JP2005173548A - Optically anisotropic substance and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optically anisotropic substance usable as an optical retardation film excellent in durability by avoiding contamination in rubbing thereby solving the problem that only alignment parallel to the traveling direction of a film is imparted. <P>SOLUTION: In the optically anisotropic substance, a layer (A) containing a compound represented by formula (1) and having liquid crystal aligning ability produced upon photoirradiation and a polymer layer (B) obtained by polymerizing a liquid crystal compound having a polymerizable group in a state aligned by the layer (A) are covalently bonded and stacked. In the formula, R<SP>1</SP>and R<SP>2</SP>each represents a polymerizable group; X<SP>1</SP>represents a single bond or a linking group comprising a combination of a divalent hydrocarbon group with -O-, -CO-O-, -OCO-, -CONH-, -NHCO-, -NHCO-O- or -OCONH-; and Y represents a group having an azobenzene, anthraquinone, benzophenone, cinnamoyl, chalcone or coumarin group. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an optical anisotropic body obtained by polymerizing a polymerizable liquid crystal composition in an aligned state and a method for producing the same.

An STN liquid crystal display (LCD) can display a large capacity by time-division driving with a simple matrix electrode structure. However, there is a problem that the screen is colored due to the retardation applied when passing through the liquid crystal, and a retardation film is used to solve this problem.
In addition, the TFT-LCD adopts the TN mode in which the alignment state of the liquid crystal molecules is twisted by 90 °, the response speed is fast (several tens of milliseconds), the white display can be easily obtained, and the display contrast is high. Therefore, it is the most powerful method for improving image quality compared to other types of LCD. However, because twisted nematic liquid crystal is used, there is a problem in viewing angle characteristics such as the display color and display contrast change depending on the viewing direction due to the principle of the display method. To solve this problem, a retardation film is used. Yes.

  These retardation films are not limited to the above-mentioned LCDs, but are IPS (In-Plane Switching) type LCDs, FLC (Ferroelectric Liquid Crystal) type LCDs, OCB (Optically Compensated Bend) type LCDs, VA (Vertically Aligned EC) type LCDs. (Electrically Controlled Birefringence) type LCD, HAN (Hybrid Aligned Nematic) type LCD, GH (Guest-Host) type LCD, and other types of LCDs are also required for the purpose of eliminating the viewing angle dependency. There is a need for a retardation film suitable for each method.

  In any case, since the liquid crystal has optical anisotropy, the image has viewing angle dependency, so it is necessary to improve the display quality by using some compensation film. Further, a retardation film that is necessary for a reflective or transflective liquid crystal display such as a quarter-wave plate is also used.

Conventionally, a birefringent stretched film has been used for the retardation film, but in recent years, as a retardation film having more complicated optical properties, a polymerizable liquid crystal is applied on a substrate provided with an alignment film, Optical anisotropic bodies have been developed in which liquid crystal molecules are cured in an aligned state. (For example, see Patent Publication 1.) This is a method in which a polymer film such as polyimide is provided on a substrate, and a polymerizable liquid crystal is applied on an alignment film that is rubbed (rubbed) with a cloth or the like in one direction. The liquid crystal molecules are aligned in the rubbing direction and then polymerized to fix the alignment. The optical properties that cannot be obtained with a stretched birefringent film due to the combination of the alignment direction of the alignment film and the alignment mode of the polymerizable liquid crystal Is obtained.
Recently, a polyimide coating film having a polymerizable group provided on a substrate is rubbed, a discotic liquid crystal having a polymerizable group is applied thereon, and an optically anisotropic film composed of a polyimide alignment film and a discotic liquid crystal. There is also known an optical compensation sheet excellent in durability, which is formed by chemically bonding a conductive layer via an interface. (For example, see Patent Document 2)

  However, the above optical compensation sheet relates to a vertical alignment film in which the diameter direction of the discotic liquid crystal molecules is aligned in the direction perpendicular to the substrate, and by introducing a long alkyl chain, an aliphatic chain, or the like. Since the surface energy on the surface of the alignment film is lowered, liquid crystal molecules tend to aggregate on the surface of the vertical alignment film, which makes it difficult to stack in a thin film state. Moreover, since it is a rubbing alignment film, there is a problem that scratches and dust are generated by rubbing. Dust generation can be removed by washing or the like, but scratches cannot be removed. Therefore, the optical uniformity of the laminated liquid crystal film may be greatly impaired.

  Furthermore, in order to remove dust, cleaning or the like must be performed, and there is a problem that the manufacturing process becomes complicated. In addition, since the orientation is performed by the rubbing roll, it is possible to change the direction within a slight angle range, but in practice, only the orientation parallel to the traveling direction can be provided. For this reason, when the retardation film to be bonded to the liquid crystal display cell is cut out from the original fabric, the alignment direction and the cutting direction cannot be made parallel, and there is a problem that a large amount of unusable film remains.

Also known is an optically anisotropic element in which an alignment film is made of a polymer having a polymerizable group, and a polymer and a liquid crystal compound are copolymerized (see, for example, Patent Document 3). As an example of the alignment film, an alignment film in which an alignment function is generated by light irradiation is mentioned. Regarding polymers used for the alignment film, “functional groups capable of photoisomerization and crosslinking reaction are possible” described in Patent Documents 4 and 5. Polymers having a compound in which a functional group is bonded to a polymer chain and having optical anisotropy are mentioned.
However, Patent Document 3 only describes an example using a rubbing film as an alignment film, and there is no specific description using a photo-alignment film. When the polymer is used for the photo-alignment film, it is a polymer, so that there is a problem that the sensitivity to light is low and it is difficult to obtain sufficient liquid crystal alignment ability.

Japanese Patent Application Laid-Open No. 5-215921 JP 2001-89657 A JP 2002-296423 A Japanese Patent Laid-Open No. 08-338913 Japanese Patent Application Laid-Open No. 07-98413

  The problem to be solved by the present invention is to avoid contamination of the retardation film due to scratches and dust generation during rubbing treatment, and in the process of producing the retardation film, the rubbing direction is limited with respect to the traveling direction of the film, An object of the present invention is to provide an optical anisotropic body that solves the problem that, in effect, only an orientation parallel to the running direction can be imparted and can be used as a retardation film having excellent durability.

The present inventors solved the above-mentioned problems by using a film that generates liquid crystal alignment ability by light irradiation, instead of the conventional rubbing alignment film.
The method of generating liquid crystal alignment ability by light irradiation is one of alignment methods in which liquid crystal molecules can be aligned without rubbing, and the film formed on the substrate can be contacted without irradiating light. The liquid crystal alignment ability can be produced. The alignment can be controlled by the direction of light, and unlike the rubbing method, it has the characteristic that there is no possibility of scratches or dust generation in principle, so a retardation film using a liquid crystal having a polymerizable group is created. In the above, the degree of freedom in controlling the alignment state is increased, and there is no light leakage due to scratches, and a uniform film can be formed.

