JP2002265541A - Photoorientation material containing maleimide derivative and production method of photoorientation film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a photoorientation film which has a voltage retention at a high temperature, a good orientation stability, and a sufficient durability to light or heat. SOLUTION: A photoorientation material which contains an alkenyl- substituted nadimide derivative and a polyfunctional maleimide derivative having constituting units exhibiting photoorientation properties is provided. The photoorientation film capable of orientating liquid crystal molecules without the necessity for rubbing is produced by using the material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for aligning liquid crystals, and more particularly, to a photo-alignment film capable of aligning liquid crystal molecules by irradiating light without rubbing. The photo alignment film of the present invention is suitably used as a liquid crystal alignment film for a liquid crystal display device or the like.

[0002]

2. Description of the Related Art In a liquid crystal display device, the state of the molecular arrangement of liquid crystal is changed by the action of an electric field or the like, and a change in optical characteristics accompanying the change is used for display. In many cases, the liquid crystal is used in a state of being sandwiched between two substrates, but here, in order to arrange the liquid crystal molecules in a specific direction,
An alignment process is performed inside the substrate.

Usually, the orientation treatment is performed by a method called rubbing, in which a polymer film such as polyimide is provided on a substrate such as glass, and the film is rubbed in one direction with a cloth or the like. As a result, the liquid crystal molecules in contact with the substrate are arranged so that their major axes (directors) are parallel to the rubbing direction. For example, in a twisted nematic (TN) cell, two substrates having an alignment film applied inside are opposed to each other between two orthogonal polarizing plates, and the rubbing directions thereof are arranged so as to be orthogonal to each other. Display by change is enabled.

However, although the rubbing method has an advantage that the manufacturing apparatus is simple, static electricity and dust are generated in the manufacturing process, so that a cleaning step is required after the alignment treatment, and especially a TFT which has been widely used in recent years.
In the liquid crystal cell of the system, the TFT element provided in advance on the substrate is destroyed by static electricity, and this also causes a reduction in the production yield. In addition, fine scratches caused by rubbing with a cloth cause display defects when manufacturing a high-definition display element such as a micro display.

On the other hand, in the liquid crystal display device, since the inclination of the liquid crystal molecules constituting the liquid crystal device has directionality, the viewing angle dependency such as that the display color or contrast changes depending on the direction in which the display device is viewed has become a problem. . As one method of improving this, a pretilt angle of liquid crystal molecules is divided for each area by dividing one pixel (Japanese Patent Application Laid-Open No. 62-159119).
Orientation division methods that change the orientation direction (Japanese Patent Application Laid-Open No. 63-106624) have been devised. However, such an orientation for each division region is not suitable for practical use because the conventional rubbing method requires a complicated process.

In order to solve such a problem, attention has been paid to a liquid crystal alignment control technique which does not perform rubbing in recent years. Such rubbingless orientation techniques include oblique deposition,
An LB (Langmuir-Blodgett) film method, a photolithography method, a photo-alignment method and the like have been studied. In particular, a photo-alignment method for irradiating a coating film provided on a substrate with polarized light to generate liquid crystal alignment is simple, does not require a washing step after the alignment treatment, and further requires a photomask or the like. Since the above-mentioned orientation division can be easily performed by using the compound, research has been actively conducted. As the photo-alignment mechanism, for example, a photo-isomerization reaction such as an azobenzene group, a cinnamoyl group, a coumarin group, a chalcone group, a photo-dimerization reaction such as benzophenone, and a photo-decomposition reaction of a polyimide resin or the like have been reported. ing.

As the photo-alignment material utilizing such photo-isomerization, photo-dimerization or photo-decomposition reaction, a polymer compound such as a polymer is used so that a uniform film can be obtained when applied to a substrate such as glass. In many cases, a structural unit exhibiting photo-alignment such as an azobenzene group or a cinnamoyl group is often introduced into a side chain or a main chain of the polymer compound. In some cases, a molecule having photo-alignment property is used as a guest molecule and dispersed in a host compound including a high molecular compound.

However, in the case of the photoisomerization type, a reversible isomerization reaction of molecules by irradiation with polarized ultraviolet light is often used, and thus there is a problem in light stability after photoalignment treatment.
In addition, in the case of the photodecomposition type, since the liquid crystal may be contaminated by decomposition products generated when performing photoalignment treatment,
It is necessary to wash the substrate after the treatment, and the advantage that the photo-alignment film need not be washed is lost. In addition, many photo-alignment materials using a polymer compound have low solubility in a solvent, and there is a problem in that the types of solvents that can be used when applying to a substrate are limited.

For example, WO9637807 discloses that
A liquid crystal alignment film using a resin having a structural unit and a reactive functional group capable of being photoisomerizable and exhibiting dichroism has been disclosed.However, this material is a polymer compound, and when applied to a substrate, The types of solvents that can be used are limited, and generally N, N-
High-boiling polar solvents such as dimethylacetamide and N-methyl-2-pyrrolidone are used. In this case, it takes a long time to volatilize the solvent after the application, and the productivity is reduced. Further, there is a problem that many of the conventional photo-alignment film materials are insufficient in terms of thermal stability.

As an example of a method for solving these problems and for stably obtaining the liquid crystal alignment ability of the photo-alignment film for a long period of time, a polymerizable monomer to which a structural unit exhibiting an alignment by polarized light irradiation is added is used. There is a method in which heat or photopolymerization is performed and photo alignment is performed by irradiation with polarized light. However, in many cases, thermal or photopolymerization of the monomer requires the addition of a polymerization initiator. Since this polymerization initiator is a low-molecular compound, even after curing of the photo-alignment film, after a long period of time, the polymerization initiator diffuses into the liquid crystal layer in the cell, and characteristics as a liquid crystal display element, for example, The voltage holding ratio may be degraded.

The unnecessary photopolymerizable group of the polymerization initiator includes:
There is a maleimide group. A photo-alignment film using this compound having a maleimide group is disclosed in JP-A-2000-53766 and JP-A-2962473. These are high molecular compounds in which a photo-alignment group is added as a side chain to polymaleimide, which also has a problem of solubility in a solvent as described above, and still has a long-term stability in heat resistance and liquid crystal alignment ability. It is enough.

Therefore, the present inventors have filed Japanese Patent Application No. 2000-2.
No. 60764 proposes a photo-alignment material capable of providing a photo-alignment film having good liquid crystal display element characteristics by using a specific maleimide derivative. However, this material is used to completely cure a maleimide group. In addition, it is necessary to perform sufficient heating and light curing, and if this is insufficient,
There has been a problem that the voltage holding ratio of the formed liquid crystal cell is reduced.

[0013]

The problem to be solved by the present invention is to provide good liquid crystal display element characteristics, especially high voltage holding ratio at high temperature, good alignment stability and sufficient light and heat resistance. An object of the present invention is to provide a photo-alignment film having excellent durability.

[0014]

Means for Solving the Problems The inventors of the present invention have made intensive studies to solve the above-mentioned problems, and as a result, it has been surprisingly found that a material containing a specific maleimide derivative and an alkenyl-substituted nadimide derivative is used. In addition, it was found that the curing proceeded very quickly by heating or light irradiation, and the above problem could be solved. Thus, the present invention was completed. That is, the present invention, in order to solve the above problems,

(A) A photo-alignment material containing a polyfunctional maleimide derivative having a structural unit exhibiting photo-alignment properties and an alkenyl-substituted nadimide derivative is provided.

Further, the present invention provides (B) a method for producing a photo-alignment film using the photo-alignment material of the above (A).

[0017]

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a photo-alignment material characterized by using a polyfunctional maleimide derivative having a structural unit exhibiting photo-alignment and an alkenyl-substituted nadimide derivative in combination, and a photo-alignment material using the same. It relates to an alignment film.

The polyfunctional maleimide derivative used in the present invention is a structural unit capable of producing a photoreaction showing an orientation such as a dimerization reaction or an isomerization reaction upon irradiation with light (hereinafter referred to as a composition showing a photoorientation property). Abbreviated as a unit). The structural unit exhibiting photo-alignment is not particularly limited, but C = C and C =
A structural unit having at least one double bond (excluding a double bond forming an aromatic ring) selected from the group consisting of N, N = N, and C = O is particularly preferably used.

