JP4924801B2 - Liquid crystal aligning agent, alignment film, liquid crystal display element and optical member - Google Patents

Description

  The present invention relates to a liquid crystal aligning agent, a liquid crystal alignment film, and a liquid crystal display element. More specifically, a liquid crystal aligning agent used for forming a liquid crystal alignment film capable of imparting liquid crystal alignment ability by irradiation with polarized or non-polarized radiation without rubbing, such a liquid crystal alignment film, and The present invention relates to a liquid crystal display element having such a liquid crystal alignment film.

Conventionally, a nematic liquid crystal having positive dielectric anisotropy is sandwiched with a substrate with a transparent electrode having a liquid crystal alignment film, and the major axis of liquid crystal molecules is continuously twisted between 0 and 360 degrees between the substrates as necessary. Liquid crystal display elements having liquid crystal cells such as TN (twisted nematic), STN (super twisted nematic), and IPS (in-plane switching) are known (see Patent Documents 1 and 2). .
In such a liquid crystal cell, it is necessary to provide a liquid crystal alignment film on the substrate surface in order to align the liquid crystal in a predetermined direction with respect to the substrate surface. This liquid crystal alignment film is usually formed by a method (rubbing method) in which the organic film surface formed on the substrate surface is rubbed in one direction with a cloth material such as rayon. However, if the liquid crystal alignment film is formed 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 was a problem. 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. Further, in liquid crystal display elements that will be further refined in the future, unevenness occurs on the surface of the substrate as the density of pixels increases, so that uniform rubbing is a problem.

As another means of aligning liquid crystals in a liquid crystal cell, light that imparts liquid crystal alignment ability by irradiating a photosensitive thin film such as polyvinyl cinnamate, polyimide, or azobenzene derivative formed on the substrate surface with polarized or non-polarized radiation. Orientation methods are known. According to this method, uniform liquid crystal alignment can be realized without generating static electricity or dust (see Patent Documents 3 to 14).
Further, as an operation mode of a liquid crystal display element different from the above, a vertical (homeotropic) alignment mode in which liquid crystal molecules having negative dielectric anisotropy are aligned perpendicularly to a substrate is also known. 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.

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 cell. That is, it is known that the tilt direction of the liquid crystal molecules at the time of voltage application can be uniformly controlled by using a vertical alignment film provided with an alignment regulating force and a pretilt angle by a photo-alignment method (Patent Documents 12 to 13 and 15). To 17).
Conventionally, in the display, optoelectronics, and optical fields, optical members such as polarizing plates, phase difference plates, and optically rotatory optical films have been used. These optical members have various uses. For example, in addition to being widely used as a member such as a polarizing plate, a compensation plate, and a viewing angle improving film in a liquid crystal display device, they are also used as a phase difference plate for an optical pickup element in an optical disk device. It has been.
As a method for producing such an optical member, many methods such as a method using a stretched and oriented resin film have been conventionally known. However, the optical member manufactured by such a method has the same optical characteristics over the entire surface, and it has not been possible to obtain an optical member having different optical characteristics in different regions within the surface.

On the other hand, the prior invention (see Patent Documents 18 to 19) reveals a method of fixing an alignment state after aligning a liquid crystal substance having an optical function on a liquid crystal alignment film formed on a substrate by a photo-alignment technique. I have to. By this method, an optical member having different optical characteristics in different regions within the surface can be easily manufactured.
As described above, the liquid crystal alignment film (hereinafter also referred to as a photo alignment film) manufactured by the photo alignment technique can be effectively applied to a liquid crystal display element and an optical member. However, the conventional photo-alignment technique has a problem that the wavelength range of radiation that can be used for providing liquid crystal alignment ability is narrow. For example, cinnamic acid derivative-based materials such as polyvinyl cinnamate are known to effectively respond to ultraviolet light having a wavelength shorter than 320 nm. (See Non-Patent Document 1). On the other hand, ultraviolet light or visible light having a wavelength longer than 320 nm is usually effectively used for conjugated enone materials and azobenzene materials (see Patent Documents 6 and 12-15).
For this reason, in the conventional photo-alignment technology, when a discharge lamp, a halogen lamp, or the like is used as a light source, only a small wavelength range of the irradiated radiation is effectively utilized. There wasn't.
JP 56-91277 A JP-A-1-120528 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 2002-98970 A JP 2003-307736 A JP 2004-163646 A JP 2002-250924 A JP 2004-83810 A Japanese Patent Laid-Open No. 9-21468 JP 2003-114437 A JP-A-6-289374 JP 2004-20658 A Macromolecules, Vol.30, No.4, 1997 p.904

  The objective of this invention is providing the liquid crystal aligning agent used for formation of the liquid crystal aligning film which can provide liquid crystal aligning ability by polarized or non-polarized radiation irradiation, without performing a rubbing process.

  Another object of the present invention is to provide a liquid crystal aligning agent used for forming a liquid crystal aligning film capable of imparting liquid crystal aligning ability with radiation in a wide wavelength range.

  Still another object of the present invention is to provide a liquid crystal alignment film.

  Still another object of the present invention is to provide a liquid crystal display device.

  Still another object of the present invention is to provide an optical member.

  Still other objects and advantages of the present invention will become apparent from the following description.

（ここで、Ｐ^１およびＰ^２は、ハロゲンまたは有機基で置換されていてもよい芳香族基又は不飽和複素環基であり、但しＰ^１は２価の基であり、Ｐ^２は３価の基である、Ｄ^１およびＤ^２は酸素原子またはＮＲ（ただし、Ｒは水素原子又は炭素数１〜１２のアルキル基を表わす。）であり、Ｒ^１、Ｒ^２、Ｒ^３、およびＲ^４は、互いに独立に、水素原子又は炭素数１〜１２のアルキル基である。）
および、下記式（ＩＩＩ）、（ＩＶ）および（Ｖ）のそれぞれで表わされる構造よりなる群から選ばれる少なくとも１つの共役エノン構造、

（ここで、Ｐ^３、Ｐ^４、Ｐ^５、Ｑ^３、Ｑ^４およびＱ^５は、互いに独立に、ハロゲンまたは有機基で置換されていてもよい、芳香族基又は不飽和複素環基であり、但しＰ^３、Ｐ^５、Ｑ^３、およびＱ^４は２価の基であり、そして、Ｐ^４およびＱ^５は３価の基であり、Ｒ^５、Ｒ^６、Ｒ^７、Ｒ^８、Ｒ^９およびＲ^１０は、互いに独立に、水素原子又は炭素数１〜１２のアルキル基である。）
を共に有する重合体を含有する液晶配向剤であって、
前記けい皮酸構造を有する重合体は、テトラカルボン酸二無水物とジアミン化合物とを反応させることにより得られるポリアミック酸、前記ポリアミック酸から得られるポリイミドまたは前記ポリアミック酸から得られるポリアミック酸エステルであり、ただし、
前記テトラカルボン酸二無水物と前記ジアミン化合物のうちの少なくとも１つの成分に、前記けい皮酸構造を有する化合物が用いられ、そして、
前記共役エノン構造を有する重合体は、テトラカルボン酸二無水物とジアミン化合物とを反応させることにより得られるポリアミック酸、前記ポリアミック酸から得られるポリイミドまたは前記ポリアミック酸から得られるポリアミック酸エステルであり、ただし、
前記テトラカルボン酸二無水物と前記ジアミン化合物のうちの少なくとも１つの成分に、前記共役エノン構造を有する化合物が用いられることを特徴とする、前記液晶配向剤により達成される。
According to the present invention, the above objects and advantages of the present invention, the first, the following formula (I) and at least one cinnamic acid structure selected from the group consisting of structures represented by the respective (II),

(Wherein P ¹ and P ² are an aromatic group or an unsaturated heterocyclic group optionally substituted with a halogen or an organic group, provided that P ¹ is a divalent group, and P ² is a trivalent group. D ¹ and D ^{2 which} are groups represented by: are an oxygen atom or NR (wherein R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), and R ¹ , R ² , R ³ , and R ⁴ Are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
And at least one conjugated enone structure selected from the group consisting of structures represented by the following formulas (III), (IV) and (V),

(Wherein P ³ , P ⁴ , P ⁵ , Q ³ , Q ⁴ and Q ⁵ are each independently an aromatic group or an unsaturated heterocyclic group which may be substituted with a halogen or an organic group. Where P ³ , P ⁵ , Q ³ and Q ⁴ are divalent groups, and P ⁴ and Q ⁵ are trivalent groups, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
The A liquid crystal alignment agent you containing both have polymer,
The polymer having a cinnamic acid structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid. However,
A compound having a cinnamic acid structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound; and
The polymer having the conjugated enone structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid, However,
The liquid crystal aligning agent is characterized in that a compound having the conjugated enone structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound .

