained polymer (polyglycine, polyphthalate or polyimide) can be easily controlled, for example, the coating of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. characteristic. The diamine substituted with a monoamine may be one type or two or more types as long as the effects of the present invention are not impaired. Examples of the monoamine include aniline, 4-hydroxyaniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-decylamine, n-decylamine, and positive ten Monoamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, and n-dodecylamine.

The polyproline, polylysine and polyimine of the present invention may further contain a monoisocyanate compound in the monomer. By containing a monoisocyanate compound in the monomer, the terminal of the obtained polyaminic acid or its derivative is modified, and the molecular weight is adjusted. By using the terminal-modified polyglycine or a derivative thereof, for example, the coating properties of the liquid crystal alignment agent can be improved without impairing the effects of the present invention. From this point of view, the content of the monoisocyanate compound in the monomer is preferably from 1 mol% to 10 mol% based on the total amount of the diamine and the tetracarboxylic dianhydride in the monomer. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.

The polyproline, polylysine and polyimine of the present invention can be obtained by reacting a mixture of the acid anhydride with a diamine in a solvent. In the synthesis reaction, conditions other than the usual polyamine synthesis can be directly applied, except for the selection of the raw materials, without special conditions. The solvent to be used will be described later.

The liquid-aligning agent for photoalignment of the present invention may further contain other components than the polyamine, polyglycolate, and polyimine of the present invention. The other components may be one type or two or more types. As another component, other polymers, compounds, etc. which are mentioned later are mentioned, for example.

The other polymer may, for example, be a polyglycolic acid, a polyphthalate, or a polyimine obtained by reacting a raw material monomer having no photoisomerization structure and not containing the diamine of the formula (1). (hereinafter, referred to as "other poly-proline or its derivative"), polyester, polyamine, polyoxyalkylene, cellulose derivative, polyacetal, polystyrene derivative, poly(styrene- A phenyl maleimide derivative, a poly(meth)acrylate, or the like. It may be one type or two or more types. Among these polymers, other polyaminic acid or a derivative thereof and polyoxyalkylene oxide are preferable, and other polylysine or a derivative thereof is more preferable.

As the tetracarboxylic dianhydride for synthesizing other polyglycine or a derivative thereof, it can be used without limitation from the tetracarboxylic acid which is an essential component for synthesizing the liquid crystal alignment agent of the present invention, that is, polylysine or a derivative thereof. The tetracarboxylic dianhydride known as the acid dianhydride is selected from the same as the above-exemplified tetracarboxylic dianhydride.

As a preferable tetracarboxylic dianhydride, the tetracarboxylic dianhydride used for the polymer which does not use the monomer of a photoisomerization structure is mentioned.

The tetracarboxylic dianhydride for synthesizing another polyaminic acid or a derivative thereof preferably contains 10 mol% or more of an aromatic tetracarboxylic dianhydride, more preferably 30 mol%, based on all tetracarboxylic dianhydrides. The above aromatic tetracarboxylic dianhydride.

Examples of the diamine and the dioxime used for the synthesis of other poly-proline or a derivative thereof include the other two as the essential component of the liquid crystal alignment agent of the present invention, that is, poly-proline or a derivative thereof. The diamine and the diterpene exemplified by the amine and the diterpene are the same.

Preferable examples of the diamine and the dioxime include the diamine and dioxime used for the polymer which does not use the monomer having a photoisomerization structure.

The diamine for synthesizing another polyamine or a derivative thereof preferably contains 30 mol% or more of an aromatic diamine with respect to all diamines, and more preferably contains 50 mol% or more of an aromatic diamine.

The other polylysine or a derivative thereof can be synthesized by the method described in the method for synthesizing polyglycine or a derivative thereof, which is an essential component of the liquid crystal alignment agent of the present invention.

The liquid alignment alignment agent for photoalignment according to the present invention comprises, as described above, at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine, and having a photoisomerization structure and a diamine At least one of a polymer obtained by reacting a raw material monomer containing at least one of the compounds represented by the following formula (1); or a mixture comprising: a tetracarboxylic dianhydride and a derivative thereof, and a diamine At least one of a polymer obtained by reacting at least one raw material monomer having a photoisomerization structure; and having no light of any of tetracarboxylic dianhydride, a derivative thereof, and a diamine At least one of the polymers obtained by reacting a raw material monomer of at least one of the compounds represented by the following formula (1) with an isomerization structure.

The liquid alignment alignment agent for photoalignment of the present invention may contain at least two polymers. If the polymer having a photoisomerization structure in two polymers is [A] and the polymer having no photoisomerization structure is [B], it is considered that the weight average molecular weight of [A] is determined. Controlled to be a weight average molecular weight smaller than [B], in the process of pre-drying a liquid crystal alignment agent containing a mixture of two polymers onto a substrate and pre-drying, photoisomerization can be performed on the upper layer of the formed polymer film. The [A] segregation of the structure causes segregation of [B] which does not have a photoisomerization structure in the lower layer. Therefore, the presence of the polymer [A] having a photoisomerization structure on the surface of the alignment film becomes dominant, even a polymer having a photoisomerization structure based on the total amount of the polymer forming the alignment film [A] The content of the alignment film formed by the liquid alignment alignment agent for photoalignment of the present invention is also small, and also exhibits high liquid crystal alignment.

As described above, in the process of forming a film using a liquid crystal alignment agent containing two kinds of polymers, 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. Whether or not the alignment film is subjected to layer separation can be confirmed, for example, by measuring the surface energy of the formed film and the value of the surface energy of the film formed using the liquid crystal alignment agent containing only the polymer [A]. Same, or a value close to it.

As described above, in order to exhibit good photo-alignment, when the total amount of the polymer to be contained is 100, the content of [A] in the photo-alignment liquid crystal alignment agent of the present invention needs to be 20 wt% (weight). The percentage is more than 30 wt% or more, more preferably 50 wt% or more. Further, in order to maintain the transmittance of the liquid crystal alignment film to be good, the content of [A] needs to be 90 wt% or less, preferably 70 wt% or less, more preferably 50 wt% or less. Here, the preferable content of [A] described herein is one criterion, and may vary depending on the combination of tetracarboxylic dianhydride or diamine used in the raw material. In particular, when a raw material compound having an azobenzene structure is used, the content of [A] is set to be less than the above ratio by about 10% by weight to 20% by weight in order to maintain good permeability.

Regarding the weight average molecular weight of the polymer, [B] is adjusted to 50,000 to 200,000 by adjusting [A] to 8,000 to 40,000, preferably by adjusting the molecular weight (Mw) of [A] to 10,000 to 30,000, [B] The molecular weight (Mw) is adjusted to 80,000 to 160,000, which causes the layer separation. The weight average molecular weight of the polymer can be adjusted, for example, according to the time during which the tetracarboxylic dianhydride is reacted with the diamine. A small amount of the reaction liquid in the polymerization reaction can be used, and the weight average molecular weight of the polymer contained in the reaction liquid can be determined by a gel permeation chromatography (GPC) method, and the reaction can be determined based on the measured value. The end point. Moreover, a method of controlling the weight average molecular weight by terminating the termination of the polymerization reaction by substituting a considerable amount of the tetracarboxylic dianhydride and the diamine into a monocarboxylic acid or a monoamine at the beginning of the reaction is well known.

The ratio of the component [A] to the total amount of the component [A] and the component [B] is preferably 10% by weight to 100% by weight, and more preferably 20% by weight to 100% by weight.

Further, it may further include Japanese Patent Laid-Open No. 2009-036966, Japanese Patent Laid-Open No. 2010-18500, Japanese Patent Laid-Open No. 2011-102963, Japanese Patent Laid-Open No. 2011-253175, Japanese Patent Laid-Open No. 2012-159825, International Publication No. 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 The polyoxyalkylene disclosed in /165354 or the like is used as the polyoxyalkylene. <Alkenyl substituted nadic ylidene compound>

For example, for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time, the liquid crystal alignment agent of the present invention may further contain an alkenyl-substituted nadic quinone imine compound. The alkenyl-substituted nadicylimine compound may be used singly or in combination of two or more. For the purpose described, the content of the alkenyl-substituted nadic ylidene compound is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, and furthermore, relative to the poly-proline or its derivative. It is preferably from 1 wt% to 50 wt%. The Nadik imine compound is specifically described below.

The alkenyl-substituted nadicylimine compound is preferably a compound which is soluble in a solvent which dissolves the poly-proline or a derivative thereof used in the present invention. Examples of such an alkenyl-substituted nadicylimine compound include compounds represented by the following formula (NA). In the formula (NA), L ¹ and L ^{2 are} independently hydrogen, an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 3 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 ～12 aryl or benzyl, n is 1 or 2.

In the formula (NA), when n=1, W is an alkyl group having 1 to 12 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, and a carbon number of 6 to 6 12 aryl, benzyl, from -Z ¹ -(O) _r -(Z ² O) _k -Z ³ -H (here, Z ¹ , Z ² and Z ^{3 are} independently 2 to 6 carbon atoms a group represented by an alkyl group, r is 0 or 1, and k is an integer of 1 to 30, and is represented by -(Z ⁴ ) _r -BZ ⁵ -H (wherein Z ⁴ and Z ^{5 are} independently carbon numbers) An alkylene group of 1 to 4 or a cycloalkyl group having a carbon number of 5 to 8, B is a phenyl group, and r is a group represented by 0 or 1), and is represented by -BTBH (here, B is a stretching Phenyl, and T is a group represented by -CH ₂ -, -C(CH ₃ ) ₂ -, -O-, -CO-, -S-, or -SO ₂ -), or a hydrogen of these groups ~ Three hydrogen-substituted groups.

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

In the formula (NA), when n=2, W is an alkylene group having 2 to 20 carbon atoms, a cycloalkyl group having 5 to 8 carbon atoms, an extended aryl group having 6 to 12 carbon atoms, and a group represented by Z ¹ -O-(Z ² O) _k -Z ³ - (here, Z ¹ - Z ³ and k are as defined above), consisting of -Z ⁴ -BZ ⁵ - (here, Z ⁴ , Z ⁵ and B are as defined above), represented by -B-(OB) _r -T-(BO) _r -B- (where B is a phenyl group and T is a carbon number) It is a group represented by an alkyl group of 1 to 3, -O- or -SO ₂ -, r as defined above), or a group in which one hydrogen to three hydrogens of these groups are substituted by -OH.

In this case, preferred W is an alkylene group having 2 to 12 carbon atoms, a cyclohexylene group, a phenylene group, a benzylidene group, a benzene dimethyl group, and a -C ₃ H ₆ -O-(Z ² -O) group. a group represented by _n -OC ₃ H ₆ - (wherein Z ² is an alkylene group having 2 to 6 carbon atoms, and n is 1 or 2), and is represented by -BTB- (wherein B is a phenylene group) Further, T is a group represented by -CH ₂ -, -O- or -SO ₂ -), a group represented by -BOBC ₃ H ₆ -BOB- (here, B is a stretching phenyl group), and these One hydrogen or two hydrogen-substituted groups.

Such an alkenyl-substituted nadicylimine compound can be maintained by heating an alkenyl-substituted nadic anhydride anhydride and a diamine at a temperature of from 80 ° C to 220 ° C for 0.5 hour, as described in Japanese Patent No. 2,729,565. A compound obtained by the synthesis in ～20 hours or a commercially available compound. Specific examples of the alkenyl-substituted nadicylimine compound include the compounds shown below.

N-methyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-methyl-allylmethylbicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-methyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-methyl-A Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(2-ethylhexyl)-allylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, N-(2-ethylhexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine, N-allyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-allyl-allylmethylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxy quinone imine, N-allyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N -Isopropenyl-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarminemine, N-isopropenyl-allyl (methyl)bicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-isopropenyl-methylallyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N- Cyclohexyl-allyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-allyl (methyl) double [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-cyclohexyl-methylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine, N-phenyl-allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-phenyl-allyl (methyl) bicyclo [2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-benzyl-allyl bicyclo [2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-benzyl -Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-benzyl-methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2 -hydroxyethyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2-hydroxyethyl)-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(2,2-dimethyl-3-hydroxypropyl)-allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine, N-(2,2-dimethyl-3-hydroxypropyl)-allyl (methyl)bicyclo[2.2.1]hept-5- Alkene-2,3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(2,3-dihydroxypropyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-hydroxy-1-propenyl)-allylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(4-hydroxycyclohexyl)-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(4-Hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine, N-(4-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(4-hydroxyphenyl)-methylallylbicyclo[2.2.1]hept-5-ene -2,3-dicarboxy quinone imine, N-(4-hydroxyphenyl)-methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-(3-hydroxyphenyl)-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(3-hydroxyphenyl)-allyl (A Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-(p-hydroxybenzyl)-allylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{2-(2-hydroxyethoxy)ethyl}-allyl (methyl)bicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine, N-{2 -(2-hydroxyethoxy)ethyl}-methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine, N-{2-(2-hydroxyethoxy)ethyl}-methylallylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxy quinone imine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-allyl (methyl) bicyclo [2.2.1] H--5-ene-2,3-dicarboxy quinone imine, N-[2-{2-(2-hydroxyethoxy)ethoxy}ethyl]-methylallyl Bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)phenyl}-allyl bicyclo [2.2.1 Gh-5-ene-2,3-dicarboxy quinone imine, N-{4-(4-hydroxyphenyl isopropylidene)phenyl}-allyl (methyl)bicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindenine, N-{4-(4-hydroxyphenylisopropylidene)phenyl}-methylallylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine, and oligomers thereof, N,N'-extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine), N,N'-extended ethyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N' -Extended ethyl-bis(methylallylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N'- Hexamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-dodecamethylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-docamethylene-bis(allylmethylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), 1,2-double {3'- (allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinlimine)propoxy}ethane, 1,2-bis{3'-(allylmethylbicyclo[ 2.2.1] hept-5-ene-2,3-dicarboxy quinone imine) propoxy}ethane, 1,2-bis{3'-(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxyindolimine)propoxy}ethane, bis[2'-{3'-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) propoxy}ethyl]ether, bis[2'-{3'-(ene Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}ethyl]ether, 1,4-double {3'-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}butane, 1,4-double {3'-(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine) propoxy}butane, N,N'-p-phenylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine), N,N'-p-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N, N'-meta-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine), N,N'-meta-phenyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-{(1-methyl)-2,4-phenylene}-bis ( Allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N, N'-p-xylylene-bis(allyl bicyclo [2.2.1] g- 5-ene-2,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- Meta-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5- -2,3-dicarboxy quinone imine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)benzene Oxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenoxy Phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenoxy}benzene Propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenimido)phenyl}methane, bis{4-(allylmethylbicyclic [2.2.1]hept-5-ene-2,3-dicarboxylimenine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2, 3-dicarboxy quinone imine) phenyl}methane, bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine)phenyl} Methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}ether, bis{4-(allylmethylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxy quinazoline)phenyl}ether, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} ether, bis {4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, double {4- Allylmethyl Ring [2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}indole, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2 , 3-dicarboxy quinone imine) phenyl} fluorene, 1,6-bis (allyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine)-3-hydroxy- Hexane, 1,12-bis(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarsenazo)-3,6-dihydroxy-dodecane, 1, 3-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)-5-hydroxy-cyclohexane, 1,5-bis{3'-(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)propoxy}-3-hydroxy-pentane, 1,4-bis(allylbicyclo[2.2.1] Hg-5-ene-2,3-dicarboxyindolimine)-2-hydroxy-benzene, 1,4-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinoid imine)-2,5-dihydroxy-benzene, N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-p-(2-hydroxy)benzenedimethyl-bis(allylmethylcyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine), N,N'-m-(2-hydroxy)benzenedimethyl-bis(methylallyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-(2,3-dihydroxy)benzenedimethyl-bis(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3 -Dicarboxy quinone imine)-2-hydroxy-phenoxy}phenyl]propane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyfluorene Imine)-2-hydroxy-phenyl}methane, bis{3-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)-4-hydroxy-phenyl }ether, bis{3-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)-5-hydroxy-phenyl}indole, 1,1,1 -Tris{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimide)}phenoxymethylpropane, N,N',N''- Tris(ethylethylallyl bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmine)isomeric cyanurate, and oligomers thereof.

