JP2010102014A - Liquid crystal aligning agent, liquid crystal alignment layer and method for forming the same, and liquid crystal display element - Google Patents

Abstract

Disclosed is a liquid crystal aligning agent capable of providing a pretilt angle by a photo-alignment method and providing a liquid crystal alignment film having excellent temporal stability of the applied pretilt angle.
The liquid crystal aligning agent includes (A) a photosensitive structure containing a conjugated double bond, (B) a C1-C3 fluoroalkyl group, and a C4-C20 optionally substituted with a fluorine atom. And at least one group selected from the group consisting of monovalent or divalent hydrocarbon groups containing a condensed alicyclic structure having 9 to 30 carbon atoms, and (C) a heavy compound having a photosensitizing structure Contains coalescence.
[Selection figure] None

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, a method for forming the same, and a liquid crystal display element. More specifically, a liquid crystal aligning agent that gives a liquid crystal alignment film that is imparted with liquid crystal alignment properties by irradiation with polarized or non-polarized radiation and has excellent pretilt angle stability, exhibits good liquid crystal alignment properties, and has excellent pretilt angle stability. The present invention relates to a liquid crystal alignment film, a method for forming the same, and a liquid crystal display element having excellent long-term reliability.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched between substrates with a transparent electrode having a liquid crystal alignment film, and the major axis of liquid crystal molecules is twisted continuously between the substrates by 0 to 360 ° as necessary. Various liquid crystal cells such as TN (Twisted Nematic) type and STN (Super Twisted Nematic) type, and IPS (In Plane Switching) type in which the long axis of liquid crystal molecules is aligned in the horizontal direction with respect to the substrate. Liquid crystal display elements having the above are known (see Patent Documents 1 to 4).
As a means for aligning the liquid crystal in such a liquid crystal cell, an organic film is formed on the surface of the substrate, and then the surface of the organic film is rubbed in one direction with a cloth material such as rayon. A monomolecular film having a long-chain alkyl group is formed by using a method for forming a liquid crystal alignment film (a method for performing a rubbing treatment), a method for obliquely depositing silicon oxide on a substrate surface, or a Langmuir-Blodgett method (LB method). There are ways to do it. Among these, from the viewpoints of substrate size, liquid crystal alignment uniformity, processing time and processing cost, it is common to provide liquid crystal alignment ability by rubbing.
However, if the alignment of the liquid crystal is performed by rubbing, dust is likely to be generated in the process or static electricity is likely to be generated, so that dust adheres to the alignment film surface and causes display defects. there were. In particular, in the case of a substrate having a TFT (Thin Film Transistor) element, there has been a problem that the circuit damage of the TFT element occurs due to the generated static electricity, resulting in a decrease in yield. Furthermore, in liquid crystal display elements that will be further refined in the future, unevenness is inevitably generated on the substrate surface as the density of pixels increases, so that uniform rubbing treatment is gradually becoming difficult.

As another means of imparting liquid crystal alignment ability to the liquid crystal alignment film in the liquid crystal cell, the liquid crystal alignment ability can be improved by irradiating a photosensitive thin film such as polyvinyl cinnamate or polyimide formed on the substrate surface with polarized or non-polarized radiation. The photo-alignment method to provide is known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 6 to 16 and 19 to 21).
By the way, in a liquid crystal cell such as a TN (twisted nematic) type or an STN (super twisted nematic) type, the liquid crystal alignment film needs to tilt and align the liquid crystal molecules at a predetermined angle (pretilt angle) with respect to the substrate surface. (See Patent Document 2). In the case of forming a liquid crystal alignment film by the photo-alignment method, the pretilt angle is usually given by irradiation with radiation whose incident direction to the substrate surface is inclined from the substrate normal (see Patent Document 6).
On the other hand, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known as an operation mode of a liquid crystal display element different from the above. In this operation mode, when a voltage is applied between the substrates and the liquid crystal molecules are tilted in the direction parallel to the substrate, the liquid crystal molecules must be tilted from the substrate normal direction to one direction in the substrate surface. There is. As a means for this, for example, a method of providing protrusions on the substrate surface, a method of providing stripes on the transparent electrode, or using a rubbing alignment film, liquid crystal molecules are slightly directed from the substrate normal direction to one direction in the substrate surface. A method of tilting (pretilting) has been proposed (see Patent Document 5 and Non-Patent Documents 1 to 3).
The photo-alignment method is known to be useful as a method for controlling the tilt direction of liquid crystal molecules in a vertical alignment mode liquid crystal display element (see Patent Documents 15 to 21).
Thus, the liquid crystal alignment film manufactured by the photo-alignment method can be effectively applied to a liquid crystal display element. However, the liquid crystal alignment film produced by the conventional photo-alignment method has an unstable pretilt angle, that is, the pretilt property decreases with time even if the pretilt angle characteristic is shown immediately after the liquid crystal alignment film is formed. There was a problem to do.
JP-A-4-153622 JP 60-107020 A JP 56-91277 A US Pat. No. 5,928,733 Japanese Patent Laid-Open No. 11-258605 JP-A-9-222605 JP-A-6-287453 JP-A-10-251646 Japanese Patent Laid-Open No. 11-2815 JP-A-11-152475 JP 2000-144136 A JP 2000-319510 A JP 2000-281724 A JP-A-9-297313 JP 2003-307736 A JP 2004-163646 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP 2006-171304 A JP 2007-224273 A JP 2007-256484 A JP 2007-191447 A “Liquid Crystal” vol. 3 No. 2, p117 (1999) “Liquid Crystal” vol. 3 No. 4, p272 (1999) “Jpn Appl. Phys.” Vol. 36, p428 (1997) T. T. J. et al. Scheffer et. al. , J. et al. Appl. Phys. vo. 19, p2013 (1980)

The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a liquid crystal alignment film that can impart a pretilt angle by a photo-alignment method and is excellent in temporal stability of the applied pretilt angle. It aims at providing a liquid crystal aligning agent.
Another object of the present invention is to provide a method for forming a liquid crystal alignment film from the liquid crystal alignment agent.
Still another object of the present invention is to provide a liquid crystal alignment film which exhibits good liquid crystal alignment and is excellent in pretilt angle stability over time.
Still another object of the present invention is to provide a liquid crystal display element having excellent long-term reliability.
Further objects and advantages of the present invention will become apparent from the following description.

According to the present invention, the above objects and advantages of the present invention are as follows.
(A) a photosensitive structure containing a conjugated double bond,
(B) a monovalent or divalent group comprising a fluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 4 to 20 carbon atoms which may be substituted with a fluorine atom, and a condensed alicyclic structure having 9 to 30 carbon atoms This is achieved by a liquid crystal aligning agent containing at least one group selected from the group consisting of hydrocarbon groups, and (C) a polymer having a photosensitizing structure.
The above objects and advantages of the present invention are secondly,
This is achieved by a method for forming a liquid crystal alignment film in which a coating film is formed by applying the liquid crystal aligning agent on a substrate, and the coating film is irradiated with polarized or non-polarized radiation.
Third, the above objects and advantages of the present invention are as follows:
Achieved by the liquid crystal alignment film formed by the above method, and fourthly,
This is achieved by a liquid crystal display device comprising the liquid crystal alignment film.

  When the liquid crystal aligning agent of this invention is used, the liquid crystal aligning film which is excellent in the temporal stability of a pretilt angle can be formed by the photo-alignment method. The liquid crystal alignment film formed from the liquid crystal aligning agent of the present invention can be suitably applied to various liquid crystal display elements. When the liquid crystal display element of the present invention having such a liquid crystal alignment film is used for a long period of time, the display performance does not deteriorate. Therefore, the liquid crystal display element of the present invention can be effectively applied to various devices, such as watches, portable games, word processors, notebook computers, car navigation systems, camcorders, portable information terminals, digital cameras, cellular phones, It can be suitably used for display devices such as various monitors and liquid crystal televisions.

Hereinafter, the present invention will be described in detail.
The liquid crystal aligning agent of the present invention is
(A) Photosensitive structure containing a conjugated double bond (hereinafter referred to as “(A) photosensitive structure”),
(B) a monovalent or divalent group comprising a fluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 4 to 20 carbon atoms which may be substituted with a fluorine atom, and a condensed alicyclic structure having 9 to 30 carbon atoms It contains at least one group selected from the group consisting of hydrocarbon groups (hereinafter referred to as “specific group (B)”), and (C) a polymer having a photosensitized structure.
When the thin film made of the polymer is irradiated with polarized or non-polarized radiation, (A) the photosensitive structure reacts to cause a photoreaction in a direction-selective manner, and a structure oriented in a certain direction is formed. On the film having such a structure, the alignment direction of the liquid crystal molecules is controlled by the alignment structure. The orientation direction of the liquid crystal molecules includes a pretilt angle characteristic. The specific group (B) is oriented in the same direction as the orientation direction of the photosensitive structure (A) and exhibits a function of easily generating a pretilt angle by reducing the surface tension of the thin film. Further, the (C) photosensitizing structure is excited by irradiation with radiation, and this excitation energy is transferred to the adjacent (A) photosensitive structure in the polymer. The photosensitive structure (A) that has received the excitation energy causes a dimerization reaction to form a crosslinked structure between the polymers. This suppresses the molecular motion of the oriented (A) photosensitive structure, and as a result, it is considered that the pretilt angle expression is stable.
(A) As the photosensitive structure, the following formula (a)

(In the formula (a), Ar is a divalent aromatic group, and R ^I and R ^II are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
It is preferable that it is a structure represented by these.
In the above formula (a), examples of the aromatic group represented by Ar include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,4-furandiyl group, 3, 4-furandyl group, 2,5-furandiyl group, 2,4-thiophenediyl group, 3,4-thiophenediyl group, 2,5-thiophenediyl group, 2,4-pyrrolediyl group, 3,4-pyrrolediyl Group, 2,5-pyrrolediyl group, 2,4-pyridinediyl group and 2,5-pyridinediyl group, and one or more hydrogen atoms contained in these groups, a halogen atom, a cyano group, a nitro group, An alkyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, an alkoxyl group having 1 to 6 carbon atoms which may be substituted with a halogen atom, or a carbon number which may be substituted with a halogen atom It can be a group obtained by substituting at least one group selected from the group consisting of which may aryloxy group optionally substituted by ~ 14 aryl group and a halogen atom. Of these, 1,4-phenylene group, 2-fluoro-1,4-phenylene group, 2,5-difluoro-1,4-phenylene group and 2,3,5,6-tetrafluoro group are preferable. A 1,4-phenylene group can be exemplified, and more preferred examples include a 1,4-phenylene group and a 2-fluoro-1,4-phenylene group.
R ^I and R ^II are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

Examples of the C1-C3 fluoroalkyl group as the specific group (B) include a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a pentafluoroethyl group, and a 3,3,3-trifluoropropyl group. Group, 2,2,3,3,3-pentafluoropropyl group, perfluoropropyl group and the like.
Examples of the alkyl group having 4 to 20 carbon atoms that may be substituted with the fluorine atom as the specific group (B) include, for example, a butyl group, a pentyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, a tetradecyl group, and a hexadecyl group. Group, octadecyl group, eicosyl group, 4,4,4-trifluorobutyl group, 3,3,4,4,4-pentafluorobutyl group, 2,2,3,3,4,4,4-heptafluoro Butyl group, perfluorobutyl group, 5,5,5-trifluoropentyl group, 4,4,5,5,5-pentafluoropentyl group, 2,2,3,3,4,4,5,5 Examples thereof include a 5-nonadecylpentyl group and a perfluoropentyl group.
Examples of the condensed alicyclic structure having 9 to 30 carbon atoms in the monovalent or divalent hydrocarbon group including the condensed alicyclic structure having 9 to 30 carbon atoms, which is the specific group (B), include, for example, a decalin skeleton and perhydroanthracene. The structure which consists of frame | skeleton or a steroid frame | skeleton can be mentioned. The steroid skeleton refers to a skeleton composed of a cyclopentano-perhydrophenanthrene nucleus or a skeleton in which one or more of the carbon-carbon bonds are double bonds. The specific group (B) is preferably a monovalent or divalent hydrocarbon group containing a steroid skeleton, and specific examples thereof include a monovalent group containing a steroid skeleton such as a cholesteryl group, a cholestanyl group, a lanosteryl group, Examples of the divalent group containing a steroid skeleton include a lanostaneyl group and the like, for example, a cholesta-3,6-diyl group, a cholesta-3,3-diyl group, a lanosta-3,3-diyl group, and the like. .

