JP2016053657A - Manufacturing method for optical film having periodic structure - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a manufacturing method for an optical film having a periodic structure, which facilitates manufacturing of an optical film having a periodic structure with sufficiently advanced periodicity formed thereon.SOLUTION: A manufacturing method for an optical film with a periodic structure includes steps of; preparing a film made of a polymerizable composition containing a first polymerizable compound and a second polymerizable compound that requires longer time to complete polymerization than the first polymerizable compound when both are polymerized under same conditions, where at least one of the first polymerizable compound, the second polymerizable compound, and a compound obtained after polymerization is a compound that exhibits a liquid crystalline property; starting polymerization of the polymerizable composition from a partial region of the film; competing the polymerization by continuously moving a border of the region toward an unpolymerized region at a speed that allows the compound with the liquid crystalline property to be oriented; and cooling the polymerized film to obtain an optical film with a periodic structure. The polymerization is done while heating the film at a heating temperature of 80-150°C, and the cooling of the film is done at a cooling rate of 0.1-30°C/minute at least until the temperature of the film is reduced to 60°C from temperature that equals the heating temperature used while polymerizing the film.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an optical film having a periodic structure.

  In general, when an object has a periodic structure in the order of the wavelength of light, there is a characteristic that it strongly acts on light having a specific wavelength corresponding to the period. When light is reflected by an object having such a periodic structure, the reflection direction of the light varies depending on the wavelength, and the light is decomposed into different wavelength components. Examples of objects having such a periodic structure include a diffraction grating and a photonic crystal. As such a diffraction grating, for example, a grating pattern in which linear grooves are arranged in parallel at equal intervals with a period of a micrometer order is widely known. Such a diffraction grating is an element having high utility value such as being used as a spectroscopic element such as a spectrometer or a monochromator. The photonic crystal is, for example, “Materials Research Outlook, P227-P231 (Non-Patent Document 1)” issued on August 1, 2006, or “Introduction to Photonic Crystal (Non-Patent Document 2)” issued in 2004. As illustrated in the above, the fine particles having the same particle diameter are formed periodically at intervals of the wavelength order of light. Thus, in the periodic structure (photonic crystal) of fine particles arranged in the order of the wavelength of light, the light energy forbidden band (photonic band gap) is formed in all orientations in the crystal, A state is formed in which light of a wavelength cannot exist. For example, by introducing a minute defect structure into a crystal having such a structure, it is possible to efficiently extract confined and amplified light, and to produce a minute laser with a very low threshold. It is thought to be.

  Regarding such a diffraction grating or photonic crystal, first, as an industrial manufacturing method of a diffraction grating, for example, a method of manufacturing by a method of mechanically engraving a linear groove of a micron order, photolithography or laser A method of manufacturing by an optical method such as a holographic exposure method using two-interference exposure is known. However, in such a conventional method for manufacturing a diffraction grating, a special machine is required for engraving a groove, or a special material having photosensitivity as an exposed material even when using an optical technique. There are many manufacturing restrictions such as the need to use a new material, and it has not always been possible to easily manufacture a diffraction grating. On the other hand, when manufacturing the photonic crystal as described above, it is necessary to uniformly arrange three-dimensionally the fine particles having a substantially uniform particle size in the wavelength order of light. Therefore, when manufacturing a photonic crystal, a structure having a fine periodic structure is required as a substrate (a template for growing a photonic crystal) serving as a base for arranging such particles. However, the manufacture of a structure having such a fine periodic structure has not always been easy to manufacture, like the diffraction grating described above. Therefore, it is possible to more easily manufacture an optical film on which a periodic structure having a sufficiently high periodicity that can be used for a diffraction grating or a template for growing a photonic crystal is formed. A new method for producing optical films is desired.

"Fiscal 2006 Materials and Materials Research Outlook", National Institute for Materials Science, August 1, 2006, P227-P231 Kazuaki Sakoda, “Introduction to Photonic Crystals”, published by Morikita Publishing, 2004

  The present invention has been made in view of the above-described problems of the prior art, and has a periodic structure capable of more easily producing an optical film on which a periodic structure having a sufficiently high periodicity is formed. It aims at providing the manufacturing method of an optical film.

  As a result of intensive studies to achieve the above object, the present inventors have found that when the first polymerizable compound is polymerized under the same conditions, the polymerization completion time is longer than that of the first polymerizable compound. And a polymerizable composition comprising at least one of the first polymerizable compound, the second compound, and the compound obtained after polymerization, wherein the compound exhibits liquid crystallinity. Using the film, polymerization of the polymerizable composition is started from a partial region of the film, and the boundary of the region is continuously directed toward the unpolymerized region at such a rate that the compound exhibiting liquid crystallinity is aligned. After the polymerization, the film after polymerization is cooled, during the polymerization, the film is polymerized while being heated to a heating temperature of 80 to 150 ° C., and the cooling is performed. Furthermore, the temperature of the film is adopted at least during the polymerization. By cooling the film at a cooling rate of 0.1 to 30 ° C./min from the same temperature as the heating temperature to 60 ° C., surprisingly, it is sufficiently advanced in the optical film after polymerization. The inventors have found that it is possible to form a periodic structure having periodicity, and have completed the present invention.

That is, the method for producing an optical film having a periodic structure according to the present invention includes the first polymerizable compound and the second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions. And a film made of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity And
Polymerization of the polymerizable composition is started from a partial region of the film, and the boundary of the region is continuously moved toward an unpolymerized region at such a speed that the compound exhibiting liquid crystallinity is aligned. After polymerization, the step of cooling the polymerized film to obtain an optical film having a periodic structure,
Polymerizing the film while heating at a heating temperature of 80 to 150 ° C. during the polymerization; and
During the cooling, the film is cooled at a cooling rate of 0.1 to 30 ° C./min until the temperature of the film reaches at least 60 ° C. from the same heating temperature employed during the polymerization,
It is the method characterized by this.

In the method for producing an optical film having the periodic structure of the present invention, the optical film having the periodic structure is:
An average value of diffraction intensities of the first-order diffracted light measured when a helium neon laser having a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of the optical film;
The method of the present invention except that the method of cooling the film by immersing the polymerized film in liquid nitrogen for 5 seconds without using the method of cooling at the cooling rate is adopted at the time of cooling. Measured when a helium neon laser with a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of a transmitted light measurement film obtained by adopting the same method as the film production method. The average value of transmitted light intensity,
Based on the following formula (1):
[E] = ([Is] / [Ir]) × 100 (1)
[In the formula (1), Is represents the average value (unit: mW) of the diffraction intensity of the first-order diffracted light of the optical film, and Ir represents the average value (unit: mW) of the transmitted light intensity of the transmitted light measurement film. ) And E represents diffraction efficiency (unit:%). ]
It is preferable that the optical film has a diffraction efficiency of 5% or more obtained by calculating.

  In the method for producing an optical film having a periodic structure according to the present invention, the cooling rate is preferably a cooling rate of 0.8 to 12 ° C./min.

  In the method for producing an optical film having a periodic structure according to the present invention, the first polymerizable compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is the second number. It is preferable that it is 1 or more larger than the number of polymerizable functional groups possessed by the compound.

  In the method for producing an optical film having a periodic structure of the present invention, the polymerizable composition is polymerized by photopolymerization, and the boundary is continuously moved toward an unpolymerized region. It is preferable that the boundary of the light irradiation region is continuously moved toward the non-light irradiation region.

  Furthermore, in the method for producing an optical film having a periodic structure according to the present invention, a photomask is used for the photopolymerization, and the photomask is continuously moved to light the boundary of the light irradiation region. It is preferable to move continuously toward the unirradiated region.

Moreover, in the manufacturing method of the optical film which has the periodic structure of the said invention, it is preferable that the speed | rate which moves the said boundary is 1 * 10 < ^-7 > -4 * 10 < ^-1 > m / s.

  Furthermore, in the method for producing an optical film having a periodic structure according to the present invention, the first polymerizable compound is at least one compound selected from the group consisting of the following compounds C11 to 15; The two compounds are preferably at least one compound selected from the group consisting of the following compounds C21 to 24. Thus, as a combination of the first polymerizable compound and the second compound in the polymerizable composition, at least one compound selected from the group consisting of the following compounds C11 to 15 and the following compound C21: A combination with at least one compound selected from the group consisting of ˜24 is preferred.

Here, the compounds C11 to C13 that can be selected as the first polymerizable compound are represented by the following general formula (1):
^{Z 1 p-M 1 -L 1} - (M 2 -L 2) q-M 3 -Z 2 r (1)
A compound represented by:
In the compound C11, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is acrylic Any one of a group and a methacryl group, S ¹ is any ^one of a single bond and a linear alkylene group having 1 to 12 carbon atoms, and L ³ is an ether group, an ester group or a carbonate group. Any (more preferably an ether group), p is 1, M ¹ is a 1,4-phenylene group, and L ¹ is either a single bond or —COO— (more preferably a single bond). ), Q is 0, M ³ is a 1,4-phenylene group, and r is 1.
In the compound C12, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is acrylic Any one of a group and a methacryl group, S ¹ is either a single bond or a linear alkylene group having 1 to 12 carbon atoms, and L ³ is an ether group, an ester group or a carbonate group. Any one (preferably an ether group), p is 1, M ¹ is a 1,4-phenylene group, L ¹ is —COO—, and M ² is a 1,4-phenylene group. , L ² is —OCO—, q is 1, M ³ is a 1,4-phenylene group, and r is 1,
In the compound C13, Z ¹ and Z ² in the formula (1) may be the same or different and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acrylic group Or a methacryl group, and S ¹ is a group represented by the formula: (CH ₂ CH ₂ O) z (z is any one of 2 and 3), and L ³ Is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is either a single bond or an ester group (more preferably a single bond), and q is 0. , M ³ is a 1,4-phenylene group, and r is 1.

  The compound C14 that can be selected as the first polymerizable compound is represented by the following general formula (2):

(In the formula, R ⁵ is either hydrogen or a methyl group, and x is 2 or 3.)
A compound represented by
The compound C15 that can be selected as the first polymerizable compound is represented by the following general formula (3):

(In the formula, R ⁵ is either hydrogen or a methyl group, and y is an integer of 2 to 12.)
It is a compound represented by these.

Compounds C21 to C24 that can be selected as the second compound are represented by the following general formula (1):
^{Z 1 p-M 1 -L 1} - (M 2 -L 2) q-M 3 -Z 2 r (1)
A compound represented by:
In compound C21, Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is A single bond, L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is 1, 4-phenylene group, and Z ² is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms (more preferably Is a cyano group) and r is 1.
In compound C22, Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is A linear alkylene group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, and q is 0 M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. A compound selected from one (more preferably a cyano group) and r is 1.
In compound C23, Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is A group represented by the formula: (CH ₂ CH ₂ O) z (z is 2 or 3), L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group. L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, or a carbon number of 1 to 12. A compound selected from an alkyl group and an alkoxy group having 1 to 12 carbon atoms (more preferably a cyano group), and r is 1.
In Compound C24, 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 has 1 to 12 carbon atoms A linear alkylene group, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is —COO—, q is 0, and M ³ Is a 1,4-phenylene group, and Z ² is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms (More preferably a cyano group) and r is 1.

  In the present invention, polymerization is performed while orienting a compound exhibiting liquid crystallinity during polymerization (at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization), After the polymerization, when the film is cooled, the periodic structure is formed in the film by cooling at the predetermined cooling rate at least in the predetermined temperature range. The principle of the formation of such an orientation or periodic structure is described with reference to an example of a preferred embodiment in which a photopolymerizable compound is used as the first polymerizable compound or the second compound. This will be briefly described with reference to FIG. In the following description and drawings, the same or corresponding elements are denoted by the same reference numerals, and redundant descriptions are omitted.

