TW201510583A - Method for producing polarizing film - Google Patents

Abstract

A method for producing a polarizing film, which uses a film that is formed of a polymerizable composition containing at least one dichroic dye and at least one polymerizable compound that exhibits liquid crystallinity before and/or after polymerization, and by which a polarizing film is obtained by starting polymerization of the polymerizable composition in a partial region of the film and then continuously moving the boundary of the region toward an unpolymerized region at such a rate that the liquid crystalline compound and the dichroic dye, which are present in the film, are aligned.

Description

Method for producing polarizing film

The present invention relates to a method for producing a polarizing film.

A method for producing a polarizing film obtained by aligning a liquid crystal compound and a dichroic dye with a liquid crystal compound and a dichroic dye on a substrate is known by a so-called rubbing method or the like. The anisotropic property is such that the substrate has an alignment control force, and then the liquid crystal compound and the dichroic dye are aligned by the substrate to obtain a polarizing film.

For example, JP-A No. 3-21904 (Patent Document 1) discloses that a substrate is rubbed in one direction by using a velvet cloth, and a mixture of a liquid crystal compound and a dichroic dye is coated on the substrate to obtain a liquid crystal compound and dichroism. A method in which the pigments are aligned in the same direction. Japanese Patent Publication No. Hei 11-101964 (Patent Document 2) discloses a solution in which a surface of a substrate is rubbed in a specific direction to perform an alignment treatment, and a liquid crystal compound and a dichroic dye are dissolved in a solvent. Forming a coating film on the substrate subjected to the alignment treatment, and subjecting the coating film to heat treatment to uniaxially align the liquid crystal compound in a specific direction, thereby aligning the dichroic dyes according to the uniaxial alignment, thereby making the liquid crystal A method in which a compound and a dichroic dye are aligned in the same direction.

However, a method of manufacturing a polarizing film, such as Patent Document 1 Or it is described that when a method using a so-called rubbing method is employed, static electricity is likely to be generated in the rubbing treatment step, and the polarizing film obtained has various problems due to the static electricity. For example, when static electricity is generated, foreign matter adheres to the surface of the obtained polarizing film, and alignment defects occur, and when the film is used in a display device or the like, display defects occur. Further, as described in Patent Document 1 or 2, when a polarizing film is formed by a rubbing method, problems such as generation of dust or dirt during rubbing occur. Further, in the field of liquid crystal display elements, since the progress toward higher precision has progressed and the density of the pixel is required to be higher, the uniformity of the rubbing treatment is also required, and the above problem is caused when the polarizing film is produced by the rubbing method. The possibility of manufacturing yield decline.

In addition, as described above, the method using the friction method is used. In the method for producing a polarizing film, a method of obtaining a polarizing film by aligning a liquid crystal compound and a dichroic dye with an external field such as an electric field or a magnetic field is also proposed. For example, Japanese Laid-Open Patent Publication No. 2001-188129 (Patent Document 3) discloses a method of aligning a mixture of a liquid crystal compound and a dichroic dye coated on a substrate under the influence of a field of external force, particularly a magnetic field or an electric field. However, in the method of obtaining a polarizing film in the past as described in Patent Document 3, the device for generating a magnetic field is not only large-scale, but also difficult to process a large area, and it is difficult to efficiently manufacture a large-area polarizing film. The problem.

Under this circumstance, in recent years, it is expected to adopt the above-mentioned special Other than the alignment method used in the prior art described in the documents 1 to 3 According to the method, a method for producing a polarizing film which is a polarizing film which aligns a liquid crystal compound and a dichroic dye can be produced in a large area.

Also, the Polymer Society pre-release issued on September 5, 2012 Seto (Polymer Preprints, vol. 61, No. 2, Pages: ROMBUNNO.1L05), the book of the Seto thick paper "The development of the optical property control and soft matter mechanism of liquid crystal polymers" (non-patent It is disclosed in Document 1)" that 4-(6-acryloxyhexyloxy)-4'-cyanobiphenyl (A6CB) or 4-propenyloxy-4'-cyano linkage is introduced into the micelle. A method in which benzene (A0CB) and ethylene glycol dimethacrylate are used as a constituent of a monomer, and a photomask is irradiated by covering a photomask and irradiating light, thereby obtaining a film having optical anisotropy at a boundary portion of the photomask. However, in Non-Patent Document 1, there is no description about the dichroic dye, and there is no description about the production of the polarizing film.

[Previous Technical Literature] [Patent Literature]

Patent Document 1: Japanese Laid-Open Patent Publication No. 3-21904

Patent Document 2: Japanese Patent Laid-Open No. 11-101964

Patent Document 3: Japanese Laid-Open Patent Publication No. 2001-188129

Non-patent literature

Non-Patent Document 1: Seto Thick, "Development of Light Matching Control and Soft Matter Mechanism of Liquid Crystal Polymers", Polymer Society Preprints (CD-ROM), vol.61, No.2, 2012 Issued on September 5, the number of pages: ROMBUNNO.1L05

The present invention has been made in view of the problems of the prior art, and an object of the invention is to provide a method for producing a polarizing film which can efficiently produce a polarizing film having a large area of an alignment region of a liquid crystal compound and a dichroic dye.

As a result of repeating the above research, the present inventors have found that the polymerization property of at least one of the polymerizable compounds having liquid crystallinity before and/or after polymerization and at least one of the dichroic dyes is used. a film formed of the composition, wherein the polymerization of the polymerizable composition is started in a portion of the film, and the region in which the liquid crystal compound having the liquid crystal property present in the film is aligned with the dichroic dye is used to align the region The boundary is continuously moved toward the unpolymerized region. Unexpectedly, not only the above-mentioned liquid crystal compound which is present in the film in the polymerization region but also the polymerizable compound before polymerization and the polymerization of the polymerizable compound can be obtained. The at least one compound of the compound and the compound exhibiting liquid crystallinity) can also align the dichroic dye present in the film, and can be moved even when a substrate or a microcell which is not subjected to rubbing treatment is used. The polymerization region efficiently forms a large-area alignment region, thereby efficiently producing a liquid crystal compound and dichroism in a large area. Su polarizing film of the alignment area, thereby completing the present invention.

In the method for producing a polarizing film of the present invention, at least one of a polymerizable compound having a liquid crystal property before and/or after polymerization and a polymerizable composition containing at least one of a dichroic dye are used. a film formed by the polymerization of the polymerizable composition from a portion of the film, such that the compound exhibiting liquid crystal properties present in the film is aligned with the dichroic dye to set the boundary of the region A method of continuously moving toward an unpolymerized region to obtain a polarizing film.

In the method for producing a polarizing film of the present invention, it is preferred that the boundary of the light-irradiated region is continuously moved toward the non-irradiated region, and the polymerization of the polymerizable composition is carried out by photopolymerization, and the boundary is oriented toward the unpolymerized region. Move continuously.

Further, in the method for producing a polarizing film of the present invention, it is preferred that the photomask and/or the film are continuously moved to cause a boundary of the light-irradiating region toward a light-irradiated region by photomask during photopolymerization. Move continuously.

Further, in the method for producing a polarizing film of the present invention, the speed at which the boundary is moved is preferably from 1 × 10 ^-7 to 4 × 10 ^-1 m/s.

Further, in the method for producing a polarizing film of the present invention, the polymerizable compound is preferably represented by the following formula (1), and wherein Z ¹ , Z ² , M ¹ , M ² , M ³ Each of L ¹ , L ² , p, q, and r is at least one selected from the group consisting of the compounds C11 to C17 shown below.

Here, the compounds C11 to C17 which are selected as the above-mentioned polymerizable compound are each a compound represented by the following formula (1): Z ¹ pM ^{1 -} L ¹ - (M ^{2 -} L ² ) qM ^{3 -} Z ² r ( 1)

The compound C11 is a compound of the formula (1), and Z ¹ and Z ² 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 acrylic group and a methacryl group. In any one, S ¹ is any one of a single bond and a linear alkyl group having 1 to 12 carbon atoms, and L ³ is any one of a single bond, an ether group, an ester group, and a carbonate group (preferably Is an ether group), p is 1, M ¹ is 1,4-phenylene, L ¹ is either a single bond or -COO- (preferably a single bond), q is 0, and M ³ is 1 , 4-phenylene, and r is a compound of 1, the compound C12 is in the formula (1), Z ¹ and Z ² may be the same or different, and are represented by the formula: -L ³ -S ¹ -F ¹ And F ¹ is any one of an acryl group and a methacryl group, and S ¹ is any one of a single bond and a linear alkyl group having 1 to 12 carbon atoms, and L ³ is a single bond or an ether group. Any one of an ester group and a carbonate group (preferably an ether group), p is 1, M ¹ is 1,4-phenylene, L ¹ is -COO-, and M ² is 1,4-stretch Phenyl group, L ² is -OCO-, q is 1, M ³ is 1,4-phenylene, and r is a compound of 1, and compound C13 is the same as Z ¹ and Z ² in formula (1). Different, respectively, is represented by the formula: -L ³ -S ¹ -F ¹ , and 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 or 3), and L ³ is a single bond. , p is 1, M ¹ is 1,4-phenylene, L ¹ is either a single bond or an ester group (preferably a single bond), q is 0, and M ³ is 1,4-phenylene. And the compound of the formula (1) wherein Z ¹ is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is any of an acrylic group and a methacryl group. In one case, S ¹ is a single bond, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, and M ³ is 1,4-phenylene. , Z ^{2 is one selected} from the group consisting of 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 the compound 1, the compound of the formula C15 (1), Z ¹ is of the formula: group -L ³ -S ¹ -F ¹ indicates, the F. and is any ^one of acrylic group and a methacrylic group of persons, S ¹ is a linear alkyl group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenyl group, L ¹ is a single bond, q is 0, and M ³ is 1 , 4-phenylene, Z ² by a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms of The selected carbon number of alkoxy having 1 to 12 of the one kind (preferably cyano), and r is a compound of a compound of the formula C16 (1), Z ¹ is of the formula: -L ³ -S ¹ -F ¹ represents a group, and F ¹ is any one of an acryl group and a methacryl group, and S ¹ is a formula: (CH ₂ CH ₂ O)z (z is any one of 2 or 3) The group represented, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ is 1,4-phenylene, Z ² is a compound selected from the group consisting of 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 (preferably a cyano group), and r is 1. C17 is a compound of the formula Z ^1: -L ³ -S ¹ -F ¹ represents the group, and F ¹ is any one of acrylic group and methacrylic group of one, S ¹ is a straight-chain carbon atoms of 1 to 12 An alkyl group, L ³ is an ether group, p is 1, M ¹ is 1,4-phenylene, L ¹ is -COO-, q is 0, M ³ is 1,4-phenylene, and Z ² is a compound selected from the group consisting of 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 (preferably a cyano group), and r is 1. .

Further, in the method for producing a polarizing film of the present invention, the polymerizable composition preferably contains a first compound and a second compound having a polymerization completion time longer than the first compound when polymerized under the same conditions, and the At least one of the first and second compounds contains at least one of the polymerizable compounds. Further, in the polymerizable composition containing the first compound and the second compound, the first compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is higher than that of the second compound. The number of functional groups is one or more. Further, as the polymerizable composition containing the first compound and the second compound, the first compound is preferably a compound represented by the following formula (C), a compound represented by the following formula (2), and a formula (3) At least one compound selected from the group consisting of:

(wherein R ⁵ is any one of hydrogen and methyl, and x is 2 or 3),

(wherein R ⁵ is any one of hydrogen and methyl, y is an integer of 2 to 12), and the second compound is preferably at least one compound selected from the group consisting of the above compounds C14 to C17.

Moreover, the reason why the above object can be attained by the method for producing a polarizing film of the present invention is not necessarily clear, but the inventors of the present invention presume as follows. Here, a preferred embodiment of the present invention in which a photopolymerizable compound is used as the polymerizable compound will be described as an example for explaining the reason for achieving the above object, and the polarizing property of the present invention will be described with reference to FIGS. 1 to 4. In the method for producing a film, a compound exhibiting liquid crystallinity (a polymerizable compound before polymerization and at least one compound obtained by polymerizing the polymerizable compound and a compound exhibiting liquid crystallinity) can be aligned with the dichroic dye. Principle (principle as speculated by the inventors). In the following description and the drawings, the same or corresponding elements are designated by the same reference numerals, and the repeated description is omitted.

Figure 1 is a schematic representation of the inclusion of the aforementioned polymerizable compound A schematic longitudinal cross-sectional view of a state before the photopolymerization of the film formed of the polymerizable composition of the dichroic dye. 2 is a schematic longitudinal cross-sectional view schematically showing a state in which light from a light source is irradiated from a partial region of the film. 3 is a schematic longitudinal cross-sectional view schematically showing a state in which the boundary of the polymerization region in FIG. 2 is moved toward the unpolymerized region, and FIG. 4 is a view schematically showing a state in which the boundary of the polymerization region in FIG. 3 is moved toward the unpolymerized region. A schematic longitudinal section view. Further, in the figure, the broken line S indicates the boundary of the polymerization region, the arrow A conceptually indicates the direction in which the boundary S of the polymerization region moves, and the arrow L conceptually indicates the light irradiated from the light source, and A1 conceptually indicates the irradiated light L. In the polymerization region (polymerization region: exposure portion), A2 conceptually indicates an unpolymerized region (unpolymerized region: light-shielding portion) in which light L is not irradiated, and A3 conceptually indicates a region in which alignment is formed.

In the embodiments shown in Figures 1 to 4, by photopolymerization When a polarizing film is produced, first, as shown in FIG. 1, a light source 11 is prepared, two substrates 12 through which light emitted from the light source 11 is transmitted, and a polymerizable composition disposed between the two substrates 12 are prepared. The film 13 is permeable to the light-shielding 14 of the light irradiated from the light source 11, and the light source 11 is disposed on one of the two substrates 12 to illuminate only a portion of the film 13 from the light of the light source 11. A photomask 14 that can partially shield the film 13 from between the film 13 and the light source 11 is disposed. Next, as shown in FIG. 2, the light source 11 is turned on, and the light L is irradiated from the light source 11. When the light L is irradiated in this manner, the light-shielding portion A2 is not polymerized and is in an unpolymerized state, and polymerization is performed in the exposure portion A1 that irradiates light. So that a part of the area is exposed, since The partial region (exposure portion) A1 of the film 13 starts the polymerization of the aforementioned polymerizable composition. Then, in the polymerization region (polymerization region: exposure portion) A1, the monomer in the polymerizable composition (the polymerizable compound or the polymerizable composition also contains other polymerizable compounds other than the polymerizable compound) In the case of a compound, the polymerizable compound and/or other polymerizable compound) are polymerized to form a polymer (polymer). Therefore, polymerization is carried out in the polymerization region (exposure portion) A1 to reduce the concentration of the monomer (the polymerizable compound and/or other polymerizable compound). Thereby, the concentration of the monomer existing in the film occurs between the polymerization region (exposure portion) A1 and the unpolymerized region (light shielding portion) A2. Further, in general, when the concentration of the compound in the film is biased, the substance diffuses in the direction of eliminating the concentration gradient due to the diffusion phenomenon of the substance. Therefore, in the case of illuminating as described above, in the boundary S between the polymerization region (exposure portion) A1 and the unpolymerized region (light-shielding portion) A2, the concentration of the monomer is biased, so that the initiating compound (monomer and/or polymer) is eliminated. Diffusion in the direction of the concentration gradient. Therefore, it is estimated that the monomer flow mainly occurs from the light-shielding portion A2 of the unpolymerized region to the exposed portion A1 of the polymerization region, and the polymer flow mainly occurs from the polymerization region (exposure portion) A1 to the unpolymerized region (light-shielding portion) A2. Further, the flow of these compounds tends to have a large flow of a compound having a smaller molecular weight and a lower flow rate. Therefore, when a compound flows between the unpolymerized region A2 and the polymerization region A1, the liquid crystallinity compound which is present in the polymerization region in the film due to the flow (the polymerizable compound before polymerization which is present in the polymerization region and A shear stress is applied to at least one of the compounds obtained by polymerizing the polymerizable compound and a compound exhibiting liquid crystallinity and the dichroic dye. Therefore, the aforementioned display liquid The crystalline compound and the dichroic dye are aligned in a region in the vicinity of the boundary S between the polymerization region (exposure portion) A1 and the unpolymerized region (light shielding portion) A2 to form (inducing) the alignment region A3. Further, the direction in which the flow occurs due to the movement of the compounds is a direction perpendicular to the boundary S between the polymerization region (exposure portion) A1 and the unpolymerized region (light-shielding portion) A2, so that, for example, a liquid crystal compound and two colors are displayed. When the pigments are all rod-shaped, the average orientation direction is generally a direction perpendicular to the boundary S.