The (C) photosensitized structure is a structure having a function of being excited by irradiation of radiation and giving this excitation energy to the adjacent (A) photosensitive structure in the polymer. This excited state may be a singlet or a triplet, but is preferably a triplet because of its long life and efficient energy transfer. The radiation absorbed by the photosensitizing structure is preferably ultraviolet rays or visible rays having a wavelength in the range of 150 to 600 nm. Since radiation having a shorter wavelength cannot be handled by a normal optical system, it cannot be suitably used for the photo-alignment method. On the other hand, radiation having a wavelength longer than this has low energy, and it is difficult to induce an excited state of the (C) photosensitizing structure. Examples of such photosensitizing structure include acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, fluorene structure, naphthalene structure, anthracene structure, acridine structure and the like. These structures are structures composed of groups obtained by removing 1 to 4 hydrogen atoms from acetophenone, benzophenone, anthraquinone, biphenyl, carbazole, nitrobenzene or dinitrobenzene, naphthalene, fluorene, anthracene or acridine, respectively. . Here, the acetophenone structure and the carbazole structure are each preferably a structure composed of groups obtained by removing 1 to 4 hydrogen atoms of the benzene ring of acetophenone or carbazole.
(C) Among these, as the photosensitizing structure, acetophenone structure, benzophenone structure, anthraquinone structure, biphenyl structure, carbazole structure, nitroaryl structure, or naphthalene structure are preferable, and acetophenone structure, anthraquinone structure, carbazole structure, or nitroaryl The structure is particularly preferred.

Each of the above (A) photosensitive structure, specific group (B) and (C) photosensitized structure may be contained in the main chain of the polymer or in the side chain. When two or more of the above (A) photosensitive structure, specific group (B) and (C) photosensitizing structure are contained in the side chain of the polymer, these structures or groups are in the same side chain. Or may be contained in separate side chains. Further, in the polymer, two or more of the (A) photosensitive structure, the specific group (B) and the (C) photosensitizing structure may share a part of the structure.
The content ratio of the photosensitive structure (A) in the polymer is preferably 1 × 10 ⁻⁵ to 1 × 10 ⁻² mol / g, and 5 × 10 ^{−4 to} 5 × 10 ⁻³ mol / g. More preferably. The content ratio of the specific group (B) in the polymer is preferably 2 × 10 ⁻⁵ to 2 × 10 ⁻² mol / g, and preferably 1 × 10 ⁻⁴ to 1 × 10 ⁻³ mol / g. Is more preferable. The content ratio of the (C) photosensitizing structure in the polymer is preferably 1 × 10 ⁻⁶ to 1 × 10 ⁻³ mol / g, and 5 × 10 ^{−6 to} 5 × 10 ⁻⁴ mol / g. More preferably.
The polymer skeleton used in the present invention is not particularly limited. For example, polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polyorganosiloxane, cellulose or a derivative thereof, polyacetal, polystyrene or a derivative thereof, poly (styrene- Phenyl maleimide) or a derivative thereof, poly (meth) acrylate, and the like. Among these, at least one selected from the group consisting of polyamic acid, polyimide, polyamic acid ester, polyorganosiloxane, polystyrene derivative, and poly (styrene-phenylmaleimide) derivative from the viewpoint of excellent polymer stability. Is preferable, at least one selected from the group consisting of polyamic acid, polyimide and polyorganosiloxane is more preferable, and at least one selected from the group consisting of polyamic acid and polyimide is particularly preferable.
Hereinafter, polyamic acid and polyimide that are particularly preferable as the polymer contained in the liquid crystal aligning agent of the present invention will be described.

Polyamic acid in the polyamic acid and the polyimide present invention can be obtained by reacting a tetracarboxylic dianhydride with a diamine, a polyimide can be obtained by imidization cyclodehydration the polyamic acid .
Here, by using tetracarboxylic dianhydride or diamine having the above-mentioned (A) photosensitive structure, specific group (B) and (C) photosensitized structure as a raw material, The polyamic acid and polyimide which have can be obtained. (A) Each of the photosensitive structure, the specific group (B) and the (C) photosensitized structure may be contained only in the raw material tetracarboxylic dianhydride, or may be contained only in the diamine. Or, both tetracarboxylic dianhydride and diamine may have, but since diamines having these structures or groups are easier to synthesize and are easier to obtain, only diamine has It is preferable.
The tetracarboxylic dianhydrides and diamines having these structures or groups can each have all of these structures and groups in one molecule, or the above (A) photosensitive structure, specific group It may be a mixture of (B) and (C) one or two of photosensitized structures. The tetracarboxylic dianhydride and diamine having one or more of (A) photosensitive structure, specific group (B) and (C) photosensitized structure are respectively (A) photosensitive structure, specific group ( B) and (C) a tetracarboxylic dianhydride (hereinafter referred to as “other tetracarboxylic dianhydride”) or a diamine (hereinafter referred to as “other diamine”) that does not include any of the photosensitizing structures. ).

[Tetracarboxylic dianhydride]
Examples of (A) tetracarboxylic dianhydride having a photosensitive structure include 3,3 ′, 4,4′-chalconetetracarboxylic dianhydride, 4,4 ′, 5,5′-chalconetetra. Carboxylic dianhydride, 3,3 ′, 4,5′-chalcone tetracarboxylic dianhydride, 4,4′-dihydroxychalcone bistrimellitate, 3,4′-dihydroxychalcone bistrimellitate, 3 ′, 5 '-Dihydroxychalcone bistrimellitate, 2,4-dihydroxychalcone bistrimellitate, 2,2'-bis (4-chalconyloxy) -3,3', 4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3′-bis (4-chalconyloxy) -4,4 ′, 5,5′-diphenyl ether tetracarboxylic dianhydride, 2,2′-bis (4-chalconyloxy) -4,4 ′ , , 5′-diphenyl ether tetracarboxylic dianhydride, 4,4′-bis (4-chalconyloxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 6,6′-bis (4-Calconyloxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 5,5′-bis (4-calconyl) -2,2 ′, 3,3′-diphenyl ether tetra Carboxylic dianhydride, 2,2′-bis (6 (4-chalconyloxy) hexyloxy) -3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 2,2′-bis ( 6 (4′-fluoro-4-calconyloxy) hexyloxy) -3,3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3′-bis (6 (4-calconyloxy) Hexyloxy) -4,4 ' 5,5′-diphenyl ether tetracarboxylic dianhydride, 3,3′-bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-diphenyl ether tetracarboxylic Acid dianhydride, 2,2′-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-diphenyl ether tetracarboxylic dianhydride, 2,2′-bis (6 (4′-Fluoro-4-calconyloxy) hexyloxy) -4,4 ′, 5,5′-diphenyl ether tetracarboxylic dianhydride, 4,4′-bis (6 (4-calconyloxy) hexyl Oxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 4,4′-bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -2,2 ′, 3,3'-diphenyl ester Tertetracarboxylic dianhydride, 6,6′-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 6,6′- Bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 5,5′-bis (6 (4-chalconyl) Oxy) hexyloxy) -2,2 ′, 3,3′-diphenyl ether tetracarboxylic dianhydride, 5,5′-bis (6 (4′-fluoro-4-calconyloxy) hexyloxy) -2, 2 ', 3,3'-diphenyl ether tetracarboxylic dianhydride, 3 (6 (4-calconyloxy) hexyloxy) -pyromellitic dianhydride, 3 (6 (4'-fluoro-4-chalconyl) Oxy) hexyl Xy) -pyromellitic dianhydride, 3,6-bis (6 (4-chalconyloxy) hexyloxy) -pyromellitic dianhydride, 3,6-bis (6 (4′-fluoro-4-) (Calconyloxy) hexyloxy) -pyromellitic dianhydride, the following formulas (1) to (22)

The compound represented by each of these can be mentioned. These can be used alone or in combination of two or more.
Examples of the tetracarboxylic dianhydride having the specific group (B) include the following formulas (23) to (26):

The compound represented by each of these can be mentioned. The benzene ring of the compound represented by each of the above formulas (23) to (26) may be substituted with one or two or more alkyl groups having 1 to 4 carbon atoms (preferably a methyl group). . These can be used alone or in combination of two or more.
(C) As tetracarboxylic dianhydride having a photosensitizing structure, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2′-dimethyl-3,3 ′, 4 , 4′-benzophenone tetracarboxylic dianhydride, 2,2 ′, 5,5′-tetramethyl-3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 2,3,6,7 -Anthraquinone tetracarboxylic dianhydride, 2,2 ', 3,3' -Biphenyltetracarboxylic dianhydride, 3,3 ', 4,4' -Biphenyltetracarboxylic dianhydride, 4,4'- Bis (2,6-dioxo-4-oxanyl) biphenyl, 2,3,6,7-carbazoletetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2, 3,6,7-naphthalenetetracarboxylic It can be exemplified dianhydride. These may be used alone or in combination of two or more.

  (A) As tetracarboxylic dianhydride having both the photosensitive structure and the specific group (B), for example, 1,3,3a, 4,5,9b-hexahydro-8- (oryzanyloxy) -5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (2 (Oryza Nyloxy) ethoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b- Hexahydro-8- (6 (oryzanyloxy) hexyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3 , 3a, 4,5,9b-Hexahydro-8- 4 ′ (3-cholestanyloxy) 4-chalconyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1, 3,3a, 4,5,9b-Hexahydro-8- (4 ′ (3-cholesteryloxy) 4-chalconyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1, 2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (4 (3-cholestanyloxy) cinnamoyloxy) -5- (tetrahydro-2,5 -Dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (4 (3-cholesteryloxy) cinnamoyl Oxy) -5- (tetrahydro 2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (4 (3-cholestanyl) Oxy) 4'-chalconyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4 5,9b-Hexahydro-8- (4 (3-cholesteryloxy) 4'-chalconyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan- Examples include 1,3-dione. Of these, 1,3,3a, 4,5,9b-hexahydro-8 (2 (oryzanyloxy) ethoxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho is preferred. [1,2-c] furan-1,3-dione and 1,3,3a, 4,5,9b-hexahydro-8 (6 (oryzanyloxy) hexyloxy) -5- (tetrahydro-2,5- Mention may be made of dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione. Here, the term “oryzanyl group” means the following formulas (b-1) to (b-7) derived from natural γ-oryzanol.

