JP2015152743A - Thermosetting composition having photo-aligning property, alignment layer, substrate with alignment layer, retardation plate, and device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting composition having a photo-aligning property, from which an alignment layer excellent in a liquid crystal aligning ability and adhesiveness to a liquid crystal layer can be formed, and an alignment layer, a substrate with an alignment layer, a retardation plate, and a device using the above composition.SOLUTION: The alignment layer includes a photo-dimerization structure or a photo-isomerization structure represented by formula (1) below and a thermally crosslinkable structural unit represented by formula (2) below. In formula (1), X represents a photo-aligning group; Lrepresents a divalent connecting group or a single bond; Rrepresents a hydrogen atom or a monovalent organic group; and k represents 1 to 5. In formula (2), Y represents a thermally crosslinkable group; Lrepresents a divalent connecting group or a single bond; Rrepresents a hydrogen atom or a monovalent organic group; and l represents 1 to 5.

Description

  The present invention relates to a thermosetting composition having photo-alignment used for an alignment layer.

  In addition to liquid crystal display elements, liquid crystals are used in various optical elements such as retardation plates and polarizing plates by utilizing their orientation and anisotropy of physical properties such as refractive index, dielectric constant, and magnetic susceptibility. Applications are being studied.

  An alignment layer is used to align the liquid crystal. As a method for forming the alignment layer, for example, a rubbing method or a photo-alignment method is known. The photo-alignment method does not generate static electricity or dust, which is a problem of the rubbing method, and can control the alignment process quantitatively. (For example, refer to Patent Document 1).

  In addition to the liquid crystal alignment ability, the alignment layer is required to have heat resistance, solvent resistance, and the like. For example, the alignment layer may be exposed to heat or a solvent during the manufacturing process of various devices, or may be exposed to a high temperature when the various devices are used. When the alignment layer is exposed to a high temperature, the liquid crystal alignment ability may be significantly reduced.

  Therefore, for example, in Patent Document 2, in order to obtain stable liquid crystal alignment ability, a liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction by light and a structure crosslinked by heat, and light. A liquid crystal aligning agent containing a polymer component having a structure capable of crosslinking reaction and a compound having a structure crosslinked by heat has been proposed.

  Patent Document 3 discloses (A) an acrylic copolymer having a photodimerization site and a thermal crosslinking site in order to obtain excellent liquid crystal alignment ability, sufficient heat resistance, high solvent resistance and high transparency; (B) The thermosetting film formation composition which has a photo-alignment property containing a crosslinking agent is proposed. (B) A crosslinking agent couple | bonds with the heat-crosslinking site | part of (A) acrylic copolymer, and the thermosetting film formation composition which has photo-orientation property can be hardened by heating.

  In Patent Document 4, in order to obtain excellent liquid crystal alignment ability, sufficient heat resistance, high solvent resistance and high transparency, (A) an acrylic copolymer having a photodimerization site and a thermal crosslinking site, and (B ) A photo-alignment property comprising an acrylic polymer having at least one of a predetermined alkyl ester group and a hydroxyalkyl ester group and at least one of a carboxyl group and a phenolic hydroxy group, and (C) a crosslinking agent. A thermosetting film-forming composition having been proposed. (C) The crosslinking agent is a thermosetting film-forming composition having a photo-alignment property, which is bonded to (A) the thermal crosslinking site of the acrylic copolymer and (B) the carboxyl group and the phenolic hydroxy group of the acrylic polymer. Can be cured by heating.

  Patent Document 5 discloses (A) a compound having a photo-alignment group and a hydroxy group, and (B) a hydroxy group in order to obtain excellent liquid crystal alignment ability, sufficient heat resistance, high solvent resistance and high transparency. And a thermosetting film-forming composition having photo-alignment properties, which contains a polymer having at least one of carboxyl groups and (C) a crosslinking agent. (C) The crosslinking agent binds to the hydroxy group of the compound (A) and the hydroxy group and carboxyl group of the polymer (B), and the thermosetting film-forming composition having photo-alignment property can be cured by heating. .

Japanese Patent No. 40947644 Japanese Patent No. 4207430 International Publication No. 2010/150748 Pamphlet International Publication No. 2011/010635 Pamphlet International Publication No. 2011/126022 Pamphlet

Thus, it has been proposed that thermosetting is performed to improve the heat resistance and solvent resistance of the alignment layer. However, when thermosetting is performed, the hardness of the alignment layer increases, and the adhesion to the liquid crystal layer formed on the alignment layer may decrease. In particular, as in Patent Documents 3 to 4, when an acrylic copolymer having a photodimerization site and a thermal crosslinking site is used, and a thermosetting with a crosslinking agent is performed, a network structure is formed inside the film. Thus, there is a problem that the adhesion between the alignment layer and the liquid crystal layer formed thereon is lowered.
Patent Documents 3 to 4 disclose that the alignment layer formed using the thermosetting film-forming composition having the above-described photo-alignment property has good alignment sensitivity, but the alignment regulation power is sufficient. However, there is room for improvement. Further, in order to increase the alignment regulating power, it is only necessary to increase the irradiation amount of polarized ultraviolet rays. In this case, the throughput is lowered.

  The present invention has been made in view of the above problems, and in a thermosetting composition containing a copolymer having both a photo-alignment site and a thermal cross-linking site, liquid crystal alignment ability and adhesion to a liquid crystal layer. It is a main object to provide a thermosetting composition having a photo-alignment property and an alignment layer, a substrate with an alignment layer, a retardation plate and a device using the same.

  In order to achieve the above object, the present invention contains a copolymer having a photoalignable structural unit represented by the following formula (1) and a thermally crosslinkable structural unit represented by the following formula (2). A thermosetting composition having a photo-alignment characteristic is provided.

(Here, in Formula (1), X is a photo-alignment group, L ¹ is a divalent linking group or a single bond, R ¹ is a hydrogen atom or a monovalent organic group, k is 1 to 5, In (2), Y represents a thermally crosslinkable group, L ² represents a divalent linking group or a single bond, R ² represents a hydrogen atom or a monovalent organic group, and l represents 1 to 5.)

  According to the present invention, both the photo-alignable structural unit and the thermally crosslinkable structural unit of the copolymer have a styrene skeleton and contain many π-electron systems. Therefore, when the alignment layer is formed using the thermosetting composition having photo-alignment property of the present invention, it is considered that an alignment layer having strong interaction with liquid crystal molecules and excellent liquid crystal alignment ability can be obtained. It is done. Furthermore, it is considered that the adhesion with the liquid crystal layer formed on the alignment layer can be improved by the interaction of the π electron system. Moreover, the thermosetting composition having photo-alignment property of the present invention has thermosetting properties, and an alignment layer having excellent heat resistance and solvent resistance can be obtained.

  The thermosetting composition having photo-alignment property of the present invention preferably further contains a crosslinking agent. It is because heat resistance and solvent resistance can be improved.

  In the present invention, the photo-alignment group is preferably a functional group that causes a photodimerization reaction or a photoisomerization reaction. The photo-alignment group is preferably a cinnamoyl group. These photo-alignment groups have the advantages of relatively high sensitivity to light and a wide range of material selection.

  Furthermore, in the present invention, the thermally crosslinkable group is preferably a hydroxy group. This is because the reactivity is high.

  Moreover, in this invention, it is preferable that all the structural units of the said copolymer have a styrene unit. As described above, when the alignment layer is formed using the thermosetting composition having photo-alignment property of the present invention, the liquid crystal alignment ability and the adhesion to the liquid crystal layer are improved by the interaction of π electrons. It is thought that it can be made.

The present invention also provides a photodimerization structure of a photoalignable group possessed by the photoalignable structural unit represented by the above formula (1) and a thermally crosslinkable group possessed by the thermally crosslinkable structural unit represented by the above formula (2). An alignment layer comprising a copolymer having a cross-linked structure is provided.
According to the present invention, since the alignment layer contains a copolymer having a predetermined photodimerization structure and a crosslinked structure, excellent liquid crystal alignment ability, heat resistance and solvent resistance can be obtained.

  The present invention also provides a photodimerization structure of a photoalignable group possessed by the photoalignable structural unit represented by the above formula (1) and a thermally crosslinkable group possessed by the thermally crosslinkable structural unit represented by the above formula (2). There is provided an alignment layer containing a copolymer having a crosslinked structure, wherein the photodimerization structure is a photodimerization structure of a cinnamoyl group.

The present invention also provides a photoisomerizable structure of a photoalignable group possessed by the photoalignable structural unit represented by the above formula (1) and a thermal crosslinkability possessed by the thermally crosslinkable structural unit represented by the above formula (2). Provided is an alignment layer containing a copolymer having a cross-linked structure of groups.
According to the present invention, since the alignment layer contains a copolymer having a predetermined photoisomerization structure and a crosslinked structure, excellent liquid crystal alignment ability, heat resistance and solvent resistance can be obtained.

  The present invention also provides a photoisomerizable structure of a photoalignable group possessed by the photoalignable structural unit represented by the above formula (1) and a thermal crosslinkability possessed by the thermally crosslinkable structural unit represented by the above formula (2). An alignment layer containing a copolymer having a cross-linked structure of a group, wherein the photoisomerization structure is a photoisomerization structure of a cinnamoyl group.

The present invention also includes a substrate and an alignment layer-provided substrate comprising: a substrate; and an alignment layer formed on the substrate and formed from the thermosetting composition having the above-described photo-alignment property or the above-described alignment layer. I will provide a.
According to the present invention, the alignment layer is formed from the thermosetting composition having the above-described photo-alignment property, or is the above-described alignment layer, so that the liquid crystal alignment ability and the adhesion with the liquid crystal layer are improved. An excellent alignment layer can be obtained.

The present invention also provides a retardation plate comprising the above-mentioned substrate with an alignment layer and a retardation layer formed on the alignment layer of the substrate with an alignment layer.
According to this invention, since it has the above-mentioned board | substrate with an alignment layer, it is excellent in liquid crystal aligning ability, heat resistance, and solvent resistance, and can obtain the phase difference plate with a favorable optical characteristic.

Furthermore, this invention provides the device characterized by having the alignment layer formed from the thermosetting composition which has the above-mentioned photo-orientation property, or the above-mentioned alignment layer.
According to the present invention, since the alignment layer is formed from the thermosetting composition having the above-described photo-alignment property or is the above-described alignment layer, the liquid crystal alignment ability and the adhesion with the liquid crystal layer are excellent. Therefore, a device having good optical characteristics can be obtained.

  In the present invention, there is an effect that it is possible to provide a thermosetting composition having a photo-alignment property capable of forming an alignment layer excellent in liquid crystal alignment ability, adhesion to a liquid crystal layer, heat resistance and solvent resistance. Play.

