KR20160025504A - Method for producing oriented film - Google Patents

Abstract

The polymerization of the polymerizable material is started from a part of the film using a film containing a polymerizable material containing only one kind of polymerizable compound exhibiting liquid crystallinity before and / or after polymerization as a polymerizable compound, The orientation film is obtained by continuously moving the boundary of the region toward the unpolymerized region at a rate so that the compound exhibiting liquid crystallinity existing in the film is oriented.

Description

[0001] METHOD FOR PRODUCING ORIENTED FILM [0002]

The present invention relates to a method for producing an oriented film.

Conventionally, as a method of uniformly orienting a liquid crystalline compound, there has been known a method of orienting a compound by using an external field such as an electric field or a magnetic field, or a so-called rubbing method, an oblique vapor deposition method, a microgroove method, an LB film method, A method of imparting anisotropy to the surface of the substrate which is in contact with the liquid crystalline compound to give an alignment regulating force to the substrate itself and orienting the liquid crystalline compound by using the alignment regulating force. From the standpoint of large-scale industrialization, and from the viewpoint of excellent processing time and processing cost, as a method of producing a liquid crystal display element or an oriented film using such a method of uniformly orienting such a liquid crystalline compound, For example, a method of rubbing an alignment film such as polyimide with a velvet-like cloth including cotton, rayon, or the like) has been generally used.

However, when an oriented film is produced using the rubbing method, static electricity is likely to be generated during the processing, and various problems have arisen due to such static electricity. For example, foreign matter adheres to the surface of the oriented film due to the generation of static electricity, or alignment defects are generated, thereby causing a problem that defective display occurs when the film is used in a display device or the like. In addition, when the oriented film is formed using the rubbing method, problems such as generation of rashes and scratches during rubbing have also occurred. In addition, in the field of liquid crystal display devices, high-definition is progressing and densification of pixel density is demanded. In addition, uniformity of rubbing treatment is required. In the case of producing an oriented film using rubbing method, The yield has been reduced. Therefore, in recent years, a method for efficiently producing a large-area oriented film by a method other than the rubbing method has been demanded.

On the other hand, as one method of producing an oriented film, In the article "Photoinduced Opposite Diffusion of Nematic and Isotropic Monomers during Patterned Photopolymerization" (Non-Patent Document 1) by Cornelus F. van Nostrum et al., Pp. 135-145 of Mater (Vol. 10, No. 1) By filling a mixture containing two kinds of monomers in a cell including two opposed glass slides subjected to the treatment and exposing a part of the layer containing the mixture using a photomask on the lattice, Are oriented in a direction perpendicular to the substrate.

In addition, it is described in Shushido Atsushi's article " Control of photo-alignment of liquid crystal polymer and soft matrices " in Polymer Preprints, vol. 61, No. 2, page: ROMBUNNO. 1L05 issued on Sep. 5, (Non-Patent Document 2), it has been found that 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl (A6CB) or 4-acryloyloxy-4'- A method of introducing a composition containing phenyl (AOCB) and ethylene glycol dimethacrylate as a monomer into a cell, and then carrying out photopolymerization by irradiating light with a photomask to obtain a film having optical anisotropy at the boundary portion of the photomask .

Cornelus F. van Nostrum et al., Chem. Mater., "Photoinduced Opposite Diffusion of Nematic and Isotropic Monomers during Patterned Photopolymerization ", Vol. 10, No. 1, 1998, pages 135-145 Shimizu Atsushi, "Optical Orientation Control of Liquid Crystalline Polymers and Pioneering of Soft Matter Mechanisms", Polymer Preprints (CD-ROM), vol.61, No.2, issued on September 5, 2012, Pages: ROMBUNNO. 1L05

However, in the method described in the above non-patent document 1, a polymer is partially formed using a lattice-shaped photomask, and the resulting film has a narrow alignment region. That is, the method disclosed in the above non-patent document 1 is merely a method of producing a partially oriented film, and a technical idea of producing an oriented film in which the orientation is continuously formed over a large area is disclosed in the above non- . In addition, in the manufacturing method actually used in the above Non-Patent Document 1, a substrate (glass slide) subjected to rubbing treatment is used. As described above, the conventional method disclosed in the above non-patent document 1 is not a method for efficiently producing a large-area oriented film.

Further, all of the conventional methods as described in the above Non-Patent Documents 1 and 2 use two or more kinds of monomers in combination, and as the mechanism for forming the orientation, there is a method of utilizing the molecular diffusion of the monomer in the photopolymerization ≪ / RTI > As described above, the conventional methods as described in the above Non-Patent Documents 1 and 2 are methods using two or more types of monomer molecule diffusion, and two or more kinds of monomers are used as essential components. On the other hand, none of the above non-patent documents 1 and 2 uses a single compound as a polymerizable compound (monomer).

SUMMARY OF THE INVENTION The present invention has been made in view of the above problems of the prior art, and it is an object of the present invention to provide a method for efficiently and efficiently producing an oriented film having an oriented region in a large area while using a polymerizable material containing only one kind of compound as a material for an oriented film And to provide a method for producing an oriented film capable of producing an oriented film.

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted intensive studies in order to achieve the above objects, and as a result, they have found that a polymerizable compound containing a polymerizable compound containing only one polymerizable compound exhibiting liquid crystallinity before polymerization and / The polymerization of the polymerizable material is started from a partial region of the film and then the boundary of the region is continuously moved toward the unpolymerized region so that it is surprisingly found that a compound exhibiting liquid crystallinity present in the film in the polymerization region It is possible to orient a compound exhibiting liquid crystallinity as a compound of at least one compound selected from the group consisting of a polymerizable compound and a compound obtained after polymerization of the polymerizable compound). Even when a substrate or cell not subjected to rubbing treatment is used, An alignment region can be efficiently formed in a large area while moving the polymerization region As a result, it has been found that it is possible to efficiently produce an oriented film having an oriented region in a large area while using a polymerizable material containing only one kind of compound as a polymerizable compound in a material for an oriented film, .

That is, the method for producing an oriented film of the present invention is a method for producing an oriented film by using a film containing a polymerizable material containing only one kind of polymerizable compound exhibiting liquid crystallinity before and /

After the polymerization of the polymerizable material is started from a partial region of the film, the boundary of the region is continuously moved toward the unpolymerized region at a rate so that the compound exhibiting liquid crystallinity present in the film is oriented, .

In the method for producing an oriented film of the present invention, in order to carry out the polymerization of the polymerizable material by photopolymerization and continuously move the boundary toward the unpolymerized region, the boundary of the irradiated region of the light is defined as the non- As shown in Fig.

Further, in the method for producing an oriented film of the present invention, a photomask is used in the photopolymerization, and the photomask and / or the film are continuously moved so that the boundary of the irradiated region of the light is continuously . It is preferable that the photomask is a mask formed by arranging a plurality of substantially rectangular openings such that long sides of each opening are substantially parallel.

In the method for producing an oriented film of the present invention, it is preferable to use a prepolymerized film as the film containing the polymerizable material.

Further, in the method of producing an orienting film of the present invention, it is preferable that the speed at which the boundary is moved is 1 × 10 ^-7 to 4 × 10 ^-1 m / s.

Further, in the production method of the oriented film of the present invention, the polymerizable compound is to be represented by the formula (1) Further, the equation of Z ^1, Z ^2, M ^1, M ^2, M ^3, L ^1, L ² , and p, q and r are each represented by the following formula: C11 to C17.

Here, the compounds C11 to C17 that can be selected as the polymerizable compound each have the following formula (1):

Z ¹ pM ¹ -L ¹ - (M ² -L ² ) qM ³ -Z ² r (1)

As the compound represented by formula

In the compound C11, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acryl group or a methacryl group either a, S ¹ two bond and carbon atoms, and any one of 1 to 12 linear alkylene group of one, L ³ is only a bond, an ether group, an ester group and a carbonate either a carbonate group (more preferably an ether group) , P is 1, M ¹ is a 1,4-phenylene group, L ¹ is any one of a single bond and -COO- (more preferably a single bond), q is 0, M ³ is 1, A 4-phenylene group, and r is 1,

Z ¹ and Z ² in formula (1) may be the same or different, and each represents a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acryl group or a methacryl group either a, S ¹ is only a bond or a carbon atoms is any one of 1 to 12 linear alkylene group of one, L ³ is only a bond, an ether group, an ester group and a carbonate either a carbonate group (more preferably an ether group) P is 1, M ¹ is a 1,4-phenylene group, L ¹ is -COO-, M ² is a 1,4-phenylene group, L ² is -OCO-, q is 1, M ³ is a 1,4-phenylene group and r is 1,

Z ¹ and Z ² in the formula (1) may be the same or different, and each represents a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acryl group or a methacryl group either a, S ¹ is the formula: a group represented by (CH ₂ CH ₂ O) z (z is any one of 2 and 3), wherein the L ³ a single bond, p is one, M ¹ 1, Phenylene group, L ¹ is any one of a single bond and an ester group (more preferably a single bond), q is 0, M ³ is a 1,4-phenylene group, and r is 1 ,

The compound C14 is a compound wherein Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, S ¹ is a single bond, L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen (More preferably a cyano group) selected from the group consisting of a halogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms,

The compound C15 is a compound wherein Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is a group having a carbon number of 1 to 12 , L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, and M ³ is 1,4-phenylene and, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C 1 -C 12 alkyl group and having 1 to 12 carbon atoms in an alkoxy group (preferably more cyano groups), one selected from the and, and r is 1 Lt; / RTI >

The compound C16 is a compound wherein Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acrylic group and a methacryl group, S ¹ is a group represented by the formula: CH ₂ CH ₂ O) z (wherein z is 2 or 3), L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group and Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (More preferably a cyano group), and r is 1,

The compound C17 is a compound wherein Z ¹ is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acrylic group and a methacryl group, S ¹ is a straight chain alkylene group having 1 to 12 carbon atoms , L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is -COO-, q is 0, M ³ is a 1,4-phenylene group, Z ² (More preferably a cyano group) selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, and r is 1.