(In formulas (b-1) to (b-7), “*” represents a bond, respectively.)
Means a mixture of groups represented by each of
Examples of tetracarboxylic dianhydrides having both (A) a photosensitive structure and (C) a photosensitizing structure include 2,2′-bis (4-chalconyloxy) -3,3 ′, 4,4. '-Biphenyltetracarboxylic dianhydride, 3,3'-bis (4-chalconyloxy) -4,4', 5,5'-biphenyltetracarboxylic dianhydride, 2,2'-bis (4 -Calconyloxy) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride, 4,4'-bis (4-calconyloxy) -2,2', 3,3'-biphenyltetra Carboxylic dianhydride, 6,6′-bis (4-chalconyloxy) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 5,5′-bis (4-chalconyloxy) ) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 2,2′-bis (6 (4 -Calconyloxy) hexyloxy) -3,3 ', 4,4'-biphenyltetracarboxylic dianhydride, 2,2'-bis (6 (4'-fluoro-4-chalconyloxy) hexyloxy) −3,3 ′, 4,4′-biphenyltetracarboxylic dianhydride, 3,3′-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-biphenyltetra Carboxylic dianhydride, 3,3′-bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, 2, 2′-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, 2,2′-bis (6 (4′-fluoro-4 -Calconyloxy) hexyloxy) -4,4 ', 5,5'-biphe Tetratetracarboxylic dianhydride, 4,4′-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 4,4′- Bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 6,6′-bis (6 (4-chalconyl) Oxy) hexyloxy) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 6,6′-bis (6 (4′-fluoro-4-calconyloxy) hexyloxy) -2, 2 ′, 3,3′-biphenyltetracarboxylic dianhydride,

5,5′-bis (6 (4-calconyloxy) hexyloxy) -2,2 ′, 3,3′-biphenyltetracarboxylic dianhydride, 5,5′-bis (6 (4′-fluoro -4-Calconyloxy) hexyloxy) -2,2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,2'-bis (6 (4-calconyloxy) hexyloxy) -3, 3 ′, 4,4′-benzophenonetetracarboxylic dianhydride, 2,2′-bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -3,3 ′, 4,4′- Benzophenone tetracarboxylic dianhydride, 3,3′-bis (6 (4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-benzophenone tetracarboxylic dianhydride, 3,3′- Bis (6 (4′-fluoro-4-carbon Conyloxy) hexyloxy) -4,4 ′, 5,5′-benzophenonetetracarboxylic dianhydride, 2,2′-bis (6 (4-calconyloxy) hexyloxy) -4,4 ′, 5 5′-benzophenone tetracarboxylic dianhydride, 2,2′-bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -4,4 ′, 5,5′-benzophenone tetracarboxylic acid Anhydride, 4,4′-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 4,4′-bis (6 (4 '-Fluoro-4-calconyloxy) hexyloxy) -2,2', 3,3'-benzophenonetetracarboxylic dianhydride, 6,6'-bis (6 (4-calconyloxy) hexyloxy) − , 2 ′, 3,3′-benzophenonetetracarboxylic dianhydride, 6,6′-bis (6 (4′-fluoro-4-calconyloxy) hexyloxy) -2,2 ′, 3,3 ′ -Benzophenone tetracarboxylic dianhydride, 5,5'-bis (6 (4-chalconyloxy) hexyloxy) -2,2 ', 3,3' benzophenone tetracarboxylic dianhydride, 5,5'- Bis (6 (4′-fluoro-4-chalconyloxy) hexyloxy) -2,2 ′, 3,3′benzophenonetetracarboxylic dianhydride and the like can be mentioned.

Examples of other tetracarboxylic dianhydrides include butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2-dimethyl-1,2,3,4- Cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dichloro-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-tetramethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 1,2, 4,5-cyclohexanetetracarboxylic dianhydride, 3,3 ′, 4,4′-dicyclohexyltetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 2,3 4,5-tetrahydrofurantetracarboxylic dianhydride, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-methyl-5 (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] -Furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-7-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2- c] -furan-1,3-dione, 1,3,3a , 4,5,9b-Hexahydro-7-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 3a, 4,5,9b-Hexahydro-8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1,3 , 3a, 4,5,9b-Hexahydro-8-ethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione, 1, 3,3a, 4,5,9b-Hexahydro-5,8-dimethyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan-1,3-dione , Bicyclo [2.2.2] -oct-7-ene-2,3,5,6 Tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 '-(tetrahydrofuran-2', 5'-dione), 5- (2, 5-Dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6 Dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, the following formulas (TI) and (T-II)

(In the above formula, R ¹ and R ³ are each a divalent organic group having an aromatic ring, R ² and R ⁴ are each a hydrogen atom or an alkyl group, and a plurality of R ² and R ² are present. ⁴ may be the same or different.
An aliphatic or alicyclic tetracarboxylic dianhydride such as a compound represented by each of the following:
Pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3 ′, 4,4′-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride 4,4′-bis (3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4′-bis (3,4-dicarboxyphenoxy) diphenylsulfone dianhydride, 4,4′-bis ( 3,4-dicarboxyphenoxy) diphenylpropane dianhydride, 3,3 ′, 4,4′-perfluoroisopropylidenediphthalic dianhydride, bis (phthalic acid) phenylphosphine oxide dianhydride P-phenylene-bis (triphenylphthalic acid) dianhydride, m-phenylene-bis (triphenylphthalic acid) dianhydride, bis (triphenylphthalic acid) -4,4′-diphenyl ether dianhydride, Bis (triphenylphthalic acid) -4,4′-diphenylmethane dianhydride, ethylene glycol-bis (anhydrotrimellitate), propylene glycol-bis (anhydrotrimellitate), 1,4-butanediol-bis (Anhydro trimellitate), 1,6-hexanediol-bis (anhydro trimellitate), 1,8-octanediol-bis (anhydro trimellitate), and 2,2-bis (4- List aromatic tetracarboxylic dianhydrides such as hydroxyphenyl) propane-bis (anhydrotrimellitate) It can be. These may be used alone or in combination of two or more.

Among these other tetracarboxylic dianhydrides, butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4 -Cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro- 5,8-dimethyl 5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, bicyclo [2.2.2] -oct-7-ene-2,3 , 5,6-tetracarboxylic dianhydride, 3-oxabicyclo [3.2.1] octane-2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, 3,5,6-tricarboxy-2-carboxymethylnorbornane-2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^2,6 ] undecane-3,5,8,10-tetraone, pyromellitic dianhydride, 3 , 3 ', 4,4'-biphenylsulfonetetracarboxylic Dianhydride, Unochi formula of the compound represented by the above formula (T-I) (T-1) and (T-2)

And the following formula (T-3) among the compounds represented by formula (T-II)

At least one selected from the group consisting of compounds represented by the following (hereinafter referred to as “specific tetracarboxylic dianhydride”) is preferred. Particularly preferred specific tetracarboxylic dianhydrides are 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 1,3,3a, 4,5. , 9b-Hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro -8-methyl-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 3-oxabicyclo [3.2.1] octane- 2,4-dione-6-spiro-3 ′-(tetrahydrofuran-2 ′, 5′-dione), 5- (2,5-dioxotetrahydro-3-furanyl) -3-methyl-3-cyclohexene-1 No 2-dicarboxylic acid Things, 3,5,6-tricarboxy-2-carboxymethyl norbornane -2: 3,5: 6-dianhydride, 4,9-dioxatricyclo [5.3.1.0 ^{2, 6]} undecane -3,5,8,10-tetraone, pyromellitic dianhydride and at least one selected from the group consisting of compounds represented by the above formula (T-1).

[Diamine]
(A) Examples of the diamine having a photosensitive structure include 3,3′-diaminochalcone, 4,4′-diaminochalcone, 3,4′-diaminochalcone, 2,3-diaminochalcone, and 2,4-diaminochalcone. 3,4-diaminochalcone, 4 (2,4-diaminophenoxy) chalcone, 4 ′ (2,4-diaminophenoxy) chalcone, the following formulas (DI) and (D-II)

(In the above formula, Ar has the same meaning as in the above formula (a), A ¹ and A ² are each a divalent aromatic group, and h and i are 1 to 3 respectively. Is an integer.)
, 6 (4-Calconyloxy) hexyloxy (2,4-diaminobenzene), 6 (4′-fluoro-4-calconyloxy) hexyloxy (2,4-diaminobenzene) 8 (4-Calconyloxy) octyloxy (2,4-diaminobenzene), 8 (4′-fluoro-4-calconyloxy) octyloxy (2,4-diaminobenzene), 10 (4-calconyl) Oxy) decyloxy (2,4-diaminobenzene), 10 (4′-fluoro-4-calconyloxy) decyloxy (2,4-diaminobenzene), 2 (2 (4-calconyloxy) ethoxy) ethyl (3 , 5-diaminobenzoate), 2 (2 (4′-fluoro-4-chalconyloxy) ethoxy) ethyl (3,5-diaminobenzoate), 2 (2 (4-Calconyloxy) ethoxy) ethoxy (2,4-diaminobenzene), 2 (2 (4′-fluoro-4-calconyloxy) ethoxy) ethoxy (2,4-diaminobenzene), 1 -((4-Calconyloxy) ethoxy) -2-((2,4-diaminophenoxy) ethoxy) ethane, 1-((4'-fluoro-4-calconyloxy) ethoxy) -2-((2 , 4-Diaminophenoxy) ethoxy) ethane, 1-((4-calconyloxy) ethoxy) -2-((3,5-diaminobenzoyloxy) ethoxy) ethane, 1-((4′-fluoro-4-) Calconyloxy) ethoxy) -2-((3,5-diaminobenzoyloxy) ethoxy) ethane, 6 (4-chalconyloxy) hexyloxy (3,5-diaminobenzoyl) 6 (4′-fluoro-4-calconyloxy) hexyloxy (3,5-diaminobenzoyl), 8 (4-calconyloxy) octyloxy (3,5-diaminobenzoyl), 8 (4′-fluoro- 4-Calconyloxy) octyloxy (3,5-diaminobenzoyl), 10 (4-Calconyloxy) decyloxy (3,5-diaminobenzoyl), 10 (4′-fluoro-4-calconyloxy) decyloxy ( 3,5-diaminobenzoyl), 6 (4-calconyloxy) hexanoic acid (2,4-diaminophenyl), 6 (4′-fluoro-4-calconyloxy) hexanoic acid (2,4-diaminophenyl) 8 (4-Calconyloxy) -octanoic acid- (2,4-diaminophenyl), 8 (4′-fluoro-4-calconyloxy) -o Tannic acid- (2,4-diaminophenyl), 10 (4-calconyloxy) -decanoic acid- (2,4-diaminophenyl), 10 (4′-fluoro-4-calconyloxy) -decanoic acid- (2,4-diaminophenyl),

Adipic acid mono (4-chalconyl) mono (2,4-diaminophenyl), adipic acid mono (4′-fluoro-4-chalconyl) mono (2,4-diaminophenyl), suberic acid mono (4-chalconyl) mono (2,4-diaminophenyl), suberic acid mono (4′-fluoro-4-chalconyloxy) mono (2,4-diaminophenyl), sebacic acid mono (4-chalconyl) mono (2,4-diaminophenyl) ), Sebacic acid mono (4′-fluoro-4-chalconyloxy) mono (2,4-diaminophenyl), bis-1,1- (4-aminophenyl) -6- (4-chalconyloxy) hexane Bis-1,1- (4-aminophenyl) -6- (4′-fluoro-4-chalconyloxy) hexane, bis-1,1- (4-aminophenyl) -8- 4-Carconyloxy) octane, bis-1,1- (4-aminophenyl) -8- (4′-fluoro-4-chalconyloxy) octane, bis-1,1- (4-aminophenyl)- 10- (4-Calconyloxy) decane, bis-1,1- (4-aminophenyl) -10- (4′-fluoro-4-calconyloxy) decane, bis-N, N- (4-amino Phenyl) -N- (6 (4-calconyloxy) hexanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (6 (4′-fluoro-4-calconyloxy) Hexanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (8 (4-chalconyloxy) octanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (8 (4'-F Olo-4-carbonyloxy) octanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (10 (4-calconyloxy) decanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (10 (4′-fluoro-4-chalconyloxy) decanoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (2 ( 2 (4-Calconyloxy) ethoxy) ethoxyphenyl) amine, bis-N, N- (4-aminophenyl) -N- (4 (2 (2 (4′-fluoro-4-calconyloxy) ethoxy) Chalcone derivatives such as ethoxy) phenyl) amine;