According to the present invention, objects and advantages of the present invention, the second polymer having the formula (I) and at least one cinnamic acid structure selected from the group consisting of structures represented by the respective (II) When the above formula (III), a liquid crystal alignment agent you containing a polymer having at least one conjugated enone structure selected from the group consisting of structures represented by the respective (IV) and (V),
The polymer having a cinnamic acid structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid. However,
A compound having a cinnamic acid structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound; and
The polymer having the conjugated enone structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid, However,
The liquid crystal aligning agent is characterized in that a compound having the conjugated enone structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound .

  According to the present invention, the objects and advantages of the present invention are thirdly achieved by a liquid crystal aligning agent in which the main chain of the polymer is polyamic acid or polyimide.

  According to the present invention, the objects and advantages of the present invention are fourthly achieved by a liquid crystal aligning agent in which the main chain of the polymer is a polyamic acid ester.

  According to the present invention, fifth, the objects and advantages of the present invention are achieved by a liquid crystal alignment film obtained by irradiating polarized or non-polarized radiation to a thin film made of the liquid crystal aligning agent to impart liquid crystal alignment ability. Is done.

  According to the present invention, sixthly, the objects and advantages of the present invention are achieved by a liquid crystal display element having the liquid crystal alignment film.

  According to the present invention, seventh, the objects and advantages of the present invention are achieved by an optical member obtained by aligning a liquid crystal substance on a liquid crystal alignment film and then fixing the alignment state.

  When the photo-alignment agent of the present invention is used, radiation in a wider wavelength range can be efficiently used for imparting liquid crystal alignment ability than in the case of using the conventional photo-alignment method. As a result, since the utilization efficiency of the radiation to be irradiated is increased, a liquid crystal alignment film can be obtained in a shorter radiation irradiation time. Therefore, when this liquid crystal alignment film is applied to a liquid crystal display element or an optical member, the liquid crystal display element or the optical member can be manufactured at a lower cost than before. Therefore, these liquid crystal display elements or optical members can be effectively applied to various devices, for example, suitable for devices such as desk calculators, watches, table clocks, coefficient display boards, word processors, personal computers, liquid crystal televisions, or optical pickup devices. Used.

  Hereinafter, the present invention will be described in detail.

The photo-alignment agent of the present invention is characterized by having a cinnamic acid structure and a conjugated enone structure in the contained polymer. The photo-alignment agent of the present invention may contain a polymer having both a cinnamic acid structure and a conjugated enone structure, and also has a polymer having a cinnamic acid derivative structure and a conjugated enone structure. It may contain a polymer.
When a thin film containing such a polymer is irradiated with radiation, a cinnamic acid structure and / or a conjugated enone structure is sensitive to the radiation, and a structure oriented in a certain direction determined by the polarization axis of the radiation is formed. Here, “sensitivity” means that electrons are excited by absorbing light energy upon irradiation with radiation, and in some cases, bonds are generated or dissociated to return to the original ground state. On the liquid crystal alignment film thus obtained, the liquid crystal alignment direction is controlled by the structure aligned in the predetermined direction.

At this time, the cinnamic acid structure is effectively sensitive to radiation having a wavelength shorter than 320 nm, while the conjugated enone structure is sensitive to radiation having a wavelength longer than 320 nm. Therefore, when the photo-alignment agent of the present invention is used in combination with a light source having a wide emission wavelength region such as a discharge lamp or a halogen lamp, radiation in the entire wavelength region can be efficiently used.
The cinnamic acid structure is any one of the structures represented by the above formulas (I) and (II), and the conjugated enone structure is represented by each of (III), (IV) and (V). One of the structures to be made.
In the above formulas (I), (II), (III), (IV) and (V), P ¹ , P ² , P ³ , P ⁴ , P ⁵ , Q ³ , Q ⁴ and Q ⁵ are independent from each other. And an aromatic group or an unsaturated heterocyclic group which may be substituted with a halogen or an organic group. Of these, P ¹ , P ³ , P ⁵ , Q ³ and Q ⁴ are divalent groups, and P ² , P ⁴ and Q ⁵ are trivalent groups.

Specific examples of the divalent aromatic group represented by P ¹ , P ³ , P ⁵ , Q ³ and Q ⁴ include a 1,2-phenylene group, a 3-fluoro-1,2-phenylene group, 4-fluoro-1,2-phenylene group, 3-methoxy-1,2-phenylene group, 4-methoxy-1,2-phenylene group, 3-methyl-1,2-phenylene group, 4-methyl-1, 2-phenylene group, 1,3-phenylene group, 2-fluoro-1,3-phenylene group, 4-fluoro-1,3-phenylene group, 5-fluoro-1,3-phenylene group, 2-methoxy-1 , 3-phenylene group, 4-methoxy-1,3-phenylene group, 5-methoxy-1,3-phenylene group, 2-methyl-1,3-phenylene group, 4-methyl-1,3-phenylene group, 5-methyl-1,3-phenylene group, 1,4- Enylene group, 2-fluoro-1,4-phenylene group, 2-methoxy-1,4-phenylene group, 2-methyl-1,4-phenylene group, 4,4′-biphenylene group, 3,4′-biphenylene Group, 3,3′-biphenylene group, 1,4-naphthylene group, 2,6-naphthylene group and the like. Specific examples of the divalent unsaturated heterocyclic group include pyrimidine-2,5-diyl group, pyridine-2,5-diyl group, 2,5-thiophenylene group and 2,5-furylene group. Etc. Of these, a 1,4-phenylene group and a 2-methoxy-1,4-phenylene group are preferred.

Specific examples of the trivalent aromatic group represented by P ² , P ⁴ and Q ⁵ include benzene, biphenyl, naphthalene, anthracene, anisole, benzotrifluoride or trifluoromethoxybenzene on the benzene ring. Mention may be made of groups obtained by removing three hydrogen atoms. Specific examples of the trivalent unsaturated heterocyclic group include groups obtained by removing three hydrogen atoms from pyrimidine, pyridine, thiophene and furan.

D ¹ and D ² are each independently an oxygen atom or NR (wherein R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), preferably an oxygen atom or NH, particularly preferably It is an oxygen atom. R ¹ , R ² , R ³ , R ⁴ , R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ and R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, preferably Is a hydrogen atom or a methyl group, particularly preferably a hydrogen atom.

  The polymer constituting the liquid crystal aligning agent of the present invention is a polymer having the cinnamic acid structure and / or the conjugated enone structure. The ratio of the repeating unit having a cinnamic acid structure and the repeating unit having a conjugated enone structure in the entire polymer contained in the aligning agent is 1 to 90% of the total repeating units, independently of each other. Preferably, 10 to 50% is particularly preferable. Each of the cinnamic acid structure and the conjugated enone structure may be in the side chain of the polymer or in the main chain, but in the side chain from the viewpoint of photoreactivity. It is preferable. Further, the cinnamic acid structure and / or the conjugated enone structure may be included in the polymer as a cyclic structure such as a coumarin skeleton.

Skeletal polymers used in the present invention, from the viewpoint of excellent heat resistance, positive polyamic acid ester, a polyamic acid and polyimide, polyamic acid and polyimide are particularly preferable.

A polyamic acid, a polyimide, and a polyamic acid ester polyamic acid are obtained by reacting a tetracarboxylic dianhydride with a diamine compound. Moreover, a polyimide is obtained by dehydrating and ring-closing the polyamic acid.
For the synthesis of polyamic acid and polyimide used as a polymer contained in the photo-alignment agent of the present invention, at least one component of tetracarboxylic dianhydride and diamine compound includes a compound having a cinnamic acid structure and A compound having a conjugated enone structure is used. Preferably, as the diamine compound, a compound having a cinnamic acid structure and a compound having a conjugated enone structure are used.
The polyamic acid ester is obtained by reacting a polyamic acid with an organic halide, alcohol or phenol. Polyamic acid ester used in the present invention, cinnamic acid structure and conjugated enone structure, that is included in at least one of the tetracarboxylic dianhydride or diamine compound.

  Examples of the tetracarboxylic dianhydride having a cinnamic acid structure include compounds represented by the following formulas (i) to (iv).

In the formula, B ¹ and B ² are independently of each other a methylene group, a polymethylene chain having 2 to 12 carbon atoms, a 1,4-phenylene group, a 1,3-phenylene group, a 1,2-phenylene group, 4 , 4′-biphenylene group, 3,3′-biphenylene group or 3,4′-biphenylene group, R ¹¹ , R ¹² , R ¹³ and R ¹⁴ are each independently a hydrogen atom or a carbon number of 1-12. In addition, X represents a structure represented by the following formula (v-1) independently of each other, and Y represents a structure represented by the following formula (v-2) independently of each other. .