The reason why the above object is achieved by the method for producing an oriented film of the present invention is not necessarily clear, but the present inventors presume as follows. Hereinafter, in order to explain the reason why the above objects are attained, a preferred embodiment of the present invention in which a photopolymerizable compound is used as the polymerizable compound will be described with reference to Figs. 1 to 4, (A principle presuming by the present inventors) in which it becomes possible to orient a compound exhibiting liquid crystallinity (a polymerizable compound before polymerization and a compound exhibiting liquid crystallinity as at least one kind of compound obtained after polymerization) Together. In the following description and drawings, the same or equivalent elements are denoted by the same reference numerals, and redundant description is omitted.

Fig. 1 is a schematic longitudinal sectional view schematically showing a state before photopolymerization is started with respect to a film containing a polymerizable material containing the polymerizable compound. Fig. 2 is a schematic vertical cross-sectional view schematically showing a state in which polymerization is initiated from a part of the film by irradiating light from a light source, and Fig. 3 is a cross-sectional view schematically showing a state in which the boundary of the polymerization region in Fig. 2 is moved toward the non- And FIG. 4 is a schematic vertical sectional view schematically showing a state after moving the boundary of the polymerization region of FIG. 3 toward the non-polymerization region. In the figure, the dotted line S represents the boundary of the polymerization region, the arrow A conceptually represents the direction of moving the boundary S of the polymerization region, the arrow L conceptually represents the light emitted from the light source, A1 conceptually shows a region (a polymerization region: an exposed portion) irradiated with light L and a conceptual representation A2 a unconverted region (a non-polymerized region: a light shielding portion) in which light L is not irradiated , And A3 conceptually represents a region in which the orientation is formed.

In the embodiment shown in Figs. 1 to 4, when the oriented film is produced by photopolymerization, as shown in Fig. 1, the light source 11 and the light source 11 A film 13 containing a polymerizable material disposed between the two substrates 12 and a photomask 14 capable of shielding light emitted from the light source 11 A light source 11 is disposed on one side of the two substrates 12 and a film 13 and a light source 11 are disposed so that light from the light source 11 is irradiated to only a part of the film 13. [ A photomask 14 capable of shielding a part of the film 13 is disposed between the photomask 11 and the photomask 14. Next, as shown in Fig. 2, the light source 11 is turned on and the light L is emitted from the light source 11. Then, as shown in Fig. When the light L is irradiated in this manner, the reaction does not proceed in the light-shielding portion A2 but remains unpolymerized, but the polymerization proceeds in the exposed portion A1 to which light is irradiated. Thus, the polymerization of the polymerizable material is initiated from a part of the area (exposed part) A1 of the film 13 by exposing a part of the area. Then, in the polymerized region (polymerization region: exposed portion) A1, the polymerizable compound (monomer) in the polymerizable material is polymerized to form a polymer (polymer). Therefore, in the polymerization region (exposed portion) A1, polymerization proceeds and the concentration of the monomer decreases. As a result, the concentration of the monomer existing in the film is shifted between the polymerization region (exposed portion) A1 and the non-polymerization region (light-shielding portion) A2. Generally, when the concentration of the compound in the film is deviated, diffusion of the substance occurs in the direction of dissolving the concentration gradient by the diffusion phenomenon of the substance. Therefore, even if a polymerizable material containing only one kind of compound as a polymerizable compound is used for the material of the film, the polymerized region (exposed portion) A1 and the non-polymerized region (A2), the diffusion of the compound (monomer and / or polymer) is induced in the direction of eliminating the concentration gradient. The flow of the monomer mainly occurs from the light-shielding portion A2 as the non-polymerization region to the exposure region A1 as the polymerization region, and the flow of the monomer mainly flows from the polymerization region (exposure portion) A1 to the non-polymerization region It is presumed that mainly a flow of the polymer occurs. Further, as the flow of such a compound, the flow of the compound which is more likely to move due to a smaller molecular weight tends to be larger. When a flow of the compound is generated between the non-polymerized region A2 and the polymerized region A1 in this manner, a compound which exhibits liquid crystallinity existing in the polymerization region in the film A compound exhibiting liquid crystallinity as a compound of at least one of a polymerizable compound (monomer) and a compound (polymer) obtained after polymerization) is subjected to one type of shearing stress, and the compound exhibiting liquid crystallinity is introduced into a polymerization region ) Is aligned in a region near the boundary S between the non-alignment region A1 and the non-polymerization region (light-shielding portion) A2, and the alignment region A3 is formed (organic). Since the direction in which the flow of such a compound is generated is in a direction substantially perpendicular to the boundary S between the polymerization region (exposed portion) A1 and the non-polymerized region (light-shielding portion) A2, When the compound exhibiting properties is in the form of a rod, the average orientation direction is generally perpendicular to the boundary S. Here, as in the prior art (Non-Patent Document 1), when examining the case where the position of the boundary S is fixed by fixing the photomask 14 at the position shown in Fig. 2, The diffusion of the compound is suppressed in that the inner viscosity of the region A1 is increased and the alignment region is limited only to the region near the boundary and the region in the direction perpendicular to the boundary of the light irradiation region is in the region of about several tens to several hundreds of micrometers Only the alignment region is formed. On the other hand, in the preferred embodiment of the present invention shown in Figs. 1 to 4, as shown in Figs. 2 to 4, the boundary between the polymerization region (exposed portion) A1 and the non- (In the present embodiment, the photomask 14 is continuously moved to move the boundary S toward the non-polymerized area A2) ). Then, after the polymerization of the polymerizable material is started from a part of the film 13 (see Fig. 2), the boundary S of the polymerization area is continuously moved toward the non-polymerization area A2 To 4), diffusion of the compound present in the film at a distance (at a new position) where the boundary S moves is induced, and it becomes possible to continuously cause alignment by photopolymerization and diffusion organic. At this time, a kind of shearing stress generated by the movement of the above-mentioned compound (monomer and / or polymer) is sufficiently added to the compound exhibiting liquid crystallinity so as to form an orientation at a rate to align the liquid crystalline compound It is possible to continuously generate the orientation by diffusion organic matter by continuously moving the boundary S. Therefore, in the present invention, the alignment region is continuously increased by continuously moving the boundary (S) of the polymerization region (A1) toward the non-polymerization region at such a rate that the liquid crystalline compound is aligned . Further, when the compound exhibiting the liquid crystalline property is oriented by the shear stress, once the orientation is started, the orientation is also amplified by the self-organizing ability of the liquid crystal, so that the orientation is formed more efficiently. As described above, in the prior art as described in the above Non-Patent Documents 1 and 2, it has been essential to use two or more kinds of monomers as the polymerizable compound, but in the present invention, only one kind of compound is used as the polymerizable compound The present inventors presume that it is possible to continuously increase the alignment region as described above. Therefore, in the present invention, although a film containing a polymerizable material containing only one kind of polymerizable compound exhibiting liquid crystallinity before and / or after polymerization is used as the polymerizable compound, The present inventors presume that it is possible to efficiently produce the oriented film formed. Further, the present invention is characterized in that the boundary (S) between the polymerization region (exposed portion) A1 and the non-polymerization region (light-shielding portion) A2 is moved toward the non-polymerization region A2, It is possible to continuously increase the orientation region by causing the diffusion phenomenon of the material to occur in the vicinity of the substrate S in a sequential manner. Therefore, a substrate (for example, a substrate having no pre- A substrate on which no rubbing treatment is carried out) or the like is used, an oriented film can be efficiently produced. Therefore, problems such as oscillation and static electricity generated by the rubbing process, problems such as adhesion and mixing of dust to the orienting film can be effectively avoided, and a pretreatment for imparting alignment restraining force to the substrate or the cell is performed And it is an efficient method in terms of workability. In the examples shown in Figs. 1 to 4, the principle of orientation is described by taking as an example the case where a photopolymerizable compound is used as the polymerizable compound. In the present invention, the polymerization regions (exposed portions) A1 and It is possible to form an orientation in the film by using the phenomenon of diffusion of a substance generated by moving the boundary S of the non-polymerization region (light-shielding portion) A2 toward the non-polymerization region A2 to make it possible to increase the alignment region The polymerizable compound is not limited to the photopolymerizable compound but may be a compound other than the photopolymerizable compound (for example, a thermo-polymerizable compound).

Further, in the method for producing an oriented film of the present invention, since the compound exhibiting the liquid crystalline property is oriented by using a compound which moves from the non-polymerization region to the polymerization region in the film after initiation of polymerization, It is possible to control the direction of the orientation in a direction (direction substantially perpendicular to the boundary of the region). Therefore, for example, when the polymerization is carried out by photopolymerization, the orientation can be controlled in various directions depending on the shape of the mask.