3,5-diaminobenzyl cinnamate, 3,5-diaminobenzyl 4-methoxycinnamate, 3,5-diaminobenzyl 4-pentylcinnamate, 3,5-diaminobenzyl 4-fluorocinnamate, 3, 5-diaminobenzyl = 4-trifluoromethylcinnamate, 3,5-diaminobenzyl = 3-methoxycinnamate, 3,5-diaminobenzyl = 3-pentylcinnamate, 3,5-diaminobenzyl = 3-fluorocinnamate Mate, 3,5-diaminobenzyl = 3-trifluoromethylcinnamate, 3,5-diaminobenzyl = 3,4-difluorocinnamate, 3,5-diaminobenzyl = 3,4,5-trifluorocinnamate, 2,4-diaminobenzyl cinnamate, 2,4-diaminobenzyl = 4 Methoxycinnamate, 2,4-diaminobenzyl = 4-pentylcinnamate, 2,4-diaminobenzyl = 4-fluorocinnamate, 2,4-diaminobenzyl = 4-trifluoromethylcinnamate, 2,4-diamino Benzyl = 3-methoxycinnamate, 2,4-diaminobenzyl = 3-pentylcinnamate, 2,4-diaminobenzyl = 3-fluorocinnamate, 2,4-diaminobenzyl = 3-trifluoromethylcinnamate, 2 , 4-Diaminobenzyl = 3,4-difluorocinnamate, 2,4-diaminobenzyl = 3,4,5-trifluorocinnamate, 2,4-diaminophenyl = cinnamate, 2,4-diaminophenyl = 4- Methoxycinnamate, 2,4-diaminophenyl = 4-pentylcinna 2,4-diaminophenyl 4-fluorocinnamate, 2,4-diaminophenyl 4-trifluoromethyl cinnamate, 2,4-diaminophenyl 3-methoxycinnamate, 2,4-diaminophenyl = 3-pentylcinnamate, 2,4-diaminophenyl = 3-fluorocinnamate, 2,4-diaminophenyl = 3-trifluoromethylcinnamate, 2,4-diaminophenyl = 3,4-difluorocinnamate, 2,4-diaminophenyl = 3,4,5-trifluorocinnamate, methyl = 4 ′-(3,5-diaminobenzoyloxy) cinnamate, ethyl = 4 ′-(3,5-diaminobenzoyloxy) cinnamate, Pentyl = 4 ′-(3,5-diaminobenzoyloxy) cinnamate, phenyl = 4′- 3,5-diaminobenzoyloxy) cinnamate, methyl = 4 ′-(3,5-diaminobenzyloxy) cinnamate, ethyl = 4 ′-(3,5-diaminobenzyloxy) cinnamate, pentyl = 4 ′-(3 5-diaminobenzyloxy) cinnamate, phenyl = 4 ′-(3,5-diaminobenzyloxy) cinnamate, methyl = 4 ′-(2,4-diaminobenzyloxy) cinnamate, ethyl = 4 ′-(2,4- Diaminobenzyloxy) cinnamate, pentyl = 4 ′-(2,4-diaminobenzyloxy) cinnamate, phenyl = 4 ′-(2,4-diaminobenzyloxy) cinnamate, methyl = 4 ′-(2,4-diaminophenoxy ) Cinnamate, ethyl = 4 ′-(2,4-diaminophenoxy) cinnamate, pentyl = '- (2,4-aminophenoxy) cinnamate and phenyl = 4' - (2,4-di-aminophenoxy) cinnamic acid derivatives such as cinnamates;
The following formulas (1a), (1b), (1c) and (1d)

And phenylene diacrylate derivatives such as compounds represented by each of the above.
Among these, (A) the diamine having a photosensitive structure is preferably at least one selected from the group consisting of cinnamic acid derivatives and phenylene diacrylate derivatives, and 3,5-diaminobenzyl = cinnamate, 3,5 -Diaminobenzyl 4-methoxycinnamate, 3,5-diaminobenzyl 4-trifluoromethyl cinnamate, 2,4-diaminobenzyl cinnamate, 2,4-diaminobenzyl 4-methoxycinnamate, 2,4 -Diaminobenzyl = 4-trifluoromethylcinnamate, methyl = 4 '-(2,4-diaminobenzyloxy) cinnamate, ethyl = 4'-(2,4-diaminobenzyloxy) cinnamate and pentyl = 4 '-( Selected from the group consisting of (2,4-diaminobenzyloxy) cinnamate It is particularly preferred to use at least one member. These may be used alone or in combination of two or more.
Examples of the diamine having the specific group (B) include the following formula (D-III)

(In the formula (D-III), R ⁵ is a divalent linking group selected from —O—, —COO—, —OCO—, —NHCO—, —CONH— and —CO—, and R ⁶ is a steroid. It is a monovalent organic group having at least one skeleton or group selected from a skeleton and a fluoroalkyl group having 1 to 3 carbon atoms or an alkyl group having 4 to 20 carbon atoms.)
A mono-substituted phenylenediamine represented by:
The following formulas (D-1) to (D-3)

2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis [ 4- (4-Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, tetrahydrodicyclopentadienylenediamine and the like can be mentioned. These can be used alone or in combination of two or more. The benzene rings of the mono-substituted phenylenediamine and the compounds represented by the formulas (D-1) to (D-3) are each one or two or more alkyl groups having 1 to 4 carbon atoms ( It may be preferably substituted with a methyl group). The meaning of the “steroid skeleton” in the above is the same as the steroid skeleton in the tetracarboxylic dianhydride described above.
Among diamines having the specific group (B), among the compounds represented by the above formulas (D-1) to (D-3), among the compounds represented by the above formula (D-III) Of dodecanoxy-2,4-diaminobenzene, pentadecanoxy-2,4-diaminobenzene, hexadecanoxy-2,4-diaminobenzene, octadecanoxy-2,4-diaminobenzene, dodecanoxy-2,5-diaminobenzene, pentadecanoxy-2, 5-diaminobenzene, hexadecanoxy-2,5-diaminobenzene, octadecanoxy-2,5-diaminobenzene and the following formulas (D-4) to (D-10)

At least one selected from the group consisting of compounds represented by each of the above is preferred.
(C) Examples of the diamine having a photosensitizing structure include 3,3′-diaminobenzophenone, 4,4′-diaminobenzophenone, 3,4′-diaminobenzophenone, 3,4-diaminobenzophenone, 4,4′- Bis (4-aminophenoxy) benzophenone, 1,2-diaminoanthraquinone, 1,4-diaminoanthraquinone, 1,5-diaminoanthraquinone, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'- Dimethyl-4,4′-diaminobiphenyl, 4,4′-bis (4-aminophenoxy) biphenyl, 2,7-diaminofluorene, 9,9-dimethyl-2,7-diaminofluorene, 9,9-bis ( 4-aminophenyl) fluorene, 2,2 ', 5,5'-tetrachloro-4,4'-diaminobiphenyl, 2,2'-dichloro -4,4'-diamino-5,5'-dimethoxybiphenyl, 3,3'-dimethoxy-4,4'-diaminobiphenyl, 4,4'-diamino-3,3'-bis (trifluoromethyl) biphenyl 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4-amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, N, N ′ -Bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl) -N, N'-dimethyl-benzidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, 3,6-diaminoacridine, 1,5-diaminonaphthalene, and 9, 9-bis (4-aminophenyl) -10-hydroanthracene, the following formula (D-VI)

(In the formula (D-VI), Z is a group having a photosensitizing structure, and X ⁰ is a divalent linking group.)
The compound etc. which are represented by these can be mentioned.
Z in the formula (D-VI) is at least selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, a fluorene structure, a naphthalene structure, an anthracene structure, and an acridine structure. A group having one type of structure is preferred. X ⁰ is preferably an ester bond, an ether bond, an amide bond, a urethane bond, a urea bond, an alkylene group or a phenylene group, or a group obtained by linking two or more groups selected from these groups (however, an ester bond, an ether bond) And two or more groups of the same or different types selected from a bond, an amide bond, a urethane bond and a urea bond are not adjacent to each other). These compounds are used alone or in combination of two or more.
(C) Among the above, 1,4-diaminoanthraquinone, 2,2′-dimethyl-4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) as the diamine having a photosensitizing structure Fluorene, 4,4′-bis (4-aminophenoxy) biphenyl, N, N′-bis (4-aminophenyl) -benzidine, N, N′-bis (4-aminophenyl) -N, N′-dimethyl Benzidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole, N-phenyl-3,6-diaminocarbazole, the above formula (D-VI) Of the compounds represented, 1 (4-acetylphenoxy) -2,4-diaminobenzene, 1 (4-benzoylphenoxy) -2,4-diaminobenzene, 1 (2 ( 4-Dimethylaminobenzoyl) -4-methylphenoxy) -2,4-diaminobenzene, 1 (4-biphenylyloxy) -2,4-diaminobenzene, 1 (2-carbazolyloxy) -2,4- Diaminobenzene,

1 (4-nitrophenoxy) -2,4-diaminobenzene, 1 (2,4-dinitrophenoxy) -2,4-diaminobenzene, 1 (2-naphthyloxy) -2,4-diaminobenzene, 1 (2 (4-acetylphenoxy) ethoxy) -2,4-diaminobenzene, 1 (2 (4-benzoylphenoxy) ethoxy) -2,4-diaminobenzene, 1 (2 (2 (4-dimethylaminobenzoyl) -4- Methylphenoxy) ethoxy) -2,4-diaminobenzene, 1 (2 (4-biphenylyloxy) ethoxy) -2,4-diaminobenzene, 1 (2 (2-carbazolyloxy) ethoxy) -2,4 -Diaminobenzene, 1 (2 (4-nitrophenoxy) ethoxy) -2,4-diaminobenzene, 1 (2 (2,4-dinitrophenoxy) ethoxy) 2,4-diaminobenzene, 1 (2 (2-naphthyloxy) ethoxy) -2,4-diaminobenzene, 1 (6 (4-acetylphenoxy) hexyloxy) -2,4-diaminobenzene, 1 (6 ( 4-Benzoylphenoxy) hexyloxy) -2,4-diaminobenzene, 1 (6 (2 (4-dimethylaminobenzoyl) -4-methylphenoxy) hexyloxy) -2,4-diaminobenzene, 1 (6 (4 -Biphenylyloxy) hexyloxy) -2,4-diaminobenzene, 1 (6 (2-carbazolyloxy) hexyloxy) -2,4-diaminobenzene, 1 (6 (4-nitrophenoxy) hexyloxy) -2,4-diaminobenzene, 1 (6 (2,4-dinitrophenoxy) hexyloxy) -2,4-diaminobenzene, 1 6 (2-naphthyloxy) hexyloxy) -2,4-diaminobenzene, 3,5-diaminobenzoic acid (4-acetylphenyl), 3,5-diaminobenzoic acid (4-benzoylphenyl), 3,5- Diaminobenzoic acid (2 (4-dimethylaminobenzoyl) -4-methylphenyl), 3,5-diaminobenzoic acid (4-biphenyl),

3,5-diaminobenzoic acid (2-carbazolyl), 3,5-diaminobenzoic acid (4-nitrophenyl), 3,5-diaminobenzoic acid (2,4-dinitrophenyl), 3,5-diaminobenzoic acid (2-naphthyl), 3,5-diaminobenzoic acid (2 (4-acetylphenoxy) ethyl), 3,5-diaminobenzoic acid (2 (4-benzoylphenoxy) ethyl), 3,5-diaminobenzoic acid ( 2 (2 (4-dimethylaminobenzoyl) -4-methylphenoxy) ethyl), 3,5-diaminobenzoic acid (2 (4-biphenylyloxy) ethyl), 3,5-diaminobenzoic acid (2 (2- Carbazolyloxy) ethyl), 3,5-diaminobenzoic acid (2 (2-naphthyloxy) ethyl), 3,5-diaminobenzoic acid (6 (4-acetylphenoxy) hexyl ), 3,5-diaminobenzoic acid (6 (4-benzoylphenoxy) hexyl), 3,5-diaminobenzoic acid (6 (2 (4-dimethylaminobenzoyl) -4-methylphenoxy) hexyl), 3,5 -Diaminobenzoic acid (6 (4-biphenylyl) hexyl), 3,5-diaminobenzoic acid (6 (2-carbazolyloxy) hexyl) and 3,5-diaminobenzoic acid (6 (2-naphthyl) hexyl) At least one selected from the group consisting of 1,4-diaminoanthraquinone, 2,2′-dimethyl-4,4′-diaminobiphenyl, 9,9-bis (4-aminophenyl) fluorene, 4, 4'-bis (4-aminophenoxy) biphenyl, N, N'-bis (4-aminophenyl) -benzidine, N, N'-bis (4-aminophenyl)- The group consisting of N, N′-dimethylbenzidine, 3,6-diaminocarbazole, N-methyl-3,6-diaminocarbazole, N-ethyl-3,6-diaminocarbazole and N-phenyl-3,6-diaminocarbazole It is particularly preferred to use at least one selected from
(A) As diamine which has both a photosensitive structure and specific group (B), for example, following formula (D-IV) and (DV)