It is a schematic sectional drawing which shows an example of the board | substrate with an alignment layer of this invention. It is a schematic sectional drawing which shows an example of the phase difference plate in this invention. It is a schematic sectional drawing which shows an example of the liquid crystal display element in this invention.

  Hereinafter, the thermosetting composition having photo-alignment property of the present invention and the alignment layer, the substrate with the alignment layer, the retardation plate and the device using the same will be described in detail.

A. Thermosetting composition having photo-alignment property The thermosetting composition having photo-alignment property of the present invention has a photo-alignment constitutional unit represented by the following formula (1) and a heat represented by the following formula (2). It contains a copolymer having a crosslinkable structural unit.

(Here, in Formula (1), X is a photo-alignment group, L ¹ is a divalent linking group or a single bond, R ¹ is a hydrogen atom or a monovalent organic group, k is 1 to 5, In (2), Y represents a thermally crosslinkable group, L ² represents a divalent linking group or a single bond, R ² represents a hydrogen atom or a monovalent organic group, and l represents 1 to 5.)

  The copolymer in the present invention has a photoalignable structural unit represented by the above formula (1) and a thermally crosslinkable structural unit represented by the above formula (2). All of the crosslinkable structural units have a styrene skeleton and contain many π electron systems. In general, many liquid crystal molecules have an aromatic ring such as a benzene ring, and also include a π electron system. Therefore, the alignment layer formed from the thermosetting composition having the photoalignment property of the present invention has a strong interaction with liquid crystal molecules. Thereby, it becomes easy to control alignment of liquid crystal molecules, and it is considered that excellent liquid crystal alignment ability can be obtained. Moreover, it is considered that the alignment layer formed from the thermosetting composition having the photo-alignment property of the present invention has high adhesion to the liquid crystal layer formed on the alignment layer due to the interaction of the π electron system. .

  Moreover, the thermosetting composition having photo-alignment property of the present invention has thermosetting properties, and an alignment layer having excellent heat resistance and solvent resistance can be obtained.

  Hereinafter, each component in the thermosetting composition having the photo-alignment property of the present invention will be described.

1. Copolymer The copolymer used in the present invention has a photo-alignable structural unit represented by the above formula (1) and a thermally crosslinkable structural unit represented by the above formula (2).
Hereinafter, each structural unit in the copolymer will be described.

(1) Photoalignment structural unit The photoalignment structural unit in this invention is represented by following formula (1).

(Here, in Formula (1), X represents a photo-alignment group, L ¹ represents a divalent linking group or a single bond, R ¹ represents a hydrogen atom or a monovalent organic group, and k represents 1 to 5.)

  The photo-alignment structural unit is a site that develops anisotropy by causing a photoreaction by light irradiation. The photoreaction is preferably a photodimerization reaction or a photoisomerization reaction. That is, the photo-alignment structural unit is a photodimerization structural unit that develops anisotropy by generating a photodimerization reaction by light irradiation, or a light that exhibits anisotropy by generating a photoisomerization reaction by light irradiation. An isomerized structural unit is preferred.

  X in the above formula (1) is a photo-alignment group. As described above, the photo-alignment group is a functional group that exhibits anisotropy by causing a photoreaction by light irradiation, and is preferably a functional group that causes a photodimerization reaction or a photoisomerization reaction.

  Examples of the photoalignable group that causes a photodimerization reaction include a cinnamoyl group, a chalcone group, a coumarin group, an anthracene group, a quinoline group, an azobenzene group, and a stilbene group. The benzene ring in these functional groups may have a substituent. Any substituent that does not interfere with the photodimerization reaction may be used, and examples thereof include an alkyl group, an aryl group, a cycloalkyl group, an alkoxy group, a hydroxy group, a halogen atom, a trifluoromethyl group, and a cyano group.

  The photo-alignment group that causes a photoisomerization reaction is preferably one that causes a cis-trans isomerization reaction, and examples thereof include a cinnamoyl group, a chalcone group, an azobenzene group, and a stilbene group. The benzene ring in these functional groups may have a substituent. Any substituent that does not interfere with the photoisomerization reaction may be used, and examples thereof include an alkoxy group, an alkyl group, a halogen atom, a trifluoromethyl group, and a cyano group.

  Among these, the photo-alignment group is preferably a cinnamoyl group. Specifically, the cinnamoyl group is preferably a group represented by the following formulas (3-1) and (3-2).

In the above formula ^{(3-1), R 11} represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group or a cycloalkyl group having 1 to 18 carbon atoms having 1 to 18 carbon atoms. However, the alkyl group, aryl group and cycloalkyl group may be bonded via an ether bond, ester bond, amide bond or urea bond, and may have a substituent. R ^{12 to} R ¹⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, a cycloalkyl group having 1 to 18 carbon atoms, or an alkyl group having 1 to 18 carbon atoms. Represents an alkoxy group or a cyano group. However, the alkyl group, aryl group and cycloalkyl group may be bonded via an ether bond, ester bond, amide bond or urea bond, and may have a substituent. R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.
Further, in the above formula ^{(3-2), R} 21 ~R ²⁵ independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, 1 to 18 aryl group or a carbon of 1 to 18 carbon atoms A cycloalkyl group, an alkoxy group having 1 to 18 carbon atoms, or a cyano group. However, the alkyl group, aryl group and cycloalkyl group may be bonded via an ether bond, ester bond, amide bond or urea bond, and may have a substituent. R ²⁶ and R ²⁷ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 1 to 18 carbon atoms, or an alkoxy group having 1 to 18 carbon atoms.

  In the case where the photo-alignment group is a cinnamoyl group and the group is represented by the above formula (3-1), the benzene ring of the styrene skeleton may be a benzene ring of the cinnamoyl group.

L ¹ in the above formula (1) is a divalent linking group or a single bond. When L ¹ is a single bond, the photoalignable group X is directly bonded to the styrene skeleton. Examples of the divalent linking group include an ether bond, a thioether bond, an ester bond, a thioester bond, a carbonyl bond, a thiocarbonyl bond, an alkylene group, an arylene group, a cycloalkylene group, and combinations thereof. Specifically, —O—, —S—, —COO—, —COS—, —CO—, —OCO—, —OCO (CH ₂ ) _n COO—, —OCO (CH ₂ CH ₂ O) _m COO _{-, - OCOC 6 H 4 O} -, - OCOC 6 H 10 O -, - COO (CH 2) n O -, - COO (CH 2 CH 2 O) m -, - COOC 6 H 4 O -, - COOC ₆ H ₁₀ O—, —O (CH ₂ ) _n O—, —O (CH ₂ CH ₂ O) _m —, —OC ₆ H ₄ O—, —OC ₆ H ₁₀ O—, — (CH ₂ ) _n O- etc. are mentioned. n is 1-20, m is 1-10.

R ¹ in the above formula (1) is a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a methyl group. Among these, R ¹ is preferably a hydrogen atom.

In the above formula (1), k is 1 to 5, and -L ¹ -X may be bonded to any of the ortho, meta, and para positions. When k is 2 to 5, L ¹ and X may be the same as or different from each other. Among them, it is preferable that k is 1 and -L ¹ -X is bonded to the para position. Specifically, the photoalignable structural unit is preferably a structural unit represented by the following formula (1-1). In addition, in the following formula | equation, each code | symbol is the same as that of the said Formula (1).

  Examples of the photoalignable structural unit include structural units represented by the following formulas (1-2) to (1-5).

In the formula (1-2), R ³¹ is the same as R ^{11 in the} formula (3-1), and R ³² and R ³³ are the same as R ¹⁶ and R ^{17 in} the formula (3-1). .
In the above formula (1-3), L ¹¹ represents a single bond or a divalent linking group. The divalent linking group is the same as L ^{1 in the} above formula (1). R ^{11 to} R ¹⁷ are the same as in the above formula (3-1).
In the above formula (1-4), L ¹² represents a single bond or a divalent linking group. The divalent linking group is the same except that the carbonyl bond and the thiocarbonyl bond are excluded from L ¹ in the above formula (1).
In the above formula (1-5), L ¹³ represents a single bond or a divalent linking group. The divalent linking group is the same as L ^{1 in the} above formula (1). R ^{35 to} R ³⁷ are the same as R ^{12 to} R ¹⁵ in the above formula (3-1), and R ³⁸ and R ³⁹ are the same as R ¹⁶ and R ^{17 in} the above formula (3-1).

  The photo-alignment structural unit possessed by the copolymer may be one type or two or more types.

Especially, it is preferable that a photo-alignment structural unit is a structural unit represented by the said Formula (1-3), (1-4).
In the above formula (1-3), L ¹¹ is a single bond, —O—, —COO—, —OCO—, —OCO (CH ₂ ) _n COO—, —OCO (CH ₂ CH ₂ O) _m COO—, _{-OCOC 6 H 10 O -, -} COO (CH 2) n O -, - COO (CH 2 CH 2 O) m -, - COOC 6 H 10 O -, - O (CH 2) n O -, - O _{(CH 2 CH 2 O) m} -, - OC 6 H 10 O- or - _{(CH 2)} n is preferably O-. n is preferably 1 to 11, and m is preferably 1 to 5.
The photo-alignment structural unit represented by the above formula (1-3) is more preferably a structural unit represented by the following formula (1-6).

In the above formula (1-6), R ^{12 to} R ¹⁷ and L ¹¹ are the same as those in the above formula (1-3). R ¹⁸ represents a hydrogen atom, an alkoxy group having 1 to 18 carbon atoms, a cyano group, an alkyl group having 1 to 18 carbon atoms, a phenyl group, a biphenyl group, or a cyclohexyl group. However, the alkyl group, phenyl group, biphenyl group and cyclohexyl group may be bonded via an ether bond, an ester bond, an amide bond or a urea bond. n represents 1 to 5, and R ¹⁸ may be bonded to any of the ortho, meta, and para positions. When n is 2 to 5, R ¹⁸ may be the same as or different from each other. Among them, it is preferable that n is 1 and R ¹⁸ is bonded to the para position.

In the above formula (1-4), L ¹² represents a single bond, —O—, —OCOC ₆ H ₁₀ O—, —COO (CH ₂ ) _n O—, —COO (CH ₂ CH ₂ O) _m —. _{, -COOC 6 H 10 O -,} - O (CH 2) n O -, - O (CH 2 CH 2 O) m -, - OC 6 H 10 O- or - _{(CH 2)} that n is O- Is preferred.

  When the photoalignable structural unit is a structural unit represented by the above formulas (1-6) and (1-4), an aromatic ring comes to be arranged near the end of the photoalignable structural unit, It has a structure similar to liquid crystal molecules. Therefore, it is considered that the affinity with the liquid crystal layer formed on the alignment layer is increased, and the liquid crystal alignment ability and adhesion are improved.