However, in the formula, A ¹ , A ² , and C ¹ may be independently substituted with a halogen atom, a C 1-20 alkyl group that may be substituted with a halogen atom, or a halogen atom. An alkoxyl group having 1 to 20 carbon atoms or an organic group containing an aromatic or alicyclic structure having 6 to 30 carbon atoms is represented. D ³ and D ⁴ each independently represent an oxygen atom or NR (wherein R represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms). E ¹ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be substituted with a hydrogen atom or a halogen atom, or an organic group containing an aromatic or alicyclic structure having 6 to 30 carbon atoms. L and m each independently represent an integer of 0 to 4, and n is 0 or 1 independently of each other.

  Of these, preferred examples of the compound represented by the above formula (i) include 1,3,3a, 4,5,9b-hexahydro-8- (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-methoxycinnamoyloxy)- 5- (Tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (3 -Methoxycinnamoyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b -Hexahydro-8- (4-fluorosilane Namoyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8 -(4- (trifluoromethyl) 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- (trifluoromethoxy) 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- (4-trifluoromethylbenzoyloxy) cinnamoyloxy) -5- (tetrahydro-2,5-dioxo -3- Ranyl) -naphtho [1,2-c] furan-1,3-dione and 1,3,3a, 4,5,9b-hexahydro-8- (4- (4-trifluoromethoxybenzoyloxy) cinna Moyloxy) -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) cinnamoyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c ] Fran-1,3-Geo Can be mentioned. Examples of the compound represented by the above formula (ii) include 1,3,3a, 4,5,9b-hexahydro-8- (2- (cinnamoyloxy) 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- (cinnamoyloxy) hexyloxy ) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione. Further, as the compound represented by the above formula (iii), 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, and the compound represented by (iv) is 1,3,3a, 4,5,9b-hexahydro-8- (2- (Oryzanyloxy) 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 -Diones can be mentioned. In the present specification, the oryzanyloxy group represents at least one structure selected from the group consisting of structures represented by the following formulas (vi-1) to (vi-7). . These tetracarboxylic dianhydrides having a cinnamic acid structure can be used alone or in combination of two or more.

Examples of tetracarboxylic dianhydrides having a conjugated enone structure include, for example, compounds exemplified as tetracarboxylic dianhydrides having a specific structure in Patent Document 4, Patent Document 6, Patent Document 7 and Patent Document 11, 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-cholestanyl) Oxy) 4'- Luconyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione and 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 Can be mentioned. Among these compounds, the compounds exemplified in Patent Document 11 can be mentioned as preferred ones, and particularly preferred are 1,3,3a, 4,5,9b-hexahydro-8- (6- (4- (Calconyloxy) hexyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5 9b-Hexahydro-8- (6- (4′-fluoro-4-chalconyloxy) hexyloxy) -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan -1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (8- (4-chalconyloxy) octyloxy) -5- (tetrahydro-2,5-dioxo-3- Furanyl)- Naphtho [1,2-c] furan-1,3-dione, 1,3,3a, 4,5,9b-hexahydro-8- (8- (4′-fluoro-4-chalconyloxy) octyloxy) Mention may be made of -5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] furan-1,3-dione.
These tetracarboxylic dianhydrides having a conjugated enone structure can be used alone or in combination of two or more.

  Examples of the diamine compound having a cinnamic acid structure include compounds represented by the following formulas (vii) to (xiv).

In the formula, A ^{3 to} A ¹⁰ are independently of each other a halogen atom, an alkyl group having 1 to 12 carbon atoms that may be substituted with a halogen atom, or carbon that may be optionally substituted with a halogen atom. Represents an alkoxyl group of formula 1 to 12, and B ^{3 to} B ⁶ each independently represent a methylene chain, a polymethylene chain of 2 to 12 carbon atoms, a 1,4-phenylene group, a 1,3-phenylene group, 1,2 -Represents a phenylene group, a 4,4'-biphenylene group, a 3,3'-biphenylene group or a 3,4'-biphenylene group. S ^{1 to} S ⁸ are each independently a bonding group selected from a single bond, a methylene chain, a polymethylene chain having 2 to 12 carbon atoms, an ether bond, an ester bond, an amide bond, a urethane bond, a urea bond, and a sulfide bond. It is. X represents a structure represented by the above formula (v-1) independently of each other, and Y represents a structure represented by the above formula (v-2) independently of each other. p represents an integer of 0 to 4 independently of each other.
These diamine compounds having a cinnamic acid structure can be used alone or in combination of two or more.

  Of these, compounds represented by the above formulas (vii), (viii), (xi), and (xii) are preferable. More preferred compounds include those represented by the above formula (xi) or (xii), such as 5-oryzanyloxy-1,3-diaminobenzene, 5-oryzanyloxycarbonyl-1,3-diaminobenzene, 5 -(6-Oryzanyloxyhexyloxycarbonyl) -1,3-diaminobenzene, (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-diaminophenoxy) hexyloxy) cinnamate, and (3-cholestanyl) -4- (6 (2,4- Mention may be made of diaminophenoxy) hexyloxy) cinnamate. Examples of the compound represented by the above formula (vii) or (viii) include (2 (3,5-diaminobenzoyloxy) ethyl) cinnamate, (2 (3,5-diaminobenzoyloxy) ethyl) -4-methoxycinna Mate, (2 (3,5-diaminobenzoyloxy) ethyl) -3-methoxycinnamate, (2 (3,5-diaminobenzoyloxy) ethyl) -4-trifluoromethylcinnamate, (2 (3,5 -Diaminobenzoyloxy) ethyl) -4-trifluoromethoxycinnamate, (2 (3,5-diaminobenzoyloxy) ethyl) -4- (n-hexyloxy) cinnamate, (2 (3,5-diaminobenzoyloxy) ) Ethyl) -4- (3-cholesteryloxy) cinnamate, (2 (3,5-diaminobenzoy) Oxy) ethyl) -4- (3-cholestanyloxy) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4-methoxycinnamate , (6 (3,5-diaminobenzoyloxy) hexyl) -3-methoxycinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4-trifluoromethylcinnamate, (6 (3,5- Diaminobenzoyloxy) hexyl) -4-trifluoromethoxycinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4- (n-hexyloxy) cinnamate, (6 (3,5-diaminobenzoyloxy) (Hexyl) -4- (3-cholesteryloxy) cinnamate, (6 (3,5-di- Minobenzoyloxy) hexyl) -4- (3-cholestanyloxy) cinnamate, (2,4-diaminophenyl) cinnamate, (2,4-diaminophenyl) -4-methoxycinnamate, (2,4-diaminophenyl) ) -3-methoxycinnamate, (2,4-diaminophenyl) -4-trifluoromethylcinnamate, (2,4-diaminophenyl) -4-trifluoromethoxycinnamate, (2,4-diaminophenyl) -4- (n-hexyloxy) cinnamate, (2,4-diaminophenyl) -4- (3-cholesteryloxy) cinnamate, (2,4-diaminophenyl) -4- (3-cholestanyloxy) cinnamate, (2 (2,4-diaminophenoxy) ethyl) cinnamate, (2 (2,4-diaminophen Noxy) ethyl) -4-methoxycinnamate, (2 (2,4-diaminophenoxy) ethyl) -3-methoxycinnamate, (2 (2,4-diaminophenoxy) ethyl) -4-trifluoromethylcinnamate , (2 (2,4-diaminophenoxy) ethyl) -4-trifluoromethoxycinnamate, (2 (2,4-diaminophenoxy) ethyl) -4- (n-hexyloxy) cinnamate, (2 (2, 4-diaminophenoxy) ethyl) -4- (3-cholesteryloxy) cinnamate, (2 (2,4-diaminophenoxy) ethyl) -4- (3-cholestanyloxy) cinnamate, (6 (2,4-diamino) Phenoxy) hexyl) cinnamate, (6 (2,4-diaminophenoxy) hexyl) -4-methoxycinnamate, 6 (2,4-diaminophenoxy) hexyl) -3-methoxycinnamate, (6 (2,4-diaminophenoxy) hexyl) -4-trifluoromethylcinnamate, (6 (2,4-diaminophenoxy) hexyl) ) -4-trifluoromethoxycinnamate, (6 (2,4-diaminophenoxy) hexyl) -4- (n-hexyloxy) cinnamate, (6 (2,4-diaminophenoxy) hexyl) -4- (3 -Cholesteryloxy) cinnamate, (6 (2,4-diaminophenoxy) hexyl) -4- (3-cholestanyloxy) cinnamate. Of these, more preferred compounds are 4-oryzanyloxy-1,3-diaminobenzene, 5-oryzanyloxycarbonyl-1,3-diaminobenzene, 5- (6-oryzanyloxyhexyloxycarbonyl) -1, 3-diaminobenzene, (6 (3,5-diaminobenzoyloxy) hexyl) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4-methoxycinnamate, (6 (3,5-diaminobenzoyloxy) ) Hexyl) -3-methoxycinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4-trifluoromethylcinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4-trifluoro Methoxycinnamate, (6 (3,5-diaminobenzoyloxy) he Syl) -4- (n-hexyloxy) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4- (3-cholesteryloxy) cinnamate, (6 (3,5-diaminobenzoyloxy) hexyl) -4- (3-cholestanyloxy) cinnamate can be mentioned, and particularly preferred is 5-oryzanyloxycarbonyl-1,3-diaminobenzene.