(In the above formula, Ar has the same meaning as in the above formula (a), A ³ and A ⁴ are each a divalent aromatic group, and j and k are 4 to 10 respectively. Integer.)
Compounds represented by each of the following formulas (VI-1) to (VI-7)

(In the above formula, R ₂ is a single bond, a divalent linking group or an organic group.)
Oryzalyl (3,5-diaminobenzoate), oryzanyl (3,5-diaminobenzoate), 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate), oryzanyl (2- ( 2,4-diaminophenoxy) acetate), 6- (oryzanyloxy) hexyl (3,5-diaminobenzoate), 1,3-diamino-4- (oryzanyloxy) benzene, 1,3-diamino-4- (2 (oryzanyloxy) ethoxy) benzene, 1,3-diamino-4- (6 (oryzanyloxy) hexyloxy) benzene, 3-cholesteryl-4- (3,5-diaminobenzoyloxy) cinnamate, 3- Cholestanyl-4- (3,5-diaminobenzoyloxy) cinnamate, 3-cholesteryl-4- (2 3,5-diaminobenzoyloxy) ethoxy) cinnamate, 3-cholestanyl-4- (2 (3,5-diaminobenzoyloxy) ethoxy) cinnamate, 3-cholesteryl-4- (6 (3,5-diaminobenzoyloxy) Hexyloxy) cinnamate, 3-cholestanyl-4- (6 (3,5-diaminobenzoyloxy) hexyloxy) cinnamate, 3-cholesteryl-4- (2,4-diaminophenoxy) cinnamate, 3-cholestanyl-4- ( 2,4-diaminophenoxy) cinnamate, 3-cholesteryl-4- (2 (2,4-diaminophenoxy) ethoxy) cinnamate, 3-cholestanyl-4- (2 (2,4-diaminophenoxy) ethoxy) cinnamate, 3, -Cholesteryl-4- (6 (2,4-diamino Enoxy) hexyloxy) cinnamate, 3-cholestanyl-4- (6 (2,4-diaminophenoxy) hexyloxy) cinnamate, 4 ′-(3-cholesteryloxy) -4- (3,5-diaminobenzoyloxy) chalcone 4 '-(3-cholestanyloxy) -4- (3,5-diaminobenzoyloxy) chalcone, 4'-(3-cholesteryloxy) -4- (2 (3,5-diaminobenzoyloxy) ethoxy) Chalcone,

4 ′-(3-cholestanyloxy) -4- (2 (3,5-diaminobenzoyloxy) ethoxy) chalcone, 4 ′-(3-cholesteryloxy) -4 (6 (3,5-diaminobenzoyloxy) Hexyloxy) chalcone, 4 ′-(3-cholestanyloxy) -4- (6 (3,5-diaminobenzoyloxy) hexyloxy) chalcone, 4 ′-(3-cholesteryloxy) -4- (2,4 -Diaminophenoxy) chalcone, 4 '-(3-cholestanyloxy) -4- (2,4-diaminophenoxy) chalcone, 4'-(3-cholesteryloxy) -4- (2 (2,4-diaminophenoxy) ) Ethoxy) chalcone, 4 '-(3-cholestanyloxy) -4- (2 (2,4-diaminophenoxy) ethoxy) chalcone, 4'-(3-cholesteryl) (Oxy) -4- (6 (2,4-diaminophenoxy) hexyloxy) chalcone, 4 ′-(3-cholestanyloxy) -4- (6 (2,4-diaminophenoxy) hexyloxy) chalcone, (2 (3,5-diaminobenzoyloxy) ethyl) -4- (3-cholesteryloxy) cinnamate, (2 (3,5-diaminobenzoyloxy) ethyl) -4- (3-cholestanyloxy) cinnamate, (6 ( 3,5-diaminobenzoyloxy) hexyl) -4- (3-cholesteryloxy) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4- (3-cholestanyloxy) cinnamate, (2,4 -Diaminophenyl) -4- (3-cholesteryloxy) cinnamate, (2,4-diaminophenyl) -4- (3 Cholestanyloxy) cinnamate, (2 (2,4-diaminophenoxy) ethyl) -4- (3-cholesteryloxy) cinnamate, (2 (2,4-diaminophenoxy) ethyl) -4- (3-cholestanyloxy) ) Cinnamate, (6 (2,4-diaminophenoxy) hexyl) -4- (3-cholesteryloxy) cinnamate, (6 (2,4-diaminophenoxy) hexyl) -4- (3-cholestanyloxy) cinnamate, 4- (3-cholesteryloxy) -4 ′-(3,5-diaminobenzoyloxy) chalcone, 4- (3-cholestanyloxy) -4 ′-(3,5-diaminobenzoyloxy) chalcone, 4- ( 3-cholesteryloxy) -4 ′-(2 (3,5-diaminobenzoyloxy) ethoxy) chalcone, 4- (3- Cholestanyloxy) -4 '-(2 (3,5-diaminobenzoyloxy) ethoxy) chalcone, 4- (3-cholesteryloxy) -4'-(6 (3,5-diaminobenzoyloxy) hexyloxy) chalcone 4- (3-cholestanyloxy) -4 ′-(6 (3,5-diaminobenzoyloxy) hexyloxy) chalcone, 4- (3-cholesteryloxy) -4 ′-(2,4-diaminophenoxy) Chalcone, 4- (3-cholestanyloxy) -4 ′-(2,4-diaminophenoxy) chalcone, 4- (3-cholesteryloxy) -4 ′-(2 (2,4-diaminophenoxy) ethoxy) chalcone 4- (3-cholestanyloxy) -4 ′-(2 (2,4-diaminophenoxy) ethoxy) chalcone, 4- (3-cholesteryloxy) 4 ′-(6 (2,4-diaminophenoxy) hexyloxy) chalcone and 4- (3-cholestanyloxy) -4 ′-(6 (2,4-diaminophenoxy) hexyloxy) chalcone, (2a) to (20a), (2b) to (20b), (2c) to (20c) and (2d) to (20d)

And the like, and the like.
The meaning of the “oryzanyl group” in the above is the same as the oryzanyl group in the tetracarboxylic dianhydride described above.
Such a diamine can be synthesized by, for example, a method described in Patent Document 22 (Japanese Patent Laid-Open No. 2007-191447).
Examples of other diamines include p-phenylenediamine, m-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenylethane, 4,4′-diaminodiphenyl sulfide, and 4,4′-diamino. Diphenylsulfone, 4,4′-diaminobenzanilide, 4,4′-diaminodiphenyl ether, 5-amino-1- (4′-aminophenyl) -1,3,3-trimethylindane, 6-amino-1- ( 4′-aminophenyl) -1,3,3-trimethylindane, 3,4′-diaminodiphenyl ether, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, bis [4- (4-amino Phenoxy) phenyl] sulfone, 1,4-bis (4-aminophenoxy) benzene, 1,3-bis (4-amino) Enoxy) benzene, 1,3-bis (3-aminophenoxy) benzene, bis (4-amino-2-chlorophenyl) methane, 4,4 ′-(p-phenylenediisopropylidene) bisaniline, 4,4 ′-( aromatic diamines such as m-phenylenediisopropylidene) bisaniline;

Metaxylylenediamine, 1,3-propanediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, heptamethylenediamine, octamethylenediamine, nonamethylenediamine, 1,4-diaminocyclohexane, isophoronediamine, hexahydro-4, 7-methanoin danylene dimethylene diamine, tricyclo [6.2.1.0 ^2,7 ] -undecylene dimethylene diamine, 4,4′-methylene bis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, Aliphatic or cycloaliphatic diamines such as 1,4-bis (aminomethyl) cyclohexane;
2,3-diaminopyridine, 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, 5,6-diamino-2,3-dicyanopyrazine, 5,6-diamino-2,4 -Dihydroxypyrimidine, 2,4-diamino-6-dimethylamino-1,3,5-triazine, 1,4-bis (3-aminopropyl) piperazine, 2,4-diamino-6-isopropoxy-1,3 , 5-triazine, 2,4-diamino-6-methoxy-1,3,5-triazine, 2,4-diamino-6-phenyl-1,3,5-triazine, 2,4-diamino-6-methyl -S-triazine, 2,4-diamino-1,3,5-triazine, 4,6-diamino-2-vinyl-s-triazine, 2,4-diamino-5-phenylthiazole, 2,6- Aminopurine, 5,6-diamino-1,3-dimethyluracil, 3,5-diamino-1,2,4-triazole, 3,8-diamino-6-phenylphenanthridine, 1,4-diaminopiperazine, N, N′-bis (4-aminophenyl) phenylamine, the following formula (D-VII)

(In Formula (D-VII), R ⁷ is a monovalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ¹ is a divalent organic group. .)
A compound represented by the following formula (D-VIII)

(In formula (D-VIII), R ⁸ is a divalent organic group having a ring structure containing a nitrogen atom selected from pyridine, pyrimidine, triazine, piperidine and piperazine, and X ² is a divalent organic group, respectively. A plurality of X ² may be the same or different.)
A diamine having two primary amino groups and a nitrogen atom other than the primary amino group in the molecule, such as a compound represented by:
The following formula (D-IX)

(In Formula (D-IX), R ⁹ is a hydrocarbon group having 1 to 3 carbon atoms, and a plurality of R ⁹ may be the same or different, and p is 1 to 3 respectively. And q is an integer of 1 to 20.)
Diaminoorganosiloxanes such as compounds represented by:
The following formulas (D-11) and (D-12)

(Y in Formula (D-11) is an integer of 2 to 12, and z in Formula (D-12) is an integer of 1 to 5.)
And the like, and the like.
Other diamines include p-phenylenediamine, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl sulfide, 4,4′-diaminodiphenyl ether, 2,2-bis [4- (4 -Aminophenoxy) phenyl] propane, 4,4 '-(p-phenylenediisopropylidene) bisaniline, 4,4'-(m-phenylenediisopropylidene) bisaniline, 1,4-bis (4-aminophenoxy) benzene , 1,4-diaminocyclohexane, 4,4′-methylenebis (cyclohexylamine), 1,3-bis (aminomethyl) cyclohexane, compounds represented by the above formulas (D-11) and (D-12) 2,6-diaminopyridine, 3,4-diaminopyridine, 2,4-diaminopyrimidine, above The following formula among the compounds represented by the formula (D-VII) (D-13)

Of the compounds represented by formula (D-VIII), the following formula (D-14)

And at least one selected from the group consisting of 1,3-bis (3-aminopropyl) -tetramethyldisiloxane among the compounds represented by the formula (D-IX) (hereinafter, It is preferable to use “specific diamine”.
[Use ratio of each tetracarboxylic dianhydride and each diamine]
The types and proportions of tetracarboxylic dianhydride and diamine used for synthesizing the polyamic acid or polyimide preferably contained in the liquid crystal aligning agent of the present invention are as follows: (A) photosensitive structure, specific group (B) And (C) The content ratio of the photosensitizing structure should be appropriately selected so as to be within the preferable range described above.
For this reason, the total use ratio of (A) tetracarboxylic dianhydride having a photosensitive structure and diamine is 10 to 90 mol% with respect to the total of all tetracarboxylic dianhydrides and all diamines. Preferably, it is 20-50 mol%. The total use ratio of the tetracarboxylic dianhydride having the specific group (B) and the diamine is preferably 1 to 90 mol% with respect to the total of all the tetracarboxylic dianhydrides and all the diamines. More preferably, it is 50 mol%. Moreover, (C) The total use rate of the tetracarboxylic dianhydride and diamine which has a photosensitizing structure is 0.1-30 mol% with respect to the sum total of all the tetracarboxylic dianhydrides and all the diamines. It is preferably 0.5 to 10 mol%. Here, when (A) a tetracarboxylic dianhydride or diamine having both a photosensitive structure and a specific group (B) is used, the total use ratio is that of all tetracarboxylic dianhydrides and all diamines. The content is preferably 10 to 90 mol%, more preferably 20 to 50 mol%, based on the total.