Further, when the photo-alignment structural unit is a structural unit represented by the above formulas (1-6) and (1-4), the photodimerization reactivity or photoisomerization reactivity is increased, and the sensitivity is increased. Can be improved. The reason for this is not clear, but is estimated as follows. That is, since the photoalignment structural unit has a styrene skeleton, a stacking structure is easily formed by the π-electron interaction between the styrene skeletons of the photoalignment structural unit. In the photo-alignment structural units represented by the above formulas (1-6) and (1-4), the photo-alignment group and the styrene skeleton are close to each other. Accordingly, it is presumed that the photo-alignment group is in a positional relationship that easily causes a photodimerization reaction or a photoisomerization reaction. For example, in the case of a photoisomerization reaction, the styrene skeletons of the photoalignment constituent units are stacked, and the photoalignment group and the styrene skeleton are close to each other, so that the orientation of the photoalignment groups is uniform. It is considered that the photoisomerization reactivity becomes high. In the case of the photodimerization reaction, the styrene skeletons of the photoalignment constitutional units are stacked, and the distance between the photoalignment groups is short because the photoalignment group and the styrene skeleton are close to each other. Therefore, it is considered that the photodimerization reactivity is increased.
Therefore, in this case, a thermosetting composition having a highly sensitive photo-orientation capable of forming an alignment layer with a small exposure amount can be obtained, which can contribute to energy saving.
Moreover, since it is highly sensitive, liquid crystal aligning ability can be obtained even when the content ratio of the photoalignable constituent unit in the copolymer is relatively small. Therefore, the content ratio of the heat-crosslinkable structural unit in the copolymer can be relatively increased, and the heat resistance and solvent resistance can be further increased. Furthermore, because of high sensitivity, it is suitable for mass production, and the productivity of a device having an alignment layer formed from a thermosetting composition having photo-alignment properties can also be improved.

  For the synthesis of the copolymer, a styrenic monomer having a photoalignable group forming the photoalignable structural unit can be used. The styrenic monomer having a photo-alignment group can be used alone or in combination of two or more.

As a content rate of the photo-alignment structural unit in a copolymer, when the whole copolymer is 100 mol%, it can set within the range of 10 mol%-90 mol%, Preferably it is 20 mol%- It is in the range of 80 mol%. When the content ratio of the photo-alignment structural unit is small, the sensitivity is lowered, and it may be difficult to impart good liquid crystal alignment ability. In addition, when the content ratio of the photo-alignable structural unit is large, the content ratio of the heat-crosslinkable structural unit is relatively small, sufficient thermosetting property cannot be obtained, and it is difficult to maintain good liquid crystal alignment ability. It may become.
In addition, the content rate of each structural unit in a copolymer can be computed from the integrated value by < ¹ > H NMR measurement.

(2) Thermally crosslinkable structural unit The thermally crosslinkable structural unit in the present invention is represented by the following formula (2). A thermally crosslinkable structural unit is a site | part couple | bonded with a crosslinking agent by heating.

(Here, in formula (2), Y represents a thermally crosslinkable group, L ² represents a divalent linking group or a single bond, R ² represents a hydrogen atom or a monovalent organic group, and l represents 1 to 5).

  Y in the above formula (2) is a thermally crosslinkable group. Examples of the thermally crosslinkable group include a hydroxy group, a carboxy group, a phenolic hydroxy group, a mercapto group, a glycidyl group, and an amide group. Among these, from the viewpoint of reactivity, an aliphatic hydroxy group is preferable, and a primary hydroxy group is more preferable.

L ² in the above formula (2) is a divalent linking group or a single bond. When L ² is a single bond, the thermally crosslinkable group Y is directly bonded to the styrene skeleton. Examples of the divalent linking group include an ether bond, a thioether bond, an ester bond, a thioester bond, a carbonyl bond, a thiocarbonyl bond, an alkylene group, an arylene group, a cycloalkylene group, and combinations thereof. _{Specifically, -OCO (CH 2) n COO} , -OCO (CH 2 CH 2 O) m -, - OCOC 6 H 4 O -, - OCOC 6 H 10 -, - COO (CH 2) n -, _{-COO (CH 2 CH 2 O)} m -, - COOC 6 H 4 O, -COOC 6 H 10 -, - O (CH 2) n -, - O (CH 2 CH 2 O) m -, - OC 6 H ₄ —, —OC ₆ H ₁₀ —, — (CH ₂ ) _n — and the like can be mentioned. n is preferably 4-11. m is preferably 2 to 5. If n and m are too large, the chain length of the linking group in the heat-crosslinkable structural unit becomes long, so that the terminal heat-crosslinkable group is unlikely to appear on the surface, and it is difficult for the crosslinking agent to bind to the heat-crosslinkable group. There is a possibility that the reactivity between the crosslinkable structural unit and the crosslinking agent may be lowered. On the other hand, if n and m are too large, the content ratio of the photo-alignment structural unit in the copolymer is relatively reduced, the sensitivity is lowered, and it may be difficult to impart good liquid crystal alignment ability. . On the other hand, if n and m are too small, the distance between the thermally crosslinkable group and the styrene skeleton in the thermally crosslinkable structural unit is shortened, so that it is difficult for the crosslinking agent to bind to the thermally crosslinkable group. There is a possibility that the reactivity with the cross-linking agent may decrease.

R ² in the above formula (2) is a hydrogen atom or a monovalent organic group. The monovalent organic group is preferably a methyl group. Among these, R ² is preferably a hydrogen atom.

In the above formula (2), l is 1 to 5, ^-L 2 -Y is ortho, meta, or may be bonded to any para position. When l is 2 to 5, L ² and Y may be the same as or different from each other. Among them, l is 1, it is preferable ^{that -L} 2 -Y is attached at the para position. Specifically, the thermally crosslinkable structural unit is preferably a structural unit represented by the following formula (2-1). In addition, in the following formula | equation, each code | symbol is the same as that of the said Formula (2).

The thermally crosslinkable structural unit may have a crosslinking group. In this case, the thermally crosslinkable structural unit can also serve as a crosslinking agent. When using the copolymer which has such a heat crosslinkable unit, the thermosetting composition which has the photo-alignment property of this invention can be utilized without adding a crosslinking agent. However, from the viewpoint of storage stability, the thermally crosslinkable structural unit preferably has no crosslinkable group.
Examples of the thermally crosslinkable structural unit having a crosslinking group include those having a phenolic hydroxy group or glycidyl group in which the ortho position is substituted with a hydroxymethyl group or an alkoxymethyl group.

  The thermal crosslinkable structural unit possessed by the copolymer may be one type or two or more types.

  For the synthesis of the copolymer, a styrenic monomer having a heat-crosslinkable group that forms the above-mentioned heat-crosslinkable structural unit can be used. The styrenic monomer having a thermally crosslinkable group can be used alone or in combination of two or more.

  As a content rate of the heat-crosslinkable structural unit in a copolymer, when the whole copolymer is 100 mol%, it can set within the range of 10 mol%-90 mol%, Preferably it is 20 mol%- It is in the range of 80 mol%. When the content ratio of the thermally crosslinkable structural unit is small, sufficient thermosetting property cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability. In addition, when the content ratio of the thermally crosslinkable structural unit is large, the content ratio of the photoalignable structural unit is relatively decreased, the sensitivity is lowered, and it may be difficult to impart good liquid crystal alignment ability. .

(3) Other Structural Units In the present invention, the copolymer has a structural unit having neither a photo-alignable group nor a heat-crosslinkable group in addition to the photo-alignment structural unit and the heat-crosslinkable structural unit. You may do it. By including other structural units in the copolymer, for example, solvent solubility, heat resistance, reactivity, and the like can be improved.

Examples of the monomer unit constituting the structural unit having no photo-alignable group and heat-crosslinkable group include acrylic acid ester, methacrylic acid ester, maleimide, acrylamide, acrylonitrile, maleic anhydride, styrene, vinyl and the like. Can be mentioned. As described above, the copolymer may be a styrene copolymer in which all the structural units have styrene units, or may have a structural unit other than styrene units.
Especially, it is preferable that the monomer unit which comprises the said structural unit is acrylic acid ester, methacrylic acid ester, and styrene. Acrylic acid ester and methacrylic acid ester monomers have the advantages of high solubility, easy availability as commercial products, and good reactivity when copolymerized. In the case of styrene, as described above, when the alignment layer is formed using the thermosetting composition having the photo-alignment property of the present invention, the liquid crystal alignment ability is improved by the interaction of π electrons. In addition, it is considered that the adhesion to the liquid crystal layer can be improved.
In particular, the monomer unit constituting the structural unit is preferably styrene. That is, the copolymer is preferably a styrene copolymer having all styrene units as structural units.

  Examples of the monomer that forms the structural unit having no photo-alignable group and heat-crosslinkable group include, for example, acrylic ester compounds, methacrylic ester compounds, maleimide compounds, acrylamide compounds, acrylonitrile, maleic anhydride, styrene. Compound, vinyl compound and the like can be mentioned.

  Examples of acrylic ester compounds include methyl acrylate, ethyl acrylate, isopropyl acrylate, benzyl acrylate, naphthyl acrylate, anthryl acrylate, anthryl methyl acrylate, phenyl acrylate, glycidyl acrylate, 2,2,2-trifluoroethyl acrylate, tert-butyl acrylate, cyclohexyl acrylate, isobornyl acrylate, 2-methoxyethyl acrylate, methoxytriethylene glycol acrylate, 2-ethoxyethyl acrylate, 2-aminoethyl acrylate, tetrahydrofurfuryl acrylate, 3-methoxybutyl acrylate, 2- Methyl-2-adamantyl acrylate, 2-propyl-2-adamantyl acrylate DOO, 8-methyl-8-tricyclodecyl acrylate, etc. 8-ethyl-8-tricyclodecyl acrylate.

  Examples of the methacrylic acid ester compound include methyl methacrylate, ethyl methacrylate, isopropyl methacrylate, benzyl methacrylate, naphthyl methacrylate, anthryl methacrylate, anthryl methyl methacrylate, phenyl methacrylate, glycidyl methacrylate, 2,2,2-trifluoroethyl methacrylate, tert-butyl methacrylate, cyclohexyl methacrylate, isobornyl methacrylate, 2-methoxyethyl methacrylate, methoxytriethylene glycol methacrylate, 2-ethoxyethyl methacrylate, 2-aminomethyl methacrylate, tetrahydrofurfuryl methacrylate, 3-methoxybutyl methacrylate, 2- Methyl-2-adamantyl methacrylate , .Gamma.-butyrolactone methacrylate, 2-propyl-2-adamantyl methacrylate, 8-methyl-8-tricyclodecyl methacrylate, 8-ethyl-8-tricyclodecyl methacrylate.