  FIG. 1 is a schematic longitudinal sectional view schematically showing a state before starting photopolymerization on a film made of a polymerizable composition. 2 is a schematic longitudinal sectional view schematically showing a state in which polymerization is started from a partial region of the film by irradiating light from a light source, and FIG. 3 shows the boundary of the polymerization region in FIG. FIG. 4 is a schematic longitudinal sectional view schematically showing a state after being moved toward an unpolymerized region, and FIG. 4 is a state after the boundary of the polymerized region in FIG. 3 is moved toward the unpolymerized region. It is a schematic longitudinal cross-sectional view which shows typically. In the figure, the dotted line S indicates the boundary of the overlapping region, the arrow A conceptually indicates the direction in which the boundary S of the overlapping region is moved, and the arrow L conceptually indicates the light emitted from the light source. A1 conceptually shows a region polymerized by irradiation with light L (polymerization region: exposed portion), and A2 shows an unpolymerized region not irradiated with light L (unpolymerized region: light shielding portion). ) Conceptually, and A3 conceptually indicates a region where orientation is formed.

  In the embodiment shown in FIGS. 1 to 4, when the alignment is formed by photopolymerization, first, as shown in FIG. 1, the light source 11 and the light emitted from the light source 11 can be transmitted. Two substrates 12, a film 13 made of a polymerizable composition disposed between the two substrates 12, and a photomask 14 capable of blocking light emitted from the light source 11. The light source 11 is disposed on one of the two substrates 12 and the light from the light source 11 is irradiated only on a partial region of the film 13 between the film 13 and the light source 11. A photomask 14 capable of shielding a part of the film 13 is disposed. Next, as shown in FIG. 2, the light source 11 is turned on and the light L is emitted from the light source 11. When the light L is irradiated in this manner, the reaction does not proceed and remains unpolymerized in the light shielding portion A2, but the polymerization proceeds in the exposed portion A1 where the light is irradiated. In this way, a part of the area is exposed, and polymerization of the polymerizable composition is started from a part of the film 13 (exposed part) A1. And in area | region (polymerization area | region: exposure part) A1 superposed | polymerized in this way, photopolymerization progresses preferentially from the 1st polymeric compound with shorter polymerization completion time, and the 1st polymeric compound Is preferentially consumed, so that the concentration of the compound in the polymerizable composition is biased between the polymerization region (exposed portion) A1 and the unpolymerized region (light-shielding portion) A2. Thus, when the concentration of the compound is biased in the composition, the diffusion of the substance usually occurs in the direction of eliminating the concentration gradient due to the diffusion phenomenon of the substance. Therefore, when light is irradiated as described above, the diffusion of the compound is induced in the direction of eliminating the concentration gradient at the boundary S between the superposed region (exposed portion) A1 and the non-polymerized region (light-shielding portion) A2, and the unpolymerized region Thus, a compound flow (mainly the flow of the first polymerizable compound) is generated from the light shielding portion A2 to the exposure portion A1 which is the polymerization region. When the flow of the compound from the unpolymerized region A2 to the polymerized region A1 occurs in this way, the compound exhibiting liquid crystallinity by the flow (the first polymerizable compound, the second compound and the polymer present in the polymerized region). At least one compound among the compounds obtained later is subjected to a kind of shear stress, and the compound exhibiting liquid crystallinity is in the vicinity of the boundary S between the polymerization region (exposed portion) A1 and the unpolymerized region (light-shielding portion) A2. In the region, the alignment region A3 is formed (induced). Note that the direction in which the flow due to the movement of such a compound occurs is substantially perpendicular to the boundary S between the polymerization region (exposure portion) A1 and the non-polymerization region (light-shielding portion) A2. In the case of a rod-like one, the average orientation direction is usually a direction substantially perpendicular to the boundary S. Thus, after the polymerization of the polymerizable composition is started from a partial region of the film 13 (see FIG. 2), for example, the photomask 14 is continuously moved so that the boundary S of the polymerization region is unpolymerized. By continuously moving toward the region A2 (see FIGS. 2 to 4), the diffusion of the compound is induced (at a new position) before the boundary S moves, and the orientation caused by photopolymerization and diffusion induction Can be caused continuously. At this time, at a speed at which the compound exhibiting liquid crystallinity is aligned (a speed at which a kind of shear stress generated by the movement of the compound is sufficiently applied to the compound exhibiting liquid crystallinity to form alignment. Thus, by continuously moving the boundary S, it is possible to continuously cause orientation induced by diffusion. And in this invention, after superposing | polymerizing, forming an orientation as mentioned above (preferably after promoting the superposition | polymerization of the whole film | membrane), the film | membrane after superposition | polymerization is at least the heating temperature employ | adopted at the time of superposition | polymerization The periodic structure is formed by cooling at a predetermined cooling rate until the temperature reaches 60 ° C. That is, the present inventors polymerized while forming a heating temperature at 80 to 150 ° C. at the time of the polymerization, and then at the time of cooling the film, the temperature of the film was at least the heating temperature adopted at the time of the polymerization. By cooling the film while controlling the cooling rate from 0.1 to 30 ° C./min from the same temperature to 60 ° C., surprisingly, in the film after polymerization in which the alignment state was formed In addition, it has been found that it is possible to form a periodic structure having a predetermined orientation such as a vortex or a spherical shape of liquid crystal molecules. According to the present invention, the periodic structure is formed by such temperature control during cooling. The manufactured optical film can be easily produced.

  Here, FIG. 5 is a schematic longitudinal sectional view schematically showing an embodiment of the optical film after formation of the periodic structure, and FIG. 6 is a schematic plan view schematically showing the optical film of the embodiment shown in FIG. FIG. In addition, the optical film of such an embodiment has a structure in which the alignment state that looks like a spiral as shown in FIG. 5 is continuously arranged in a direction perpendicular to the paper surface of FIG. 5 (depth direction of the paper surface) ( (See FIGS. 5 and 6). Further, in the schematic plan view shown in FIG. 6, the arrangement state of the vortex-like liquid crystal molecules shown in FIG. 5 is shown for half of the vortices in the depth direction when viewed from the substrate 12 side so that the arrangement state becomes easier to understand. The alignment state of the liquid crystal molecules (the number of liquid crystal molecules forming the outermost layer of the vortex in the depth direction from the substrate 12 side) is schematically shown. Here, the symbol D in FIG. 6 conceptually shows the lattice period (width of one period) of the periodic structure. As described above, a portion that looks like a vortex in the longitudinal cross-sectional view shown in FIG. 5 is the bottom, and has a width in the depth direction of the paper (the vortex alignment state is continuously arranged) (hereinafter referred to as “cylinder shape”). .) Orientation is formed. A state in which the vortex array structure is arranged in three rows in the thickness direction of the paper surface with the region A4 where the vortex array surrounded by dotted lines in FIG. This is schematically shown in FIG. 7 using a cylindrical drawing. Here, in FIG. 7, only the outermost layer in a vortex-like orientation state is schematically shown in consideration of easy viewing. In addition, the arrow A in FIG. 5 is the moving direction of the boundary S at the time of polymerization, and the arrangement of the structure imitating the above-described cylinder (the cylinder imitating the cylinder shown in FIG. 7) They are arranged in a direction perpendicular to the moving direction of the boundary S. In addition, by applying the cooling conditions of the present invention, the liquid crystal molecules are not only aligned in a cylindrical shape as shown in FIGS. 5 to 7, but may be aligned in a spherical shape by appropriately selecting the conditions. obtain. The spherical structure in this case is oriented in the polymerization progress direction (direction in which the boundary S moves).

  In the present invention, as described above, when the polymerization is performed while forming an alignment structure, the polymerization is performed while the heating temperature of the film during polymerization is 80 to 150 ° C., and at least the same temperature as the heating temperature employed during the polymerization. (The temperature at the time of the polymerization: a temperature of 80 to 150 ° C.) to 60 ° C., the cooling rate is 0.1 to 30 ° C./min, and the film after polymerization has a periodic structure. This is a method for obtaining a structure. The principle that the periodic structure is formed is not necessarily clear, but the polymer is generated in the monomer solution by polymerization, and the monomer component that is thermodynamically stable by gradually cooling from the mixed state of the polymer and the monomer. Phase separation occurs in an excessively large area and an excessively large polymer component area, and a cylindrical structure as shown in FIGS. The present inventors infer that. Note that, in the method of forming such a periodic structure, a substrate that has not been subjected to a pretreatment for imparting an alignment regulating force to align liquid crystal molecules in-plane (for example, a rubbing treatment is not performed). It is clear that an optical film having a periodic structure can be efficiently manufactured even after an alignment structure that becomes a precursor structure of the periodic structure is efficiently formed even in the case of using a simple substrate. Therefore, it is possible to efficiently avoid problems such as dust generation and static electricity generated by the rubbing process, dust adhesion and mixing on the optical film, and a periodic structure precursor structure in advance on the substrate or cell. It can be said that it is an efficient method from the viewpoint of workability because it is not necessary to carry out pretreatment for imparting alignment regulating force for aligning liquid crystal molecules in the plane.

  In addition, in the example shown in FIGS. 1-7, the case where the photopolymerizable compound is used as the first polymerizable compound or the second compound is taken as an example, and the principle of orientation formation or formation of a periodic structure is used. However, the present invention uses a diffusion phenomenon of a substance generated by moving the boundary S between the polymerization region (exposure portion) A1 and the unpolymerization region (light-shielding portion) A2 toward the unpolymerization region A2. Since the in-plane orientation of the liquid crystal molecules that become the precursor structure of the periodic structure is induced, the film after polymerization is cooled under a predetermined cooling condition, thereby enabling the formation of the periodic structure. The first polymerizable compound and the second compound are not limited to photopolymerizable compounds as long as they can induce in-plane orientation, and are not photopolymerizable compounds. Other compounds (for example, thermally polymerizable compounds) It may be used. Further, the method for forming the periodic structure of the compound exhibiting liquid crystallinity uses a compound that migrates from an unpolymerized region to a polymerized region in the film after the start of polymerization, and performs in-plane alignment of the compound exhibiting liquid crystallinity After the induction, the phase separation as described above is used to form a periodic structure (preferably a periodic structure in which vortex arrays are periodically arranged). It is possible to form a periodic structure while controlling the direction of orientation in a direction substantially perpendicular to the boundary of. Therefore, for example, when polymerization is performed by photopolymerization, it is possible to change the characteristics of the periodic structure by controlling the orientation in various directions according to the shape of the mask.

  ADVANTAGE OF THE INVENTION According to this invention, it becomes possible to provide the manufacturing method of the optical film which has a periodic structure which can manufacture the optical film in which the periodic structure which has sufficiently high periodicity was formed more simply.

  Such a method for producing an optical film having a periodic structure according to the present invention is obtained in principle because there are few restrictions on the molecular structure and it can be applied to the control of various molecular orientations and higher order structures. An optical film having a periodic structure can be expected to develop into a wide range of functional films, and can be used, for example, as a template for growing a diffraction grating or a photonic crystal.