  Examples of the diamine compound having a conjugated enone structure include the compounds exemplified as the diamine compounds having a specific structure in Patent Document 4, Patent Document 6, Patent Document 7, and Patent Document 11, 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-cholestanyl Xyl) -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, 4- (3-cholesteryloxy)- '-(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-cholesteryl) Oxy) -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-cholestanyl) Oxy) -4 '-(6- (2,4-diaminophenoxy) hexyloxy) chalcone. Among these compounds, the compounds exemplified in Patent Document 11 can be mentioned as preferred ones, and particularly preferred are 6- (4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 6- (4′-fluoro-4-chalconyloxy) hexyloxy (2,4-diaminobenzene), 8- (4-chalconyloxy) octyloxy (2,4-diaminobenzene), and 8- (4 ′ -Fluoro-4-calconyloxy) octyloxy (2,4-diaminobenzene). These diamino compounds having a conjugated enone structure can be used alone or in combination of two or more.

  In the synthesis of the polyamic acid, a tetracarboxylic dianhydride containing a cinnamic acid structure and / or a conjugated enone structure is used in order to improve the properties of the polyamic acid and to provide functions such as pretilt angle expression or vertical alignment. In addition to the diamine compound, other tetracarboxylic dianhydrides and other diamine compounds not containing these structures can be used in combination.

  Examples of such other tetracarboxylic dianhydrides include, for example, “other tetracarboxylic dianhydrides” and “tetracarboxylic dianhydrides having a specific hydrophobic group” in [0039] to [0042] of Patent Document 13. Can be mentioned as examples. Of these, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -naphtho [1,2-c] -furan is preferable. 1,3-dione, 1,3,3a, 4,5,9b-hexahydro-5- (tetrahydro-2,5-dioxo-3-furanyl) -8-methyl-naphtho [1,2-c]- Furan-1,3-dione, 2,3,5-tricarboxycyclopentylacetic acid dianhydride, butanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride 1,2,3,4-cyclobutanetetracarboxylic dianhydride, pyromellitic dianhydride, 3,3 ′, 4,4′-biphenylsulfone tetracarboxylic dianhydride, 1,4,5 8-Naphthalenetetra Rubonic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3 ′, 4,4′-biphenyl ether tetracarboxylic dianhydride and the following formulas (1) to (4) The compound represented by these can be mentioned. These can be used alone or in combination of two or more.

  Moreover, as another diamine compound, the compound illustrated as "another diamine compound" and "diamine compound which has a specific hydrophobic group" in [0044]-[0046] of patent document 13, for example can be mentioned. Of these, preferred are p-phenylenediamine, 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene, 2,7-diaminofluorene, 4,4′-diaminodiphenyl ether, 4,4′- (P-phenyleneisopropylidene) bisaniline, 2,2-bis [4- (4-aminophenoxy) phenyl] hexafluoropropane, 2,2-bis (4-aminophenyl) hexafluoropropane, 2,2′-bis [4- (4-Amino-2-trifluoromethylphenoxy) phenyl] hexafluoropropane, 4,4′-diamino-2,2′-bis (trifluoromethyl) biphenyl, 4,4′-bis [(4 -Amino-2-trifluoromethyl) phenoxy] -octafluorobiphenyl, 1-hexadecanoxy -2,4-diaminobenzene, 1-octadecanoxy-2,4-diaminobenzene, 1-cholesteryloxy-2,4-diaminobenzene, 1-cholestanyloxy-2,4-diaminobenzene, hexadecanoxy (3,5- Diaminobenzoyl), octadecanoxy (3,5-diaminobenzoyl), cholesteryloxy (3,5-diaminobenzoyl), and cholestanyloxy (3,5-diaminobenzoyl), and the following formulas (5) and (6) The compound represented by these can be mentioned. These can be used alone or in combination of two or more.

The ratio of the tetracarboxylic dianhydride and the diamine compound used for the polyamic acid synthesis reaction is such that the acid anhydride group of the tetracarboxylic dianhydride is 0.1 relative to 1 equivalent of the amino group contained in the diamine compound. A ratio of 2 to 2 equivalents is preferable, and a ratio of 0.3 to 1.2 equivalents is more preferable.
The synthetic reaction of polyamic acid is preferably carried out in an organic solvent under a temperature condition of -20 to 150 ° C, more preferably 0 to 100 ° C. Here, the organic solvent is not particularly limited as long as it can dissolve the synthesized polyamic acid. For example, N-methyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, N, Aprotic polar solvents such as N-dimethylimidazolidinone, dimethyl sulfoxide, γ-butyrolactone, tetramethylurea, hexamethylphosphortriamide; and phenolic solvents such as m-cresol, xylenol, phenol, halogenated phenol Can do. The amount of organic solvent used (a) is preferably such that the total amount (b) of tetracarboxylic dianhydride and diamine compound is 0.1 to 30% by weight based on the total amount (a + b) of the reaction solution. It is preferable that the amount is small.

  For the organic solvent, alcohols, ketones, esters, ethers, halogenated hydrocarbons, hydrocarbons, etc., which are poor solvents for polyamic acid, are used in combination as long as the polyamic acid to be produced does not precipitate. be able to. Specific examples of the poor solvent include, for example, methyl alcohol, ethyl alcohol, isopropyl alcohol, cyclohexanol, ethylene glycol, propylene glycol, 1,4-butanediol, triethylene glycol, ethylene glycol monomethyl ether, ethyl lactate, butyl lactate, Acetone, 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- Chill ether, 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, tetrahydrofuran, dichloromethane, 1,2-dichloroethane, 1 , 4-dichlorobutane, trichloroethane, chlorobenzene, o-dichlorobenzene, hexane, heptane, octane, benzene, toluene, xylene and the like.

  As described above, a reaction solution obtained by dissolving polyamic acid is obtained. The reaction solution is poured into a large amount of poor solvent to obtain a precipitate, and the precipitate is dried under reduced pressure to obtain a polyamic acid. Moreover, this product can be refine | purified by performing the process of dissolving again in an organic solvent, and making it precipitate with a poor solvent once or several times.

The polyimide used in the present invention can be prepared by dehydrating and ring-closing the polyamic acid. The polyamic acid is dehydrated and closed by (i) a method of heating the polyamic acid, or (ii) dissolving the polyamic acid in an organic solvent, adding a dehydrating agent and a dehydrating ring-closing catalyst to this solution, and heating as necessary. By the method.
The reaction temperature in the method of heating the polyamic acid (i) 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 imidized polymer (polyamic acid) obtained may decrease.

  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. The amount of the dehydrating agent used is preferably 0.01 to 20 mol with respect to 1 mol of the polyamic acid repeating unit. 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 closure catalyst used is preferably 0.01 to 10 moles per mole of the dehydrating agent used. In addition, as an organic solvent used for dehydration ring closure reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned. And reaction temperature of dehydration ring closure reaction becomes like this. Preferably it is 0-180 degreeC, More preferably, it is 10-150 degreeC. Moreover, a polyimide can be refine | purified by performing operation similar to the purification method of a polyamic acid with respect to the reaction solution obtained in this way.

Examples of the tetracarboxylic dianhydride and diamine compound used for the synthesis of the polyamic acid ester include the compounds already exemplified as the tetracarboxylic dianhydride and diamine compound. At least one of the tetracarboxylic dianhydride and diamine compound, as used herein, Ru Monodea containing cinnamic acid structure and / or conjugated enone structure.