As described above, in the present invention, tetracarboxylic dianhydride and diamine are selected so that (A) the photosensitive structure, the specific group (B), and (C) the photosensitizing structure are all derived from diamine. Therefore, the tetracarboxylic dianhydride and the diamine used for synthesizing the polyamic acid or polyimide preferably contained in the liquid crystal aligning agent of the present invention are preferably used as the types and the proportions of use. It is as follows.
It is preferable to use only other tetracarboxylic dianhydrides as tetracarboxylic dianhydrides. In this case, the tetracarboxylic dianhydride includes the specific tetracarboxylic dianhydride, and the use ratio of the specific tetracarboxylic dianhydride is preferably based on the total tetracarboxylic dianhydride. It is 50 mol% or more, More preferably, it is 80 mol% or more.
Examples of the diamine include (A) a diamine having a photosensitive structure, a diamine having a specific group (B) and (C) a diamine having a photosensitizing structure and, if necessary, the above-mentioned specific diamine, or
(A) A diamine having both a photosensitive structure and a specific group (B) and (C) a diamine having a photosensitizing structure and, if necessary, the above-mentioned specific diamine are preferably included.
As the ratio of use with respect to the total diamine,
(A) The diamine having a photosensitive structure is preferably 20 to 90 mol%, more preferably 40 to 70 mol%, and the diamine having a specific group (B) is preferably 2 to 50 mol%, more preferably 20 It is preferably about 50 to 50 mol%, and (C) about 0.2 to 60 mol%, more preferably about 1 to 20 mol% for the diamine having a photosensitizing structure, and preferably about the specific diamine used as necessary. Is 80 mol% or less, more preferably 50 mol% or less,
On the other hand,
(A) The diamine having both the photosensitive structure and the specific group (B) is preferably 20 to 99 mol%, more preferably 40 to 95 mol%, and (C) the diamine having a photosensitized structure is preferable. It is 0.2-60 mol%, More preferably, it is 1-20 mol%, Preferably it is 80 mol% or less about the specific diamine used as needed, More preferably, it is 50 mol% or less.

[Synthesis of polyamic acid]
The polyamic acid preferably contained in the liquid crystal aligning agent of the present invention can be obtained by reacting the tetracarboxylic dianhydride as described above with a diamine. The ratio of the tetracarboxylic dianhydride and the diamine used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.5 to 1 equivalent to 1 equivalent of the amino group of the diamine. A ratio of 2 equivalents is preferable, and a ratio of 0.7 to 1.2 equivalents is more preferable.
The polyamic acid synthesis reaction is preferably performed in an organic solvent, preferably at a temperature of −20 ° C. to 150 ° C., more preferably 0 to 100 ° C., and preferably 0.1 to 24 hours, more preferably 0.00. It takes 5 to 12 hours. Here, the organic solvent is not particularly limited as long as it can dissolve the polyamic acid to be produced. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide, Examples include aprotic polar solvents such as γ-butyrolactone, tetramethylurea and hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol and halogenated phenol. The amount of the organic solvent used (a) is such that the total amount (b) of the tetracarboxylic dianhydride and the diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. Preferably there is. In addition, when using an organic solvent together with the below-mentioned poor solvent, the usage-amount (a) of the said organic solvent should be understood as meaning the total usage-amount of an organic solvent and a poor solvent. is there.

For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are generally believed to be poor solvents for polyamic acids, may be used in combination as long as the resulting polyamic acid does not precipitate. it can. Specific examples of such poor solvents include methanol, ethanol, isopropanol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, acetone, and methyl ethyl ketone. , Methyl isobutyl ketone, cyclohexanone, methyl acetate, ethyl acetate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, diethyl oxalate, diethyl malonate, diethyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether Ethylene glycol-n-propyl ether, ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether, Lenglycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1,4 -Dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene, isoamylpropionate, isoamylisobutyrate, diisopentyl ether and the like.
When the organic solvent and the poor solvent as described above are used in combination, the use ratio of the poor solvent can be appropriately set within a range in which the polyamic acid to be produced does not precipitate, but it is 50% by weight or less based on the total amount of the solvent. It is preferably 40% by weight or less, more preferably 30% by weight or less.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, may be used for the preparation of the liquid crystal aligning agent after isolating the polyamic acid contained in the reaction solution, or the isolated polyamic acid was purified. You may use for preparation of a liquid crystal aligning agent. Polyamic acid can be isolated by pouring the reaction solution into a large amount of poor solvent to obtain a precipitate, and drying the precipitate under reduced pressure, or by distilling the reaction solution under reduced pressure using an evaporator. it can. The polyamic acid can be purified by a method of dissolving the polyamic acid again in an organic solvent and then precipitating with a poor solvent, or a method of performing the step of evaporating under reduced pressure with an evaporator once or several times.

[Polyimide]
The polyimide that can be preferably contained in the liquid crystal aligning agent of the present invention can be obtained by dehydrating and ring-closing and imidizing the polyamic acid as described above.
The polyimide in the present invention may be a completely imidized product obtained by dehydrating and cyclizing all of the amic acid structure possessed by the polyamic acid as a raw material, and by dehydrating and cyclizing only a part of the amic acid structure, It may be a partially imidized product in which an imide ring structure coexists.
The polyimide in the liquid crystal aligning agent of the present invention preferably has an imidization ratio of 30% or more, and more preferably 50% or more. The said imidation rate represents the ratio which the number of the imide ring structure accounts with respect to the sum total of the number of the amic acid structures of polyimide, and the number of imide ring structures in percentage. At this time, a part of the imide ring may be an isoimide ring.
The dehydration ring closure of the polyamic acid is preferably performed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, and adding a dehydrating agent and a dehydration ring closure catalyst to this solution as necessary. This is done by heating.
The reaction temperature in the method (i) of heating the polyamic acid is preferably 50 to 200 ° C, more preferably 60 to 170 ° C. When the reaction temperature is less than 50 ° C., the dehydration ring-closing reaction does not proceed sufficiently, and when the reaction temperature exceeds 200 ° C., the molecular weight of the resulting polyimide may decrease. The reaction time is preferably 1.0 to 24 hours, more preferably 1.0 to 12 hours.

On the other hand, in the method (ii) of adding a dehydrating agent and a dehydrating ring-closing catalyst to the polyamic acid solution, an acid anhydride such as acetic anhydride, propionic anhydride, or trifluoroacetic anhydride is used as the dehydrating agent. Can do. Although the usage-amount of a dehydrating agent is based on the desired imidation rate, it is preferable to set it as 0.01-20 mol with respect to 1 mol of the amic acid structure of a polyamic acid. Moreover, as a dehydration ring closure catalyst, tertiary amines, such as a pyridine, a collidine, a lutidine, a triethylamine, can be used, for example. However, it is not limited to these. The amount of the dehydration ring-closing catalyst used is preferably 0.01 to 10 mol with respect to 1 mol of the dehydrating agent used. The imidation rate can be increased as the amount of the above dehydrating agent and dehydrating ring-closing agent increases. Examples of the organic solvent used in the dehydration ring-closing reaction include the organic solvents exemplified as those used for the synthesis of polyamic acid. The reaction temperature of the dehydration ring closure reaction is preferably 0 to 180 ° C, more preferably 10 to 150 ° C. The reaction time is preferably 1.0 to 120 hours, more preferably 2.0 to 30 hours.
The polyimide obtained in the above method (i) may be used for the preparation of the liquid crystal aligning agent as it is, or may be used for the preparation of the liquid crystal aligning agent after purifying the obtained polyimide. On the other hand, in the above method (ii), a reaction solution containing polyimide is obtained. This reaction solution may be used as it is for the preparation of the liquid crystal aligning agent, or may be used for the preparation of the liquid crystal aligning agent after removing the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution. It may be used for the preparation of a liquid crystal aligning agent or may be used for the preparation of a liquid crystal aligning agent after purifying the isolated polyimide. In order to remove the dehydrating agent and the dehydrating ring-closing catalyst from the reaction solution, for example, a method such as solvent replacement can be applied. The isolation and purification of the polyimide can be performed by performing the same operation as described above as the isolation and purification method of the polyamic acid.

[Terminal-modified polymer]
The polyamic acid and the polyimide in the liquid crystal aligning agent of the present invention may be terminal-modified types each having a controlled molecular weight. By using the terminal-modified polymer, the coating properties of the liquid crystal aligning agent can be further improved without impairing the effects of the present invention. Such a terminal-modified polymer can be obtained by adding a molecular weight modifier to a polymerization reaction system when synthesizing a polyamic acid. Examples of molecular weight regulators include acid monoanhydrides, monoamine compounds, monoisocyanate compounds, and the like.
Examples of the acid monoanhydride include maleic anhydride, phthalic anhydride, itaconic anhydride, n-decyl succinic anhydride, n-dodecyl succinic anhydride, n-tetradecyl succinic anhydride, n -Hexadecyl succinic acid anhydride etc. can be mentioned. Examples of the monoamine compound include aniline, cyclohexylamine, n-butylamine, n-pentylamine, n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine, n-undecylamine, n-dodecylamine, n-tridecylamine, n-tetradecylamine, n-pentadecylamine, n-hexadecylamine, n-heptadecylamine, n-octadecylamine, n-eicosylamine, etc. it can. Examples of the monoisocyanate compound include phenyl isocyanate and naphthyl isocyanate.
The use ratio of the molecular weight regulator is preferably 20 parts by weight or less, more preferably 10 parts by weight or less, with respect to 100 parts by weight of the total of tetracarboxylic dianhydride and diamine used when synthesizing the polyamic acid. is there.
[Solution viscosity]
The polyamic acid and polyimide obtained as described above preferably have a solution viscosity of 20 to 800 mPa · s, and a solution viscosity of 30 to 500 mPa · s, respectively, when a 10% by weight solution is obtained. It is more preferable that it has.
The solution viscosity (mPa · s) of the above polymer is E for a polymer solution having a concentration of 10% by weight prepared using a good solvent for the polymer (for example, γ-butyrolactone, N-methyl-2-pyrrolidone, etc.). It is a value measured at 25 ° C. using a mold rotational viscometer.

Other Additives The liquid crystal aligning agent of the present invention is a polymer having (A) a photosensitive structure, a specific group (B) and a (C) photosensitizing structure as described above, preferably a group consisting of polyamic acid and polyimide. It contains at least one selected as an essential component, but may contain other components as necessary. Examples of such other components include other polymers, compounds having at least one epoxy group in the molecule (hereinafter referred to as “epoxy compound”), and functional silane compounds.
The other polymer is a polymer other than the polymer having (A) a photosensitive structure, a specific group (B), and (C) a photosensitizing structure. Such other polymers can be used in the liquid crystal aligning agent of the present invention for improving solution properties and electrical properties.
Examples of such other polymers include polyamic acid obtained by reacting the other tetracarboxylic dianhydride with the other diamine (hereinafter referred to as “other polyamic acid”), the polyamic acid. And the like (hereinafter referred to as “other polyimides”).
The ratio of other polymers used is the total of the polymers ((A) the photosensitive structure, the specific group (B) and the polymer having the photosensitizing structure (C) and other polymers). .) Is preferably 80% by weight or less, more preferably 70% by weight or less, and further preferably 50% by weight or less.