It is a schematic longitudinal cross-sectional view which shows typically the state before starting photopolymerization with respect to the film | membrane which consists of polymeric compositions. It is a schematic longitudinal sectional view schematically showing a state in which polymerization is started from a partial region of the film by irradiating light from a light source, It is a schematic longitudinal cross-sectional view which shows typically the state after moving the boundary of the superposition | polymerization area | region in FIG. 2 toward the unpolymerization area | region. It is a schematic longitudinal cross-sectional view which shows typically the state after moving the boundary of the superposition | polymerization area | region in FIG. 3 toward the unpolymerization area | region. It is a schematic longitudinal cross-sectional view which shows typically the state of suitable one Embodiment of the optical film which has a periodic structure. It is a schematic plan view which shows typically the state at the time of seeing the periodic structure of the optical film shown in FIG. 5 from the base material side. It is a schematic diagram which shows notionally what is called a cylindrical periodic structure of the optical film shown in FIG.5 and FIG.6. FIG. 8A is a schematic plan view schematically showing a relationship before starting photopolymerization between the photomask and the substrate when viewed from the light source side (state before moving the boundary of the light irradiation region), FIG. 8B is a schematic plan view schematically showing the relationship after the start of photopolymerization between the photomask and the substrate when the light source side is viewed (a state where the boundary of the light irradiation region is moved). It is a schematic plan view which shows typically the relationship before the photoinitiation of the photomask and substrate which formed the edge diagonally when it sees from the light source side. It is a schematic plan view which shows typically the relationship before the photopolymerization start of the photomask which has a some rectangular opening part, and a board | substrate when it sees from the light source side. It is a schematic plan view which shows typically the relationship before the photopolymerization start of the photomask which has a some rectangular opening part, and a board | substrate when it sees from the light source side. 2 is a photograph of a film (thin film) formed in a glass cell in Example 1. In Example 1, it is a polarizing microscope photograph which shows the state of a film in case the angle which the vibration direction of an analyzer and the moving direction of a photomask make is 45 degrees. In Example 1, it is a polarizing microscope photograph which shows the state of the film in the direction in which the moving direction of a photomask is parallel with respect to the vibration direction of an analyzer. In Example 1, it is a polarizing microscope photograph which shows the state of a film in case the angle which the vibration direction of an analyzer and the moving direction of a photomask make is 45 degrees. It is a polarizing microscope photograph of the state of a film in case the direction of the optical axis of a test plate and the moving direction of a photomask are parallel. It is a polarizing microscope photograph of the state of a film in case the angle which the direction of the optical axis of a test plate and the moving direction of a photomask make is 45 degrees. It is a polarizing microscope photograph of the state of a film in case the direction of the optical axis of a test plate and the moving direction of a photomask are parallel. It is a conceptual diagram which shows notionally the orientation direction of the liquid crystal compound (molecule | numerator) confirmed from the polarizing microscope photograph shown in FIG.13 and FIG.16. It is a conceptual diagram which shows notionally the orientation direction of the liquid crystal compound (molecule | numerator) confirmed from the polarizing microscope photograph shown in FIG.14 and FIG.17. It is a conceptual diagram which shows notionally the orientation direction of the liquid crystal compound (molecule) confirmed from the polarization micrographs shown in FIG.15 and FIG.18. It is a photograph of the pattern (diffraction image) of the diffracted light which projected the light which permeate | transmitted the film obtained in Example 1 on the screen. It is a photograph of the film (thin film) formed in the glass cell in Example 2. It is a photograph of the pattern (diffraction image) of the diffracted light which projected the light which permeate | transmitted the film obtained in Example 2 on the screen. 2 is a polarizing micrograph of the film (thin film) obtained in Example 2. 2 is a photograph of a film (thin film) formed in a glass cell in Comparative Example 1. It is the photograph of the pattern of the light which projected the light which permeate | transmitted the film obtained in the comparative example 1 on the screen. It is a photograph of the film (thin film) formed in the glass cell in the comparative example 2. It is a photograph of the pattern (diffraction image) of the diffracted light which projected the light which permeate | transmitted the film obtained in the comparative example 2 on the screen.

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

The method for producing an optical film having a periodic structure according to the present invention includes a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions. And a film made of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity,
Polymerization of the polymerizable composition is started from a partial region of the film, and the boundary of the region is continuously moved toward an unpolymerized region at such a speed that the compound exhibiting liquid crystallinity is aligned. After polymerization, the step of cooling the polymerized film to obtain an optical film having a periodic structure,
Polymerizing the film while heating at a heating temperature of 80 to 150 ° C. during the polymerization; and
During the cooling, the film is cooled at a cooling rate of 0.1 to 30 ° C./min until the temperature of the film reaches at least 60 ° C. from the same heating temperature employed during the polymerization,
It is the method characterized by this.

  First, the film | membrane which consists of polymeric composition is demonstrated. As such a polymerizable composition, a composition containing a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions. Use.

As such a first polymerizable compound and a second compound, those having different polymerization completion times when polymerized under the same conditions are used. Here, the matters such as the long and short polymerization completion time are relatively required between the first polymerizable compound and the second compound, and here, “when polymerized under the same conditions” Is a condition that allows the first polymerizable compound to be polymerized (temperature condition in the case of thermal polymerization, light irradiation condition in the case of photopolymerization, etc.) as appropriate, and the same selected condition This is the case where polymerization is carried out. The “polymerization completion time” is, for example, when the polymerizable composition is polymerized by photopolymerization, and is irradiated with light (for example, light of 366 nm) while being held at a constant temperature condition (for example, 85 ° C.). Then, using each of the first polymerizable compound and the second compound, each of them is introduced into the cell and separately polymerized, and the time until the polymerization of each compound is completed is determined as the film is formed. You may obtain | require by measuring as time until it comes. Thus, in this invention, you may judge that superposition | polymerization was completed when a superposition | polymerization is started in a cell and a film is formed. For example, two soda glass substrates having a size of 25 mm square and a thickness of 1.1 mm are used, and these are bonded to each other with 100 μm-thick polyimide tape as spacers (two places on the left and right sides) to produce a glass cell with a cell thickness of 100 μm. (Note that in this cell, spacers are formed in two places on two parallel vertical sides (left and right) of the glass substrate so that the overlapping area of the planar portions of the upper and lower substrates is 15 mm long and 25 mm wide (spacer The glass substrate portions where the spacers are not formed are openings, and the internal size of the cell is 15 mm long, 10 mm wide, and 100 μm thick. The photopolymerization initiator may be contained in a predetermined amount (for example, 1 mol%) with respect to the compound for measuring the polymerization completion time. A mixed mixture is prepared, and then the mixture is poured into the glass cell while melting at 100 ° C. until the inside of the cell is filled by capillarity, and up to 85 ° C. at a rate of 0.5 ° C./min. After the temperature was lowered, the film was held at 85 ° C. for 3 minutes to form a film of the polymerizable composition (film size: length 15 mm, width 10 mm, thickness 100 μm), and then the film was removed from the high pressure mercury lamp with a filter at 366 nm The glass cell is coated with the film irradiated with light at an intensity of 1.9 mW / cm ² for photopolymerization and irradiated with light every predetermined time (for example, 5 seconds, 15 seconds, 30 seconds, and 60 seconds). The time until the completion of polymerization may be measured by taking out the sample and washing the surface with chloroform and visually confirming whether or not a film is formed. In the present invention, the first polymerizable compound and the second compound to be used are compared, and a compound having a shorter polymerization completion time is used as the first polymerizable compound. A compound (including a non-polymerizable compound) in which polymerization does not proceed under the polymerization conditions of the first polymerizable compound and the polymerization completion time is infinite is used as the second compound.

  As the first polymerizable compound and the second compound, the first polymerizable compound is a compound having one or more polymerizable functional groups, and the number of the polymerizable functional groups is the first number. Those satisfying the condition that it is 1 or more larger than the number of polymerizable functional groups (may be 0) of the two compounds are preferable. It is a compound having 1 or more (more preferably 2 or more, more preferably 2 to 4) polymerizable functional groups, and the second compound has 0 or 1 (more preferably 1) polymerizable functional groups. More preferably, it is a compound having By using compounds having different numbers of polymerizable functional groups in this way as the first polymerizable compound and the second compound, respectively, it is possible to increase the difference in polymerization rate between these compounds, and the polymerization region during polymerization In the vicinity of the boundary, the concentration of the compound can be generated more efficiently, and the diffusion of the compound can be caused more efficiently, and the alignment can be formed more efficiently near the boundary of the polymerization region. In addition, when the number of polymerizable functional groups of the first polymerizable compound is less than the lower limit, it does not polymerize or it becomes difficult to polymerize the first polymerizable compound at a sufficiently high speed, and the efficiency It tends to be difficult to enlarge the alignment region well. In addition, if the number of polymerizable functional groups of the first polymerizable compound exceeds the upper limit, the polymerization proceeds faster than the diffusion of the compound, so that it tends to be difficult to form an orientation associated with the diffusion. is there.

  In addition, such a polymerizable functional group is not particularly limited, and a known functional group can be appropriately used. For example, a vinyl group, an allyl group, a vinyl ether group, an acrylic group, a methacryl group, an oxetane group, an epoxy group. , Cinnamoyl group, chalcone group, coumarin group and the like. Among them, vinyl ether group, acryl group, methacryl group, oxetane group, epoxy group, cinnamoyl group, chalcone group from the viewpoint of ease of synthesis of compound, handling property, etc. Are preferable, and an acrylic group, a methacryl group, an oxetane group, and an epoxy group are more preferable.

  Further, in the present invention, the in-plane alignment of the liquid crystal molecules that become the precursor structure of the periodic structure is induced by the self-organization ability of the liquid crystal, and then the film is cooled at the above cooling rate at least in a predetermined temperature range From the viewpoint that the phase separation as described above can be induced efficiently and the periodic structure is formed by the self-organizing ability of the liquid crystal, the first polymerizable compound, the second compound and after the polymerization At least one of the obtained compounds needs to be a compound exhibiting liquid crystallinity. That is, at least one of the first polymerizable compound and the second compound needs to be a compound exhibiting liquid crystallinity before and / or after polymerization. Here, the “compound obtained after polymerization” refers to a compound obtained when the polymerizable composition is polymerized, for example, a homopolymer of a first polymerizable compound, a second compound A homopolymer and a copolymer of a first polymerizable compound and a second compound are included. The compound exhibiting liquid crystallinity is preferably a compound exhibiting liquid crystallinity in a predetermined temperature range (so-called thermotropic liquid crystal compound). Note that such a thermotropic liquid crystal compound is an enantiotropic liquid crystal compound that exhibits liquid crystallinity in both the temperature rising process and the temperature lowering process when the behavior of the liquid crystal phase is confirmed when the temperature is raised and lowered. Alternatively, it may be a monotropic liquid crystal compound exhibiting liquid crystallinity only in one of the temperature raising process and the temperature lowering process. In the present invention, at least one of the first polymerizable compound, the second compound, and the compound obtained after the polymerization is a compound exhibiting liquid crystallinity (a compound having liquid crystallinity). By starting, the diffusion of the compound in the film is excited, and it becomes possible to apply shear stress (shear stress) to the compound exhibiting liquid crystallinity. Thus, once the alignment of the compound having liquid crystallinity starts, the liquid crystal Since the orientation is amplified by the self-organizing ability of the material, the orientation can be formed efficiently.

As the compound exhibiting liquid crystallinity, the following general formula (1):
^{Z 1 p-M 1 -L 1} - (M 2 -L 2) q-M 3 -Z 2 r (1)
[Wherein, Z ¹ and Z ² are each independently a hydrogen atom; a halogen atom (more preferably F, Cl, Br); CN; NO ₂ ; OCF ₃ ; a linear or branched group having 1 to 18 carbon atoms. Alkyl group {in addition, the alkyl group is an oxygen atom, —COO—, —OCO—, —OCOO—, —CONR ¹ —, in which one or a plurality of carbons are not continuously bonded. , —NR ¹ CO—, —OCO—NR ¹ —, or —NR ¹ COO— may be substituted (wherein R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms). . }; Alkoxy group having 1 to 18 carbon atoms; and the ^formula: -L 3 ^-S 1 -F ¹
{In the formula: F ¹ represents 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),
Any one of the groups represented by
S ¹ is a single bond, a linear or branched alkylene group having 1 to 18 carbon atoms (in the alkylene group, one or a plurality of carbons in the alkylene group are not continuously bonded). oxygen atom, -COO -, - OCO -, - OCOO -, - CONR 3 -, - NR 3 CO -, - OCO-NR 3 -, or ^-NR 3 may be substituted with COO- (wherein, R ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms)).
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). }
Any one of the groups represented by
L ^{1, L 2} are each independently 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),
M ¹ and M ³ are each independently 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6. -Diyl group, naphthalene-1,4-diyl group, 1,3-dioxane-2,6-diyl group, 1,3,4-benzenetoluyl group, 1,3,5-benzenetoluyl group, 1,3,3 4,5-benzenetetrayl group, M ² is 1,4-phenylene group, 1,4-cyclohexylene group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- Represents a 2,6-diyl group, a naphthalene-1,4-diyl group or a 1,3-dioxane-2,6-diyl group;
The hydrogen atoms contained in the groups selected as M ¹ , M ² and M ³ may each independently be substituted with an alkyl group, a halogenated alkyl group, an alkoxy group, a halogen group, a cyano group or a nitro group. ,
p and r each independently represent 1, 2, or 3;
q represents 0, 1, or 2;
When there are a plurality of Z ¹ and / or Z ² , they may be the same or different. ]
The compound represented by these is preferable. In addition, you may utilize such a compound which shows liquid crystallinity individually by 1 type or in combination of 2 or more types.