Examples of organic halides having a cinnamic acid structure include 2-bromoethyl cinnamate, 6-bromohexyl cinnamate, 2-bromoethyl (4-methoxycinnamate), and 6-bromohexyl (4-methoxycinnamate). 2-bromoethyl (3-methoxycinnamate), 6-bromohexyl (3-methoxycinnamate), 2-bromoethyl (4-fluorocinnamate), 6-bromohexyl (4-fluorocinnamate), 2-bromoethyl (4-trifluoromethylcinnamate), 6-bromohexyl (4-trifluoromethylcinnamate), 2-bromoethyl (4-trifluoromethoxycinnamate), 6-bromohexyl (4-trifluoromethoxycinnamate) Methyl (4- (2-bromoethoxy) silane Nameto), ethyl (4- (2-bromoethoxy) cinnamate), phenyl (4- (2-bromoethoxy) cinnamate), 3- cholesteryl (4- (2-bromoethoxy) cinnamate), 3- cholestanyl (
4- (2-bromoethoxy) cinnamate), methyl (4- (6-bromohexyloxy) cinnamate), ethyl (4- (6-bromohexyloxy) cinnamate), phenyl (4- (2-bromoethoxy) cinnamate) ), 3-cholesteryl) (4- (6-bromohexyloxy) cinnamate), 3-cholestanyl (4- (6-bromohexyloxy) cinnamate,), 1-bromo-2- (oryzanyloxy) ethane, 1 Mention may be made of bromides such as bromo-6- (oryzanyloxy) hexane and the corresponding fluorides, chlorides and iodides. These organic halides can be used alone or in combination of two or more.
Of these organic halides, bromides and iodides are preferred and bromides are particularly preferred because of their high reactivity.

  Examples of the organic halide having a conjugated enone structure include, for example, compounds exemplified as a halide having a specific group in Patent Document 12, 4- (2-bromoethoxy) -4 ′-(3-cholesteryloxy) chalcone, 4 -(2-bromoethoxy) -4 '-(3-cholestanyloxy) chalcone, 4- (6-bromohexyloxy) -4' (cholesteryloxy) chalcone and 4- (6-bromohexyloxy)- Mention may be made of 4 ′-(3-cholestanyloxy) chalcone. Of these, 1-bromo-6- (4-chalconyloxy) -hexane is particularly preferred.

As the alcohol having a cinnamic acid structure and the alcohol having a conjugated enone structure, the halogen atom of the halide having the cinnamic acid structure and the halide having the conjugated enone structure, respectively, exemplified above, is a hydroxyl group. A compound substituted with can be exemplified. These can be used alone or in combination of two or more.
Examples of phenols having a cinnamic acid structure include methyl 4-hydroxycinnamate, ethyl 4-hydroxycinnamate, phenyl 4-hydroxycinnamate, cetyl 4-hydroxycinnamate, and 4-hydroxy cinnamic acid. Stearyl acid, 4-hydroxycinnamic acid-3-cholesteryl, 4-hydroxycinnamic acid-3-cholestanyl, methyl ferulate, ethyl ferrate, phenyl ferrate, cetyl ferulate, stearyl ferulate, ferulic acid-3- Mention may be made of cholesteryl, ferulic acid-3-cholestanyl and γ-oryzanol. Among these, γ-oryzanol can be mentioned as a preferable one. These can be used alone or in combination of two or more.

  Examples of phenols having a conjugated enone structure include 4′-hydroxychalcone, 4-hydroxychalcone, 4′-hydroxy-4- (3-cholestanyloxy) chalcone, 4′-hydroxy-4- (3-cholesteryl). Oxy) chalcone, 4′-hydroxy-4- (3-cholestanyloxy) chalcone, 4-hydroxy-4 ′-(3-cholesteryloxy) chalcone and 4-hydroxy-4 ′-(3-cholestanyloxy) chalcone Can be mentioned. These can be used alone or in combination of two or more.

In the synthesis of polyamic acid ester, in order to improve its properties and to provide functions such as pretilt angle expression or vertical alignment, organic halides and alcohols that do not contain a cinnamic acid structure and / or a conjugated enone structure Or phenols can also be used. (Acid anhydride or diamine, because that contain cinnamic acid structure and conjugated enone structure, so may not be included in the halide-alcohol phenols.)
Such other organic halides include, for example, cetyl bromide, stearyl bromide, methyl bromide, ethyl bromide, propyl bromide, cetyl chloride, stearyl chloride, methyl chloride, ethyl chloride, propyl chloride, and 1,1 , 1-trifluoro-2-iodoethane.
Of these, stearyl bromide, 1,1,1-trifluoro-2-iodoethane, acetyl chloride and stearoyl chloride are preferred. These can be used alone or in combination of two or more.

Examples of other alcohols include cetyl alcohol, stearyl alcohol, 1,1,1-trifluoroethanol, methanol, ethanol, isopropanol, and normal propanol.
Of these, cetyl alcohol, stearyl alcohol, and 1,1,1-trifluoroethanol are preferred. These can be used alone or in combination of two or more.
Examples of other phenols include phenol, cresol, 4-cetyloxyphenol, 4-cetylphenol, 4-stearyloxyphenol, 4-stearylphenol and 4-trifluoromethylphenol. These can be used alone or in combination of two or more.

The polyamic acid ester is obtained by polycondensation of the tetracarboxylic dianhydride component and the diamine component to obtain a polyamic acid, and then in the presence of a catalyst, if necessary, with an organic halide, alcohol or phenol. It is obtained by reacting.
As a method for synthesizing the polyamic acid used for synthesizing the polyamic acid ester, the same method as the method for synthesizing the polyamic acid which is the specific polymer described above can be used.

Examples of the catalyst used when the polyamic acid and the organic halide are reacted include lithium hydroxide, sodium hydroxide, potassium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, sodium methoxide, potassium methoxide, sodium ethoxy. And base catalysts such as potassium, ethoxide, sodium propoxide, potassium propoxide, sodium butoxide, potassium butoxide, trimethylamine, triethylamine and pyridine. Moreover, as an organic solvent used for this esterification reaction, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned.
Examples of the catalyst used when reacting the polyamic acid with alcohols or phenols include dehydration catalysts such as dicyclohexylcarbodiimide and methyl chloroformate. These dehydration catalysts can be used in combination with a promoter such as dimethylaminopyridine, if necessary.
The synthesis reaction of the polyamic acid ester is preferably performed in an organic solvent under a temperature condition of 0 to 200 ° C, more preferably 50 to 150 ° C. Moreover, a polyimide can be refine | purified by performing operation similar to the purification method of a polyamic acid with respect to the reaction solution obtained in this way.

Solvent The liquid crystal aligning agent of the present invention comprises a solution containing a polymer having a cinnamic acid structure and / or a conjugated enone structure. The solvent used at this time is not particularly limited as long as it is an organic solvent capable of dissolving the polymer. As such a solvent, the organic solvent illustrated as what is used for the synthesis | combination of a polyamic acid can be mentioned, for example. These can be used alone or in combination of two or more. Moreover, the poor solvent illustrated as what is used for the synthesis | combination of a polyamic acid can also be used together.

Other Additives The liquid crystal aligning agent of the present invention can contain a polymer having no specific structure in order to improve solution properties and electrical properties. Examples of such a polymer include polyamic acid, polyimide, polyamic acid ester, polyester, polyamide, polysiloxane, cellulose derivative, polyacetal, polystyrene derivative, poly (styrene-phenylmaleimide) derivative, poly (meth) acrylate, and the like. However, polyamic acid is preferable from the viewpoint of heat resistance and electrical characteristics. The ratio of the polymer having no specific structure to the total polymer contained in the liquid crystal aligning agent is preferably 0 to 99% by weight, more preferably 10 to 90% by weight, and particularly preferably 50 to 90% by weight. .

Moreover, the liquid crystal aligning agent of this invention can also contain various thermosetting crosslinking agents for stabilization of a pretilt angle and a coating-film intensity | strength improvement. As the thermosetting crosslinking agent, a polyfunctional epoxy-containing compound is effective, and bisphenol A type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, cyclic aliphatic epoxy resin, glycidyl ester type epoxy resin, glycidyl diamine. Epoxy resins, heterocyclic epoxy resins, epoxy group-containing acrylic resins, and the like can be used. Examples of commercially available products include Epolite 400E and 3002 (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), Epicoat 828 and 152, and Epoxy Novolak 180S (manufactured by Yuka Shell Epoxy Co., Ltd.). The content of the thermosetting cross-linking agent is preferably 0 to 80% by weight, more preferably 5 to 50% by weight, and 10 to 40% by weight with respect to 100 parts by weight of the total polymer contained in the liquid crystal aligning agent. Particularly preferred.
Furthermore, when using the above-mentioned polyfunctional epoxy-containing compound, a base catalyst such as 1-benzyl-2-methylimidazole can be added for the purpose of efficiently causing a crosslinking reaction.