Here, the control of such an alignment direction will be briefly described with reference to another embodiment suitable for the present invention shown in Fig. 5A shows the relationship (the boundary S of the light irradiation area) between the photomask 14 and the substrate 12 before initiation of photopolymerization in the case of viewing from the light source side (the direction of the optical axis of the irradiated light) 5B is a schematic plan view showing the relationship between the photomask 14 and the substrate 12 after the initiation of photopolymerization (the boundary of the light irradiation region S ) Is moved in the direction of the arrow A). 5, the boundary S of the polymerization region A1 is perpendicular to the two sides of the substrate 12, and the boundary S (see Fig. 5) The flow of the compound occurs almost vertically with respect to the boundary S and the alignment direction is controlled almost perpendicular to the boundary S (the arrow P in the drawing indicates the direction of the boundary S with respect to the boundary S) And the flow of the compound is presumed to occur in a direction substantially the same as the arrow P and / or in a direction opposite to the direction indicated by the arrow P). On the other hand, when the boundary S is shifted by making the edge of the mask 14 oblique and bringing the boundary S into contact with the two sides of the substrate 12 at an angle other than the perpendicular direction, The alignment direction is controlled in the direction of the vector of the moving direction of the boundary S and the vector sum of the vectors in the vertical direction with respect to the boundary S when the moving speed of the boundary S is fast. The control of the alignment direction when the edge of the mask 14 is oblique as described above will be described in more detail with reference to another embodiment suitable for the present invention shown in Fig. 6 is a schematic plan view schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from the light source side (the direction of the optical axis of the irradiated light). The photomask 14 shown in Fig. 6 is disposed such that its edges are formed obliquely, and the boundary S is in contact with the substrate 12 so as to form an angle other than perpendicular to the two sides of the substrate 12. When the photopolymerization is carried out while the boundary S is continuously moved in the direction of the arrow A in the figure (for example, when the photopolymerization is carried out while continuously moving the mask 14 toward the direction of the arrow A) Basically, the diffusion of the compound (monomer and / or polymer) in the film causes a flow of the compound in a direction substantially perpendicular to the boundary S of the mask (the arrow P in the figure is perpendicular to the boundary S And the flow of the compound is assumed to occur in a direction substantially the same as the arrow P and / or in a direction opposite to the direction of the arrow P). Therefore, when photopolymerization is performed while continuously moving the boundary S toward the direction of the arrow A in the drawing, the alignment direction is substantially perpendicular to the oblique boundary S (substantially the same direction as the arrow P) . When the moving speed of the boundary S is high as described above, the vector of the moving direction of the boundary S (the direction indicated by the arrow A) and the vector perpendicular to the boundary S (indicated by the arrow P) Direction) in the direction of the vector sum.

Therefore, when the boundary S is shifted as schematically shown in Figs. 5 (a) to 5 (b) and when the edge of the mask 14 is shown obliquely as shown schematically in Fig. 6 When the boundary S is moved, the alignment direction is controlled in the other direction. As described above, in the case of employing light polymerization, it is also possible to obtain a film having a different orientation direction depending on the edge shape of the mask 14.

As described above, the present invention is a method in which the orientation is formed by using the diffusion phenomenon of the material while moving the boundary of the polymerization region, thereby making it possible to increase the orientation region, The present inventors presume that it is possible to efficiently produce an oriented film having a region formed thereon.

According to the present invention, as the polymerizable compound, it is possible to produce an oriented film capable of efficiently producing an oriented film having an oriented region formed on a large area while using a polymerizable material containing only one kind of compound as a material for the oriented film It is possible to provide a method.

BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a schematic longitudinal sectional view schematically showing a state before photopolymerization is started with respect to a film containing a polymerizable material. Fig.
2 is a schematic vertical sectional view schematically showing a state in which polymerization is started from a part of a film by irradiating light from a light source.
3 is a schematic vertical sectional view schematically showing a state after the boundary of the polymerization region in Fig. 2 is moved toward the non-polymerization region.
Fig. 4 is a schematic vertical sectional view schematically showing a state after the boundary of the polymerization region in Fig. 3 is moved toward the non-polymerization region; Fig.
5A is a schematic plan view schematically showing the relationship between the photomask and the substrate before starting the photopolymerization (the state before moving the boundary of the light irradiation region) in the case of viewing from the light source side, Is a schematic plan view schematically showing the relationship between the photomask in the case of viewing from the light source side and the substrate after starting the photopolymerization (the state in which the boundary of the light irradiation region is shifted).
FIG. 6 is a schematic plan view schematically showing the relationship between the photomask in which the edges are formed obliquely when viewed from the light source side and the substrate before the photopolymerization is started. FIG.
7 is a schematic plan view schematically showing the relationship between the photomask having a plurality of substantially rectangular openings in the case of viewing from the light source side and the substrate before the photopolymerization is started.
8 is a schematic plan view schematically showing the relationship between the photomask having a plurality of substantially rectangular openings in the case viewed from the light source side and the substrate before the photopolymerization is started.

Hereinafter, the present invention will be described in detail based on its preferred embodiments.

The method for producing an oriented film of the present invention is a method for producing an oriented film using a film containing a polymerizable material containing only one kind of polymerizable compound exhibiting liquid crystallinity before and /

After the polymerization of the polymerizable material is started from a partial region of the film, the boundary of the region is continuously moved toward the unpolymerized region at a rate so that the compound exhibiting liquid crystallinity present in the film is oriented, .

Such a polymerizable material contains only one kind of polymerizable compound exhibiting liquid crystallinity before and / or after polymerization as a polymerizable compound in the material. As described above, in the present invention, it is possible to obtain an oriented film having a sufficiently uniform orientation over a large area, while using a film containing a polymerizable material using only one kind of compound as the polymerizable compound.

As such a polymerizable compound, those having a polymerizable functional group of 1 or more (more preferably, 1 to 6) are preferable. When the number of such polymerizable functional groups is less than the above lower limit, polymerization is not carried out, and it becomes difficult to form an oriented film by orientation using the diffusion of a compound derived from the change in the concentration of the polymerizable compound (monomer). If the number of the polymerizable functional groups exceeds the upper limit, the polymerization tends to proceed more rapidly than the diffusion of the compound, so that it becomes difficult to form an orientation accompanying diffusion.

The polymerizable functional group is not particularly limited, and any known polymerizable functional group can be suitably used. Examples thereof include a vinyl group, an allyl group, a vinyl ether group, an acryl group, a methacryl group, an oxetane group, an epoxy group, There can be mentioned a vinyl ether group, an acryl group, a methacryl group, an oxetane group, an epoxy group, a cinnamoyl group and a chalcone group from the viewpoints of easiness of synthesis of the compound, And more preferably an acryl group, a methacryl group, an oxetane group or an epoxy group.

Further, in the present invention, from the viewpoint of amplifying the orientation by the self-organizing ability of the liquid crystal, the polymerizable compound needs to be a compound exhibiting liquid crystallinity before and / or after polymerization (at least, (Polymerizable compound itself, polymeric compound of polymerizable compound) derived from the polymerizable compound must exhibit liquid crystallinity. The term "compound exhibiting liquid crystallinity after polymerization" as used herein means that the compound obtained when the above polymerizable compound is polymerized exhibits liquid crystallinity (the homopolymer (polymer) of the polymerizable compound is a compound exhibiting liquid crystallinity ). In addition, as the " compound exhibiting liquid crystallinity " referred to herein, it is preferable to be a compound (so-called thermotropic liquid crystal compound) that exhibits liquid crystallinity within a predetermined temperature range. Examples of the thermotropic liquid crystal compound include an enantiotropic liquid crystal compound exhibiting liquid crystallinity both in the temperature raising process and in the temperature raising process in the case where the behavior of the liquid crystal phase is observed when the temperature is raised or lowered, It may be a monotropic liquid crystal compound exhibiting liquid crystallinity only in the process. Further, in the present invention, at least one of the polymerizable compound (monomer) before polymerization and the compound (polymer: polymer) obtained by polymerizing the polymerizable compound is a compound having liquid crystallinity (a compound having liquid crystallinity) , When the diffusion of the compound (monomer and / or polymer) is excited in the film by initiation of polymerization, it becomes possible to apply shear stress to the compound exhibiting liquid crystallinity, whereby the orientation of the compound having liquid crystallinity When the alignment is started, the alignment is amplified by the self-organizing ability of the liquid crystal, so that it is possible to form the alignment efficiently.

Examples of the polymerizable compound include compounds represented by the following formula (1):

Z ¹ pM ¹ -L ¹ - (M ² -L ² ) qM ³ -Z ² r (1)

[Wherein Z ¹ and Z ² are each independently a hydrogen atom; A halogen atom (more preferably F, Cl, Br); CN; NO ₂ ; OCF ₃ ; A straight-chain or branched alkyl group having 1 to 18 carbon atoms (wherein the alkyl group is an oxygen atom in which one or more carbon atoms of the alkyl group are not continuously bonded, -COO-, -OCO-, -OCOO-, -CONR ¹ -, -NR ¹ CO-, -OCO-NR ¹ - or -NR ¹ COO- (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms); An alkoxy group having 1 to 18 carbon atoms; And a group represented by the formula: -L ³ -S ¹ -F ¹

(Wherein F ¹ represents a group represented by the following formulas (F-1) to (F-20):

(In the formula, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

S ¹ represents a single bond, a straight-chain or branched alkylene group having 1 to 18 carbon atoms (wherein the alkylene group is an oxygen atom in which one or more carbons of the alkylene group is not continuously bonded, -COO-, -OCO -, -OCOO-, -CONR ³ -, -NR ³ CO-, -OCO-NR ³ - or -NR ³ COO- (in the formula, R ³ represents a hydrogen atom or a C 1-6 An alkyl group)),

L ³ is a single bond, -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ -, -COO-, ^{OCO-, -OCOO-, -CONR 4 -,} -NR 4 CO-, -OCO-NR 4 -, -NR 4 COO-, -CH = CH-, -CF = CF-, -CH = CH-COO- , -OCO-CH = CH- or -C? C- (in the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

, ≪ / RTI > < RTI ID = 0.0 >

L ¹ and L ² each independently represents a single bond, -O-, -S-, -OCH ₂ -, -CH ₂ O-, -CO-, -CH ₂ -CH ₂ -, -CF ₂ -CF ₂ - ^{, -COO-, -OCO-, -CONR 4 -} , -NR 4 CO-, -OCO-NR 4 -, -NR 4 COO-, -CH = CH-, -CF = CF-, -CH = CH- COO-, -OCO-CH = CH- or -C? C- (in the formula, R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)

M ¹ and M ³ each independently represent a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, 1,3-dioxane-2,6-diyl group, 1,3,4-benzenetoluyl group, 1,3,5-benzenetoluyl group, 1,3, Benzene tetrayl group, M ² represents a 1,4-phenylene group, a 1,4-cyclohexylene group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, A 2,6-diyl group, a naphthalene-1,4-diyl group or a 1,3-dioxane-2,6-diyl group,

The hydrogen atoms contained in the groups selected as M ¹ , M ² and M ³ may be independently substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group,

p and r each independently represents 1, 2 or 3,

q represents 0, 1 or 2,

And when Z ¹ and / or Z ² are plural, they may be the same or different from each other]

Are preferred.