Examples of the epoxy compound include ethylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, and 1,6-hexane. Diol diglycidyl ether, glycerin diglycidyl ether, trimethylolpropane triglycidyl ether, 2,2-dibromoneopentyl glycol diglycidyl ether, N, N, N ′, N′-tetraglycidyl-m-xylenediamine, 1,3 -Bis (N, N-diglycidylaminomethyl) cyclohexane, N, N, N ', N'-tetraglycidyl-4,4'-diaminodiphenylme Emissions, N, N-diglycidyl - benzylamine, N, N-diglycidyl - aminomethyl cyclohexane, N, N-diglycidyl - cyclohexyl amine may be mentioned as preferred.
The compounding ratio of these epoxy compounds is preferably 40 parts by weight or less, more preferably 0.1 to 30 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

Examples of the functional silane compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, N- (2-aminoethyl)- 3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-aminopropyl Trimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxysilyl-1,4 7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9- Triethoxysilyl-3,6-diazanonyl acetate, methyl 9-trimethoxysilyl-3,6-diazananoate, methyl 9-triethoxysilyl-3,6-diazananoate, N-benzyl-3-aminopropyltri Methoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, glycidoxymethyltrimethoxysilane, glycidoxy Methyltriethoxysilane, 2-glycidoxyethyltrimeth Shishiran, 2-glycidoxyethyl triethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glycidoxypropyl triethoxy silane and the like.
The blending ratio of these functional silane compounds is preferably 2 parts by weight or less, more preferably 0.02 to 0.2 parts by weight with respect to 100 parts by weight of the total amount of the polymer.

Liquid crystal aligning agent The liquid crystal aligning agent of the present invention comprises (A) a polymer having a photosensitive structure, a specific group (B) and (C) a photosensitizing structure as described above, and others optionally blended as necessary. The additive is preferably dissolved and contained in an organic solvent.
Examples of the organic solvent that can be used in the liquid crystal aligning agent of the present invention include N-methyl-2-pyrrolidone, γ-butyrolactone, γ-butyrolactam, N, N-dimethylformamide, N, N-dimethylacetamide, 4-hydroxy-4. -Methyl-2-pentanone, ethylene glycol monomethyl ether, butyl lactate, butyl acetate, methyl methoxypropionate, ethyl ethoxypropionate, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol-n-propyl ether, Ethylene glycol-i-propyl ether, ethylene glycol-n-butyl ether (butyl cellosolve), ethylene glycol dimethyl ether, ethylene glycol ethyl ether acetate, diethylene glycol dimethyl Ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, diisobutyl ketone, isoamyl propionate, isoamyl isobutyrate, diisopentyl ether, ethylene carbonate, propylene carbonate, etc. Can be mentioned. These can be used alone or in combination of two or more.

The solid content concentration in the liquid crystal aligning agent of the present invention (the ratio of the total weight of components other than the solvent of the liquid crystal aligning agent to the total weight of the liquid crystal aligning agent) is appropriately selected in consideration of viscosity, volatility, and the like. The range is preferably 1 to 10% by weight. That is, the liquid crystal aligning agent of the present invention is applied to the substrate surface as described later, and preferably, when heated, a coating film that becomes a liquid crystal aligning film is formed, but the solid content concentration is less than 1 wt%. In this case, the film thickness of the coating film becomes too small to obtain a good liquid crystal alignment film. On the other hand, when the solid content concentration exceeds 10% by weight, the film thickness of the coating film becomes excessive. Thus, a good liquid crystal alignment film cannot be obtained, and the viscosity of the liquid crystal aligning agent increases, resulting in poor coating properties.
The particularly preferable solid content concentration range varies depending on the method used when applying the liquid crystal aligning agent to the substrate. For example, when the spinner method is used, the solid content concentration is particularly preferably in the range of 1.5 to 4.5% by weight. In the case of the printing method, it is particularly preferable that the solid content concentration is in the range of 3 to 9% by weight, and thereby the solution viscosity is in the range of 12 to 50 mPa · s. In the case of the inkjet method, it is particularly preferable that the solid content concentration is in the range of 1 to 5% by weight, and thereby the solution viscosity is in the range of 3 to 15 mPa · s.
The temperature at the time of preparing the liquid crystal aligning agent of this invention becomes like this. Preferably it is 10 to 50 degreeC, More preferably, it is 20 to 30 degreeC.

Liquid crystal display element The liquid crystal display element of this invention comprises the liquid crystal aligning film formed from the liquid crystal aligning agent of this invention as mentioned above.
The liquid crystal display element of the present invention can be produced, for example, by the following steps (1) to (3).
(1) As a pair of two substrates provided with a patterned transparent conductive film, the liquid crystal aligning agent of the present invention is preferably applied on each transparent conductive film forming surface, preferably by an offset printing method, a spin coating method or Each of the coated surfaces is coated by an ink jet printing method, and then the coated surface is formed by heating each coated surface. Here, as the substrate, for example, a glass such as float glass or soda glass; a transparent substrate made of a plastic such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone, polycarbonate, or poly (alicyclic olefin) can be used. As the transparent conductive film provided on one surface of the substrate, a NESA film (registered trademark of PPG, USA) made of tin oxide (SnO ₂ ), an ITO film made of indium oxide-tin oxide (In ₂ O ₃ —SnO ₂ ), etc. In order to obtain a patterned transparent conductive film which can be used, for example, a method of forming a pattern by photo-etching after forming a transparent conductive film without a pattern, a mask having a desired pattern when forming a transparent conductive film The method using can be used. When applying the liquid crystal aligning agent, in order to further improve the adhesion between the substrate surface and the transparent conductive film and the coating film, a functional silane compound or functional titanium is formed on the surface of the substrate surface on which the coating film is to be formed. You may give the pretreatment which apply | coats a compound etc. previously.

After application of the liquid crystal aligning agent, preheating (pre-baking) is preferably performed for the purpose of preventing dripping of the applied aligning agent. The pre-bake temperature is preferably 30 to 200 ° C, more preferably 40 to 150 ° C, and particularly preferably 40 to 100 ° C. The pre-bake time is preferably 0.25 to 10 minutes, more preferably 0.5 to 5 minutes. Thereafter, a firing (post-bake) step is performed for the purpose of completely removing the solvent. The firing (post-bake) temperature is preferably 80 to 300 ° C, more preferably 120 to 250 ° C, and the post-bake time is preferably 5 to 200 minutes, more preferably 10 to 100 minutes. Thus, the liquid crystal aligning agent of this invention forms the coating film used as a liquid crystal aligning film by removing an organic solvent after application | coating, but the polymer contained in the liquid crystal aligning agent of this invention has an amic acid structure. In the case of a polymer having, dehydration ring closure of the amic acid structure may be advanced by further heating.
Thus, the coating film used as a liquid crystal aligning film can be formed. The film thickness of the formed coating film is preferably 0.001-1 μm, more preferably 0.005-0.5 μm.

(2) The coating film formed as described above is then irradiated with linearly or partially polarized radiation or non-polarized radiation, and in some cases, a heat treatment is performed at a temperature of 150 to 250 ° C. Provides orientation ability. As the radiation, ultraviolet rays and visible rays having a wavelength of 150 to 600 nm can be used, but ultraviolet rays having a wavelength of 300 to 400 nm are preferable. When the used radiation is linearly polarized or partially polarized, irradiation may be performed from a direction perpendicular to the substrate surface, or from an oblique direction to give a pretilt angle, or a combination of these. You may go. When irradiating non-polarized radiation, the direction of irradiation needs to be an oblique direction.
Examples of the light source that can be used include a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, and an excimer laser. Further, the ultraviolet rays in the preferable wavelength region can be obtained by means of using a filter, a diffraction grating or the like together with the light source.
The radiation dose is preferably 50 J / m ² or more and less than 10,000 J / m ² , more preferably 100 to 5,000 J / m ² , and even more preferably 200 to 4,000 J / m ² . It is preferable. The liquid crystal aligning agent of this invention can form the liquid crystal aligning film which has favorable liquid crystal aligning ability, even if the irradiation amount of a radiation is 4,000 J / m < ² > or less. The irradiation amount of this radiation can be further set to 2,000 J / m ² or less, particularly 1,000 J / m ² or less.
In step (2), it is preferable not to perform heat treatment after radiation irradiation.

(3) A liquid crystal cell is manufactured by preparing two substrates on which a liquid crystal alignment film is formed as described above, and disposing a liquid crystal between the two substrates opposed to each other. Here, the two substrates are arranged to face each other so that the radiation direction of each coating film is a predetermined angle, for example, orthogonal or antiparallel.
In order to manufacture a liquid crystal cell, the following two methods are mentioned, for example.
The first method is a conventionally known method. First, two substrates are arranged to face each other through a gap (cell gap) so that the respective liquid crystal alignment films are opposed to each other, and the peripheral portions of the two substrates are bonded using a sealant, and the substrate surface and the sealant are bonded. A liquid crystal cell can be manufactured by injecting and filling liquid crystal into the cell gap partitioned by the step, and then sealing the injection hole.
The second method is a method called an ODF (One Drop Fill) method. For example, an ultraviolet light curable sealing material is applied to a predetermined location on one of the two substrates on which the liquid crystal alignment film is formed, and liquid crystal is dropped on the liquid crystal alignment film surface. The other substrate is bonded so as to face each other, and then the entire surface of the substrate is irradiated with ultraviolet light to cure the sealant, whereby a liquid crystal cell can be manufactured.
Regardless of which method is used, the liquid crystal cell produced as described above is further heated to a temperature at which the liquid crystal used takes an isotropic phase, and then gradually cooled to room temperature, so that the liquid alignment at the time of filling the liquid crystal is achieved. It is desirable to remove.
And the liquid crystal display element of this invention can be obtained by bonding a polarizing plate on the outer surface of a liquid crystal cell.

Here, as the sealant, for example, an epoxy resin containing a curing agent and aluminum oxide spheres as a spacer can be used.
As the liquid crystal, for example, nematic liquid crystal, smectic liquid crystal, or the like can be used, and among these, nematic liquid crystal is preferable. In the case of a VA liquid crystal cell, a nematic liquid crystal having negative dielectric anisotropy is preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal, and phenylcyclohexane liquid crystal are used. It is done. In the case of a TN type liquid crystal cell or an STN type liquid crystal cell, a nematic type liquid crystal having positive dielectric anisotropy is preferable. For example, biphenyl type liquid crystal, phenyl cyclohexane type liquid crystal, ester type liquid crystal, terphenyl type liquid crystal, biphenyl cyclohexane type A liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like is used. Cholesteric liquid crystals such as cholesteryl chloride, cholesteryl nonate, and cholesteryl carbonate; chiral agents such as those sold under the trade names “C-15” and “CB-15” (manufactured by Merck); p- A ferroelectric liquid crystal such as decyloxybenzylidene-p-amino-2-methylbutylcinnamate may be further added and used.
As a polarizing plate bonded to the outer surface of the liquid crystal cell, a polarizing film or an H film in which a polarizing film called an “H film” that absorbs iodine while stretching and aligning polyvinyl alcohol is sandwiched between protective films of cellulose acetate The polarizing plate which consists of itself can be mentioned.

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples. The polymer solution viscosity and polyimide imidation ratio in the following were evaluated by the following methods, respectively.
[Solution viscosity of polymer]
The solution viscosity (mPa · s) of the polymer is a value measured at 25 ° C. using an E-type rotational viscometer for an N-2-methylpyrrolidone solution containing 10% by weight of each polymer.
[Imidation rate of polyimide]
The polyimide imidation rate was determined by taking a small amount of the polyimide solution obtained in each synthesis example, putting it into pure water, drying the precipitate obtained at room temperature under reduced pressure, and then dissolving it in deuterated dimethyl sulfoxide. methylsilane from ^{1 H-NMR} was measured at room temperature as a reference substance, was calculated according to the following equation (1).