  In the present invention, as a material of the film that generates the liquid crystal alignment ability, a compound that combines a group that generates liquid crystal alignment ability upon irradiation with light and a polymerizable group is used. By forming a laminated film of a film (layer) and a liquid crystal compound layer having a polymerizable group on a substrate, and introducing a bonding relationship between both layers while maintaining the alignment state of the liquid crystal compound having the polymerizable group The present inventors have found that an optical anisotropic body excellent in adhesion and durability can be obtained.

  That is, the present invention includes a layer (A) containing a compound represented by the general formula (1) and having a liquid crystal alignment ability produced by light irradiation, and a liquid crystal compound having a polymerizable group is aligned by the layer (A). Provided is an optical anisotropic body in which a polymer layer (B) obtained by polymerization in a state of being bonded is bonded and laminated by a covalent bond.

(In the formula, R ¹ and R ² are each independently selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, vinyloxy group, and maleimide group). Represents a polymerizable group.
X ¹ represents a linking group represented by — (A ¹ -B ¹ ) _m —, and X ² represents a linking group represented by — (B ² -A ² ) _n —. Here, A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group, and B ¹ and B ² each independently represent a single bond, —O—, —CO—O—, — OCO-, -CONH-, -NHCO-, -NHCO-O-, or -OCONH- is represented. m and n each independently represents an integer of 0 to 4. When m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or two B ² is not a single bond.
Y represents a group having an azobenzene group, an anthraquinone group, a benzophenone group, a cinnamoyl group, a chalcone group or a coumarin group. )

  The present invention also provides the method for producing an optical anisotropic body as described above, wherein a layer containing a compound represented by the general formula (1) is formed on a substrate, and the layer is irradiated with polarized light or obliquely. After forming the layer (A) by non-polarized light irradiation from the above, a layer containing a polymerizable liquid crystal compound is laminated on the layer (A), and by light irradiation or heating, the general formula (1) Provided is a method for producing an optical anisotropic body in which a compound represented by the formula and a polymerizable liquid crystal compound are polymerized.

The optical anisotropic body of the present invention uses the compound represented by the general formula (1) as the photo-alignment film layer. Since the compound has a low molecular weight, it is excellent in sensitivity to light when formed into a coating film. Therefore, liquid crystal alignment ability can be easily imparted by light irradiation. In addition, since the polymerizable group has a higher degree of freedom than the polymerizable group bonded to the polymer, the reaction rate is high, and the layer (A) and the polymer layer (B) that cause liquid crystal alignment ability react well at the interface. It is possible to obtain an optical anisotropic body having excellent adhesion at the interface and excellent durability.
In addition, the method of generating liquid crystal alignment ability by light irradiation can control the alignment according to the direction of light, unlike the rubbing method, in principle there is no possibility of dust generation, and scratches due to rubbing are generated. In order to create a retardation film using a liquid crystal having a polymerizable group, the degree of freedom in controlling the alignment state is increased, and a film that is uniform and free of light leakage can be formed. it can.
Also, the photo-alignment film layer and the polymer layer are generally disadvantageous in that the anchoring force of the photo-alignment film (the magnitude of the interaction between the alignment film and the liquid crystal molecules) is weaker than that of the rubbing alignment film and the alignment regulation force is weak. It can also be improved by linking them with a covalent bond.

(Layer (A) containing a compound represented by the general formula (1) and causing liquid crystal alignment ability by light irradiation)
In the general formula (1), R ¹ and R ² are each independently a group consisting of a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, and a maleimide group. Represents a polymerizable group selected from: Of these, a (meth) acryloyl group, a (meth) acryloyloxy group, or a (meth) acrylamide group is preferable because photopolymerization and thermal polymerization are relatively easy. A maleimide group is more preferable because a polymerization initiator is not required.

In General Formula (1), X ¹ represents a linking group represented by — (A ¹ -B ¹ ) _m —, and X ² represents a linking group represented by — (B ² -A ² ) _n —. Represent. Here, A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include an alkylene group having 1 to 20 carbon atoms such as an ethylene group, a methylene group, a propylene group, a pentamethylene group, and a heptylene group; and 3 to 3 carbon atoms such as a cyclopropylene group and a cyclohexylene group. 20 cycloalkylene group; arylene groups having 6 to 20 carbon atoms such as phenylene group and naphthylene group. Among these, an alkylene group is preferable and an alkylene group having 1 to 4 carbon atoms is more preferable.

B ¹ and B ² each independently represents a single bond, —O—, —CO—O—, —OCO—, —CONH—, —NHCO—, —NHCO—O—, or —OCONH—. m and n each independently represents an integer of 1 to 4. When m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or B ² is not a single bond. Specifically, when m is ^{2, - (A 1 -B 1} ) m - linking group represented _{by, -CH 2 CH 2 -O-CH} 2 CH 2 CH 2 CH 2 -CO-O- or _{represents -O-CH 2 CH 2 CH 2} -CO-O- and the like, when n is ^{2, - (B 2 -A 2} ) n - linking group represented by, -O-CO-Ph It represents the like - (phenylene _group) -O- _(CH 2) _6.

  Y represents a group having an azobenzene group, an anthraquinone group, a benzophenone group, a cinnamoyl group, a chalcone group or a coumarin group. Among these, a group having the following structure is preferable.

In the above structure, p _{1 to} p ₁₁ are each independently a hydrogen atom, a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an alkoxy group. A carbonyl group, a carboxyl group, a sulfonic acid group, an amino group, or a hydroxy group is represented. However, the carboxyl group and the sulfonic acid group may form a salt with an alkali metal.
Among them, an azobenzene group is preferable, and an azobenzene structure having the following structure is particularly preferable.

In the above structure, p _{1 to} p ₄ are each independently a hydrogen atom, halogen atom, halogenated alkyl group, halogenated alkoxy group, cyano group, nitro group, alkyl group, alkoxy group, aryl group, allyloxy group, alkoxy group. A carbonyl group, a carboxyl group, a sulfonic acid group, an amino group, or a hydroxy group is represented. However, the carboxyl group and the sulfonic acid group may form a salt with an alkali metal. Among these, a carboxyl group, a sulfonic acid group, an amino group, a hydroxy group, or a salt thereof is preferable, and a carboxyl group, a sulfonic acid group, or a salt thereof is most preferable.

  Specific examples of the compound represented by the general formula (1) include the compounds described in JP-A No. 2002-250924 and JP-A No. 2002-317013. It can be easily synthesized.

  Since the compound represented by the general formula (1) has a low molecular weight, it is excellent in sensitivity to light when formed into a coating film. Therefore, liquid crystal alignment ability can be easily imparted by light irradiation. In addition, since the polymerizable group has a higher degree of freedom than the polymerizable group bonded to the polymer, the reaction rate is high, and the layer (A) and the polymer layer (B) that cause liquid crystal alignment ability react well at the interface. Excellent adhesion at the interface.