  Moreover, the liquid crystal aligning agent of this invention can contain a functional silane containing compound for the purpose of improving adhesiveness with a board | substrate. Examples of the functional silane-containing compound include 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 2-aminopropyltrimethoxysilane, 2-aminopropyltriethoxysilane, and N- (2-aminoethyl). -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropylmethyldimethoxysilane, 3-ureidopropyltrimethoxysilane, 3-ureidopropyltriethoxysilane, N-ethoxycarbonyl-3-amino Propyltrimethoxysilane, N-ethoxycarbonyl-3-aminopropyltriethoxysilane, N-triethoxysilylpropyltriethylenetriamine, N-trimethoxysilylpropyltriethylenetriamine, 10-trimethoxyylsilyl-1 4,7-triazadecane, 10-triethoxysilyl-1,4,7-triazadecane, 9-trimethoxysilyl-3,6-diazanonyl acetate, 9-triethoxysilyl-3,6-diazanonyl acetate, N-benzyl-3-aminopropyltrimethoxysilane, N-benzyl-3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-3-aminopropyltriethoxysilane, N- Bis (oxyethylene) -3-aminopropyltrimethoxysilane, N-bis (oxyethylene) -3-aminopropyltriethoxysilane, and the like, and tetracarboxylic acid described in JP-A-63-291922 Examples include reaction products of dianhydrides and amino group-containing silane compounds. It is possible.

Liquid crystal alignment film As a method of forming a liquid crystal alignment film using the liquid crystal aligning agent of this invention, the following method is mentioned, for example. First, the liquid crystal aligning agent of this invention is apply | coated by the roll coater method, the spinner method, the printing method etc. on the transparent conductive film side of the board | substrate with which the transparent conductive film was provided, for example, it heats at the temperature of 40-200 degreeC. To form a coating film. The film thickness of the coating film is preferably 0.001 to 1 μm, more preferably 0.005 to 0.5 μm, as a solid content.
As the substrate, for example, a glass such as float glass or soda glass, or a transparent substrate made of a plastic film such as polyethylene terephthalate, polybutylene terephthalate, polyethersulfone or polycarbonate can be used.
As the transparent conductive film, a NESA film made of SnO ₂ , an ITO film made of In ₂ O ₃ —SnO _2, or the like can be used. For patterning these transparent conductive films, a photo-etching method, a method using a mask in advance, or the like is used.
When applying the liquid crystal aligning agent, a functional silane-containing compound or titanate may be applied in advance on the substrate and the transparent conductive film in order to further improve the adhesion between the substrate and the transparent conductive film and the coating film. it can.

Next, the coating film is irradiated with linearly polarized light, partially polarized radiation, or non-polarized radiation, and further subjected to heat treatment at a temperature of 150 to 250 ° C. to impart liquid crystal alignment ability. As radiation, ultraviolet rays and visible rays having a wavelength of 150 nm to 800 nm can be used, but ultraviolet rays having a wavelength of 200 nm 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.
As the light source, for example, a low-pressure mercury lamp, a high-pressure mercury lamp, a deuterium lamp, a metal halide lamp, an argon resonance lamp, a xenon lamp, an excimer laser, or the like can be used. 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 “pretilt angle” in the present invention represents an angle of inclination of liquid crystal molecules from a direction parallel to the substrate surface.

Liquid crystal display element The liquid crystal display element formed using the liquid crystal aligning agent of this invention is manufactured as follows. A substrate on which the liquid crystal alignment film is formed is prepared, the two sheets are opposed so that the polarization direction of the linearly polarized radiation irradiated on the liquid crystal alignment film is a predetermined angle, and the periphery between the substrates is sealed with a sealant. The liquid crystal cell is configured by sealing, filling the liquid crystal, and sealing the filling hole. Next, it is desirable that the liquid crystal cell is heated to a temperature at which the liquid crystal used takes an isotropic phase, and then cooled to room temperature to remove the flow alignment at the time of injection.

Then, the polarizing plates are bonded to both surfaces so that the polarization directions of the polarizing plates form a predetermined angle with the alignment axis of the liquid crystal alignment film of the substrate, respectively, thereby obtaining a liquid crystal display element. When the liquid crystal alignment film is horizontally aligned, the angle between the polarization directions of the irradiated linearly polarized radiation and the angle between each substrate and the polarizing plate are adjusted on the two substrates on which the liquid crystal alignment film is formed. Thus, a liquid crystal display element having a TN type or STN type liquid crystal cell can be arbitrarily obtained. On the other hand, in the case where the liquid crystal alignment film is vertically aligned, the cell is configured so that the directions of easy alignment axes of the two substrates on which the liquid crystal alignment film is formed are parallel, A liquid crystal display element having a vertical alignment type liquid crystal cell can be obtained by bonding the polarization directions so as to form an angle of 45 degrees with the easy alignment axis.
As the sealing agent, 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, a nematic liquid crystal, a smectic liquid crystal, or the like can be used. In the case of the TN liquid crystal cell and the STN liquid crystal cell, those having positive dielectric anisotropy for forming a nematic liquid crystal are preferable. For example, biphenyl liquid crystal, phenylcyclohexane liquid crystal, ester liquid crystal, terphenyl liquid crystal, biphenyl A cyclohexane liquid crystal, a pyrimidine liquid crystal, a dioxane liquid crystal, a bicyclooctane liquid crystal, a cubane liquid crystal, or the like is used. Further, for example, a cholesteric liquid crystal such as cholestyl chloride, cholesteryl nonate, cholesteryl carbonate or a chiral agent such as that sold under the trade name C-15, CB-15 (manufactured by Merck) is added to the liquid crystal. It can also be used. Furthermore, a ferroelectric liquid crystal such as p-decyloxybenzylidene-p-amino-2-methylbutylcinnamate can also be used. In the case of a vertical alignment type liquid crystal cell, those having a negative dielectric anisotropy for forming a nematic type liquid crystal are preferable. For example, dicyanobenzene liquid crystal, pyridazine liquid crystal, Schiff base liquid crystal, azoxy liquid crystal, biphenyl liquid crystal Phenylcyclohexane-based liquid crystal or the like is used.
The polarizing plate used outside the liquid crystal cell is a polarizing plate composed of a polarizing film called an H film that absorbs iodine while stretching and aligning polyvinyl alcohol, and a cellulose acetate protective film, or a polarizing film composed of the H film itself. A board etc. 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 pretilt angle, voltage holding ratio, and retardation in Examples and Comparative Examples were evaluated by the following methods.

[Pretilt angle]
T.A. J. et al. Scheffer et. al. J. et al. Appl. Phys. vo. 19, p. In accordance with the method described in 2013 (1980), it was measured by a crystal rotation method using a He—Ne laser beam.

[Orientation of liquid crystal]
The presence / absence of an abnormal domain when the voltage was turned on / off (applied / released) to the liquid crystal display element was observed with a polarizing microscope, and the case where there was no abnormal domain was determined as “good”.

[Voltage holding ratio]
A voltage of 5 V was applied to the liquid crystal display element with an application time of 60 microseconds and a span of 167 milliseconds, and then the voltage holding ratio after 167 milliseconds from the release of application was measured. The measuring apparatus used was VHR-1 manufactured by Toyo Corporation. The case where the voltage holding ratio was 90% or more was judged as good, and the other cases were judged as bad.

Synthesis example 1
Polymerization of polyamic acid 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride, 38.4 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate), 6 -(4-Calconyloxy) hexyloxy (2,4-diaminobenzene) 0.05 mol (21.5 g) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours. . The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried at 40 ° C. under reduced pressure for 15 hours to obtain 77 g of a polyamic acid (hereinafter referred to as “polymer 1a”) having a cinnamic acid structure and a conjugated enone structure.
The 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) was synthesized by reacting natural γ-oryzanol with 2-chloroethanol to synthesize γ-oryzanyloxyethanol. Prepared by reacting with 5-dinitrobenzoyl halide, which was then reduced.

Imidization reaction Polymer 1a 41.2g, N-methyl-2-pyrrolidone 760g, pyridine 7.9g and acetic anhydride 10.2g were added, and imidation reaction was carried out at 120 degreeC for 4 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 35 g of a polyimide having a cinnamic acid structure and a conjugated enone structure (hereinafter referred to as “polymer 1b”).