Further, if, for example, as described above, the aforementioned first chemical is used The compound and the second compound having a polymerization completion time longer than the first compound when polymerized under the same conditions can be preferably used as the polymerizable composition of the present invention as the polymerizable composition, and light is used. When the polymerizable compound is further examined as the first and second compounds, in the polymerization region (exposure portion) A1, the first compound having a short polymerization completion time is preferentially photopolymerized, and the first compound is preferentially consumed. When the first compound is preferentially consumed as described above, the concentration of the compound in the film is more likely to be deviated between the polymerization region (exposure portion) A1 and the unpolymerized region (light-shielding portion) A2, which is more efficient because of this. The ground causes the diffusion (flow) of the compound. Therefore, when the polymerizable composition contains the first compound and the second compound having different polymerization completion times, the concentration gradient of the components in the film can be more efficiently generated between the unpolymerized region A2 and the polymerization region A1, which is more efficient. The compound flows between the unpolymerized region A2 and the polymerization region A1. Based on these viewpoints, the present inventors presumed that in the present invention, when the polymerizable composition contains the first compound and the second compound having different polymerization completion times, the shearing may occur more efficiently due to the flow of the compound. The force can align the compound exhibiting liquid crystal properties and the dichroic dye present in the polymerization region in the film more efficiently.

Here, it is assumed that light is fixed in the position shown in FIG. When the cover 14 is used to fix the position of the boundary S, when the boundary S is photopolymerized, the viscosity of the inside of the polymerization region A1 is increased, so that the diffusion of the compound is suppressed, and the alignment region is limited to the region near the boundary. (In addition, the alignment region is formed only in a region of about several tens to several hundreds of μm in the vertical direction from the boundary of the light irradiation region). 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 S of the polymerization region (exposure portion) A1 and the unpolymerized region (light shielding portion) A2 is oriented toward The polymerization region A2 moves (in addition, in the present embodiment, the boundary S is moved toward the unpolymerized region A2 by continuously moving the photomask 14). Therefore, after the polymerization of the polymerizable compound is started from a partial region of the film 13 (see FIG. 2), the boundary S of the polymerization region is continuously moved toward the unpolymerized region A2 (see FIGS. 2 to 4), and is moved at the boundary S. The initial (new position) causes diffusion of the compound present in the film, which may continuously cause photopolymerization and alignment due to diffusion. In this case, the rate at which the liquid crystallinity-displaying compound and the dichroic dye are aligned (the shear stress generated by the movement of the compound such as the monomer and/or the polymer is sufficiently applied to form the alignment) The above-described liquid crystal compound and the speed of the dichroic dye are such that the boundary S is continuously moved, whereby the diffusion-induced alignment may be continuously generated. Therefore, in the present invention, the liquid crystallinity of the polymerization region A1 is continuously moved toward the unpolymerized region at a rate at which the compound exhibiting liquid crystallinity and the dichroic dye are aligned, whereby the liquid crystal property can be improved. The alignment region of the compound and the aforementioned dichroic dye continuously increases. Further, when the compound exhibiting liquid crystallinity is aligned with the dichroic dye by the shear stress, when the alignment of the compound exhibiting liquid crystallinity starts, the self-organization ability of the liquid crystal also increases the alignment, so that the alignment can be increased. Form the alignment efficiently. Therefore, the present inventors presumed that in the present invention, since the alignment region can be continuously increased, the polarizing film which forms the alignment region in a large area can be efficiently produced. Further, in the present invention, as described above, by moving the boundary S of the polymerization region (exposure portion) A1 and the unpolymerized region (light shielding portion) A2 toward the unpolymerized region A2, the region in the vicinity of the boundary S where the movement is performed is sequentially continuous. A method of causing a diffusion of a substance to continuously increase an alignment region, so that it can be efficiently used even when a substrate (for example, a substrate not subjected to rubbing treatment) which is processed before the alignment control force is applied A polarizing film is produced. Therefore, not only the problem of dust or static electricity generated by the rubbing treatment, the adhesion of dust or the incorporation into the polarizing film, but also the pre-treatment of the substrate or the microcell for the purpose of having the alignment control force can be effectively avoided. It can be said that it is an effective method in terms of workability. In the example shown in FIGS. 1 to 4, the photopolymerizable compound is used as the polymerizable compound as an example, and the principle of forming the alignment is described. However, the present invention utilizes a polymerization region (exposure portion). The material diffusion phenomenon occurs when the boundary S between the A1 and the unpolymerized region (light-shielding portion) A2 moves toward the unpolymerized region A2, and the alignment is formed in the film to increase the alignment region. Therefore, the polymerizable compound is not limited to light. The polymerizable compound may be a compound other than the photopolymerizable compound (for example, a thermally polymerizable compound).

Moreover, in the method for producing a polarizing film of the present invention, After the polymerization, the compound which moves from the unpolymerized region to the polymerization region in the film is used to align the liquid crystal compound with the dichroic dye, so that the direction of movement of the compound (the direction substantially perpendicular to the boundary of the region) can be controlled. ) The direction of the alignment. Therefore, for example, when polymerization is carried out by photopolymerization, the alignment in various directions can be controlled depending on the shape of the mask.

Here, regarding the control of the alignment directions, refer to FIG. 5. A preferred embodiment of the invention shown is briefly described. Further, Fig. 5(a) schematically shows the relationship between the photomask 14 and the substrate 12 before the photopolymerization is started when viewed from the light source side (the optical axis direction of the irradiated light) (before the boundary S of the light irradiation region is moved) FIG. 5(b) is a view schematically showing the relationship between the photopolymer 14 and the substrate 12 after the photopolymerization is started (the state in which the boundary S of the light irradiation region moves in the direction of the arrow A) when viewed from the light source side. A rough top view. In Fig. 5, the boundary S of the polymerization region A1 is perpendicular to the two sides of the substrate 12, and when the boundary S is moved as shown schematically in Figs. 5(a) to (b), it is generated substantially perpendicular to the boundary S. The compound flows, and the direction of alignment is controlled to be substantially perpendicular to the boundary S (the arrow P in the figure is used to conceptually indicate that the direction is perpendicular to the boundary S, and the speculation is substantially the same direction as the arrow P and/or The 180° opposite side direction produces a compound flow). On the other hand, when the edge of the reticle 14 is inclined such that the boundary S moves the boundary S so as to be in contact with the two sides of the substrate 12 at an angle other than the vertical direction, it is substantially perpendicular to the inclined boundary S, or the movement of the boundary S When the velocity is fast, the alignment direction controls the direction of the vector sum of the vector in the direction of movement of the boundary S and the vector in the direction perpendicular to the boundary S. Moreover, the alignment direction when the edge of the reticle 14 is tilted in this way The control is described in more detail with reference to a preferred embodiment of the present invention shown in FIG. 6. Fig. 6 is a schematic plan view schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from a light source (the direction of the optical axis of the irradiated light). The photomask 14 shown in Fig. 6 is formed such that its edge is inclined such that the boundary S is disposed in contact with the two sides of the substrate 12 at an angle other than the vertical. Therefore, when the photopolymerization is carried out while continuously moving the boundary S in the direction of the arrow A in the drawing (for example, when the photomask 14 is continuously moved while moving in the direction of the arrow A), the compound in the film is basically caused. Diffusion (monomer and/or polymer) produces a compound flow in a direction substantially perpendicular to the boundary S of the reticle (the arrow P in the figure is used to conceptually indicate the direction perpendicular to the boundary S) And it is assumed that the flow of the compound is generated in substantially the same direction as the arrow P and/or the direction opposite to the 180° side thereof). Therefore, when the boundary S is continuously moved while moving in the direction of the arrow A in the figure, the alignment direction is controlled to be substantially perpendicular to the oblique boundary S (substantially the same direction as the arrow P). Further, as described above, when the moving speed of the boundary S is fast, the alignment direction is controlled as a vector of the moving direction of the boundary S (the direction indicated by the arrow A) and a vector perpendicular to the boundary S (indicated by the arrow P). Direction) The direction of the vector sum.

Therefore, the boundary S is made as shown schematically in FIGS. 5(a) to (b). When moving, when the edge of the reticle 14 is tilted to move the boundary S as schematically shown in Fig. 6, the alignment direction is controlled in different directions. Therefore, when photopolymerization is employed, it is also possible to obtain films having different alignment directions depending on the shape of the edge of the photomask 14.

Thus, the inventors have speculated that the present invention can When the boundary of the bonding region is moved and the alignment is formed by the diffusion phenomenon of the substance, the alignment region is increased, so that the compound exhibiting the liquid crystal property and the dichroic dye can be efficiently aligned in a desired direction to form an alignment region over a large area. Polarized film.

According to the present invention, it is possible to provide a method for producing a polarizing film which can efficiently produce a polarizing film which forms a alignment region of a liquid crystal compound and a dichroic dye in a large area.

11‧‧‧Light source

12‧‧‧Substrate

13‧‧‧film made of polymerizable composition

14‧‧‧Photomask

14A‧‧‧ Opening

X‧‧‧ Short side length of opening 14A

Y‧‧‧Long side length of opening 14A

S‧‧‧Boundary of the aggregated area

A‧‧‧ conceptually showing the arrow of the direction of movement of the boundary of the aggregated area

P‧‧‧ conceptual display of arrows perpendicular to the boundary S of the aggregated area

L‧‧‧Light from the light source

A1‧‧‧A region where light is irradiated and polymerized (polymerized area: exposure part)

A2‧‧‧Unpolymerized area where light is not irradiated (unpolymerized area: shading part)

A3‧‧‧ forming an area of alignment

Fig. 1 is a schematic longitudinal cross-sectional view schematically showing a state before photopolymerization of a film formed of a polymerizable composition.

Fig. 2 is a schematic longitudinal cross-sectional view schematically showing a state in which light from a light source is irradiated from a portion of a film to start polymerization.

Fig. 3 is a schematic longitudinal cross-sectional view schematically showing a state in which the boundary of the polymerization region in Fig. 2 is moved toward the unpolymerized region.

Fig. 4 is a schematic longitudinal cross-sectional view schematically showing a state in which the boundary of the polymerization region in Fig. 3 is moved toward the unpolymerized region.

Fig. 5(a) is a schematic plan view showing the relationship between the photomask and the substrate before the photopolymerization is started (the state before the boundary of the light irradiation region is moved) when viewed from the light source side, and Fig. 5(b) is schematically shown. Photomask when viewed from the light source side A schematic plan view of the relationship between the start of photopolymerization of the substrate and the state in which the boundary of the light irradiation region moves.

Fig. 6 is a schematic plan view showing the relationship between the photomask formed by tilting the edge and the photopolymerization of the substrate when viewed from the light source side.

Fig. 7 is a schematic plan view showing the relationship between the photomask having a plurality of substantially rectangular openings and the photopolymerization of the substrate when viewed from the light source side.

Fig. 8 is a schematic plan view showing the relationship between the photomask having a plurality of substantially rectangular openings and the photopolymerization of the substrate when viewed from the light source side.

Fig. 9 is a schematic plan view showing the relationship between a mask having a rectangular opening and a substrate when viewed from the light source side.

Fig. 10 is a graph showing the absorption spectrum of the polarizing film obtained in Example 1.

Fig. 11 is an enlarged view showing the relationship between the absorbances of 0 to 0.2 of the absorption spectrum of the polarizing film obtained in Example 1 shown in Fig. 10.

Fig. 12 is a graph showing the absorption spectrum of DR1 of a dichroic dye.

Figure 13 is a graph showing the absorption spectrum of the polarizing film obtained in Example 2.

Figure 14 is a graph showing the absorption spectrum of TR5 of a dichroic dye.

Fig. 15 is a graph showing the absorption spectrum of the polarizing film obtained in Example 3.

Hereinafter, the present invention will be described in detail with reference to preferred embodiments.

In the method for producing a polarizing film of the present invention, a film comprising at least one of a polymerizable compound exhibiting liquid crystallinity before and/or after polymerization and a polymerizable composition of at least one of a dichroic dye is used. And

After the polymerization of the polymerizable composition is started in a portion of the film, the boundary between the compound and the dichroic dye present in the film is aligned so that the boundary of the region faces the unpolymerized region. A method of continuously moving to obtain a polarizing film.

The polymerizable composition of the present invention contains at least one of a polymerizable compound which exhibits liquid crystallinity before and/or after polymerization. In the present invention, as described above, since the aligning agent is formed by a shear stress caused by diffusion (movement) of the compound in the film generated by the polymerization, the polymerizable compound can be used only when one compound is used. The area forms an orientation. Therefore, the polymerizable composition of the present invention may contain at least one of the above-mentioned polymerizable compounds.

The polymerizable compound preferably has one or more (preferably 1 to 6) polymerizable functional groups. When the number of the polymerizable functional groups is less than the lower limit, the polymerization cannot be efficiently carried out, so that it is difficult to effectively cause the compound derived from the change in the concentration of the monomer (including the polymerizable compound) in the film to diffuse, and it is difficult to The compound is diffused to form an alignment, and a polarizing film is obtained. Further, when the number of the polymerizable functional groups exceeds the above upper limit, the polymerization proceeds more rapidly than the diffusion of the compound, so that it tends to be difficult to form an alignment with diffusion.

Further, there is no particular limitation as such a polymerizable functional group. The system can be suitably used, for example, as a vinyl group, an allyl group, a vinyl ether group, an acrylic group, a methacryl group, an oxetanyl group, an epoxy group, a cinnamyl group, a chalcone ( Chalcone), coumarin group, etc., among which vinyl ether group, acrylic group, methacryl group, oxetanyl group, epoxy group, cassia are preferred from the viewpoints of easy synthesis and handling of the compound. The mercapto group and the chalcone group are more preferably an acryl group, a methacryl group, an oxetanyl group or an epoxy group.

Furthermore, in the present invention, based on self-grouping due to liquid crystal From the viewpoint of the weaving ability to increase the orientation, the polymerizable compound must be a compound which exhibits liquid crystallinity before and/or after polymerization (at least, a component derived from a polymerizable compound present in the film after polymerization (polymerizable compound) The polymer itself obtained by polymerizing a polymerizable compound must exhibit liquid crystallinity). In addition, the "compound exhibiting liquid crystallinity after polymerization" means a compound (polymer) obtained by polymerizing the above polymerizable compound as a compound exhibiting liquid crystallinity. In addition, the "polymer (polymer) obtained by polymerizing the polymerizable compound", for example, in addition to the homopolymer of the polymerizable compound, the polymerizable composition also contains a plurality of polymerizable compounds, or the foregoing When the polymerizable composition contains a polymerizable compound other than the polymerizable compound, a copolymer containing a plurality of polymerizable compounds or a polymerizable compound other than the polymerizable compound exhibits polymerizability. a copolymer of a compound. Therefore, the "compound exhibiting liquid crystallinity after polymerization" means a polymerization obtained by polymerizing a plurality of monomers containing the polymerizable compound alone or in combination with the polymerizable compound. Any of the compounds and exhibits liquid crystallinity. The "compound exhibiting liquid crystallinity" herein is preferably a compound which exhibits liquid crystallinity in a specific temperature range (so-called thermotropic liquid crystal compound). Further, when the thermotropic liquid crystal compound confirms the behavior of the liquid crystal phase when the temperature is raised and lowered, the liquid crystallinity exhibits an enantiotropic liquid crystal compound in both the temperature rising process and the temperature decreasing process, and may be only A single-denatured liquid crystal compound exhibiting liquid crystallinity during one of a temperature rising process or a cooling process. In the present invention, at least one of the polymerizable compound before polymerization and the compound (polymer) obtained by polymerizing the polymerizable compound is a compound exhibiting liquid crystallinity (a compound having liquid crystallinity), and is polymerized. When the diffusion of the compound (the monomer containing the polymerizable compound and/or the polymer) in the film is initiated, a shear stress (shear stress) can be applied to the compound exhibiting liquid crystallinity in the film and the foregoing two By using a coloring pigment, when the compound having the liquid crystal property starts to be aligned, the self-organization ability of the liquid crystal can also increase the alignment, so that the compound exhibiting liquid crystallinity and the dichroic dye can be efficiently formed. Orientation.

Further, the polymerizable compound is preferably a compound 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 each independently represent a hydrogen atom; a halogen atom (more preferably F, Cl, Br); CN; NO ₂ ; OCF ₃ ; a linear or branched alkyl group having 1 to 18 carbon atoms; The alkyl group may also be one or a plurality of carbon atoms of the aforementioned alkyl group substituted with a discontinuously bonded oxygen atom, -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; L ³ -S ¹ -F ¹

In the formula: F ¹ represents any of the groups represented by the following formulas (F-1) to (F-20):

(wherein R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and S ¹ is a single bond or a linear or branched alkyl group having 1 to 18 carbon atoms (again, the aforementioned alkylene group may also be One or more carbons of the alkylene group are substituted with a discontinuously bonded oxygen atom, -COO-, -OCO-, -OCOO-, -CONR ³ -, -NR ³ CO-, -OCO-NR ³ -, or -NR ³ COO- (wherein R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and L ³ represents 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- (wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)}.

L ^1, 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- (wherein R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms), and M ¹ and M ³ each independently represent 1,4-extension Phenyl, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl, 1,3 - Dioxane-2,6-diyl, 1,3,4-benzenetriyl, 1,3,5-benzenetriyl, 1,3,4,5-phenyltetrayl, M ² represents 1,4 - phenyl, 1,4-cyclohexylene, pyridine-2,5-diyl, pyrimidine-2,5-diyl, naphthalene-2,6-diyl, naphthalene-1,4-diyl or 1 , 3-dioxane-2,6-diyl, the hydrogen atom selected as the group of M ¹ , M ² and M ³ may also be independently alkyl, halogenated alkyl, alkoxy, halo, The cyano group and the nitro group are substituted, and p and r each independently represent 1, 2 or 3, and q represents 0, 1 or 2. When Z ¹ and/or Z ² are plural, they may be the same or different.