The polymerizable compound is not particularly limited as long as it exhibits liquid crystallinity before and / or after the polymerization. Therefore, the compound other than the compound represented by the formula (1) may exhibit liquid crystallinity before polymerization and / And can be suitably used. Examples of the compound usable in addition to the compound represented by the formula (1) include a compound having a structure other than the structure represented by the formula (1), and also a vinyl group, allyl group, vinyl ether group, acryl group, methacryl group, A compound having a functional group such as an oxetane group, an epoxy group, a cinnamoyl group, a chalcone group or a coumarin group can be suitably used. The components usable as such a polymerizable compound (for example, various thermopolymerizable compounds or photopolymerizable compounds exhibiting liquid crystallinity before and / or after polymerization) are commercially available, and these may be suitably used.

In addition, as the polymerizable compound contained in the polymerizable material, it is possible to control the boundary position between the polymerization region and the non-polymerization region at the time of polymerization, and to form a film having the desired orientation property more efficiently, It is preferable to use a photopolymerizable compound because it is possible to further improve the efficiency. That is, in the present invention, it is preferable that the polymerizable compound is a photopolymerizable compound, and the polymerization of the polymerizable material is carried out by photopolymerization. The photopolymerizable compound referred to herein may be a compound which reacts with a functional group by the presence of a photoinitiator such as a vinyl group, an allyl group, a vinyl ether group, an acrylic group, a methacrylic group, an oxetane group or an epoxy group, May be a compound which reacts with light. Examples of the photopolymerizable compound to which the functional group reacts even without the photoinitiator include a compound having a functional group capable of photo-dimerization reaction such as cinnamoyl group, calcon group, and coumarin group.

From the standpoint that the polymerizable compound is a monomer capable of promoting polymerization more efficiently, from the viewpoint that it is possible to form an oriented film more efficiently, the compound represented by the formula (1) Z ¹ and Z ² are both a group represented by -L ³ -S ¹ -F ¹ (and Z ¹ and Z ² may be the same or different and are preferably the same group in terms of easiness of synthesis) Wherein F ¹ is an acrylic group or a methacryl group, S ¹ is a single bond or a straight chain alkylene group having 1 to 12 carbon atoms, L ³ is a single bond, an ether group (-O-), an ester group (-COO-, -OCO -) and a carbonate group (-OCOO-) (more preferably an ether group), p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond and -COO- (More preferably a single bond), q is 0, M ³ is a 1,4-phenylene group, and r is 1 Compounds C11,

Wherein Z ¹ and Z ² in the formula are all groups represented by -L ³ -S ¹ -F ¹ (wherein Z ¹ and Z ² may be the same or different, It is preferable that F ¹ is an acrylic group or a methacryl group, S ¹ is a single bond or a straight chain alkylene group having 1 to 12 carbon atoms, L ³ is a single bond, an ether group, an ester group (More preferably an ether group), p is 1, M ¹ is a 1,4-phenylene group, L ¹ is -COO-, M ² is 1,4-phenylene group, A compound C12 in which L ² is -OCO-, q is 1, M ³ is a 1,4-phenylene group and r is 1,

Wherein Z ¹ and Z ² in the formula are all groups represented by -L ³ -S ¹ -F ¹ (wherein Z ¹ and Z ² may be the same or different, F ¹ is an acrylic group or a methacryl group, S ¹ is a group represented by the formula: (CH ₂ CH ₂ O) z (z is 2 or 3), and , L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is any one of a single bond and an ester group (more preferably a single bond), q is 0, A compound C13 in which M < ³ > is a 1,4-phenylene group and r is 1,

Wherein Z ¹ in the formula is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acrylic group or methacryl group, S ¹ is a single bond, L ³ is a P is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, halogen (More preferably a cyano group) selected from the group consisting of an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms,

Wherein Z ¹ in the formula is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acrylic group or a methacryl group, S ¹ is a straight chain alkyl having 1 to 12 carbon atoms is a group, L ³ is an ether group, p is 1, and M ¹ is 1,4-phenylene group, and L ¹ is a single bond, and q is 0, and M ³ is 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, a C 1 -C 12 alkyl group and having 1 to 12 carbon atoms in the alkoxy group (more preferably a cyano group), one selected from a, in addition, r is 1 compound C15 ,

Wherein Z ¹ in the formula is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acrylic group or a methacryl group, and S ¹ is a group represented by the formula: (CH ₂ CH ₂ O) z wherein z is 2 or 3, L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0 and, M ³ is a 1,4-phenylene group, Z ² is (more preferably one selected from an alkoxy group of a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and having 1 to 12 carbon atoms in the A cyano group), a compound C16 in which r is 1, and

Wherein Z ¹ in the formula is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acrylic group or a methacryl group, S ¹ is a straight chain alkyl having 1 to 12 carbon atoms Phenylene group, L ¹ is -COO-, q is 0, M ³ is a 1,4-phenylene group, L ³ is an ether group, p is 1, M ¹ is a 1,4- Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, one selected from an alkoxy group having 1 to 12 alkyl group and having 1 to 12 (more preferably a cyano group), and the compound also r is 1 C17 is more preferable.

Examples of such compounds C11 to C17 include 4,4'-bis (8- (meth) acryloyloxy-3,6-dioxaoctyl-1-oxy) biphenyl, 4,4'- (Meth) acryloyloxy) nonyloxybiphenyl, 4,4'-bis (6- (meth) acryloyloxy) hexyloxybiphenyl, 1,4- Cyanobiphenyl, 4- (9- (meth) acryloyloxynyloxy) -4'-cyanopyridine, 4- (6- (meth) acryloyloxyhexyloxy) Naphthylphenyl, 4- (5- (meth) acryloyloxy-3-oxapentyl-1-oxy) 1-oxy) -4'-cyanobiphenyl, and 4-cyanophenyl-4- (2-acryloyloxyethoxy) benzoate.

Such a polymerizable material is one containing only one kind of compound (only one type of polymerizable compound exhibiting liquid crystallinity before and / or after polymerization) as a polymerizable compound in the material. In such a polymerizable material, components other than the compound that exhibits polymerizability together with the polymerizable compound (a compound that does not exhibit polymerizability) may be appropriately contained within a range that does not impair the effects of the present invention. Examples of other components (compounds which do not exhibit polymerizability) that can be contained in such a polymerizable material include various solvents, photopolymerization initiators, viscosity regulators, plasticizers, polymerization inhibitors, and surfactants. When the other components (various additives, etc.) are contained in the polymerizable material, the content of the polymerizable material in the polymerizable material is preferably 70 mol% or more (more preferably 80 mol% or more) . When the content of the polymerizable material is less than the lower limit described above, the amount of the compound exhibiting liquid crystallinity in the film after polymerization tends to decrease, and it tends to be difficult to form an alignment.

In addition, when the above-mentioned polymerizable compound in the polymerizable material is photopolymerized, it is preferable to use a photopolymerization initiator together with the above-mentioned polymerizable compound since polymerization can proceed more efficiently. The photopolymerization initiator is not particularly limited, and any known photopolymerization initiator can be appropriately used and commercially available ones (for example, "Irgacure 651", trade name, manufactured by BASF) may be used. In the case of using such a photopolymerization initiator, the amount thereof to be used can be appropriately designed according to the kind of the polymerizable compound in the polymerizable material to be used, the wavelength of light absorption, and the like. For example, Mol%. When the content of the photopolymerization initiator is less than the above lower limit, the effect of using a photopolymerization initiator tends to be insufficient. On the other hand, when the content exceeds the upper limit, the liquid crystalline property tends to be lowered, There is a tendency that it is not obtained.

The shape (including the thickness and the like) of the film containing such a polymerizable material is not particularly limited and may be appropriately changed in accordance with the intended design. For example, even if the thickness is 0.1 to 200 탆 do. The film containing such a polymerizable material may be a coating film obtained by applying the above polymerizable material onto a substrate, or may be a film in which a polymerizable material is introduced into a so-called cell so that the polymerizable material is in the form of a film. The method of forming the film and the presence or absence of the substrate during its production are not particularly limited, and known methods can be appropriately used. The conditions and the like can be appropriately selected depending on the kind of the polymerizable compound in the polymerizable material, the polymerization method (photopolymerization or thermal polymerization) , The end use of the product, and the like. In addition, the substrate or the like used when the film containing the polymerizable material is produced on a substrate or in a cell need not be horizontal.

As the film containing such a polymerizable material, from the viewpoint of forming an oriented film while sufficiently retaining the shape and uniformity of the film, a film of a polymerizable material is disposed between the two substrates to support the film by the substrate For example, it is preferable that a film containing the polymerizable material is formed on one substrate and the other surface is a gas phase boundary surface by arranging a film in a cell using cells including two substrates) . In addition, the material of such a substrate or cell is not particularly limited, and known materials (for example, glass or plastic) can be suitably used. When the polymerization is carried out by photopolymerization, in the case where the substrate is in contact with the incident surface of the light of the above-mentioned film, light must be incident through the substrate. Therefore, It is preferable to include a permeable material.

Further, in the present invention, the polymerization of the polymerizable material is started from a part of the film using a film containing such a polymerizable material. The term " initiating polymerization of the polymerizable material from a partial region of the film " as used herein means, for example, when a part of the film is initially set as a region for initiating polymerization, For example, in the case of photopolymerization, a state in which a part of the film is present in a portion irradiated with light from a light source (exposure portion), and the polymerization of the polymerizable material is started from the exposed portion of the film) (For example, in the case of photopolymerization using a photomask, the whole of the film is covered with the mask so that the film is entirely contained in the portion shielded by the mask) , The film is gradually exposed to the light irradiation area at the time of irradiation with light, and the film is exposed When the polymerization is started from a part (film part of the film): In this case, it is preferable to introduce (expose) the film at such a rate as to cause the compound exhibiting the liquid crystalline property to be oriented in the light irradiation area .