Synthesis example 2
Polymerization of polyamic acid Synthesis Example 1 except that 37.0 g of oryzanyloxy (3,5-diaminobenzoate) was used instead of 38.4 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) Similarly, 68 g of polyamic acid (hereinafter referred to as “polymer 2a”) having a cinnamic acid structure and a conjugated enone structure was obtained.
The oryzanyloxy (3,5-diaminobenzoate) was produced by reacting natural γ-oryzanol with 3,5-dinitrobenzoyl halide and then reducing it.

A polyimide having a cinnamic acid structure and a conjugated enone structure (hereinafter referred to as “polymer 2b”) was prepared in the same manner as in Synthesis Example 1, except that 40.5 g of polymer 2a was used instead of 41.2 g of imidation reaction polymer 1a. 34 g).

Synthesis example 3
Polymerization of polyamic acid 38.4 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) and 0.05 mol of 6- (4-calconyloxy) hexyloxy (2,4-diaminobenzene) (21 1) g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) and 0.025 mol of 6- (4-chalconyloxy) hexyloxy (2,4-diaminobenzene) (10.8 g) and 0.025 mol (2.54 g) of p-phenylenediamine, and a polyamic acid having a cinnamic acid structure and a conjugated enone structure (hereinafter referred to as “polymer”) in the same manner as in Synthesis Example 1. 3g ") was obtained.

A polyimide having a cinnamic acid structure and a conjugated enone structure (hereinafter referred to as “polymer 3b”) was prepared in the same manner as in Synthesis Example 1 except that 36.6 g of polymer 3a was used instead of 41.2 g of imidation reaction polymer 1a. 31g) was obtained.

Synthesis example 4
Polymerization of polyamic acid 0.13 mol (22.4 g) of 2,3,5-tricarboxycyclopentyl acetic acid dianhydride and 78.1 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) -Methyl-2-pyrrolidone was dissolved in 400 g and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 99 g of a polyamic acid having a cinnamic acid structure (hereinafter referred to as “polymer 4a”).

Imidization reaction polymer 4a 20.1 g, was added N- methyl-2-pyrrolidone 380 g, pyridine 3.2g and acetic anhydride 4.08 g, was 4 hours imidization reaction at 120 ° C.. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 19 g of a polyimide having a cinnamic acid structure (hereinafter referred to as “polymer 4b”).

Synthesis example 5
Polymerization of polyamic acid Oryzanyl (2- (2,4-diaminophenoxy) acetate) synthesized from natural γ-oryzanol instead of 78.1 g of 2- (oryzanyloxy) ethyl (3,5-diaminobenzoate) A polyamic acid having a cinnamic acid structure (hereinafter referred to as “polymer 5a”) was prepared in the same manner as in Synthesis Example 3 except that 38.4 g and 0.05 mol (5.4 g) of p-phenylenediamine were used in combination. 70 g was obtained.

13 g of polyimide having a cinnamic acid structure (hereinafter referred to as “polymer 5b”) in the same manner as in Synthesis Example 4 except that 14.3 g of polymer 5a was used instead of 20.1 g of imidation reaction polymer 4a. Got.

Synthesis Example 6
Polymerization of polyamic acid In the same manner as in Synthesis Example 5 except that 37.0 g of oryzanyloxy (3,5-diaminobenzoate) was used instead of 38.4 g of oryzanyl (2 (2,4-diaminophenoxy) acetate). 69 g of polyamic acid (hereinafter referred to as “polymer 6a”) was obtained.

13 g of polyimide having a cinnamic acid structure (hereinafter referred to as “polymer 6b”) in the same manner as in Synthesis Example 4 except that 14.0 g of polymer 6a was used instead of 20.1 g of imidation reaction polymer 4a. Got.

Synthesis example 7
Polymerization of polyamic acid 0.1 mol (21.8 g) of pyromellitic dianhydride, 0.05 mol (21.5 g) of 6- (4-chalconyloxy) hexyloxy (2,4-diaminobenzene) and p -Phenylenediamine 0.05 mol (5.4 g) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at room temperature for 6 hours.

  The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 47 g of a polyamic acid having a conjugated enone structure (hereinafter referred to as “polymer 7a”).

Synthesis Example 8
Polymerization of polyamic acid 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 0.05 mol of 6- (4-calconyloxy) hexyloxy (2,4-diaminobenzene) (21.5 g) and 0.05 mol (5.4 g) of p-phenylenediamine were dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at 60 ° C. for 6 hours.
The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 48 g of a polyamic acid having a conjugated enone structure (hereinafter referred to as “polymer 8a”).
Imidation reaction 300 g of N-methyl-2-pyrrolidone, 8.2 g of pyridine and 9.6 g of acetic anhydride were added to 20.0 g of the obtained polymer 8a, and an imidization reaction was performed at 120 ° C. for 4 hours.
The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 15 g of a polyimide having a conjugated enone structure (hereinafter referred to as “polymer 8b”).

Synthesis Example 9
Polymerization of polyamic acid 0.1 mol (22.4 g) of 2,3,5-tricarboxycyclopentylacetic acid dianhydride and 0.1 mol (10.8 g) of p-phenylenediamine were added to 300 g of N-methyl-2-pyrrolidone. It was dissolved and reacted at 60 ° C. for 6 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 27.4 g of polyamic acid (hereinafter referred to as “polymer Aa”).

Imidization reaction To 20.0 g of the polymer Aa, 380 g of N-methyl-2-pyrrolidone, 9.5 g of pyridine and 12.3 g of acetic anhydride were added, and an imidization reaction was performed at 120 ° C. for 4 hours. The reaction mixture was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure for 15 hours to obtain 15.3 g of polyimide (hereinafter referred to as “polymer Ab”).

Synthesis Example 10
Polymerization of polyamic acid 0.1 mole (19.6 g) of 1,2,3,4-cyclobutanetetracarboxylic dianhydride and 0.1 mole of 2,2′-dimethyl-4,4′-diaminobiphenyl (21. 2 g) was dissolved in 400 g of N-methyl-2-pyrrolidone and reacted at room temperature for 3 hours. The reaction solution was then poured into a large excess of methanol to precipitate the reaction product. Thereafter, it was washed with methanol and dried under reduced pressure at 40 ° C. for 15 hours to obtain 40 g of polyamic acid (hereinafter referred to as “polymer Ba”).

Reference Example The polymer Ab obtained in Synthesis Example 9 was dissolved in N-methyl-2-pyrrolidone to obtain a solution having a solid concentration of 2.5% by weight, and this solution was filtered through a filter having a pore size of 1 μm to obtain liquid crystal alignment. An agent (hereinafter referred to as “liquid crystal aligning agent P”) was prepared. This solution was applied onto the transparent electrode surface of the glass substrate with a transparent electrode made of an ITO film using a spinner so that the film thickness became 0.1 μm, and dried at 180 ° C. for 1 hour to form a thin film. The thin film was rubbed at a rotational speed of 500 rpm and a stage moving speed of 1 cm / sec using a rubbing machine having a roll around which a nylon cloth was wound. Next, with respect to the pair of substrates subjected to the rubbing treatment, an epoxy resin adhesive containing aluminum oxide spheres having a diameter of 5.5 μm is screen-printed on the surface on which the liquid crystal alignment film is formed, and then the rubbing direction becomes antiparallel. The substrate was superposed and pressure-bonded, and the adhesive was thermally cured at 150 ° C. for 1 hour. Next, a nematic liquid crystal (ZLI-1565 manufactured by Merck & Co., Inc.) was filled between the pair of substrates from the liquid crystal injection port, and then the liquid crystal injection port was sealed with an epoxy adhesive. Furthermore, in order to remove the flow alignment at the time of liquid crystal injection, this was heated at 150 ° C. and then gradually cooled to room temperature. Next, a polarizing plate was bonded to both sides of the substrate so that the polarization directions were orthogonal to each other and at an angle of 45 degrees with the rubbing direction of the liquid crystal alignment film. The orientation of was good. When a voltage of 5 V was applied, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage. Further, the pretilt angle in this liquid crystal cell was 0.5 °, and the voltage holding ratio was judged to be good.

Examples 1-4
Polymers 1a and 1b to 2b obtained in Synthesis Examples 1 and 2 were dissolved in a mixed solvent of N-methyl-2-pyrrolidone / butyl cellosolve (60/40) (weight ratio) with the composition shown in Table 1 to form a solid. A solution having a partial concentration of 2.5% by weight was prepared, and this solution was filtered through a filter having a pore size of 1 μm to prepare liquid crystal alignment agents B-1 to B-4.