In addition, the polymerizable compound may be liquid crystallinity before and/or after polymerization, and may be other than the compound represented by the above formula (1), or may be displayed before and/or after polymerization. Anyone with liquid crystal properties can be used as appropriate. As the polymerizable compound which can be used other than the compound represented by the above formula (1), for example, a structure other than the structure represented by the formula (1) and having a vinyl group, an allyl group or a vinyl ether group can be suitably used. a compound having a functional group such as an acrylic group, a methacryl group, an oxetanyl group, an epoxy group, a cinnamyl group, a chalcone group or a coumarin group. A component which is a component of the polymerizable compound (for example, various thermopolymerizable compounds or photopolymerizable compounds which exhibit liquid crystallinity before and/or after polymerization) is commercially available, and these may be suitably used.

Further, the polymerizable property contained in the polymerizable composition The compound is more easily controlled based on the control of the boundary position between the polymerization region and the unpolymerized region during polymerization, and a polarizing film which forms a desired alignment of the liquid crystal-displaying compound and the dichroic dye can be formed more efficiently, and the operation can be further improved. In terms of efficiency, a photopolymerizable compound is preferably used. In the present invention, the polymerizable compound is preferably a photopolymerizable compound, and the polymerization of the polymerizable composition is carried out by photopolymerization. Further, the "photopolymerizable compound" herein may be a photoinitiator such as a vinyl group, an allyl group, a vinyl ether group, an acrylic group, a methacryl group, an oxetanyl group or an epoxy group. There is a compound which reacts with a functional group, and a compound which is a light-free initiator and which can react with a functional group by light. As an example of the photopolymerizable compound in which the functional group of the photoinitiator is still reactive, a compound having a functional group capable of photodimerization such as cinnamyl or chalcone group or coumarin group can be exemplified. .

Further, the polymerizable compound is more preferably a compound represented by the above formula (1), from the viewpoint of a monomer which can be polymerized more efficiently, or a polarizing film can be formed more efficiently. In the formula, Z ¹ and Z ² are each a group represented by -L ³ -S ¹ -F ¹ (again, Z ¹ and Z ² may be the same or different, and are preferably the same base from the viewpoint of easy synthesis) , F ¹ is an acrylic group or a methacryl group, S ¹ is a single bond or a linear alkyl group having 1 to 12 carbon atoms, and L ³ is a single bond, an ether group (-O-), an ester group (-COO-) Any of -OCO-) and a carbonate group (-OCOO-) (more preferably an ether group), p is 1, M ¹ is a 1,4-phenylene group, and L ¹ is a single bond and -COO Or a compound represented by the above formula (1), wherein any one of the compounds (more preferably a single bond), q is 0, M ³ is a 1,4-phenylene group, and r is 1 Z ¹ and Z ² are each a group represented by -L ³ -S ¹ -F ¹ (again, Z ¹ and Z ² may be the same or different, and are preferably the same base from the viewpoint of easy synthesis), and F ¹ is an acrylic group or a methacrylic group, S ¹ is a single bond or a straight-chain alkylene group having a carbon number 1 to 12 of, L ³ is a single bond, an ether group, an ester group A carbonate of any one group (more preferably an ether group), p is ^1, M 1 is 1,4-phenylene, L ¹ is -COO-, M ² is 1,4-phenylene, L ² is -OCO-, q is 1, M ³ is 1,4-phenylene, and compound C12 wherein r is 1, the compound represented by the above formula (1), wherein Z ¹ and Z ² are both a group represented by -L ³ -S ¹ -F ¹ (again, Z ¹ and Z ² may be the same or different, preferably the same group based on the viewpoint of easy synthesis), and F ¹ is an acrylic group or a methacrylic acid. a group, S ¹ is a group represented by the formula: (CH ₂ CH ₂ O)z (z is 2 or 3), L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ a compound C13 which is a compound of the above formula (1), which is a single bond or an ester group (more preferably a single bond), q is 0, M ³ is a 1,4-phenylene group, and r is 1. a compound wherein Z ¹ is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acryl group or a methacryl group, S ¹ is a single bond, L ³ is a single bond, p is 1, and M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ is 1,4-phenylene, Z ² is hydrogen atom, halogen atom, cyano group, nitro group, carbon number 1~12 One selected from the group consisting of an alkyl group and an alkoxy group having 1 to 12 carbon atoms (more preferably a cyano group), and a combination of r of 1 C14, in the compound represented by the general formula (1) wherein Z ¹ is in the -L ³ -S ¹ -F ¹ represents, F. ¹ is an acrylic group or a methacrylic group, S ¹ is a number from 1 to 12 carbon The linear alkyl group, L ³ is an ether group, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ is 1,4-phenylene, Z ^{2 is one 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 (more preferably a cyano group), and r is 1 The compound C15 is a compound represented by the above formula (1), wherein Z ¹ is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acryl group or a methacryl group, and S ¹ is of the formula: (CH ₂ CH ₂ O)z (z is 2 or 3) represents a group, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, and Z ^{2 is one selected} from the group consisting of 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. (Compound is more preferably cyano), and compound C16 wherein r is 1, a compound represented by the above formula (1), wherein Z ¹ is represented by -L ³ -S ¹ -F ¹ and F ¹ is an acryl group Or a methacrylic group, S ¹ is a linear alkyl group having 1 to 12 carbon atoms L ³ is an ether group, p is 1, M ¹ is 1,4-phenylene, L ¹ is -COO-, q is 0, M ³ is 1,4-phenylene, and Z ² is a hydrogen atom. And a compound C17 in which one of halogen atoms, 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 is selected (more preferably, a cyano group), and r is 1.

In addition, the preferred compounds C11~17 are listed as 4,4'-bis(8-(methyl)propenyloxy-3,6-dioxaoctyl-1-oxy)biphenyl, 4,4'-bis(9-(methyl)propene醯oxy)decyloxybiphenyl, 4,4'-bis(6-(methyl)propenyloxy)hexyloxybiphenyl, 1,4-bis(6-(methyl)propenyloxy Hexyloxy)methylhydroquinone, 4-(6-(methyl)propenyloxyhexyloxy)-4'-cyanobiphenyl, 4-(9-(methyl)propenyloxyoxyl -4'-cyanobiphenyl, 4-(5-(methyl)propenyloxy-3-oxapentyl-1-oxy)-4'-cyano linkage Benzene, 4-(8-(methyl)propenyloxy-3,6-dioxaoctyl-1-oxy)-4'-cyanobiphenyl, 4-cyanophenyl-4-( 2-propenyloxyethoxy)benzoate.

Further, in the invention, the polymerizable composition preferably contains There is a first compound, a second compound having a polymerization completion time longer than the first compound under the same conditions, and at least one of the first and second compounds contains at least one of the polymerizable compounds. According to the above, the polymerizable composition preferably contains at least one of the polymerizable compounds as the first and/or second compound, and the first compound and the second compound having different polymerization completion times are used in combination. Further, the first and second compounds may be formed of at least one of the above polymerizable compounds, or both of them may be composed of the above polymerizable compound.

Regarding the first compound and the second compound, the matter of the long and short polymerization completion time is relatively required between the first compound and the second compound, and the phrase "polymerization under the same conditions" means an appropriate selection. The conditions for polymerizing the first compound (temperature conditions during thermal polymerization, light irradiation conditions during photopolymerization, etc.), and polymerization under the same conditions as those selected. In addition, when the polymerization completion time is, for example, polymerization of a polymerizable composition by photopolymerization, it is also possible to measure light by irradiating light (for example, light of 366 nm) while maintaining a constant temperature condition (for example, 85 ° C). The first compound and the second compound are used, and they are separately introduced into a cell to be separately polymerized until the time at which each compound is completed as the time until formation of the film. Accordingly, in the present invention, polymerization can be started in the cell, and it is judged that the polymerization is completed when the film is formed. For example, two sheets of a soda glass substrate having a size of 25 mm square and a thickness of 1.1 mm are used, and a 100 μm thick polyimide tape is used as a separator (two places on the left and right sides) to be bonded to each other to prepare a glass unit having a cell thickness of 100 μm (again, The unit may be formed such that the diaphragm is formed at two sides (left and right) of the parallel longitudinal direction of the glass substrate so that the area where the planar portions of the upper and lower substrates overlap is 15 mm in the longitudinal direction and 25 mm in the lateral direction (parallel to the longitudinal direction of the diaphragm). When the film is overlapped by 15 mm, the portions of the glass substrate on which the separator is not formed are respectively formed as openings, and the internal dimensions of the cells may be set to 15 mm in the longitudinal direction, 10 mm in the lateral direction, and 100 μm in the thickness, for the compound for measuring the polymerization completion time. Preparing the mixture by mixing the photopolymerization initiator content in a quantitative amount (for example, 1 mol%), and then injecting the mixture into the unit by capillary action while melting the mixture at a temperature of 100 ° C in the glass unit. Until it was filled, and after cooling to 85 ° C at a rate of 0.5 ° C / min, it was kept at 85 ° C for 3 minutes to form a film of a polymerizable composition (film size: length 15 mm, width 10 mm, thickness 100 μm) At an intensity of 1.9mW / cm ² of irradiation on the membrane filter to remove the light from the 366nm high pressure mercury lamp photopolymerization removed from the glass per certain unit time (e.g., 5 seconds, 15 seconds, 30 seconds and 60 seconds The film was irradiated with light, and the surface was washed with chloroform, and it was visually confirmed whether or not a film was formed, thereby measuring the time until the completion of the polymerization. Further, in the present invention, the first compound and the second compound used are compared, and a compound having a shorter polymerization completion time is used as the first compound, and a compound having a longer polymerization completion time (also included in the polymerization condition of the first compound) is used. A compound (non-polymerizable compound) having an infinite polymerization completion time is not used as the second compound.

By utilizing the first compound and the second compound, When the polymerization is started, the first compound is preferentially utilized for the polymerization, and in particular, the concentration of the first compound is biased between the polymerization region and the unpolymerized region of the membrane, and the concentration gradient of the compound can be formed more efficiently in the membrane, and the concentration can be eliminated. The direction of the concentration gradient produces diffusion of the substance more efficiently, and the alignment of the compound exhibiting liquid crystallinity and the dichroic dye can be formed more efficiently.

As such first compound and second compound, preferably full The first compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is one or more larger than the number (or 0) of the polymerizable functional groups of the second compound. Further, in the range satisfying the preferable conditions, the first compound is preferably a compound having one or more (more preferably two or more, more preferably two to four) polymerizable functional groups, and the foregoing The di compound is a compound having 0 or 1 (more preferably 1) polymerizable functional groups. By using the compounds having different numbers of the polymerizable functional groups as the first compound and the second compound, respectively, the difference in polymerization rate between the compounds can be made larger, and the polymerization can be more efficiently performed near the boundary of the polymerization region. The concentration of the resulting compound is biased to cause diffusion of the compound more efficiently and to form the alignment more efficiently near the boundaries of the polymerization zone. Further, when the number of the polymerizable functional groups of the first compound does not reach the above lower limit, polymerization cannot be carried out, or it is difficult to polymerize the first compound at a sufficiently fast rate, and it is difficult to effectively expand the alignment region. Further, when the number of the polymerizable functional groups of the first compound exceeds the above upper limit, since the polymerization is more rapidly spread than the compound, it tends to be difficult to form an alignment with diffusion.

Accordingly, the polymerizable composition of the present invention contains the first and the first In the case of the di-compound, any of the first and second compounds may be formed of a compound other than the polymerizable compound which exhibits liquid crystallinity before and/or after the polymerization. Other compounds other than the polymerizable compound may, for example, have a vinyl group, an allyl group, a vinyl ether group, an acrylic group, a methacryl group, an oxetanyl group, an epoxy group, a cinnamyl group, a chalcone group. a compound (including a thermopolymerizable compound or a photopolymerizable compound, etc.) having a functional group such as a coumarin group. Various thermopolymerizable compounds or photopolymerizable compounds which can be used as a compound other than the polymerizable compound which exhibits liquid crystallinity before and/or after the polymerization are also commercially available, and these can be suitably used.

Can be used as liquid crystallinity before and/or after polymerization Examples of the compound having a vinyl group (vinyl compound) other than the polymerizable compound are styrene, α-methylstyrene, vinyl acetate, N-vinylpyrrolidone, and N-vinyl. Caprolactam and the like.

Can be used as the display liquid crystal before and/or after the polymerization Examples of the compound having a vinyl ether group (vinyl ether compound) other than the compound other than the polymerizable compound are n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether. , isobutyl vinyl ether, 2-ethylhexyl vinyl ether, cyclohexyl vinyl ether, 4-hydroxybutyl vinyl ether, cyclohexane dimethanol monovinyl ether, tricyclodecane vinyl ether, Benzyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol Vinyl ether, dicyclopentadienyl vinyl ether, and the like.

Can be used as the display liquid crystal before and/or after the polymerization The foregoing compounds other than the polymerizable compound have an acrylic group The compound and the compound having a methacryl group ((meth)acrylic compound), and the monofunctional monomer are exemplified by methyl (meth)acrylate, ethyl (meth)acrylate, and butyl (meth)acrylate. , (meth)acrylic acid alkyl ester such as isobutyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; 2-hydroxyethyl (meth)acrylate; 2-hydroxypropyl (meth)acrylate Esters and hydroxyalkyl (meth)acrylates such as 2-hydroxy-3-phenylpropyl acrylate; cyclohexyl (meth)acrylate, isobornyl (meth)acrylate, dicyclopentene (meth)acrylate a saturated or unsaturated alicyclic (meth) acrylate such as ester, dicyclopentenyloxyethyl (meth) acrylate; substituted (meth) acrylate such as benzyl (meth) acrylate (meth)acrylic acid alkoxylate such as ester, 2-methoxyethyl (meth)acrylate and 2-ethoxyethyl (meth)acrylate; unsaturated oxime (meth) acryloyl morpholine Amine compound; monohydroxyethyl phthalate (meth) acrylate and monohydroxyethyl succinate (meth) acrylate and other carboxyl group-containing (meth) acrylate; (meth) hexahydro acrylate A quinone imine (meth) acrylate such as phthalic acid imine ethyl ester or (am) succinimide ethyl (meth)acrylate.

Further, as the (meth)acrylic compound, The polyfunctional monomer is exemplified by, for example, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol II. (meth) acrylate, tricyclodecane dimethanol di(meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, ginseng ((meth) propylene醯 oxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, di-trimethylolpropane tetra (meth) acrylate, and the like.

Can be used as the display liquid crystal before and/or after the polymerization Examples of the compound having an epoxy group other than the compound other than the polymerizable compound include ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, and 1,6-hexanediol diglycidyl. Ether, cyclohexanedimethanol diglycidyl ether, diethylene glycol diglycidyl ether, triethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, dipropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, Neopentyl glycol diglycidyl ether, trimethylolpropane diglycidyl ether, trimethylolpropane triglycidyl ether, bisphenol A diglycidyl ether, hydrogenated bisphenol A diglycidyl ether, 3', 4 '-Epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4-(2-methyloxiranethyl)-1-methylcyclohexane Alkane, 1,2-epoxy-4-vinylcyclohexane, vinylcyclohexene monooxide, 1,2:8,9-dicyclooxylimene, and the like.

Can be used as the display liquid crystal before and/or after the polymerization The compound having an oxetanyl group as the other compound other than the polymerizable compound may be exemplified by 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxybutane, and Toluene dioxetane, 3-ethyl-3(((3-ethyloxetan-3-yl)methoxy)methyl)oxetane, 1,4-bis(( (3-ethyl-3-oxetanyl)methoxy)methyl)benzene, 3-ethyl-3-(phenoxymethyl)oxetane, bis(3-ethyl- 3-oxetanylmethyl)ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and the like.

And, when the first compound and the second compound are contained, The photopolymerizable compound is preferably used because it is easy to control the boundary position between the polymerization region and the unpolymerized region during polymerization, to form a desired alignment more efficiently, to form a film having polarizing properties, and to improve work efficiency. also In the case where the first compound and the second compound are contained in the present invention, it is preferred that at least one or both of the first compound and the second compound are photopolymerizable compounds, and the polymerizable composition is carried out by photopolymerization. For the polymerization of the particles, it is preferred to use a photopolymerizable compound for both the first polymerizable compound and the second compound. Further, the photopolymerizable compound may be, for example, a vinyl group, an allyl group, a vinyl ether group, an acryl group, a methacryl group, an oxetanyl group or an epoxy group, which is present by a photoinitiator. a functional group-reactive compound, which may also be a compound which is a light-free initiator and which can react with a functional group by light (for example, has a photodimerization reaction such as a cinnabarinyl group or a chalcone group or a coumarin group). a compound of a functional group, etc.).