  Examples of the vinyl compound include methyl vinyl ether, benzyl vinyl ether, vinyl naphthalene, vinyl carbazole, allyl glycidyl ether, 3-ethenyl-7-oxabicyclo [4.1.0] heptane, 1,2-epoxy-5-hexene, 1,7-octadiene monoepoxide etc. are mentioned.

  Examples of the styrene compound include styrene, p-methylstyrene, α-methylstyrene, chlorostyrene, bromostyrene, p-trifluoromethylstyrene, p-trifluoromethyl-α-methylstyrene, and 4 (4-trifluoromethyl). Benzoyloxy) styrene, p-cetyloxystyrene, p-palmitoyloxystyrene and the like.

  Examples of the maleimide compound include maleimide, N-methylmaleimide, N-phenylmaleimide, N-cyclohexylmaleimide and the like.

  The constitutional unit having no photo-alignable group and heat-crosslinkable group in the copolymer may be one kind or two or more kinds.

  The content of the structural unit in the copolymer is preferably in the range of 0 mol% to 50 mol%, and in the range of 0 mol% to 30 mol%, assuming that the entire copolymer is 100 mol%. More preferably, it is within. When the content ratio of the structural unit is large, the content ratio of the photoalignable structural unit and the thermally crosslinkable structural unit is relatively reduced, the sensitivity is lowered, and it becomes difficult to impart good liquid crystal alignment ability. Moreover, sufficient thermosetting cannot be obtained, and it may be difficult to maintain good liquid crystal alignment ability.

(4) Copolymer The number average molecular weight of the copolymer is not particularly limited, and can be, for example, about 3,000 to 200,000, preferably in the range of 4,000 to 100,000. It is. If the number average molecular weight is too large, the solubility in a solvent may be lowered or the viscosity may be increased, resulting in a decrease in handleability, and it may be difficult to form a uniform film. On the other hand, if the number average molecular weight is too small, curing may be insufficient during thermosetting, and solvent resistance and heat resistance may be reduced.
The number average molecular weight can be measured by gel permeation chromatography (GPC) method.

Examples of the method for synthesizing the copolymer include a method of copolymerizing a styrene monomer having a photoalignable group and a styrene monomer having a thermally crosslinkable group.
The method for synthesizing the copolymer is not particularly limited. For example, a polymerization reaction is performed in a solvent in which a styrene monomer having a photo-alignment group, a styrene monomer having a thermally crosslinkable group, and a polymerization initiator coexist. Can be obtained. In that case, the solvent used will not be specifically limited if it dissolves the styrene-type monomer which has a photo-alignment group, the styrene-type monomer which has a heat crosslinkable group, a polymerization initiator, etc. Specifically, it can be the same as that of the solvent used for the thermosetting composition which has the photo-alignment property mentioned later. Moreover, the temperature in the case of a polymerization reaction can be set, for example at about 50 to 120 degreeC. The copolymer obtained by the above method is usually in the state of a solution dissolved in a solvent.

The copolymer obtained by the above method can be used as it is, but can also be purified and used by the method shown below.
That is, the copolymer solution obtained by the above method is poured into diethyl ether, methanol, water or the like while stirring to reprecipitate, and the resulting precipitate is filtered and washed, and then at normal pressure or reduced pressure. Then, it can be dried at room temperature or by heating to obtain a powder of the copolymer. By this operation, the polymerization initiator coexisting with the copolymer and the unreacted monomer can be removed, and as a result, a purified copolymer powder is obtained. If sufficient purification cannot be achieved by a single operation, the obtained powder may be redissolved in a solvent and the above operation may be repeated.

  The copolymer may be used in the form of a solution when the copolymer is synthesized, in the form of a powder, or in the form of a solution in which purified powder is redissolved in a solvent described later.

  Further, the copolymer may be one kind or a mixture of plural kinds of copolymers.

2. Crosslinking agent The thermosetting composition having photo-alignment property of the present invention preferably contains a crosslinking agent. A crosslinking agent couple | bonds with the heat-crosslinkable structural unit of the said copolymer, and can improve heat resistance and solvent resistance.

  As a crosslinking agent, an epoxy compound, a methylol compound, an isocyanate compound etc. are mentioned, for example. Of these, methylol compounds are preferred.

Examples of the methylol compound include alkoxymethylated glycoluril, alkoxymethylated benzoguanamine, and alkoxymethylated melamine.
Examples of the alkoxymethylated glycoluril include 1,3,4,6-tetrakis (methoxymethyl) glycoluril, 1,3,4,6-tetrakis (butoxymethyl) glycoluril, 1,3,4,6- Tetrakis (hydroxymethyl) glycoluril, 1,3-bis (hydroxymethyl) urea, 1,1,3,3-tetrakis (butoxymethyl) urea, 1,1,3,3-tetrakis (methoxymethyl) urea, , 3-bis (hydroxymethyl) -4,5-dihydroxy-2-imidazolinone, 1,3-bis (methoxymethyl) -4,5-dimethoxy-2-imidazolinone, and the like. As commercially available products, compounds such as glycoluril compounds (trade names Cymel 1170, Powderlink 1174) manufactured by Mitsui Cytec Co., Ltd., methylated urea resins (trade name UFR65), butylated urea resins (trade names UFR300, U-VAN10S60, U-VAN10R, U-VAN11HV), Dainippon Ink & Chemicals Co., Ltd. urea / formaldehyde resin (high condensation type, trade name Beccamin J-300S, Beccamin P-955, Beccamin N), Sanwa Chemical Co., Ltd. Examples include glycoluril compound (trade name: Nicarak MX-270), imidazolidine compound (trade name: Nicalac MX-280), and the like.
Examples of the alkoxymethylated benzoguanamine include tetramethoxymethyl benzoguanamine. Examples of commercially available products include Mitsui Cytec Co., Ltd. (trade name: Cymel 1123), Sanwa Chemical Co., Ltd. (trade names: Nicarak BX-4000, Nicarac BX-37, Nicarac BL-60, Nicarac BX-55H) and the like. It is done.
Examples of the alkoxymethylated melamine include hexamethoxymethyl melamine. As commercially available products, methoxymethyl type melamine compounds (trade names Cymel 300, Cymel 301, Cymel 303, Cymel 350, Cymel 3745) manufactured by Mitsui Cytec Co., Ltd., butoxymethyl type melamine compounds (trade names My Coat 506, My Coat 508, Cymel 1156), methoxymethyl type melamine compound manufactured by Sanwa Chemical Co., Ltd. (trade names: Nicarak MW-30, Nicarak MW-22, Nicarac MW-11, Nicarak MS-001, Nicarac MX-002, Nicarac MX-730, Nicarac MX-750 , Nicarax MX-035, Nicarak MW-390, Nicarak MW-100LM, Nicarax MX-750LM), Butoxymethyl type melamine compounds (trade names Nicarax MX-45, Nicarac MX-4) 0 include NIKALAC MX-302) or the like.

  A cross-linking agent containing a plurality of benzene rings in the molecule can also be used. Examples of the crosslinking agent containing a plurality of benzene rings in the molecule include, for example, a phenol derivative having at least two hydroxymethyl groups or alkoxymethyl groups and a molecular weight of 1200 or less, or at least two free N-alkoxymethyl groups. Melamine-formaldehyde derivatives and alkoxymethylglycoluril derivatives having A phenol derivative having a hydroxymethyl group can be obtained by reacting a corresponding phenol compound having no hydroxymethyl group with formaldehyde in the presence of a base catalyst.

  Further, the crosslinking agent may be a compound obtained by condensing such a melamine compound, urea compound, glycoluril compound and benzoguanamine compound in which a hydrogen atom of an amino group is substituted with a methylol group or an alkoxymethyl group. For example, the high molecular weight compound manufactured from the melamine compound and the benzoguanamine compound which are described in US Patent 6,323,310 is mentioned. As a commercial product of the melamine compound, trade name Cymel 303 (manufactured by Mitsui Cytec Co., Ltd.) and the like can be mentioned. As a commercial item of a benzoguanamine compound, trade name Cymel 1123 (manufactured by Mitsui Cytec Co., Ltd.) and the like can be mentioned.

Furthermore, as a crosslinking agent, an acrylamide compound or methacrylamide substituted with a hydroxymethyl group or an alkoxymethyl group such as N-hydroxymethylacrylamide, N-methoxymethylmethacrylamide, N-ethoxymethylacrylamide, N-butoxymethylmethacrylamide, etc. Polymers produced using the compounds can also be used.
Examples of such a polymer include poly (N-butoxymethylacrylamide), a copolymer of N-butoxymethylacrylamide and styrene, a copolymer of N-hydroxymethylmethacrylamide and methylmethacrylate, and N-ethoxymethyl. Examples thereof include a copolymer of methacrylamide and benzyl methacrylate, and a copolymer of N-butoxymethylacrylamide, benzyl methacrylate and 2-hydroxypropyl methacrylate. The weight average molecular weight of such polymers is in the range of 1,000 to 500,000, preferably in the range of 2,000 to 200,000, more preferably in the range of 3,000 to 150,000. More preferably, it is in the range of 3,000 to 50,000.

  These crosslinking agents can be used alone or in combination of two or more.

  The content of the crosslinking agent in the thermosetting composition having photo-alignment property of the present invention is preferably in the range of 1 to 40 parts by mass, more preferably 100 parts by mass of the copolymer. It is in the range of 2 to 30 parts by mass. If the content is too small, the heat resistance and solvent resistance of the cured film formed from the thermosetting composition having photo-alignment properties may decrease, and the liquid crystal alignment ability may decrease. Moreover, when there is too much content, liquid crystal aligning ability and storage stability may fall.

3. Acid or acid generator The thermosetting composition having photo-alignment property of the present invention may contain an acid or an acid generator. With the acid or the acid generator, the thermosetting reaction of the thermosetting composition having photo-alignment property of the present invention can be promoted.