The following are examples of the structural units exhibiting the photo-alignment property. For example, structural units having a C 有 す る C bond include skeletons of polyene, stilbene, stilbazole, stilbazolium, cinnamate, hemithioindigo, chalcone, and the like. Examples of the structural unit having a C = N bond include skeletons such as aromatic Schiff bases and aromatic hydrazones. Examples of the structural unit having an N = N bond include an azo skeleton such as azobenzene, azonaphthalene, an aromatic heterocyclic azo, bisazo, and formazan, and azoxybenzene. Examples of the structural unit having a C ＝ O bond include skeletons such as benzophenone, coumarin, and anthraquinone.

Specifically, for example, the following skeleton is mentioned. Of course, as shown by X in the following skeletons, one of an alkyl group, an alkoxy group, an aryl group, an allyloxy group, a cyano group, an alkoxycarbonyl group, a hydroxyl group, a sulfonic acid group, a halogenated alkyl group, etc. These residues may be bonded.

[0021]

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Above all, maleimide derivatives having a skeleton of cinnamate, coumarin, chalcone or benzophenone exhibiting photo-alignment by a photodimerization reaction or an azobenzene or anthraquinone skeleton exhibiting photo-alignment by a photoisomerization reaction are used. This is particularly preferable because the amount of light irradiation necessary for the photo-alignment film is small, and the obtained photo-alignment film has excellent thermal stability and temporal stability. Among them, a maleimide derivative having a benzophenone skeleton is most preferable.

The polyfunctional maleimide derivative used in the present invention has a structural unit exhibiting photo-alignment, and has at least 2
The derivative is not particularly limited as long as it is a derivative having two maleimide groups.

[0024]

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(Wherein, each R ₁ is independently at least one hydrocarbon group optionally selected from the group consisting of an alkylene group, a cycloalkylene group, and an arylene group; or R ₂ represents an organic group in which a plurality of these hydrocarbon groups are connected by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond. Wherein R ₃ and R ₄ each represent a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a phenyl group or a halogen atom, and n represents an integer of 2 to 10.) The maleimide derivatives represented are preferred.

In the general formula (1-1), R ₁ represents at least one hydrocarbon group selected from the group consisting of an alkylene group, a cycloalkylene group and an arylene group.

Specific examples of these hydrocarbon groups include methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, and the like. Examples thereof include a linear alkylene group such as a decamethylene group, an undecamethylene group and a dodecamethylene group, a cycloalkylene group such as a cyclopentylene group and a cyclohexylene group, and an arylene group such as a phenylene group.

These hydrocarbon groups may have a substituent. Examples of the substituent include, but are not particularly limited to, an alkyl group such as a methyl group, an ethyl group, and a propyl group, a cycloalkyl group such as a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, an aryl group such as a phenyl group, an alkoxy group, and an allyloxy group. Group, cyano group, alkoxycarbonyl group, hydroxyl group, sulfonic acid group,
And a halogenated alkyl group. Further, a reactive functional group such as an acryl group, an epoxy group, and a maleimide group may be directly bonded to a hydrocarbon group as a substituent, and may be a bonding group such as an ester bond, an ether bond, an amide bond, and a urethane bond. It may be bonded as a substituent via a linked hydrocarbon group.

In R ₁ , a plurality of the above-mentioned hydrocarbon groups are each connected by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond. Is also good.

Examples of such linked organic groups include, for example, a group composed of (poly) ether in which at least two hydrocarbon groups are bonded by an ether bond, and at least two hydrocarbon groups bonded by an ester bond. Group composed of (poly) ester, at least two hydrocarbon groups bound by amide bond, and at least two hydrocarbon groups bound by urethane bond (poly) ) Groups composed of urethane,
(Poly) carboxylic acid {(poly) ether (poly) ol} ester obtained by esterifying (poly) ether (poly) ol in which at least two hydrocarbon groups are ether-bonded and (poly) carboxylic acid And the like.

In the above general formula (1-1), R ₂ is
It represents a structural unit having the above-described photo-orientability. Here, R ₂ is bonded to R ₁ via a single bond or a bonding group such as an ester bond, an ether bond, an amide bond, or a urethane bond.

In the above general formula (1-1), R ₃ and R ₄ are each a hydrogen atom, a methyl group, an ethyl group or the like.
Represents an alkyl group containing up to 8 carbon atoms, a phenyl group or a halogen atom, and n represents an integer of 2 to 10. Above all, n is 2 to 8 because the polymerization of the maleimide group proceeds easily to form a stable maleimide polymer and the amount of light energy required for photo-alignment is relatively small.
Is preferable, and it is especially preferable that it is 2-4.

The maleimide derivative represented by the general formula (1-1) includes, among others, the following general formula (1-2):

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[0034] (wherein, R ₅ are each independently a single bond, a straight-chain alkylene group, a branched alkylene group, at least one hydrocarbon group selected from the group consisting of cycloalkylene groups and arylene groups, or they a plurality of hydrocarbon radicals are a single bond, an ester bond, ether bond, amide bond, and configuration .R ₆ is showing a photoalignable represents an organic group linking at a linking group selected from the group consisting of urethane bonds Wherein R ₇ , R ₈ , R ₉ , and R ₁₀ each represent a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a phenyl group, or a halogen atom. preferable.

R ₅ in the general formula (1-2) is independently at least one hydrocarbon group selected from the group consisting of a single bond, a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an arylene group. Or an organic group in which a plurality of these hydrocarbon groups are connected by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond.

Examples of these hydrocarbon groups include, for example, methylene, ethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, octamethylene, nonamethylene, Linear alkylene groups such as decamethylene group, undecamethylene group and dodecamethylene group; cycloalkylene groups such as cyclopentylene group and cyclohexylene group; and arylene groups such as phenylene group.

R ₅ represents a single bond, an ester bond, an ether bond, a plurality of the above-mentioned hydrocarbon groups.
They may be linked by a bonding group selected from the group consisting of an amide bond and a urethane bond. Specific examples of such a linked group include, for example, a group composed of a (poly) ether in which at least two hydrocarbon groups are linked by an ether bond, and at least two hydrocarbon groups. A group consisting of a (poly) ester linked by an ester bond, at least two hydrocarbon groups comprising at least two groups consisting of a (poly) amide linked by an amide bond
Two hydrocarbon groups linked by a urethane bond, (poly)
(Poly) ether (poly) in which a group composed of urethane and at least two hydrocarbon groups are ether-bonded
And a group composed of (poly) carboxylic acid {(poly) ether (poly) ol} ester obtained by esterifying all and (poly) carboxylic acid.

R ₆ represents a structural unit exhibiting photo-alignment. Specific examples of the structural units exhibiting the photo-alignment include the same structural units as those described for R ₂ in the general formula (1-1). R ₇ , R ₈ , R ₉ , and R ₁₀ each represent a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms such as a methyl group or an ethyl group, a phenyl group, or a halogen atom.

The formula (1-1) is represented by the following general formula (1-
3),

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(Wherein R ₁₁ is independently at least one hydrocarbon group selected from the group consisting of a single bond, an alkylene group, a cycloalkylene group, and an arylene group, or a plurality of these hydrocarbon groups. R ₁₂ represents a trivalent hydrocarbon group, R ₁₃ represents a trivalent hydrocarbon group, and R ₁₃ represents an organic group in which R ₁₂ is a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond. Represents a structural unit exhibiting photo-alignment, wherein R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ are each a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms,
Represents a phenyl group or a halogen atom. ) Is also preferable.

R ₁₁ in the general formula (1-3) is each independently at least one hydrocarbon group selected from the group consisting of a single bond, an alkylene group, a cycloalkylene group, and an arylene group; An organic group in which a plurality of hydrogen groups are connected by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond. These groups are represented by the general formula (1-2)
Similar hydrocarbon groups as mentioned above for R ₅ in, or include organic groups. R ₁₁ is a group represented by the general formula (1-2)
Similarly to _5, a plurality of hydrocarbon group or an organic group, mentioned above, a single bond, an ester bond, ether bond, amide bond, and may be one which is linked by linking groups selected from the group consisting of urethane bonds .