Further, in the polymerizable composition containing the first compound and the second compound, the first compound is preferably a compound represented by the following compound (C11 to C13), a compound represented by the following formula (2), and a formula (3) At least one compound selected from the group consisting of:

(wherein R ⁵ is any one of hydrogen and methyl, and x is 2 or 3),

(wherein R ⁵ is any one of hydrogen and methyl, and y is an integer of 2 to 12).

As described above, the first compound may be one of the above-mentioned polymerizable compounds, or a polymerizable compound other than the above may be preferably used. In addition, when the second compound does not contain the polymerizable compound, the first compound contained in the polymerizable composition must contain the polymerizable compound.

Moreover, the first compound is preferably ethylene glycol di(meth) propylene. Acid ester, 1,6-hexanediol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, 4,4'-double (8 -(Meth)propenyloxy-3,6-dioxaoctyl-1-oxy)biphenyl, 4,4'-bis(9-(methyl)acryloxy)oxyl linkage Benzene, 4,4'-bis(6-(methyl)propenyloxy)hexyloxybiphenyl, 1,4-bis(6-(methyl)propenyloxyhexyloxy)methylhydroquinone .

Further, as the aforementioned second compound, the foregoing polymerization may be One of the compounds may be other than the above polymerizable compound. The second compound is preferably selected from the group consisting of the aforementioned compounds C14 to C17. At least one compound of the group. Further, the second compound contained in the polymerizable composition is preferably a polymerizable compound from the viewpoint of forming a polarizing film more efficiently, but the first compound is not necessarily a polymerizable compound. The aforementioned polymerizable compound.

The second compound is preferably 4-(6-(methyl)propene oxime Hexyloxy)-4'-cyanobiphenyl, 4-(9-(methyl)acryloxycarbonyloxy)-4'-cyanobiphenyl, 4-(5-(methyl)propene醯oxy-3-oxapentyl-1-oxy)-4'-cyanobiphenyl, 4-(8-(methyl)propenyloxy-3,6-dioxaoctyl-1 -oxy)-4'-cyanobiphenyl, 4-cyanophenyl-4-(2-propenyloxyethoxy) benzoate.

Furthermore, as for the first compound and the second compound The polymerizable composition is preferably a compound represented by the above formula (2) from the above-mentioned compounds C11 to C13, from the viewpoints of ease of reaction control, ease of obtaining monomers, and ease of handling of a monomer. And at least one compound selected from the group consisting of the compounds represented by the above formula (3), and the second compound is preferably at least one compound selected from the group consisting of the compounds C14 to C17.

Further, the polymerizable composition contains the first and the aforementioned first In the case of the di-compound, the content ratio of the first compound to the second compound is not particularly limited, but the molar ratio of the first compound to the second compound ([first compound]: [second compound]) is preferred. It is 0.1:99.9~99.9:0.1, more preferably 2:98~98:2, and even better 4:96~96:4. Further, the molar ratio of the first compound to the second compound ([first compound]: [second compound]) depends on the type of compound to be combined Preferably, it is preferably 5:95 to 95:5, more preferably 10:90 to 80:20. When the content ratio of the first compound is less than the lower limit, the diffusion rate is slow, so that the rate of movement of the boundary tends to be slow. On the other hand, when the content exceeds the upper limit, the polymerization proceeds more rapidly than the diffusion of the compound. It is difficult to form a tendency to align with diffusion.

Further, the polymerizable composition of the present invention contains before polymerization and/or Or at least one of a liquid crystalline polymerizable compound and at least one of a dichroic dye after polymerization. In the present invention, the dichroic dye is not particularly limited as long as it has a property that the absorbance in the long-axis direction of the molecule is different from the absorbance in the short-axis direction, and a conventional dichroic dye can be suitably used. . Moreover, such a dichroic dye may also be, for example, a so-called dye or pigment. Further, such a dichroic dye may be used alone or in combination of two or more kinds. Therefore, as the dichroic dye, for example, a plurality of the dyes may be used, and a plurality of the pigments may be used, or the dye and the pigment may be used in combination.

In addition, the aforementioned dichroic pigment usually has a great absorption. Wavelength (λmax). The maximum absorption wavelength of the dichroic dye is not particularly limited and may be appropriately selected depending on the use. For example, when a polarizing film having absorption in a visible light region is produced, the dichroic dye is preferably selected from a dichroic dye having a maximum absorption wavelength (λmax) in a visible light region, and is also used to produce a polarized light having absorption in an infrared region. In the case of a film, it is preferred to use a dichroic dye having a maximum absorption wavelength (λmax) in the infrared region. Further, the dichroic dye may be liquid crystal.

These dichroic dyes are not particularly limited and are listed, for example, as Acridine dye, oxazine dye, oxazolone dye, cyanine dye, naphthalene dye, azo dye, anthraquinone dye, benzotriazole dye, benzophenone dye, pyrazole a porphyrin dye, a diphenyl polyene dye, a binaphthyl polyene dye, a diphenylene dye, a benzothiazole dye, a benzimidazole dye, a coumarin dye, a nitro group A phenylamine dye, a merocyanine dye, a thiophene dye, or the like. In addition, the dichroic dye can be suitably used by a commercially available person, and for example, DR1: trade name "Disperse Red 1" manufactured by Sigma Aldrich Co., Ltd., etc., can be used as appropriate.

In addition, the dichroic pigment which can be used in the present invention An example of the pigment number numbered in the Handbook of Colors (Dahe Yuanxin, Beiwei Yujiro, Hiratsuka Hengliang, and Song Gangxian's editorial Society: First Edition, 1986) is shown in Table 1 below.

Further, in the present invention, as described above, with the single sheet in the aforementioned film The bulk polymerization utilizes a compound to diffuse (move) in the film to distribute the film. In the case where the polarizing film is produced, the dichroic dye in the present invention basically imparts a component which is aligned by shear stress of a compound (mainly a monomer) which moves in the film. Therefore, the dichroic dye of the present invention can preferably utilize a shape having a shear stress imparted by a compound (mainly a polymerizable compound) which moves in a film with polymerization (for example, if the shape has a different shape) In the case of tropism, it is possible to easily accept stress by moving the compound. In view of the above, the dichroic dye of the present invention is not particularly limited, and a conventional dichroic dye (for example, a dye as described above) can be suitably used depending on the design of the polarizing film.

Hereinafter, the dichroic dye which can be preferably used in the present invention is exemplified An azo dye, an anthraquinone dye, an acridine dye, an oxazolone dye, a cyanine dye, and the like are described.

Examples of the azo dye include, for example, a monoazo dye, a disazo dye, a azo dye, a quinone azo dye, and a diphenylethylene azo dye. Among them, a diazo dye and a ginseng can be preferably used. Azo dyes and derivatives of these series of pigments. Further, the azo dye is more preferably an azo dye (I) represented by the following formula (I-1):

Or an azo-based dye containing a nitro group (further, n, Ar ₁ , Ar ₂ and Ar ₃ in the formula (I-1) are described later).

n in the above formula (I-1) is any one of 0, 1, and 2. When the value of n exceeds the above upper limit, the synthesis of the dye becomes complicated, and it tends to be difficult to manufacture at a low cost.

In the above formula (I-1), each of Ar ₁ and Ar _{3 is} independently selected from the group consisting of the groups represented by the following general formulae (A-1) to (A-4): ]

[In the formulae (A-1) to (A-4), A ₁ and A ₂ each independently represent any one selected from the group consisting of the groups represented by the following formula:

(In the formula, m is an integer from 0 to 10, and when m is two in the same group, the two m values may be the same or different)].

Further, Ar ₂ in the above formula (I-1) is a group selected from the group consisting of the groups represented by the following general formulae (A-5) to (A-7): [Chemical 9]

The positional isomerism of the azobenzene moiety of the azo dye (I) represented by the above formula (I-1) is preferably trans. Specific examples of the azo dye (I) represented by the formula (I-1) are, for example, compounds represented by the following formula (I-101) to formula (I-127).

[化10]

[化12]

The azo dye (I) is preferably the above formula (I-102), upper The general formula (I-105), the above formula (I-106), the above formula (I-108), the above formula (I-110), the above formula (I-112), and the above formula (I) -113), the above formula (I-115), the above formula (I-116), the above formula (I-119), the above formula (I-120), the above formula (I-121), and the above The compound represented by the formula (I-122), the above formula (I-123), the above formula (I-124) and the above formula (I-126) is preferably a compound of the above formula (I-102). ), the above formula (I-105), the above formula (I-108), the above formula (I-110), the above formula (I-115), the above formula (I-121), and the above formula (I-122) and the compound represented by the above formula (I-126).

Further, as the azo-based dye, the former is preferably used. The azo-based dye containing a nitro group is more preferably an azobenzene-based dye containing a nitro group. The nitrobenzene-containing dye containing nitro is exemplified by, for example, Disperse Red 1 (DR1), Disperse Red 13, Disperse Red 19, Disperse Yellow 7, Disperse Orange 1, Disperse Orange 25, 4-N, N-bis (2- Hydroxyethyl)amino-2,2'-dimethyl-4'-nitroazobenzene and the like.

Further, the quinone dye as the dichroic dye is preferably a compound represented by the following formula (II-1):

[In the formula (II-1), R ^a to R ^h each independently represent a hydrogen atom, -Rx, -NH ₂ , -NHRx, -NRx ₂ , -SRx or a halogen atom, and the aforementioned Rx represents a carbon number of 1 to 6; An alkyl group or an aryl group having 6 to 12 carbon atoms].

Further, the acridine-based dye which is the dichroic dye is preferably a compound represented by the following formula (III-1): [Chemical Formula 14]

[In the formula (III-1), R ⁱ to R ^o each independently represent a hydrogen atom, -Rx, -NH ₂ , -NHRx, -NRx ₂ , -SRx or a halogen atom, and the aforementioned Rx represents a carbon number of 1 to 6; An alkyl group or an aryl group having 6 to 12 carbon atoms].

Further, the oxazolone-based dye is preferably a compound represented by the following formula (IV-1):

[In the formula (IV-1), R ^p to R ^w each independently represent a hydrogen atom, -Rx, -NH ₂ , -NHRx, -NRx ₂ , -SRx or a halogen atom, and the aforementioned Rx represents a carbon number of 1 to 6; An alkyl group or an aryl group having 6 to 12 carbon atoms].

In the above formula (II-1), the above formula (III-1) and the above formula (IV-1), an alkyl group having 1 to 6 carbon atoms as the above Rx may be selected as For example, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group or a hexyl group, and an aryl group having 6 to 12 carbon atoms are exemplified by a phenyl group, a tolyl group, a xylyl group, a naphthyl group and the like.

The cyanine dye is preferably a compound represented by the following formula (V-1) or a compound represented by the following formula (V-2):

[In the formula (V-1), D ¹ and D ² each independently represent any of the groups represented by the following formula (V-101) to formula (V-104):

And n represents an integer from 1 to 3], [Chem. 18]

In the formula (V-2), D ³ and D ⁴ each independently represent any of the groups represented by the following formula (V-201) to formula (V-208):

And n represents an integer from 1 to 3].

Further, as the dichroic dye, an acridine dye, an oxazolone dye, a cyanine dye, a cyanine dye, a thiophene dye, an anthraquinone dye, and an azo dye are preferable, and more preferably A cyanine dye, a thiophene dye, an anthraquinone dye, the above azo dye (I), and an azobenzene dye containing a nitro group. Further, as the dichroic dye, an appropriate use example can be used. For example, it contains two or more kinds of azo dyes (I) having mutually different maximum absorption wavelengths.

Further, in the present invention, the polymerizable composition contains a polymerization. At least one of the above-mentioned polymerizable compounds exhibiting liquid crystallinity before and/or after polymerization, and at least one of the above-described dichroic dyes. Further, the polymerizable composition further contains the first compound, the second compound, and the dichroic dye (wherein at least one of the first and second compounds contains the polymerizable property) At least one of the compounds). In addition, the polymerizable composition may contain the first compound and the second compound (at least one of the first compound and the second compound) containing the polymerizable property as appropriate within a range that does not impair the effects of the present invention. At least one of the compounds) and other components other than the dichroic dye. Examples of other components which may be contained in the polymerizable composition include various solvents, photopolymerization initiators, viscosity modifiers, plasticizers, polymerization inhibitors, and surfactants. In addition, when the polymerizable composition contains other components (such as various additives), and all of the other components are the polymerizable compound which exhibits liquid crystallinity before and/or after polymerization, the total amount of the polymerizable compound is relatively The total amount of the compound in the polymerizable composition is preferably 70 mol% or more (more preferably 80 mol% or more) in terms of a molar ratio. In addition, when the polymerizable composition contains other components (such as various additives), the polymerizable composition contains the first and second compounds, and any of the first and second compounds contains the polymerizable compound. In the case of other compounds than the above, the total amount (content) of the first and second compounds described above is preferably 70 mol per mol of the compound in the polymerizable composition. More than % (more preferably 80% or more). When the content of the polymerizable compound in the polymerizable composition or the total amount (content) of the first and second compounds does not reach the lower limit, the amount of the compound exhibiting liquid crystallinity decreases in the film after polymerization. However, there is a tendency to form an alignment.

The content of the dichroic pigment in the aforementioned polymerizable composition It is not particularly limited, and may be appropriately adjusted depending on the design of the obtained polarizing film or the type of the dichroic dye to be used, and the dichroism may be appropriately determined within the range of the alignment of the compound which exhibits liquid crystallinity in the film. The content of the pigment can be. The content of the dichroic dye in the polymerizable composition is, for example, preferably 0.1% by mass or more and 20% by mass or less, more preferably 0.1% by mass or more and 15% by mass or less based on the total amount of the polymerizable composition. More preferably, it is 0.1% by mass or more and 10% by mass or less. When the content of the dichroic dye is within the above range, the alignment of the polymerizable composition in the film is not disturbed, and the formation of the polymerizable composition or the polymerization of the polymerizable compound can be performed. On the other hand, when the content of the dichroic dye exceeds the above content, the alignment of the liquid crystalline compound is inhibited during polymerization of the polymerizable compound, and the transmittance of the film is lowered by the absorption of the dye. In addition, when the content of the dichroic dye referred to herein is two or more kinds of dichroic dyes, it is calculated based on the total amount.

Further, the dichroic dye in the above polymerizable composition contains The amount is preferably from 0.1 to 10 mol%, more preferably from 0.2 to 5 mol%, based on all the compounds in the polymerizable composition. When the molar amount of the dichroic dye does not reach the lower limit, a film having a sufficient polarizing property may not be obtained. On the other hand, when the amount exceeds the upper limit, the polymerizable compound may be present. In the polymerization, the alignment of the compound exhibiting liquid crystallinity is hindered, and the transmittance of the film tends to decrease due to absorption of the dye.

Further, the polymerizable compound in the polymerizable composition When the material is photopolymerized, a photopolymerization initiator is preferably used together with the above polymerizable compound in order to carry out the polymerization more efficiently. The photopolymerization initiator is not particularly limited, and a commercially available person (for example, a product name "Irgacure 651" manufactured by BASF Corporation) can be used. In addition, when the photopolymerization initiator is used, the amount thereof to be used may be appropriately designed depending on the kind of the polymerizable compound or the absorption wavelength of light in the polymerizable composition to be used, for example, relative to all compounds in the polymerizable composition. Set to 0.1 to 10 mol%. In addition, when the content ratio of the photopolymerization initiator is less than the lower limit, the effect of using a photopolymerization initiator may not be sufficiently obtained. On the other hand, when the content exceeds the upper limit, liquid crystallinity tends to decrease. There is a tendency to not be able to effectively achieve a better alignment.

Further, the method for preparing the polymerizable composition is not particularly limited. A conventional method of preparing a composition containing at least one of the above-mentioned polymerizable compounds which exhibit liquid crystallinity before and/or after polymerization and at least one of the above-mentioned dichroic dyes can be suitably used. For example, all of the compounds (including at least one of the above-mentioned polymerizable compounds which exhibit liquid crystallinity before and/or after polymerization and at least one of the above-mentioned dichroic dyes) can be used in a solvent. After stirring to a homogeneous mixture, the method (A) of preparing a polymerizable composition is carried out by distilling off the solvent. The solvent to be used in the method (A) is not particularly limited, and may be uniformly mixed depending on the type of the polymerizable compound or the dichroic dye or the photopolymerization initiator used. The form of the substance can be suitably selected from the conventional solvent, and for example, tetrahydrofuran (THF), dichloromethane, chloroform, acetone or the like can be used. Further, the method for distilling off the solvent is not particularly limited, and a conventional method can be suitably employed. For example, a step of drying under reduced pressure at room temperature (25 ° C) may be employed. Further, the pressure-reducing condition in the vacuum drying step is preferably 15 kPa or less, more preferably 0.1 to 10 kPa. Further, the decompression time is preferably from 0.1 to 100 hours. Further, the vacuum drying step may be carried out once or may be carried out in plural times. In the case where the vacuum drying step is carried out in plural times, when the pressure is dried under reduced pressure, the pressure reduction time can be appropriately adjusted by confirming the degree of drying.