  As a compound that can be used in addition to the compound exhibiting liquid crystallinity, similarly to the compound exhibiting liquid crystallinity, vinyl group, allyl group, vinyl ether group, acrylic group, methacryl group, oxetane group, epoxy group, cinnamoyl group, chalcone group, A compound having a functional group such as a coumarin group can be used. There are many commercially available thermal polymerization compounds and photopolymerization compounds that can be used as compounds that can be used in addition to the compound exhibiting liquid crystallinity, and these can be used as appropriate.

  Examples of the vinyl-based compound having a vinyl group include styrene, α-methylstyrene, vinyl acetate, N-vinylpyrrolidone, N-vinylcaprolactam and the like.

  Examples of the vinyl ether group compound having a vinyl ether group include 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, Examples include cyclodecane vinyl ether, benzyl vinyl ether, 1,4-butanediol divinyl ether, cyclohexane dimethanol divinyl ether, ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and dicyclopentadiene vinyl ether.

  As the (meth) acrylic compound having an acrylic group or a methacrylic group, as a monofunctional monomer, methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate and 2-ethylhexyl Alkyl (meth) acrylates such as (meth) acrylate; hydroxyalkyl (meth) acrylates such as 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and 2-hydroxy-3-phenylpropyl acrylate; cyclohexyl ( Saturated or unsaturated alicyclic alkyl (meth) acrylates such as (meth) acrylate, isobornyl (meth) acrylate, dicyclopentenyl (meth) acrylate, dicyclopentenyloxyethyl (meth) acrylate Relate; Substituted aryl (meth) acrylate such as benzyl (meth) acrylate, Alkoxy (meth) acrylate such as 2-methoxyethyl (meth) acrylate and 2-ethoxyethyl (meth) acrylate; Unsaturation such as (meth) acryloylmorpholine Amide compounds; carboxyl group-containing (meth) acrylates such as monohydroxyethyl (meth) acrylate phthalate and monohydroxyethyl (meth) acrylate succinate; hexahydrophthalimidoethyl (meth) acrylate and succinimide ethyl (meth) acrylate Examples thereof include imide (meth) acrylate.

  Examples of the (meth) acrylic polyfunctional monomer include ethylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, Tricyclodecane dimethanol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, tris ((meth) acryloxyethyl) isocyanurate, pentaerythritol tetra (meth) acrylate, ditrimethylol Propane tetra (meth) acrylate and the like can be mentioned.

  Examples of the compound having an epoxy group include ethylene glycol diglycidyl ether, 1,4-butanediol diglycidyl ether, 1,6-hexanediol diglycidyl ether, cyclohexanedimethanol diglycidyl ether, diethylene glycol diglycidyl ether, and 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'-epoxy Cyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 1,2-epoxy-4- (2-methyloxiranyl) -1-methylcyclohexane, 1,2-epoxy-4-vinylcyclohexane, vinylcyclohexene monooxide, 1 , 2: 8,9-diepoxy limonene.

  Examples of the compound having an oxetane group include 3-ethyl-3-hydroxymethyloxetane, 2-ethylhexyloxetane, xylylenebisoxetane, 3-ethyl-3 (((3-ethyloxetane-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, And 3-ethyl-3- (2-ethylhexyloxymethyl) oxetane.

  Further, as the first polymerizable compound and the second compound to be contained in the polymerizable composition, it is easy to control the position of the boundary between the polymerized region and the unpolymerized region at the time of polymerization, and more efficiently as desired. Since a film having a periodic structure can be formed and the working efficiency can be further improved, it is preferable to use a photopolymerizable compound. That is, in the present invention, it is preferable that at least one or both of the first polymerizable compound and the second compound is a photopolymerizable compound, and the polymerizable composition is polymerized by photopolymerization. It is more preferable to use a photopolymerizable compound as both the one polymerizable compound and the second compound. In addition, the photopolymerizable compound mentioned here is a compound in which a functional group reacts due to the presence of a photoinitiator such as vinyl group, allyl group, vinyl ether group, acrylic group, methacryl group, oxetane group, and epoxy group. Alternatively, a compound in which a functional group reacts with light without a photoinitiator may be used. Examples of photopolymerizable compounds that react with functional groups without a photoinitiator include compounds having functional groups capable of photodimerization such as cinnamoyl groups, chalcone groups, and coumarin groups. it can.

In addition, the first polymerizable compound is a compound represented by the general formula (1) from the viewpoint of being a monomer capable of proceeding polymerization more efficiently, and Z ^{1 in} the formula And Z ² are groups represented by -L ³ -S ¹ -F ¹ (Z ¹ and Z ² may be the same or different, and from the viewpoint of ease of synthesis, F ¹ is an acrylic group or a methacryl group, S ¹ is a single bond or a linear alkylene group having 1 to 12 carbon atoms, and L ³ is an ether group (—O—). ), An ester group (—COO—, —OCO—) and a carbonate group (—OCOO—) (preferably an ether group), p is 1, M ¹ is 1,4-phenylene. a group, ^{L 1} is a single bond and -C Any of O- (more preferably single bond) and, q is 0, ^{M 3} is 1,4-phenylene group, and a compound wherein r is 1 C11,
The compound represented by the general formula (1), wherein Z ¹ and Z ² are both groups represented by -L ³ -S ¹ -F ¹ (wherein Z ¹ and Z ² are They may be the same or different, and are preferably the same group from the viewpoint of ease of synthesis.), F ¹ is an acrylic group or a methacryl group, and S ¹ is a single bond or a carbon number. 1 to 12 linear alkylene groups, L ³ is an ether group, an ester group or a carbonate group (more preferably an ether group), p is 1, M ¹ is 1,4- A phenylene group, L ¹ is —COO—, M ² is a 1,4-phenylene group, L ² is —OCO—, q is 1, and M ³ is a 1,4-phenylene group. And Compound C12 wherein r is 1;
The compound represented by the general formula (1), wherein both Z ¹ and Z ² are groups represented by -L ³ -S ¹ -F ¹ (wherein Z ¹ and Z ² are They may be the same or different, and are preferably the same group from the viewpoint of ease of synthesis.), F ¹ is an acrylic group or a methacryl group, and S ¹ is 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 a 1,4-phenylene group, and L ¹ 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, Compound C13,
The following general formula (2):

(In the formula, R ⁵ is either hydrogen or a methyl group (in addition, a plurality of R ⁵ may be the same or different), and x is 2 or 3. .)
Compound C14 represented by:
The following general formula (3):

(Wherein R ⁵ is any one of hydrogen and methyl group (in addition, a plurality of R ⁵ may be the same or different), and y is an integer of 2 to 12) .)
Compound C15 represented by
Is also preferable. These may be a polymerizable compound exhibiting liquid crystallinity at least before and after polymerization, or may not exhibit liquid crystallinity when a second compound described later exhibits liquid crystallinity.

  Examples of the first polymerizable compound include ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, diethylene glycol di (meth) acrylate, triethylene glycol di (meth) acrylate, 4,4′-bis (8- (meth) acryloyloxy-3,6-dioxaoctyl-1-oxy) biphenyl, 4,4′-bis (9- (meth) acryloyloxy) nonyloxybiphenyl, 4, 4′-bis (6- (meth) acryloyloxy) hexyloxybiphenyl and 1,4-bis (6- (meth) acryloyloxyhexyloxy) methylhydroquinone are particularly preferred.

  In addition, the second compound to be contained in the polymerizable composition is preferably a compound that exhibits liquid crystallinity at least before and after polymerization from the viewpoint of forming an optical film more efficiently. When the first polymerizable compound exhibits liquid crystallinity, it is not necessarily required to be a compound exhibiting liquid crystallinity.

Furthermore, as such a second compound, since an optical film can be formed more efficiently by using a compound exhibiting liquid crystallinity as the second compound, the general formula (1) In which 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, and L ³ Is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is 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 compound C21 wherein r is 1;
A compound represented by the general 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 carbon. A linear alkylene group of 1 to 12, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, and q is 0 Yes, M ³ is a 1,4-phenylene group, and Z ² is selected from a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and an alkoxy group having 1 to 12 carbon atoms A compound C22 in which r is 1 (more preferably a cyano group) and r is 1;
A compound represented by the general formula (1), wherein Z ¹ is represented by -L ³ -S ¹ -F ¹ , F ¹ is an acrylic group or a methacryl group, and S ¹ is 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 a 1,4-phenylene group. Yes, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, or an alkyl having 1 to 12 carbon atoms. A compound selected from the group consisting of a group and an alkoxy group having 1 to 12 carbon atoms (more preferably a cyano group) and r is 1, and a compound represented by the general formula (1) In which Z ¹ is represented by -L ³ -S ¹ -F ¹ and F ¹ is an acrylic group Is a methacryl group, S ¹ is a linear alkylene group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, and L ¹ Is —COO—, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, and carbon. Compound C24, which is one type (more preferably a cyano group) selected from the alkoxy groups of 1 to 12, and r is 1.
Is preferred.

  Examples of the second compound include 4- (6- (meth) acryloyloxyhexyloxy) -4′-cyanobiphenyl, 4- (9- (meth) acryloyloxynonyloxy) -4′-cyanobiphenyl, 4- (5- (meth) acryloyloxy-3-oxapentyl-1-oxy) -4′-cyanobiphenyl, 4- (8- (meth) acryloyloxy-3,6-dioxaoctyl-1-oxy) It is particularly preferable to use -4'-cyanobiphenyl or 4-cyanophenyl-4- (2-acryloyloxyethoxy) benzoate.

  Further, the content ratio of the first polymerizable compound and the second compound to be contained in the polymerizable composition is not particularly limited, but the first polymerizable compound and the second compound are not limited. The molar ratio of the compound ([first polymerizable compound]: [second compound]) is preferably 0.1: 99.9 to 99.9: 0.1, and 0.5: 99. More preferably, it is 5-99.5: 0.5, and it is still more preferable that it is 2: 98-98: 2. The molar ratio of the first polymerizable compound to the second compound ([first polymerizable compound]: [second compound]) is 5:95 to 95: depending on the type of compound to be combined. 5 is more preferable, and 10:90 to 80:20 is even more preferable. When the content ratio of the first polymerizable compound is less than the lower limit, the diffusion rate is slow, and therefore, the rate of moving the boundary tends to be slow.On the other hand, when the upper limit is exceeded, polymerization is performed rather than compound diffusion. Since it progresses too quickly, it tends to be difficult to form an orientation accompanying diffusion.

  Further, in such a polymerizable composition, in addition to the first polymerizable compound and the second compound, various solvents, photopolymerization initiators, viscosity modifiers, plastics are used within a range not impairing the effects of the present invention. An agent, a polymerization inhibitor, a surfactant and the like can be appropriately contained. In addition, when various additives and the like are included in the polymerizable composition in this way, the total amount of the first polymerizable compound and the second compound in the polymerizable composition is 70 mol% in molar ratio. It is preferable that it is more (more preferably 80 mol% or more). When the total amount of the first polymerizable compound and the second compound is less than the lower limit, the liquid crystallinity is lowered and it is difficult to form a periodic structure.