R ₁₂ in the general formula (1-3) represents a trivalent hydrocarbon group. The valence, that is, the free valence, may be present at any position of the hydrocarbon group, and a maleimide group may be added to two of the three valences via the organic groups represented by R ₁ and R ₂ above.
One is bonded to a structural unit having photo-orientation represented by R ₅ via an organic group represented by R ₃ . These hydrocarbon groups may be linear or branched. Specifically, for example, a methylidyne group, a 1-ethanyl-2-ylidene group,
2,3-propanetriyl group, 1-propanyl-3-ylidene group, 1,2,4-butanetriyl group, 1-butanyl-4-ylidene group, 1,2,5-pentanetriyl group, 1,3 , 5-pentanetriyl group, 1-pentanyl-5-ylidene group, 1,2,6-hexanetriyl group,
1,3,6-hexanetriyl group, 1-hexanyl-6
-Ylidene group, 2-propanyl-1-ylidene group, 2-
Methylene-1,3-propanediyl group, 1-propanyl-3-ylidene group, 3-butanyl-1-ylidene group,
1,2,3-butanetriyl group, 1-butanyl-2-ylidene group, 2-methyl-1-propanyl-3-ylidene group, 2-methyl-1,2,3-propanetriyl group,

2-ethyl-1,2,3-propanetriyl group, 2-butanyl-1-ylidene group, 2-butanyl-
Groups consisting of trivalent acyclic hydrocarbons such as 3-ylidene group and 2-butanyl-4-ylidene group; 1,2,3-cyclopentanetriyl group and 1,2,5-cyclopentanetriyl group , 1-cyclopentyl-2-ylidene group, 1-cyclopentyl-3-ylidene group, 1,2,3-cyclohexanetriyl group, 1,2,4-cyclohexanetriyl group, 1,3,5-cyclohexanetriyl Group, 1-cyclohexyl-2-ylidene group, 1-cyclohexyl-
3-ylidene group, 1-cyclohexyl-4-ylidene group, cyclohexylmethylidine group, 4-cyclohexylenemethylene group, 1-cyclohexyl-2-ethanyl-1
An organic group consisting of a trivalent hydrocarbon including a cycloaliphatic hydrocarbon such as ylidene; 1,3,5-benzenetriyl, benzylidine, 2-phenyl-1,2,3-propanetriyl And organic groups composed of trivalent hydrocarbons including aromatic hydrocarbons.

R ₁₃ represents a structural unit exhibiting photo-alignment. Specific examples of the structural units exhibiting the photo-alignment include the same structural units as those described for R ₂ in the general formula (1-1). R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms such as a methyl group or an ethyl group, a phenyl group or a halogen atom.

Next, the alkenyl-substituted nadimide derivative used in the present invention is not particularly limited as long as it has the structure of the general formula (2), and known and commonly used ones can be used.

[0046]

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(Wherein, R ₁₈ and R ₁₉ each represent a hydrogen atom or a methyl group). Specific examples of the alkenyl-substituted nadimide derivatives include, for example, N-methyl-allylbicyclo [2.2.1] hept- 5-ene-2,3-dicarboximide, N-methyl-allylmethylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N-methyl-methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N-methyl-methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-ethylhexyl) -allylbicyclo [2.2.1] Hept-5-ene-2,3-dicarboximide;

N- (2-ethylhexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N-allyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-allyl-allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N-allyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-isopropenyl -Allylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N-isopropenyl-allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N-isopropenyl-methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-cyclohexyl-allylbicyclo [2.2 .1] Hept-5-ene-
2,3-dicarboximide, N-cyclohexyl-allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximide, N-cyclohexyl-methallylbicyclo [2.2.1] hept-5-ene-2,
3-dicarboximide, N-phenyl-allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

N-phenyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N-benzyl-allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-benzyl-methallylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 '
-Hydroxyethyl) -allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- (2'-hydroxyethyl) -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxy Imide,

N- (2 ', 2'-dimethyl-3'-hydroxypropyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
(2 ', 2'-dimethyl-3'-hydroxypropyl)
-Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2 ', 3'-
Dihydroxypropyl) -allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- (2 ', 3'-dihydroxypropyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- (3'-hydroxy-1 '
-Propenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (4 '
-Hydroxy-cyclohexyl) -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide,

N- (4'-hydroxyphenyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide, N- (4'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (4'-hydroxyphenyl) -methallylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
(4'-Hydroxyphenyl) -methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (3'-hydroxyphenyl) -allylbicyclo [2.2. 1] Hept-5-ene-2,3-
Dicarboximide, N- (3'-hydroxyphenyl) -allylmethylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximide, N- (p-hydroxybenzyl) -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
{2 ′-(2 ″ -hydroxyethoxy) ethyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide,

N- {2 '-(2 "-hydroxyethoxy) ethyl} -allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N-
{2 ′-(2 ″ -hydroxyethoxy) ethyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3
-Dicarboximide, N- {2 '-(2 "-hydroxyethoxy) ethyl} -methallylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide, N- [2 '-{2 "-(2'"-hydroxyethoxy) ethoxy} ethyl] -allylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- [2 '-{2 "-(2'"-hydroxyethoxy)
Ethoxydiethyl] -allylmethylbicyclo [2.2.
1] hept-5-ene-2,3-dicarboximide,
N- [2 '-{2 "-(2'"-hydroxyethoxy)
Ethoxydiethyl] -methallylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide, N-
{4 '-(4 "-hydroxyphenylisopropylidene) phenyl} -allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- {4'
-(4 "-hydroxyphenylisopropylidene) phenyl} -allylmethylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide, N- {4'-
(4 "-hydroxyphenylisopropylidene) phenyl} -methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide and oligomers thereof.

Also, N, N'-ethylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-ethylene-bis (allylmethylbicyclo) [2.2.1] Hept-5-ene-
2,3-dicarboximide), N, N'-ethylene-
Bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-trimethylene-bis (allylbicyclo [2.2.1] hept-
5-ene-2,3-dicarboximide), N, N'-
Hexamethylene-bis (allylbicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide),
N, N'-hexamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-dodecamethylene-bis (allylbicyclo [2. 2.1] Hept-5-ene-2,3-
Dicarboximide), N, N'-dodecamethylene-bis (allylmethylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide), N, N'-cyclohexylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-cyclohexylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

1,2-bis {3 '-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane, 1,2-bis {3'-
(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} ethane, 1,2-bis {3 ′-(methallylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximido) propoxydiethane, bis [2 '-{3 "-(allylbicyclo [2.2.1] hept-5-ene-2,3) −
Dicarboximide) propoxydiethyl] ether,
Bis [2 '-{3 "-(allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximido) propoxy {ethyl] ether, 1,4-bis {3 ′-(allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide) propoxy {butane, 1,4-bis {3 '-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) propoxy} butane,

N, N'-p-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p-phenylene-bis (allyl Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-m-phenylene-bis (allylbicyclo [2.2.1] hept-5-ene- 2,3-dicarboximide), N, N '
-M-phenylene-bis (allylmethylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide), N, N '-{(1-methyl) -2,4-phenylene} -bis (allylbicyclo [2.2.1] hept -5
-Ene-2,3-dicarboximide), N, N'-p
-Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N,
N'-p-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-m-xylylene-bis (allylbicyclo [2. 2.1] Hept-5-ene-2,3-dicarboximide), N, N'-m-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3- Dicarboximide),

2,2-bis [4 '-{4 "-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenoxy} phenyl] propane;
2,2-bis [4 '-{4 "-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) phenoxy} phenyl] propane, 2,2-
Bis [4 '-{4 "-(methallylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide)
Phenoxy {phenyl} propane, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylmethylbicyclo [2.2] .1] Hept-5-ene-
2,3-dicarboximido) phenyl @ methane,

Bis {4- (methallylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide)
Phenyl} methane, bis {4- (methallylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} methane, bis {4- (allylbicyclo [2.2. 1] Hept-5-ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-
2,3-dicarboximido) phenyl} ether, bis {4- (methallylbicyclo [2.2.1] hept-5
-Ene-2,3-dicarboximido) phenyl} ether, bis {4- (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone, bis} 4 -(Allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximido) phenyl} sulfone,

Bis {4- (methallylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide)
Phenyl disulfone, 1,6-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -3-hydroxy-hexane, 1,12-bis (methallylbicyclo [ 2.2.1] Hept-5-ene-2,3-dicarboximide) -3,6-dihydroxy-dodecane, 1,3-bis (allylbicyclo [2.
2.1] Hept-5-ene-2,3-dicarboximide) -5-hydroxy-cyclohexane, 1,5-bis {3 '-(allylbicyclo [2.2.1] hept-5-
Ene-2,3-dicarboximide) propoxy｝ -3
-Hydroxy-pentane, 1,4-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-benzene,

1,4-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2,5-dihydroxy-benzene, N,
N'-p- (2-hydroxy) xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-
Dicarboximide), N, N'-p- (2-hydroxy) xylylene-bis (allylmethylcyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide), N, N'-m- (2-hydroxy) xylylene-
Bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-m- (2
-Hydroxy) xylylene-bis (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), N, N'-p- (2,3-dihydroxy)
Xylylene-bis (allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide),

2,2-bis [4 '-{4 "-(allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2" -hydroxy-phenoxy} phenyl] Propane, bis {4- (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -2-hydroxy-phenyl} methane, bis {3- (allylbicyclo [2. 2.1] Hept-5-ene-2,3-dicarboximido) -4-hydroxy-
Phenyl} ether, bis {3- (methallylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) -5-hydroxy-phenyl} sulfone,
1,1,1-tri {4 ′-(allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide)} phenoxymethylpropane, N, N ′,
N "-tri (ethylene methallyl bicyclo [2.2.1]
Hept-5-ene-2,3-dicarboximide) isocyanurate and oligomers thereof.