Further, the alkenyl-substituted nadicylimine compound used in the present invention may be a compound represented by the following formula containing an asymmetric alkylene group. Preferred compounds among the alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-phenylene-bis(allyl Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-p-phenylene-bis(allylmethylbicyclo[2.2.1]hept-5 -ene-2,3-dicarboxy quinone imine), N,N'- Phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-meta-phenyl-bis(allylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allyl bicyclol) [2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene- 2,3-dicarboxy quinone imine), N,N'-p-xylylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N, N'-m-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide), N,N'-m-xylylene Base-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), 2,2-bis[4-{4-(allylbicyclo[2.2 .1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(allylmethylbicyclo[2.2.1 ]hept-5-ene-2,3-dicarboxy quinone imine)phenoxy}phenyl]propane, 2,2-bis[4-{4-(methylallylbicyclo[2.2.1]g -5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyl醯imino)phenyl}methane, double {4-(allylmethyl double [2.2.1] hept-5-ene-2,3-dicarboximide (PEI)) phenyl} methane.

Double {4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}methane, bis{4-(methylallylmethylbicyclo) [2.2.1]hept-5-ene-2,3-dicarboxyinimide)phenyl}methane, bis{4-(allylbicyclo[2.2.1]hept-5-ene-2,3- Dicarboxy quinone imine) phenyl} ether, bis {4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine) phenyl} ether, double { 4-(Methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolide)phenyl}ether, bis{4-(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine) phenyl} fluorene, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy fluorene Amine) phenyl} hydrazine, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}indole. More preferred alkenyl substituted nadic quinone imine compounds are shown below.

N,N'-Extended ethyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-extended ethyl-bis(allyl Methylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-extended ethyl-bis(methylallylbicyclo[2.2.1]heptane- 5-ene-2,3-dicarboxy quinone imine), N,N'-trimethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine ), N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-hexamethylene- Bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecyl-bis(allylbicyclo[2.2. 1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-dodecamethylene-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine), N,N'-cyclohexylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine), N,N '-Extended cyclohexyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyinylimine).

N,N'-p-phenyl-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-p-phenylene-bis( Allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine), N,N'-meta-phenyl-bis(allylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine), N,N'-meta-phenyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-{(1-methyl)-2,4-phenylene}-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-di Carboxylimine), N,N'-p-xylylene-bis(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'- P-Benzyl-bis(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindenine), N,N'-m-xylylene-bis(ene) Propyl bicyclo [2.2.1] hept-5-ene-2,3-dicarboxy quinone imine), N,N'-m-xylylene-bis(allylmethylbicyclo[2.2.1]g -5-ene-2,3-dicarboxy quinone imine).

2,2-bis[4-{4-(allylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2- Bis[4-{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, 2,2-dual [ 4-{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenoxy}phenyl]propane, double {4-(allyl) Bicyclo[2.2.1]hept-5-ene-2,3-dicarboxyindolimine)phenyl}methane, bis{4-(allylmethylbicyclo[2.2.1]hept-5-ene-2 ,3-dicarboxy quinone imine)phenyl}methane, bis{4-(methylallylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxy quinone imine)phenyl}methane , bis{4-(methylallylmethylbicyclo[2.2.1]hept-5-ene-2,3-dicarboxyarmineimine)phenyl}methane.

Further, as a particularly preferred alkenyl-substituted nadicylimine compound, a bis{4-(allylbicyclo[2.2.1]hept-5-ene represented by the following formula (NA-1) is exemplified. -2,3-dicarboxy quinhomine)phenyl}methane, N,N'-m-xylylene-bis(allylbicyclo[2.2.1]heptane represented by formula (NA-2) 5-ene-2,3-dicarboxy quinimine), and N,N'-hexamethylene-bis(allylbicyclo[2.2.1]hept-5 represented by formula (NA-3) -ene-2,3-dicarboxy quinone imine). <Compound having a radical polymerizable unsaturated double bond>

For example, the liquid crystal alignment agent of the present invention may further contain a compound having a radical polymerizable unsaturated double bond for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The compound having a radical polymerizable unsaturated double bond may be one kind of compound or two or more types of compounds. Further, an alkenyl-substituted nadic quinone imine compound is not contained in the compound having a radical polymerizable unsaturated double bond. For the purpose, the content of the compound having a radical polymerizable unsaturated double bond is preferably from 1% by weight to 100% by weight, more preferably from 1% by weight to 70% by weight, based on the polyphthalic acid or a derivative thereof. More preferably, it is 1 wt% - 50 wt%.

In addition, the ratio of the compound having a radically polymerizable unsaturated double bond to the alkenyl substituted imidide compound is reduced in order to reduce the ion density of the liquid crystal display element, suppress the increase in the ion density over time, and further suppress The generation of the afterimage, the compound having a radical polymerizable unsaturated double bond/alkenyl-substituted nadic ylidene compound is preferably 0.1 to 10, more preferably 0.5 to 5 by weight.

The compound having a radical polymerizable unsaturated double bond will be specifically described below.

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

Specific examples of the (meth) acrylate include cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, and dicyclopentanyl (meth)acrylate. Dicyclopentyloxyethyl acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl methacrylate.

Specific examples of the difunctional (meth) acrylate include, for example, an exoethyl diacrylate and an Aronix M-210 (Aronix M-210) which is a product of the East Asian synthetic chemical industry. Ronex M-240 and Aronix M-6200, KAYARAD HDDA, Kayad HX-220, Kayad R-604 and Kaya as products of Nippon Chemical Co., Ltd. R-684, V260, V312 and V335HP, which are products of the Osaka Organic Chemical Industry Co., Ltd., and Light Acrylate BA-4EA, which is a product of the Kyoei Oil & Fat Chemical Industry Co., Ltd. Light acrylate BP-4PA and light acrylate BP-2PA.

Specific examples of the trifunctional or higher polyfunctional (meth) acrylate include, for example, 4,4′-methylenebis(N,N-dihydroxyethyl acrylate), which is a synthetic chemical industry in East Asia. (Shares) products of the Aronix M-400, Aronix M-405, Aronix M-450, Aronix M-7100, Aronix M-8030, Aronix M-8060, as a product of Nippon Kayaku (share), Kayad TPTA, Kayad DPCA-20, Kayad DPCA-30, Kayad DPCA-60, Kayad DPCA-120, and as Osaka VGPT for products of the organic chemical industry (shares).

Specific examples of the (meth) acrylamide derivative include N-isopropyl acrylamide, N-isopropyl methacrylamide, N-n-propyl acrylamide, and N-positive Propyl methacrylamide, N-cyclopropyl acrylamide, N-cyclopropyl methacrylamide, N-ethoxyethyl acrylamide, N-ethoxyethyl methacrylate Amine, N-tetrahydrofurfuryl acrylamide, N-tetrahydrofurfuryl methacrylamide, N-ethyl acrylamide, N-ethyl-N-methyl acrylamide, N, N-di Ethyl acrylamide, N-methyl-N-n-propyl acrylamide, N-methyl-N-isopropyl acrylamide, N-propylene hydrazinopyridine, N-propenylpyrrolidine, N,N'-methylenebispropene decylamine, N,N'-extended ethyl bis acrylamide, N,N'-dihydroxyethylidene bis decylamine, N-(4-hydroxyphenyl) Methacrylamide, N-phenylmethacrylamide, N-butylmethacrylamide, N-(isobutoxymethyl)methacrylamide, N-[2-(N,N- Dimethylamino)ethyl]methacrylamide, N,N-dimethylmethacrylamide, N-[3-(dimethylamino)propyl]methacrylamide, N-( Methoxymethyl)methacrylamide, N-(hydroxyl Yl) -2-methyl-acrylamide, N- benzyl-2-methyl acrylamide, and N, N'- methylene bis methyl acrylamide.

Among the (meth)acrylic acid derivatives, N,N'-methylenebisacrylamide, N,N'-dihydroxyethylidene-bispropenylamine, ethylidene diacrylate, And 4,4'-methylenebis(N,N-dihydroxyethyl acrylate).

Examples of the bis-s-butylene diimide include BMI-70 and BMI-80 manufactured by KI Chemical Co., Ltd., and BMI-1000, BMI-3000, and BMI-4000 manufactured by Daiwa Kasei Kogyo Co., Ltd. BMI-5000 and BMI-7000. <oxazine compound>

For example, the liquid crystal alignment agent of the present invention may further contain an oxazine compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazine compound may be one compound or two or more compounds. For the purpose described, the content of the oxazine compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20%, based on the poly phthalic acid or a derivative thereof. Wt%. The oxazine compound will be specifically described below. The oxazine compound is preferably an oxazine compound which is soluble in a solvent which dissolves poly-proline or a derivative thereof and has ring-opening polymerizability. Further, the number of the oxazine structure in the oxazine compound is not particularly limited.

The structure of the oxazine is known in various structures. In the present invention, the structure of the oxazine is not particularly limited, and examples of the oxazine structure in the oxazine compound include an aldehyde having a condensed polycyclic aromatic group such as benzoxazine or naphthoxazine. The structure of the azine.

Examples of the oxazine compound include compounds represented by the following formula (OX-1) to formula (OX-6). Further, in the following formula, a bond represented toward the center of the ring means that the bond is bonded to any one of the carbons constituting the ring and the bondable substituent.

In the formula (OX-1) to the formula (OX-3), L ³ and L ⁴ are an organic group having 1 to 30 carbon atoms, and in the formula (OX-1) to the formula (OX-6), L ⁵ to L ⁸ is hydrogen or a hydrocarbon group having 1 to 6 carbon atoms. In the formula (OX-3), the formula (OX-4) and the formula (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 the formula (OX-5) and formula (OX-6), Q ^{2 is} independently a single bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ - or an alkylene group having a carbon number of 1 to 3, a benzene ring in Q ² The hydrogen bonded to the naphthalene ring is independently and may be substituted by -F, -CH ₃ , -OH, -COOH, -SO ₃ H, -PO ₃ H ₂ . Further, the oxazine compound includes an oligomer or polymer having an oxazine structure in a side chain, and an oligomer or polymer having an oxazine structure in the main chain. 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 an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group 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 an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms. The oxazine compound represented by the formula (OX-3) includes 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, and 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 an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group 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, it is exemplified by the formula (OX-2-1), the formula (OX-3-1), the formula (OX-3-3), the formula (OX-3-5), and the 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 An oxazine compound represented by the formula (OX-6-2) to the formula (OX-6-4).

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

The oxazine compound represented by the formula (OX-1) can be obtained by reacting a phenol compound with a primary amine and an aldehyde (refer to International Publication No. 2004/009708).

The oxazine compound represented by the formula (OX-2) can be obtained by reacting a compound having a naphthol-based hydroxyl group by a method in which a primary amine is slowly added to formaldehyde, and reacting (refer to International Publication 2004/ 009708).

The oxazine compound represented by the formula (OX-3) can be obtained by subjecting the phenol compound to 1 mol in the presence of a secondary aliphatic amine, a tertiary aliphatic amine or a basic nitrogen-containing heterocyclic compound. The aldehyde having at least 2 mols of a phenolic hydroxyl group of the phenol compound and the 1 mol of the primary amine are reacted in an organic solvent (refer to International Publication No. 2004/009708 and Japanese Patent Laid-Open No. Hei 11-12258).

The oxazine compound represented by the formula (OX-4) to the formula (OX-6) can be obtained by having a 4,4'-diaminodiphenylmethane or the like at a temperature of 90 ° C or higher. A benzene ring, an organic group-containing diamine bonded to these benzene rings, an aldehyde such as formalin, and a phenol are subjected to a dehydration condensation reaction in n-butanol (refer to Japanese Patent Laid-Open Publication No. 2004-352670). <oxazoline compound>

For example, the liquid crystal alignment agent of the present invention may further contain an oxazoline compound for the purpose of stabilizing the electrical characteristics of the liquid crystal display element for a long period of time. The oxazoline compound is a compound having an oxazoline structure. The oxazoline compound may be one compound or two or more compounds. For the purpose, the content of the oxazoline compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to the polylysine or a derivative thereof. 20 wt%. Alternatively, when the oxazoline structure in the oxazoline compound is converted to an oxazoline, the content of the oxazoline compound is preferably 0.1 wt% with respect to the polyamine or its derivative. 40 wt%. The oxazoline compound will be specifically described below.