Imidation rate (%) = (1-A ¹ / A ² × α) × 100 (1)

(In Formula (1), A ¹ is a peak area derived from protons of NH groups appearing near a chemical shift of 10 ppm, A ² is a peak area derived from other protons, and α is a polyimide precursor (polyamic acid). The number ratio of other protons to one proton of NH group in

Synthesis example 1
Synthesis of polyamic acid and other tetracarboxylic dianhydride 2,3,5-tricarboxycyclopentyl acetic acid dianhydride 0.01 mol (2.2 g) and (A) both photosensitive structure and specific group (B) 7.0 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) synthesized from natural γ-oryzanol by a method described in Patent Document 22 (Japanese Patent Laid-Open No. 2007-191447) as a diamine containing (C) As a diamine containing a sensitizing structure, 0.001 mol (0.23 g) of 1,4-diaminoanthraquinone is dissolved in 85 g of N-methyl-2-pyrrolidone (NMP) and reacted at 60 ° C. for 6 hours. Thus, a solution containing 10% by weight of polyamic acid (A-1) was obtained. The solution viscosity of this solution was 50 mPa · s.
Synthesis of polyimide 1.6 g of pyridine and 2.0 g of acetic anhydride were added to a solution containing 10% by weight of the above polyamic acid (A-1), and a dehydration ring closure reaction was performed at 110 ° C. for 4 hours. After the dehydration cyclization reaction, the solvent in the system was replaced with new NMP (by removing the pyridine and acetic anhydride used in the dehydration cyclization reaction from the system), and the imidation rate was about 80%. A solution containing about 15% by weight of polyimide (B-1) was obtained. A small amount of the obtained polyimide solution was collected, NMP was added, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight was 52 mPa · s.

Synthesis Examples 2-7 and Comparative Synthesis Example 1
“Synthesis of polyamic acid” in Synthesis Example 1 except that the types and amounts of use of tetracarboxylic dianhydride and diamine and the amount of NMP as a solvent are as shown in Table 1, respectively in Synthesis Example 1 above. In the same manner as above, a solution containing 10% by weight of polyamic acids (A-2) to (A-7) and (A-r) was obtained. A solution containing about 15% by weight of (B-2) to (B-7) and (Br) was obtained.
Table 1 shows the solution viscosity of these polyamic acid solutions, the imidation ratio of the polyimide, and the solution viscosity measured as a solution having a polyimide concentration of 10% by weight by adding a small amount of NMP to the polyimide solution.
Synthesis example 8
Synthesis of other polyamic acids 1,2,3,4-cyclobutanetetracarboxylic dianhydride 200 g (1.0 mol) as tetracarboxylic dianhydride and 2,2'-dimethyl-4,4'- as diamine By dissolving 210 g (1.0 mol) of diaminobiphenyl in 3,700 g of NMP and reacting at 40 ° C. for 3 hours, a solution containing 10% by weight of polyamic acid (A-8) was obtained. The solution viscosity of this solution was 130 mPa · s.

In Table 1, the abbreviations of tetracarboxylic dianhydride and diamine have the following meanings, respectively.
<Tetracarboxylic dianhydride>
TCA: 2,3,5-tricarboxycyclopentyl acetic acid dianhydride TDA: 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1 , 2-c] -furan-1,3-dione CB: cyclobutanetetracarboxylic dianhydride <diamine>
ANT: 1,4-diaminoanthraquinone PDA: p-phenylenediamine DDB: 2,2′-dimethyl-4,4′-diaminobiphenyl O-1: 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate)
O-2: 6- (Oryzanyloxy) hexyl (3,5-diaminobenzoate)
O-3: 1,3-diamino-4- (6 (oryzanyloxy) hexyloxy) benzene O-4: oryzanyloxy (2 (2,4-diaminophenoxy) acetate)
O-5: Oryzanyl (3,5-diaminobenzoate)

Example 1
[Preparation of liquid crystal aligning agent]
NMP and butyl cellosolve are added to the solution containing the polyimide (B-1) obtained in Synthesis Example 1 above, and the solvent composition is diluted to NMP: butyl cellosolve = 60: 40 (weight ratio) to obtain a solid content concentration of 3 A liquid crystal aligning agent was prepared by preparing a 0.0 wt% solution and further filtering the solution through a filter having a pore size of 1 μm.
[Manufacture of liquid crystal display elements]
The liquid crystal aligning agent prepared above was applied on the transparent electrode surface of a glass substrate with a transparent electrode made of an ITO film using a spinner, and heated at 180 ° C. for 1 hour to form a coating film having a thickness of 0.06 μm. . The surface of the coating film is irradiated with polarized ultraviolet light containing a 313 nm emission line using a Hg-Xe lamp and a Grand Taylor prism for 50 seconds from a direction inclined by 45 ° from the substrate normal line, thereby providing liquid crystal alignment ability. An alignment film was obtained. At this time, the illuminance at the wavelength of 313 nm on the irradiated surface was ² mW / cm ² . The same operation was repeated to prepare two (one pair) substrates having a coating film (liquid crystal alignment film) subjected to polarized ultraviolet irradiation treatment.
Next, for the pair of substrates, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is applied to the outer periphery of the surface on which the liquid crystal alignment film is formed by screen printing. The substrates were stacked and pressure-bonded so as to face each other and the irradiation direction of polarized ultraviolet rays was antiparallel, and heated at 150 ° C. for 1 hour to thermally cure the adhesive. Next, a nematic liquid crystal (MLC-6608, manufactured by Merck & Co., Inc.) was filled into the gap between the liquid crystal inlet and the substrate, and then the liquid crystal inlet was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated to 150 ° C. and then gradually cooled to room temperature. Next, a polarizing plate was bonded to both the outer surfaces of the substrate so that the polarization directions thereof were orthogonal to each other and at an angle of 45 ° with the polarization direction of ultraviolet rays of the liquid crystal alignment film, thereby producing a liquid crystal display element.

[Evaluation of liquid crystal display elements]
(1) Measurement of pretilt angle The method described in Non-Patent Document 4 (TJ Scheffer et. Al., J. Appl. Phys. Vo. 19, p2013 (1980)) for the liquid crystal display device produced above. The pretilt angle was 89 ° as determined as the value of the tilt angle from the substrate surface of the liquid crystal molecules measured by the crystal rotation method using He—Ne laser light in accordance with the above.
(2) Evaluation of liquid crystal orientation When the presence or absence of an abnormal domain was visually observed when the voltage of 5 V was turned on / off (applied / released) for the liquid crystal display element produced above, the abnormal domain was not observed, The liquid crystal alignment was “good”.
(3) Evaluation of pretilt angle stability After the liquid crystal display element produced above was stored at 25 ° C for 30 days, the pretilt angle was measured again according to the method of (1) above. The pretilt angle was 89 °, There was no change in the pretilt angle during storage.

Examples 2-7
In the said Example 1, it replaced with the solution containing a polyimide (B-1), and except having used the solution which each contains a polyimide (B-2)-(B-7), it is the same as that of Example 1. When the liquid crystal display element was manufactured and evaluated, the vertical alignment of the liquid crystal was good. Further, in the same manner as in Example 1, the pretilt angle, the liquid crystal orientation, and the pretilt angle stability were evaluated. The evaluation results are shown in Table 2.
Example 8
[Preparation of liquid crystal aligning agent]
A solution containing the polyimide (B-1) obtained in Synthesis Example 1 and a solution containing the polyamic acid (A-8) obtained in Synthesis Example 8 are used as polyimide (B-1) contained in each solution. And the polyamic acid (A-8) were mixed so that the weight ratio was 20:80. Further, NMP and butyl cellosolve were added to this mixed solution, and diluted so that the solvent composition was NMP: butyl cellosolve = 60: 40 (weight ratio) to obtain a solution having a solid content concentration of 3.0% by weight. The liquid crystal aligning agent was prepared by filtering with a 1 micrometer filter.
[Manufacture of liquid crystal display elements]
When the liquid crystal display element was produced and evaluated in the same manner as in Example 1 except that the liquid crystal aligning agent prepared above was used, the vertical alignment properties of the liquid crystals were all good. Further, in the same manner as in Example 1, the pretilt angle, the liquid crystal orientation, and the pretilt angle stability were evaluated. The evaluation results are shown in Table 2.

Examples 9-14
In the said Example 8, it replaced with the solution containing a polyimide (B-1), and except having used the solution which each contains a polyimide (B-2)-(B-7), it is the same as that of Example 8. When the liquid crystal display element was manufactured and evaluated, the vertical alignment of the liquid crystal was good. Further, in the same manner as in Example 1, the pretilt angle, the liquid crystal orientation, and the pretilt angle stability were evaluated. The evaluation results are shown in Table 2.
Examples 15 and 16
In the said Example 8, the weight ratio of a solution containing a polyimide (B-1) and a solution containing a polyamic acid (A-8) is 30: polyimide (B-1) and a polyamic acid (A-8) respectively. A liquid crystal display device was manufactured and evaluated in the same manner as in Example 8 except that the mixing ratio was 70 and 50:50. As a result, the vertical alignment of the liquid crystal was good. Further, in the same manner as in Example 1, the pretilt angle, the liquid crystal orientation, and the pretilt angle stability were evaluated. The evaluation results are shown in Table 2.
Comparative Example 1
In Example 1 above, a liquid crystal display device was produced in the same manner as in Example 1 except that a solution containing polyimide (Br) was used instead of the solution containing polyimide (B-1). As a result of evaluation, the vertical alignment of the liquid crystal was good. Further, in the same manner as in Example 1, the pretilt angle, the liquid crystal orientation, and the pretilt angle stability were evaluated. The evaluation results are shown in Table 2.
The pretilt angle immediately after the production of this liquid crystal display element was 89 °, but the pretilt angle after storage for 30 days was 90 °, and the pretilt angle characteristics were lost over time.

Claims (9)

(A) a photosensitive structure containing a conjugated double bond,
(B) A monovalent or divalent group comprising a fluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 4 to 20 carbon atoms which may be substituted with a fluorine atom, and a condensed alicyclic structure having 9 to 30 carbon atoms. A liquid crystal aligning agent comprising at least one group selected from the group consisting of hydrocarbon groups, and (C) a polymer having a photosensitizing structure. The photosensitive structure containing the (A) conjugated double bond is represented by the following formula (a):
(In the formula (a), Ar is a divalent aromatic group, and R ^I and R ^II are each independently a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
The liquid crystal aligning agent of Claim 1 which is a structure represented by these.   The liquid crystal aligning agent of Claim 1 or 2 whose said polymer is at least 1 sort (s) of polymer selected from the group which consists of a polyamic acid and a polyimide.   The (C) photosensitizing structure is at least one selected from the group consisting of an acetophenone structure, a benzophenone structure, an anthraquinone structure, a biphenyl structure, a carbazole structure, a nitroaryl structure, a fluorene structure, a naphthalene structure, an anthracene structure, and an acridine structure. The liquid crystal aligning agent as described in any one of Claims 1-3 which is.   A liquid crystal, wherein the liquid crystal aligning agent according to any one of claims 1 to 4 is applied onto a substrate to form a coating film, and the coating film is irradiated with polarized or non-polarized radiation. Method for forming alignment film.   A liquid crystal alignment film formed by the method according to claim 5.   The liquid crystal alignment film according to claim 6, which is vertically aligned.   A liquid crystal display element comprising the liquid crystal alignment film according to claim 6. (A) a photosensitive structure containing a conjugated double bond,
(B) A monovalent or divalent group comprising a fluoroalkyl group having 1 to 3 carbon atoms, an alkyl group having 4 to 20 carbon atoms which may be substituted with a fluorine atom, and a condensed alicyclic structure having 9 to 30 carbon atoms. A polymer having at least one group selected from the group consisting of hydrocarbon groups, and (C) a photosensitizing structure.