  The compound represented by the general formula (1) is preferably used after being dissolved in an appropriate solvent. The solvent is not particularly limited, but N-methylpyrrolidone (hereinafter abbreviated as NMP), butyl cellosolve, phenyl cellosolve, N, N-dimethylformamide (hereinafter abbreviated as DMF), γ-butyrolactone, dimethyl sulfoxide (hereinafter, abbreviated as “MP”). DMSO)), ethylene glycol, propylene glycol, toluene, tetrahydrofuran, chlorobenzene, dimethylacetamide and the like. Among these, a solution of NMP, butyl cellosolve, and DMF is particularly preferable because it has a good coating property on a substrate such as glass and a uniform film can be obtained. These solutions are preferably selected in consideration of applicability and the volatilization rate of the solvent after application, and two or more kinds can be mixed and used.

  Since the solvent is volatilized and removed after being applied to the substrate, when used, the solid content concentration of the compound represented by the general formula (1) needs to be at least 0.2% by mass or more. Especially, the range of 0.3-10 mass% is especially preferable. Moreover, polymer materials such as polyvinyl alcohol and polyimide can be mixed within a range not impairing the effects of the present invention. (Hereinafter, the composition containing the compound represented by the general formula (1) is abbreviated as a photoalignable polymerizable composition)

(Polymer layer (B))
In the present invention, the liquid crystal compound having a polymerizable group constituting the polymer layer (B) is not particularly limited as long as it is a compound having a polymerizable group that exhibits liquid crystallinity alone or in a composition with another liquid crystal compound. Absent. For example, Handbook of Liquid Crystals (D. Demus, J. W. Goodbye, GW Gray, H. W. Spiss, V. Vill, edited by Wiley-VCH, 1998), Quarterly Chemical Review. 22, Liquid Crystal Chemistry (Edited by Chemical Society of Japan, 1994), or JP-A-7-294735, JP-A-8-3111, JP-A-8-29618, JP-A-11-80090, 1,4-phenylene group, 1,4-cyclohexene, as described in Kaihei 11-148079, JP-A 2000-178233, JP-A 2002-308831, and JP-A 2002-145830. A rod-like polymerizable liquid crystal compound having a rigid site called a mesogen in which a plurality of structures such as a silene group are connected, and a polymerizable functional group such as a (meth) acryloyl group, a vinyloxy group, and an epoxy group,

  Alternatively, for example, Handbook of Liquid Crystals (D. Demus, J. W. Goodby, GW Gray, H. W. Spiss, V. Vill, edited by Wiley-VCH, No. 1998) . 22. Liquid crystal chemistry (edited by Chemical Society of Japan, 1994) and discotic polymerizable compounds described in JP-A-07-146409. Among these, a rod-like liquid crystal compound having a polymerizable group is preferable because it can easily produce a liquid crystal having a temperature range around room temperature.

(Production method)
The optical anisotropic body of the present invention comprises a compound (A) (hereinafter abbreviated as layer (A)) containing a compound represented by the general formula (1) and having a liquid crystal alignment ability by light irradiation, polymerization, Forming a laminated film with a polymer layer (B) (hereinafter abbreviated as layer (B)) obtained by polymerizing a liquid crystal compound having a functional group in a state aligned by the layer (A) on a substrate; It can be obtained by causing the layer (A) to react with the polymerizable groups in both layers while maintaining the alignment state of the liquid crystal compound while generating or generating the liquid crystal alignment ability. In the optical anisotropic body of the present invention, each layer does not need to be completely polymerized and cured, as long as the interface between the layer (A) and the layer (B) is covalently bonded.
Examples are given as specific embodiments of the present invention.

1. Method 1 of adding a photopolymerization initiator to the layer (B)
A layer (A) is formed by applying and drying a photo-alignable polymerizable composition not containing a polymerization initiator on a substrate, and the layer side (substrate side opposite to the layer forming side) or From the surface side of the layer (A), polarized light having a wavelength that can be absorbed by the photoalignable group of the compound (C) is irradiated to give liquid crystal alignment ability. When the photo-alignable group is a group utilizing molecular orientation induction or isomerization reaction by the Weigert effect, the liquid crystal is irradiated with non-polarized light having a wavelength that the group efficiently absorbs from the oblique direction. An alignment function may be given (this is the same for other embodiments. In addition, polarized light irradiated for alignment and non-polarized light obliquely with respect to the substrate are collectively referred to as “alignment light”) . Next, a polymerizable liquid crystal composition solution containing a photopolymerization initiator is applied and dried thereon to form a layer (B). The polymerizable liquid crystal of the layer (B) assumes the intended alignment state due to the effect of the liquid crystal alignment ability of the layer (A). Next, two layers of light having a wavelength that is absorbed by the added photopolymerization initiator are irradiated to advance curing of the polymerizable liquid crystal, and at the same time, photopolymerization existing at the interface between the layer (A) and the layer (B). Polymerization is performed between the molecules of both layers with an initiator. Since radicals generated by the cleavage of the photopolymerization initiator can move between both layers, if a photopolymerization initiator is contained in either layer, the polymerizable groups present at the interface between the two layers are polymerized. Thus, the layer (A) and the layer (B) are covalently bonded, the adhesion at both interfaces is improved, and an optical anisotropic body excellent in durability can be obtained. Further, in this method, since the photoalignable polymerizable composition does not contain a photopolymerization initiator, there is no possibility that unexpected polymerization occurs during irradiation of alignment light or the like, and the alignment treatment can be performed uniformly.

2. Method 2 in which a photopolymerization initiator is added to the layer (B)
A photo-alignment polymerizable composition not containing a polymerization initiator is applied onto a transparent substrate and dried to form a layer (A), and then the layer (A) is not oriented, and a photo-polymerization initiator is included thereon. The polymerizable liquid crystal composition is applied and dried to form the layer (B).
Next, alignment light is irradiated from the transparent substrate side or from the surface side of the layer (B) to impart alignment ability to the layer (A). Since the polymerizable liquid crystal compound of the layer (B) is also aligned according to the provision of the alignment ability of the layer (A), the alignment ability can be further enhanced. In particular, from the layer (A) side, a method of irradiating oriented light having a wavelength that can be absorbed by the photoalignable group of the compound (C) or non-oriented light from an oblique direction to the substrate is preferable. In this method, the photo-alignment group in the layer (A) absorbs most of the irradiation light, the liquid crystal alignment ability is generated, and the molecules of the stacked layer (B) are aligned. As the irradiation progresses, the irradiation light passes through the layer (A) by the mechanism described below, reaches the layer (B), cleaves the photopolymerization initiator in the layer, and induces a polymerization reaction. Bonding between layer (A) and layer (B) also occurs. That is, when light irradiation is performed from the transparent substrate side, an isomerization reaction such as an azobenzene group is caused to induce molecular orientation by the Weigert effect. The orientation direction of the film changes to take an orientation state that minimizes absorption, so that the irradiation light gradually leaks into the layer (B), inducing polymerization of the layer (B). Similarly, even when a compound utilizing a dimerization reaction (eg, cinnamoyl group), photocrosslinking reaction (eg, benzophenone group), or photodecomposition reaction (eg: polyimide group) is used as the layer (A) The components oriented in this direction by light absorption are dimerized, photocrosslinked, photodecomposed, and the group that absorbs gradually decreases, so that the irradiation light leaks to the layer (B), and the polymerization of the layer (B) Induces. In this aspect, since the light to be irradiated serves as both alignment light and polymerization light, polymerization is performed while controlling the alignment, and an excellent alignment in which the alignment is not disturbed can be obtained. When the alignment does not proceed sufficiently with the light, polymerization light may be superimposed and irradiated.
Therefore, the layer (A) and the layer (B) are covalently bonded, the adhesion at both interfaces is improved, and an optical anisotropic body excellent in durability can be obtained. Also in this case, since the photo-alignable polymerizable composition does not contain a photopolymerization initiator, there is no possibility of unexpected polymerization during irradiation of alignment light, and the alignment process can be performed uniformly.