The oxazoline compound may have only one oxazoline structure in one compound, or may have two or more types. Further, the oxazoline compound may have one oxazoline structure in one compound, but preferably has two or more. Further, the oxazoline compound may be a polymer having an oxazoline structure in a side chain, or may be a copolymer. The polymer having an oxazoline structure on the side chain may be a homopolymer of a monomer having an oxazoline structure in a side chain, or a monomer having an oxazoline structure in a side chain and having no oxazoline structure. Copolymer of monomer. The copolymer having an oxazoline structure in a side chain may be a copolymer of two or more monomers having an oxazoline structure in a side chain, or may be a monomer having two or more monomers having an oxazoline structure in a side chain. Copolymer with a monomer having no oxazoline structure.

The oxazoline structure is preferably a structure which exists in the oxazoline compound in such a manner that one or both of oxygen and nitrogen in the oxazoline structure can react with the carbonyl group of the polyphthalic acid.

Examples of the oxazoline compound include 2,2'-bis(2-oxazoline), 1,2,4-tris-(2-oxazolinyl-2)-benzene, and 4-furan-2. - benzylidene-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'-isopropylidene bis(4-tert-butyl-2-oxazoline , 2,2'-isopropylidene bis(4-phenyl-2-oxazoline), 2,2'-methylenebis(4-tert-butyl-2-oxazoline), and 2,2'-methylenebis(4-phenyl-2-oxazoline). In addition to these oxazoline compounds, a polymer or oligomer having an oxazolyl group, such as Epocros (trade name, manufactured by Nippon Shokubai Co., Ltd.), may be mentioned. Among these oxazoline compounds, 1,3-bis(4,5-dihydro-2-oxazolyl)benzene is more preferable. <epoxy compound>

For example, the liquid crystal alignment agent of the present invention may further contain an epoxy compound for the purpose of stabilizing the electrical properties of the liquid crystal display element for a long period of time. The epoxy compound may be one compound or two or more compounds. For the purpose, the content of the epoxy compound is preferably from 0.1% by weight to 50% by weight, more preferably from 1% by weight to 40% by weight, even more preferably from 1% by weight to 20%, relative to the polyaminic acid or a derivative thereof. Wt%. The epoxy compound will be specifically described below.

Examples of the epoxy compound include various compounds having one or two or more epoxy rings in the molecule. Examples of the compound having an epoxy ring in the molecule include phenyl glycidyl ether, butyl glycidyl ether, 3,3,3-trifluoromethyl propylene oxide, styrene oxide, and hexafluoropropylene oxide. , cyclohexane oxide, 3-glycidoxypropyltrimethoxydecane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane, N-glycidyl phthalic acid Dimethyl imine, (nonafluoro-N-butyl) epoxide, perfluoroethyl glycidyl ether, 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, and polypropylene glycol dihydrate. Glycerol ether, neopentyl glycol diglycidyl ether, 1,6-hexanediol diglycidyl ether, glycerol diglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, 3,4-ring Oxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate and 3-(N,N-diglycidyl)aminopropyltrimethoxydecane.

As a compound having three epoxy rings in the molecule, for example, 2-[4-(2,3-epoxypropoxy)phenyl]-2-[4-[1,1-bis[4] -([2,3-Epoxypropoxy]phenyl)]ethyl]phenyl]propane (trade name "Tieke Moya VG3101L (Techmore 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. Base-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetraglycidyl-4,4' -Diaminodiphenylmethane, and 3-(N-allyl-N-glycidyl)aminopropyltrimethoxydecane.

In addition to the above, an oligomer having an epoxy ring or a polymer may be exemplified as a compound having an epoxy ring in the molecule. Examples of the monomer having an epoxy ring include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and methyl glycidyl (meth)acrylate.

Examples of the other monomer copolymerized with the monomer having an epoxy ring include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, and isopropyl (meth)acrylate. , (butyl) (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, benzyl (meth)acrylate, (meth)acrylic acid 2-hydroxyethyl ester, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-ethyl-3-oxetanyl) Methyl ester, N-cyclohexyl maleimide and N-phenyl maleimide.

Preferable specific examples of the polymer of the monomer having an epoxy ring include polyglycidyl methacrylate and the like. Further, preferred examples of the copolymer of the monomer having an epoxy ring and another monomer include N-phenyl maleimide-glycidyl methacrylate copolymer and N-ring. Hexyl maleimide-glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, methyl 2-hydroxyethyl acrylate-glycidyl methacrylate copolymer, (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and styrene-A Glycidyl acrylate copolymer.

Among these, N,N,N',N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane is particularly preferred. , N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane, trade name "Tieke Moya VG3101L", 3,4-epoxycyclohexenyl Methyl-3',4'-epoxycyclohexene carboxylate, N-phenyl maleimide-glycidyl methacrylate copolymer, and 2-(3,4-epoxy) Cyclohexyl)ethyltrimethoxydecane.

More specifically, examples of the epoxy compound include glycidyl ether, glycidyl ester, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, and isocyanuric glycidyl glycol. A chain aliphatic epoxy compound and a cyclic aliphatic epoxy compound. Further, the epoxy compound means a compound having an epoxy group, and the epoxy resin means a resin having an epoxy group.

Examples of the epoxy compound include glycidyl ether, glycidyl glycol, glycidylamine, epoxy group-containing acrylic resin, glycidyl decylamine, glycidyl isocyanurate, and chain aliphatic. An epoxy compound and a cyclic aliphatic epoxy compound.

Examples of the glycidyl ether include a bisphenol A epoxy compound, a bisphenol F epoxy compound, a bisphenol S epoxy compound, a bisphenol epoxy compound, and a hydrogenated bisphenol-A epoxy compound. Hydrogenated bisphenol-F type epoxy compound, hydrogenated bisphenol-S type epoxy compound, hydrogenated bisphenol type epoxy compound, brominated bisphenol-A type epoxy compound, brominated bisphenol-F type epoxy compound, Phenolic novolak type epoxy compound, cresol novolak type epoxy compound, brominated phenol novolac type epoxy compound, brominated cresol novolak type epoxy compound, bisphenol A novolac type epoxy compound, containing naphthalene Skeleton epoxy compound, aromatic polyglycidyl ether compound, dicyclopentadiene phenol type epoxy compound, alicyclic diglycidyl ether compound, aliphatic polyglycidyl ether compound, polysulfide type diglycidyl ether A compound and a biphenol type epoxy compound.

Examples of the glycidyl ester include a diglycidyl ester compound and a glycidyl ester epoxy compound.

Examples of the glycidylamine include a polyglycidylamine compound and a glycidylamine type epoxy resin.

Examples of the epoxy group-containing acrylic compound include a homopolymer and a copolymer of a monomer having an oxiranyl group.

Examples of the glycidyl decylamine include a glycidyl guanamine type epoxy compound.

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

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

Examples of the bisphenol A type epoxy compound include jER828, jER1001, jER1002, jER1003, jER1004, jER1007, and jER1010 (all manufactured by Mitsubishi Chemical Corporation), and Eptoto YD-128 (Epotohto YD) -128) (Manufactured by Tohto Kasei Co., Ltd.), DER-331, DER-332, DER-324 (all manufactured by The Dow Chemical Company), Ai Piklon 840 (Epiclon 840), Ai Piklon 850, Ai Piklon 1050 (all manufactured under the trade name, Di Ai Sheng (DIC) (share)), Apollo R-140 (Epomik R-140), Apollo R-301, and Apollok R-304 (all manufactured by Mitsui Chemicals Co., Ltd.).

Examples of the bisphenol F-type epoxy compound include jER806, jER807, and jER4004P (all manufactured by Mitsubishi Chemical Corporation), Eptoto YDF-170, Apttoto YDF-175S, and Epp. Toto YDF-2001 (both trade names, manufactured by Tohto Kasei Co., Ltd.), DER-354 (trade name, manufactured by Dow Chemical Co., Ltd.), Ai Piklon 830, and Ai Pik 835 (all are trade names, Di Aisheng (share) manufacturing).

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

Examples of the hydrogenated bisphenol-A type epoxy compound include: TOPTO ST-3000 (trade name, manufactured by Tohto Kasei Co., Ltd.), and Rikaresin HBE-100 (Rikaresin HBE- 100) (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), and Danacol EX-252 (trade name, manufactured by Nagase ChemteX (share)).

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 type epoxy compound include jER5050 and jER5051 (all manufactured by Mitsubishi Chemical Corporation), Aptuoto YDB-360, and Aptuoto YDB-400 (both For the trade name, manufactured by Tohto Kasei (share), DER-530, DER-538 (all trade names, manufactured by Dow Chemical Company), Ai Piklon 152, and Ai Piklon 153 (all are trade names, Di Aisheng (shares) manufacturing).

Examples of the phenol novolak-type epoxy compound include jER152 and jER154 (all manufactured by Mitsubishi Chemical Corporation), YDPN-638 (trade name, manufactured by Tohto Kasei Co., Ltd.), and DEN431 and DEN438 (all products). Name, manufactured by Dow Chemical Co., Ltd., Ai Piklon N-770 (trade name, manufactured by Di Ai Sheng (share)), EPPN-201, and EPPN-202 (all manufactured by Nippon Chemical Co., Ltd.).

Examples of the cresol novolac type epoxy compound include jER180S75 (trade name, manufactured by Mitsubishi Chemical Corporation), YDCN-701, YDCN-702 (all manufactured by Dongdu Chemical Co., Ltd.), and Ai Piklon N. -665, Ai Piklon N-695 (all manufactured under the trade name, Di Ai Sheng (share)), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020, EOCN-1025, and EOCN-1027 (both Product name, manufactured by Nippon Kay (Pharmaceuticals).

Examples of the bisphenol A novolak-type epoxy compound include jER157S70 (trade name, manufactured by Mitsubishi Chemical Corporation), and Ai Piklon N-880 (trade name, manufactured by Di Ai Sheng (share)).

Examples of the epoxy compound containing a naphthalene skeleton include eppylon HP-4032, eppylon HP-4700, and ipexlon HP-4770 (all manufactured under the trade name, Di Ai Sheng (share)), and NC- 7000 (trade name, manufactured by Nippon Kayaku Co., Ltd.).

Examples of the aromatic polyglycidyl ether compound include hydroquinone diglycidyl ether (formula: EP-1), catechol diglycidyl ether (formula: EP-2), and 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), tris(4-glycidoxyphenyl)methane (formula EP-5 below) ), jER1031S, jER1032H60 (all manufactured by Mitsubishi Chemical Corporation), TACTIX-742 (trade name, manufactured by Dow Chemical Co., Ltd.), Dana Kerr EX-201 (product) Name, Changsong Huacheng (share) manufacturing), DPPN-503, DPPN-502H, DPPN-501H, NC6000 (all manufactured by Nippon Chemical Co., Ltd.), Temmoiya VG3101L (trade name, Mitsui Chemicals) (manufactured by the company), a compound represented by the following formula EP-6, and a compound represented by the following formula EP-7.

Examples of the dicyclopentadiene phenol type epoxy compound include Tekexix-556 (trade name, manufactured by The Dow Chemical Company), and Ai Piklon HP-7200 (trade name, Di Ai Sheng (share) Manufacturing).

Examples of the alicyclic diglycidyl ether compound include a cyclohexane dimethanol diglycidyl ether compound and Ricardo new DME-100 (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.).

Examples of the aliphatic polyglycidyl ether compound include ethylene glycol diglycidyl ether (hereinafter, EP-8), diethylene glycol diglycidyl ether (hereinafter, EP-9), and polyethylene glycol. Diglycidyl ether, propylene glycol diglycidyl ether (formula EP-10), tripropylene glycol diglycidyl ether (formula EP-11 below), polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether ( Formula EP-12), 1,4-butanediol diglycidyl ether (formula EP-13 below), 1,6-hexanediol diglycidyl ether (formula EP-14 below), dibromo Neopentyl glycol diglycidyl ether (EP-15 below), Dana Kerr EX-810, Dana Kerr EX-851, Dana Kerr EX-8301, Dana Kerr EX-911, Dana Kerr EX- 920, Dana Kerr EX-931, Dana Kerr EX-211, Dana Kerr EX-212, Dana Kerr EX-313 (all manufactured by Changchun Huacheng (share)), DD-503 (trade name) , ADEKA (manufactured by ADEKA), Rikari New W-100 (trade name, manufactured by Nippon Chemical and Chemical Co., Ltd.), 1,3,5,6-tetraglycidyl-2,4- Hexanediol (Equation EP-16), Gan Polyglycidyl ether, sorbitol polyglycidyl ether, trimethylolpropane polyglycidyl ether, pentaerythritol polyglycidyl ether, Dana Kerr EX-313, Dana Kerr EX-611, Dana Kerr EX-321, and Dana Kerr EX-411 (all manufactured under the trade name, Changchun Huacheng (share)).

Examples of the polysulfide-type diglycidyl ether compound include FLDP-50 and FLDP-60 (both of which are trade names, manufactured by Toray Thiokol Co., Ltd.).

Examples of the biphenol-based epoxy compound include YX-4000 and YL-6121H (all manufactured by Mitsubishi Chemical Corporation), NC-3000P, and NC-3000S (all are trade names, Japanese chemical drugs). (shares) manufacturing).

Examples of the diglycidyl ester compound include diglycidyl terephthalate (formula: EP-17), diglycidyl phthalate (formula: EP-18), and phthalic acid (2-methyloxiranylmethyl) ester (Equation EP-19), hexahydrophthalic acid diglycidyl ester (Equation EP-20), and the following formula EP-21 The compound represented by the formula, the compound represented by the following formula EP-22, and the compound represented by the following formula EP-23.