As described above, the method of polymerizing the film containing the polymerizable material from a partial region is not particularly limited, and a known method can be suitably employed. As a method for initiating polymerization from a part of such a film, for example, a method of irradiating light (X-ray, electron beam, ultraviolet ray, visible ray, infrared ray Or a method of initiating heating from a partial region and initiating polymerization from the heating region, and the like. As such a polymerization method, from the viewpoint of easy control of the polymerization area, from the viewpoints of easiness of handling, irradiation intensity of irradiated light, setting of irradiation energy and ease of management, It is preferable to adopt the method of In the case where the film, which is the object of photopolymerization, is supported by a cell or the like in such photopolymerization, when the substrate or the like on the light-irradiation surface is not transparent, it can be photopolymerized by using an electron beam. It is useful if you do not.

In the case of employing photopolymerization as the polymerization method of the polymerizable material, it is preferable to use ultraviolet rays or visible light because it is possible to proceed the polymerization reaction more efficiently. The light source for irradiating such light is not particularly limited and a known light source usable for photopolymerization can be suitably used. For example, a high pressure mercury lamp, an ultra high pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an LED lamp or the like may be used .

The irradiation wavelength of the light used in such photopolymerization is not particularly limited and may be determined in consideration of the absorption spectrum of the compound and the recommended use wavelength of the photoinitiator. Further, for example, in the case where a film containing a polymerizable material is formed on a substrate and polymerization is carried out in a state in which one of the interfaces of the film is in contact with the surrounding atmospheric gas, a compound containing an acryl group or a methacryl group is used In the case of using a radical reaction, it is preferable to carry out the polymerization under an inert gas atmosphere such as nitrogen from the viewpoint that polymerization is difficult to proceed due to oxygen inhibition in the presence of oxygen. In the case of a polymerizable functional group which does not affect oxygen inhibition by cationic reaction such as an oxetane group or an epoxy group, it is not necessary to carry out the polymerization under an inert atmosphere, and the polymerization may be carried out in the atmosphere. On the other hand, when a film containing a polymerizable material is not in contact with the atmosphere gas by using a cell or the like, polymerization may be started in the atmosphere. As described above, in the present invention, the polymerization may be carried out in a state where the film containing the polymerizable material is in contact with the atmospheric gas (the state where the interface of the film is in contact with the gas phase), or the film containing the polymerizable material is not in contact with the atmosphere gas (The state in which the interface of the membrane is in contact with the wall surface (solid phase) of the cell).

When photopolymerization is employed as the polymerization method of the polymerizable material, light irradiation may be carried out under heating conditions. The heating temperature may be selected depending on the type of the polymerizable material to be used, the type of polymerization reaction, liquid crystallinity, Viscosity, ease of heating, and the like, but it is usually preferable to set the temperature to about room temperature (about 25 ° C) to about 300 ° C. When the heating temperature is lower than the lower limit described above, it is difficult to efficiently advance the polymerization reaction or the formation of the alignment film due to crystallization of the polymerizable material or one of the components thereof, or the polymerization reaction speed becomes slower as the viscosity of the polymerizable material increases On the other hand, when the upper limit is exceeded, polymerization of the entire film proceeds due to heat before irradiation of light to the polymerizable compound, so that an oriented film can not be obtained, or when the reaction is carried out in air There is a high possibility that the polymerizable compound is decomposed, and it tends to be difficult to stably obtain an oriented film.

In light of such a photopolymerization, it is preferable to irradiate light with an intensity of 0.1 μW / cm ² to 30 mW / cm ² , and it is more preferable to irradiate light with an intensity of 0.5 μW / cm ² to 10 mW / cm ² . If the light intensity of the light is lower than the lower limit described above, the reaction speed is lowered, and therefore the traveling speed of the boundary is lowered and the productivity is lowered. On the other hand, if the upper limit is exceeded, As the film becomes too fast, the diffusion of the compound does not occur sufficiently and the orientation film tends to be not obtained.

A method for irradiating light from a part of the region during the photopolymerization is not particularly limited. For example, a light source capable of irradiating light to only a part of the region may be used, or a part It is preferable to use a photomask because it is easier to control the polymerization region and the non-polymerization region.

Further, in the present invention, after the polymerization of the polymerizable material is initiated from a part of the film containing the polymerizable material as described above, the compound exhibiting liquid crystallinity present in the film (the polymerizable compound The boundary of the region is continuously moved toward the unpolymerized region at such a rate that the polymerizable compound (monomer) and / or the compound (polymer) obtained after polymerization of the polymerizable compound exhibits liquid crystallinity. By thus continuously moving the boundary between the polymerization region and the non-polymerization region toward the non-polymerization region, the polymerization is continuously carried out, and in the region in the vicinity of the moving boundary, the substance (the monomer and / or polymer) It becomes possible to cause the diffusion phenomenon to occur consecutively in succession, whereby it becomes possible to obtain an oriented film by successively increasing the orientation region. The polymerization conditions for continuously moving the boundaries of the regions toward the unpolymerized region may be the same as the polymerization conditions at the time of polymerization initiation described above.

Here, the " rate at which the compound exhibiting liquid crystallinity is oriented ", which is the moving speed at the time of moving the boundary, depends on the kind of the compound exhibiting liquid crystallinity, the kind of the compound that diffuses and moves, ), It is necessary to align the compound exhibiting liquid crystallinity in the film according to the kind of the polymerizable compound, the kind of the polymerizable compound, the polymerization conditions employed in polymerization (for example, light irradiation conditions in the case of employing photopolymerization) It is not possible to speak uniformly in terms of a difference in time to be released and the like. That is, in the present invention, the compound (mainly monomer and / or polymer) in the polymerizable material in the vicinity of the boundary between the polymerization region and the non-polymerization region due to the concentration gradient of the compound generated in the polymerization region and the non- And a compound exhibiting liquid crystallinity is oriented in the vicinity of the boundary by adding one kind of shearing stress to the compound exhibiting liquid crystallinity present in the polymerizable material, Of the compound exhibiting liquid crystallinity is different depending on the kind of the compound exhibiting liquid crystallinity, the kind of the compound to be diffused and moved, and the like. For example, when the polymerization rate of the polymerizable compound is very high, a concentration gradient of a compound (monomer and / or polymer) in the film in the polymerization region and the non-polymerization region is abruptly generated, The movement speed is very fast. In this case, even if the boundary speed is relatively fast, the shear stress generated by the movement of the polymerizable compound into the polymerization region can be sufficiently added to the compound exhibiting liquid crystallinity present in the polymerization region, It becomes possible to sufficiently orient the compound which is represented by the formula On the other hand, for example, when the polymerization rate of the polymerizable compound is low and the concentration gradient of the compound in the polymerization region and the non-polymerization region occurs mildly, in order to impart sufficient shear stress to the compound exhibiting liquid crystallinity in the film It is difficult to orient compounds sufficiently liquid crystalline in the vicinity of the boundary. As described above, the " rate at which the compound exhibiting liquid crystallinity is oriented " is appropriately determined depending on the kind of the compound exhibiting liquid crystallinity, the kind of the compound to be diffused and moved, the kind of the compound And the setting of the speed can be appropriately changed.

It is preferable that the rate at which the compound exhibiting liquid crystallinity is aligned (the movement speed for moving the boundary) is preferably 1 x 10 ^-7 to 4 x 10 ^-1 m / s, more preferably 1 x 10 ^-6 to 4 X 10 < ^-2 > m / s. If the rate is lower than the lower limit described above, the polymerization reaction proceeds faster than the diffusion of the compound. Thus, the higher the viscosity, the more the diffusion movement of the compound is suppressed and the shear stress can not be sufficiently imparted to the compound exhibiting liquid crystallinity. On the other hand, if the upper limit is exceeded, the speed becomes too fast, and it becomes difficult to sufficiently carry out diffusion of the compound near the boundary, and it tends to be difficult to form an alignment in the polymerization region . In addition, in the case of using one kind of compound C11 to 17 as a polymeric material, in the case of employing a photo-polymerization method which irradiated during the polymerization of the polymerizable material in the intensity of 0.1μW / cm ² to 30mW / cm ^2, wherein The rate at which the compound exhibiting liquid crystallinity is oriented (the moving speed for moving the boundary) is preferably set to 1 x 10 ^-7 to 4 x 10 ^-1 m / s from the viewpoint that the oriented film can be efficiently formed desirable.

The method of continuously moving the boundary of the region toward the non-polymerization region is not particularly limited. For example, when the polymerization method is thermal polymerization, it is possible to continuously move the heating region to the non-polymerization region Method may be suitably employed, and when the polymerization method is photopolymerization, a method capable of continuously moving the irradiation region of the light to the unirradiated region may be suitably employed.

As a method of continuously moving the boundaries of these regions toward the non-polymerized region, it is preferable that the moving speed of the boundary can be more easily controlled and the alignment region can be formed more efficiently, It is preferable to adopt a method of continuously moving the boundary of the irradiation region of the light toward the unirradiated region of the light in order to carry out polymerization of the copolymer by photopolymerization and continuously move the boundary toward the non-polymerization region. As a method for continuously moving the boundary of the irradiation region of the light toward the unirradiated region of the light, any method can be used as long as the boundary can be moved. The method is not particularly limited. For example, A method of continuously moving the light source itself so that the light can be irradiated only to the region, a method of continuously moving the film of the polymerizable material while fixing the light source, a method of continuously moving the photomask A method of continuously moving the film of the polymerizable material while fixing the photomask using a photomask may be used.

Among the methods of continuously moving the boundary of the irradiation region of such light toward the unirradiated region of light, there is a method of continuously moving the photomask and / or the film by using a photomask in the light polymerization (for example, A method of continuously using the mask and moving the photomask, a method of continuously moving the film of the polymerizable material while using the photomask, and the like) are preferably employed. As described above, by photopolymerizing the polymerization of the polymerizable material and using a photomask, it is possible to more easily move the boundary of the light irradiation region continuously toward the unirradiated region of the light.