3. A method in which a photopolymerization initiator having a light absorption wavelength band different from the light absorption band of compound (C) is added to one or both of the polymerizable liquid crystal composition and the photoalignable polymerizable composition. After the photopolymerizable composition solution is applied and dried on the substrate to form the layer (A), the wavelength that can be absorbed by the photoalignable group of the compound (C) from the substrate side or the surface side of the layer (A) The liquid crystal alignment ability is given by irradiating the alignment light or non-alignment light from the oblique direction to the substrate. When the polymerizable liquid crystal composition solution is applied and dried thereon to form the layer (B), the polymerizable liquid crystal compound is in the intended alignment state. Next, the laminated two layers are irradiated with light having a wavelength that is absorbed by the added photopolymerization initiator, and bonds between molecules at the interface between the layer (B) and the layer (A). The curing of each of C) is also advanced. Also by such an operation, the layer (A) and the layer (B) are covalently bonded, the adhesion at both interfaces is improved, and an optical anisotropic body excellent in durability can be obtained.
After laminating the layer (A) and the layer (B), the above-described alignment light irradiation and polymerization light irradiation may be performed.

4). A method in which a thermal polymerization initiator is added to one or both of a polymerizable liquid crystal composition and a photoalignable polymerizable composition. A layer (A) is formed by applying and drying a photoalignable polymerizable composition solution on a substrate. After the formation, from the substrate side or the surface side of the layer (A), the alignment light having a wavelength that can be absorbed by the photoalignable group of the compound (C) or non-alignment light from an oblique direction is irradiated to the substrate. Provides liquid crystal alignment ability. A layer (B) is formed thereon, both layers are heated to cleave the thermal polymerization initiator to advance curing of both layers, and at the same time, heat existing at the interface between the layers (B) and (A). Polymerization is performed between the molecules of both layers by a polymerization initiator. The radicals generated by the cleavage of the thermal polymerization initiator can move in both layers, so if they are contained in either layer, the polymerizable groups present at the interface between both layers can be polymerized. The layer (A) and the layer (B) are covalently bonded, the adhesion at both interfaces is improved, and an optical anisotropic body excellent in durability can be obtained.
After laminating the layer (A) and the layer (B), the above-described alignment light irradiation and polymerization light irradiation may be performed.

5). Method of Using Thermal Polymerization Initiator and Photopolymerization Initiator After Forming Layer (A) by Applying and Drying Photoalignable Polymerizable Composition Containing Thermal Polymerization Initiator on Substrate, then Substrate Side or Layer (A ) From the surface side, liquid crystal alignment ability is imparted by irradiating alignment light having a wavelength that can be absorbed by the photoalignable group of compound (C) or non-alignment light from an oblique direction to the substrate. Next, a layer (B) containing a photopolymerization initiator is formed on the layer, and the wavelength that the photopolymerization initiator absorbs while heating the two laminated layers to an appropriate temperature at which the thermal polymerization initiator is cleaved. By irradiating the light, the curing of both layers proceeds and at the same time the molecules of both layers are polymerized.

Alternatively, a photopolymerization initiator having a light absorption wavelength band different from that of the photoalignable polymerizable composition itself is added to the photoalignable polymerizable composition, and the layer (A) is coated on the substrate and dried. After formation, liquid crystal alignment is performed by irradiating alignment light that can be absorbed by the photoalignable group of the compound (C) or non-alignment light from an oblique direction to the substrate from the substrate side or the surface side of the layer (A). Give the ability. Next, a layer (B) added with a thermal polymerization initiator is formed on the layer, and both layers are simultaneously cured by irradiating light absorbed by the photopolymerization initiator while heating both layers. Polymerize between molecules. Also by such an operation, it is possible to obtain an optical anisotropic body having excellent durability by providing bonding between the layer (A) and the layer (B), improving the adhesion at both interfaces.
After laminating the layer (A) and the layer (B), the above-described alignment light irradiation and polymerization light irradiation may be performed.

(Application method)
The method of forming each composition layer on the substrate includes spin coating method, extrusion method, gravure coating method, die coating method, bar coating method, application method such as applicator method and printing method such as flexo method, etc. Any known method can be used.

(substrate)
The substrate is not particularly limited as long as it is substantially transparent, and glass, ceramics, plastics, and the like can be used. As plastic substrates, cellulose, triacetyl cellulose, cellulose derivatives of diacetyl cellulose, polyethylene terephthalate, polyester such as polyethylene naphthalate, polyolefin such as polypropylene and polyethylene, polycarbonate , Polyvinyl alcohol, polyvinyl chloride, polyvinylidene chloride, nylon, polystyrene, polyacrylate, polymethyl methacrylate, polyethersulfone, polyarylate and the like can be used.
The optical anisotropic body according to the present invention produced by coating on a substrate may be bonded to the substrate of the liquid crystal cell, and the optical anisotropic body formed by coating is peeled off from the substrate and bonded to the substrate of the liquid crystal cell. The optical anisotropic body of the present invention can also be formed directly on the glass substrate or plastic substrate of the liquid crystal cell.

(Optical alignment operation)
In order to impart liquid crystal alignment ability to the layer (A) (hereinafter abbreviated as photoalignment operation), the coating film is polarized with a wavelength that can be absorbed by the photoalignable group of the compound represented by the general formula (1). Irradiation may be performed from the substrate side opposite to the surface or the coating film surface, perpendicularly to the surface, or from an oblique direction. In addition, when the photo-alignable group is a group utilizing molecular orientation induction or isomerization reaction due to the Weigert effect, non-polarized light having a wavelength that the group efficiently absorbs from the coating film surface or the substrate side. The liquid crystal alignment function may be given by irradiating the surface from an oblique direction. Also, polarized light and non-polarized light may be combined.
The polarized light may be either linearly polarized light or elliptically polarized light, but it is preferable to use linearly polarized light having a high extinction ratio in order to perform photoalignment efficiently.