Examples of the glycidyl ester epoxy compound include jER871 and jER872 (all of which are trade names, manufactured by Mitsubishi Chemical Corporation), Ai Piklon 200, and Ai Piklon 400 (all manufactured under the trade name, Di Ai Sheng (share)). ), Dana Kerr EX-711, and Dana Kerr EX-721 (all manufactured by Changchun Huacheng (share)).

Examples of the polyglycidylamine compound include N,N-diglycidylaniline (Equation EP-24), N,N-diglycidyl-o-toluidine (Equation EP-25), N,N-diglycidyl-m-toluidine (formula EP-26), N,N-diglycidyl-2,4,6-tribromoaniline (formula EP-27), 3- (N,N-diglycidyl)aminopropyltrimethoxydecane (formula EP-28), N,N,O-triglycidyl-p-aminophenol (formula EP-29) , N, N, O-triglycidyl-m-aminophenol (formula EP-30), N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl Methane (formula EP-31), N,N,N',N'-tetraglycidyl-m-xylylenediamine (TETRAD-X) (trade name, Mitsubishi Gas Chemical (manufactured by the company), the following formula EP-32), 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane (iron-trad-C (trade name, Mitsubishi Gas Chemicals) (manufactured by the company), the following formula EP-33), 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane (formula: EP-34), 1,3-double (N,N-diglycidylamino)cyclohexane (described below) EP-35), 1,4-bis(N,N-diglycidylamino)cyclohexane (formula EP-36 below), 1,3-bis(N,N-diglycidylamino group) Benzene (formula EP-37 below), 1,4-bis(N,N-diglycidylamino)benzene (formula EP-38 below), 2,6-bis (N,N-diverted water) Glycerylaminomethyl)bicyclo[2.2.1]heptane (formula EP-39 below), N,N,N',N'-tetraglycidyl-4,4'-diaminodicyclohexyl Methane (formula EP-40), 2,2'-dimethyl-(N,N,N',N'-tetraglycidyl)-4,4'-diaminobiphenyl (the following formula) EP-41), N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenyl ether (formula EP-42), 1,3,5-tri (4- (N,N-diglycidyl)aminophenoxy)benzene (formula EP-43 below), 2,4,4'-tris(N,N-diglycidylamino)diphenyl ether ( Formula EP-44), tris(4-(N,N-diglycidyl)aminophenyl)methane (Equation EP-45), 3,4,3',4'-tetra (N , N-diglycidylamino)biphenyl (formula EP-46 below), 3,4,3',4'-tetrakis(N,N-diglycidylamino)diphenyl ether (described below) Formula EP-47), a compound represented by the following formula EP-48, and a compound represented by the following formula EP-49.

Examples of the homopolymer of the monomer having an oxiranyl group include polyglycidyl methacrylate. Examples of the copolymer of the monomer having an oxiranyl group include N-phenyl maleimide-glycidyl methacrylate copolymer and N-cyclohexylmethylene iodide. - Glycidyl methacrylate copolymer, benzyl methacrylate-glycidyl methacrylate copolymer, butyl methacrylate-glycidyl methacrylate copolymer, 2-hydroxyethyl methacrylate-A A glycidyl acrylate copolymer, a (3-ethyl-3-oxetanyl)methyl methacrylate-glycidyl methacrylate copolymer, and a styrene-glycidyl methacrylate copolymer.

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

Examples of the monomer other than the monomer having an oxiranyl group in the copolymer of the monomer having an oxiranyl group include (meth)acrylic acid, methyl (meth)acrylate, and (a) Ethyl acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate Benzyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, styrene, methylstyrene, chloromethylstyrene, (meth)acrylic acid (3-Ethyl-3-oxetanyl)methyl ester, N-cyclohexylmethyleneimine, and N-phenylmaleimide.

As the glycidyl iso-glycidyl cyanide, for example, 1,3,5-triglycidyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione (EP-50 of the following formula), 1,3-diglycidyl-5-allyl-1,3,5-triazine-2,4,6-(1H,3H,5H)-trione ( The following formula EP-51) and an isomeric isocyanurate type epoxy resin.

Examples of the chain aliphatic epoxy compound include epoxidized polybutadiene and Eprod PB3600 (Epolead PB3600) (trade name, manufactured by Daicel).

As the cyclic aliphatic epoxy compound, for example, 3,4-epoxycyclohexenylmethyl-3',4'-epoxycyclohexenecarboxylate (矽罗基赛2021) (Celloxide 2021) (manufactured by Daicel (product), the following formula EP-52), 2-methyl-3,4-epoxycyclohexylmethyl-2'-methyl-3', 4'-ring Oxycyclohexyl carboxylate (formula EP-53 below), 2,3-epoxycyclopentane-2',3'-epoxycyclopentane ether (formula EP-54 below), ε - caprolactone modified 3,4-epoxycyclohexylmethyl-3',4'-epoxycyclohexanecarboxylate, 1,2:8,9-dicyclooxy limonene (Celloxide 3000 ( The product name, Daicel (manufactured by the company), the following formula EP-55), the compound represented by the following formula EP-56, CY-175, CY-177, CY-179 (all are trade names, Ciba Manufactured by The Ciba-Geigy Chemical Corp. (available from Huntsman Japan (shares)), EHPD-3150 (trade name, manufactured by Daicel (share)), and ring An aliphatic epoxy resin.

The epoxy compound is preferably one or more of a polyglycidylamine compound, a bisphenol A novolac type epoxy compound, a cresol novolak type epoxy compound, and a cyclic aliphatic type epoxy compound, and more preferably N, N, N' , N'-tetraglycidyl-m-xylylenediamine, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, N,N,N',N'-tetrahydration Glyceryl-4,4'-diaminodiphenylmethane, trade name "Tieke Moya VG3101L", 3,4-epoxycyclohexenylmethyl-3', 4'-epoxy ring Hexene carboxylate, N-phenyl maleimide-glycidyl methacrylate copolymer, N, N, O-triglycidyl-p-aminophenol, bisphenol A novolac type ring One or more of an oxygen compound and a cresol novolac type epoxy compound.

Further, for example, the liquid crystal alignment agent of the present invention may further contain various additives. Examples of the various additives include a polymer compound other than polyglycine and a derivative thereof, and a low molecular compound, and can be selected and used according to each purpose.

For example, examples of the polymer compound include polymer compounds which are soluble in an organic solvent. From the viewpoint of controlling the electrical characteristics or the alignment property of the liquid crystal alignment film formed, it is preferred to add such a polymer compound to the liquid crystal alignment agent of the present invention. Examples of the polymer compound include polyamine, polyurethane, polyurea, polyester, polyepoxide, polyester polyol, anthrone modified polyurethane, and hydrazine. Ketone modified polyester.

Further, as the low molecular compound, for example, 1) when it is desired to improve the coatability, a surfactant suitable for the purpose may be mentioned, 2) an antistatic agent may be cited when it is desired to raise the antistatic property, and 3) when it is desired to lift the substrate. In the case of adhesion, a decane coupling agent or a titanium-based coupling agent may be mentioned, and 4) a ruthenium imidization catalyst may be mentioned when ruthenium imidization is carried out at a low temperature.

Examples of the decane coupling agent include vinyltrimethoxydecane, vinyltriethoxydecane, and N-(2-aminoethyl)-3-aminopropylmethyldimethoxydecane. N-(2-Aminoethyl)-3-aminopropylmethyltrimethoxydecane, p-aminophenyltrimethoxydecane, p-aminophenyltriethoxydecane, m-aminophenyl Trimethoxydecane, m-aminophenyltriethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-glycidoxypropyltrimethoxy Decane, 3-glycidoxypropylmethyldimethoxydecane, 3-chloropropylmethyldimethoxydecane, 3-chloropropyltrimethoxydecane, 3-methylpropenyloxypropane Trimethoxy decane, 3-mercaptopropyltrimethoxydecane, N-(1,3-dimethylbutylene)-3-(triethoxydecyl)-1-propylamine, and N,N' - bis[3-(trimethoxydecyl)propyl]ethylenediamine. A preferred decane coupling agent is 3-aminopropyltriethoxydecane.

Examples of the ruthenium amide catalyst include aliphatic amines such as trimethylamine, triethylamine, tripropylamine, and tributylamine; N,N-dimethylaniline, N,N-diethylaniline, and methyl group. Aromatic amines such as aniline and hydroxy-substituted aniline; pyridine, methyl-substituted pyridine, hydroxy-substituted pyridine, quinoline, methyl-substituted quinoline, hydroxy-substituted quinoline, isoquinoline, methyl-substituted isoquinoline, hydroxy substitution Cyclic amines such as isoquinoline, imidazole, methyl substituted imidazole, and hydroxy substituted imidazole. The ruthenium amide catalyst is preferably selected from the group consisting of N,N-dimethylaniline, o-hydroxyaniline, m-hydroxyaniline, p-hydroxyaniline, o-hydroxypyridine, m-hydroxypyridine, p-hydroxypyridine, and isoquinoline. Or two or more.

The amount of the decane coupling agent to be added is usually from 0 wt% to 20 wt%, preferably from 0.1 wt% to 10 wt%, based on the total weight of the polyaminic acid or its derivative.

The amount of the ruthenium imidization catalyst added is usually from 0.01 equivalents to 5 equivalents, preferably from 0.05 equivalents to 3 equivalents, based on the carbonyl group of the polyamic acid or a derivative thereof.

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

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

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

The poly-proline or a derivative thereof of the present invention can be confirmed by the following means: using poly Infrared (IR), Nuclear Magnetic Resonance (NMR) to make the polylysine of the present invention or its derivative The solid component obtained by precipitation in a large amount of poor solvent was analyzed. In addition, the monomer to be used can be confirmed by gas chromatography (GC), high performance liquid chromatography (HPLC) or gas chromatography mass spectrometry (Gas). Chromatography-Mass Spectrometry (GC-MS) is an extract obtained by decomposing the polyaminic acid or a derivative thereof using an aqueous solution of a strong base such as KOH or NaOH, and extracting the extract from the decomposition product using an organic solvent.

Further, for example, from the viewpoint of the coatability of the liquid crystal alignment agent or the adjustment of the concentration of the polyaminic acid or its derivative, the liquid crystal alignment agent of the present invention may further contain a solvent. The solvent is not particularly limited as long as it has a solvent having the ability to dissolve a polymer component. The solvent widely includes a solvent which is generally used for a production step or a use of a polymer component such as polyacrylic acid or a soluble polyimine, and can be appropriately selected depending on the purpose of use. The solvent may be one type or a mixture of two or more types.

The solvent may, for example, be a lyophilic solvent of the polyaminic acid or a derivative thereof or another solvent for the purpose of improving coatability.

Examples of the aprotic polar organic solvent which is a solvophilic solvent with respect to polyglycine or a derivative thereof include N-methyl-2-pyrrolidone, dimethylimidazolidinone, and N-methylene. Indoleamine, N-methylpropionamide, N,N-dimethylacetamide, dimethyl hydrazine, N,N-dimethylformamide, N,N-diethylformamide, Lactone such as diethyl acetamide or γ-butyrolactone.

Examples of other solvents for the purpose of improving coatability and the like include alkyl lactate, 3-methyl-3-methoxybutanol, tetrahydronaphthalene, isophorone, and ethylene glycol monobutyl ether. Ethylene glycol monoalkyl ether, diethylene glycol monoethyl ether, etc. diethylene glycol monoalkyl ether, ethylene glycol monoalkyl acetate or ethylene glycol monophenyl acetate, triethylene glycol single a propylene glycol monoalkyl ether such as an alkyl ether, propylene glycol monomethyl ether or propylene glycol monobutyl ether; a dialkyl malonate such as dialkyl malonate; dipropylene glycol monoalkyl ether such as dipropylene glycol monomethyl ether; An ester compound such as an ester.

Among these solvents, the solvent is particularly preferably N-methyl-2-pyrrolidone, dimethylimidazolidinone, γ-butyrolactone, ethylene glycol monobutyl ether, diethylene glycol monoethyl ether, propylene glycol monobutyl ether. , propylene glycol monomethyl ether, and dipropylene glycol monomethyl ether.

The concentration of the polylysine in the alignment agent of the present invention is preferably from 0.1% by weight to 40% by weight. When the alignment agent is applied onto a substrate, in order to adjust the film thickness, it is necessary to perform an operation of diluting the contained polyamic acid with a solvent in advance.

The solid content concentration in the alignment agent of the present invention is not particularly limited, and may be selected in accordance with various coating methods described below. In general, in order to suppress unevenness at the time of coating, pinholes, and the like, it is preferably 0.1 wt% to 30 wt%, more preferably 1 wt% to 10 wt%, based on the weight of the varnish.

The viscosity of the liquid crystal alignment agent of the present invention differs depending on the method of coating, the concentration of polyglycine or a derivative thereof, the type of polyglycine or a derivative thereof used, and the kind and ratio of the solvent. For example, when coating is performed by a printing machine, it is 5 mPa·s to 100 mPa·s (more preferably 10 mPa·s to 80 mPa·s). If it is less than 5 mPa·s, it becomes difficult to obtain a sufficient film thickness; if it exceeds 100 mPa·s, there is a phenomenon that printing unevenness becomes large. In the case of coating by spin coating, it is preferably 5 mPa·s to 200 mPa·s (more preferably 10 mPa·s to 100 mPa·s). In the case of coating using an inkjet coating device, it is preferably 5 mPa·s to 50 mPa·s (more preferably 5 mPa·s to 20 mPa·s). The viscosity of the liquid crystal alignment agent can be measured by a rotational viscosity measurement method, for example, using a rotary viscometer (TVE-20L type manufactured by Toki Sangyo Co., Ltd.) (measurement temperature is 25 ° C).