The additives in Table 1 are as follows.
E-1: N, N, N ′, N′-Tetraglycidyl-4,4′-diaminodiphenylphenylmethane E-2: Bisphenol A diglycidyl ether Next, a liquid crystal aligning agent B- A thin film was formed on the substrate in the same manner as in the reference example except that 1 to B-4 was used. The thin film surface was irradiated with polarized ultraviolet rays including emission lines with wavelengths of 313 nm and 365 nm for 50 seconds from a direction inclined by 40 degrees from the substrate normal line using a Hg-Xe lamp, a shortcut filter, and a Grand Taylor prism. At this time, the illuminance at wavelengths of 313 nm and 365 nm on the irradiated surface was ² mW / cm ² and 5 mW / cm ² , respectively.
Next, in the pasting of the substrate and the polarizing plate, instead of the rubbing direction, according to the projection direction of the optical axis of the ultraviolet rays onto the substrate surface, the liquid crystal is replaced with Merck MLC- A liquid crystal display device was produced in the same manner as in the reference example except that 6608 was used, and the vertical alignment of the liquid crystal was good. When a voltage was applied under the same conditions as in Reference Example 1, a change in brightness of the liquid crystal display element was observed in response to ON / OFF of the applied voltage in any liquid crystal display element.
Table 2 shows the determination of the pretilt angle and voltage holding ratio of these liquid crystal display elements.

Examples 5-8
The polymers 3a and 3b obtained in Synthesis Example 3 and the polymers Aa and Ba obtained in Synthesis Examples 9 to 10 were mixed with N-methyl-2-pyrrolidone / butyl cellosolve (60 / 40) (weight ratio) is dissolved in a mixed solvent to obtain a solution having a solid content concentration of 2.5% by weight, and this solution is filtered through a filter having a pore size of 1 μm to prepare liquid crystal alignment agents B-5 to B-8. did.

However, the symbols of additives in Table 3 are the same as those in Table 1.
Next, liquid crystal aligning agents B-5 to B-8 were used in place of liquid crystal aligning agent B-1, and the liquid crystal was replaced with Merck MLC-6221 instead of Merck ZLI-6608. A liquid crystal display device was produced in the same manner as in Example 1. In any liquid crystal display element, the liquid crystal exhibited good horizontal alignment. When a voltage is applied under the same conditions as in the reference example, a change in brightness of the liquid crystal display element is observed in response to ON / OFF of the applied voltage in any liquid crystal display element, and the liquid crystal orientation during voltage application is good Met.
Table 4 shows the determination of the pretilt angle and voltage holding ratio of these liquid crystal display elements.

Examples 9-11
The polymer 4b obtained in Synthesis Example 4 and the polymer 8b obtained in Synthesis Example 8 were mixed with N-methyl-2-pyrrolidone / butyl cellosolve (60/40) (weight ratio) with the composition shown in Table 5. It was dissolved in a solvent to obtain a solution having a solid content concentration of 2.5% by weight, and this solution was filtered through a filter having a pore size of 1 μm to prepare liquid crystal aligning agents B-9 to B-11.

However, the additive symbols in Table 5 are the same as those in Table 1.
Next, a liquid crystal display device was produced in the same manner as in Example 1 except that the liquid crystal aligning agents B-9 to B-11 were used instead of the liquid crystal aligning agent B-1. In any liquid crystal display element, the liquid crystal showed good vertical alignment. When a voltage is applied under the same conditions as in Reference Example 1, a change in brightness of the liquid crystal display element is observed in response to ON / OFF of the applied voltage in any liquid crystal display element, and the liquid crystal orientation during voltage application is It was good.
Table 6 shows the determination of the pretilt angle and voltage holding ratio of these liquid crystal display elements.

Examples 12-15
Polymers 5a and 6b obtained in Synthesis Examples 5 to 6, Polymers 7a and 8b obtained in Synthesis Examples 7 to 8, and Polymers Aa and Ba obtained in Synthesis Examples 9 to 10, The composition shown in Table 7 was dissolved in a mixed solvent of N-methyl-2-pyrrolidone / butyl cellosolve (60/40) (weight ratio) to obtain a solution having a solid content concentration of 2.5% by weight. This solution was a filter having a pore size of 1 μm. To prepare liquid crystal aligning agents B-12 to B-15.

However, the additive symbols in Table 7 are the same as those in Table 1.
Next, a liquid crystal display device was produced in the same manner as in Example 5 except that the liquid crystal aligning agents B-12 to B-15 were used in place of the liquid crystal aligning agent B-5. In any liquid crystal display element, the liquid crystal exhibited good horizontal alignment. When a voltage is applied under the same conditions as in the reference example, a change in brightness of the liquid crystal display element is observed in response to ON / OFF of the applied voltage in any liquid crystal display element, and the liquid crystal orientation during voltage application is good Met.
Table 8 shows the determination of the pretilt angle and voltage holding ratio of these liquid crystal display elements.

Comparative Example 1
A liquid crystal display device was produced in the same manner as in Example 5 except that the liquid crystal aligning agent P was used in place of the liquid crystal aligning agent B-5, and no liquid crystal alignment was observed.

Claims (7)

Formula (I) and at least one cinnamic acid structure selected from the group consisting of structures represented by the respective (II),

(Wherein P ¹ and P ² are an aromatic group or an unsaturated heterocyclic group optionally substituted with a halogen or an organic group, provided that P ¹ is a divalent group, and P ² is a trivalent group. D ¹ and D ² are oxygen atoms or NR (where R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), and R ¹ , R ² , R ³ and R ⁴ are And independently of each other, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
And at least one conjugated enone structure selected from the group consisting of structures represented by the following formulas (III), (IV) and (V),

(Wherein P ³ , P ⁴ , P ⁵ , Q ³ , Q ⁴ and Q ⁵ are each independently an aromatic group or an unsaturated heterocyclic group which may be substituted with a halogen or an organic group. Where P ³ , P ⁵ , Q ³ and Q ⁴ are divalent groups, and P ⁴ and Q ⁵ are trivalent groups, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ And R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
The A liquid crystal alignment agent you containing both have polymer,
The polymer is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid or a polyamic acid ester obtained from the polyamic acid,
The liquid crystal aligning agent, wherein the compound having a cinnamic acid structure and the compound having a conjugated enone structure are used as at least one component of the tetracarboxylic dianhydride and the diamine compound . Under following formula (I) and (II) at least one inter-connected by disulfide bonds cinnamic acid structure selected from the group consisting of the structures represented by the respective

(Wherein P ¹ and P ² are an aromatic group or an unsaturated heterocyclic group optionally substituted with a halogen or an organic group, provided that P ¹ is a divalent group, and P ² is a trivalent group. D ¹ and D ² are oxygen atoms or NR (where R represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms), and R ¹ , R ² , R ³ and R ⁴ are And independently of each other, a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
A polymer having a lower following formula (III), (IV), and at least one conjugated enone structure selected from the group consisting of structures represented by the respective (V)

(Wherein P ³ , P ⁴ , P ⁵ , Q ³ , Q ⁴ and Q ⁵ are each independently an aromatic group or an unsaturated heterocyclic group which may be substituted with a halogen or an organic group. Where P ³ , P ⁵ , Q ³ and Q ⁴ are divalent groups, and P ⁴ and Q ⁵ are trivalent groups, R ⁵ , R ⁶ , R ⁷ , R ⁸ , R ⁹ And R ¹⁰ are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms.)
A liquid crystal aligning agent containing a polymer having
The polymer having a cinnamic acid structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid. However,
A compound having a cinnamic acid structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound; and
The polymer having the conjugated enone structure is a polyamic acid obtained by reacting a tetracarboxylic dianhydride and a diamine compound, a polyimide obtained from the polyamic acid, or a polyamic acid ester obtained from the polyamic acid, However,
The liquid crystal aligning agent, wherein a compound having the conjugated enone structure is used as at least one component of the tetracarboxylic dianhydride and the diamine compound. The liquid crystal aligning agent according to claim 1, wherein the diamine compound includes a compound having a cinnamic acid structure and a compound having the conjugated enone structure . A compound having a cinnamic acid structure is used as the diamine compound which is a raw material of the polymer having a cinnamic acid structure; and
The liquid crystal aligning agent of Claim 2 by which the compound which has the said conjugated enone structure is used for the said diamine compound which is a raw material of the polymer which has the said conjugated enone structure . The liquid crystal aligning film formed by irradiating the thin film consisting of the liquid crystal aligning agent in any one of Claims 1-4 with a polarized or non-polarized radiation, and providing liquid crystal aligning ability. A liquid crystal display element comprising the liquid crystal alignment film according to claim 5. An optical member obtained by aligning a liquid crystal substance on the liquid crystal alignment film according to claim 5 and then fixing the alignment state.