  Moreover, since it is necessary to use a polarizing filter in order to obtain polarized light, there is a disadvantage that the light intensity irradiated on the film surface is reduced, but in the method of irradiating non-polarized light from an oblique direction with respect to the film surface The irradiation apparatus does not require a polarizing filter, and there is an advantage that a large irradiation intensity can be obtained and the irradiation time for photo-alignment can be shortened. At this time, the incident angle of non-polarized light is preferably in the range of 10 ° to 80 ° with respect to the normal to the substrate. In consideration of the uniformity of the irradiation energy on the irradiated surface, the pretilt angle obtained, the alignment efficiency, etc. A range of 60 ° is most preferred.

The light to be irradiated may be light in a wavelength region in which the photoalignable group of the compound represented by the general formula (1) has absorption. For example, when the photo-alignment group has an azobenzene structure, ultraviolet rays having a wavelength of 350 to 500 nm that have strong absorption due to the π → π ^* transition of azobenzene are particularly preferable. Examples of the light source for irradiation light include xenon lamps, high-pressure mercury lamps, ultra-high pressure mercury lamps, metal halide lamps, ultraviolet lasers such as KrF and ArF, and the like. In particular, when the photo-alignment group has an azobenzene structure, the ultra-high pressure mercury lamp is particularly preferable because the emission intensity of ultraviolet light at 365 nm is large. Ultraviolet linearly polarized light can be obtained by passing the light from the light source through a polarizing prism such as a polarizing filter, Glan-Thompson, and Glan-Teller. Moreover, it is particularly preferable that the irradiated light is substantially parallel light regardless of whether polarized light or non-polarized light is used. The light to be irradiated may be irradiated from the surface side of the coating film or from the substrate side. In the case of irradiation from the substrate side, a transparent substrate is used as the substrate.

Further, when irradiating polarized light, if a photomask is used, the liquid crystal alignment ability can be produced in the direction of two or more different directions in the pattern of the layer (A). Specifically, the substrate on which the layer (A) is formed is covered with a photomask, and the entire surface is irradiated with polarized light or non-polarized light to give liquid crystal alignment ability to the exposed portion in a pattern. By repeating this a plurality of times as necessary, liquid crystal alignment ability can be generated in a plurality of directions. Next, the layer (B) is laminated, and the liquid crystal molecules are aligned on the substrate, and then the layers (A) and (B) are polymerized by irradiating ultraviolet rays, and the two layers are bonded.

Specific modes when using a photomask are shown in FIGS.
FIG. 1 is a plan view of an optical anisotropic body of the present invention as viewed from the normal direction of a substrate when a layer (A) is provided with an alignment pattern in which a plurality of different alignment regions are alternately arranged in the in-plane alignment direction. It is. FIG. 2 is a plan view of the optical anisotropic body of the present invention as viewed from the normal direction of the substrate when a layer (A) is provided with an alignment pattern in which a plurality of different alignment regions having different pretilt angles are alternately arranged. FIG.
The direction of arrow 1 indicates the orientation direction of the layer (B) in the same orientation region. The layer (B) cured in a state of being aligned by the layer (A) in which the liquid crystal alignment ability is generated in a plurality of directions in an intended pattern shows a pattern based on the alignment of (A).

(polymerization)
The polymerization operation of the photo-alignable polymerizable composition and the polymerizable liquid crystal composition of the present invention is generally performed by irradiation with light such as ultraviolet rays or heating.
When the polymerization is performed by light irradiation, in order not to disturb the alignment state of the photo-alignable polymerizable composition layer that has already been obtained, generally, the light of the compound represented by the general formula (1) It is preferable to carry out at a wavelength other than an absorption band, for example, an absorption band of an azobenzene skeleton or an anthraquinone skeleton. Specifically, it is preferable to irradiate ultraviolet light of 320 nm or less, and most preferable to irradiate light having a wavelength of 250 to 300 nm. However, when the photo-alignment polymerizable composition and the polymerizable liquid crystal composition cause decomposition or the like due to ultraviolet light of 320 nm or less, it may be preferable to perform polymerization treatment with ultraviolet light of 320 nm or more. This light is preferably diffused light and unpolarized light so as not to disturb the orientation of the photoalignable group already obtained. Therefore, usually, it is preferable to use a photopolymerization initiator having a light absorption wavelength band different from the light absorption band of the compound represented by the general formula (1). On the other hand, when the light for polymerization is irradiated from the same direction as the photo-alignment operation, any wavelength can be used because there is no fear of disturbing the alignment state of the photo-alignment material.

  As the photopolymerization initiator, known ones can be used. For example, 2-hydroxy-2-methyl-1-phenylpropan-1-one ("Darocur 1173" manufactured by Merck & Co., Inc.), 1-hydroxycyclohexyl phenyl ketone (Ciba Specialty Chemicals “Irgacure 184”), 1- (4-Isopropylphenyl) -2-hydroxy-2-methylpropan-1-one (Merck “Darocur 1116”), 2-methyl-1-[( Methylthio) phenyl] -2-morpholinopropane-1 (“Irgacure 907” manufactured by Ciba Specialty Chemicals). Benzylmethylketal ("Irgacure 651" manufactured by Ciba Specialty Chemicals). A mixture of 2,4-diethylthioxanthone (“Kayacure DETX” manufactured by Nippon Kayaku Co., Ltd.) and ethyl p-dimethylaminobenzoate (“Kayacure EPA” manufactured by Nippon Kayaku Co., Ltd.), isopropylthioxanthone (“Kantacure” manufactured by Word Prekinsop Co., Ltd.) -ITX ") and a mixture of ethyl p-dimethylaminobenzoate, acylphosphine oxide (" Lucirin TPO "manufactured by BASF), and the like. 10 mass% or less is preferable with respect to a composition, and, as for the usage-amount of a photoinitiator, 0.5-5 mass% is especially preferable.

  The light for polymerization may be irradiated from the surface of the layer (A) or the layer (B) or from the substrate side, and may be optional, but is usually irradiated from the side to which a photopolymerization initiator is added. To do.

  On the other hand, the polymerization by heating is preferably performed at a temperature at which the polymerizable liquid crystal composition exhibits a liquid crystal phase or at a temperature lower than that. In particular, when a thermal polymerization initiator that releases radicals by heating is used, the cleavage temperature is the above. It is preferable to use the one in the temperature range. In the case where the thermal polymerization initiator and the photopolymerization initiator are used in combination, the polymerization temperature and the polymerization temperature are set so that the polymerization rates of the layers (A) and (B) are not greatly different together with the limitation of the temperature range. It is preferred to select each initiator. Although the heating temperature depends on the transition temperature from the liquid crystal phase to the isotropic phase of the polymerizable liquid crystal composition, it is preferably performed at a temperature lower than the temperature at which inhomogeneous polymerization is induced by heat. 300 degreeC is preferable, 30 to 200 degreeC is more preferable, and 30 to 120 degreeC is especially preferable. For example, when a polymeric group is a (meth) acryloyl group, it is preferable to carry out at a temperature lower than 90 degreeC.