  In the case of photopolymerizing the polymerizable composition, it is preferable to use a photopolymerization initiator because the polymerization can proceed more efficiently. Such a photopolymerization initiator is not particularly limited, and known ones can be used as appropriate, and commercially available products (for example, trade name “Irgacure 651” manufactured by BASF) may be used. In the case of using such a photopolymerization initiator, the amount used can be appropriately designed according to the type of compound in the polymerizable composition to be used, the light absorption wavelength, and the like. It is good also as 0.1-10 mol% with respect to all the compounds in a composition. In addition, when the content ratio of such a photopolymerization initiator is less than the lower limit, the effect of using the photopolymerization initiator tends to be insufficient, and on the other hand, when the upper limit is exceeded, liquid crystallinity tends to be reduced, This tends to prevent a good periodic structure from being obtained efficiently.

  Moreover, the form (size including thickness etc.) of such a polymerizable composition is not particularly limited, and the form can be appropriately changed according to the intended design. It is good also as 1-200 micrometers. Further, the film made of such a polymerizable composition may be a coating film obtained by applying the polymerizable composition on a substrate, and the polymerizable composition is introduced into a so-called cell. The polymerizable composition may be in the form of a film by a cell, and there is no particular limitation on the method of forming the film and the presence or absence of use of the substrate at the time of production, and a known method can be used as appropriate. Etc. can be appropriately selected according to the type of the polymerizable composition, the polymerization method (photopolymerization or thermal polymerization), the use of the final product, and the like. Furthermore, when manufacturing the film | membrane which consists of said polymeric composition on a board | substrate or in a cell, the board | substrate etc. to be used may not be horizontal.

  In addition, as a film made of such a polymerizable composition, from the viewpoint of forming an optical film while sufficiently maintaining the shape and uniformity of the film, a film of the polymerizable composition is provided between two substrates. Arrange and support the film by the substrate (for example, arrange a film in the cell using a cell including two substrates), or form a film made of the polymerizable composition on one substrate The other surface is preferably a gas phase interface. Moreover, the material of such a substrate or cell is not particularly limited, and a known material (for example, glass or plastic) can be appropriately used. Further, in the case where the polymerization is performed by photopolymerization, in the case where the substrate is in contact with the light incident surface side of the film, it is necessary to make light incident through the substrate. It is preferable to be made of a material that can transmit at least light having a wavelength used for photopolymerization.

  Next, polymerization of the polymerizable composition is started from a partial region of the film, and the boundary of the region is continuously directed toward the unpolymerized region at such a speed that the compound exhibiting liquid crystallinity is aligned. A process of obtaining an optical film having a periodic structure by cooling and polymerizing the polymerized film after being transferred and polymerized will be described.

  In such a process, first, using the film | membrane which consists of the said polymeric composition, superposition | polymerization of the said polymeric composition is started from the one part area | region of this film | membrane. In addition, in the matter such as “start polymerization of the polymerizable composition from a partial region of the film”, for example, a part of the film is set as a region for starting the polymerization from the beginning, and the region (For example, in the case of photopolymerization, a part of the film is previously present in the part irradiated with light from the light source (exposure part), and the polymerization is performed from the exposed part of the film. In the case of starting polymerization from a partial region of the film while gradually forming a region for polymerization (for example, in the case of photopolymerization using a photomask) Then, after covering the entire film with the mask and making all the film enter the portion shielded from light by the mask, the film is gradually exposed to the light irradiation region during light irradiation, Exposed part of film (partial area of film) If so as to initiate et Polymerization: Note, including this case, introducing the film at a rate such that the compound in the irradiated region of the light indicating the liquid crystal is oriented (exposure) is to be preferred)..

  As described above, the method for polymerizing the film composed of the polymerizable composition from a partial region is not particularly limited, and a known method can be appropriately employed. As a method for starting polymerization from a partial region of such a film, for example, light (X-ray, electron beam, ultraviolet ray, visible light, infrared ray (heat ray), etc.) is irradiated on a partial region, Examples thereof include a photopolymerization method in which polymerization is started from an irradiation region, and a thermal polymerization method in which heating is started from a partial region and polymerization is started from the heating region. As such a polymerization method, in part from the viewpoint of easier control of the region to be polymerized, ease of handling, ease of setting and management of irradiation intensity and irradiation energy of light to be irradiated. It is preferable to employ a photopolymerization method in which light is irradiated to the region. In such photopolymerization, when the film that is the object of photopolymerization is supported by a cell or the like, if the substrate on the light irradiation surface side is not transparent, photopolymerization is performed by using an electron beam. And the use of electron beams is useful when the substrate is not transparent.

  Further, in the present invention, regardless of the polymerization method of the polymerizable composition, the polymerization composition starts from a partial region of the film, and the rate at which the liquid crystalline compound is aligned is obtained. In the polymerization by continuously moving the boundary of the region toward the unpolymerized region (at the time of polymerization), the film is 80 to 150 ° C. (more preferably 85 to 140 ° C., still more preferably 90 to 130). It is necessary to adopt a temperature condition of heating to ° C. When the heating temperature condition employed during the polymerization is less than the lower limit, it is difficult to efficiently advance the polymerization reaction or the formation of the alignment film due to crystallization of the polymerizable composition or one component therein. Or the viscosity of the polymerizable composition is increased, resulting in a problem that the rate of the polymerization reaction is slowed.On the other hand, when the upper limit is exceeded, polymerization of the entire film easily proceeds by heat, and the orientation structure When the reaction is carried out in air, there is a high possibility that the polymerizable compound is decomposed, and it becomes difficult to obtain an optical film stably. Even when the so-called post-polymerization step is performed, the same temperature conditions (80 to 150 ° C., more preferably 85 to 140 ° C., still more preferably 90 to 130 ° C.) as the temperature conditions during the polymerization should be adopted. Is preferred.

  Furthermore, when photopolymerization is employed as the polymerization method of the polymerizable composition, it is possible to proceed the polymerization reaction more efficiently, and it is preferable to use ultraviolet rays or visible light. A light source for irradiating such light is not particularly limited, and a known light source that can be used for photopolymerization can be used as appropriate. A lamp or the like may be used.

  Moreover, there is no limitation in particular as the irradiation wavelength of the light utilized in such photopolymerization, What is necessary is just to consider and consider the absorption spectrum of a compound, the recommended use wavelength of a photoinitiator, etc. Further, for example, in the case where polymerization is performed in a state where a film made of a polymerizable composition is formed on a substrate and one interface of the film is in contact with the surrounding atmospheric gas, a compound containing an acryl group or a methacryl group is used. When a radical reaction is used, polymerization is preferably performed in an atmosphere of an inert gas such as nitrogen from the viewpoint that, when oxygen is present, it is difficult for the polymerization to proceed due to oxygen inhibition. In the case of a polymerizable functional group having no influence of oxygen inhibition using a cation reaction such as an oxetane group or an epoxy group, it is not necessary to perform polymerization in an inert atmosphere, and the polymerization may be performed in the air. On the other hand, when the film made of the polymerizable composition using a cell or the like is not in contact with the atmospheric gas, the polymerization may be started in the air. Thus, in the present invention, the polymerization may be performed in a state where the film made of the polymerizable composition is in contact with the atmospheric gas (the state where the interface of the film is in contact with the gas phase), and the film made of the polymerizable composition The polymerization may be carried out in such a state that does not come into contact with the atmospheric gas (a state in which the interface of the film is in contact with the cell wall (solid phase)).

At the time of the photopolymerization, it is preferable to irradiate light at an intensity of ^{0.1μW / cm 2 ~30mW / cm 2} , the light intensity of 0.5μW ^/ cm ² ~10mW ^/ cm 2 Irradiation is more preferable. When the illuminance of such light is less than the lower limit, the reaction rate is slow, so the moving speed of the boundary is slow, and the productivity tends to decrease. On the other hand, the rate at which the polymerizable compound diffuses when the upper limit is exceeded. When the polymerization reaction rate is too high, the compound does not sufficiently diffuse and it is difficult to form a sufficient orientation structure in the film, and as a result, it is difficult to form a periodic structure during cooling. It tends to be.

  Furthermore, the method for irradiating light from a part of the region during such photopolymerization is not particularly limited. For example, a light source that can irradiate only part of the region can be used. Alternatively, light may be irradiated from a part of the region using a photomask, but it is preferable to use a photomask because the control of the polymerized region and the unpolymerized region becomes easier.

  Further, in the present invention, as described above, the polymerization composition is started from a partial region of the film made of the polymerizable composition, and the rate at which the compound exhibiting liquid crystallinity is aligned. The boundary of the region is continuously moved toward the unpolymerized region. In this way, by continuously moving the boundary between the polymerized region and the unpolymerized region toward the unpolymerized region, the polymerization is continuously performed, and in the region near the moving boundary, It is possible to cause the diffusion phenomenon sequentially and continuously, thereby increasing the alignment region continuously to form the in-plane alignment of the liquid crystal molecules that become the precursor structure of the periodic structure and the structure having the periodic structure. It becomes possible. As the polymerization conditions for continuously moving the boundary of the region toward the unpolymerized region in this way, the same conditions as the polymerization conditions at the start of the polymerization described above may be employed.

  Here, “the speed at which the compound exhibiting liquid crystallinity is oriented”, which is the moving speed when moving the boundary, is formed by polymerization, the type of compound exhibiting liquid crystallinity, the type of compound that diffuses and moves, and polymerization. Type of compound (polymerized product) (first polymerizable compound, type of second compound, type of compound obtained after polymerization), polymerization conditions employed during polymerization (for example, light irradiation when employing photopolymerization) The time required for aligning the compound exhibiting liquid crystallinity in the film differs depending on the conditions and the like. That is, in the present invention, due to the concentration gradient of the compound that occurs in the polymerized region and the unpolymerized region, the diffusion movement (flow of the compound in the polymerizable composition near the boundary between the polymerized region and the unpolymerized region) ) And applying a kind of shear stress to the liquid crystal compound present in the polymerizable composition to align the liquid crystal compound in the vicinity of the boundary. The “speed at which the compound is aligned” varies depending on the type of the compound exhibiting liquid crystallinity, the type of the compound that diffuses and moves, the type of the compound formed by polymerization (polymer), and the like. For example, using a compound exhibiting liquid crystallinity as the second compound, polymerizing the first polymerizable compound at the start of polymerization, causing the first polymerizable compound to move to the polymerization region, Considering the case of using the first polymerizable compound and the second compound, the polymerization rate of the first polymerizable compound is very fast, and the concentration gradient of the compound suddenly occurs in the polymerized region and the unpolymerized region, In the case where the moving speed of the first polymerizable compound to the polymerization region is very high, even if the moving speed of the boundary is relatively high, the first polymerizable compound can move to the polymerization region. The shear stress generated along with the movement can be sufficiently applied to the compound exhibiting liquid crystallinity existing in the polymerization region, and the compound exhibiting liquid crystallinity can be sufficiently aligned. The polymerization rate of the polymerizable compound is In the case where the concentration gradient of the compound is gently generated in the polymerized region and the unpolymerized region, and the moving speed of the first polymerizable compound to the polymerized region is slow, the compound exhibiting liquid crystallinity is sufficiently displaced. Since it takes time to apply the stress, if the moving speed of the boundary is increased, it becomes difficult to align a compound exhibiting sufficient liquid crystallinity in the vicinity of the boundary. Thus, “the rate at which a compound exhibiting liquid crystallinity is aligned” refers to the type of compound exhibiting liquid crystallinity, the type of compound that diffuses and moves, the type of compound formed by polymerization (polymer), What is necessary is just to determine so that orientation may arise suitably according to superposition | polymerization conditions etc., and the setting of the speed | rate can be changed suitably.