Hereinafter, preferred embodiments of a method for producing an oriented film of the present invention in which the polymerization of the polymerizable material is performed by photopolymerization and a photomask is used in the photopolymerization will be briefly described with reference to Figs. 1 to 4 . In the preferred embodiment shown in Figs. 1 to 4, at first, a photo (light shielding film) is provided which can shield light between the film 13 and the light source 11 so that light from the light source 11 is irradiated to only a part of the film 13 After the mask 14 is disposed (Fig. 1), the polymerization of the polymerizable material is initiated from the partial area A1 of the film 13 by irradiating light from the light source 11 (see Fig. 2) The photomask 14 is continuously moved at such a rate that the compound exhibiting liquid crystallinity is oriented so that the boundary S of the polymerization region is directed toward the non-polymerization region A2 at such a rate as to cause the liquid crystalline compound to align (Toward the direction of arrow A) (see Figs. 3 to 4), thereby obtaining an oriented film. When photopolymerization is used for polymerization of the polymerizable material as described above, it is possible to move the boundary S between the polymerization region and the non-polymerization region by a simple method such as a method of moving the photomask 14, It becomes possible to manufacture the film more efficiently. 1 to 4, a preferred embodiment of the process for producing an oriented film of the present invention in the case of using a photomask has been described. However, the process for producing the oriented film of the present invention in the case of using a photomask The shape is not limited to the above embodiment. For example, in the embodiment shown in Figs. 1 to 4, the photomask 14 is moved in order to move the boundary S between the polymerization region and the non-polymerization region, And the film 13 itself is moved by fixing it. In the embodiment shown in Figs. 1 to 4, the polymerization of the polymerizable material is started after the state in which the light is irradiated to the partial region R1 of the film 13 is initiated. However, The polymerization method which can be adopted in the production method is not limited to the method adopted in this embodiment, and for example, it is possible to cover all of the film with a photomask and align the compound exhibiting liquid crystallinity (A part of the film) introduced into the irradiated area (exposed area) of the light by causing the photomask or film to be continuously moved at such a speed as to be irradiated with light at the speed , Moving the boundary of the polymerization region toward the non-polymerization region at such a rate that the compound exhibiting liquid crystallinity is intact It is also possible to adopt a method in which to obtain an oriented film.

When the photopolymerization of the polymerizable material is carried out by photopolymerization and a photomask is used in the photopolymerization, it is possible to easily control the alignment direction according to the edge shape of the photomask. Hereinafter, the control of the orientation in accordance with the shape of the edge of the photomask will be briefly described with reference to the embodiments shown in Figs. 5 and 6, respectively. For example, when the photomask 14 as shown in FIG. 5 is used as the photomask, a flow of the compound occurs in a direction substantially perpendicular to the boundary S shown in FIG. 5, It is possible to control the alignment direction almost perpendicularly with respect to the direction of the alignment. 6 is used as the photomask, the flow of the compound occurs in a direction substantially perpendicular to the boundary S shown in Fig. 6 A vector (arrow A) in the moving direction of the boundary S and a vector in the vertical direction (arrow A) with respect to the boundary S are obtained when the moving speed of the boundary S is substantially perpendicular to the oblique boundary S, P in the direction of the vector sum. Therefore, in the case of photopolymerization using a photomask, it is possible to more easily control the alignment direction in a desired direction according to the edge shape of the photomask. Therefore, in order to form a desired alignment direction, the edge shape of the photomask may be used while appropriately changing, thereby making it possible to easily control the alignment direction.

When the photopolymerization of the polymerizable material is carried out by photopolymerization and a photomask is used in the photopolymerization, a photomask formed by arranging a plurality of substantially rectangular openings as long as the long sides of the openings are substantially parallel Can be used to make. Hereinafter, a preferred embodiment of the photopolymerization method in the case of using such a mask in which the plurality of substantially rectangular openings are formed such that the longer sides of the respective openings are substantially parallel, will be briefly described with reference to Figs. 7 and 8. Fig. 7 and 8 are schematic plan views schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from the light source side (the direction of the optical axis of the irradiated light). In these embodiments, the light source, the photomask 14, and the substrate 12 are disposed so that the film disposed on the substrate 12 can be light-cured by the light transmitted through the opening 14A.

The photomask 14 shown in Figs. 7 and 8 has a plurality of substantially rectangular openings 14A. Here, the term " roughly rectangular " means a shape in which four corners of a rectangle are formed in an arc, in addition to a rectangular shape such as the opening 14A shown in Fig. 7, a shape corresponding to a long side or a short side of the rectangle, A shape of a parallelogram with four corners such as the opening 14A shown in Fig. 8 is not 90 degrees (in the case of such a shape, four corners are arc-shaped, but also a long side or a short side And a shape in which the corresponding portion is circular arc-shaped). As described above, the substantially rectangular opening portion is intended to be an elongated shape that is longer than a side corresponding to a short side (which may be an arc-shaped side) of the opening corresponding to a long side such as a rectangle Expression.

The substantially rectangular shape (elongated shape) of the opening 14A is not particularly limited, and the length Y of the long side may be longer than the length X of the short side. The ratio (Y / X) of the length (Y) to the length (X) of the short side of the long side is preferably 2.0 or more, more preferably 5.0 to 2.0x10 ⁵ .

The length X of the short side of the opening 14A differs depending on the size of the substrate 12 and the film used for polymerization. It is preferably 1 to 10 mm, more preferably 10 to 10 mm, (Also, it is preferable that the average value of the length X of the short side of the plurality of opening portions 14A is in the same numerical range). If the length X of the short side of the opening 14A is less than the lower limit, orientation tends to be difficult to occur. On the other hand, if the length exceeds the upper limit, a film having a uniform orientation in the film surface tends not to be obtained.

In addition, such openings 14A are arranged such that long sides of the respective openings are substantially parallel. By arranging the openings 14A in such a manner that the long sides of the openings are substantially parallel to each other, it is possible to control the alignment direction in a uniform direction when forming the orientation film on a large area. As the mask having the opening 14A, it is preferable that the opening 14A is periodically formed, and it is more preferable that the opening 14A having the same shape is periodically formed. When the opening 14A is periodically formed, the pitch of the opening 14A (the distance from the center of one opening to the center of the adjacent opening) is not particularly limited, but is preferably 1 to 10 mm (More preferably, the average value of the pitches of the plurality of openings 14A is preferably in the same numerical range). If the pitch of the openings 14A is less than the above lower limit, orientation tends to be difficult to occur. On the other hand, if the above-mentioned upper limit is exceeded, a film having a uniform orientation in the film surface tends to be hardly obtained. In the photomask having a plurality of such openings, the number of openings is not limited particularly, and the design can be appropriately changed depending on the size of the mask and the substrate.

For example, the substrate 12 is moved toward the direction opposite to the direction A or the same direction by using the mask 14 in which the plurality of rectangular openings are formed substantially parallel to each other, 14A, the boundary of the polymerization region is formed for each opening 14A, and each of the boundaries can be moved continuously toward the non-polymerization region, and each of the openings 14A It is possible to form an alignment region for each pixel. Therefore, in the case of using the mask 14 in which a plurality of rectangular openings are formed substantially in parallel, it is possible to form an alignment region in a large area by moving the mask and / or the film to the same distance as the distance And it becomes possible to efficiently form an orientation film.

In the case of using the mask 14 in which the plurality of rectangular openings are formed substantially in parallel, it is also possible to control the alignment direction according to the shape of the edge of the opening 14A. For example, In the embodiment, when the substrate 12 on which the film (not shown) is formed is moved in the direction opposite to the direction A (or the same direction) while performing the photopolymerization, the alignment direction is changed to the longer side of the opening 14A It is possible to perform control in a direction perpendicular to the direction 8, the substrate 12 on which the film (not shown) is formed is moved toward the direction opposite to the direction A (thereby forming the boundary S The edge of the opening portion 14A is formed in the substrate 12 in the oblique direction with respect to the two sides when viewed from the light source side, A flow of the compound is generated in a direction substantially perpendicular to the long side of the opening 14A and when the traveling speed of the substrate 12 is substantially perpendicular to the long side or in the direction of movement of the boundary S It is possible to control the alignment direction in the direction of the vector and the vector sum of the vector in the substantially vertical direction with respect to the long side of the opening 14A. 7 to 8, a method of photopolymerization which can be suitably employed in the present invention has been described. However, the method of photopolymerization that can be employed in the present invention is not limited to these methods. For example, in the above-described embodiment, the method of moving the substrate 12 is described. However, the method of fixing the substrate 12, moving the mask and the light source, and the like may be appropriately employed to perform the light polymerization.

Further, in the present invention, after the polymerization of the polymerizable material is started from a part of the film containing the polymerizable material, the boundary of the region is not polymerized at a rate so that the compound exhibiting liquid crystallinity existing in the film is aligned To prepare an oriented film. Alternatively, a film obtained by preliminarily polymerizing a film containing a polymerizable material used for producing such an oriented film may be used. By using such a prepolymerized film, it becomes possible to form an alignment structure sufficiently even if the speed at which the boundary of the polymerization zone is continuously moved toward the non-polymerization zone is made faster, and the alignment film can be formed more efficiently It becomes possible to form a thin film. The term " preliminary polymerization " as used herein means that the film of the above-mentioned polymerizable material is slightly polymerized to such an extent that the fluidity of the polymerizable compound is not impaired (for example, when photopolymerization is used for both the preliminary polymerization and the main polymerization, The polymerizable compound in the film is slightly polymerized to such an extent that the fluidity is not impaired by irradiating the film of the material material with light having lower intensity than that of the present polymerization).

As described above, in the present invention, the film after the prepolymerization can be suitably used from the viewpoint that the orientation film is formed in a shorter time as the speed at which the boundary of the polymerization region is continuously moved toward the non-polymerization region is made faster. The method of such a prepolymerization is not particularly limited, and for example, in the case of employing photopolymerization for the prepolymerization, preliminary polymerization using a photomask or preliminary polymerization without using a photomask may be used. As described above, the preliminary polymerization may be a preliminary polymerization by photopolymerization using, for example, a photomask in which a plurality of substantially rectangular openings are formed such that long sides of the respective openings are substantially parallel.