Moreover, the form of the film formed of the polymerizable composition (including The thickness and the like are not particularly limited, and may be appropriately changed depending on the intended purpose. For example, the thickness may be set to 0.1 to 200 μm. Further, the film formed of the polymerizable composition may be a coating film obtained by applying the polymerizable composition on a substrate, or may be polymerized by a unit introduced into a so-called unit by a polymerizable composition. The composition of the film is not limited, and the method of forming the film or the use thereof is not particularly limited, and a conventional method can be suitably used, and the conditions and the like can be determined depending on the kind of the polymerizable compound in the polymerizable composition. The polymerization method (photopolymerization or thermal polymerization), the use of the final product, and the like are appropriately selected. Further, when a film made of the above polymerizable composition is produced on a substrate or in a cell, the substrate or the like used may not be horizontal.

Further, as a film formed of the polymerizable composition, a base On one side, the shape or uniformity of the film is sufficiently maintained, and a polarizing thinness is formed on one side. From the viewpoint of the film, it is preferred to use a substrate supporting film by disposing a film of a polymerizable composition between two substrates (for example, a film is disposed in a cell using a unit including two substrates) or formed on a single substrate. The film formed by the polymerizable composition is the same as the film formed on the other side. Further, the material of the substrate or the unit is not particularly limited, and a conventional material (for example, glass or plastic) can be suitably used. Further, when polymerization is carried out by photopolymerization, when the substrate is brought into contact with the light incident surface side of the film, since it is necessary to transmit light through the substrate, the substrate is preferably at least transmitted by light of a wavelength which can be used for photopolymerization. The material is made.

Further, in the present invention, the polymerizable composition is used. The film is polymerized from the partial region of the film to the polymerizable composition. Further, in the matter of "the polymerization of the above-mentioned polymerizable composition from a portion of the film portion", in addition to setting a part of the film from the beginning to the region for starting the polymerization, when the polymerization is started from the region (for example, In the case of photopolymerization, the portion (exposed portion) irradiated with light from the light source is partially present in a state of the film, and the polymerization of the polymerizable composition is started from the exposed portion of the film) Slowly forming a region for polymerization to start polymerization from a portion of the film (for example, when photopolymerization is performed using a photomask, the entire film is coated with the photomask to completely enter the portion of the film that is shielded by the photomask. After the state, when the film is slowly exposed in the light irradiation region at the time of light irradiation, polymerization is started from the exposed portion of the film (a portion of the film): in this case, the light irradiation region is preferably The film exhibiting the liquid crystallinity and the dichroic dye are introduced (exposed) into the film at a rate of alignment.

According to this, the film formed of the above polymerizable composition is made from one The method of polymerizing the partial regions is not particularly limited, and a conventional method can be suitably employed. The method of starting polymerization from a partial region of the film is exemplified by, for example, a method of photopolymerizing a part of the region (X-ray, electron beam, ultraviolet ray, visible light, infrared ray (hot wire), etc.), and polymerization is started from the irradiation region, Or a method in which heating is started from a portion of the region, polymerization is started from the heating region, and thermal polymerization is carried out. These polymerization methods are preferably based on the viewpoint that it is easier to control the polymerization region, or that it is easier to handle, the irradiation intensity of the irradiated light, or the setting or management of the irradiation energy is easier. The method of polymerization. In the photopolymerization, when a film of a photopolymerizable object is supported by a unit or the like, when the substrate or the like on the light-irradiated surface side is opaque, photopolymerization can be performed by using an electron beam, and the electron beam is used when the substrate is opaque. it works.

Furthermore, photopolymerization is employed as the aforementioned polymerizable composition. In the polymerization method, it is preferred to use ultraviolet rays or visible light because the polymerization reaction can be carried out more efficiently. The light source for illuminating light is not particularly limited, and a conventional light source usable in photopolymerization can be suitably used. For example, a high pressure mercury lamp, an ultrahigh pressure mercury lamp, a low pressure mercury lamp, a metal halide lamp, an LED lamp, or the like can be used.

Moreover, the wavelength of the light used in the photopolymerization is not In particular, it may be determined by considering the absorption spectrum of the compound and the recommended wavelength of use of the photoinitiator. Further, when a film formed of a polymerizable composition is formed on a substrate, and polymerization is carried out in a state where one interface of the film is in contact with ambient gas, an acrylic group or a methacryl group is used. When the compound is subjected to a radical reaction, it is preferred to carry out polymerization in an inert gas atmosphere such as nitrogen from the viewpoint that it is difficult to carry out polymerization due to inhibition of oxygen in the presence of oxygen. In the case where an oxetanyl group or an epoxy group is reacted with a cation to prevent the influence of the polymerizable functional group, it is not particularly necessary to carry out the polymerization in an inert gas atmosphere, or to carry out polymerization in the atmosphere. On the other hand, a film formed of a polymerizable composition such as a cell can be polymerized in the atmosphere without being in contact with the ambient gas. According to the present invention, in the state in which the film formed of the polymerizable composition is brought into contact with the ambient gas (the state in which the interface of the film is in contact with the gas phase), the polymerizable composition may be used. The film is formed in a state in which the film is not in contact with the ambient gas (the state in which the interface of the film is in contact with the wall surface (solid phase) of the unit).

And photopolymerization is used as the polymerization of the aforementioned polymerizable composition In the case of the method, the light irradiation may be carried out under heating conditions, and the heating temperature may be appropriately selected in consideration of the type of the polymerizable composition to be used, the type of polymerization reaction, the liquid crystal property, the viscosity of the polymerizable composition, and the ease of heating, etc., but usually It is preferably at room temperature (about 25 ° C) to about 300 ° C. When the heating temperature is less than the lower limit, the polymerizable composition or one of the components is crystallized, and it is difficult to efficiently carry out the polymerization reaction or the formation of the alignment film, and the viscosity of the polymerizable composition becomes high, which may occur. On the other hand, when the polymerization temperature exceeds the above upper limit, the entire polymer film is polymerized by heat before the polymerizable compound is irradiated, and a polarizing film cannot be obtained, and the reaction is carried out in the air. When the polymerizable compound is decomposed, the possibility of decomposing is high, and there is a tendency that it is difficult to obtain a polarizing film stably.

Further, it is preferred to irradiation light intensity ^{0.1μW / cm 2 ~ 30mW / cm} 2 , the better to 0.5μW / cm ² ~ 10mW / cm ² of irradiation light intensity during the photopolymerization. When the illuminance of the light does not reach the lower limit, the reaction rate becomes slow, so that the moving speed of the boundary is slow, and the productivity tends to decrease. On the other hand, when the upper limit is exceeded, the polymerization rate of the polymerizable compound is higher than the diffusion rate. The speed is too fast, so that the compound cannot be sufficiently diffused, and there is a tendency that a polarizing film cannot be obtained.

Furthermore, when the photopolymerization is used, it is used to irradiate from a part of the area. The method of light is not particularly limited. For example, a light source that can illuminate only a part of the area may be used, or light may be irradiated from a part of the area by a reticle, but it is better to use it in order to more easily control the polymerization area and the unpolymerized area. Photomask.

Further, in the present invention, as described above, the aforementioned polymerizability is free After the polymerization of the polymerizable composition is started in a portion of the film formed by the composition, the boundary between the region and the dichroic dye present in the film is shifted so that the boundary of the region is continuously moved toward the unpolymerized region. . By continuously moving the boundary between the polymerization region and the unpolymerized region toward the unpolymerized region, the polymerization is continuously performed, and the diffusion of the compound (substance) in the film can be continuously caused in the region near the boundary where the movement is performed. The alignment region is continuously increased to obtain a polarizing film. Moreover, the polymerization conditions when the boundary of the above-mentioned region is continuously moved toward the unpolymerized region may be the same as the polymerization conditions at the time of the polymerization.

Here, the speed of the movement when the boundary is moved is The rate at which the liquid crystal compound and the dichroic dye are aligned is based on the type of the liquid crystal compound and the type of the dichroic dye, and the diffusion and movement. The type of the compound, the type of the compound (polymer: polymer) formed by polymerization, the type of the polymerizable compound, the polymerization conditions used in the polymerization (for example, light irradiation conditions during photopolymerization), and the like, and the liquid crystal property is exhibited in the film. The time required for the compound to align with the dichroic dye is different, and thus cannot be generalized. That is, in the present invention, the concentration gradient of the compound generated in the polymerization region and the unpolymerized region causes the compound (mainly monomer and/or polymer) in the polymerizable composition to be in the polymerization region and the unpolymerized region. a diffusion movement (flow) in the vicinity of the boundary, and a shear stress is applied to the compound exhibiting liquid crystallinity and the dichroic dye present in the polymerizable composition, so that the compound exhibiting liquid crystallinity and the dichroic dye are at the aforementioned boundary Nearby. Therefore, the "speed at which the compound exhibiting liquid crystallinity and the dichroic dye are aligned" differs depending on the type of the liquid crystal compound and the type of the dichroic dye or the type of the compound which diffuses and moves. For example, when only one kind of polymerizable compound is contained as a monomer component in the above-mentioned polymerizable composition, and the polymerization rate of the above polymerizable compound is very fast, a compound in the film (monomer and/or) is rapidly generated in the polymerization region and the unpolymerized region. The concentration gradient of the polymer or the polymer makes the moving speed of the aforementioned polymerizable compound to the polymerization zone very fast. In this case, even if the moving speed of the boundary is fast, the shear stress generated by the movement of the polymerizable compound toward the polymerization region can be sufficiently applied to the liquid crystal-displaying compound and the dichroic dye present in the polymerization region. The compound exhibiting liquid crystallinity can be sufficiently aligned with the dichroic dye. On the other hand, for example, only one type of polymerizable compound is contained as a monomer component in the polymerizable composition, and the polymerization rate of the polymerizable compound is slow, and the compound is stably formed in the polymerization region and the unpolymerized region. In the case of a gradient, it takes time to sufficiently impart shear stress to the compound exhibiting liquid crystallinity and the dichroic dye in the film. Therefore, when the moving speed of the boundary is fast, it is difficult to make the liquid crystal compound and the second in the vicinity of the boundary. The coloring pigment is fully aligned. Further, when the first polymer and the second compound are contained as described above in the polymerizable composition (in this case, at least one of the first compound and the second compound contains at least one of the polymerizable compounds) And using the polymerizable compound which exhibits liquid crystallinity before and/or after the polymerization in the second compound, the first compound is preferentially polymerized by starting polymerization, and the first compound is caused to move toward the polymerization region, and the first compound is used. In the case of the compound and the second compound, the polymerization rate of the first compound is very fast, and a concentration gradient of the compound is rapidly generated in the polymerization region and the unpolymerized region, so that the rate at which the first compound moves toward the polymerization region is extremely fast, even if The movement speed of the boundary is relatively fast, and the liquid crystal property can be exhibited by sufficiently applying the shear stress generated by the movement of the first compound toward the polymerization region to the liquid crystal-displaying compound and the dichroic dye present in the polymerization region. The compound is sufficiently aligned with the dichroic dye, and the polymerization rate of the first compound is slow. When the concentration gradient of the compound is stably generated in the polymerization region and the unpolymerized region, and the moving speed of the first compound toward the polymerization region is slow, it takes time to impart sufficient shear stress to the liquid crystal compound and the dichroic dye. Therefore, when the moving speed of the boundary is fast, it is difficult to sufficiently align the liquid crystal-displaying compound and the dichroic dye in the vicinity of the boundary. Therefore, "the rate at which the compound exhibiting liquid crystallinity and the dichroic dye are aligned" is determined by the type of compound which causes the compound which exhibits liquid crystallinity and the type or diffusion of the dichroic dye to be polymerized. The type of the compound (polymer) to be formed, the polymerization conditions, and the like may be determined by appropriate alignment, and the setting of the speed may be appropriately changed.

Further, the speed at which the compound exhibiting liquid crystallinity and the dichroic dye are aligned (moving speed at which the boundary is moved) is preferably 1 × 10 ^-7 to 4 × 10 ^-1 m / s, more preferably 1 × 10 ^-6 ~ 4 × 10 ^-2 m / s. When the speed is less than the lower limit, the polymerization reaction proceeds faster than the diffusion of the compound. Therefore, since the viscosity is increased, the diffusion and movement of the compound are inhibited, and the shearing stress is not sufficiently imparted to the liquid crystal compound and the dichroic dye. On the other hand, when the above-mentioned upper limit is exceeded, the speed is too fast, and it is difficult to sufficiently diffuse and move the compound in the vicinity of the boundary, and it is difficult to form an alignment in the polymerization region. Further, when one of the compounds C11 to 17 is used as the polymerizable composition (more preferably, the first compound and the second compound are used as the polymerizable composition, and the first compound is the compound C11 to C13; At least one compound selected from the group consisting of the compound represented by the above formula (2) and the compound represented by the above formula (3), and the second compound is at least one selected from the group consisting of the compounds C14 to C17. In the case of a compound, when the polymerizable composition is polymerized, when the photopolymerization method is used to irradiate light at an intensity of 0.1 μW/cm ² to 30 mW/cm ² , the compound exhibiting liquid crystallinity and the dichroic dye are aligned. The speed (the moving speed at which the boundary is moved) is preferably set to 1 × 10 ^-7 to 4 × 10 ^-1 m/s from the viewpoint of efficiently forming the polarizing film.

Further, the method of continuously moving the boundary of the region toward the unpolymerized region is not particularly limited. For example, when the polymerization method is thermal polymerization, only The method of continuously moving the heating region toward the unpolymerized region may be suitably employed. Further, when the polymerization method is photopolymerization, a method of continuously moving the light irradiation region toward the non-irradiated region may be employed as appropriate.

In addition, the boundary of the region is continuous toward the unpolymerized region The method of moving is based on the fact that the moving speed of the boundary can be more easily controlled, and the alignment region is formed more efficiently, and the polymerization of the polymerizable composition is preferably carried out by photopolymerization, and the boundary is oriented toward the unpolymerized region. For continuous movement, a method of continuously moving the boundary of the light irradiation region toward the region where the light is not irradiated is preferably employed. In addition, the method of continuously moving the boundary of the light irradiation region toward the region where the light is not irradiated is not particularly limited as long as it is a method for moving the boundary, and for example, a film formed of the polymerizable composition can be suitably used. a method of continuously moving a light source itself by illuminating only a part of a region; or a method of continuously moving a film of the polymerizable composition while fixing the light source; and a method of continuously moving the mask by using a mask; or A method of continuously moving a film of the polymerizable composition while fixing a mask by using a photomask.

Moreover, the boundary of the illuminated area of the light is not irradiated toward the light. In the method of continuously moving the region, a method of continuously moving the photomask and/or the film by using a photomask during photopolymerization (for example, a method of continuously moving the photomask by using a photomask, or utilizing a mask, a method of continuously moving the film of the polymerizable composition while fixing the mask, and the like). According to this, photopolymerization is employed in the polymerization of the polymerizable composition, and the boundary of the light irradiation region can be more easily moved toward the light non-irradiation region by the photomask.

Here, the aforementioned polymerizable composition is carried out by photopolymerization A preferred embodiment of the method for producing a polarizing film of the present invention in which the film is polymerized and the photomask is used in the photopolymerization will be briefly described with reference to Figs. In the preferred embodiment shown in FIGS. 1 to 4, first, a light mask 14 that shields light is disposed between the film 13 and the light source 11 by irradiating only a portion of the film 13 with light from the light source 11. 1), by irradiating light from the light source 11, polymerization of the polymerizable composition is started from a partial region A1 of the film 13 (refer to FIG. 2), and subsequently, the compound exhibiting liquid crystallinity is aligned with the dichroic dye. The speed of the photomask 14 is continuously moved, whereby the boundary between the polymerizable region and the dichroic dye is caused to continuously move the boundary S of the polymerization region toward the unpolymerized region A2 (in the direction of the arrow A) (refer to FIG. 3). ~4), whereby a polarizing film is obtained. When photopolymerization is used for the polymerization of the polymerizable composition, the boundary S between the polymerization region and the unpolymerized region can be moved by a simple method of moving the mask 14, and the polarization can be more efficiently produced. film. Further, a preferred embodiment of the method for producing a polarizing film of the present invention in the case of using a photomask will be described with reference to Figs. 1 to 4, but the embodiment of the method for producing a polarizing film of the present invention in the case of using a photomask is not It is limited to the above embodiment. For example, in the embodiment shown in Figs. 1 to 4, in order to move the boundary S between the polymerization region and the unpolymerized region, a method of moving the mask 14 is employed. However, the film 13 itself may be moved by fixing the mask 14. The method. Further, in the embodiment shown in FIGS. 1 to 4, the polymerization of the polymerizable composition is started after the partial region R1 of the film 13 is irradiated with light, but in the method for producing a polarizing film of the present invention, can The polymerization method to be used is not limited to the method employed in the embodiment, and it is also possible to use, for example, a mask to cover the entire film, to start irradiation of light, and to align the compound exhibiting liquid crystallinity with the dichroic pigment. Or the film is continuously moved, and the film is introduced into the irradiation region (exposure portion) of the light at the aforementioned speed, thereby starting polymerization from the region (a portion of the film) introduced into the irradiation region (exposure portion) of the light to directly A method of obtaining a polarizing film by moving a boundary of a polymerization region toward an unpolymerized region at a rate at which a compound exhibiting liquid crystallinity and a dichroic dye are aligned.