The liquid crystal alignment film of the present invention will be described in detail. The liquid crystal alignment film of the present invention is a film formed by heating the coating film of the liquid crystal alignment agent of the present invention. The liquid crystal alignment film of the present invention can be obtained by a usual method for producing a liquid crystal alignment film from a liquid crystal alignment agent. For example, the liquid crystal alignment film of the present invention can be obtained by a step of forming a coating film of the liquid crystal alignment agent of the present invention, a step of performing heat drying, and a step of performing heating and calcination. In the liquid crystal alignment film of the present invention, if necessary, the film obtained by the heating and drying step and the heating and calcining step may be subjected to a rubbing treatment to impart anisotropy. Alternatively, if necessary, the light may be irradiated after the coating step, the heat drying step, or the light may be irradiated after the heating calcination step to impart anisotropy. Further, it can also be used as a liquid crystal alignment film for vertical alignment (VA) which is not subjected to rubbing treatment.

The coating film can be formed by applying the liquid crystal alignment agent of the present invention to a substrate in a liquid crystal display element, similarly to the production of a normal liquid crystal alignment film. The substrate may be an electrode or color in which an indium tin oxide (ITO), an indium zinc oxide (In ₂ O ₃ -ZnO, IZO), an indium gallium zinc oxide (In-Ga-ZnO ₄ , IGZO) electrode, or the like may be provided. A glass substrate such as a filter.

As a method of applying a liquid crystal alignment agent onto a substrate, a rotator method, a printing method, a dipping method, a dropping method, an inkjet method, and the like are generally known. These methods can also be equally applied to the present invention.

The heating and drying step is generally known as a method of performing heat treatment in an oven or an infrared furnace, a method of performing heat treatment on a hot plate, and the like. The heat drying step is preferably carried out at a temperature within a range in which the solvent can be evaporated, more preferably at a relatively low temperature with respect to the temperature in the heating calcination step. Specifically, the heating and drying temperature is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C.

The heating calcination step can be carried out under the conditions required for the polyglycine or its derivative to exhibit a dehydration/ring closure reaction. The calcination of the coating film is generally known as a method of heat treatment in an oven or an infrared oven, a method of performing heat treatment on a hot plate, and the like. These methods can also be equally applied to the present invention. It is usually preferably carried out at a temperature of from about 100 ° C to about 300 ° C for from 1 minute to 3 hours, more preferably from 120 ° C to 280 ° C, still more preferably from 150 to 250 ° C.

In the method for forming a liquid crystal alignment film of the present invention, in order to align the liquid crystal in one direction with respect to the horizontal direction and/or the vertical direction, a known formation method such as a rubbing method or a photo-alignment method can be suitably used as the alignment film. A method of imparting anisotropy.

The liquid crystal alignment film of the present invention using a rubbing method can be formed by the steps of applying the liquid crystal alignment agent of the present invention onto a substrate, heating and drying the substrate coated with the alignment agent, and heating the film. The step of calcining, and the step of subjecting the film to a rubbing treatment.

The rubbing treatment can be carried out in the same manner as the rubbing treatment for the alignment treatment of the liquid crystal alignment film, as long as it is a condition that a sufficient retardation can be obtained in the liquid crystal alignment film of the present invention. The preferred conditions are a hair intrusion of 0.2 mm to 0.8 mm, a platform moving speed of 5 mm/sec to 250 mm/sec, and a roll rotation speed of 500 rpm to 2,000 rpm.

A method of forming the liquid crystal alignment film of the present invention by the photo-alignment method will be described in detail. The liquid crystal alignment film of the present invention using the photo-alignment method can be formed by heating and drying the coating film, imparting anisotropy to the coating film by linearly polarizing or non-polarizing light irradiated with radiation, and then heating the film. Calcination. In addition, it can be formed by heating and drying the coating film, heating and calcining, and then irradiating the linearly polarized light or the non-polarized light of the radiation. From the viewpoint of the alignment, it is preferred to carry out the irradiation step of the radiation before the heating and calcining step.

Further, in order to improve the liquid crystal alignment ability of the liquid crystal alignment film, it is also possible to face the linearly polarized light or the non-polarized light which irradiates the radiation while the coating film is heated. The irradiation of the radiation may be carried out in the step of heating and drying the coating film or in the step of heating and calcining the coating film, or between the heating drying step and the heating and calcining step. The heating and drying temperature in this step is preferably in the range of 30 ° C to 150 ° C, and more preferably in the range of 50 ° C to 120 ° C. Further, the heating calcination temperature in this step is preferably in the range of from 30 ° C to 300 ° C, more preferably in the range of from 50 ° C to 250 ° C.

As the radiation, ultraviolet light or visible light containing light having a wavelength of, for example, 150 nm to 800 nm, preferably ultraviolet light containing light of 300 nm to 400 nm can be used. In addition, linear or unpolarized light can be used. The light is not particularly limited as long as it can impart a liquid crystal alignment ability to the coating film, and when it is desired to exhibit a strong alignment regulating force to the liquid crystal, linear polarization is preferable.

The liquid crystal alignment film of the present invention can exhibit high liquid crystal alignment ability even under low-energy light irradiation. The irradiation amount of the linearly polarized light in the radiation irradiation step is preferably 0.05 J/cm ² to 20 J/cm ² , and more preferably 0.5 J/cm ² to 10 J/cm ² . Further, the wavelength of the linearly polarized light is preferably 200 nm to 400 nm, and more preferably 300 nm to 400 nm. The irradiation angle of the linearly polarized light on the surface of the film is not particularly limited. When the liquid crystal exhibits a strong alignment regulating force, it is preferable that the alignment treatment time is shortened as far as possible from the viewpoint of shortening the alignment treatment time. Further, the liquid crystal alignment film of the present invention can align the liquid crystal in a direction perpendicular to the polarization direction of the linearly polarized light by irradiating the linearly polarized light.

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

In the light source used in the step of irradiating the linearly polarized or non-polarized light of the radiation, an ultrahigh pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a deep ultraviolet lamp, a halogen lamp, a metal halide lamp, and a high power can be used without limitation. Metal halide lamps, xenon lamps, mercury xenon lamps, excimer lamps, KrF excimer lasers, fluorescent lamps, light emitting diode (LED) lamps, sodium lamps, microwave-emitting electrodeless lamps, etc. .

The liquid crystal alignment film of the present invention can be suitably obtained by a method including further steps other than the above steps. For example, the liquid crystal alignment film of the present invention does not require a step of washing the film after firing or radiation irradiation with a cleaning liquid, but a cleaning step may be provided depending on other steps.

Examples of the cleaning method using the cleaning liquid include brushing, spraying, steam cleaning, or ultrasonic cleaning. These methods can be performed separately or in combination. As the cleaning liquid, pure alcohol or various alcohols such as methanol, ethanol, and isopropyl alcohol, aromatic hydrocarbons such as benzene, toluene, and xylene, halogen solvents such as dichloromethane, acetone, and methyl ethyl ketone can be used. Ketones are not limited to these cleaning solutions. Of course, these cleaning liquids can use a cleaning liquid which is sufficiently refined and has less impurities. Such a cleaning method can also be applied to the cleaning step in forming the liquid crystal alignment film of the present invention.

In order to improve the liquid crystal alignment ability of the liquid crystal alignment film of the present invention, annealing treatment by heat or light may be applied before and after the heating calcination step, before and after the rubbing step, or before or after the polarized or unpolarized radiation irradiation. In the annealing treatment, the annealing temperature is from 30 ° C to 180 ° C, preferably from 50 ° C to 150 ° C, and the time is preferably from 1 minute to 2 hours. Further, examples of the annealing light used for the annealing treatment include a UV lamp, a fluorescent lamp, an LED lamp, and the like. The amount of light irradiation is preferably from 0.3 J/cm ² to 10 J/cm ² .

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

The liquid crystal alignment film of the present invention is characterized by an anisotropy having a particularly large alignment. The size of such anisotropy can be evaluated by a method using polarized light described in JP-A-2005-275364 or the like. Further, as shown in the following examples, it can also be evaluated by a method using ellipsometry. In detail, the retardation value of the liquid crystal alignment film can be measured using a spectroscopic ellipsometer. The retardation value of the film increases in proportion to the degree of alignment of the polymer backbone. That is, a film having a large retardation value has a large degree of alignment, and when the alignment film of the present invention is used as a liquid crystal alignment film, an alignment film having greater anisotropy can be considered to have a large alignment limit for a liquid crystal composition. force.

The liquid crystal alignment film of the present invention can be suitably used in a liquid crystal display device of a transverse electric field type. In the case of a liquid crystal display element used in a lateral electric field mode, the smaller the Pt angle and the higher the liquid crystal alignment ability, the higher the black display level in the dark state, and the higher the contrast. The Pt angle is preferably 0.1 or less.

In addition to the alignment use of the liquid crystal composition for liquid crystal displays, the liquid crystal alignment film of the present invention can be used for alignment control of optical compensation materials or all other liquid crystal materials. Further, since the alignment film of the present invention has a large anisotropy, it can be used alone for optical compensation materials.

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

The present invention provides a liquid crystal display element including a pair of substrates disposed oppositely, electrodes formed on one or both of opposite surfaces of the pair of substrates, and pairs formed on the pair of substrates a liquid crystal alignment film on the surface and a liquid crystal layer formed between the pair of substrates, and the liquid crystal alignment film is an alignment film of the present invention.

The electrode is not particularly limited as long as it is an electrode formed on one surface of the substrate. Examples of such an electrode include a vapor deposited film of ITO or metal. Further, the electrode may be formed on the entire surface of one face of the substrate, or may be formed, for example, in a patterned desired shape. The desired shape of the electrode may, for example, be a comb type or a sawtooth structure or the like. The electrodes may be formed on one of the pair of substrates or may be formed on the two substrates. The form of formation of the electrode differs depending on the type of the liquid crystal display element. For example, in the case of an IPS type liquid crystal display element, the electrode is disposed on one of the pair of substrates, and in the case of another liquid crystal display element, the electrode is disposed. On both of the pair of substrates. The liquid crystal alignment film is formed on the substrate or the electrode.

The liquid crystal layer is formed in a form of sandwiching a liquid crystal composition by the pair of substrates facing each other in which the liquid crystal alignment film is formed. In the formation of the liquid crystal layer, a spacer such as a fine particle or a resin sheet interposed between the pair of substrates and forming an appropriate interval may 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. A preferred liquid crystal composition having a positive dielectric anisotropy is exemplified by Japanese Patent No. 3086228, Japanese Patent No. 2635435, Japanese Patent Laid-Open No. Hei 5-501735, Japanese Patent Laid-Open No. Hei 8-157826, and Japanese Patent Laid-Open No. Hei 8-231960. Japanese Patent Laid-Open No. Hei 9-241644 (EP 885272 A1), Japanese Patent Laid-Open No. Hei 9-302346 (EP 806 466 A1), Japanese Patent Laid-Open No. Hei 8-199168 (EP722998A1), Japanese Patent Laid-Open No. Hei 9-235552, Japanese Patent Laid-Open No. Hei 9-255956, Japan Patent Publication No. Hei 9-241643 (EP885271A1), Japanese Patent Laid-Open No. Hei 10-204016 (EP844229A1), Japanese Patent Laid-Open No. Hei 10-204436, Japanese Patent Laid-Open No. Hei 10-231482, Japanese Patent Laid-Open No. 2000-087040, Japanese Patent Laid-Open No. 2001 Liquid crystal composition disclosed in -48822 or the like.

Even if one or more optically active compounds are added to a liquid crystal composition having a positive or negative dielectric anisotropy, it has no effect.

A liquid crystal composition having a negative dielectric anisotropy will be described. The liquid crystal composition containing a liquid crystal compound represented by the following formula (NL-1) as a composition of the first component is exemplified as a liquid crystal composition having a negative dielectric anisotropy.

Here, R ^1a and R ^{2a are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon having at least one hydrogen substituted by fluorine. The number of 2 to 12 alkenyl groups, 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-difluoro-6-methyl-1,4-phenylene, or 7,8-difluorochroman-2,6-di a group, Z ^{1 is} independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -COO-, or -CF ₂ O-, j is 1, 2, or 3, and j is 2 or 3, Any two rings A ² may be the same or different, and any two Z ¹ may be the same or different.

In order to increase the dielectric anisotropy, it is preferred that ring A ² and ring B ² are 2,3-difluoro-1,4-phenylene or tetrahydropyran-2,5-diyl, respectively. The viscosity is lowered, and preferred ring A ² and ring B ² are each a 1,4-cyclohexylene group.

In order to improve the dielectric anisotropy, Z ¹ is preferably -CH ₂ O-, and in order to lower the viscosity, Z ¹ is preferably a single bond.

In order to lower the lower limit temperature, it is preferable that j is 1, and in order to increase the upper limit temperature, it is preferable that j is 2.

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

Here, R ^1a and R ^{2a are} independently an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkenyl group having 2 to 12 carbon atoms, or a carbon having at least one hydrogen substituted by fluorine. The number of 2 to 12 alkenyl groups, 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, Z ¹¹ and Z ^{12 is} independently a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, or -COO-.

In order to improve the stability against ultraviolet rays or heat, R ^1a and R ^2a are preferably an alkyl group having 1 to 12 carbon atoms, or preferably R ^1a and R in order to increase the absolute value of dielectric anisotropy. ^2a is an alkoxy group having 1 to 12 carbon atoms.

Preferred alkyl groups are methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl or octyl. In order to lower the viscosity, a more preferred alkyl group is an ethyl group, a propyl group, a butyl group, a pentyl group or a heptyl group.

Preferred alkoxy groups are methoxy, ethoxy, propoxy, butoxy, pentyloxy, hexyloxy or heptyloxy. In order to lower the viscosity, a more preferred alkoxy group is a methoxy group or an ethoxy group.

Preferred alkenyl groups are ethenyl, 1-propenyl, 2-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 1-pentenyl, 2-pentenyl, 3- Pentenyl, 4-pentenyl, 1-hexenyl, 2-hexenyl, 3-hexenyl, 4-hexenyl, or 5-hexenyl. In order to lower the viscosity, a more preferred alkenyl group is a vinyl group, a 1-propenyl group, a 3-butenyl group or a 3-pentenyl group. The preferred steric configuration of -CH=CH- in these alkenyl groups depends on the position of the double bond. From the viewpoints of lowering the viscosity and the like, in an alkenyl group such as 1-propenyl, 1-butenyl, 1-pentenyl, 1-hexenyl, 3-pentenyl or 3-hexenyl It is preferably trans. Among the alkenyl groups such as 2-butenyl, 2-pentenyl and 2-hexenyl, cis is preferred. Among these alkenyl groups, a linear alkenyl group is preferred from the branch.