When photopolymerization is employed in such a prepolymerization, it is preferable to irradiate light with an intensity of 0.001 μW / cm ² to 10 mW / cm ² , and to irradiate light with an intensity of 0.05 μW / cm ² to 1 mW / cm ² More preferable. If the light intensity is lower than the lower limit described above, the reaction tends to be insufficient and the effect of the prepolymerization tends to be difficult to obtain. On the other hand, if the upper limit is exceeded, the polymerization of the polymerizable compound becomes too advanced, After the initiation of the polymerization of the polymerizable material (polymerization of the polymerizable compound) from a part of the film, the boundary of the region is continuously moved toward the non-polymerization region at a rate so that the liquid crystalline compound present in the film is aligned The compound does not sufficiently diffuse even when it is moved, and an oriented film tends not to be obtained. When photopolymerization is employed in the prepolymerization, the same conditions as the photopolymerization conditions described above for the polymerization method of the polymerizable material may be adopted as the conditions of the photopolymerization except for the conditions relating to the light intensity.

As described above, in the present invention, after the polymerization of the polymerizable material is started from a part of the film using a film containing the polymerizable material, the polymerizable material is allowed to polymerize at a rate The boundary of the region is continuously moved toward the unpolymerized region, thereby making it possible to obtain an oriented film. Further, in the method for producing an oriented film of the present invention, by using a kind of shearing stress generated by a compound (the monomer and / or the polymer) moving from a non-polymerization region to a polymerization region in a film after initiation of polymerization (The monomer and / or the polymer) present in the film is controlled, the direction of orientation is basically controlled in the direction in which the compound moves (direction perpendicular to the boundary of the region) When the polymerization is carried out by photopolymerization, it is possible to control the orientation in various directions depending on the shape of the mask, or to achieve pattern orientation in which the orientation direction is changed depending on the place. Further, the present invention is characterized in that, as the polymerizable compound, a film containing a polymerizable material containing only one kind of polymerizable compound (monomer) exhibiting liquid crystallinity before at least one of polymerization and after polymerization is used, (In the case of using only one kind of polymerizable compound, it is possible to use the diffusion phenomenon of the substance by moving the boundary of the polymerization region even if only one kind of polymerizable compound is used) The present inventors presume that the orientation can be formed).

Further, in the present invention, after the polymerization of the polymerizable material is started from a part of the film containing the polymerizable material, the boundary of the region is set at a rate such that the compound exhibiting liquid crystallinity existing in the film is aligned After the boundary of the region is continuously moved toward the non-polymerization region to form the alignment region in the film, the polymerization reaction of the polymerizable material is completed or In order to sufficiently cure the oriented film, the film may be left under a temperature condition in which polymerization is further advanced, for example. Further, in order to more efficiently polymerize the unpolymerized component (polymerizable compound) remaining in the alignment region, light is further irradiated under a condition that the formed alignment state can be maintained, and the polymerization is further advanced by suitably changing the temperature condition or the like The process may be performed separately. As described above, in the present invention, the orientation is formed by using the diffusion phenomenon of the material while moving the boundary of the polymerization region, but it is not necessary to completely polymerize the components in the film in the polymerization process accompanying the movement of the boundary, (The post-polymerization step) in which the boundary is moved continuously toward the non-polymerization region and further polymerization is carried out while maintaining the alignment structure, thereby obtaining an oriented film in which the alignment structure is finally fixed. The conditions of such a post-polymerization step are not particularly limited, and may be carried out while appropriately changing them depending on the kind of the components in the polymerizable material to be used.

Further, in the method for producing an oriented film of the present invention, it is possible to produce a long oriented film by roll-to-roll by using a long substrate film or the like on the substrate.

As described above, the oriented film obtained by the method for producing an oriented film of the present invention can be used as a film in which the orientation of the compound exhibiting liquid crystallinity is formed on a large area. Therefore, the oriented film obtained by the method for producing a polarizing plate or liquid crystal display It can be used as a retardation film or as a retardation film for use in a circular polarizer for anti-reflection of an organic EL display or a pattern retardation film for 3D.

<Examples>

Hereinafter, the present invention will be described more specifically based on examples, but the present invention is not limited to the following examples.

(Synthesis Example 1: Synthesis of A6CB and a homopolymer thereof)

<Synthesis of A6CB and evaluation of its properties>

4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl (A6CB) was synthesized by the following method. Namely, 4-cyano-4'-hydroxybiphenyl (100 mmol) was dissolved in 120 mL of N, N-dimethylformamide (DMF) to obtain a dissolution solution. Subsequently, 1-bromohexanol (110 mmol), potassium carbonate (110 mmol) and potassium iodide (catalytic amount: 1 mmol of 1 mol of calcium carbonate) were added to the above solution, and the mixture was heated and stirred at 100 ° C for 5 hours. Subsequently, heating and stirring were stopped to terminate the reaction, and the resulting reaction solution was extracted with ethyl acetate. The formed organic layer was washed with 1 N hydrochloric acid and saturated brine in this order. Subsequently, the washed organic layer was dried over anhydrous magnesium sulfate, the drying agent was removed by filtration, and the solvent was distilled off under reduced pressure. Thereafter, the objective product (4-cyano-4 '- (6-hydroxyhexyloxy) biphenyl) was separated and purified by silica gel chromatography and then recrystallized from chloroform and hexane to obtain Compound A (72 mmol) of 4-cyano-4 '- (6-hydroxyhexyloxy) biphenyl).

Subsequently, Compound A (50 mmol), triethylamine (20.7 mL, 150 mmol) and THF (30 mL) were mixed in a flask and hydroquinone (catalytic amount: 2 mmol relative to 1 mol of the compound) was added to obtain a mixture. The flask was immersed in a water bath at 23 占 폚, and the atmosphere inside the flask was brought to a nitrogen atmosphere. Then, acryloyl chloride (150 mmol) was slowly added dropwise to the mixture while stirring under a nitrogen atmosphere to obtain a reaction solution. After stirring for 48 hours in a nitrogen atmosphere, 300 mL of a saturated aqueous solution of sodium hydrogencarbonate was added to the reaction solution, followed by stirring for 30 minutes. Thereafter, the obtained reaction solution was extracted with chloroform, and the organic layer was washed with 1N hydrochloric acid and saturated brine in this order. Subsequently, the solvent was distilled off from the obtained organic layer under reduced pressure at room temperature, and the objective product (4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl) was separated and purified by silica gel chromatography, To obtain 9.8 g (28 mmol) of 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl. The structure of the thus obtained compound was confirmed by NMR and IR measurements. As a result, it was confirmed that the compound was 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl represented by the following formula (2) .

The 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl thus obtained is a compound having a rigid cyanobiphenyl structure as a mesogen as apparent from the above formula (2). The temperature was raised and lowered at a rate of 1 ° C / minute using a differential scanning calorimeter (DSC 6220, manufactured by DSC SII, Nanotechnology), and 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl , Phase transition from crystalline phase to isotropic phase at 69 ℃ and phase transition from isotropic phase to crystalline phase at 53 ℃ in the temperature decreasing process.

<Synthesis of homopolymer of A6CB and evaluation of its properties>

15 mmol of 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl obtained as described above was added to 35 ml of N, N-dimethylformamide (DMF) and then 0.75 mmol of azo Bisisobutyronitrile (AIBN) was added as a thermal polymerization initiator, and the mixture was stirred at a temperature of 70 ° C for 6 hours, and the reaction was allowed to proceed to obtain a polymerization solution. Subsequently, the polymerization solution after completion of the reaction was poured into 0.5 L of methanol, the polymer was precipitated, washed again in 0.5 L of methanol, and then filtered to obtain a solid fraction. Subsequently, the resulting solid was vacuum-dried at room temperature (25 캜) for 24 hours to obtain 4.7 g of a polymer (homopolymer of A6CB).

The thus obtained polymer was subjected to GPC measurement. As a result, it was confirmed that the number average molecular weight Mn of the polymer was 8000 g / mol as a result of conversion to polystyrene standards. As a result of differential scanning calorimetry using the differential scanning calorimeter (DSC), the polymer exhibited a glass transition temperature at 38 ° C in the temperature raising process, liquid crystallinity at 38 to 126 ° C, and a temperature of 124 to 29 ° C , And showed a glass transition temperature at 29 캜. From these results, it was found that the 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl obtained in Synthesis Example 1 was a compound showing liquid crystallinity after polymerization.

(Example 1)

First, by using 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl (A6CB: monofunctional acrylate) obtained in Synthesis Example 1 as a polymerizable compound (monomer) (Manufactured by BASF) as a photopolymerization initiator at a ratio of 1 mol%, the obtained mixture was once dissolved in dichloromethane, and then the solvent was distilled off to obtain only A6CB (1 Only species) were prepared.

Subsequently, two epoxy resin soda glass substrates each having a size of 25 mm square and a thickness of 1.1 mm were mixed with silica particles having a diameter of 2 탆 and epoxy adhesive was applied to the left and right ends of the glass substrate (two parallel sides on the left and right sides) To form a glass cell having a cell thickness of 2 占 퐉 (the adhesive functioned also as a spacer, and the portion not coated with the adhesive was an opening). The soda glass substrate was subjected to ultrasonic cleaning in the order of a neutral detergent, ion exchanged water, acetone, and isopropanol, followed by UV ozone treatment.