  Examples of the acid or acid generator include a sulfonic acid group-containing compound, hydrochloric acid or a salt thereof, and a compound that generates an acid upon thermal drying and curing of a coating film, that is, a thermal decomposition at a temperature of 50 ° C. to 250 ° C. The compound is not particularly limited as long as it is a compound that generates an acid. Examples of such compounds include hydrochloric acid, methanesulfonic acid, ethanesulfonic acid, propanesulfonic acid, butanesulfonic acid, pentanesulfonic acid, octanesulfonic acid, benzenesulfonic acid, p-toluenesulfonic acid, camphorsulfonic acid, trifluoromethane. Sulfonic acid, p-phenolsulfonic acid, 2-naphthalenesulfonic acid, mesitylenesulfonic acid, p-xylene-2-sulfonic acid, m-xylene-2-sulfonic acid, 4-ethylbenzenesulfonic acid, 1H, 1H, 2H, 2H -Sulfonic acids such as perfluorooctane sulfonic acid, perfluoro (2-ethoxyethane) sulfonic acid, pentafluoroethane sulfonic acid, nonafluorobutane-1-sulfonic acid, dodecylbenzene sulfonic acid, or hydrates or salts thereof. Can be mentioned. Examples of the compound that generates an acid by heat include bis (tosyloxy) ethane, bis (tosyloxy) propane, bis (tosyloxy) butane, p-nitrobenzyl tosylate, o-nitrobenzyl tosylate, 1,2.3-phenylene. Tris (methylsulfonate), p-toluenesulfonic acid pyridinium salt, p-toluenesulfonic acid morphonium salt, p-toluenesulfonic acid ethyl ester, p-toluenesulfonic acid propyl ester, p-toluenesulfonic acid butyl ester, p-toluene Sulfonic acid isobutyl ester, p-toluenesulfonic acid methyl ester, p-toluenesulfonic acid phenethyl ester, cyanomethyl p-toluenesulfonate, 2,2,2-trifluoroethyl p-toluenesulfonate, 2-hydroxybutyrate Le p- tosylate, N- ethyl-4-toluenesulfonamide, and the like. Moreover, what is described in the international publication 2010/150748 pamphlet can also be used as a compound which generate | occur | produces an acid by a heat | fever.

  The content of the acid or acid generator in the thermosetting composition having photo-alignment property of the present invention is preferably within a range of 0.01 to 20 parts by mass with respect to 100 parts by mass of the copolymer. More preferably, it is in the range of 0.05 to 10 parts by mass, and further preferably in the range of 0.1 to 5 parts by mass. By making content of an acid or an acid generator into the said range, sufficient thermosetting and solvent tolerance can be provided, and also the high sensitivity with respect to light irradiation can be provided. On the other hand, when there is too much content, the storage stability of the thermosetting composition which has photoalignment may fall.

4). Sensitizer The thermosetting composition having photo-alignment property of the present invention may contain a sensitizer. Photosensitizers such as photodimerization reaction and photoisomerization reaction can be promoted by the sensitizer.

  Examples of the sensitizer include benzophenone, anthracene, anthraquinone, thioxanthone and derivatives thereof, and nitrophenyl compounds. Of these, benzophenone derivatives and nitrophenyl compounds are preferred. Preferable compounds include N, N-diethylaminobenzophenone, 2-nitrofluorene, 2-nitrofluorenone, 5-nitroacenaphthene, 4-nitrobiphenyl and the like. Sensitizers can be used alone or in combination of two or more compounds.

  The content of the sensitizer in the thermosetting composition having photo-alignment property of the present invention is preferably in the range of 0.1 to 20 parts by mass with respect to 100 parts by mass of the copolymer. More preferably, it exists in the range of 0.2 mass part-10 mass parts. If the content is too small, the effect as a sensitizer may not be sufficiently obtained. If the content is too large, the transmittance may be lowered and the coating film may be roughened.

5. Solvent The thermosetting composition having photo-alignment property of the present invention is mainly used in a solution state dissolved in a solvent.
The solvent is not particularly limited as long as it can dissolve the above-described components. For example, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate, diethylene glycol monomethyl ether, diethylene glycol mono Ethyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol propyl ether acetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, toluene, xylene, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-butanone, 3-methyl -2-pentanone, 2-pentanone, 2 Heptanone, γ-butyrolactone, ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, ethyl ethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-3-methylbutanoate, methyl 3-methoxypropionate, 3 -Ethyl methoxypropionate, ethyl 3-ethoxypropionate, methyl 3-ethoxypropionate, methyl pyruvate, ethyl pyruvate, ethyl acetate, butyl acetate, ethyl lactate, butyl lactate, N, N-dimethylformamide, N, N -Dimethylacetamide, N-methylpyrrolidone and the like. A solvent can be used individually by 1 type or in combination of 2 or more types.

  Among them, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, ethylene glycol dimethyl ether, propylene glycol dimethyl ether, methyl ethyl ketone, cyclohexanone, 2-heptanone, propylene glycol propyl ether, propylene glycol propyl ether acetate, ethyl lactate, butyl lactate, 3-methoxypropion Methyl acid, ethyl 3-methoxypropionate, ethyl 3-ethoxypropionate, and methyl 3-ethoxypropionate are preferable because they have good film formability and high safety.

6). Additives The thermosetting composition having the photo-alignment property of the present invention is a silane coupling agent, a surfactant, a rheology modifier, a pigment, a dye, a storage as long as the effects of the present invention are not impaired. Stabilizers, antifoaming agents, antioxidants and the like can be contained. Moreover, a liquid crystalline monomer can be contained in order to improve the liquid crystal alignment ability.

7). Thermosetting composition having photo-alignment property The thermosetting composition having photo-alignment property of the present invention is usually used as a solution in which each component is dissolved in a solvent. The ratio of the solid content in the thermosetting composition having photo-alignment property of the present invention is not particularly limited as long as each component is uniformly dissolved in the solvent, and is 0.1% by mass to 80% by mass. It is within the range, preferably within the range of 0.5% by mass to 60% by mass, and more preferably within the range of 0.5% by mass to 40% by mass. If the ratio of the solid content is too small, it may be difficult to impart liquid crystal alignment ability and thermosetting property. Moreover, when there are too many ratios of solid content, the viscosity of the thermosetting composition which has photo-orientation property will become high, and it will become difficult to form a uniform film | membrane.
In addition, solid content means what remove | excluded the solvent from all the components of the thermosetting composition which has photo-orientation property.

The method for preparing the thermosetting composition having photo-alignment property of the present invention is not particularly limited, but since the storage stability becomes long, a copolymer, a crosslinking agent, a sensitizer, and other additives. Is preferably used, and an acid or an acid generator is added later. In addition, when adding an acid or an acid generator from the beginning, it is preferable to use as the acid or an acid generator a compound that generates an acid by thermal decomposition during drying and heat curing of the coating film.
In the preparation of the thermosetting composition having photo-alignment property of the present invention, a copolymer solution obtained by a polymerization reaction in a solvent can be used as it is. In this case, as described above, a crosslinking agent, a sensitizer, and other additives are added to the copolymer solution to form a uniform solution, and an acid or an acid generator is added later. At this time, a solvent may be further added for the purpose of adjusting the concentration. At this time, the solvent used in the process of forming the copolymer and the solvent used for adjusting the concentration of the thermosetting composition having photo-alignment property may be the same or different.

  Moreover, it is preferable to use, after filtering the prepared solution of the thermosetting composition which has photo-alignment property using the filter etc. with a pore diameter of about 0.2 micrometer.

8). Uses Examples of uses of the thermosetting composition having photo-alignment properties of the present invention include alignment layers for various optical elements such as retardation plates and alignment layers for liquid crystal display elements. The thermosetting composition having photo-alignment property of the present invention can also be used for insulating films and protective films in various devices such as liquid crystal display elements, organic EL elements, TFTs, and color filters. For example, organic EL elements Insulating film, TFT interlayer insulating film, color filter overcoat layer, and the like.

B. Alignment layer The alignment layer of the present invention has two embodiments. In the following, each embodiment will be described separately.

1. First Embodiment The alignment layer according to this embodiment includes a photo-dimerization structure of a photo-alignment group included in a photo-alignment unit represented by the above formula (1) and a heat crosslinkable structure represented by the above formula (2). It contains a copolymer having a crosslinked structure of thermally crosslinkable groups in the unit.

  According to the present invention, since the alignment layer contains a copolymer having a predetermined photodimerization structure and a crosslinked structure, excellent liquid crystal alignment ability, heat resistance and solvent resistance can be obtained.

  Here, the cross-linked structure refers to a three-dimensional network structure. The crosslinked structure does not include a structure in which photoalignable groups described later are crosslinked by a photodimerization reaction.

The copolymer has a crosslinked structure of thermally crosslinkable groups that the thermally crosslinkable structural unit represented by the above formula (2) has. The cross-linked structure is composed of a photo-alignable constituent unit represented by the above formula (1) and a heat cross-linkable constitution represented by the above formula (2) described in “A. Thermosetting composition having photo-alignment”. It can be formed by thermosetting a copolymer having units. The cross-linked structure is a three-dimensional network structure and is a structure in which the heat crosslinkable group of the heat crosslinkable structural unit is cross-linked. Usually, the heat crosslinkable group which a thermal crosslinkable structural unit has couple | bonds with the crosslinking group which a crosslinking agent or a heat crosslinkable structural unit has. Accordingly, the crosslinked structure is a structure in which the thermally crosslinkable group and the crosslinking group of the crosslinking agent or the thermally crosslinkable structural unit are crosslinked by heating.
For example, when the cross-linking agent is hexamethoxymethylmelamine, the cross-linked structure is as shown below. In addition, in the following formula | equation, each code | symbol is the same as that of the said Formula (1).

In addition, since each structural unit of the copolymer was described in detail in the above-mentioned “A. Thermosetting composition having photo-alignment”, description thereof is omitted here.
It can be confirmed that the alignment layer contains the copolymer by collecting and analyzing the material from the alignment layer. As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a combination thereof can be applied.

In addition, the alignment layer has a photodimerization structure of a photoalignment group included in the photoalignment structural unit represented by the above formula (1). The photodimerization structure is a structure in which the photoalignment groups of the photoalignment structural unit represented by the above formula (1) are cross-linked by a photodimerization reaction, and has a cyclopropane skeleton.
The photodimerization reaction is a reaction as shown below, and is a reaction in which an olefin structure contained in a photoalignable group forms a cyclopropane skeleton by a photoreaction. Xa to Xd and Xa ′ to Xd ′ differ depending on the type of photo-alignment group.

  The photodimerization structure is preferably a photodimerization structure of a cinnamoyl group. Specifically, a structure in which cinnamoyl groups described in “A. Thermosetting composition having photo-alignment property” are cross-linked by a photodimerization reaction is preferable. In particular, the alignment layer preferably has a photodimerization structure represented by the following formulas (5-1) and (5-2). In addition, in the following formula | equation, each code | symbol is the same as that of said formula (1-6) and (1-4).

  When the alignment layer has a photodimerization structure represented by the above formulas (5-1) and (5-2), many aromatic rings are arranged and many π electrons are contained. Therefore, it is considered that the affinity with the liquid crystal layer formed on the alignment layer is increased, the liquid crystal alignment ability is improved, and the adhesion with the liquid crystal layer is increased.