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

In order to lower the viscosity, preferred ring A ²¹ , ring A ²² , ring A ²³ , ring B ²¹ , and ring B ²² are each a 1,4-cyclohexylene group.

In order to improve the dielectric anisotropy, Z ¹¹ and Z ¹² are preferably -CH ₂ O-, and in order to lower the viscosity, Z ¹¹ and Z ¹² are preferably a single bond.

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

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

Further, for example, from the viewpoint of improving the alignment property, for example, the liquid crystal composition used in the element of the present invention may further contain an additive. Such additives are photopolymerizable monomers, optically active compounds, antioxidants, ultraviolet absorbers, dyes, antifoaming agents, polymerization initiators, polymerization inhibitors, and the like.

In order to improve the alignment of the liquid crystal, the most preferable structure of the photopolymerizable monomer or oligomer is a structure of the formula (PM-1-1) to the formula (PM-1-6).

In order to exhibit the effect of determining the tilt direction of the liquid crystal after polymerization, the photopolymerizable monomer or oligomer is preferably 0.01 wt% or more. Further, in order to make the alignment effect of the polymer after polymerization suitable, or to prevent the unreacted monomer or oligomer from eluting into the liquid crystal after ultraviolet irradiation, it is preferably 30% by weight or less.

In order to cause a helical structure of the liquid crystal to impart a twist angle, an optically active compound is mixed in the composition. Examples of such compounds are the compound (PAC-1-1) to the compound (PAC-1-4).

A preferred ratio of the optically active compound is 5% by weight or less. A still more preferred ratio is in the range of 0.01 wt% to 2 wt%.

In order to prevent a decrease in specific resistance due to heating in the atmosphere, or to maintain a large voltage holding ratio not only at room temperature but also at a high temperature after using the element for a long time, in liquid crystal The composition is mixed with an antioxidant.

Preferable examples of the antioxidant are compounds (AO-1) and the like in which w is an integer of 1 to 10. In the compound (AO-1), preferred w is 1, 3, 5, 7, or 9. Still more preferably w is 1 or 7. The compound (AO-1) having a w of 1 has a large volatility, and therefore is effective in preventing a decrease in specific resistance due to heating in the atmosphere. The compound (w-1) having a w of 7 has a small volatility, so that after a component is used for a long period of time, a large voltage holding ratio can be effectively maintained not only at room temperature but also at a high temperature. In order to obtain the effect, the preferable ratio of the antioxidant is 50 ppm or more, and in order not to lower the upper limit temperature or to increase the lower limit temperature, the preferable ratio of the antioxidant is 600 ppm or less. A still more preferred ratio is in the range of 100 ppm to 300 ppm.

Preferable examples of the ultraviolet absorber are a benzophenone derivative, a benzoate derivative, a triazole derivative, and the like. Further, a light stabilizer such as an amine having a steric hindrance is also preferable. In order to obtain the effect, a preferable ratio of these absorbents or stabilizers is 50 ppm or more, and a preferable ratio of these absorbents or stabilizers is 10000 ppm or less in order not to lower the upper limit temperature or to increase the lower limit temperature. A still more preferred ratio is in the range of 100 ppm to 10,000 ppm.

In order to fit the element of the guest host (GH) mode, a dichroic dye such as an azo dye or an anthraquinone dye is mixed in the composition. A preferred ratio of the pigment is in the range of 0.01 wt% to 10 wt%.

In order to prevent foaming, an antifoaming agent such as dimethyl hydrazine oil or methyl phenyl hydrazine oil is mixed in the composition. In order to obtain the effect, the preferable ratio of the antifoaming agent is 1 ppm or more, and a preferable ratio of the antifoaming agent is 1000 ppm or less in order to prevent display failure. A still more preferred ratio is in the range of 1 ppm to 500 ppm.

In order to be suitable for a polymer sustained alignment (PSA) mode element, a polymerizable compound may be mixed in the composition. Preferable examples of the polymerizable compound are acrylate, methacrylate, vinyl compound, vinyloxy compound, propenyl ether, epoxy compound (oxirane, oxetane), vinyl ketone, etc. A compound having a polymerizable group. A particularly preferred example is a derivative of acrylate or methacrylate. Examples of such compounds are the compound (PM-2-1) to the compound (PM-2-9). In order to obtain the effect thereof, a preferable ratio of the polymerizable compound is about 0.05% by weight or more, and a preferable ratio of the polymerizable compound is about 10% by weight or less in order to prevent display defects. A still more preferred ratio is in the range of from about 0.1 wt% to about 2 wt%.

Here, R ^3a , R ^4a , R ^5a , and R ^{6a are} independently propylene fluorenyl or methacryl fluorenyl groups, and R ^7a and R ^{8a are} independently hydrogen, halogen, or an alkyl group having 1 to 10 carbon atoms, Z. ¹³ , Z ¹⁴ , Z ¹⁵ , and Z ^{16 are} independently a single bond or an alkylene group having a carbon number of 1 to 12, and at least one -CH ₂ - may also be substituted by -O- or -CH=CH-, s, t And u are independent of 0, 1, or 2.

As a substance which is required to generate radicals or ions and initiate chain polymerization, a polymerization initiator may be mixed. For example, Irgacure 651 (registered trademark), Yanjiagu 184 (registered trademark), or Darocure 1173 (registered trademark) as a photopolymerization initiator (Ciba, Japan) Japan KK)) is suitable for radical polymerization. The polymerizable compound preferably contains a photopolymerization initiator in the range of 0.1 wt% to 5 wt%. It is particularly preferred to include a photopolymerization initiator in the range of 1 wt% to 3 wt%.

In the radical polymerization system, the polymerization inhibitor can be mixed by rapidly reacting with a radical generated by a polymerization initiator or a monomer to change to a stable radical or a neutral compound, and as a result, polymerization is achieved. The reaction stopped. The polymerization inhibitors can be classified into several kinds in structure. One of them is a self-stabilizing radical such as tri-p-nitrophenylmethyl or di-p-fluorophenylamine, and the other is easily reacted with a radical existing in the polymerization system to become The stable free radicals are represented by nitro, nitroso, amine, polyhydroxy compounds and the like. Representative examples of the latter include hydroquinone, dimethoxybenzene, and the like. In order to obtain the effect, a preferable ratio of the polymerization inhibitor is 5 ppm or more, and a preferable ratio of the polymerization inhibitor is 1000 ppm or less in order to prevent display defects. A still more preferred ratio is in the range of 5 ppm to 500 ppm.

In the liquid crystal display device of the present invention, a liquid crystal composition having negative dielectric anisotropy is used, whereby a liquid crystal display element having excellent afterimage characteristics and excellent alignment stability can be provided. [Examples]

Hereinafter, the present invention will be described by way of examples. In addition, the evaluation methods and compounds used in the examples are as follows. 1. Weight average molecular weight (Mw)

The weight average molecular weight of polylysine was determined by using a 2695 separation module, 2414 differential refractometer (manufactured by Waters), and measuring by a GPC method, followed by polystyrene conversion. The obtained polylysine was obtained by using a mixed solution of phosphoric acid-dimethylformamide (DMF) (phosphoric acid/DMF=0.6/100: weight ratio) to a polyglycine concentration of about 2 wt%. Dilute. The column was measured using HSPgel RT MB-M (manufactured by Waters), and the mixed solution was used as a developing solvent under the conditions of a column temperature of 50 ° C and a flow rate of 0.40 mL / min. Standard polystyrene uses TSK standard polystyrene manufactured by Tosoh. 2. Voltage retention rate

This was carried out by the method described in "Water Margin et al., Proceedings of the 14th Liquid Crystal Symposium, p. 78 (1988)". A rectangular wave having a wave height of ±5 V was applied to the cell and measured. The measurement was carried out at 60 °C. This value is an index indicating how much the applied voltage remains after the frame period. If the value is 100%, it means that all charges are held. When it is 99.0% or more in the unit in which the positive liquid crystal is mounted, and 97.5% or more in the unit in which the negative liquid crystal is mounted, the liquid crystal display element having good display quality is obtained. 3. Determination of ion amount in liquid crystal (ion density)

The liquid crystal physical property measurement system 6254 type manufactured by Dongyang Technology Co., Ltd. was used for measurement according to the method described in "Applied Physics", Vol. 65, No. 10, and 1065 (1996). A triangular wave having a frequency of 0.01 Hz was used for measurement at a voltage range of ±10 V and a temperature of 60 ° C (the area of the electrode was 1 cm ² ). If the ion density is large, problems such as burn marks due to ionic impurities are likely to occur. That is, the ion density is a physical property value which is an index for predicting the occurrence of burn marks. When the value is 40 pC or less, the liquid crystal display element having good display quality is obtained. <tetracarboxylic dianhydride> <Diamine> <Other monomers> Aniline phthalic anhydride <solvent> NMP: N-methyl-2-pyrrolidone BC: butyl cellosolve (ethylene glycol monobutyl ether) GBL: γ-butyrolactone diethylene glycol diethyl ether Diisobutyl ketone 2-butoxypropanol <Additive> Additive (Ad1): N, N, N', N'-tetraglycidyl-4,4'-diaminodiphenylmethane additive (Ad2 : 1,3-bis(4,5-dihydro-2-oxazolyl)benzene additive (Ad3): 2-(3,4-epoxycyclohexyl)ethyltrimethoxydecane [Example 1] Synthesis of varnish

To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube, 0.3075 g of a compound represented by the formula (1-1-1) and a compound represented by the formula (DI-5-1) (m=4) were added. 2.0361 g and 0.2863 g of the compound represented by the formula (DI-5-30) (k=2), and N-methyl-2-pyrrolidone 35.0 g was added. After cooling the solution to 5 ° C in an ice bath, 3.3701 g of the compound represented by the formula (II-1-1) was added, and the mixture was stirred at room temperature for 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, thereby obtaining a solute. Varnish 1 having a weight average molecular weight of about 13,000 and a resin component concentration of 6 wt%. [Examples 2 to 96]

Further, in the same manner as in Example 1, except that the tetracarboxylic dianhydride and the diamine were changed, varnish 2 to varnish 96 having a polymer solid content concentration of 6 wt% was prepared. Regarding the weight average molecular weight, the polymer using the raw material having a photoisomerization structure is adjusted to about 12,000 to 13,000, and the polymer having no raw material having a photoisomerization structure is adjusted to 40,000 to 50,000. The weight average molecular weight of the tetracarboxylic dianhydride and the diamine used and the obtained polymer are shown in Table 1-1 to Table 1-9. Example 1 is again disclosed in Table 1-1.

Table 1-1

Table 1-2

Table 1-3

Table 1-4

Table 1-5

Table 1-6

Table 1-7

Table 1-8

Table 1-9 [Example 97] Preparation of single layer type alignment agent, preparation of electric characteristics measuring unit, and measurement of electric characteristics

10.0 g of the varnish synthesized in Example 1 was weighed into a 50 mL eggplant type flask equipped with a stirring blade and a nitrogen introduction tube, and 5.0 g of N-methyl-2-pyrrolidone and 5.0 g of butyl cellosolve were added thereto. The mixture was stirred at room temperature for 1 hour to obtain an alignment agent 1 having a resin component concentration of 3 wt%. This alignment agent was applied to a glass substrate with an IPS electrode and a glass substrate with a column spacer (2,000 rpm, 15 seconds) by a spinner. After coating, the substrate was heated at 80 ° C for 3 minutes to evaporate the solvent, and then Multi-Light ML-501C/B manufactured by Ushio Electric Co., Ltd. was used to be perpendicular to the substrate. The direction is a linearly polarized light that is irradiated with ultraviolet rays via a polarizing plate. The exposure energy at this time was measured by using an ultraviolet ray cumulative photometer UIT-150 (photoreceptor: UVD-S365) manufactured by Oxtail Motor Co., Ltd. to become 1.3 J/cm ² ±0.1 J/ at a wavelength of 365 nm. The exposure time is adjusted in cm ² way. Then, the film was calcined at 230 ° C for 20 minutes to form a liquid crystal alignment film having a film thickness of about 100 nm. The two substrates on which the alignment film is formed are bonded so as to face each other in such a manner that the alignment film is formed and the liquid crystal composition is injected into the gap between the opposing alignment films. At this time, the polarization directions of the linearly polarized lights that are irradiated to the respective alignment films are made parallel. A positive liquid crystal composition A was injected into the cell to fabricate a liquid crystal cell (liquid crystal display element) having a cell thickness of 7 μm. <Positive liquid crystal composition A> Physical property values: NI 100.1 ° C; Δ ε 5.1; Δn 0.093; η 25.6 mPa·s.

The liquid crystal cell has a voltage holding ratio of 99.5% at 5 V to 30 Hz and an ion density of 15 pC. The unit was placed in a backlighting tester (Fuji Film (Fuji COLOR LED Viewer) Pro HR-2; brightness 2,700 cd/m ² ) for more than 1,000 hours. Sex test. The voltage holding ratio of the measuring cell after the reliability test was 99.4%, and the ion density was 15 pC. [Example 98 to Example 133]

A liquid crystal cell was produced in accordance with Example 97 except that the varnish used was changed, and the voltage holding ratio, ion density measurement, and reliability test were performed. The measurement results are shown in Table 2 together with Example 97.