  In the above case, it is preferable to use a thermal polymerization initiator as appropriate. As the thermal polymerization initiator, known and commonly used ones can be used. For example, methyl acetoacetate peroxide, cumene hydroperoxide, benzoyl peroxide, bis (4-t-butylcyclohexyl) peroxydicarbonate, t -Butyl peroxybenzoate, methyl ethyl ketone peroxide, 1,1-bis (t-hexyl peroxy) 3,3,5-trimethylcyclohexane, p-penta hydroperoxide, t-butyl hydroperoxide, dicumylpa Organic peroxides such as oxide, isobutyl peroxide, di (3-methyl-3-methoxybutyl) peroxydicarbonate, 1,1-bis (t-butylperoxy) cyclohexane, 2,2′-azo Bisisobutyronitrile, 2,2′-azobis (2, Azonitrile compounds such as 2-dimethylvaleronitrile), azoamidin compounds such as 2,2′-azobis (2-methyl-N-phenylpropion-amidin) dihydrochloride, 2,2′azobis {2-methyl-N- [1 , 1-bis (hydroxymethyl) -2-hydroxyethyl] propionamide}, alkyl azo compounds such as 2,2′azobis (2,4,4-trimethylpentane), and the like can be used. 10 mass% or less is preferable with respect to a composition, and, as for the usage-amount of a thermal-polymerization initiator, 0.5-5 mass% is especially preferable.

  The polymerization initiators such as the photopolymerization initiator and the thermal polymerization initiator described above may be included in either the layer (A) or the layer (B), and may be included in both. Since the interface between both layers is liquid, the polymerization initiator and radicals generated by the cleavage of the polymerization initiator can move to both layers to some extent. Therefore, if it is contained in either layer, both layers can be polymerized at the same time, and an optical anisotropic body in which layers (A) and (B) are covalently bonded and laminated can be obtained.

  For example, the photo-alignable polymerizable composition does not contain a polymerization initiator, and when the polymerizable liquid crystal composition contains a polymerization initiator, the polymerization initiator slightly shifts from the layer (B) to the layer (A). Further, by applying light or heat, radicals generated in the layer (B) migrate to the layer (A), and both layers and their interfaces can be polymerized.

  Hereinafter, the present invention will be described more specifically with reference to examples.

(Adjustment of composition for layer (A))
The compound represented by the formula (f) was dissolved in N-methylpyrrolidone to obtain a 1 wt% solid content solution. It was set as the composition for layer (A).

(Preparation of composition for layer (B))
A liquid crystal composition comprising 20 parts by mass of the compound represented by the formula (a), 40 parts by mass of the compound represented by the formula (b), and 40 parts by mass of the compound represented by the formula (c) was prepared, and a polymerizable liquid crystal It was set as the composition (B-1).
The polymerizable liquid crystal composition (B-1) had a CN transition temperature of 31 ° C. and an NI transition temperature of 48 ° C. When the temperature of the polymerizable liquid crystal composition (B-1 was lowered from 48 ° C., it became a supercooled state at 31 ° C. or lower and exhibited a liquid crystal phase even at 25 ° C.

A liquid crystal composition comprising 50 parts by mass of the compound represented by formula (d) and 50 parts by mass of the compound represented by formula (e) was prepared, filtered through a filter having a pore size of 0.1 μm, and a polymerizable liquid crystal composition. (B-2). The N-I transition temperature of the liquid crystal composition (B-2) was 74 ° C. When the temperature of the liquid crystal composition was lowered from 90 ° C., the liquid crystal composition became a nematic state at 71 ° C. or lower and exhibited a liquid crystal phase even at 25 ° C.
In addition, the polymerizable liquid crystal compositions (A-1) and (A-2) are diluted with xylene so that the solid content concentration becomes 50% by weight, and used with a filter having a pore diameter of 0.1 μm. Filtered.

(Example 1)
A TN type glass cell with an ITO electrode with a gap of 10 μm is made of two opposing glass substrates, and a polyimide alignment film whose rubbing directions are substantially orthogonal to each other is formed inside each substrate of the cell.
An ethanol solution (concentration 2 wt%) of a silane coupling agent 3-vinyltriethoxysilane was applied to both outer surfaces of the glass substrate of the cell and heat-treated at 110 ° C. for 10 minutes. Next, the composition for layer (A) was uniformly coated on the one-side substrate outside the cell by a spin coater, and dried with hot air at 80 ° C. for 10 minutes. In the plane of the substrate, the direction is orthogonal to the rubbing direction of the alignment film formed on the inner side of the substrate, and the output is 1 nm from an ultrahigh pressure mercury lamp having a wavelength of about 365 nm from a direction inclined by 45 ° from the normal of the coating film surface. Non-polarized light was irradiated with an integrated light amount of 5 J / cm ^{2 in} the state of parallel light, and liquid crystal alignment ability was imparted to the layer (A).

Next, a photopolymerization initiator “Irgacure 907” manufactured by Ciba Specialty Chemicals was added to the polymerizable liquid crystal composition (B-1) so that the mass ratio was 98: 2. This was applied onto the layer (A) at room temperature using an applicator to form a layer (B) having a thickness of 6 μm. The cell was placed in a nitrogen atmosphere, and an ultraviolet ray having an intensity of 0.25 W / cm ² was irradiated for 4 seconds from the same direction as the ultraviolet ray irradiation imparting the liquid crystal alignment ability, and the layers (A) and The polymerizable component of the layer (B) was polymerized to form an optical anisotropic body composed of the layer (A) and the layer (B). Similarly, the outside of the other glass substrate of the cell is irradiated with non-polarized light from a direction orthogonal to the rubbing direction of the inner surface and inclined by 45 ° from the normal line of the substrate, and a layer ( An optical anisotropic body composed of A) and the layer (B) was formed.

Liquid crystal cell 11-3323 manufactured by Dainippon Ink & Chemicals, Inc. was poured into the glass cell to prepare liquid crystal cell 1.
The light intensity ratio of the backlight that passes through the glass cell with and without an AC electric field of 10V-30Hz is measured by changing the tilt angle from the normal of the cell surface along the rubbing direction, and the viewing angle of contrast Dependency was measured. The viewing angle at which the contrast is 10 or more is shown in Table 1.
In addition, in order to evaluate the adhesive strength between the layer (A) and the layer (B), the produced optical anisotropic body is cut into 2 mm square grids with a cutter, and serotape (Cerotape is a registered trademark). Table 1 shows the ratio of the number of grids in which the optical anisotropic bodies remain. Since the layer (A) remained in the peeled portion by observation with a polarizing microscope, it was confirmed that the peeling occurred at the interface between the layer (A) and the layer (B). Further, no scratches or foreign substances were found on the surface and the inner surface of the optical anisotropic body, and the uniformity of retardation within the surface was good at a coefficient of variation of about 3%.