Moreover, it is preferable to set it as 1 * 10 < ^-7 > -4 * 10 < ^-1 > m / s as a speed | rate (moving speed which moves the said boundary) that such a compound which shows liquid crystallinity aligns, 1 *. It is more preferable to set it as 10 ^{< -6} > ^-4 * 10 ^<-2 > m / s. When such a rate is less than the lower limit, the polymerization reaction proceeds faster than the diffusion of the compound, so that the diffusion transfer of the compound is suppressed by increasing the viscosity, and the shear stress is sufficiently applied to the compound exhibiting liquid crystallinity. Tends to become difficult to orient in a wide range, and on the other hand, if the upper limit is exceeded, the speed becomes too high, and the compound can sufficiently diffuse and move in the vicinity of the boundary. It becomes difficult and it tends to be difficult to form an orientation in the polymerization region. Also, the combination of the first polymerizable compound and the second compound is any of a suitable combination of the foregoing, the polymerization of the polymerizable composition, of 0.1μW / cm ² ~30mW / cm ² In the case of adopting a photopolymerization method that irradiates with an intensity, the speed at which the compound exhibiting liquid crystallinity is oriented (moving speed for moving the boundary) can efficiently form an optical film. From the viewpoint, it is preferably set to 1 × 10 ⁻⁷ to 4 × 10 ⁻¹ m / s.

  In addition, 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, the heating region is continuously connected to the unpolymerized region. It is only necessary to adopt a method that can be moved in an appropriate manner, and when the polymerization method is photopolymerization, the light irradiation region may be continuously moved to an unirradiated region. Any possible method may be adopted as appropriate.

  In addition, as a method of continuously moving the boundary of such a region toward an unpolymerized region, the moving speed of the boundary can be controlled more easily, and an alignment region can be formed more efficiently. In order to perform polymerization of the polymerizable composition by photopolymerization, and to continuously move the boundary toward the unpolymerized region, the boundary of the light irradiation region is directed to the unexposed region of light. It is preferable to adopt a method of continuously moving them. Further, the method of continuously moving the boundary of the light irradiation region toward the non-irradiated region is not particularly limited as long as it is a method capable of moving the boundary, and the polymerizable composition A method of continuously moving the light source itself so that only a part of the region can be irradiated with light, or a film of the polymerizable composition is continuously moved while fixing the light source. A method of using a photomask to move the photomask continuously, and a method of using a photomask to move the polymerizable composition film continuously while fixing the photomask. May be.

  Further, among the methods of continuously moving the boundary of the light irradiation region toward the light non-irradiation region, a photomask is used during the photopolymerization, and the photomask is continuously moved. It is preferable to employ a method of using a photomask during the photopolymerization and a method of continuously moving the film of the polymerizable composition while fixing the photomask. As described above, by adopting photopolymerization for the polymerization of the polymerizable composition and using a photomask, the boundary of the light irradiation region can be continuously moved toward the light non-irradiation region. Can be achieved more easily.

  Here, with reference to FIGS. 1-4, the suitable embodiment in case the superposition | polymerization of the said polymeric composition is performed by photopolymerization and a photomask is utilized in the case of the photopolymerization is demonstrated easily. In the preferred embodiment shown in FIGS. 1 to 4, first, light is shielded between the film 13 and the light source 11 so that only a part of the film 13 is irradiated with light from the light source 11. After disposing a possible photomask 14 (FIG. 1), polymerization of the polymerizable composition is started from a partial region A1 of the film 13 by irradiating light from the light source 11 (see FIG. 2). By continuously moving the photomask 14 at a speed at which the compound exhibiting liquid crystallinity is aligned, the boundary S of the polymerization region is directed toward the unpolymerized region A2 at a speed at which the compound exhibiting liquid crystallinity is aligned. The film can be polymerized while forming an alignment structure by continuously moving (toward the direction of arrow A) (see FIGS. 3 to 4). Thus, when photopolymerization is used for the polymerization of the polymerizable composition, the boundary S between the polymerized region and the unpolymerized region can be moved by a simple method such as a method of moving the photomask 14. It can be achieved, and it is possible to form a polymerized film (an oriented film as a precursor of an optical film having a periodic structure) in which an oriented structure is formed. In addition, although suitable embodiment in the case of utilizing a photomask when superposing | polymerizing a film | membrane was described with reference to FIGS. 1-4, embodiment in the case of utilizing a photomask is limited to the said embodiment. is not. For example, in the embodiment shown in FIGS. 1 to 4 described above, a method of moving the photomask 14 is adopted to move the boundary S between the overlapped region and the unpolymerized region. A method of moving the film 13 itself may be employed. In the embodiment shown in FIGS. 1 to 4, the polymerization of the polymerizable composition is started after the light is applied to a part of the region A1 of the film 13. The polymerization method that can be employed in the method for producing an optical film is not limited to the method employed in such an embodiment. For example, the entire film is covered with a photomask, and with the start of light irradiation, liquid crystallinity. The photomask or film is continuously moved at such a speed that the compound showing the orientation is aligned, and the film is introduced into the light irradiation region (exposure portion) at the speed, thereby irradiating the light. Polymerization starts from the area (partial area of the film) introduced into the area (exposed area), and the boundary of the polymerized area moves toward the unpolymerized area at such a speed that the liquid crystalline compound is oriented as it is. Let it polymerize The method may be employed, such as.

  In addition, when the polymerizable composition is polymerized by photopolymerization and a photomask is used for the photopolymerization, the orientation direction of the liquid crystal molecules that become the precursor structure of the periodic structure is changed according to the edge shape of the photomask. It can be easily controlled. Hereinafter, the control of the orientation according to the edge shape of the photomask will be briefly described with reference to the embodiments shown in FIGS. For example, when a photomask 14 as shown in FIG. 8 is used as a photomask, the compound flows in a direction substantially perpendicular to the boundary S shown in FIG. The orientation direction of the liquid crystal molecules that are the precursor structure of the periodic structure can be controlled. In addition, when a photomask 14 having an edge formed in an oblique direction as shown in FIG. 9 is used as the photomask, the flow of the compound is basically in a direction substantially perpendicular to the boundary S shown in FIG. Occurs, when the boundary S is substantially perpendicular to the oblique boundary S, or when the movement speed of the boundary S is high, a vector in the direction of movement of the boundary S (arrow A) and a vector in the direction perpendicular to the boundary S (arrow P) The orientation direction can be controlled in the direction of the vector sum. Therefore, when photopolymerization using a photomask is performed, the alignment direction of liquid crystal molecules serving as a precursor structure of a periodic structure can be easily controlled in a desired direction according to the edge shape of the photomask. Accordingly, in order to form the alignment direction of the liquid crystal molecules to be a precursor structure of a desired periodic structure, the edge shape of the photomask may be changed as appropriate, and thereby the liquid crystal to easily form the precursor structure of the periodic structure. It is possible to control the orientation direction of the molecules.

  When the polymerizable composition is polymerized by photopolymerization and a photomask is used for the photopolymerization, a plurality of substantially rectangular openings are used as the photomask, and the long sides of the openings are A photomask formed so as to be substantially parallel can be preferably used. Hereinafter, a preferred embodiment of a photopolymerization method in the case of using a mask in which a plurality of such substantially rectangular openings are formed so that the long sides of each opening are substantially parallel will be described with reference to FIG. This will be briefly described with reference to FIG. 10 and 11 are schematic plan views schematically showing the relationship between the photomask 14 and the substrate 12 when viewed from the light source side (in the optical axis direction of the irradiated light). In these embodiments, the light source, the photomask 14 and the substrate 12 are disposed so that the film disposed on the substrate 12 can be photopolymerized by the light transmitted through the opening 14A. Yes.

  The photomask 14 shown in FIGS. 10 and 11 has a plurality of substantially rectangular openings 14A. Here, the “substantially rectangular shape” means a shape corresponding to a rectangular shape such as the opening 14A shown in FIG. 11 is an arcuate side shape, or a parallelogram shape such as the opening 14A shown in FIG. 11 where the angle of the four corners is not 90 degrees. Includes arc-shaped ones and shapes in which a portion corresponding to a long side or a short side is an arc-shaped side). Thus, the substantially rectangular opening is such that the side of the opening corresponding to the long side (or an arcuate side) as in the rectangle corresponds to the short side (or an arcuate side). It is an expression intended to be an elongated shape that is longer than the side.

Such a substantially rectangular shape (elongate shape) of the opening 14A is not particularly limited, and the long side length Y may be longer than the short side length X. The ratio (Y / X) of the long side length Y to the short side length X is preferably 2.0 or more, more preferably 5.0 to 2.0 × 10 ^5. preferable. ).

  Further, the length X of the short side of the opening 14A varies depending on the substrate 12 used in the polymerization, the size of the film, and the like, and cannot be generally described, but is 1 μm to 10 mm. It is preferably 10 μm to 1 mm. When the length X of the short side of the opening 14A is less than the lower limit, the orientation tends to hardly occur. On the other hand, when the upper limit exceeds the upper limit, it is difficult to obtain a film having a uniform in-plane orientation. There is a tendency.

  In addition, in such an opening 14A, the long sides of the openings are arranged substantially in parallel. Thus, by arranging the openings 14A so that the long sides of the openings are substantially parallel, when the oriented film is formed in a large area, the orientation direction is basically uniform. It becomes possible to control. Moreover, as such a mask having the openings 14A, the openings 14A are preferably formed periodically, and it is more preferable that the openings 14A having the same shape are formed periodically. As described above, when the openings 14A are periodically formed, the pitch of the openings 14A is not particularly limited, but is preferably 1 μm to 10 mm, and more preferably 10 μm to 1 mm. . When the pitch of the openings 14A is less than the lower limit, the orientation tends to be difficult to occur. On the other hand, when the pitch exceeds the upper limit, a film having a uniform in-plane orientation tends to be hardly obtained. Note that in such a photomask having a plurality of openings, the number of openings may be two or more and is not particularly limited, and the design may be changed as appropriate depending on the size of the mask and the substrate. it can.

  Using such a mask 14 in which a plurality of rectangular openings are formed substantially in parallel, for example, an opening is formed in the film formed on the substrate while moving the substrate 12 in the same direction as the direction A. When photopolymerization is performed by irradiating light through the portion 14A, the boundary S of the polymerization region is formed for each opening 14A, and each boundary S is continuously moved toward the unpolymerized region. Thus, it is possible to form an alignment region for each opening 14A. Therefore, when using a mask 14 in which a plurality of rectangular openings are formed substantially in parallel, the mask is moved to the same length as the interval (distance) between adjacent openings, and oriented in a large area. It becomes possible to form a region, and it is possible to efficiently form alignment of liquid crystal molecules that becomes a precursor structure of a periodic structure.

  Further, in the case of using the mask 14 in which such a plurality of rectangular openings are formed substantially in parallel, the orientation direction can be controlled according to the shape of the edge of the opening 14A. In the embodiment shown in FIG. 10, when the photopolymerization is performed while moving the substrate 12 in the direction A, the orientation direction can be controlled in a direction perpendicular to the long side of the opening 14A. In the embodiment shown in FIG. 11, when the photopolymerization is performed while moving the substrate 12 in the same direction as the direction A, the edge of the opening 14 </ b> A has two sides of the substrate 12 when viewed from the light source side. The compound flows in a direction substantially perpendicular to the long side of the opening 14A due to the polymerization, and is substantially perpendicular to the long side, or the moving speed of the substrate 12 Is fast, the orientation direction can be controlled in the direction of the vector sum of the vector in the moving direction (arrow A) and the vector in the direction substantially perpendicular to the long side (arrow P). In addition, although the photopolymerization method which can be suitably employ | adopted for this invention was demonstrated with reference to FIGS. 10-11, the photopolymerization method which can be employ | adopted in this invention is limited to these methods. Is not to be done. For example, although the method of moving the substrate 12 has been described in the above-described embodiment, photopolymerization may be performed by appropriately adopting a method of fixing the substrate 12 and moving the mask and the light source.

  Further, in the present invention, the polymerization of the polymerizable composition is started from a partial region of the film made of the polymerizable composition, and the boundary between the regions is not set at such a speed that the compound exhibiting liquid crystallinity is aligned. The film is made by continuously moving toward the polymerization region to form an alignment structure of liquid crystal molecules that becomes a precursor structure of a periodic structure in the film, and as a film made of a polymerizable composition used for such polymerization. Alternatively, a prepolymerized film may be used. By using such a pre-polymerized film, it becomes possible to form a sufficiently oriented structure even if the speed of continuously moving the boundary of the polymerization region toward the unpolymerized region is increased. There is a tendency that a periodic structure can be formed in a large area of the film more efficiently. As used herein, “preliminary polymerization” means that the film of the polymerizable composition is slightly polymerized to such an extent that the fluidity of the polymerizable composition is not impaired (for example, light is applied to both prepolymerization and main polymerization). When using polymerization, the film of the polymerizable composition is irradiated with light that is weaker than the main polymerization to slightly polymerize the components in the film to such an extent that fluidity is not impaired. Say.