Subsequently, the glass cell was placed on a hot stage (trade name "FP-90, FP-82HT", manufactured by Mettler Toledo), and the polymerizable material was melted at a temperature of 100 ° C., , A polymerizable material was injected into the glass cell by capillary phenomenon from the opening of the glass cell, and the polymerizable material was held at 100 캜 for 10 minutes to obtain a film of a polymerizable material (film size: 20 mm in length, 20 mm in width and 2 탆 in thickness). Subsequently, a photomask having a shape of a square of 30 mm in length and 30 mm in width was fixedly arranged so as to cover the whole of the film in the glass cell (so that the film enters the light shielding portion). Further, the light source is disposed at a position where light is irradiated on the entire surface of the film, for example, when no mask is present. Subsequently, irradiation of light from a light source is started, and the mask is moved at a rate of 20 占 퐉 / s while irradiating light to gradually form a light irradiation region on the film, whereby a part of the film introduced into the exposure portion (light irradiation portion) The polymerization was started and the mask was continuously moved at 20 占 퐉 / s so that the boundary between the irradiated area and the unirradiated area of light was continuously moved toward the unirradiated area at 20 占 퐉 / s, ). 5, the exposure unit A1 on the cell soda glass substrate 12 before the mask 14 is moved is set as a rectangular region of 5 mm in length and 25 mm in width (The region is a region 5 mm in length vertically from the opening on the side where the polymerizable material is not implanted, the film does not exist in the region, and the longitudinal direction referred to herein refers to the direction indicated by the arrow A in the drawing) , And the moving direction of the mask was the direction perpendicular to the boundary S of the light irradiation area A1 (the direction indicated by the arrow A in the figure) as shown in Figs. 5 (a) to 5 (b). 5 is a schematic plan view schematically showing a state in which the substrate and the photomask are viewed from the light source side (the direction of the optical axis of the irradiated light). In this photopolymerization, a color glass filter (IRA-265, UV-D54C, ND (90%) manufactured by AGC Technoglass Co., Ltd.) was used as a light source using a high-pressure mercury lamp (trade name "SX-UI501HQ" , ND (40%)) were used in combination, and ultraviolet light having an illuminance of 1.0 mW / cm ² (peak wavelength: 366 nm) was irradiated. In this manner, the polymerization is started from a partial region using a mask, and the polymerizable material is polymerized while moving the boundary between the polymerized region and the non-polymerized region to irradiate light to the entire region of the polymerizable material in film form, . After such photopolymerization, the glass cell was allowed to stand at a temperature of 100 캜 for 10 minutes to further polymerize the polymerizable compound in the film (post polymerization step). After this post-polymerization process, the glass cell was taken out from the hot stage to obtain a film (clear uncolored, thickness after curing: 1.7 mu m) formed in the glass cell.

In order to confirm the characteristics of the thus obtained film, the glass cell was inserted between two polarizing plates arranged in an orthogonal manner, and the glass cell was observed while rotating. As a result, the film had a dark field and a bright field, It was confirmed that the film was an oriented film which was almost uniformly oriented in a region of about 20 mm square. Further, the direction of darkness was parallel or perpendicular to the absorption axis of the two polarizing plates arranged orthogonally (dark and light appear every 45 degrees by the rotation of the cell). The alignment state was confirmed using a polarizing microscope (trade name "BX50", manufactured by Olympus Corporation). As a result, the obtained film was uniformly oriented, and alignment was confirmed in a microdomain.

Then, in order to confirm the alignment direction of the compound in the obtained film, the absorption spectrum (A⊥) in the direction perpendicular to the mask edge of the photomask and the absorption spectrum (A //) in the direction parallel to the mask edge of the photomask were measured Respectively. The absorption spectrum was measured using an ultraviolet visible spectrophotometer (V-650ST, manufactured by Nippon Bunko Co., Ltd.), and the polarization direction was adjusted using a Gantay prism.

From the results of the measurement of the absorption spectrum, it was found that the absorption spectrum (A //) in the direction perpendicular to the mask edge of the photomask has higher absorbance than the absorption spectrum (A //) in the parallel direction. From the measurement results of the absorption spectrum, the order parameter S indicative of the degree of orientation of the molecules is calculated by the following equation (1):

S = (A⊥-A //) / (A⊥ + 2A //) (One)

[Wherein A⊥ represents the absorption spectrum intensity in the vertical direction and A // represents the absorption spectrum intensity in the parallel direction]

As a result, the order parameter S was 0.22, which was a very large value. Further, the order parameter S was obtained from an average value obtained by obtaining the order parameter S of each wavelength from the data of the absorbance (A) in units of 1 nm within the measurement wavelength of 330 nm to 345 nm.

From the above results, it was found that in the film obtained in Example 1, the compound having liquid crystallinity (polymer of A6CB) was oriented in the direction perpendicular to the mask edge (boundary S in Fig. 5) of the photomask. Further, the retardation? Nd was confirmed using Berek Compensate (U-CBE, manufactured by Olympus), and the resultant? Nd for the light with a wavelength of 546 nm was 130 nm. Further, the birefringence Δn was calculated from the relationship between the birefringence Δn and the thickness of the film after curing, and as a result, Δn for the light having a wavelength of 546 nm was 0.076. The obtained results are shown in Table 1.

As is evident from the results as described above, it was confirmed that in the film obtained in Example 1, an oriented film uniformly oriented over substantially the entire surface of the polymerization region was formed, and the production method of the oriented film of the present invention It has been found that it becomes possible to produce an oriented film having an oriented region in a large area while using a polymerizable material containing only one kind of compound as the polymerizable compound in the material of the oriented film.

INDUSTRIAL APPLICABILITY As described above, according to the present invention, as the polymerizable compound, it is possible to efficiently produce an oriented film having an oriented region in a large area while using a polymerizable material containing only one kind of compound as a material for the oriented film It becomes possible to provide a method for producing an oriented film. As described above, the method of producing an oriented film of the present invention is a particularly excellent method in that an orientation region can be formed over a large area. Therefore, for example, a method of manufacturing a retardation film for use in a polarizing plate or a liquid crystal display (LCD) A retardation film for use in a circular polarizing plate for prevention, a pattern retardation film for 3D, and the like.

11: Light source
12: substrate
13: A film containing a polymerizable material
14: Photomask
14A: opening
X: length of the short side of the opening 14A
Y: length of the long side of the opening 14A
S: boundary of the polymerization region
A: An arrow representing the direction of moving the boundary S of the polymerization region conceptually
P: an arrow representing a direction perpendicular to the boundary S of the polymerization region
L: light emitted from a light source
A1: a region irradiated with light and polymerized (polymerization region: exposure unit)
A2: non-irradiated area (unpolymerized area: shielding part)
A3: area where alignment is formed

Claims (7)

As the polymerizable compound, a film containing a polymerizable material containing only one kind of polymerizable compound exhibiting liquid crystallinity before and / or after polymerization is used,
After the polymerization of the polymerizable material is started from a partial region of the film, the boundary of the region is continuously moved toward the unpolymerized region at a rate so that the compound exhibiting liquid crystallinity present in the film is oriented, To obtain an oriented film. The method according to claim 1, wherein the polymerization of the polymerizable material is carried out by photopolymerization and the boundary of the irradiation region of light is continuously moved toward the unirradiated region of the light so as to continuously move the boundary toward the non- A method for producing an oriented film. The method for producing an oriented film according to claim 2, wherein the photomask and / or the film are continuously moved by using a photomask at the time of light curing so as to continuously move the boundary of the irradiation region of the light toward the non- . The method of producing an orientation film according to claim 3, wherein the photomask is a mask formed by arranging a plurality of substantially rectangular openings such that long sides of the openings are substantially parallel. The method of producing an orientation film according to any one of claims 1 to 4, wherein the prepolymerized film is used as a film containing the polymerizable material. The method of producing an orientation film according to any one of claims 1 to 5, wherein the rate of moving the boundary is 1 x 10 ^-7 to 4 x 10 ^-1 m / s. The polymerizable composition according to any one of claims 1 to 6, wherein the polymerizable compound is a compound represented by the following formula (1):
Z ¹ pM ¹ -L ¹ - (M ² -L ² ) qM ³ -Z ² r (1)
In the compounds C11 to C17, wherein Z ¹ , Z ² , M ¹ , M ² , M ³ , L ¹ , L ² , p, q and r in the formulas are shown below, Z ¹ and Z ² in the formula (1) may be the same or different, and each represents a group represented by the formula: -L ³ -S ¹ -F ¹ , wherein F ¹ is any one of an acryl group and a methacryl group, Wherein S ¹ is any one of a single bond and a straight chain alkylene group having 1 to 12 carbon atoms, L ³ is any one of a single bond, an ether group, an ester group and a carbonate group, p is 1, M ¹ is 1, Phenylene group, L ¹ is any one of a single bond and -COO-, q is 0, M ³ is a 1,4-phenylene group, r is 1,
In the compound C12, Z ¹ and Z ² in the formula (1) may be the same or different, and each represents a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ represents an acryl group and a methacryl group , S ¹ is any one of a single bond and a straight chain alkylene group having 1 to 12 carbon atoms, L ³ is any one of a single bond, an ether group, an ester group and a carbonate group, p is 1, Wherein M ¹ is a 1,4-phenylene group, L ¹ is -COO-, M ² is a 1,4-phenylene group, L ² is -OCO-, q is 1, M ³ is 1,4- Phenylene group, r is 1,
In the compound C13, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acryl group and a methacryl group , S ¹ is a group represented by the formula: (CH ₂ CH ₂ O) z (z is any one of 2 and 3), L ³ is a single bond, p is 1, M ¹ is 1 Phenylene group, L ¹ is any of a single bond and an ester group, q is 0, M ³ is a 1,4-phenylene group, r is 1,
In the compound C14, Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, S ¹ is a single bond , L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is A hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, r is 1,
In the compound C15, formula (1) Z ¹ of the formula: -L ³ -S ¹ is a group represented by -F ^1, F ^1, and the any one of acrylic group and methacrylic group, S ¹ is C 1 -C L ¹ is a straight chain alkylene group, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is 1,4- and a group, Z ² is one selected from an alkoxy group of a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and having 1 to 12 carbon atoms, and r is 1, and,
Wherein Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is a group represented by the formula: CH ₂ CH ₂ O) z (z is any one of 2 and 3), L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a And q is 0, M ³ is a 1,4-phenylene group, and Z ² is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms 1, and r is 1,
In the compound C17, formula (1) Z ¹ of the formula: -L ³ -S ¹ is a group represented by -F ^1, F ^1, and the any one of acrylic group and methacrylic group, S ¹ is C 1 -C L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is -COO-, q is 0, M ³ is 1,4- A phenylene group, and Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, and r is 1] And at least one kind of compound selected from the group consisting of the compound

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