And the polymerization of the aforementioned polymerizable composition is carried out by photopolymerization When the photomask is used in the photopolymerization, the alignment direction can be easily controlled according to the shape of the edge of the mask. Hereinafter, the embodiment in which the alignment is controlled according to the edge shape of the mask will be described with reference to FIGS. 5 and 6 respectively. For example, when the photomask 14 shown in FIG. 5 is used as the photomask, the compound flow can be generated in a direction substantially perpendicular to the boundary S shown in FIG. 5, and the alignment direction can be controlled to be substantially perpendicular to the boundary S. Further, when the reticle 14 having the edge formed in the oblique direction as shown in FIG. 6 is used as the reticle, the compound flow can be substantially generated in the direction substantially perpendicular to the boundary S shown in FIG. 6, and the alignment direction can be controlled for When the slope S of the slope is substantially perpendicular, or when the moving speed of the boundary S is fast, the vector (arrow A) controlling the direction of movement of the boundary S and the vector of the vector (arrow P) perpendicular to the boundary S are oriented. . Therefore, when photopolymerization is performed using a photomask, the alignment direction can be more easily controlled in a desired direction according to the shape of the edge of the mask. Accordingly, in order to form a desired alignment direction, the edge shape of the photomask can be appropriately changed and used, whereby the alignment can be controlled more easily. to.

And the polymerization of the aforementioned polymerizable composition is carried out by photopolymerization When the photomask is used in the photopolymerization, it is preferable to use a plurality of openings having a slightly rectangular shape so that the long sides of the openings are formed to be slightly parallel. Hereinafter, a preferred embodiment of the photopolymerization method in the case where the plurality of substantially rectangular openings are formed so that the long sides of the openings are slightly parallel will be briefly described with reference to FIG. 7 or FIG. form. 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 optical axis direction of the irradiated light). Moreover, in these embodiments, the light source, the photomask 14 and the substrate 12 are arranged such that the film disposed on the substrate 12 can be photopolymerized by light transmitted through the opening portion 14A.

The reticle 14 shown in FIG. 7 and FIG. 8 has a plurality of slightly longer The square-shaped opening portion 14A. Here, the "slightly rectangular shape" includes a rectangular shape of the opening portion 14A as shown in FIG. 7, and includes a shape in which four corners of the rectangle are arcuate, and a portion corresponding to the long side or the short side of the rectangle becomes The shape of the arc-shaped side, and further, the angle of the four corners of the opening portion 14A shown in FIG. 8 is not a shape of a parallelogram of 90 degrees (again, in the case of the shape, the four corners are also round The concept of an arc, or a shape corresponding to a long side or a short side, is the shape of an arcuate side. Accordingly, the opening portion having a substantially rectangular shape is intended to be expressed such that the opening portion has a rectangular shape, and the long side (which may be an arc-shaped side) corresponds to a short side (which may also be an arc-shaped side). The longer side has a slender shape.

The slightly rectangular shape (slender shape) of the opening portion 14A is not particularly limited as long as the length Y of the long side is longer than the length X of the short side. Further, the ratio (Y/X) of the length Y of the long side to the length X of the short side is preferably 2.0 or more, more preferably 5.0 to 2.0 × 10 ⁵ .

Further, the short side length X of the opening portion 14A is based on the poly The size of the substrate 12 or the film to be used at the same time may not be uniform, but is preferably 1 μm to 10 mm, more preferably 10 μm to 1 mm (again, the average of the short side length X of the plurality of openings 14A is also good. For the same range of values). When the short side length X of the opening portion 14A does not reach the lower limit, the alignment tends to be less likely to occur. On the other hand, when the length exceeds the upper limit, it tends to be difficult to obtain a uniform film in the film surface.

Further, the opening portion 14A is slightly parallel to the long sides of the respective opening portions. Ground configuration. In this manner, the opening portion 14A is disposed such that the long sides of the respective openings are slightly parallel, and when the polarizing film is formed over a large area, the alignment direction can be controlled in the same direction. Further, the mask having the opening portion 14A preferably forms the opening portion 14A periodically, and the opening portion 14A having the same shape is formed more preferably. When the opening portion 14A is formed periodically, the distance between the openings 14A (the distance from the center of the one opening portion to the center of the adjacent opening portion) is not particularly limited, but is preferably 1 μm to 10 mm, more preferably 10 μm. 1 mm (again, the average value of the distance between the plurality of openings 14A is preferably the same numerical range). When the distance between the openings 14A is less than the lower limit, the alignment tends to be less likely to occur. On the other hand, when the distance exceeds the upper limit, it is difficult to obtain a uniform film in the film surface. Further, in the reticle having a plurality of openings, the number of the openings is not particularly limited, and may be appropriately changed depending on the size of the mask or the substrate, etc., in the reticle having a plurality of openings. More its design.

Using the plurality of rectangular openings to form a parallel For example, when the substrate 12 is moved in the direction opposite to the direction A or in the same direction, the film formed on the substrate is photopolymerized by the opening portion 14A, and a polymerization region is formed in each of the openings 14A. At the boundary, each boundary can be continuously moved toward the unpolymerized region, and an alignment region can be formed for each of the openings 14A. Therefore, when a plurality of rectangular mask-shaped openings are formed in parallel, the large area of the alignment area can be formed by moving the mask and/or the film to the same length (distance) as the adjacent opening. The polarizing film can be formed efficiently.

In addition, the plurality of rectangular openings are slightly flattened When the mask 14 is formed in a row, the alignment direction can be controlled according to the shape of the edge of the opening 14A. For example, in the embodiment shown in Fig. 7, the substrate 12 having the film (not shown) formed is oriented and oriented. When the side of the opposite side (or the same direction) is moved while performing photopolymerization, the alignment direction can be controlled to be perpendicular to the long side of the opening portion 14A. Further, in the embodiment shown in Fig. 8, for example, the substrate 12 on which the film (not shown) is formed is moved in a direction opposite to the direction A (the edge S can be made to face the arrow A in the figure). When the photopolymerization is carried out in the direction of the light source side, since the edge of the opening portion 14A is formed in the oblique direction with respect to the two sides of the substrate 12 when viewed from the light source side, the compound is oriented substantially perpendicular to the long side of the opening portion 14A by polymerization. The direction generates a flow, and when the longitudinal direction of the substrate 12 is substantially perpendicular, or the moving speed of the substrate 12 is fast, the direction of the alignment direction is controlled to be the vector of the moving direction of the boundary S and the long side of the opening portion 14A is The vector and direction of the vector in the approximate vertical direction. Further, the photopolymerization method which can be preferably used in the present invention will be described with reference to Figs. 7 to 8, but the photopolymerization method which can be employed in the present invention is not limited to these methods. For example, although the method of moving the substrate 12 is described in the above embodiment, photopolymerization may be carried out by appropriately fixing the substrate 12, moving the mask and the light source, and the like. Further, although a method of using a photomask having a plurality of openings as a photomask will be described with reference to FIGS. 7 to 8, in the present invention, the photomask may have no opening portion, or may be appropriately formed using only one. One opening.

Further, in the present invention, the polymerizable composition is free After the polymerization of the polymerizable composition is started in a portion of the film, the boundary between the regions is continuously moved toward the unpolymerized region at a rate at which the liquid crystal-displaying compound present in the film is aligned with the dichroic dye, thereby producing polarized light. As the film formed of the polymerizable composition used for the production of the polarizing film, a film obtained by prepolymerization may be used. By using the prepolymerized film, even if the boundary of the polymerization region continuously moves toward the unpolymerized region at a faster rate, a sufficiently aligned structure can be formed, and a large-area polarizing film can be formed more efficiently. In addition, the term "prepolymerization" as used herein means that the film of the above polymerizable composition is polymerized without impairing the fluidity of the polymerizable compound (for example, when photopolymerization is used for both prepolymerization and formal polymerization) The polymerizable composition has a film irradiation intensity lower than that of the formal polymerization, whereby the polymerizable compound in the film is slightly polymerized to the extent that the fluidity is not impaired.

Thus, in the present invention, based on the boundary of the polymerization region Continuously moving to unpolymerized areas is faster and forms as short as possible From the viewpoint of the polarizing film, the film after prepolymerization can be preferably used. The prepolymerization method is not particularly limited. For example, in the case of photopolymerization in the prepolymerization, prepolymerization using a photomask or prepolymerization without using a photomask may be employed. Accordingly, the prepolymerization may be a photomask formed by using a plurality of openings having a substantially rectangular shape so that the long sides of the openings are slightly parallel, and prepolymerization by photopolymerization.

In the prepolymerization, in the case of photopolymerization, it is preferred to irradiate light at an intensity of 0.001 μW/cm ² to 10 mW/cm ² , more preferably at a strength of 0.05 μW/cm ² to 1 mW/cm ² . When the illuminance of the light is less than the lower limit, the reaction tends to be insufficient, and it is difficult to obtain a prepolymerization effect. On the other hand, when the radiance is more than the upper limit, the polymerization of the polymerizable compound is excessively performed, and the polymerizable composition is allowed to be free. After the polymerization of the polymerizable composition is started in a portion of the formed film, even if the boundary between the compound and the dichroic dye present in the film is continuously shifted toward the unpolymerized region, There is no tendency to cause diffusion of the compound at all, and there is a tendency that a polarizing film cannot be obtained. Further, in the case of photopolymerization in the prepolymerization, the photopolymerization conditions may be the same as those described in the polymerization method of the polymerizable composition, except for the conditions relating to the illuminance of the light.

Accordingly, in the present invention, the aforementioned polymerizable composition is used. In the film formed, the polymerization of the polymerizable composition is started from a portion of the film, so that the boundary between the compound and the dichroic dye present in the film is aligned to the unpolymerized region. The film is continuously moved, whereby a polarizing film can be obtained. Further, the polarizing film of the present invention In the manufacturing method, the display liquid crystal present in the film is formed by a shear stress generated by a compound (mainly a monomer and/or a polymer) which is moved from the unpolymerized region to the polymerization region in the film after the polymerization is started. The compound is aligned with the dichroic dye, so basically, the alignment direction can be controlled to the direction in which the compound moves (the direction perpendicular to the boundary of the aforementioned region), and the polymerization can be carried out by photopolymerization depending on the shape of the mask. The alignment is controlled in various directions, or the pattern alignment of the alignment direction is changed depending on the location. Further, in the present invention, a film formed of a polymerizable composition containing a polymerizable compound having liquid crystallinity in at least one of pre-polymerization and post-polymerization is used, and the boundary of the polymerization region is moved to form an alignment side. A method of obtaining a polarizing film by moving the polymerization region while increasing the alignment region and aligning the liquid crystal compound and the dichroic dye (when only one polymerizable compound is used, the boundary of the polymerization region can be utilized Since the substance diffusion phenomenon caused by the movement, the compound exhibiting the liquid crystal property and the dichroic dye can be sufficiently aligned. According to the invention, the polarizing film in which the liquid crystal compound and the dichroic dye are aligned is obtained. Further, the term "polarizing property" as used herein refers to the property of the emitted light which is different from the intensity of the light which vibrates in a certain direction when the film is incident on the non-polarized light (natural light). Further, in the polarizing film, the presence or absence of alignment between the liquid crystal compound and the dichroic dye, or the alignment direction thereof may be appropriately confirmed by a known method, and may be, for example, in two specific directions perpendicular to each other. The ultraviolet visible light absorption spectrum is separately determined, and the so-called order parameter is determined, and the direction of the alignment or the presence or absence of alignment is confirmed by the value of the absorption spectrum data or the ordered parameter, or in the orthogonal A polarizing film is inserted between the two polarizing plates, and the polarizing film is rotated to confirm the presence or absence of a dark field and a bright field, and the method of confirming the alignment of the liquid crystal compound is used, or a polarizing microscope (for example, Olympas Co., Ltd.) is used. The product name "BX50") is a method of measuring a polarizing film.

Further, in the present invention, it is formed from a polymerizable composition. After the polymerization of the polymerizable composition is started in a portion of the film, the boundary between the regions is continuously moved toward the unpolymerized region at a rate at which the liquid crystal-displaying compound present in the film is aligned with the dichroic dye, thereby producing polarized light. a film, but the boundary between the regions is continuously moved toward the unpolymerized region, and after the alignment region is formed in the film, in order to complete the polymerization reaction of the polymerizable composition or to more sufficiently harden the polarizing film, for example, polymerization may be performed. The film is allowed to stand still under the temperature conditions further. In addition, in order to more efficiently polymerize the unpolymerized component (polymerizable compound) remaining in the alignment region, it is also possible to additionally irradiate light, appropriately change temperature conditions, etc. under the condition that the formed alignment state can be maintained. The step of further carrying out the polymerization. Accordingly, in the present invention, the alignment is formed by the diffusion phenomenon of the substance while moving the boundary of the polymerization region, but in the polymerization step accompanying the boundary movement, it is not necessary to completely polymerize the components in the film, but at the boundary of the aforementioned region After continuously moving toward the unpolymerized region, a step of further polymerizing while maintaining the alignment structure (post-polymerization step) is carried out, and finally, a polarizing film in which the alignment structure is immobilized can be obtained. In addition, the conditions of the post-polymerization step are not particularly limited as long as they are appropriately changed depending on the type of the component in the polymerizable composition to be used.

Moreover, in the method for producing a polarizing film of the present invention, Since a long-length substrate film or the like is used on the substrate, a long-length polarizing film can be produced by a roll-to-roller.

According to the method for producing a polarizing film of the present invention, When the obtained polarizing film is formed into a region in which the liquid crystal compound exhibiting a liquid crystal property and a dichroic dye are formed in a large area, the method for producing a polarizing film of the present invention can be preferably used for production and use as a manufacturing process. A polarizing film such as a material of a polarizing element used in various display devices (for example, a liquid crystal display) (for example, a polarizing film used for forming a polarizing plate or the like in combination with other optical elements).

Example

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

(Synthesis Example 1: Synthesis of A6CB and its homopolymer, etc.) <A6CB Synthesis and Its Characteristics Evaluation>

4-(6-Acetoxycarbonylcyclohexyloxy)-4'-cyanobiphenyl (A6CB) was synthesized by the method shown below. Namely, 4-cyano-4'-hydroxybiphenyl (100 mmol) was dissolved in 120 mL of N,N-dimethylformamide (DMF) to obtain a solution. Next, 1-bromohexanol (110 mmol), potassium carbonate (110 mmol), and potassium iodide (amount of catalyst: 1 mol of 1 mol of calcium carbonate) were added to the solution, and the mixture was heated and stirred at 100 ° C for 5 hours. Then, the reaction mixture was terminated by heating and stirring, and the resulting reaction liquid was extracted with ethyl acetate, and washed with 1 N hydrochloric acid and saturated brine. Organic layer. Next, the washed organic layer was dried over anhydrous magnesium sulfate, and the desiccant was removed by filtration, and then the solvent was evaporated under reduced pressure. Subsequently, the target (4-cyano-4'-(6-hydroxyhexyloxy)biphenyl was separated and purified by silica gel column chromatography, and then recrystallized from chloroform and hexane to obtain Compound A as a white solid. 4-cyano-4'-(6-hydroxyhexyloxy)biphenyl) 21.3 g (72 mmol).

Next, the above compound is mixed in a pear-shaped flask. A (50 mmol), triethylamine 20.7 mL (150 mmol), THF 30 mL, and hydroquinone (catalyst amount: 2 mmol relative to 1 mol of the above compound) was added to obtain a mixture, and the above-mentioned pear-shaped flask was submerged at 23 ° C. In a water bath, after the atmosphere inside the pear-shaped flask was set to a nitrogen atmosphere, propylene chloride (150 mmol) was slowly added dropwise to the mixture under stirring in a nitrogen atmosphere to obtain a reaction solution. After stirring for 48 hours in a nitrogen atmosphere as described above, 300 mL of a saturated aqueous sodium hydrogencarbonate solution was added to the reaction solution, followed by stirring for 30 minutes. Subsequently, the resulting reaction solution was extracted with chloroform, and the organic layer was washed sequentially with 1N hydrochloric acid and brine. Next, the solvent is distilled off from the obtained organic layer under reduced pressure at room temperature, and the target (4-(6-propenyloxyhexyloxy)-4'-cyanobiphenyl) is separated and purified by silica gel chromatography. Methanol was recrystallized to obtain 9.8 g (28 mmol) of 4-(6-propenyloxyhexyloxy)-4'-cyanobiphenyl. In addition, the structure of the compound thus obtained was confirmed by NMR and IR, and it was confirmed to be 4-(6-acryloxyhexyloxy)-4'-cyanobiphenyl represented by the following formula (4).