  Thus, in the present invention, from the viewpoint of forming an optical film in as short a time as possible by increasing the speed of continuously moving the boundary of the polymerization region toward the unpolymerized region, A membrane can be suitably used. Such a prepolymerization method is not particularly limited. For example, when photopolymerization is employed for the prepolymerization, even if the prepolymerization is performed using a photomask, the photomask is not used. It may be a preliminary polymerization. Thus, the preliminary polymerization is, for example, preliminary polymerization by photopolymerization using a photomask in which a plurality of substantially rectangular openings are formed so that the long sides of each opening are substantially parallel. There may be.

During such preliminary polymerization, when using the photopolymerization, it is preferable to irradiate light at an intensity of ^{0.001μW / cm 2 ~10mW / cm 2} , 0.05μW / cm 2 ~1mW / cm More preferably, the light is irradiated with an intensity of ² . If the illuminance of light is less than the lower limit, the reaction tends to be inadequate and the effect of prepolymerization tends to be difficult to obtain. On the other hand, when the upper limit is exceeded, polymerization of the polymerizable compound proceeds excessively, resulting in the polymerization. After the polymerization of the polymerizable composition is started from a partial region of the film made of the conductive composition, the boundary of the region is continuously directed toward the unpolymerized region at such a rate that the compound exhibiting liquid crystallinity is oriented. Even if it is moved, the compound does not sufficiently diffuse, and sufficient orientation is not formed on the film during polymerization, and as a result, it tends to be difficult to sufficiently form a periodic structure. In addition, when adopting photopolymerization in the case of such preliminary polymerization, the photopolymerization conditions are the same as the photopolymerization conditions described as the polymerization method of the polymerizable composition, except for the conditions relating to the illuminance of the light. The following conditions can be adopted.

  Thus, in the present invention, the first polymerizable compound and the second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions, and A film composed of a polymerizable composition, wherein at least one of the first polymerizable compound, the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity. Polymerization of the polymerizable composition is started from the region of the part, and the boundary of the region is continuously moved toward the unpolymerized region at a speed such that the compound exhibiting liquid crystallinity is aligned. In addition, the method for forming such an orientation is a method of orienting the compound exhibiting liquid crystallinity using a kind of shear stress generated by a compound that moves from an unpolymerized region to a polymerized region in the film after polymerization is started. Therefore, it is basically possible to control the orientation direction in the direction in which the compound moves (direction perpendicular to the boundary of the region), and the shape of the mask when polymerization is performed by photopolymerization. Accordingly, it is possible to control the orientation in various directions according to the pattern orientation and change the orientation direction of the liquid crystal molecules that become the precursor structure of the periodic structure depending on the location.

  In addition, after the boundary of the region is continuously moved toward the unpolymerized region to form the alignment region in the film, a so-called post-polymerization step is performed from the viewpoint of completing the polymerization reaction. You may give it. Note that such a post-polymerization step is a step of further proceeding the polymerization by irradiating light in order to more efficiently polymerize the unpolymerized component remaining in the alignment region, and the boundary of the polymerization region. Is a process of continuously polymerizing the alignment region formed after forming the alignment region in the film by continuously moving toward the unpolymerized region. As described above, in the present invention, the alignment is formed by utilizing the diffusion phenomenon of the substance while moving the boundary of the polymerization region. If not, after the boundary of the region is continuously moved toward the unpolymerized region, a step of further proceeding the polymerization (post-polymerization step) is performed to complete (more accelerate) the polymerization reaction. May be. The conditions for such a post-polymerization step are not particularly limited, and may be carried out while appropriately changing according to the type of components in the polymerizable composition to be used. In the present invention, the temperature condition employed during the polymerization in the post-polymerization step is a temperature condition for heating the film to 80 to 150 ° C. (more preferably 85 to 140 ° C., more preferably 90 to 130 ° C.). Is preferred. Moreover, when forming an oriented structure in a film in this way, a long oriented structure may be formed by roll-to-roll using a long board | substrate film etc. for a board | substrate.

  In addition, after polymerizing the film in this way, the film is heated (heated) to a temperature higher than the heating temperature employed during the polymerization, so that the compound exhibiting liquid crystallinity (liquid crystalline compound) is isotropic. You may hold | maintain to the temperature which becomes. Thus, after forming the alignment structure, the periodic structure can be formed more efficiently by heating to a temperature at which the compound exhibiting liquid crystallinity (liquid crystalline compound) becomes an isotropic phase. The “temperature at which the liquid crystal compound becomes isotropic phase” is a temperature higher than the temperature at which the compound exhibits a liquid crystal phase (temperature at which a phase transition occurs in the isotropic phase). Since the mobility of the liquid crystal molecules is increased and the liquid crystal molecules are in a random alignment state, the optical anisotropy of the liquid crystal molecules starts to disappear when the temperature is continued (maintained) for a long time. As described above, after the film is polymerized, when the heating (temperature raising) step is performed before the cooling step, the heating temperature is higher than the heating temperature employed during the polymerization, and the liquid crystal property is exhibited. The temperature is preferably such that the compound (liquid crystalline compound) can be in an isotropic phase. In addition, when performing such a heating (temperature rising) process, it is preferable that the upper limit of heating temperature shall be 200 degreeC. When such a heating temperature is lower than the temperature at which the liquid crystalline compound becomes isotropic, it tends to be difficult to form a periodic structure more efficiently, and on the other hand, it is higher than the upper limit temperature. In some cases, the mobility of the molecules becomes too high, and the order of the alignment direction of the liquid crystal compound formed at the time of polymerization is lost, and the formation of a regular periodic structure tends to be difficult. In addition, it is preferable that it is 0.5 to 10 minutes (more preferably 1 to 5 minutes) as a heating time in the process of heating to such a temperature that becomes an isotropic phase. When the heating time is less than the lower limit, it tends to be difficult to achieve more efficient periodic structure formation. On the other hand, when the upper limit is exceeded, the mobility of the molecule becomes too high and formed during polymerization. The order of the alignment direction of the liquid crystal compound is lost, and on the contrary, the formation of a regular periodic structure tends to be difficult.

  Further, in the present invention, polymerization is performed at such a rate that the compound exhibiting liquid crystallinity is aligned under the temperature condition in which the film composed of the polymerizable composition is heated at a heating temperature of 80 to 150 ° C. as described above. After polymerization by continuously moving the boundary of the region toward the unpolymerized region (in some cases, after performing the polymerization, the liquid crystalline compound was heated to a temperature at which it becomes an isotropic phase as described above. After), the film after polymerization is cooled. In such cooling, the temperature of the film is at least the same temperature as the heating temperature employed during the polymerization (a temperature between 80 ° C. and 150 ° C., and the rate at which the compound exhibiting liquid crystallinity is aligned. In this case, the temperature is from 0.1 to 30 ° C. until the temperature reaches 60 ° C. (when the polymerization is performed by continuously moving the boundary of the polymerization region toward the unpolymerized region at the time of polymerization). The membrane is cooled at a cooling rate of / min. The “heating temperature employed during the polymerization” relating to the temperature of the film means that the boundary of the polymerization region is continuously moved toward the unpolymerized region at a speed at which the compound exhibiting liquid crystallinity is aligned. This refers to the temperature employed when polymerizing (not the heating temperature employed during post-polymerization when employing the post-polymerization step, but the temperature employed when polymerizing so that the compound exhibiting liquid crystallinity is aligned). Here, the temperature of such a film can be measured by attaching a thermocouple and using the trade name “Data Logger GR-3500” manufactured by Keyence Corporation. When the film is present in the glass cell The temperature measured by attaching a thermocouple to the glass cell can be employed.

  It should be noted that such control of the cooling rate is started from “the same temperature as the heating temperature employed during the polymerization” as described above, so that the liquid crystalline compound flows in the film at the temperature that is the starting point of the control of the cooling rate. Therefore, the periodic structure corresponding to the cooling rate can be formed. In the case where the cooling step is directly performed after the polymerization without performing the temperature raising step, the film may be cooled as it is after the completion of the polymerization at the above cooling rate (from the temperature at the end of the polymerization after the completion of the polymerization). The film may be cooled while controlling at the cooling rate until the temperature reaches 0 ° C.). On the other hand, when the further temperature raising step as described above is performed, The temperature may be returned to the same temperature and then cooled while controlling the cooling conditions. Alternatively, after the temperature is raised, the film is cooled while controlling the cooling rate from the temperature after the temperature rise as it is. The film may be cooled at the cooling rate in the temperature range from the same temperature as the heating temperature employed during the polymerization to 60 ° C.

  In the present invention, as described above, when the polymerized film is cooled (in some cases, the polymerized film is heated to a temperature at which the liquid crystalline compound becomes isotropic phase, and then cooled. The cooling rate is 0.1 to 30 ° C./min (more preferably 0.5 to 20 ° C./min) until the temperature of the film reaches at least 60 ° C. from the same temperature as the heating temperature employed during the polymerization. Min, more preferably 0.8 to 12 ° C./min). If the cooling rate is less than the lower limit, the periodic structure tends not to be formed. On the other hand, if the cooling rate exceeds the upper limit, a periodic structure having a sufficiently high periodicity is formed in the film in which the alignment structure is formed. Tend to be difficult. The “cooling rate” referred to in the present invention is measured by attaching a thermocouple to a membrane or a cell (for example, a glass cell) containing the membrane and using a trade name “Data Logger GR-3500” manufactured by Keyence Corporation. The cooling rate (so-called instantaneous rate) at each timing (instantaneous) from the heating temperature at the time of polymerization to 60 ° C. is adopted (the same temperature as the heating temperature employed at the time of polymerization (in the polymerization step)). Per unit time as determined by measuring the time from the same temperature as the temperature adopted at the time of heating) to 60 ° C. and dividing the temperature obtained by subtracting 60 ° C. from the heating temperature. Not the average cooling rate.) Therefore, in the cooling step according to the present invention, the measuring device (manufactured by Keyence Corporation) is used at any timing until the temperature of the film reaches 60 ° C. from the same temperature as the heating temperature employed during the polymerization. The cooling rate measured using the product name “Data Logger GR-3500”) is in the range of 0.1 to 30 ° C./min.

  Further, in the present invention, the cooling rate is controlled within the above range until the temperature of the film reaches at least 60 ° C. from the same temperature as the heating temperature employed during the polymerization. Thus, a periodic structure (periodic structure in which molecular orientation changes periodically) is formed. The orientation state in the optical film in which such a periodic structure is formed is, for example, that a layer in which molecules are oriented in parallel to the direction of polymerization and a layer in which the orientation is perpendicular are alternated. In the intermediate layer, molecules can be obliquely oriented (see FIGS. 5 to 7). Such orientation state and periodic structure can also be confirmed with a polarizing microscope.

  Further, in such cooling, since it becomes possible to fix the periodic structure more stably, the temperature of the film after polymerization is 30 ° C. (more preferably, from the same temperature as the heating temperature employed during the polymerization). It is preferable to cool within the range of the cooling rate until it reaches room temperature (about 25 ° C.).