  In addition, it can be analyzed by NMR or IR that the alignment layer has the photodimerization structure.

  The alignment layer may contain a crosslinking agent, an acid or acid generator, a sensitizer, and other additives. In addition, about these additives, it is the same as that of what was described in said "A. Thermosetting composition which has photo-orientation property".

  About the formation method and film thickness of an alignment layer, since it is the same as that of the alignment layer in the board | substrate with an alignment layer mentioned later, description here is abbreviate | omitted.

2. Second Embodiment The alignment layer of this embodiment includes a photoisomerizable structure of a photoalignable group contained in the photoalignable structural unit represented by the above formula (1) and a thermal crosslinkability represented by the above formula (2). It contains a copolymer having a crosslinked structure of a thermally crosslinkable group in a structural unit.

  According to this embodiment, since the alignment layer contains a copolymer having a predetermined photoisomerization structure and a crosslinked structure, excellent liquid crystal alignment ability, heat resistance and solvent resistance can be obtained.

The alignment layer has a photoisomerization structure of a photoalignment group included in the photoalignment structural unit represented by the above formula (1). The photoisomerization structure is a structure in which the photoalignment group of the photoalignment structural unit represented by the above formula (1) is isomerized by a photoisomerization reaction. For example, in the case of a cis-trans isomerization reaction, the photoisomerization structure may be either a structure in which a cis isomer is changed to a trans isomer or a structure in which a trans isomer is changed to a cis isomer.
For example, when the photoalignment group is a cinnamoyl group, the photoisomerization reaction is a reaction as shown below, and the olefin structure contained in the photoalignment group is a reaction that forms a cis isomer or a trans isomer by the photoreaction. . Xa to Xd differ depending on the type of photo-alignment group.

  The photoisomerization structure is preferably a photoisomerization structure of a cinnamoyl group. Specifically, a structure in which the cinnamoyl group described in “A. Thermosetting composition having photo-alignment property” is isomerized by a photoisomerization reaction is preferable. In this case, the photoisomerization structure may be either a structure in which the cis form is changed to a trans form or a structure in which the trans form is changed to a cis form. Especially, it is preferable that an orientation layer has a photoisomerization structure of the cinnamoyl group represented by the said Formula (1-3) as shown by a following formula.

  The photoisomerization structure can be confirmed by the same method as in the first embodiment.

Since the crosslinked structure and the copolymer are the same as those in the first embodiment, description thereof is omitted here.
The crosslinked structure can be confirmed by the same method as in the first embodiment.

C. Substrate with alignment layer The substrate with alignment layer of the present invention comprises a substrate and an alignment layer formed on the substrate and formed from the thermosetting composition having the above-described photo-alignment property or the above-described alignment layer. It is characterized by.

  FIG. 1 is a schematic sectional view showing an example of a substrate with an alignment layer of the present invention. In the substrate with alignment layer 1 illustrated in FIG. 1, an alignment layer 3 is formed on the substrate 2, and the alignment layer 3 is formed from the thermosetting composition having the above-described photo-alignment property, or the above-described one. Orientation layer.

  According to the present invention, the alignment layer is formed from the thermosetting composition having the above-mentioned photo-orientation property, or by being the above-described alignment layer, it has excellent liquid crystal alignment ability and adhesion with the liquid crystal layer. , Heat resistance and solvent resistance can be obtained.

  Hereinafter, each structure in the board | substrate with an alignment layer of this invention is demonstrated.

1. Alignment layer The alignment layer in this invention is formed from the thermosetting composition which has the above-mentioned photo-alignment property, or is the above-mentioned alignment layer, and has a function to orient liquid crystal molecules.

Here, the alignment layer formed from the thermosetting composition having photo-alignment refers to an alignment layer obtained by thermo-curing a film containing a thermo-setting composition having photo-alignment and further photo-aligning. Say.
That is, in forming the alignment layer, first, a thermosetting composition having photo-alignment property is applied onto the substrate, dried and heated to form a cured film. Next, the cured layer is irradiated with polarized ultraviolet rays to form an alignment layer.

  The application method of the thermosetting composition having photo-alignment is not particularly limited as long as it is a method capable of forming a uniform film on the substrate. For example, spin coating method, roll coating method, rod bar coating Method, spray coating method, air knife coating method, slot die coating method, wire bar coating method, flow coating method, ink jet method and the like.

  For example, a hot plate or an oven can be used for drying the coating film. The temperature can be set, for example, at about 30 ° C. to 160 ° C., and preferably within the range of 50 ° C. to 140 ° C. The time can be set, for example, for about 20 seconds to 60 minutes, and is preferably in the range of 30 seconds to 10 minutes.

  A hot plate, an oven, or the like can also be used for heat curing of the coating film. The temperature can be set, for example, at about 30 ° C to 250 ° C. The time can be set, for example, for about 20 seconds to 60 minutes. Moreover, drying and heat curing of the coating film may be performed simultaneously or separately.

  The film thickness of the cured film obtained by thermosetting the thermosetting composition having photo-alignment is appropriately selected according to the application and the like, and can be, for example, about 0.05 μm to 30 μm. In addition, when the film thickness of a cured film is too thin, sufficient liquid crystal aligning ability may not be obtained.

  The obtained cured film can be irradiated with polarized ultraviolet rays to cause a photoreaction and develop anisotropy. The wavelength of polarized ultraviolet light is usually in the range of 150 nm to 450 nm. Moreover, the irradiation direction of polarized ultraviolet rays can be perpendicular or oblique to the substrate surface.

  In addition, it can confirm that an alignment layer is formed from the thermosetting composition which has the above-mentioned photo-alignment property by extract | collecting and analyzing a material from an alignment layer. As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a combination thereof can be applied.

2. Substrate The substrate used in the present invention supports the alignment layer.
The substrate is not particularly limited, and is appropriately selected depending on the application. Examples of the material for the substrate include glass, quartz, polyethylene terephthalate, polycarbonate, triacetyl cellulose, polyester, acrylic and other resins, metals such as aluminum, and ceramics such as silicon and silicon nitride. The substrate may be subjected to a surface treatment.
The substrate may or may not have flexibility, and is appropriately selected according to the use or the like.

3. Conductive layer In the present invention, a conductive layer may be formed between the substrate and the alignment layer. The conductive layer functions, for example, as an electrode for various devices. Examples of the material for the conductive layer include transparent conductive materials such as ITO and IZO, and metal materials such as aluminum, molybdenum, and chromium.

4). Applications Examples of the use of the substrate with an alignment layer of the present invention include various optical elements such as a retardation plate, liquid crystal display elements, and light emitting elements.

D. Retardation plate The retardation plate of the present invention comprises the above-mentioned substrate with an alignment layer and a retardation layer formed on the alignment layer of the above-mentioned substrate with alignment layer.

  FIG. 2 is a schematic sectional view showing an example of the retardation plate of the present invention. In the retardation plate 10 illustrated in FIG. 2, the alignment layer 12 is formed on the substrate 11, and the retardation layer 13 is formed on the alignment layer 12. The alignment layer 12 is formed from the above-described thermosetting composition having photo-alignment or the above-described alignment layer, and the retardation layer 13 corresponds to a liquid crystal layer.

The retardation layer can be obtained by applying a liquid crystal composition on the alignment layer, heating to the phase transition temperature of the liquid crystal composition, aligning the liquid crystal molecules by the alignment layer, and curing.
As the liquid crystal composition used for the retardation layer, those generally used for retardation layers can be used. Some liquid crystal compositions have alignment properties such as horizontal alignment, cholesteric alignment, vertical alignment, and hybrid alignment, and are appropriately selected according to the combination with the alignment layer, a desired retardation, and the like. In addition, the thickness and the forming method of the retardation layer can be the same as those of a general retardation layer.

  The phase difference plate may or may not have flexibility.

E. Device The device of the present invention is characterized by having an alignment layer formed from the thermosetting composition having the above-mentioned photo-orientation or the above-mentioned alignment layer.

The device is not particularly limited as long as it has an alignment layer, and examples thereof include various optical elements such as a retardation plate, liquid crystal display elements, and light emitting elements.
Hereinafter, the description will be divided into a retardation plate and a liquid crystal display element.

1. Retardation Plate The retardation plate in the present invention is formed on a substrate and an alignment layer formed on the substrate and formed from the thermosetting composition having the above-described photo-orientation property or the alignment layer and the alignment layer. And a retardation layer.
In addition, since it described in said "D. phase difference plate" about the phase difference layer, description here is abbreviate | omitted.
A conductive layer may be formed between the substrate and the alignment layer. The substrate, the alignment layer, and the conductive layer are the same as the substrate, the alignment layer, and the conductive layer in the “B. Substrate with alignment layer” described above, and thus description thereof is omitted here.
The phase difference plate may or may not have flexibility.

2. Liquid crystal display element The liquid crystal display element in this invention has two aspects. Hereinafter, the description will be made separately for each aspect.

(1) First Aspect A first aspect of the liquid crystal display element in the present invention is a substrate with a first alignment layer in which a first alignment layer is formed on a first substrate, and a second alignment layer is formed on a second substrate. And a liquid crystal layer disposed between the substrate with the first alignment layer and the substrate with the second alignment layer. The first alignment layer and the second alignment layer are the above-described ones. It is formed from the thermosetting composition which has the photo-alignment property, or the above-mentioned alignment layer.

  FIG. 3 is a schematic cross-sectional view showing an example of the liquid crystal display element in the present invention. The liquid crystal display element 20 illustrated in FIG. 3 is disposed between the first alignment layer-attached substrate 21a, the second alignment layer-attached substrate 21b, the first alignment layer-attached substrate 21a, and the second alignment layer-attached substrate 21b. And a liquid crystal layer 25. In the substrate 21a with the first alignment layer, the first electrode 23a and the first alignment layer 24a are sequentially stacked on the first substrate 22a. In the substrate with the second alignment layer 21b, the second electrode is formed on the second substrate 22b. 23b and the second alignment layer 24b are sequentially stacked. The first alignment layer 24a and the second alignment layer 24b are formed from the thermosetting composition having the above-described photo-alignment property, or the above-described alignment layer.

  As the liquid crystal composition used for the liquid crystal layer, those generally used for the liquid crystal layer can be used. For example, a nematic liquid crystal or a smectic liquid crystal can be used. Further, the film thickness and the forming method of the liquid crystal layer can be the same as those of a general liquid crystal layer.

In addition, a conductive layer is usually formed as an electrode between at least one of the first substrate and the alignment layer and between the second substrate and the alignment layer.
The first substrate, the second substrate, the alignment layer, and the conductive layer are the same as the substrate, the alignment layer, and the conductive layer in “B. Substrate with alignment layer” described above, and thus description thereof is omitted here.
Further, the other configuration of the liquid crystal display element can be the same as that of a general liquid crystal display element.