[Chemistry 20]

4-(6-acryloxyhexyloxy)-4'-cyanide thus obtained The bisphenyl group is a compound having a straight cyanobiphenyl structure as a mesogen as understood from the compound of the above formula (4). Further, using a differential scanning calorimeter (DSC6220 manufactured by DSC SIS. Nanotechnology), the temperature was raised and lowered at a rate of 1 ° C/min, and it was confirmed that 4-(6-acryloxyhexyloxy)-4'-cyano group was used. The behavior of the liquid crystal formed by biphenyl did not show liquid crystallinity. During the heating process, the phase transition from the crystal phase to the isotropic phase was carried out at 69 ° C, and the isotropic phase toward crystallinity was carried out at 53 ° C during the cooling process. Phase transfer.

<Synthesis and Characterization of Homopolymer of A6CB>

15 mmol of 4-(6-acryloxyhexyloxy)-4'-cyanobiphenyl obtained as described above was added to 35 mL of N,N-dimethylformamide (DMF), and then 0.75 was added. Methyl azobisisobutyronitrile (AIBN) was used as a thermal polymerization initiator, and stirred at a temperature of 70 ° C for 6 hours to carry out a reaction to obtain a polymerization solution. Next, the polymerization solution after completion of the reaction was poured into 0.5 L of methanol to precipitate a polymer, washed again in 0.5 L of methanol, and filtered to obtain a solid component. Next, the obtained solid component was allowed to stand at room temperature (25 ° C). Drying under vacuum for 24 hours gave 4.7 g of a polymer (a homopolymer of A6CB).

GPC measurement of the polymer thus obtained, before the result The number average molecular weight Mn of the polymer was calculated to be 8000 g/mol in terms of polystyrene standards. In addition, the polymer was subjected to differential scanning calorimetry using a differential scanning calorimeter (DSC). As a result, the glass transition temperature was displayed at 38 ° C during the temperature rise, and the liquid crystallinity was exhibited at 38 to 126 ° C, and the liquid crystal was displayed at 124 to 29 ° C during the cooling process. Properties, and the glass transition temperature was shown at 29 °C. From the results, it was found that the 4-(6-acryloxyhexyloxy)-4'-cyanobiphenyl obtained in Synthesis Example 1 was polymerized to exhibit a liquid crystallinity.

(Example 1) <Modulation of Polymeric Composition>

First, 1,6-hexanediol dimethacrylate represented by the following general formula (5) (HDDMA, a bifunctional methacrylate manufactured by Tokyo Chemical Industry Co., Ltd., hereinafter referred to as "first compound") ),

And 4-(6-acryloxyhexyloxy)-4'-cyano group obtained in Synthesis Example 1. After biphenyl (A6CB, a monofunctional acrylate, a compound which exhibits liquid crystallinity after polymerization, and hereinafter referred to as a "second compound"), Irgacure 651 (manufactured by BASF Corporation) as a photopolymerization initiator is added as a second The coloring matter was a compound represented by the following formula (6) (DR1, trade name "Disperse Red 1" manufactured by Sigma Aldrich Co., Ltd.) to obtain a mixture.

Next, the mixture thus obtained is added to tetrahydrofuran In (THF), the mixture was stirred for 1 hour to obtain a mixture. Then, the solvent was distilled off under the conditions of a temperature of 25 ° C and a pressure of 1 kPa, and dried under reduced pressure for 6 hours, and further subjected to a vacuum drying treatment for 6 hours under the same conditions as those described above. This was distilled off from the above mixture to prepare a polymerizable composition. Further, when the foregoing mixture is obtained, the first compound (HDDMA) and the second compound (A6CB) are used in such a manner that the mixing ratio thereof is 5:95 in terms of molar ratio ([first compound]: [second compound]). However, as the solvent is distilled off under the reduced pressure, some of the components are steamed together with the solvent. The molar ratio of the first compound to the second compound ([first compound]: [second compound]) in the polymerizable composition obtained was 4:96. Further, the photopolymerization initiator (Irgacure 651) is used in an amount of 1 mol% based on the total amount of the compound of the polymerizable composition, and the dichroic dye (DR1) is used in the photopolymerization initiator (DR1). The content is used in an amount of 0.5 mol% based on the total amount of the compound in the polymerizable composition (0.45 mass% based on the total amount of the polymerizable composition).

<Measurement of polymerization completion time of the first and second compounds used for preparation of the above polymerizable composition>

The polymerization completion times of the first compound and the second compound were each measured as follows. A 100 μm-thick polyimide tape is used as a separator so that the area where the planar portions of the upper and lower substrates overlap each other is 15 mm long and 25 mm wide (the side parallel to the longitudinal direction of the separator overlaps 15 mm). The bonding size is 25 mm. Two sheets of a soda glass substrate having a thickness of 1.1 mm were fabricated into a glass unit having a cell thickness of 100 μm (again, the unit was formed into a separator on two sides of the parallel longitudinal direction (left and right) of the glass substrate, and the glass substrate in which the separator was not formed) The portions are each an opening, and the size of the inside of the unit is set to be 15 mm long, 10 mm wide, and 100 μm thick. Next, the compound for measuring the completion time of the polymerization was mixed so that the content of the photopolymerization initiator Irgacure 651 was 1 mol%, and the mixture was prepared. Then, after the glass unit is placed on a heating stage (trade name "FP-90, FP-82HT" manufactured by METLER TOLEDO Co., Ltd.), the mixture is melted at a temperature of 100 ° C, and the capillary phenomenon is used to cause the above-mentioned glass unit. A mixture (containing 1 mol% of a photopolymerization initiator Irgacure 651) was injected into the aforementioned glass unit until it was filled inside the cell, and then cooled to 85 ° C at a rate of 0.5 ° C / min, and kept at 85 ° C for 3 minutes to obtain the aforementioned mixture. Film (film size: 1.5 cm in length, 1.0 cm in width, and 100 μm in thickness). Next, the film was irradiated with light of 366 nm taken out from the high pressure mercury lamp with a strength of 1.9 mW/cm ² to carry out photopolymerization. After the photopolymerization was started, the film was taken out from the glass unit after 5 seconds, 15 seconds, 30 seconds, and 60 seconds, and the surface was washed with chloroform to visually confirm the state of formation of the film. The first compound (HDDMA) was confirmed to form a film at an irradiation time of 30 seconds, and the polymerization completion time was confirmed to be more than 15 seconds and 30 seconds or less. On the other hand, the second compound (A6CB) confirmed that a film was formed at an irradiation time of 60 seconds. Confirm that the polymerization completion time is more than 30 seconds and 60 seconds or less.

<Modulation of film of polymerizable composition>

Two pieces of a soda glass substrate having a size of 25 mm and a thickness of 1.1 mm were applied to the left and right ends of the glass substrate by an epoxy-based adhesive containing 2 μm of cerium oxide particles having a diameter of 25 mm and a width of 2.5 mm. The two parallel sides were bonded together to form a glass unit having a cell thickness of 2 μm (the adhesive also functions as a separator, and portions not coated with the adhesive are respectively provided as openings). Further, the soda glass substrate is subjected to ultrasonic cleaning after being ultrasonically washed with a neutral detergent, ion-exchanged water, acetone, or isopropyl alcohol, and then subjected to UV ozone treatment. Next, after the glass unit was placed on a heating stage (trade name "FP-90, FP-82HT" manufactured by METLER TOLEDO Co., Ltd.), the polymerizable composition was melted at a temperature of 120 ° C. In one of the openings of the glass unit, the polymerizable composition was injected into the glass unit from the opening by capillary action, and then cooled to 85° C. at a rate of 0.5° C./min and held at 85° C. for 10 minutes to obtain a polymerizable composition. Film of the material (film size: length 20 mm, width 20 mm, thickness 2 μm).

<Modulation of polarizing film>

Hereinafter, a method of modulating the polarizing film used in the first embodiment will be described with reference to Fig. 9 . FIG. 9 is a schematic plan view schematically showing the relationship between the substrate 12 (the soda glass substrate on which the glass unit forming the film of the polymerizable composition is formed) and the photomask 14 when viewed from the light source side.

That is, when the polarizing film is prepared, a mask having a rectangular opening portion as schematically shown in Fig. 9 is used. Further, in the photopolymerization, the angle between the long side of the opening 14A of the mask 14 and the two sides of the substrate 12 (in the figure, the two sides adjacent to the long side) is 90° when viewed from the light source side. The reticle 14 is arranged in such a manner. In the case of the photopolymerization, the film (not shown) of the polymerizable composition in the glass unit is covered with a light-shielding portion (a portion other than the opening portion) of the photomask. (Making the film into the light shielding portion) The photomask is placed. Further, when the photomask is disposed, when the light source is viewed from the light source side, the end portion (outer edge portion) of the photomask is placed so as not to pass through the film (as viewed from the light source side) The photomask is disposed in such a manner that the photomask 14 is always present on the film. Further, when viewed from the light source side, the mask is moved (again, the moving direction is described later) so that the short side of the opening does not pass through the film (the opening portion 14A is viewed from the light source side). The short side is adjacent to the opening in the figure The two sides of the long-side substrate 12 of 14A are arranged in a parallel manner. Further, the light source is disposed such that the film is irradiated with light through the opening of the reticle (assuming that the reticle is not present, the light source is disposed at a position where the light can be irradiated to the entire surface of the film). Accordingly, by the movement of the photomask, the photomask, the film, and the light source are arranged such that the light is irradiated onto the entire film. Further, at the time of light irradiation, only the light that has passed through the opening 14A is irradiated onto the film. Further, the length (mm) of the long side of the opening portion 14A of the photomask 14 is designed to be longer (length: 30 mm) than the length (25 mm) of the soda glass substrate forming the glass unit, and the length of the short side is set to 3.0 mm.

After the light source, the mask, and the film are disposed in this way, the light is irradiated from the light source, and the mask is moved at a speed of 20 μm/s while irradiating the light, and the film is introduced into the exposure portion formed by the opening 14A, and is introduced into the exposure. A part of the film of the part begins to polymerize. Subsequently, the photomask was continuously moved at a speed of 20 μm/s while directly irradiating the light, and the boundary S between the light-irradiated region and the non-irradiated region (the boundary of the light-irradiated region formed by one of the long sides of the opening portion 14A) was 20 μm/ s moves toward the unirradiated region of the film, and irradiates light to the entire film to perform photopolymerization of the film. Further, the photopolymerization was carried out under the conditions of 100 ° C (heating conditions). In the photopolymerization, a high-pressure mercury lamp (trade name "SX-UI501HQ" manufactured by USHIO Co., Ltd.) was used as a light source, and a color filter (IRA-265, UV-D54C, ND (90) manufactured by AGC Technology Co., Ltd. was used in combination. %), ND (40%)), ultraviolet light having an illuminance of 0.2 mW/cm ² (peak wavelength: 366 nm). Further, the moving direction of the boundary S of the irradiation region of the light formed by the opening portion 14A is a direction indicated by an arrow A in the drawing (a direction perpendicular to the long side of the opening portion 14A and parallel to the short side of the opening portion 14A). Direction). In this manner, the entire film was irradiated with light, and after photopolymerization, the film was allowed to stand at 100 ° C for 10 minutes to carry out polymerization of the compound in the film, followed by polymerization. A post-polymerization step is applied to obtain a polarizing film in a glass unit.

<Evaluation of characteristics of polarizing film>

In order to confirm the film characteristics thus obtained, the glass unit was inserted between two polarizing plates arranged orthogonally, and while rotating the glass unit, the dark glass field and the bright field of view were observed, and it was confirmed that the obtained film was about 20 mm square. The film is a film in which the liquid crystal compound is substantially uniformly aligned. Further, the direction of the dark field of view is parallel or perpendicular to the absorption axis of the two polarizing plates arranged orthogonally (light and dark appear when the unit is rotated by 45°). In addition, the alignment state of the compound exhibiting liquid crystallinity and the dichroic dye (DR1) in the polarizing film was confirmed using a polarizing microscope (trade name "BX50" manufactured by Olympas Co., Ltd.), and the components in the obtained film were uniformly aligned to each other. The area is also confirmed to be aligned.

Further, in order to confirm the alignment direction of the compound in the polarizing film thus obtained, the absorption spectrum (A⊥) perpendicular to the long side of the opening portion 14A of the mask and the long side of the opening portion 14A of the mask are measured. Absorption spectrum in parallel direction (A//). Further, the absorption spectrum was measured by using an ultraviolet-visible spectrophotometer (V-650ST manufactured by JASCO Corporation), and the direction of polarization was adjusted using Glan Taylor. Fig. 10 is a graph showing the absorption spectrum, and an enlarged view of the graph of the absorbance of the absorption spectrum of Fig. 10 between 0 and 0.2 is shown in Fig. 11. Further, for reference, the absorption spectrum of the dichroic dye (DR1) used in Example 1 is shown in Fig. 12. Further, the measurement of the absorption spectrum of the dichroic dye (DR1) is prepared by dissolving the dichroic dye (DR1) in THF (concentration: 2.86 × 10 ^-5 mol/L), and the solution is prepared. After the measurement sample was produced by introducing it into a quartz cell, it was measured using an ultraviolet-visible spectrophotometer (V-650ST manufactured by JASCO Corporation).

As can be seen from the results shown in FIGS. 10 to 11, the absorption spectrum (A⊥) of the obtained polarizing film in the direction perpendicular to the long side of the opening is in the range of about 350 nm or less, and the ratio of the absorbance to the opening is confirmed. The absorption spectrum (A//) in the direction parallel to the long side is large, and the absorption spectrum (A⊥) perpendicular to the long side of the opening is in a region having a wavelength of 400 nm or more and 600 nm or less, and the ratio of the absorbance to the opening is confirmed. The absorption spectrum (A//) of the long side parallel direction is large. Further, as is understood from the results shown in Fig. 12, it was confirmed that the absorption maximum wavelength of light of the dichroic dye (DR1) was 487 nm, and the molar absorption coefficient ε was 24587 M ^-1 cm ^-1 . From the results, it is understood that in the absorption spectrum of the polarizing film shown in FIGS. 10 to 11, the absorbance of the absorption spectrum (A⊥) in the direction perpendicular to the long side of the opening is increased in a region having a wavelength of 400 nm or more and 600 nm or less. Mostly derived from dichroic pigments (DR1). Further, the absorption spectrum (A//) in the direction parallel to the long side of the opening portion and the absorption spectrum (A⊥) in the vertical direction in the region having a wavelength of about 350 nm or less are greatly increased by the absorption of A6CB. Since the wavelength is 295 nm, it is derived from a compound exhibiting liquid crystallinity (a polymer having a structural unit derived from A6CB).

Further, as a result of the absorption spectrum shown in Figs. 10 to 11, a compound exhibiting liquid crystallinity (having a cluster derived from a structural unit derived from A6CB) The ordered parameter S of the alignment of the dichroic dye (DR1) is obtained by the following formula (1): S = (A ⊥ - A / /) / (A ⊥ + 2A / /) ( 1)

[wherein A ⊥ represents the intensity of the absorption spectrum in the vertical direction, and A / / represents the intensity of the absorption spectrum in the parallel direction]. Further, the order parameter S of the compound exhibiting liquid crystallinity (polymer having a structural unit derived from A6CB) is obtained by measuring absorbance data per 1 nm scale from 330 nm to 341 nm at the wavelength, and determining the order parameter of each wavelength. The values of the ordered parameters of the respective wavelengths are averaged and obtained. On the other hand, the ordered parameter S of the dichroic dye (DR1) is obtained by measuring the absorbance data per 1 nm scale between 470 nm and 570 nm, and determining the order parameters of each wavelength, and then ordering the parameters of each wavelength. The values are averaged and found. The order parameter S of the dichroic dye (DR1) thus obtained was 0.360, and the order parameter S of the liquid crystal compound (polymer having a structural unit derived from A6CB) was 0.243, and the order of each component was The parameter S shows a very large value.

From the above results, it was confirmed that the compound exhibiting liquid crystallinity (polymer having a structural unit derived from A6CB) and the dichroic dye (DR1) of the polarizing film obtained in Example 1 were attached to the opening of the photomask. The sides (the sides adjacent to the boundary S in Fig. 9) are aligned in the vertical direction. Thus, it was confirmed that the liquid crystal-displaying compound of the film obtained in Example 1 was aligned in the same direction as the dichroic dye (DR1), and the polarizing property was exhibited. From the results, it can be seen that according to the method adopted in Embodiment 1, even if there is no utilization with alignment control The substrate of the force can efficiently align the compound exhibiting liquid crystallinity with the dichroic dye (DR1) in the same direction, and the polarizing film can be efficiently produced.

(Example 2)

In place of the use of the thiophene-based dye compound represented by the following formula (7) (hereinafter sometimes referred to as "TR5"), the compound (DR1) represented by the above formula (6) is used as the dichroic dye:

A polarizing film was obtained in the same manner as in Example 1 (the content of the dichroic dye (TR5) was 0.5 mol% based on the total amount of the polymerizable composition. It is 0.82% by mass)).

<Evaluation of characteristics of polarizing film>

In order to confirm the film characteristics thus obtained, the glass unit was inserted between two polarizing plates arranged orthogonally, and while viewing the glass unit, the dark glass field and the bright field of view were observed, and it was confirmed that the obtained film was about A film of a substantially uniform alignment of a liquid crystalline compound in a region of 20 mm square. Further, the direction of the dark field is parallel or perpendicular to the absorption axis of the two polarizing plates arranged orthogonally (light and dark appear when the unit is rotated by 45°). In addition, the alignment state of the liquid crystal compound and the dichroic dye (TR5) in the polarizing film was confirmed using a polarizing microscope (trade name "BX50" manufactured by Olympas Co., Ltd.), and as a result, each component in the obtained film was uniformly aligned, even if it was minute. The area is also confirmed to be aligned.