Further, the following compounds containing an asymmetric alkylene phenylene group may be used.

[0062]

Embedded image

In these alkenyl-substituted nadimide derivatives, a polyene, stilbene, stilbazole, stilbazolium, cinnamic acid, hemithioindigo, chalcone, a substituent other than the main structure represented by the general formula (2) is used. Contains reactive functional groups such as aromatic Schiff bases, aromatic hydrazones, azobenzene, azonaphthalene, aromatic heterocyclic azo, bisazo, formazan, benzophenone, and coumarin structures, acrylic groups, epoxy groups, and maleimide groups. Of course, you can do it. Such alkenyl-substituted nadimide derivatives may be used alone or as a mixture thereof.

The weight ratio of the maleimide derivative having the above-described structural unit having photo-alignment property to the alkenyl-substituted nadimide derivative is preferably 15/80 to 95/5, and 35/65 to 70/5. / 30 is particularly preferred. When the amount of the maleimide derivative is less than 15%, the photoreactivity decreases, and when the amount of the alkenyl-substituted nadiimide derivative is less than 5%, no curing reaction promoting effect is obtained.

The photo-alignment material of the present invention is used for the purpose of adjusting the introduction density of the structural units exhibiting photo-alignment to improve the alignment state of the liquid crystal, or a maleimide represented by the general formula (1-1). The following general formula (3) is used for the purpose of reducing the crystallinity of the derivative and improving the coating property and film forming property on the substrate.
A mixture obtained by appropriately mixing a maleimide derivative containing no structural unit exhibiting photo-alignment as shown in, coated with a maleimide derivative containing a structural unit exhibiting photo-alignment, and mixed with an alkenyl-substituted nadimide derivative to react. Is also good.

[0066]

Embedded image

(Wherein, R ₂₀ is at least one hydrocarbon group selected from the group consisting of a linear alkylene group, a branched alkylene chain, a cycloalkylene group, and an arylene group, or a plurality of these hydrocarbon groups. Represents an organic group linked by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond, wherein R ₂₁ , R ₂₂ , R ₂₃ , and R ₂₄ are each independently , A hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a phenyl group or a halogen atom.)

In the above formula (3), R ₂₀ represents the same organic group as described for R ₁ in the formula (1-1). Further, as in the case of these general formulas (1-1), R ₂₀ represents a single bond, an ester bond,
They may be linked by a bonding group selected from the group consisting of an ether bond, an amide bond, and a urethane bond.
R ₂₁ , R ₂₂ , R ₂₃ and R _{24 each} represent a hydrogen atom, 1 to 8
Represents an alkyl group, phenyl group or halogen atom containing carbon atoms.

The mixing ratio of the maleimide derivative containing no photo-alignable structural unit represented by the general formula (3) is preferably in the range of 0 to 80% by weight based on the entire photo-alignment material, and particularly preferably. Ranges from 0 to 50% by weight.

In addition, the photo-alignment material of the present invention may be a curable ethylenic compound, an epoxy compound, a polyvinyl compound such as polyvinyl alcohol or polyvinyl cinnamate, or a poly (meta) as long as the purpose of the present invention is not impaired. ) Polymer materials such as acrylate compounds, polyesters, polyamides, polyimides, polycarbonates,
Further, a material known as a photo-alignment film material, such as a surfactant, a chelating agent, an antioxidant, and a viscosity modifier, can be contained.

The photo-alignment material of the present invention comprises a polyfunctional maleimide derivative and an alkenyl-substituted nadimide having the above-described photo-alignment structural unit (hereinafter, the photo-alignment structural unit is abbreviated as a photo-alignment group). It is characterized by containing a derivative. Next, an example of a method for manufacturing a photo-alignment film and a liquid crystal display device having the same using the photo-alignment material of the present invention will be described.

The photo-alignment material of the present invention is used after being dissolved in an appropriate solvent. At this time, the solvent is not particularly limited.
Methylpyrrolidone, dimethylformamide, butyl cellosolve, γ-butyrolactone, chlorobenzene, dimethylsulfoxide, dimethylacetamide, tetrahydrofuran and the like are generally used. Among them, N-methylpyrrolidone, butyl cellosolve, and γ-butyrolactone are particularly preferable since they have good coatability and can provide a uniform film.

The solution of the photo-alignment material is applied to a substrate such as glass by a method such as spin coating or printing, and after drying, curing of the maleimide group and the alkenyl-substituted nadimide derivative and alignment operation of the photo-alignment group are performed. Do. Curing of the maleimide group and the alkenyl-substituted nadimide derivative is performed by light irradiation or heating. The curing operation by light or heat may affect the already-aligned photo-alignable groups, so it is preferable to perform the curing operation prior to the alignment of the photo-alignable groups, but by a reversible photo-isomerization such as azobenzene. For the purpose of fixing the state of photo-alignment, a curing operation may be performed after performing photo-alignment.

When the wavelength of the light at which the maleimide group and the alkenyl-substituted nadimide derivative are cured is different from the wavelength of the light at which the alignment of the photo-alignment group occurs, the curing operation by the light is performed so that no photo-alignment occurs and the maleimide group is cured. It is preferable to use light having a wavelength as close as possible to the wavelength of the light to be emitted. On the other hand, when the wavelength of the light to be cured is close to the wavelength of the light at which the alignment of the photo-alignment group occurs, the curing with the maleimide group and the alkenyl-substituted nadimide derivative and the photo-alignment operation of the photo-alignment group are performed in one light cycle. Simultaneous irradiation is possible. The irradiation light used for such photocuring is not particularly limited, but ultraviolet light is preferably used. The irradiation method is also not particularly limited, and non-polarized light or polarized light such as linearly polarized light or elliptically polarized light is used.

On the other hand, when the curing operation of the maleimide derivative and the alkenyl-substituted nadimide derivative is performed by heating, the step may be performed before or after the alignment operation of the photo-alignment group. Further, in order to complete the curing, the curing may be first performed by light irradiation or heating, and then the light orientation or heating may be performed again after performing the photo-alignment operation.

The alignment of the photo-alignment group is performed by irradiating polarized or unpolarized light. The wavelength of the irradiation light is selected to be a wavelength at which the photo-alignment group efficiently reacts with light, and includes visible light, ultraviolet light, etc., and particularly preferably ultraviolet light. The irradiation method is not particularly limited. For example, in the case of performing light alignment operation by irradiating polarized light, linearly polarized light or elliptically polarized light is often used. At this time, in order to obtain the pretilt of the liquid crystal molecules, a method of irradiating the substrate with polarized light in an oblique direction or a method of irradiating polarized light with unpolarized light in an oblique direction may be used. In the case where light alignment is performed by irradiating only unpolarized light, a method of irradiating the substrate from an oblique direction is preferable.

A liquid crystal cell using the photo-alignment material of the present invention
The two substrates on which the alignment films are formed are arranged so that the directions of polarized light applied to the alignment films are at a predetermined angle, and are opposed to each other via a spacer of a predetermined size. When filling the liquid crystal in the liquid crystal cell, it is preferable that the liquid crystal be heated to a temperature at which the liquid crystal becomes an isotropic phase and then filled by a capillary method, a vacuum injection method, or the like.

Examples of the liquid crystal material include 4-substituted benzoic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted phenyl ester, 4-substituted cyclohexanecarboxylic acid 4′-substituted biphenyl ester, (4-substituted cyclohexanecarbonyloxy)
Benzoic acid 4'-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4'-substituted phenyl ester, 4- (4-substituted cyclohexyl) benzoic acid 4'-substituted cyclohexyl ester, 4-substituted 4'-substituted Biphenyl, 4-substituted phenyl-4′-substituted cyclohexane,
4-substituted 4 "-substituted terphenyl, 4-substituted biphenyl 4'-substituted cyclohexane, 2- (4-substituted phenyl)
-5-substituted pyrimidine and the like can be mentioned.