(2) Second Aspect A second aspect of the liquid crystal display element according to the present invention has the retardation plate.
The configuration of the liquid crystal display element can be the same as that of a general liquid crystal display element. For example, a retardation plate may be arranged outside the substrate constituting the liquid crystal display element, and the substrate constituting the liquid crystal display element also serves as the substrate constituting the retardation plate, and the alignment layer and the position are arranged inside the substrate. A phase difference layer may be disposed.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

  Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples.

[Synthesis Example a] Synthesis of Thermally Crosslinkable Monomer 1 In a 300 mL flask, under ice cooling, 20.15 g (136 mmol) of 4-vinylbenzoic acid, 7.3 g (118 mmol) of ethylene glycol, 0.458 g (3. 82 mmol) was dissolved in 130 ml of dichloromethane, and 28.0 g (136 mmol) of N, N′-dicyclohexylcarbodiimide dissolved in 40 ml of dichloromethane was added dropwise over about 10 minutes. After stirring for 15 hours, the reaction solution was cooled and the precipitate was filtered off. The solvent was distilled off, methanol was added, and 15.5 g of thermally crosslinkable monomer 1 was obtained by recrystallization.

[Synthesis Example b] Synthesis of Thermally Crosslinkable Monomer 2 In Synthesis Example a, instead of using ethylene glycol, an equimolar amount of diethylene glycol is used and condensed in the same manner as in Synthesis Example a to obtain thermally crosslinkable monomer 2. It was.

[Synthesis Example c] Synthesis of Thermally Crosslinkable Monomer 3 In Synthesis Example a, instead of using ethylene glycol, an equimolar amount of 1,4-cyclohexanediol is used to condense in the same manner as in Synthesis Example a, thereby thermally crosslinking. Monomer 3 was obtained.

[Synthesis Example d] Synthesis of Thermally Crosslinkable Monomer 4 In a 200 mL flask, in a nitrogen atmosphere, 20.0 g (118 mmol) of p-acetoxystyrene was dissolved in 80 mL of ethyl acetate, and 9.08 g (47.1 mmol) of sodium methoxide was dissolved. Was slowly added dropwise over about 30 minutes. After stirring for 1 hour and a half, the completion of the reaction was confirmed by TLC, extracted with ethyl acetate, washed with 1N hydrochloric acid, pure water and saturated brine, and dried over sodium sulfate. The solvent was distilled off and dried to obtain thermally crosslinkable monomer 4.

[Synthesis Example e] Synthesis of Thermally Crosslinkable Monomer 5 Thermally crosslinkable monomer 4 was obtained in the same manner as in Synthesis Example d. In a 200 mL flask, 14.0 g (118 mmol) of thermally crosslinkable monomer 4 was dissolved in 100 ml of dimethylformamide under nitrogen atmosphere and zero ice, 7.07 g (177 mmol) of sodium hydroxide was added, and the mixture was stirred for 15 minutes, then 2 -10.5 g (130 mmol) of chloroethanol was added dropwise over about 10 minutes. After stirring for 16 hours, the completion of the reaction was confirmed by TLC, extracted with ethyl acetate, washed with saturated aqueous bicarbonate solution, 1N hydrochloric acid, pure water and saturated brine, and dried over sodium sulfate. The solvent was distilled off and dried to obtain thermally crosslinkable monomer 5.

[Synthesis Example f] Synthesis of Thermally Crosslinkable Monomer 6 Thermally crosslinkable monomer 4 was obtained in the same manner as in Synthesis Example d. In Synthesis Example e, instead of using 2-chloroethanol, an equimolar amount of 6-chlorohexanol was used for etherification in the same manner as in Synthesis Example d to obtain thermally crosslinkable monomer 6.

[Synthesis Example g] Synthesis of Thermally Crosslinkable Monomer 7 Thermally crosslinkable monomer 4 was obtained in the same manner as in Synthesis Example d. In a 500 mL flask, 12 g (100 mmol) of thermally crosslinkable monomer 4, 16.1 g (110 mmol) of adipic acid and 1.2 g (9.8 mmol) of dimethylaminopyridine were dissolved in 130 ml of dichloromethane, and N, N ′ dissolved in 40 ml of dichloromethane. -22.6 g (110 mmol) of dicyclohexylcarbodiimide was added dropwise over about 10 minutes. After stirring for 15 hours, the reaction solution was cooled and the precipitate was filtered off. The solvent was distilled off, methanol was added, and carboxylic acid derivative 1 was obtained by recrystallization.
Subsequently, 13.82 g (50 mmol) of carboxylic acid derivative 1, 5.5 g (50 mmol) of hydroquinone, and 0.176 g (1.47 mmol) of dimethylaminopyridine were dissolved in 50 ml of dichloromethane in a 300 mL flask under ice-cooling, and 10 ml of dichloromethane. N, N′-dicyclohexylcarbodiimide (11.3 g, 55 mmol) dissolved in was added dropwise over about 10 minutes. After stirring for 15 hours, the reaction solution was cooled and the precipitate was filtered off. The solvent was distilled off, methanol was added, and thermally crosslinkable monomer 7 was obtained by recrystallization.

Synthesis Example h Synthesis of Thermally Crosslinkable Monomer 8 In a 200 mL flask, 20.0 g (118 mmol) of p-acetoxystyrene was dissolved in 80 mL of ethyl acetate in a nitrogen atmosphere, and 9.08 g (47.1 mmol) of sodium methoxide was dissolved. Was slowly added dropwise over about 30 minutes. After stirring for 1.5 hours and confirming the completion of the reaction by TLC, 56.0 mL (944 mmol) of 37% formalin aqueous solution was slowly added to this solution at room temperature. Furthermore, after stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was poured into 200 mL of water in a beaker. While cooling this in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was collected by filtration, sufficiently washed with water, dried, and purified by column chromatography to obtain thermally crosslinkable monomer 8.

[Synthesis Example i] Synthesis of Thermally Crosslinkable Monomer 9 Thermally crosslinkable monomer 7 was obtained in the same manner as in Synthesis Example g. To a solution consisting of 20 mL of a 10 wt% aqueous potassium hydroxide solution and 20 mL of ethanol was added 7.68 g (10 mmol) of a heat-crosslinkable monomer, and the mixture was stirred and dissolved at room temperature. To this solution, 7.0 mL (80 mmol) of 37% formalin aqueous solution was slowly added at room temperature. Furthermore, after stirring at 40 ° C. for 24 hours under a nitrogen atmosphere, the mixture was poured into 200 mL of water in a beaker. While cooling this in an ice bath, a 2.0 wt% acetic acid aqueous solution was slowly added until the pH reached 5.0. The precipitate was collected by filtration, sufficiently washed with water, dried, and purified by column chromatography to obtain thermally crosslinkable monomer 9.

[Synthesis Example 1] Synthesis of photo-alignment monomer 1 In a 300 mL flask, 14.7 g (80 mmol) of 4-bromostyrene, 0.18 g (800 μmol) of palladium chloride, and 0.98 g (3.2 mmol) of tris (2-tolyl) phosphine. ), 32.4 g (320 mmol) of triethylamine was dissolved in 135 mL of dimethylacetamide. Next, it was added to a mixed solution of 8.3 g (97 mmol) of methyl acrylate with a syringe and stirred. This mixed solution was further heated and stirred at 120 ° C. for 3 hours. After confirming the completion of the reaction by TLC, the reaction solution was cooled to room temperature. After the precipitate was filtered off, the filtrate was poured into 300 mL of 1N hydrochloric acid aqueous solution to collect the precipitate. These precipitates were recrystallized with a 1: 1 (mass ratio) solution of ethyl acetate and hexane to obtain photoalignable monomer 1.

[Synthesis Example 2] Synthesis of Photo-Orienting Monomer 2 In Synthesis Example 1, instead of using methyl acrylate, phenyl acrylate is used in an equimolar amount and reacted in the same manner as in Synthesis Example 1 to produce a photo-orienting monomer. 2 was obtained.

[Synthesis Example 3] Synthesis of Photo-Orienting Monomer 3 In Synthesis Example a, instead of using ethylene glycol, an equimolar amount of methyl trans-4-hydroxycinnamate is used to condense as in Synthesis Example a. The photo-alignment monomer 3 was obtained.

[Synthesis Example 4] Synthesis of Photoalignment Monomer 4 In a 500 mL flask, 15.4 g (50 mmol) of photoalignment monomer 3 was dissolved in 200 mL of methanol in a nitrogen atmosphere, and 8.3 g (60 mmol) of potassium carbonate was added. , Stirred overnight. After confirming the completion of the reaction by TLC, the precipitate was filtered and concentrated. The concentrate was extracted with ethyl acetate, washed with 1N hydrochloric acid, pure water and saturated brine, and dried over sodium sulfate. The styrene derivative 1 was obtained by distilling off the solvent and drying.
Subsequently, in Synthesis Example a, styrene derivative 1 is used in an equimolar amount instead of 4-vinylbenzoic acid, and 4-cyanophenol is used in an equimolar amount instead of ethylene glycol. The photo-alignment monomer 4 was obtained by condensation.

[Synthesis Example 5] Synthesis of Photoalignable Monomer 5 Thermally crosslinkable monomer 4 was obtained in the same manner as in Synthesis Example d. In a 500 mL flask, 12 g (100 mmol) of thermally crosslinkable monomer 4, 11.0 g (110 mmol) of succinic anhydride and 1.2 g (9.8 mmol) of 4-dimethylaminopyridine were added, and the inside of the system was sufficiently dried. To this system, 11.2 g (110 mmol) of triethylamine and 200 mL of tetrahydrofuran were added and reacted under reflux for 5 hours. After completion of the reaction, dilute hydrochloric acid was added, and the organic layer obtained by extraction with ethyl acetate was washed with water, dried over magnesium sulfate, concentrated, and recrystallized from ethanol to obtain styrene derivative 2.
Subsequently, in Synthesis Example a, styrene derivative 2 is used in an equimolar amount instead of 4-vinylbenzoic acid, and 4-hydroxycinnamic acid is used in an equimolar amount instead of ethylene glycol. The photo-alignment monomer 5 was obtained by condensing to.

[Synthesis Example 6] Synthesis of photo-alignment monomer 6 In Synthesis example 4, instead of using photo-alignment monomer 3, photo-alignment monomer 5 is used in an equimolar amount to perform deprotection in the same manner as in synthesis example 4. The styrene derivative 3 was obtained.
Subsequently, in Synthesis Example a, styrene derivative 3 was used in an equimolar amount instead of 4-vinylbenzoic acid, and 4-methoxyphenol was used in an equimolar amount instead of ethylene glycol. The photo-alignment monomer 6 was obtained by condensation.