Table 2

In all of the cells of Examples 98 to 133, good values were obtained for both the initial value and the reliability test. Here, the initial value refers to a result of measurement without being placed on the backlight tester after the cell is produced. [Example 134] Preparation of a blending type alignment agent, preparation of an electric property measuring unit, and measurement of electrical characteristics

6 8.0 g of the varnish synthesized in Example 6 and 39 8.0 g of the varnish synthesized in Example 39 were weighed into a 50 mL eggplant type flask equipped with a stirring blade and a nitrogen introduction tube, and N-methyl-2- was added thereto. 5.0 g of pyrrolidone and 5.0 g of butyl cellosolve were stirred at room temperature for 1 hour to obtain an alignment agent 38 having a resin component concentration of 3 wt%. A liquid crystal cell was produced according to the method described in Example 97. The liquid crystal cell has a voltage holding ratio of 99.8% at 5 V to 30 Hz and an ion density of 10 pC. The voltage holding ratio of the measuring cell after the reliability test was 99.7%, and the ion density was 10 pC. In Table 3, varnish A indicates a varnish containing a polymer using a raw material having a photoisomerization structure, and varnish B indicates a varnish containing a polymer not using a material having a photoisomerization structure. [Examples 135 to 164]

A liquid crystal cell was produced in accordance with Example 134 except that the varnish used was changed, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The varnish used and the measurement results are shown in Table 3 together with Example 134. Further, in Table 3, varnish A indicates a varnish containing a polymer using a raw material having a photoisomerization structure, and varnish B indicates a varnish containing a polymer not using a material having a photoisomerization structure.

table 3

In all of the units of Examples 135 to 164, good values were obtained for both the initial value and the reliability test. [Example 165]

An alignment agent was prepared according to the method described in Example 97 except that the positive liquid crystal composition A injected into the cell was replaced with the negative liquid crystal composition B, and a liquid crystal cell was produced to measure electrical characteristics. <negative liquid crystal composition B> Physical property values: NI 75.7 ° C; Δ ε -4.1; Δn 0.101; η 14.5 mPa·s. [Example 166 - Example 201]

A liquid crystal cell was produced in accordance with Example 165 except that the varnish used was changed, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The measurement results are shown together with Example 165 in Table 4.

Table 4

In all of the units of Examples 166 to 201, good results were obtained for both the initial value and the reliability test. [Example 202]

An alignment agent was prepared according to the method described in Example 134, and a liquid crystal cell was prepared by replacing the positive liquid crystal composition A injected into the cell with the negative liquid crystal composition B, thereby performing voltage holding ratio and ion. Density measurement and reliability test. [Example 203 to Example 232]

A liquid crystal cell was produced in accordance with Example 202 except that the varnish used was changed, and the voltage holding ratio, ion density measurement, and reliability test were performed. The measurement results are shown in Table 5 together with Example 202.

table 5

In all of the cells of Examples 203 to 232, good values were obtained for both the initial value and the reliability test. [Example 233]

To the varnish 8 having a polymer solid content concentration of 6 wt% prepared in Example 8, 5 parts by weight of an additive (Ad1) based on 100 parts by weight of the polymer was added. This polyaminic acid solution was set to varnish 97. The polyamine acid contained in the varnish 97 had a weight average molecular weight of 12,000. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the solid content of the polymer was diluted to 3 wt% to prepare an alignment agent 69. Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. [Example 234]

To the varnish 8 having a polymer solid content concentration of 6 wt% prepared in Example 8, 5 parts by weight of an additive (Ad2) based on 100 parts by weight of the polymer was added. This polyaminic acid solution was set to varnish 98. The polyamine acid contained in the varnish 98 had a weight average molecular weight of 12,000. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the solid concentration of the polymer was diluted to 3 wt% to prepare an alignment agent 70. Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. [Example 235]

To the varnish 8 having a polymer solid content concentration of 6 wt% prepared in Example 8, 5 parts by weight of an additive (Ad3) based on 100 parts by weight of the polymer was added. This polyaminic acid solution was set to varnish 99. The polyamine acid contained in the varnish 99 had a weight average molecular weight of 12,000. Then, a mixed solvent of NMP/BC = 1/1 (weight ratio) was added, and the solid concentration of the polymer was diluted to 3 wt% to prepare an alignment agent 71. Using the obtained liquid crystal alignment agent, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. [Example 236]

To the alignment agent 48 having a polymer solid content concentration of 3 wt% prepared in Example 144, 5 parts by weight of an additive (Ad1) based on 100 parts by weight of the polymer was added. Using the obtained alignment agent 72, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. [Example 237]

To the alignment agent 48 having a polymer solid content concentration of 3 wt% prepared in Example 144, 5 parts by weight of an additive (Ad2) based on 100 parts by weight of the polymer was added. Using the obtained alignment agent 73, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. [Example 238]

To the alignment agent 48 having a polymer solid content concentration of 3 wt% prepared in Example 144, 5 parts by weight of an additive (Ad3) based on 100 parts by weight of the polymer was added. Using the obtained alignment agent 74, a liquid crystal cell was produced by the method according to Example 97, and voltage holding ratio, ion density measurement, and reliability test were performed. The measurement results of Examples 233 to 238 are shown in Table 6.

Table 6

In all of the units of Examples 233 to 238, even after the addition of the additive, the initial value and the value after the reliability test gave good results. [Comparative Example 1 to Comparative Example 3]

A liquid crystal cell was produced by the method described in Example 97 except that the varnish 1 was replaced with the varnish 65, the varnish 75, or the varnish 85, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The measurement results are shown in Table 7.

Table 7

In all the cells of Comparative Examples 1 to 3, in particular, the results obtained after the reliability test were greatly reduced. [Comparative Example 4 to Comparative Example 6]

A liquid crystal cell was produced by the method described in Comparative Example 1 to Comparative Example 3, except that the positive liquid crystal composition A injected into the cell was replaced with the negative liquid crystal composition B, and voltage holding ratio and ion density were performed. Determination and reliability test. The measurement results are shown in Table 8.

Table 8

In all the cells of Comparative Example 4 to Comparative Example 6, in particular, the results obtained by the reliability test were greatly reduced. [Comparative Example 7 to Comparative Example 17]

A liquid crystal cell was produced in accordance with Example 134 except that the varnish used was changed, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The varnish used and the measurement results are shown in Table 9.

Table 9

In all the cells of Comparative Example 7 to Comparative Example 17, in particular, the results obtained after the reliability test were greatly reduced. [Comparative Example 18 to Comparative Example 28]

A liquid crystal cell was produced according to the method described in Comparative Example 7 to Comparative Example 17, except that the positive liquid crystal composition A injected into the cell was replaced with the negative liquid crystal composition B, and voltage holding ratio and ion density were performed. Determination and reliability test. The measurement results are shown in Table 10.

Table 10

In all the cells of Comparative Example 18 to Comparative Example 28, in particular, the results obtained after the reliability test were greatly reduced. [Examples 239 to 241] Synthesis of varnish

In the same manner as in Example 1, except that the tetracarboxylic dianhydride and the diamine were changed, varnish 97 to varnish 99 having a polymer solid content concentration of 6 wt% was prepared. The weight average molecular weight is adjusted to 40,000 to 50,000. The weight average molecular weight of the tetracarboxylic dianhydride and the diamine used and the obtained polymer are shown in Table 11.

Table 11 [Examples 242 to 244] Preparation of an alignment agent, preparation of an electric property measuring unit, and measurement of electrical characteristics

A liquid crystal cell was produced in accordance with Example 134 except that the varnish used was changed, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The varnish used and the measurement results are shown in Table 12. Further, in Table 12, varnish A indicates a varnish containing a polymer using a material having a photoisomerization structure, and varnish B indicates a varnish containing a polymer not using a material having a photoisomerization structure.

Table 12

In all of the units of Examples 242 to 244, good values were obtained for both the initial value and the reliability test. [Confirmation of printability by inkjet method]

The liquid crystal alignment agent of the present invention is a liquid crystal alignment agent suitable for coating by an inkjet method by appropriately selecting a solvent to be used. Preparation of liquid crystal alignment agent for inkjet coating [Example 245]

To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube, 0.1390 g of the compound represented by the formula (1-1-1) and 1.6254 g of the compound represented by the formula (V-2-1) and a formula ( DI-5-1) 0.3451 g of the compound represented by (m=4), and N-methyl-2-pyrrolidone 34.0 g was added. After cooling the solution in an ice bath and setting the liquid temperature to 5 ° C, 3.8905 g of the compound represented by the formula (AN-4-17) (m = 8) was added, and the mixture was stirred at room temperature for 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, thereby obtaining a solute. The varnish 100 having a weight average molecular weight of about 12,000 and a resin component concentration of 6 wt%. [Example 246]

To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 1.5052 g of a compound represented by the formula (DI-5-9) and 1.6504 g of a compound represented by the formula (DI-13-1) were added and added. N-methyl-2-pyrrolidone 34.0 g. After cooling the solution in an ice bath and setting the liquid temperature to 5 ° C, 1.3539 g of the compound represented by the formula (AN-1-1) and 1.4905 g of the compound represented by the formula (AN-3-2) were added at room temperature. Stir under 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of butyl cellosolve were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the polymer of the solute became the desired weight average molecular weight, thereby obtaining a solute. The varnish 101 having a weight average molecular weight of about 49,000 and a resin component concentration of 6 wt%. [Example 247]

17.5 g of the varnish 100 synthesized in Example 245 and 40.8 g of the varnish 101 synthesized in Example 246 were weighed, and NMP 16.7 g, GBL 7.5 g, butyl cellosolve 7.5 g, and diethylene glycol diethyl ether 10.0 g were added thereto, thereby A liquid crystal alignment agent 1 for inkjet coating for solid content concentration of 3.5 wt% and a solvent composition of NMP: GBL: butyl cellosolve: diethylene glycol diethyl ether = 36.5:25:25:10 was prepared.

The inkjet coating liquid crystal alignment agent 1 was applied onto a glass substrate by an inkjet coating apparatus (manufactured by Fujifilm Co., Ltd., DMP-2831). Further, the droplet interval was adjusted, and a voltage was applied to the cartridge so that the film thickness of the liquid crystal alignment film became 100 nm. After the application, the unevenness of the entire printing surface and the linearity of the printing side were visually confirmed, but unevenness was not caused, and the linearity was also good. [Example 248]

17.5 g of the varnish 100 synthesized in Example 245 and 40.8 g of the varnish 101 synthesized in Example 246 were weighed, and NMP 16.7 g, GBL 7.5 g, butyl cellosolve 5.5 g, diethylene glycol diethyl ether 10.0 g and two were added thereto. 2.0 g of isobutyl ketone to prepare a solid concentration of 3.5 wt%, and the solvent composition is NMP: GBL: butyl cellosolve: diethylene glycol diethyl ether: diisobutyl ketone = 36.5: 25: 23: 10: 2 liquid crystal alignment agent 2 for inkjet coating. According to the method described in Example 247, the applicability of the inkjet printing was confirmed. As a result, the unevenness of the entire printing surface was not produced, and the linearity of the printing side was good. [Example 249] Synthesis of Polylysine Using Amine and Anhydride

To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen introduction tube, 0.1336 g of a compound represented by the formula (1-1-1), a compound represented by the formula (V-2-1): 1.8547 g, and an aniline 0.0865 were added. g, and added N-methyl-2-pyrrolidone 34.0 g. After cooling the solution in an ice bath and setting the liquid temperature to 5 ° C, 3.9253 g of the compound represented by the formula (AN-4-17) (m = 8) was added, and the mixture was stirred at room temperature for 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of 2-butoxypropanol were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the solute polymer became the desired weight average molecular weight. Thus, a varnish 102 having a weight average molecular weight of the solute of about 11,000 and a resin component concentration of 6 wt% was obtained. [Example 250]

To a 100 mL three-necked flask equipped with a stirring blade and a nitrogen inlet tube, 0.1344 g of the compound represented by the formula (1-1-1) and 1.9652 g of the compound represented by the formula (V-2-1) were added and added. N-methyl-2-pyrrolidone 34.0 g. After cooling the solution in an ice bath and setting the liquid temperature to 5 ° C, 3.7632 g of the compound represented by the formula (AN-4-17) (m=8) and 0.1372 g of phthalic anhydride were added, and the mixture was stirred at room temperature. 12 hours. 30.0 g of γ-butyrolactone and 30.0 g of 2-butoxypropanol were added thereto, and the solution was heated and stirred at 60 ° C until the weight average molecular weight of the solute polymer became the desired weight average molecular weight. Thus, a varnish 103 having a weight average molecular weight of the solute of about 10,000 and a resin component concentration of 6 wt% was obtained. [Example 251, Example 252] Preparation of an alignment agent, preparation of an electric property measurement unit, and measurement of electrical characteristics

A liquid crystal cell was produced in accordance with Example 134 except that the varnish used was changed, and the voltage holding ratio, the ion density measurement, and the reliability test were performed. The varnish used and the measurement results are shown in Table 13. Further, in Table 13, varnish A indicates a varnish containing a polymer using a material having a photoisomerization structure, and varnish B indicates a varnish containing a polymer not using a material having a photoisomerization structure.

Table 13

In all the cells of Example 251 and Example 252, good values were obtained for both the initial value and the reliability test. [Industrial availability]

When the liquid alignment alignment agent for photoalignment of the present invention is used, it is possible to provide a liquid crystal display element which can maintain a high voltage holding ratio, light resistance, and display quality even when used for a long period of time. The liquid alignment alignment agent for photoalignment of the present invention can be suitably applied to a lateral electric field type liquid crystal display element.