(Example 2)
In the composition for layer (A), 2,2′-azobis (2,4-dimethylvaleronitrile) “V65” manufactured by Wako Pure Chemical Industries, Ltd. as a thermal polymerization initiator is added to 2% by weight based on the solid content. In the same manner as in Example 1, it was uniformly applied on the one-side substrate outside the cell treated with the silane coupling agent, and dried with hot air at 40 ° C. for 30 minutes. Next, in the substrate plane, the direction is orthogonal to the rubbing direction of the alignment film formed on the inner side of the substrate, and the wavelength is around 365 nm from the ultrahigh pressure mercury lamp whose output is 1 kW from the direction inclined by 45 ° from the normal of the coating film surface. The non-polarized light was irradiated with an accumulated light amount of 5 J / cm ^{2 in} the state of parallel light, and the liquid crystal alignment ability was imparted to the layer (A).

Subsequently, 2,2′-azobis (2,4-dimethylvaleronitrile, W65 manufactured by Wako Pure Chemical Industries, Ltd.) as a thermal polymerization initiator was added to the polymerizable liquid crystal composition (B-2) at a mass ratio of 98: 2. It added so that it might become. This was applied onto the layer (A) at room temperature using an applicator to form a layer (B) having a thickness of 6 μm. This cell coated with the oriented layer (B) was heat treated in nitrogen at 60 ° C. for 120 minutes to polymerize the polymerizable components in the layer (A) and the layer (B), and the layer (A) and the layer ( An optically anisotropic body consisting of B) was formed. Similarly, an optical anisotropic body composed of the layer (A) and the layer (B) oriented in a direction orthogonal to the rubbing direction of the inner surface was formed on the other glass surface of the cell.
Liquid crystal was injected in the same manner as in Example 1 to prepare a liquid crystal cell 2. Tests were conducted in the same manner as in Example 1, and the results are shown in Table 1.

(Example 3)
In Example 1, non-polarized light having a wavelength of around 365 nm from an ultrahigh pressure mercury lamp having an output of 1 KW from a direction inclined 45 ° from the normal line of the coating film surface to the layer (A), an integrated light amount of 5 J / cm in the state of parallel light. ^{2 and} applying a liquid crystal alignment capability to the layer (A), and then placing a photomask having a rectangular slit with a period of 20 μm on the layer (A), in the in-plane alignment direction of the layer (A) A non-polarized light with a wavelength of about 365 nm was irradiated in a parallel light state with a total light quantity of 5 J / cm ² using a super high pressure mercury lamp having a right angle to the coating film surface and inclined by 45 ° from the normal of the coating surface. An optical anisotropic body was prepared in the same manner as in Example 1 except that the layer (A) was provided with an alignment pattern in which rectangular alignment regions with in-plane alignment directions differing by 90 ° were alternately arranged.

When a He—Ne laser (633 nm) that has passed through a polarizing plate is incident perpendicularly to the substrate surface and the polarization vibration direction is parallel to one orientation direction of the rectangular pattern, Raman-Nath scattering is exhibited. A diffraction peak up to ± 5th order was observed, confirming that it functions as a diffraction grating.
In addition, in order to evaluate the adhesive strength between the layer (A) and the layer (B), the produced optical anisotropic body is cut into 2 mm square grids with a cutter, and serotape (Cerotape is a registered trademark). A) was attached and pulled up in the vertical direction, and the ratio of the number of grids in which the optical anisotropic bodies remained was examined. As a result, it was 87%. Since the layer (A) remained in the peeled portion by observation with a polarizing microscope, it was confirmed that the peeling occurred at the interface between the layer (A) and the layer (B).

(Comparative Example 1)
A phenol novolac type epoxy acrylate “NK” having an acrylic group in the side chain of Dainippon Ink & Chemicals, Inc. on the outside of a TN type glass cell with an ITO electrode having a gap of 10 μm treated with a silane coupling agent as in Example 1. An ethyl cellosolve acetate solution (concentration of 30 wt%) of “Ester EA-6310 new” was uniformly applied on one side substrate outside the cell with a spin coater and dried at 60 ° C. for 30 minutes. By rubbing this, in-plane horizontal alignment ability was imparted. At that time, the orientation direction was set to be perpendicular to the orientation direction of the polyimide film inside the substrate. After rubbing treatment, a lot of dust of about 10 μm was adhered on the alignment film. Therefore, the surface was washed with running water to prevent deterioration of optical properties of the optical anisotropic body, rinsed with pure water, and rinsed at 70 ° C. for 30 minutes. Dried.

Next, a photopolymerization initiator “Irgacure 907” was added to the polymerizable liquid crystal composition (B-1) so as to have a mass ratio of 98: 2, and this was rubbed and aligned on the phenol novolac acrylate layer. Application was carried out using an applicator at room temperature to form a polymerizable liquid crystal composition layer having a thickness of 6 μm. Subsequently, the applied surface is irradiated with ultraviolet rays with an integrated light amount of ² J / cm ² from an ultrahigh pressure mercury lamp with an output of 1 KW at room temperature in a nitrogen atmosphere, and a rubbing-oriented phenol novolac-type acrylate layer and an oriented polymerizable liquid crystal composition The material layer was polymerized to form an optical anisotropic body.
Similarly, an optical anisotropic body was formed on the other side of the cell. In the same manner as in Example 1, liquid crystal was injected to perform viewing angle measurement and cross-cut test. The results are shown in Table 1. When the optical anisotropic body was observed with a polarizing microscope, many scratches due to rubbing were observed along the alignment direction, and a decrease in optical uniformity was observed.

(Comparative Example 2)
In the same manner as in Example 1, on the outside of a TN type glass cell with an ITO electrode having a gap of 10 μm treated with a silane coupling agent, a composition for layer (A) and 2 manufactured by Wako Pure Chemical Industries, Ltd. as a thermal polymerization initiator were used. A composition having a mass ratio of 98: 2 with 2′-azobis (2,4-dimethylvaleronitrile “V65”) was uniformly applied on one side substrate outside the cell and dried with hot air at 40 ° C. for 30 minutes. In the surface of the substrate, the wavelength is around 365 nm from an ultrahigh pressure mercury lamp whose output is 1 KW from a direction perpendicular to the rubbing direction of the alignment film formed inside the substrate and inclined by 45 ° from the normal of the coating film surface. The non-polarized light was irradiated with a cumulative amount of light of 5 J / cm ^{2 in} the state of parallel light to give the layer (A) a liquid crystal alignment ability, and this cell was then heat-treated in nitrogen at 60 ° C. for 120 minutes to fix the alignment. did.

On the layer (A), a composition obtained by adding a photopolymerization initiator “Irgacure 907” to the polymerizable liquid crystal composition (B-1) so as to have a mass ratio of 98: 2, using an applicator at room temperature. Then, a layer (B) having a film thickness of 6 μm was formed. Subsequently, an ultraviolet ray having an accumulated light amount of ² J / cm ² is irradiated onto the coated surface at a room temperature in a nitrogen atmosphere from an ultrahigh pressure mercury lamp having an output of 1 KW, and an optical anisotropic body composed of the layer (A) and the layer (B) is formed. Formed. Similarly, an optical anisotropic body composed of the layer (A) and the layer (B) was formed on the other side of the cell. In the same manner as in Example 1, liquid crystal was injected to perform viewing angle measurement and cross-cut test. The results are shown in Table 1. The optical anisotropic body was also observed with a polarizing microscope.