[Synthesis Example 7] Synthesis of Photo-Orienting Monomer 7 In Synthesis Example a, instead of using 4-vinylbenzoic acid, equimolar amount of styrene derivative 2 is used, and instead of using ethylene glycol, equimolar amount of methyl ferulate is used. Then, the photo-alignment monomer 7 was obtained by condensation in the same manner as in Synthesis Example a.

[Synthesis Example 8] Synthesis of Photo-Orienting Monomer 8 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 4 was used, and instead of using ethylene glycol, trans-cinnamic acid was used. The photoalignment monomer 8 was obtained by condensing using equimolar amount similarly to the synthesis example a.

[Synthesis Example 9] Synthesis of Photo-Orienting Monomer 9 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 4 was used, and instead of using ethylene glycol, 4-methoxycinnamic acid. Was used in an equimolar amount to condense in the same manner as in Synthesis Example a to obtain photoalignable monomer 9.

[Synthesis Example 10] Synthesis of Photoalignable Monomer 10 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 1 was used, and instead of using ethylene glycol, trans-cinnamic acid was used. The photoalignment monomer 10 was obtained by condensing using equimolar amount similarly to the synthesis example a.

[Synthesis Example 11] Synthesis of Photo-Orienting Monomer 11 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 3 was used, and instead of using ethylene glycol, trans-cinnamic acid was used. The photoalignment monomer 11 was obtained by condensing using equimolar amount similarly to the synthesis example a.

[Synthesis Example 12] Synthesis of Photo-Orienting Monomer 12 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 5 was used, and instead of using ethylene glycol, trans-cinnamic acid was used. The photoalignment monomer 12 was obtained by condensing using equimolar amount similarly to the synthesis example a.

[Synthesis Example 13] Synthesis of Photoalignment Monomer 13 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 5 was used, and instead of using ethylene glycol, 4-methoxycinnamic acid. Was used in an equimolar amount to condense in the same manner as in Synthesis Example a to obtain photoalignable monomer 13.

[Synthesis Example 14] Synthesis of Photoalignment Monomer 14 In Synthesis Example a, instead of using 4-vinylbenzoic acid, an equimolar amount of thermally crosslinkable monomer 6 was used, and instead of using ethylene glycol, trans-cinnamic acid was used. The photoalignment monomer 14 was obtained by condensing using equimolar amount similarly to the synthesis example a.

Synthesis Example 15 Synthesis of Photo-Orienting Monomer 15 In a 300 mL flask, 14.8 g (100 mmol) of trans-cinnamic acid and 20.2 g (200 mmol) of triethylamine were dissolved in 200 ml of dichloromethane and stirred for 15 minutes in an ice bath. To this system, 16.7 g (110 mmol) of 4- (chloromethyl) styrene was slowly added and stirred for 18 hours. After completion of the reaction, dilute hydrochloric acid was added, and the organic layer obtained by extraction with ethyl acetate was washed with water, dried over magnesium sulfate, concentrated, and recrystallized with ethanol to obtain photoalignable monomer 15.

[Synthesis Example 16] Synthesis of photo-alignment monomer 16 In a 300 mL flask, 14.6 g (100 mmol) of 4-acetylstyrene and 10.6 g (100 mmol) of benzaldehyde were added to 100 mL of dimethylformamide, and the mixture was stirred. 4 g (110 mmol) was added. The reaction was carried out at about 110 ° C. for about 4 hours. After cooling, 100 mL of water and 20.0 g of acetic acid were added in order, and the mixture was further cooled with ice, and the precipitated crystals were filtered. The obtained crystal was recrystallized from methanol to obtain a photoalignment monomer 16.

[Synthesis Example 17] Synthesis of Photo-Orienting Monomer 17 In Synthesis Example a, instead of using ethylene glycol, 7-hydroxycoumarin is used in an equimolar amount and condensed in the same manner as in Synthesis Example a to obtain a photo-orienting monomer. 17 was obtained.

The structure of each monomer is shown in Table 1 and Table 2 below.
Each synthesized monomer was confirmed for its chemical structure by ¹ H NMR measurement using JEOL JNM-LA400WB manufactured by JEOL Ltd.

[Production Example 1] Synthesis of Copolymer 1 Thermally crosslinkable monomer 1 3.46 g, photo-alignment monomer 3 0.62 g, α, α'-azobisisobutyronitrile (AIBN) 50 mg as a polymerization catalyst, 25 ml of dioxane And reacted at 90 ° C. for 6 hours. After completion of the reaction, the copolymer 1 was obtained by purification by a reprecipitation method. The number average molecular weight of the obtained copolymer was 8,500.

[Production Examples 2-44] Synthesis of Copolymers 2-44 4-Vinylbenzoic acid or the above thermal crosslinkable monomers 1-9 as a heat crosslinkable monomer, and the above photoalignable monomers 1-17 as a photoalignment monomer are necessary. According to the above, copolymers 2 to 44 were synthesized in the same manner as in Production Example 1 using other monomers.

[Comparative Production Examples 1 and 2] Synthesis of Comparative Copolymers 1 and 2 2-Hydroxyethyl methacrylate (HEMA) or thermally crosslinkable monomer 1 as the thermally crosslinkable monomer, 4- (6-methacrylic acid) as the comparative photoalignment monomer 1 Comparative copolymers 1 and 2 were synthesized in the same manner as in Production Example 1 using oxyhexyl-1-oxy) cinnamic acid methyl ester.

Each copolymer is shown in Table 3 below.
The number average molecular weight (hereinafter referred to as “Mn”) of each copolymer synthesized was determined by gel permeation chromatography (GPC) using HLC-8220 GPC manufactured by Tosoh Corp. with polystyrene as a standard substance and NMP as an eluent. It calculated in.

[Example 1]
(Preparation of thermosetting composition 1)
A thermosetting composition 1 having the following composition was prepared.
-Copolymer 1: 0.1 g
-Hexamethoxymethylmelamine (HMM): 0.01 g
-P-Toluenesulfonic acid monohydrate (PTSA): 0.0015 g
Propylene glycol monomethyl ether (PGME): 2.1 g

(Formation of alignment layer)
The thermosetting composition prepared in Example 1 was applied to one surface of the transparent glass substrate by spin coating, and was heated and dried in an oven at 100 ° C. for 1 minute to form a cured film, whereby a coating film was obtained. An alignment layer was formed on the cured film surface by irradiating polarized ultraviolet rays containing a 313 nm emission line in a direction perpendicular to the substrate normal by 10 mJ / cm ² using a Hg—Xe lamp and a Grand Taylor prism.

(Production of retardation plate)
5% by mass of BASF Corporation photopolymerization initiator Irgacure 184 is added to a solution in which a liquid crystalline monomer represented by the following formula is dissolved in cyclohexanenon so as to have a solid content of 15% by mass. Was prepared.

The polymerizable liquid crystal composition was applied to the surface of the transparent glass substrate on which the alignment layer was formed by spin coating, and heated in a 70 ° C. oven for 1 minute to form a coating film. A retardation plate was produced by irradiating the surface of the polymerizable liquid crystal composition coated with 300 mJ / cm ² of non-polarized ultraviolet light containing a 365 nm emission line using a Hg—Xe lamp in a nitrogen atmosphere.

[Examples 2-52 and Comparative Examples 1-2]
Hexamethoxymethylmelamine (HMM) or 1,3,4,6-tetrakis (methoxymethyl) glycoluril (TMGU) as the cross-linking agent, p-toluenesulfonic acid monohydrate (PTSA) or p as the acid or acid generator -The thermosetting properties of Examples 2-52 and Comparative Examples 1-2 as in Example 1 using pyridinium salt of toluenesulfonic acid (PPTS) and propylene glycol monomethyl ether (PGME) or methyl ethyl ketone (MEK) as the solvent. A composition was prepared, an alignment layer was formed, and a retardation plate was produced.
The composition of each thermosetting composition is shown in Table 4 below.

[Evaluation]
The following evaluation was performed about each obtained phase difference plate.

(Liquid crystal orientation)
Two linearly polarizing plates were placed in a crossed Nicol state, a retardation plate was sandwiched between them, and the samples were visually observed. When the substrate was rotated, the bright and dark patterns observed in the plane were clearly evaluated as “◯”, and those with alignment defects were evaluated as “x”.

(Adhesion)
A 10 × 10 lattice pattern was formed on the phase difference plate by using an equally spaced spacer and cutting with a cutter knife at 1 mm intervals. Subsequently, the cellophane tape was placed on the lattice pattern and brought into close contact, and then the cellophane tape was peeled off. The cut part of the coating film after peeling off the cellophane tape was observed. A case where the number of grids where peeling occurs at a point along or intersecting the cut line of the coating film is less than 15% with respect to the total number of grid patterns, is “A”. Was designated as “B”.

  In the case where the alignment layer was formed using the thermosetting compositions of Examples 1 to 52, the liquid crystal alignment and adhesion were all good. This is thought to be because a π-electron interaction is acting between liquid crystal molecules because both the photo-alignment structural unit and the thermally crosslinkable structural unit of the copolymer have a styrene skeleton.

Claims (2)

A retardation plate having a substrate, an alignment layer formed on the substrate, and a retardation layer formed on the alignment layer,
The alignment layer has a photo-dimerization structure or photoisomerization structure of a photo-alignment group included in a photo-alignment structural unit represented by the following formula (1) and a thermally crosslinkable structural unit represented by the following formula (2). A phase difference plate comprising a copolymer having a crosslinked structure of a thermally crosslinkable group.

(Here, in Formula (1), X is a photo-alignment group, L ¹ is a divalent linking group or a single bond, R ¹ is a hydrogen atom or a monovalent organic group, k is 1 to 5, In (2), Y represents a thermally crosslinkable group, L ² represents a divalent linking group or a single bond, R ² represents a hydrogen atom or a monovalent organic group, and l represents 1 to 5.) A device having an alignment layer,
The alignment layer has a photo-dimerization structure or photoisomerization structure of a photo-alignment group included in a photo-alignment structural unit represented by the following formula (1) and a thermally crosslinkable structural unit represented by the following formula (2). A device comprising a copolymer having a crosslinked structure of a thermally crosslinkable group.

(Here, in Formula (1), X is a photo-alignment group, L ¹ is a divalent linking group or a single bond, R ¹ is a hydrogen atom or a monovalent organic group, k is 1 to 5, In (2), Y represents a thermally crosslinkable group, L ² represents a divalent linking group or a single bond, R ² represents a hydrogen atom or a monovalent organic group, and l represents 1 to 5.)

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