Further, in order to confirm the alignment direction of the compound in the polarizing film thus obtained, the absorption spectrum (A⊥) perpendicular to the longitudinal direction of the opening portion 14A of the mask was measured in the same manner as in Example 1, and The absorption spectrum (A//) of the long side parallel direction of the opening portion 14A of the mask. Figure 13 shows the absorption spectrum. Further, for reference, the absorption spectrum of the dichroic dye (TR5) used in Example 2 is shown in Fig. 14 . Further, the measurement of the absorption spectrum of the dichroic dye (TR5) is prepared by dissolving the dichroic dye (TR5) in THF (concentration: 1.57 × 10 ^-5 mol/L), and the solution is prepared. After the measurement sample was produced by introducing it into a quartz cell, it was measured using an ultraviolet-visible spectrophotometer (V-650ST manufactured by JASCO Corporation).

As is clear from the results shown in FIG. 13, it is confirmed that the absorption spectrum (A⊥) of the obtained polarizing film perpendicular to the longitudinal direction of the opening is in the region of about 340 nm or less, and the absorbance ratio is longer than the opening. The absorption spectrum (A//) in the side parallel direction is large, and the absorption spectrum (A⊥) perpendicular to the long side of the opening is in a region of a wavelength of 390 nm or more and 500 nm or less, and the absorbance ratio is longer than the opening. The absorption spectrum (A//) in the parallel direction is large. Further, as is clear from the results shown in Fig. 12, it was confirmed that the absorption maximum wavelength of light of the dichroic dye (TR5) was 423 nm, and the molar absorption coefficient ε: 59400 M ^-1 cm ^-1 . From the results, in the absorption spectrum of the polarizing film shown in FIG. 13 , in the region of the wavelength of 390 nm or more and 500 nm or less, the absorbance of the absorption spectrum (A⊥) perpendicular to the longitudinal direction of the opening is increased. From the dichroic pigment (TR). Further, the absorption spectrum (A//) in the direction parallel to the long side of the opening is increased in absorbance (A⊥) in the vertical direction in a region having a wavelength of about 340 nm or less, which is derived from liquid crystallinity. A compound (a polymer having a structural unit derived from A6CB).

Next, based on the results of the absorption spectrum shown in FIG. 13, The compound exhibiting liquid crystallinity in the film obtained in Example 2 (having a source derived from A6CB) was obtained in the same manner as in the first embodiment except that the absorbance data per 1 nm scale between the measurement wavelengths of 324 nm and 340 nm was used. Ordered parameter S of the polymer of the structural unit). Further, based on the result of the absorption spectrum shown in Fig. 13, the ordered parameter S of the dichroic dye (TR5) was also determined. Further, the order parameter S of the dichroic dye (TR5) is the same as in the first embodiment except that the absorbance data (the result of the absorption spectrum shown in Fig. 13) per 1 nm scale from 390 nm to 500 nm is used. The method used is also obtained. As a result of the measurement, the order parameter S of the liquid crystal-displaying compound (polymer having a structural unit derived from A6CB) in the film obtained in Example 2 was a very large value showing 0.271, and dichroism The ordered parameter S of the pigment (TR5) also shows a very large value of 0.126.

From the above results, it was confirmed that the polarizing property obtained in Example 2 was obtained. The film exhibiting liquid crystallinity (polymer having a structural unit derived from A6CB) and the dichroic dye (TR5) are perpendicular to the long side of the opening of the mask (the side adjacent to the boundary S in FIG. 9). Direction alignment. From this, it was confirmed that the liquid crystal-displaying compound of the film obtained in Example 2 was aligned in the same direction as the dichroic dye (TR5), and the polarizing property was exhibited. From this result, it was confirmed that, according to the method used in Example 2, even if the substrate having the alignment control force is not used, the liquid crystal-displaying compound and the dichroic dye (TR5) can be efficiently aligned in the same direction, and The polarizing film can be efficiently produced.

(Example 3)

Except that the UV illumination from 0.20mW / cm ² was changed to 1.0mW / cm ² (peak wavelength: 366nm) except that in Example 2 than the same obtained polarizing film.

<Evaluation of characteristics of polarizing film>

In order to confirm the film characteristics thus obtained, the glass unit was inserted between two polarizing plates arranged orthogonally, and while viewing the glass unit, it had a dark field of view and a bright field of view, and it was confirmed that the obtained film was about 20 mm square. A film in which a regional liquid crystalline compound is substantially uniformly aligned. Further, the direction of the dark field is parallel or perpendicular to the absorption axis of the two polarizing plates arranged orthogonally (light and dark appear when the unit is rotated by 45°). In addition, a polarizing microscope (trade name "BX50" manufactured by Olympas Co., Ltd.) was used to confirm the liquid crystal compound and the dichroic dye (TR5) in the polarizing film. In the alignment state, the components in the obtained film were uniformly aligned, and the alignment was confirmed even in the minute regions.

In order to confirm the compound in the polarizing film thus obtained In the alignment direction, the absorption spectrum (A ⊥) perpendicular to the long side of the opening portion 14A of the mask and the absorption in the direction parallel to the long side of the opening portion 14A of the mask were measured in the same manner as in the first embodiment. Spectrum (A//). Figure 15 shows the absorption spectrum.

It can be understood from the results shown in Fig. 15 that the obtained polarized light is confirmed. The absorption spectrum (A⊥) of the film in the direction perpendicular to the long side of the opening is larger in the region of the wavelength of 500 nm or less, and the absorbance is larger than the absorption spectrum (A//) in the direction parallel to the long side of the opening. In addition, in FIG. 15, in the region of the wavelength of 400 nm or more and 500 nm or less, the increase in the absorbance of the absorption spectrum (A⊥) perpendicular to the long side of the opening is derived from the dichroic dye (TR5) (see Fig. 14), and the increase in absorbance spectrum (A ⊥) in a region having a wavelength of about 360 nm or less is derived from a compound exhibiting liquid crystallinity (a polymer having a structural unit derived from A6CB).

Next, based on the result of the absorption spectrum shown in FIG. 15, The compound exhibiting liquid crystallinity in the film obtained in Example 3 (having a structure derived from A6CB) was obtained in the same manner as in Example 1 except that the absorbance data per 1 nm scale between 335 nm and 365 nm was measured. Ordered parameter S of the polymer of the unit). Further, based on the results of the absorption spectrum shown in FIG. 15, the dichroic dye (TR5) was determined in the same manner as in the second embodiment except that the absorbance data per 1 nm scale between 400 nm and 460 nm was measured. Ordered parameter S. By this As a result of the measurement, the order parameter S of the compound exhibiting liquid crystallinity (polymer having a structural unit derived from A6CB) in the film obtained in Example 3 showed a very large value of 0.105, and the dichroic dye (TR5) The ordered parameter S also shows a very large value of 0.113.

From the above results, it was confirmed that the polarizing property obtained in Example 3 was obtained. The film exhibiting liquid crystallinity (polymer having a structural unit derived from A6CB) and the dichroic dye (TR5) are perpendicular to the long side of the opening of the mask (the side adjacent to the boundary S in FIG. 9). Direction alignment. From this, it was confirmed that the liquid crystal-displaying compound of the film obtained in Example 3 was aligned in the same direction as the dichroic dye (TR5), and the polarizing property was exhibited. From the results, it was confirmed that according to the method used in Example 3, even if the substrate having the alignment control force is not used, the compound exhibiting liquid crystallinity can be efficiently aligned with the dichroic dye (TR5) in the same direction, and The polarizing film is efficiently produced.

As understood from the above results, it is confirmed that the examples 1 to 3 are In the obtained film, a polarizing film which uniformly aligns the liquid crystalline compound and the dichroic dye throughout the polymerization region is formed, and it is understood that a large-area polarizing film can be produced by the method for producing a polarizing film of the present invention.

[Industrial availability]

As described above, according to the present invention, it is possible to provide a method for producing a polarizing film which can efficiently produce a large-area polarizing film which forms an alignment region of a liquid crystal compound and a dichroic dye.

Accordingly, the method for producing a polarizing film of the present invention is A method which is particularly excellent in the alignment of the liquid crystal compound and the dichroic dye can be used in a wide area, and can be used as a polarizing element used in an image display device such as a liquid crystal display (LCD) or an organic EL display. A method for producing a polarizing film or the like.

Claims (8)

A method for producing a polarizing film, which comprises a film comprising at least one of a polymerizable compound exhibiting liquid crystallinity before and/or after polymerization, and a polymerizable composition of at least one of a dichroic dye. After the polymerization of the polymerizable composition is started from a portion of the film, the boundary between the region is oriented toward unpolymerized at a rate at which the liquid crystal-displaying compound present in the film is aligned with the dichroic dye. The region is continuously moved to obtain a polarizing film. The method for producing a polarizing film according to claim 1, wherein the boundary of the light irradiation region is continuously moved toward the light non-irradiated region to carry out polymerization of the polymerizable composition by photopolymerization, and the boundary is continuously moved toward the unpolymerized region. . The method for producing a polarizing film according to claim 2, wherein a photomask is used for the photopolymerization, and the boundary between the light irradiation region is continuously moved toward the light non-irradiation region by continuously moving the photomask and/or the film. The method for producing a polarizing film according to any one of claims 1 to 3, wherein the speed at which the boundary is moved is 1 × 10 ^-7 to 4 × 10 ^-1 m/s. The method for producing a polarizing film according to any one of claims 1 to 4, wherein the polymerizable compound is represented by the following formula (1), and wherein Z ¹ , Z ² , M ¹ , M ² , M ³ , L ¹ , L ² , p, q, and r are each at least one compound selected from the group consisting of the following compounds C11 to C17: Z ¹ pM ¹ -L ¹ -(M ² -L ² qM ³ -Z ² r (1) [In compound C11, Z ¹ and Z ² in the formula (1) may be the same or different, and each is represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acrylic group and a methacryl group, and S ¹ is any one of a single bond and a linear alkyl group having 1 to 12 carbon atoms, and L ³ is a single bond, an ether group, or an ester group. And any one of the carbonate groups, p is 1, M ¹ is 1,4-phenylene, L ¹ is any of a single bond and -COO-, q is 0, and M ³ is 1,4 - phenyl group, and r is 1, in the compound C12, Z ¹ and Z ² in the formula (1) may be the same or different, respectively, a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is any one of an acrylic group and a methacryl group, and S ¹ is any one of a single bond and a linear alkyl group having 1 to 12 carbon atoms, and L ³ is a single bond, an ether group, or an ester group. And carbon According to any one of the ester group, p is ^1, M 1 is 1,4-phenylene, L ¹ is -COO-, M ² is 1,4-phenylene, L ² is -OCO-, q is 1, M ³ is 1,4-phenylene, and r is 1, and in compound C13, Z ¹ and Z ² in the formula (1) may be the same or different, and are respectively of the formula: -L ³ -S ¹ -F ¹ represents a group, and F ¹ is any one of an acryl group and a methacryl group, and S ¹ is a formula: (CH ₂ CH ₂ O)z (z is any one of 2 or 3) The group represented by L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is any of a single bond and an ester group, q is 0, and M ³ is 1,4-extension. Phenyl, and 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 , and F ¹ is an acryl group and a methacryl group Either S ¹ is a single bond, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, and M ³ is 1,4-Benzene. Further, Z ^{2 is one selected} from the group consisting of 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 the compound C15 is formula Z (1) is ¹ in the formula: -L ³ -S ¹ -F ¹ represents the group, and F. ¹ is any acrylic group and methacrylic group of Who, S ¹ is a C 1-4 straight-chain alkylene group of 1 to 12, L ³ is an ether group, p is ^1, M 1 is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ Is a 1,4-phenylene group, and Z ^{2 is one selected} from the group consisting of 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 in the compound C16, Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is any one of 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 or 3), L ³ is a single bond, p is 1, and M ¹ is a 1,4-phenylene group. , L ¹ is a single bond, q is 0, M ³ is 1,4-phenylene, 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 a carbon number of 1. One of the alkoxy groups of ~12, and r is 1, and in the compound C17, Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is Any one of an acrylic group and a methacrylic group, S ¹ is a linear alkyl group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, and M ¹ is a 1,4-phenyl group, L ¹ is -COO-, q is 0, M ³ is 1,4-phenylene, and Z ² is hydrogen atom, halogen atom, cyano group, nitro group, carbon number 1 One of the alkyl group of ~12 and the alkoxy group of 1 to 12 carbon atoms, and r is 1]. The method for producing a polarizing film according to any one of claims 1 to 5, wherein the polymerizable composition contains the first compound and is in the same strip In the case of polymerization under polymerization, the polymerization is completed in a second compound longer than the first compound, and at least one of the first and second compounds contains at least one of the polymerizable compounds. The method for producing a polarizing film according to claim 6, wherein the first compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is higher than that of the polymerizable functional group of the second compound. The number is one or more. The method for producing a polarizing film according to claim 6 or 7, wherein the first compound is a compound represented by the following formula (1) and wherein Z ¹ , Z ² , M ¹ , M ² , M ³ , L ¹ , L ² , p, q, and r are selected from the group consisting of the compounds C11 to C13 shown below, the compound represented by the following formula (2), and the compound represented by the following formula (3), respectively. At least one compound, general formula (1): Z ¹ pM ^{1 -} L ¹ - (M ^{2 -} L ² ) qM ^{3 -} Z ² r (1) [in compound C11, Z ¹ in formula (1) Z ² 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 any one of an acrylic group and a methacryl group, and S ¹ is a single bond and a carbon number. Any one of linear alkyl groups of 1 to 12, wherein L ³ is any one of a single bond, an ether group, an ester group and a carbonate group, p is 1, and M ¹ is a 1,4-phenylene group. , L ¹ is any one of a single bond and -COO-, q is 0, M ³ is 1,4-phenylene, and r is 1, in compound C12, Z ¹ and Z in formula (1) ² may be identical or different, are represented by the formula: -L ³ -S ¹ -F ¹ represents the group, F ¹ is any one of acrylic group and methacrylic group of one, S ¹ is a single bond Any carbon atoms of straight-chain alkylene group having 1 to 12 in the one, L ³ is a single bond, ether group, an ester group and a carbonate of any group of one, p is ^1, M 1 1,4 Phenyl group, L ¹ is -COO-, M ² is 1,4-phenylene, L ² is -OCO-, q is 1, M ³ is 1,4-phenylene, and r is 1, compound C13 In the formula (1), Z ¹ and Z ² 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 acrylic group and a methacryl group. In one case, S ¹ is a group represented by the formula: (CH ₂ CH ₂ O)z (z is any one of 2 or 3), L ³ is a single bond, p is 1, and M ¹ is 1,4- Phenyl is extended, L ¹ is any of a single bond and an ester group, q is 0, M ³ is 1,4-phenylene, and r is 1], and formula (2): (wherein R ⁵ is any one of hydrogen and methyl, x is 2 or 3), and formula (3): [Chemical 2] (wherein R ⁵ is any one of hydrogen and methyl, y is an integer of 2 to 12), and the aforementioned second compound is represented by the following formula (1) and Z ¹ and Z ² in the formula And M ¹ , M ² , M ³ , L ¹ , L ² , p, q, and r are at least one compound selected from the group consisting of compounds C14 to C17 shown below: Z ¹ pM ¹ -L ¹ -(M ² -L ² )qM ³ -Z ² r (1) [In compound C14, the Z ¹ in the formula (1) is represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is Any one of an acrylic group and a methacrylic group, S ¹ is a single bond, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, and q is 0. M ³ is a 1,4-phenylene group, and Z ^{2 is one selected} from the group consisting of 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 in the compound C15, Z ¹ in the formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is any one of an acrylic group and a methacryl group. , S ¹ is a linear alkyl 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 a single bond, q is 0, and M ³ is 1,4-phenylene, Z ^{2 is} composed of hydrogen atom, halogen atom, cyano group, nitro group, carbon One of the alkyl group having 1 to 12 carbon atoms and the alkoxy group having 1 to 12 carbon atoms, and r is 1, and in the compound C16, the Z ¹ in the formula (1) is of the formula: -L ³ -S ¹ -F ¹ represents a group, and F ¹ is any one of an acryl group and a methacryl group, and S ¹ is represented by the formula: (CH ₂ CH ₂ O)z (z is any one of 2 or 3) a group, L ³ is a single bond, p is 1, M ¹ is 1,4-phenylene, L ¹ is a single bond, q is 0, M ³ is 1,4-phenylene, and Z ² is hydrogen. One selected from the group consisting of an 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, in the compound C17, in the formula (1) Z 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 linear alkyl group having 1 to 12 carbon atoms. L ³ is a ketone group, p is 1, M ¹ is 1,4-phenylene, L ¹ is -COO-, q is 0, M ³ is 1,4-phenylene, and Z ² is a hydrogen atom. One selected from the group consisting of 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].