In the present invention, after a photo-alignment material containing a maleimide derivative having a photo-alignment group and an alkylene-substituted nadiimide derivative is applied to a substrate, a curing operation and a photo-alignment operation are performed to obtain a photo-alignment film. . Since the material to be applied is a monomer, the solvent solubility is high,
It has the feature that application is easy. After curing, the photo-alignment film has a photo-alignment group in the cross-linked structure, so that a photo-alignment film having high stability to light and heat can be obtained.

Further, the curing reaction of the maleimide derivative and the alkylene-substituted nadiimide derivative does not require a reaction initiator, and the curing speed is high, so that the curing operation can be performed in a short time, and after the liquid crystal cell is manufactured, the reaction is started in the liquid crystal. It is possible to eliminate the cause of performance degradation of the liquid crystal display element such as a decrease in voltage holding ratio without elution of the agent.

[0081]

EXAMPLES Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the scope of these Examples.

Reference Example 1 Synthesis of Maleimide Acetic Acid In a 500 ml four-necked flask equipped with a stirrer, thermometer, dropping funnel, Dean-Stark fractionator and condenser, 140 g of toluene and p-toluenesulfonic acid were added. 5.2 g of monohydrate and 2.8 g of triethylamine were sequentially charged, and 30 g of maleic anhydride was added with stirring, followed by dissolving while heating to 30 ° C. After further adding 23 g of glycine, the mixture was reacted at 70 ° C. for 3 hours with stirring. 50 g of toluene and 60 g of triethylamine were added, and the mixture was reacted for 1 hour while heating and refluxing the solvent to remove generated water. To the residue obtained by evaporating the solvent from the reaction mixture was added 4 mol / dm3 hydrochloric acid to adjust the pH to 2.
After heating to recrystallization, 7.3 g of a pale yellow solid of maleimide acetic acid was obtained.

[Reference Example 2] Synthesis of 4,4'-bis (2-hydroxyethoxy) benzophenone Capacity 3 equipped with a stirrer, thermometer, dropping funnel and cooling tube
62.5 g of 2-bromoethanol was placed in a 00 ml four-necked flask, and 100 g of N-methylpyrrolidone was added thereto while stirring under cooling with an ice bath. This is p-
Toluenesulfonic acid monohydrate (10 mg) was added, and dihydropyran (42.1 g) was added dropwise over about 10 minutes. After stirring for 2 hours under ice-cooling and further for 2 hours at room temperature,
42.8 g of 4'-dihydroxybenzophenone and 69.1 g of potassium carbonate were added and reacted at 120 ° C for 3 hours. After cooling, the reaction mixture was added to 400 ml of water,
The mixture was extracted twice with 0 ml of toluene, the obtained toluene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off with an evaporator. 450 g of methanol and 70 g of water were added to the obtained residue.
g and concentrated hydrochloric acid (1.0 g) were added, and the mixture was stirred at room temperature overnight. The resulting precipitate was filtered, washed well with methanol, and dried to obtain 4,4′-bis (2-hydroxyethoxy) benzophenone (52 g). .

Synthesis Example 1 Synthesis of Maleimide Derivative Containing Benzophenone The maleimide obtained in Reference Example 1 was placed in a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser. 8.8 g of acetic acid, 6.1 g of 4,4'-bis (2-hydroxyethoxy) benzophenone obtained in Reference Example 2, 0.4 p-toluenesulfonic acid monohydrate
g, 20 mg of hydroquinone and 150 ml of toluene were sequentially charged, and the mixture was heated at 90 ° C. under reduced pressure, and reacted for 15 hours while refluxing the solvent to remove generated water. After completion of the reaction, the reaction mixture was filtered while hot, and the obtained solid was thoroughly washed with methanol and dried to obtain the compound of the formula (4).

[0085]

Embedded image 8.6 g of a bifunctional maleimide derivative represented by the following formula was obtained.

[Synthesis Example 2] Synthesis of maleimide derivative containing no benzophenone The maleimide obtained in Reference Example 1 was placed in a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser. Acetic acid 8.8 g, number average molecular weight 4
5.0 g of polypropylene glycol, 0.4 g of p-toluenesulfonic acid monohydrate, 20 mg of hydroquinone
And 150 ml of toluene were sequentially charged, and the pressure was reduced to 90 ° C.
The mixture was reacted for 15 hours while the solvent was refluxed to remove generated water. After completion of the reaction, the reaction mixture was washed twice with dilute sodium hydroxide solution and then three times with pure water,
Toluene is distilled off and the formula (5)

[0087]

Embedded image 7.7 g of a maleimide derivative represented by the following formula was obtained.

Reference Example 3 Synthesis of 4- (2-hydroxyethoxy) cinamic acid-2-hydroxyethyl ester Sodium hydroxide 4 was added to an autoclave having a capacity of 500 ml.
80 g of ethanol of 0.0 g (1.0 mol), water 1
A mixed solution of 00 ml is charged, and 82.1 g (0.5 mol) of 4-hydroxycinnamic acid is added and dissolved. While cooling with ice, 132.2 g (3.0 mol) of oxirane was added, and the mixture was sealed and reacted at 80 ° C. for 6 hours. 200 ml of water
, And the mixture is extracted twice with 100 ml of ethyl acetate. After the extract was purified by silica gel chromatography, ethyl acetate was distilled off under reduced pressure, evaporated to dryness, recrystallized from butanol, and 90.8 g of 4- (2-hydroxyethoxy) cinamic acid-2-hydroxyethyl ester was obtained.
(72%).

[Synthesis Example 3] Synthesis of Maleimide Derivative Containing Cinnamoyl Group Obtained in Reference Example 1 in a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser. 8.8 g of maleimide acetic acid, 5.1 g of 4- (2-hydroxyethoxy) cinamic acid-2-hydroxyethyl ester obtained in Reference Example 3, 0.4 g of p-toluenesulfonic acid monohydrate, 20 mg of hydroquinone
And 150 ml of toluene were sequentially charged, and the pressure was reduced to 90 ° C.
The mixture was reacted for 15 hours while the solvent was refluxed to remove generated water. After completion of the reaction, the reaction mixture was filtered while hot, and the obtained solid was thoroughly washed with methanol and dried to obtain the compound of the formula (6).

[0090]

Embedded image 7.8 g of a bifunctional maleimide derivative represented by the formula was obtained.

[Reference Example 4] Synthesis of 2,2-dimethyl-5-ethyl-5- (bromomethyl) -1,3-dioxane A capacity equipped with a stirrer, a thermometer and a cooling tube equipped with a calcium chloride drying tube. In a 500 ml four-necked flask,
67.1 g of trimethylolpropane, 57.3 g of 2,2-dimethoxypropane, 100 g of toluene and 2.9 g of p-toluenesulfonic acid monohydrate were added.
Stirred for hours. After cooling, add 2.5 g of potassium carbonate,
Stirred overnight at room temperature. The solid in the flask is removed by filtration,
The solvent was distilled off under reduced pressure to obtain 80.6 g (liquid) of an intermediate of 2,2-dimethyl-5-ethyl-5- (bromomethyl) -1,3-dioxane.

In a 500 ml four-necked flask equipped with a stirrer, a thermometer, a nitrogen inlet tube and a condenser tube equipped with a calcium chloride drying tube, 43.8 g of the above intermediate, 116.6 g of carbon tetrabromide and N, N-dimethylformamide 3
Then, the mixture was sufficiently cooled in an ice-salt bath with stirring under a nitrogen atmosphere, and 91.9 g of triphenylphosphine was added.
Was added little by little so that the liquid temperature did not exceed 0 ° C. After completion of the addition of triphenylphosphine, the mixture was stirred in an ice-salt bath for 30 minutes, and then in an ice bath for 1 hour and at room temperature for 2 hours, and then the solvent was distilled off at 50 ° C under reduced pressure. The concentrated mixture was extracted three times with 200 g of an acetone-hexane mixed solvent (1/3), and the obtained extract was purified by column chromatography using silica gel to give 2,2-dimethyl-5.
47 g of -ethyl-5- (bromomethyl) -1,3-dioxane were obtained. (Yield 79%)

Synthesis Example 4 Synthesis of Maleimide Derivative Having Coumarin Group in Side Chain (1) A 100-ml three-necked flask equipped with a stirrer, a thermometer, and a cooling tube equipped with a calcium chloride drying tube was prepared. 11.9 g of 2,2-dimethyl-5-ethyl-5- (bromomethyl) -1,3-dioxane, 8.3 g of 7-hydroxycoumarin, and 40 g of N-methylpyrrolidone were added and stirred. When a homogeneous solution was obtained, 7.1 g of potassium carbonate was added and reacted at 150 ° C. for 2 hours. After cooling, the solvent was distilled off under reduced pressure, and the concentrated mixture was dissolved in 4 liters of ethyl acetate. The solution was washed three times with 500 g of water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. 13.5 g of the obtained solid was dissolved in 100 g of tetrahydrofuran, 30 g of 6% hydrochloric acid was added, and the mixture was stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, and the obtained solid was washed with water, filtered and dried.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser, 9.4 g of the solid obtained above and the maleimide acetic acid obtained in Reference Example 1 were added. 6 g, p-toluenesulfonic acid monohydrate 0.8 g, hydroquinone 40 mg and toluene 2
And then heated to 90 ° C. under reduced pressure to reflux the solvent and remove water while removing water.
Allowed to react for hours. After completion of the reaction, 200
The mixture was diluted by adding milliliters, and washed four times with 50 g of water. After drying this toluene solution with sodium sulfate, the solvent obtained was distilled off under reduced pressure, and the obtained solid was purified by column chromatography using silica gel to obtain the compound of formula (7).