(Comparative Example 3)
In the same manner as in Example 1, on the outside of a TN type glass cell with an ITO electrode with a gap of 10 μm treated with a silane coupling agent, a phenol novolac type epoxy acrylate having a side chain with an acrylic group “NK ester EA-6310 new” and Ciba A toluene solution (concentration 5 wt%) of a composition in which a photopolymerization initiator “Irgacure 907” manufactured by Specialty Chemicals Co., Ltd. was mixed so as to have a mass ratio of 98: 2, was placed on one side substrate outside the cell using a spin coater. It was uniformly coated on top and dried at 60 ° C. for 30 minutes. Subsequently, in a nitrogen atmosphere, the coated surface was irradiated with an ultraviolet ray with an integrated light amount of ² J / cm ² from an ultrahigh pressure mercury lamp with an output of 1 KW and cured, and then this was rubbed to impart in-plane horizontal alignment ability. At that time, the orientation direction was set to be perpendicular to the orientation direction of the polyimide film inside the substrate. The surface was washed with running water, rinsed with pure water, and dried at 70 ° C. for 30 minutes.

Next, a composition having a mass ratio of 98: 2 between the polymerizable liquid crystal composition (B-1) and the photopolymerization initiator “Irgacure 907” was applied to the rubbing-oriented phenol novolac acrylate layer using an applicator. This was applied to form a polymerizable liquid crystal composition layer having a thickness of 6 μm. Subsequently, in a nitrogen atmosphere, the coated surface is irradiated with ultraviolet rays having an integrated light amount of ² J / cm ² from an ultrahigh pressure mercury lamp having an output of 1 KW, and is made of a rubbing-oriented phenol novolac acrylate layer and an anisotropic polymer layer. Anisotropic bodies were formed. Similarly, an optical anisotropic body composed of a phenol novolak acrylate layer and an anisotropic polymer layer that were rubbed and aligned was formed on the other side of the cell.
In the same manner as in Example 1, liquid crystal was injected to perform viewing angle measurement and cross-cut test. The results are shown in Table 1. The optical anisotropic body was also observed with a polarizing microscope.

  As a result, the optical anisotropic bodies obtained in Examples 1 and 2 have uniform and good orientation without surface scratches and the like, and a desired retardation is obtained. Therefore, the viewing angle with respect to the TN liquid crystal display element The effect of enlargement was excellent, and there was little interfacial peeling between the photo-alignment film layer and the polymerizable liquid crystal layer. In Comparative Example 1, since the scratches were observed on the surface of the alignment film, a decrease in optical uniformity was observed. Comparative Examples 2 and 3 were inferior in performance and interface peelability of the optical anisotropic body as an optical compensator.

  The optical anisotropic body of the present invention is an optical film having a birefringence such as a retardation film, a quarter-wave plate, a half-wave plate, an optical compensation film and the like used for a liquid crystal display device and a polarization separation element. It can be used for functional elements.

In the optical anisotropic body of the present invention, the layer (A) is a plan view showing a specific embodiment when the layer (A) is a layer in which liquid crystal alignment ability is generated in the direction of two or more different patterns. . In the optical anisotropic body of the present invention, a plan view and a side view showing a specific embodiment when the layer (A) is a layer in which liquid crystal alignment ability is generated in the direction of two or more different patterns. FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Arrow which shows the orientation direction of the layer (B) in the same orientation area | region 2 Substrate 3 Layer (A) which produced liquid crystal orientation ability in the direction of two or more different directions in pattern form
4 layers (B)

Claims (8)

Polymerized in a state in which the layer (A) containing the compound represented by the general formula (1) and having the liquid crystal alignment ability by light irradiation and the liquid crystal compound having a polymerizable group are aligned by the layer (A). An optical anisotropic body, wherein the polymer layer (B) thus obtained is bonded and laminated by covalent bonds.

(In the formula, R ¹ and R ² are each independently selected from the group consisting of (meth) acryloyl group, (meth) acryloyloxy group, (meth) acrylamide group, vinyl group, vinyloxy group, and maleimide group). Represents a polymerizable group.
X ¹ represents a linking group represented by — (A ¹ -B ¹ ) _m —, and X ² represents a linking group represented by — (B ² -A ² ) _n —. Here, A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group, and B ¹ and B ² each independently represent a single bond, —O—, —CO—O—, — OCO-, -CONH-, -NHCO-, -NHCO-O-, or -OCONH- is represented. m and n each independently represents an integer of 0 to 4. When m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or two B ² is not a single bond.
Y represents a group having an azobenzene group, an anthraquinone group, a benzophenone group, a cinnamoyl group, a chalcone group or a coumarin group. ) The optical anisotropic body according to claim 1, wherein in the general formula (1), Y is a group represented by the following structure.

(Wherein p _{1 to} p ₁₁ are each independently a hydrogen atom, a halogen atom, a halogenated alkyl group, a halogenated alkoxy group, a cyano group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an allyloxy group, an alkoxy group. Represents a carbonyl group, a carboxyl group, a sulfonic acid group, an amino group, or a hydroxy group, provided that the carboxyl group and the sulfonic acid group may form a salt with an alkali metal. The optical anisotropic body according to claim 1 or 2, wherein the layer (A) is a layer in which liquid crystal alignment ability is generated in a direction of two or more different directions in a pattern. A state in which a laminated film of a layer containing a compound represented by the general formula (1) and a layer containing a liquid crystal compound having a polymerizable group is formed on a substrate, and the liquid crystal compound having the polymerizable group is aligned. The optical anisotropic body according to claim 1, wherein both layers are polymerized. The optically anisotropic body according to any one of claims 1 to 4, wherein the liquid crystal compound having a polymerizable group is a rod-like liquid crystal compound having a polymerizable group or a discotic liquid crystal compound having a polymerizable group. The optical anisotropic body according to claim 1, wherein the substrate is a glass substrate or a plastic substrate. It is a manufacturing method of the optical anisotropic body of Claim 1, Comprising: The layer containing the compound represented by General formula (1) is formed on a board | substrate, Polarization irradiation or a diagonal direction is formed in this layer. After forming the layer (A) by non-polarized irradiation, a layer containing a polymerizable liquid crystal compound is laminated on the layer (A), and expressed by the general formula (1) by light irradiation or heating. A method for producing an optical anisotropic body, comprising polymerizing a polymerizable compound and a polymerizable liquid crystal compound. The layer (A) is a layer in which liquid crystal alignment ability is generated in two or more different directions in a pattern by irradiation with polarized light or non-polarized light from an oblique direction through a photomask. A method for producing an optical anisotropic body.

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