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Claims (18)

A liquid alignment alignment agent comprising at least one polymer selected from the group consisting of polylysine, polylysine, and polyamidene obtained by ruthenium imidization thereof, The polyamidamine, the polyamidomate, and the polyimine obtained by ruthenium imidation thereof are obtained by reacting at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof with a diamine. At least one of the raw material monomers of the polymer has a photoisomerization structure, and the raw material monomer of the polymer comprises at least one of the compounds represented by the following formula (1); In the formula (1), R ^a is hydrogen or a methyl group; R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms; and the tetracarboxylic acid The derivative of the dianhydride is a tetracarboxylic acid diester or a tetracarboxylic acid diester dichloride. The liquid alignment alignment agent for photo-alignment according to claim 1, comprising: photoisomerization of at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine a compound of the structure, and at least one of the polymers obtained by reacting a raw material monomer containing at least one of the compounds represented by the formula (1); or a mixture comprising: a tetracarboxylic dianhydride and a derivative thereof And at least one of a polymer obtained by reacting a raw material monomer of at least one compound having a photoisomerization structure in a group consisting of diamines; and a tetracarboxylic dianhydride, a derivative thereof, and a diamine At least one of the polymers obtained by reacting a raw material monomer having at least one of the compounds represented by the formula (1) and having a photoisomerization structure. The liquid alignment alignment agent for photo-alignment according to claim 2, which comprises photoisomerization of at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine. At least one of a polymer obtained by reacting a compound having at least one of a compound represented by the formula (1); and a polymer mixed with the polymer; and the other The polymer is a polymer obtained by reacting a raw material monomer having no photoisomerization structure in any of tetracarboxylic dianhydride, a derivative thereof, and a diamine. The liquid alignment alignment agent for photo-alignment according to claim 2, which comprises photoisomerization of at least one selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof and a diamine. At least one of a polymer obtained by reacting a compound having at least one of a compound represented by the formula (1); and a polymer mixed with the polymer; and the other The polymer is a raw material monomer in which at least one of the tetracarboxylic dianhydride and its derivative and the diamine does not have a photoisomerization structure, and the diamine contains at least one of the compounds represented by the formula (1) The polymer obtained. The liquid alignment alignment agent for photoalignment according to claim 1, which comprises at least one of a group selected from the group consisting of tetracarboxylic dianhydride and a derivative thereof, and a diamine. At least one of a polymer obtained by reacting a raw material monomer of a compound of a structured structure; and having neither a tetracarboxylic dianhydride nor a derivative thereof and a diamine having a photoisomerization structure, and the diamine contains At least one of the polymers obtained by reacting a raw material monomer of at least one of the compounds represented by the formula (1). The liquid-aligning liquid-aligning agent according to any one of the above-mentioned, wherein the diamine represented by the formula (1) is a diamine represented by the formula (1-1) and At least one of the group consisting of diamines represented by formula (1-2): In the formulae (1-1) and (1-2), R ^b is hydrogen, -OH, an alkyl group having 1 to 6 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms. The liquid-aligning liquid-aligning agent according to any one of the above-mentioned items (1), wherein the diamine represented by the formula (1) is selected from the following formula (1-1-1) to (1-1-6), Formula (1-1-17), Formula (1-1-18), Formula (1-2-1) to Formula (1-2-6), Formula (1-2- At least one of the group consisting of 17) and a diamine represented by the formula (1-2-18): . The liquid alignment alignment agent for photoalignment according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is a formula (II) to a formula (VI) At least one of the compounds represented: In the formulae (II) to (V), R ² and R ³ are a monovalent organic group having -NH ₂ or a monovalent organic group having -CO-O-CO-, and in the formula (IV), R ⁴ is In the divalent organic group, in the formula (VI), R ⁵ is an aromatic ring having -NH ₂ or -CO-O-CO-. The photo-alignment liquid crystal alignment agent according to claim 8, wherein the tetracarboxylic dianhydride or diamine having a photoisomerization structure is selected from the group consisting of formula (II-1) and formula (II-2). ), Formula (III-1), Formula (III-2), Formula (IV-1), Formula (IV-2), Formula (V-1) to Formula (V-3), Formula (VI-1) And at least one of the group of compounds represented by formula (VI-2): In the above formula, the group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; in the formula (V-2), R ^{6 is} independently -CH ₃ , -OCH ₃ , -CF ₃ , or -COOCH ₃ , a is an integer of 0 to 2; in the formula (V-3), ring A and ring B are each independently selected from a monocyclic hydrocarbon, a condensed polycyclic hydrocarbon And at least one of the heterocyclic rings, R ¹¹ is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ )CO-, or -CON(CH ₃ )-, R ¹² is a linear alkylene group having 1 to 20 carbon atoms, -COO-, -OCO-, -NHCO-, -CONH-, -N(CH ₃ )CO-, or In -CON(CH ₃ )-, R ¹¹ and R ¹² , one or two of -CH ₂ - of the linear alkyl group may be substituted by -O-, and R ⁷ to R ¹⁰ are independently -F, -CH, respectively. ₃ , -OCH ₃ , -CF ₃ , or -OH, and b to e are each independently an integer of 0 to 4. The liquid alignment alignment agent for photoalignment according to any one of claims 1 to 5, wherein the tetracarboxylic dianhydride having no photoisomerization structure is selected from the following formula (AN-I) At least one of the group of tetracarboxylic dianhydrides represented by the formula (AN-VII): Of formula (AN-I), the formula (AN-IV) and formula (AN-V), X is independently a single bond or -CH ₂ -; of formula (AN-II), G is a single bond, a carbon number of 1 ～20 alkylene, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; formula (AN-II)～ In the formula (AN-IV), Y is independently one selected from the group of trivalent groups described below, At least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group; in the formula (AN-III) to the formula (AN-V), the ring A ¹⁰ is a group of a monocyclic hydrocarbon having a carbon number of 3 to 10. Or a group of a condensed polycyclic hydrocarbon having 6 to 30 carbon atoms, wherein at least one hydrogen of the group may be substituted by a methyl group, an ethyl group or a phenyl group, and a bond bonded to the ring may be bonded to any carbon constituting the ring, Two bonding bonds may be bonded to the same carbon; in the formula (AN-VI), X ¹⁰ is an alkylene group having 2 to 6 carbon atoms, Me represents a methyl group, and Ph represents a phenyl group, in the formula (AN-VII) , G ^{10 is} independently -O-, -COO- or -OCO-; and r is independently 0 or 1. The liquid alignment alignment agent for photoalignment according to claim 10, wherein the tetracarboxylic dianhydride having no photoisomerization structure is selected from the following 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-10-1), formula (AN-11-3), formula (AN-16-1), formula (AN-16-3), and formula (AN-16-4) At least one of: In the formula (AN-1-2) and the formula (AN-4-17), m is an integer of 1 to 12. The liquid alignment alignment agent for photoalignment according to any one of claims 1 to 5, wherein the diamine having no photoisomerization structure is selected from the following formula (DI-1) to (formula) At least one of a group consisting of DI-16), (DIH-1) to (DIH-3), and (DI-31) to (DI-35): In the formula (DI-1), G ²⁰ is -CH ₂ -, at least one -CH ₂ - may be substituted by -NH-, -O-, m is an integer of from 1 to 12, and at least one hydrogen of the alkyl group may be -OH substituents; in formula (DI-3) and formula (DI-5) ~ of formula (DI-7), G ²¹ are each 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 An integer of 1 to 5, n is 1 or 2; in the formula (DI-4), s is independently an integer of 0 to 2; in the formula (DI-6) and the formula (DI-7), G ^{22 is} independently a single a bond, -O-, -S-, -CO-, -C(CH ₃ ) ₂ -, -C(CF ₃ ) ₂ -, -NH-, or an alkylene group having a carbon number of 1 to 10; In DI-2) to (DI-7), at least one hydrogen of the cyclohexane ring and the benzene ring may be -F, -Cl, an alkyl group having 1 to 3 carbon atoms, -OCH ₃ , -OH, -CF ₃ , -CO ₂ H, -CONH ₂ , -NHC ₆ H ₅ , phenyl, or benzyl substitution, Further, in the formula (DI-4), at least one hydrogen of the benzene ring may be substituted by one selected from the group consisting of a group represented by the following formula (DI-4-a) to formula (DI-4-e). ; In the formula (DI-4-a) and the formula (DI-4-b), R ^{20 is} independently hydrogen or -CH ₃ ; the bond site is not fixed at the carbon atom constituting the ring, and is represented on the ring. bonding position is arbitrary, -NH ₂ bonding position on the cyclohexane ring or benzene ring is bonded to any position other than G ²¹ or G ²² in position; In the formula (DI-11), r is 0 or 1; in the formula (DI-8) to the formula (DI-11), the bonding position of -NH ₂ bonded to the ring is an arbitrary position; In the formula (DI-12), R ²¹ and R ^{22 are} independently an alkyl group having 1 to 3 carbon atoms or a phenyl group, and G ^{23 is} independently an alkylene group having a carbon number of 1 to 6, a phenyl group or an alkyl group. The substituted phenyl group, w is an integer of 1 to 10; in the formula (DI-13), R ^{23 is} independently an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms or -Cl, p is independently an integer of 0 to 3, q is an integer of 0 to 4; in the formula (DI-14), ring B is a monocyclic heteroaromatic, R ²⁴ is hydrogen, -F, -Cl, and the carbon number is 1. An alkyl group of ～6, an alkoxy group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, an alkynyl group having 1 to 6 carbon atoms, and q independently an integer of 0 to 4; In 15), ring C is a monocyclic ring containing a hetero atom; in the formula (DI-16), G ²⁴ is a single bond, an alkylene group having a carbon number of 2 to 6 or a 1,4-phenylene group, and r is 0. Or 1; in the formula (DI-13) to the formula (DI-16), the group in which the bonding position is not fixed to the carbon atom constituting the ring means that the bonding position on the ring is arbitrary; In the formula (DIH-1), G ²⁵ is a single bond, an alkylene group 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 of the ring may be a methyl group, an ethyl group, or a phenyl group. In the formula (DIH-3), the ring E is independently a cyclohexane ring or a benzene ring, and at least one hydrogen of the ring may be substituted by a methyl group, an ethyl group or a phenyl group, and Y is a single bond and a carbon number. Is an alkyl group of 1 to 20, -CO-, -O-, -S-, -SO ₂ -, -C(CH ₃ ) ₂ -, or -C(CF ₃ ) ₂ -; (DIH-2 And in the formula (DIH-3), the bonding position of -CONHNH ₂ bonded to the ring is an arbitrary 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 an alkyl group having 3 to 30 carbon atoms, a phenyl group, a group having a steroid skeleton, or a group represented by the formula (DI-31-a) wherein at least one hydrogen of the alkyl group may be substituted by -F, and at least one -CH ₂ - may be -O-, -CH=CH- or -C≡C - Substituting, the hydrogen of the phenyl group may be -F, -CH ₃ , -OCH ₃ , -OCH ₂ F, -OCHF ₂ , -OCF ₃ , an alkyl group having 3 to 30 carbon atoms or a carbon number of 3 to 30 The alkoxy group is substituted, and the bonding position of -NH ₂ bonded to the benzene ring means an arbitrary position in the ring. 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 group having 1 to 12 carbon atoms, and more than one alkyl group of the alkylene group -CH ₂ - may be substituted by -O-, -COO-, -OCO-, -CONH-, -CH=CH-, and ring B ²¹ , ring B ²² , ring B ²³ and ring B ^{24 are} independently 1,4-stretched Phenyl, 1,4-cyclohexylene, 1,3-dioxane-2,5-diyl, pyrimidine-2,5-diyl, pyridine-2,5-diyl, naphthalene-1,5- In the diyl, naphthalene-2,7-diyl or inden-9,10-diyl, ring B ²¹ , ring B ²² , ring B ²³ and ring B ²⁴ , at least one hydrogen may be substituted by -F or -CH ₃ , s, t, and u are independent integers of 0 to 2, and their total is 1 to 5. 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 different. R ²⁶ may be the same or different, and R ²⁶ is hydrogen, -F, -OH, an alkyl group having 1 to 30 carbon atoms, a fluorine-substituted alkyl group having 1 to 30 carbon atoms, or an alkoxy group having 1 to 30 carbon atoms. , -CN, -OCH ₂ F, -OCHF ₂ or -OCF ₃ , at least one -CH ₂ - of the alkyl group having 1 to 30 carbon atoms may be represented by the following formula (DI-31-b) Bivalent base substitution, In formula (DI-31-b), R 27 and R ²⁸ are independently alkyl having 1 to 3, v is an integer of 1 to 6; In the formula (DI-32) and the formula (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, and the carbon number is 1. An alkyl group of -20 or an alkenyl group having 2 to 20 carbon atoms; a hydrogen of the benzene ring of the formula (DI-33) may be substituted by an alkyl group having 1 to 20 carbon atoms or a phenyl group, and the formula (DI- 32) and in the formula (DI-33), a group in which the bonding position is not fixed to any one of the carbon atoms constituting the ring means that the bonding position on the ring is arbitrary; In the formula (DI-34) and the formula (DI-35), G ^{31 is} independently -O- or an alkylene group having 1 to 6 carbon atoms, and G ³² is a single bond or an alkylene group having 1 to 3 carbon atoms. And R ³¹ is hydrogen or an alkyl group having 1 to 20 carbon atoms, and at least one -CH ₂ - of the alkyl group may be substituted by -O-, -CH=CH- or -C≡C-, and R ³² is a carbon number Is an alkyl group of 6 to 22, R ³³ is hydrogen or an alkyl group having 1 to 22 carbon atoms, and ring B ²⁵ is 1,4-phenylene or 1,4-cyclohexylene, and r is 0 or 1, and The -NH ₂ bonded to the benzene ring indicates that the bonding position on the ring is arbitrary. The liquid alignment alignment agent for photo-alignment according to claim 12, wherein the diamine having no photoisomerization structure is selected from the following formula (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-5-17), formula (DI-5-28 ), formula (DI-5-30), formula (DI-6-7), formula (DI-7-3), formula (DI-11-2), formula (DI-13-1), formula (DI -16-1), at least one of the group consisting of: (DI-31-44), and (DIH-2-1): In the formula (DI-5-1), the formula (DI-5-12), the formula (DI-5-13), and the formula (DI-7-3), m is an integer of 1 to 12; 5-30), k is an integer from 1 to 5; and in the formula (DI-7-3), n is 1 or 2; . The liquid alignment alignment agent for photoalignment according to any one of claims 1 to 5, which further comprises a radically polymerizable unsaturated double bond selected from the group consisting of an alkenyl-substituted nadic ylidene compound. At least one of the group consisting of a compound, an oxazine compound, an oxazoline compound, and an epoxy compound. The liquid alignment alignment agent for photoalignment according to any one of claims 1 to 5, which is used for the production of a lateral electric field type liquid crystal display device. A liquid crystal alignment film which is formed by the liquid alignment alignment agent for photoalignment according to any one of claims 1 to 15. A liquid crystal display element comprising the liquid crystal alignment film according to item 16 of the patent application. A transverse electric field type liquid crystal display element comprising the liquid crystal alignment film according to claim 16 of the patent application.