[0095]

Embedded image 12 g of a bifunctional maleimide derivative represented by the formula was obtained.

[Synthesis Example 5] Synthesis of maleimide derivative having coumarin group in side chain (2) Capacity 3 equipped with stirrer, thermometer, dropping funnel and condenser
In a 00 ml four-necked flask, 6.3 g of 2-bromoethanol was added, and 10 g of N-methylpyrrolidone was added with stirring under cooling with an ice bath. To this, 2 mg of p-toluenesulfonic acid monohydrate was added, and 4.2 g of dihydropyran was added dropwise over about 10 minutes. After stirring for 2 hours under ice-cooling and further for 2 hours at room temperature, 8.5 g of 7-hydroxycoumarin and 6.9 g of potassium carbonate were added,
The reaction was performed at 120 ° C. for 3 hours. After cooling, the reaction mixture was added to 100 ml of water, extracted twice with 100 ml of toluene, the obtained toluene layer was dried over anhydrous sodium sulfate, and the solvent was distilled off with an evaporator. 45 g of methanol, 7 g of water and 0.5 g of concentrated hydrochloric acid were added to the obtained residue, and the mixture was stirred at room temperature overnight. After the solvent was distilled off, 250 g of toluene was added to make a solution, and the solution was washed twice with 50 g of water.

Capacity 5 equipped with stirrer, thermometer and cooling pipe
The toluene solution obtained above was placed in a 00 ml three-necked flask, and the compound 10.5 synthesized in Reference Example 4 was added.
g, tetrabutylammonium bromide 0.9 g and 4
80 g of a 0% aqueous sodium hydroxide solution was added, and the mixture was refluxed for 5 hours while stirring. After cooling, the mixture was transferred to a separatory funnel, and the aqueous layer was separated and removed.
Washed twice. The solvent was distilled off from the obtained toluene solution under reduced pressure, and the residue was dissolved in 100 g of tetrahydrofuran.
30% hydrochloric acid was added, and the mixture was stirred at room temperature for 4 hours. Under reduced pressure,
The solvent was distilled off, and the obtained solid was washed with water, filtered and dried. In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser, 10.8 g of the solid obtained above, 12.6 g of the maleimide acetic acid obtained in Reference Example 1, p 0.8 g of toluenesulfonic acid monohydrate, 40 mg of hydroquinone and 200 g of toluene
Milliliters were sequentially charged, and the mixture was heated at 90 ° C. under reduced pressure, and reacted for 15 hours while refluxing the solvent to remove generated water. After completion of the reaction, the reaction solution was diluted by adding 200 ml of toluene, and washed with 50 g of water four times. After drying this toluene solution with sodium sulfate, the solvent obtained was distilled off under reduced pressure, and the resulting solid was purified by column chromatography using silica gel to obtain the compound of formula (8).

Embedded image 16 g of a bifunctional maleimide derivative represented by the following formula was obtained.

[Synthesis Example 6] 2 having chalcone group in side chain
Synthesis of Functional Maleimide Derivative 11.9 g of the compound obtained in Reference Example 4 and 11.5 g of 4-hydroxychalcone were placed in a 100 ml three-necked flask equipped with a stirrer, a thermometer and a condenser fitted with a calcium chloride drying tube. And 40 g of N-methylpyrrolidone were added and stirred. When a homogeneous solution was obtained, 7.1 g of potassium carbonate was added and reacted at 150 ° C. for 2 hours. After cooling, the solvent was distilled off under reduced pressure, and the concentrated mixture was dissolved in 4 liters of ethyl acetate. The solution was washed three times with 500 g of water, dried over sodium sulfate, and the solvent was distilled off under reduced pressure. The obtained 15.0 g of solid was dissolved in 100 g of tetrahydrofuran, and 30 g of 6% hydrochloric acid was added.
Stirred at room temperature for 4 hours. The solvent was distilled off under reduced pressure, and the obtained solid was washed with water, filtered and dried.

In a 500 ml three-necked flask equipped with a stirrer, a thermometer, a Dean-Stark fractionator and a condenser, 10.4 g of the solid obtained above, 12.6 g of the maleimide acetic acid obtained in Reference Example 1, 0.8 g of p-toluenesulfonic acid monohydrate, 40 mg of hydroquinone and 20 parts of toluene
0 ml was sequentially charged, and the mixture was heated to 90 ° C. under reduced pressure, and reacted for 15 hours while refluxing the solvent to remove generated water. After completion of the reaction, the reaction solution was diluted by adding 200 ml of toluene, and washed with 50 g of water four times. After drying this toluene solution with sodium sulfate, the solvent obtained was distilled off under reduced pressure, and the obtained solid was purified by column chromatography using silica gel to obtain the compound represented by the formula (9).

Embedded image 13 g of a bifunctional maleimide derivative represented by the following formula was obtained.

[Synthesis Example 7] Alkenyl-substituted nadimide derivative (N, N'-2,2-bis (4-phenylene) propane-bis (allylbicyclo [2.2.1] hept-5)
-Ene-2,3-dicarboximide), hereinafter NI-M
151.0 g of allylbicyclo [2.2.1] hept-5-ene-2,3-dicarboxylic anhydride (98% pure) in a 500-ml flask purged with nitrogen. 7
4 mol) and 200 ml of toluene,
While stirring, 81.4 g (0.3
6 mol) of 2,2-bis (4-aminophenyl) propane was added in small portions over 60 minutes. The reaction was continued for 4 hours while separating and removing generated water by a water separator, and then a trace amount of solid residue was separated by filtration, and toluene as a solvent was distilled off. Next, when the content was heat-treated at 200 ° C. under a reduced pressure of 1 mmHg for 1.5 hours, 208.8 g (yield based on amine: 97
%), N, N'-2,2-bis (4-phenylene) propane-bis (allylbicyclo [2.2.
1] Hept-5-ene-2,3-dicarboximide)
(NI-M) was obtained.

[Synthesis Example 8] Alkenyl-substituted nadimide derivative (N, N'm-xylylene-bis (allylmethylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide), hereinafter NI Synthesis of Allylmethylbicyclo [2.2.1] hept-5-ene-2,3 in a 500-ml flask purged with nitrogen.
-Dicarboxylic anhydride (98% purity) 161.3 g
(0.74 mol) and 200 ml of toluene, 49.0 under reflux of toluene while heating and stirring.
g (0.36 mol) of m-xylylenediamine in 60
Added in small portions over minutes. The reaction was continued for 4 hours while separating and removing generated water by a water separator, and then a trace amount of solid residue was separated by filtration, and toluene as a solvent was distilled off. Then, the content was heat-treated at 200 ° C. under a reduced pressure of 1 mmHg for 1.5 hours. As a result, 208.8 g (yield based on amine: 97%) of N, N′m-xylylene-bis (allyl) was obtained. Methylbicyclo [2.2.1] hept-5-ene-2,3-dicarboximide) (NI-X) was obtained.

[Comparative Synthesis Example 1] Synthesis of Acrylic Acid Derivative Containing Benzophenone In the synthesis of the maleimide derivative of Synthesis Example 1, the formula (10) was obtained by using acrylic acid instead of maleimide acetic acid.

[0103]

Embedded image The bifunctional acrylic acid derivative represented by was obtained.

[Comparative Synthesis Example 2] Synthesis of Acrylic Acid Derivative Having Coumarin Group in Side Chain In the synthesis of the maleimide derivative of Synthesis Example 4, the formula (11) was obtained by using acrylic acid instead of maleimide acetic acid.

[0105]

Embedded image The bifunctional acrylate represented by was obtained.

[Comparative Reference Example 1] Synthesis of polyhydroxyphenylmaleimide A three-necked round-bottomed flask filled with nitrogen was placed in a polyscience co., USA, USA.
A. 5) g of the maleic anhydride polymer and 3 g of aminophenol in 100 ml of xylene were stirred at room temperature for 30 minutes, 2.9 g of isoquinoline was further added, the temperature was gradually raised to 150 ° C., and the mixture was formed during the reaction. The reaction was continued for about 3 hours while continuously removing water. After confirming that water was no longer generated, the reaction was terminated, the temperature was lowered to room temperature, and the product was precipitated by pouring into 500 ml of methanol, filtered under reduced pressure, and then vacuum-dried at 100 ° C. to remove polyhydroxyphenylmaleimide. Obtained.

Comparative Example 2 Synthesis of Side Chain (Parafluorobenzoylcinnamoyl Chloride) 16.42 g (0.1 mol) of parahydroxycinnamic acid, 8 g of sodium hydroxide, 100 ml of water, and dimethyl sulfoxide (DMSO) Dissolved in 100 ml and stirred vigorously at 0 ° C. with parafluorobenzoyl chloride 1
5.86 g (0.1 mol) was gradually added dropwise. After reacting at room temperature for about 2 hours, the mixture was neutralized to pH = 6-7 with dilute hydrochloric acid. The resulting solid intermediate was filtered and washed thoroughly with water. After completely drying under vacuum, recrystallization in ethanol gave parafluorobenzoyloxycinnamic acid in 90% yield. This was added with 1.2 equivalents of thionyl chloride and about 50 ml of methylene chloride, and reacted at room temperature until a clear solution was obtained. After the reaction, the solvent and thionyl chloride were removed under vacuum and dried completely to obtain parafluorobenzoylcinnamoyl chloride.

[Comparative Synthesis Example 3] Synthesis of polymeric photo-alignment material having maleimide in the main chain and photo-alignment group in the side chain 1.7 g of polyhydroxyphenylmaleimide obtained in Comparative Reference Example 1 was N- Methylpyrrolidone (NMP) 50m
and then add 1.0 g of triethylamine and add
Stirred for 0 minutes. The reaction temperature was lowered to 5 ° C., and 2.13 g of parafluorobenzoylcinnamoyl chloride obtained in Comparative Reference Example 2 was slowly added dropwise with vigorous stirring. After dropping all of parafluorobenzoylcinnamoyl chloride, the mixture was continuously stirred for about one hour to complete the reaction. The reaction solution was 200 m each of water and methanol.
The product was precipitated by pouring the mixture into a mixed beaker and subsequently washed thoroughly with excess water and methanol,
After vacuum filtration and vacuum drying, a polymer photoalignment material having a parafluorobenzoylcinnamoyl group in the side chain and maleimide in the main chain was finally obtained.

A photo-alignment film was prepared using the photo-alignment materials obtained in the above synthesis examples and comparative synthesis examples, and physical properties were evaluated. The method for forming the photo-alignment film and the method for evaluating physical properties were performed according to the following methods.

[Method of Forming Photo-Alignment Film] a. Preparation of Photo-Alignment Material Solution The maleimide derivative and the alkylene-substituted nadiimide derivative obtained in the synthesis example were dissolved in a mixed solvent of N-methylpyrrolidone / butyl cellosolve = 1/1 to obtain a solution having a solid content concentration of 5%. The solution was filtered through a 1 μm filter to obtain a photo-alignment material solution.

B-1. Preparation of photo-alignment film (thermosetting method) a. The photo-alignment material solution obtained by the method of the above is uniformly coated on a glass substrate with an ITO electrode by a spin coater,
Drying and curing were performed at 190 ° C. for 1 hour. Next, an integrated light intensity of 10 μm was applied to the surface of the obtained coating film using an ultra-high pressure mercury lamp.
A photo-alignment film was prepared by irradiating linearly polarized ultraviolet light having a wavelength of about 365 nm of J / cm ² .

B-2. Preparation of photo-alignment film (photo-curing method) a. The solution of the photo-alignment film obtained by the method described in 1) is evenly applied on a glass substrate with an ITO electrode by a spin coater.
After drying at 00 ° C. for 15 minutes, a wavelength of 313 nm at an integrated light amount of 10 J / cm ² was applied to the coating film surface from an ultra-high pressure mercury lamp.
A photo-alignment film was prepared by irradiating near linearly polarized ultraviolet light and simultaneously performing photo-curing of the maleimide derivative and the alkenyl-substituted nadiimide derivative and alignment by dimerization of the photo-alignment group.

C. Preparation of Liquid Crystal Cell An epoxy adhesive containing styrene beads having a diameter of 8 μm is applied around the photo-alignment film substrate obtained in b-1 or 2 above, leaving a liquid crystal injection port, so that the alignment surfaces face each other. ,
In addition, the adhesive was overlaid in a direction orthogonal to the direction of the polarized light and pressed, and the adhesive was cured at 150 ° C. for 90 minutes. Next, a chiral nematic liquid crystal composition (4- (4-ethoxyphenyl) cyclohexylpropane 19%, 4- (4- (3,4-difluorophenyl) cyclohexyl) cyclohexylethane 18) is used as an example from the liquid crystal injection port.
%, 4- (4- (3,4-difluorophenyl) cyclohexyl) cyclohexylpentane 18%, 4- (4-
(3,4-difluorophenyl) cyclohexyl) cyclohexylpropane 18%, 4- (4-butylcyclohexyl) cyclohexylpropane 7%, 4-fluorophenyl-4- (4-pentylcyclohexyl) cyclohexylcarboxylic acid ester 6% 4-fluoro Phenyl-4- (4-propylcyclohexyl) cyclohexylcarboxylic acid ester 6% 4- (4-chlorophenyl) cyclohexylpentane 5%, 4- (4- (4-
Chlorophenyl) cyclohexyl) cyclohexylbutane 3% and 0.1% chiral material SPE-01 manufactured by Dainippon Ink and Chemicals, Inc.) are vacuum-injected and filled in the isotropic phase, and then the liquid crystal is mixed with an epoxy adhesive. The inlet was sealed.

[Evaluation Method of Photo Alignment Film] d. Evaluation of liquid crystal alignment property The above c. The liquid crystal cell obtained by the method described above is sandwiched between two polarizing plates whose polarization directions are orthogonal to each other, and a voltage of 5 V is applied between the electrodes to turn on / off and switch between light and dark, thereby changing the orientation of the liquid crystal. evaluated.

E. Measurement of voltage holding ratio c. A DC voltage of 5 V was applied to the liquid crystal cell obtained at the temperature of 80 ° C. for 64 microseconds while maintaining the temperature at 80 ° C., and then the holding voltage was measured while the cell was opened for 16.6 milliseconds. The ratio of (initial applied voltage × opening time) was expressed as a holding ratio.

F. Measurement of Durability After maintaining the liquid crystal cell at 80 ° C. for 1000 hours, the orientation was visually evaluated.

[Example 1] A photo-alignment material having a weight ratio of maleimide derivative (4) obtained in Synthesis Example 1 / alkylene-substituted nadimide derivative (NI-M) obtained in Synthesis Example 7 = 50/50 was used. And a. A photo-alignment material solution is prepared according to the preparation method described above, and then b-1. A photo-alignment film was prepared according to the method for preparing a thermosetting photo-alignment film described above. Using the obtained photo-alignment film, the above c. , And physical properties were evaluated according to the above evaluation methods. As a result, the voltage holding ratio at a temperature of 80 ° C. was 94%, and both the liquid crystal orientation and the durability were good.

Example 2 A photo-alignment material (NI-M) consisting of a maleimide derivative (4) obtained in Synthesis Example 1 / alkylene-substituted nadimide derivative obtained in Synthesis Example 7 = 50/50 weight ratio was used. And a. A photo-alignment material solution is prepared according to the preparation method described in b., And then b-2. A photo-alignment film was prepared according to the photo-curing method for photo-alignment film of No. 1. A liquid crystal cell was prepared using the obtained photo-alignment film, and physical properties were evaluated according to the above evaluation methods. As a result, the voltage holding ratio at a temperature of 80 ° C. was 95%, and both the liquid crystal orientation and the durability were good.

Example 3 The photo-alignment material was a maleimide derivative (4) obtained in Synthesis Example 1 / a maleimide derivative (5) obtained in Synthesis Example 2 / a nadimide derivative (NI) obtained in Synthesis Example 7. -M) = Evaluated in the same manner as in Example 1, except that a mixture of 40/20/40 was used. As a result, 8
The voltage holding ratio at a temperature of 0 ° C. was 93%, and both the liquid crystal orientation and the durability were good.

Example 4 Evaluation was performed in the same manner as in Example 1 except that the maleimide derivative (4) obtained in Synthesis Example 1 was replaced with the maleimide derivative (6) obtained in Synthesis Example 3. went. As a result, the voltage holding ratio at a temperature of 80 ° C. was 94%, and both the liquid crystal orientation and the durability were good.

Example 5 The photo-alignment material was the maleimide derivative (4) obtained in Synthesis Example 1 / the maleimide derivative (5) obtained in Synthesis Example 2 / the nadimide derivative (NI -X) = 65/10/25, except that the mixture was evaluated in the same manner as in Example 1. As a result, the voltage holding ratio at a temperature of 80 ° C. was 94%, and both the liquid crystal orientation and the durability were good.

Example 6 Evaluation was performed in the same manner as in Example 1 except that the maleimide derivative (4) obtained in Synthesis Example 1 was replaced with the maleimide derivative (7) obtained in Synthesis Example 4. went. As a result, the voltage holding ratio at a temperature of 80 ° C. was 94%, and both the liquid crystal orientation and the durability were sufficient.

Example 6 Evaluation was performed in the same manner as in Example 2 except that the maleimide derivative (4) obtained in Synthesis Example 1 was replaced with the maleimide derivative (7) obtained in Synthesis Example 4. went. As a result, the voltage holding ratio at a temperature of 80 ° C. was 94%, and both the liquid crystal orientation and the durability were sufficient.

Example 7 Evaluation was performed in the same manner as in Example 1 except that the maleimide derivative (4) obtained in Synthesis Example 1 was replaced with the maleimide derivative (8) obtained in Synthesis Example 5. Was. As a result, the voltage holding ratio at a temperature of 80 ° C. was 95%, and both the liquid crystal orientation and the durability were sufficient.

[Example 8] The maleimide derivative (9) obtained in Synthesis Example 6 / the maleimide derivative (5) obtained in Synthesis Example 2 / the nadimide derivative (NI -X) = Evaluated in the same manner as in Example 1 except that a mixture of 40/30/30 was used. As a result, 8
The voltage holding ratio at a temperature of 0 ° C. was 94%, and both the liquid crystal orientation and the durability were sufficient.

Comparative Example 1 The maleimide derivative (4) obtained in Synthetic Example 1 was replaced with the acrylic acid derivative (10) synthesized in Comparative Synthetic Example 1 and 2,2′-azobisisobutyronitrile. Except that 0.1% was added.
Evaluation was performed in the same manner as in Example 2. As a result, the liquid crystal alignment and the durability were good, but the voltage holding ratio in the state of being kept at 80 ° C. was as low as 80%.

Comparative Example 2 A polymer having a parafluorobenzoylcinnamoyl group in the side chain synthesized in Comparative Synthesis Example 3 and a polymer having maleimide in the main chain was used as the photo-alignment material.
Evaluation was performed in the same manner as in Example 1. As a result, 80 ° C
The liquid crystal alignment was good with a voltage holding ratio of 94% in the state of holding, but after the durability test, the switching between light and dark was unclear and the alignment was low.

Comparative Example 3 The maleimide derivative (4) obtained in Synthetic Example 1 was replaced with the acrylic acid derivative (11) synthesized in Comparative Synthetic Example 2 and 2,2′-azobisisobutyronitrile. Except that 0.1% was added.
Evaluation was performed in the same manner as in Example 2. As a result, the liquid crystal alignment and the durability were good, but the voltage holding ratio in the state of being kept at 80 ° C. was as low as 80%.

[Comparative Example 4] The above a. Was prepared using only the maleimide derivative (4) obtained in Synthesis Example 1 without using the alkenyl-substituted nadimide derivative. A photo-alignment material solution is prepared according to the preparation method described above, and then b-1. A photo-alignment film was prepared according to the method for preparing a thermosetting photo-alignment film described above. Using the obtained photo-alignment film, the above c. , And physical properties were evaluated according to the above evaluation methods. As a result, both the liquid crystal alignment and the durability were good, but the voltage holding ratio in the state of being kept at 80 ° C. was as low as 83%.

By using the photo-alignment material comprising the maleimide derivative and the alkenyl-substituted nadimide derivative of the present invention, good liquid crystal display element characteristics, especially high voltage holding ratio at high temperature and good alignment stability can be obtained. And a photo-alignment film having sufficient durability against light and heat.

 ──────────────────────────────────────────────────続 き Continued on the front page F term (reference) 2H090 HB08Y HC05 MB12 4J100 AM55Q AS13P BA02Q BA11Q BA15Q BC01P BC03P BC04P BC43P BC43Q BC53Q CA04 JA39

Claims (10)

[Claims] 1. A photo-alignment material containing a polyfunctional maleimide derivative having a structural unit exhibiting photo-alignment, and an alkenyl-substituted nadimide derivative. 2. The photo-alignment material according to claim 1, wherein the maleimide derivative has a structural unit exhibiting photo-alignment by a photodimerization reaction or a photoisomerization reaction. 3. The structural unit exhibiting photo-alignment by a photodimerization reaction is a skeleton selected from the group consisting of cinnamate, coumarin, chalcone, and benzophenone.
The photo-alignment material according to 1. 4. The photo-alignment material according to claim 2, wherein the structural unit exhibiting photo-alignment by the photo-isomerization reaction is an azobenzene skeleton or an anthraquinone skeleton. 5. A maleimide derivative represented by the following general formula (1-1): (In the formula, R ₁ is each independently at least one hydrocarbon group selected from the group consisting of an alkylene group, a cycloalkylene group, and an arylene group, or a plurality of these hydrocarbon groups is a single bond, R ₂ represents an organic group linked by a bonding group selected from the group consisting of an ester bond, an ether bond, an amide bond, and a urethane bond, R ₂ represents a structural unit exhibiting photo-alignment, and R ₃ and R ₄ each represent , A hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a phenyl group or a halogen atom, and n represents an integer of 2 to 10.) 3. The photo-alignment material according to 1. 6. A maleimide derivative represented by the following general formula (1-2): (Wherein, each R ₅ is independently at least one hydrocarbon group selected from the group consisting of a single bond, a linear alkylene group, a branched alkylene group, a cycloalkylene group, and an arylene group, or a hydrocarbon such as these. A plurality of groups represents an organic group connected by a bonding group selected from the group consisting of a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond, and R ₆ represents a structural unit exhibiting photo-alignment. , R ₇ , R ₈ , R ₉ and R ₁₀ are each a hydrogen atom, 1-8
Represents an alkyl group, phenyl group or halogen atom containing carbon atoms. The photo-alignment material according to any one of claims 1 to 5, which is represented by: 7. A maleimide derivative represented by the following general formula (1-3): (Wherein, R ₁₁ is each independently a single bond, an alkylene group,
A cycloalkylene group, and at least one hydrocarbon group selected from the group consisting of an arylene group, or a group in which a plurality of these hydrocarbon groups are a single bond, an ester bond, an ether bond, an amide bond, and a urethane bond. Represents an organic group linked by a selected linking group. R ₁₂ represents a trivalent hydrocarbon group. R ₁₃ represents a structural unit exhibiting photo-alignment, and R ₁₄ , R ₁₅ , R ₁₆ and R ₁₇ each represent a hydrogen atom, an alkyl group containing 1 to 8 carbon atoms, a phenyl group or a halogen atom. ).
The photo-alignment material according to any one of the above. 8. The light according to claim 1, wherein the weight ratio of the polyfunctional maleimide derivative having a structural unit exhibiting photo-alignment property to the alkenyl-substituted nadimide derivative is 15/80 to 95/5. Orientation material. 9. A photo-alignment material according to any one of claims 1 to 8, which is applied onto a substrate, and then cured by irradiation with light to cure the maleimide derivative and the alkenyl-substituted nadimide derivative.
And a method of producing a photo-alignment film for performing a photo-reaction of a structural unit exhibiting photo-alignment. 10. A photo-alignment material according to any one of claims 1 to 8, which is applied on a substrate, and the maleimide derivative and the alkenyl-substituted nadimide derivative are cured by heating.
Next, a method for producing a photo-alignment film in which a photoreaction of a structural unit exhibiting photo-alignment properties is performed by light irradiation.