  In addition, the method for controlling the cooling rate is not particularly limited, and a method capable of achieving the cooling rate can be appropriately employed. For example, a temperature control unit (for example, a hot stage) Heating means, etc .: A film is arranged and heat can be applied according to the cooling rate, etc.) while adjusting the temperature of the film so that the desired cooling rate (almost constant) is obtained. A cooling method or the like may be employed. During cooling, the film after polymerization is not contacted with an atmospheric gas without using a cooling substrate (for example, a temperature-controlled hot stage substrate), and the temperature of the atmospheric gas is controlled. It may be cooled, or may be cooled on the cooling substrate using the cooling substrate, but from the viewpoint that strict temperature control can be performed more efficiently, It is preferable to cool the substrate while using the cooling substrate. Here, “cooling on a cooling substrate” means that the film itself is brought into direct contact with the cooling substrate and is cooled using the heating from the substrate or the thermal conductivity of the substrate. In addition to the case, for example, in the case of cooling the polymer film in the cell, the cell is brought into contact with the cooling substrate, and the cooling substrate is not indirectly cooled by only the atmospheric gas but indirectly through the cell. It includes the case of cooling while utilizing the thermal conductivity of the substrate for heating and cooling from the outside.

By adopting such cooling conditions and cooling the polymerized film, an optical film having a periodic structure can be produced. The “periodic structure” referred to in the present invention is a first-order diffracted light measured when a helium neon laser having a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of the optical film. And the intensity of transmitted light measured when a helium neon laser having a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of the transmitted light measurement film. Based on the average value, the following formula (1):
[E] = ([Is] / [Ir]) × 100 (1)
[In the formula (1), Is represents the average value (unit: mW) of the diffraction intensity of the first-order diffracted light of the optical film, and Ir represents the average value (unit: mW) of the transmitted light intensity of the transmitted light measurement film. ) And E represents diffraction efficiency (unit:%). ]
A structure in which the diffraction efficiency obtained by calculating the above is 5% or more. Here, the film for measuring transmitted light has a temperature of 0.1 to 30 ° C./min during the cooling until the temperature of the film reaches at least 60 ° C. from the same temperature as the heating temperature employed during the polymerization. The optical system having the periodic structure of the present invention, except that the method of cooling the film by immersing the polymerized film in liquid nitrogen for 5 seconds without using the method of cooling the film at a cooling rate of A film obtained by adopting the same method as the film production method is used. That is, in the present invention, the method of cooling the film by immersing the polymerized film in liquid nitrogen for 5 seconds without adopting the method of cooling at the cooling rate at the time of the cooling is employed. Uses a film obtained by adopting a method similar to the method for producing an optical film having a periodic structure of the present invention as a film for measuring transmitted light. Thus, the film obtained by changing only the cooling step to the step of cooling the membrane by immersing the polymerized membrane in liquid nitrogen for 5 seconds is based on the cooling condition (condition for immobilizing the membrane). It can be assumed that the state after polymerization (arrangement state) is a fixed film as it is, and in this film, it can be considered that only an orientation structure which is a precursor structure of a periodic structure is formed. Therefore, such a film for measuring transmitted light is composed of the same components as the optical film obtained by the method for producing an optical film having a periodic structure of the present invention, but is a film in which no periodic structure is formed. It can be considered. Then, the diffraction efficiency (from the ratio of the average value of the diffraction intensity of the first-order diffracted light of the optical film to the average value of the transmitted light (0th-order light) of the film for transmitted light measurement in which such a periodic structure is not formed ( E) can be determined. It is clear that the higher the diffraction efficiency (E) is, the higher the value (the larger the ratio), the higher the periodic structure (the higher the uniformity of periodicity). From such a viewpoint, in the present invention, a film having a periodicity such that the diffraction efficiency (E) is 5% or more is determined as an optical film having a periodic structure. That is, it is clear that the case where the diffraction efficiency (E) is less than 5% is not periodic enough to cause regular diffraction even if diffracted light is confirmed. In addition, a sufficiently regular repeating structure (periodic structure) is basically not formed. From such a viewpoint, in the present invention, a film having a diffraction efficiency of less than 5% is determined as a film in which a periodic structure is not formed even when diffracted light is confirmed.

  The average value of the transmitted light and the average value of the first-order diffracted light referred to here are measured using a helium neon laser (He-Ne laser) having a wavelength of 633 nm, and an object to be measured for the transmitted light or the first-order diffracted light (optical film and transmitted light measurement). Irradiate any three or more measurement points on the film) from the direction perpendicular to the object to be measured, and obtain the intensity peak of transmitted light or first-order diffracted light at each measurement point. It is obtained by averaging. For example, an arbitrary three or more measurement points of the optical film having the periodic structure are irradiated with a helium neon laser (He-Ne laser) having a wavelength of 633 nm from a direction perpendicular to the optical film, and each measurement point is measured. In this case, the average value of the diffraction intensity of the first-order diffracted light of the optical film is measured by measuring the peak of the diffracted light intensity at a position away from the structure in an arbitrary distance (for example, 74 mm) in the parallel direction. In addition, except that the object to be measured is changed from an optical film to a film for measuring transmitted light, the same conditions as those for obtaining the average value of the diffraction intensity of the first-order diffracted light are employed, and an arbitrary 3 By measuring the peak of transmitted light at each measurement point above the point and calculating the average value, the average value of the transmitted light intensity of the transmitted light measurement film can be determined. That. In the case of a periodic structure having a period large enough to be observed with a microscope, the periodic structure can also be confirmed by confirming periodic fluctuations in the alignment direction of liquid crystal molecules by observation with a polarizing microscope.

Further, as a method for measuring the average value of the peak of the diffracted light intensity and the average value of the intensity of the transmitted light and a method for calculating the diffraction efficiency, more specifically, a method as described below is adopted. Can do. That is, first, a trade name “Optical Power Meter 3664” and a trade name “Optical Sensor 9742” manufactured by Hioki Electric Co., Ltd. are used as measurement devices, and a He—Ne laser manufactured by MELLES GRIOT (trade name “05- LHR-151 ") is used to irradiate a helium neon laser (He-Ne laser) having a wavelength of 633 nm to an arbitrary measurement point on the film from a direction perpendicular to the optical film having the periodic structure. The peak of the first-order diffracted light intensity on the screen arranged in parallel with the film is measured. At this time, the distance to the screen installed in parallel with the structure may be arbitrarily set, and the diffracted light may be condensed using a lens or the like so as to be within the measurement range of the measurement apparatus. Such measurement is performed at least three times while sequentially changing the measurement points on the film to arbitrary positions (measurement is performed at three or more arbitrary measurement points). Based on the peak value of each diffracted light intensity obtained at each measurement point, the average value of the peak of the first-order diffracted light intensity can be obtained by obtaining the average. In addition, by using a film for measuring transmitted light instead of an optical film and measuring the transmitted light instead of diffracted light, the same as the method for obtaining the average value of the first-order diffracted light intensity peak, An average value of the intensity of the transmitted light can be obtained. In this way, the average value of the intensity of transmitted light of the sample (film for measuring transmitted light) in which no periodic structure is generated is obtained by rapidly cooling the polymerization with liquid nitrogen and fixing the uniform orientation. be able to. And based on these average values, the following formula (1):
[E] = ([Is] / [Ir]) × 100 (1)
[In the formula (1), Is represents the average value (unit: mW) of the diffraction intensity of the first-order diffracted light of the optical film, and Ir represents the average value (unit: mW) of the transmitted light intensity of the transmitted light measurement film. ) And E represents diffraction efficiency (unit:%). ]
By calculating the diffraction efficiency (%) of the optical film having a periodic structure can be obtained.

  In addition, according to the method for producing an optical film having a periodic structure of the present invention, a periodic structure having a sufficiently high periodicity in which the diffraction efficiency is 5% or more (more preferably 7% or more) is reliably produced. It becomes possible to do. If the diffraction efficiency is less than the lower limit, the degree of periodicity is not sufficient, and a periodic structure that can be used for various purposes is not formed in the film.

  Moreover, in such a periodic structure, when the first-order diffracted light is confirmed only in two positions in the polymerization movement direction and in two positions in the polymerization movement direction, two positions in the vertical direction are confirmed in a total of four positions. There is a case. In particular, when the first-order diffracted light is generated only at two positions in the polymerization movement direction, the cylindrical alignment state is formed, and the alignment direction of the liquid crystal periodically changes in the polymerization movement direction. On the other hand, when the first-order diffracted light is generated at four locations, the spherical alignment state is formed, and the alignment direction of the liquid crystal periodically changes in the polymerization movement direction and in the direction perpendicular to the polymerization movement direction. The number of generated first-order diffracted light varies depending on the liquid crystal compound to be used, the compounding ratio, the concentration of additives, the direction of polymerization movement, the temperature during polymerization, the light intensity, the cooling rate after polymerization, and the like. In addition, as such a periodic structure, when a two-dimensional periodic structure is formed, diffracted light is transmitted in four directions: a vertical direction (vertical direction: two vertical directions) and a horizontal direction (overlapping movement direction: two horizontal directions). Those that are confirmed at (four locations) are preferable, and when a one-dimensional periodic structure is formed, those in which the first-order diffracted light is confirmed at two locations only in the polymerization movement direction are preferable.

In addition, since such a periodic structure differs depending on the use of the periodic structure, it cannot be generally described. For example, the grating period is preferably 0.3 to 5.0 μm, and preferably 0.5 to 3 More preferably, it is 0.0 μm. As such a grating period, a value calculated as follows is adopted. That is, first, by adopting a method similar to the above-described method for measuring the peak of diffracted light intensity, a helium neon laser (He) having a wavelength of 633 nm from an arbitrary point on the film from a direction perpendicular to the film. -Ne laser) and diffracted light is projected onto a screen arranged in parallel with the film. Then, assuming that the distance between the film and the screen is L, and the distance between the point closest to the 0th order light and the 0th order light among the primary lights is D, the following formula (2):
[Diffraction angle (α)] = arctan (D / L) (2)
To obtain the diffraction angle α. Next, based on the diffraction angle α thus determined, the wavelength λ (= 633 nm) of the irradiation light, and the diffraction order m (= 1), the following calculation formula (3):
[Lattice period (Λ)] = (m × λ) / sin α (3)
The lattice period can be calculated by calculating.

  Thus, the optical film having a periodic structure obtained by the method for producing an optical film having a periodic structure of the present invention can be suitably used for a template such as a diffraction grating or a photonic crystal.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example, this invention is not limited to a following example.

(Synthesis Example 1: Synthesis of A6CB and homopolymer thereof)
4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl (A6CB) was synthesized by the method shown below. That is, 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 mmol with respect to 1 mol of calcium carbonate) were added to the solution, and the mixture was heated and stirred at 100 ° C. for 5 hours. . Next, the heating and stirring was stopped to complete the reaction, and the obtained reaction solution was extracted with ethyl acetate, and the formed organic layer was washed with 1N hydrochloric acid and saturated brine in this order. Next, the washed organic layer was dried over anhydrous magnesium sulfate, the desiccant was removed by filtration, and the solvent was distilled off under reduced pressure. Thereafter, the target product (4-cyano-4 ′-(6-hydroxyhexyloxy) biphenyl) is separated and purified by silica gel chromatography, and then recrystallized from chloroform and hexane to give a white solid compound A (4-cyano-). 21.3 g (72 mmol) of 4 ′-(6-hydroxyhexyloxy) biphenyl) was obtained.

  Next, after compound A (50 mmol), triethylamine 20.7 mL (150 mmol), and THF 30 mL were mixed in an eggplant flask, hydroquinone (amount of catalyst: ratio of 2 mmol to 1 mol of the compound) was added to obtain a mixture. The eggplant flask was submerged in a 23 ° C. water bath, and the atmosphere inside the eggplant flask was changed to a nitrogen atmosphere. Then, acryloyl chloride (150 mmol) was slowly added dropwise to the mixture with stirring in a nitrogen atmosphere. Got. After stirring in this manner for 48 hours under a nitrogen atmosphere, 300 mL of a saturated aqueous sodium hydrogen carbonate solution was added to the reaction solution, followed by further stirring for 30 minutes. Thereafter, the obtained reaction solution was extracted with chloroform, and the organic layer was washed with 1N hydrochloric acid and saturated brine in this order. Subsequently, the solvent was distilled off from the obtained organic layer under reduced pressure at room temperature, and the target product (4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl) was separated and purified by silica gel chromatography, and then re-reacted with methanol. By crystallizing, 9.8 g (28 mmol) of 4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl was obtained. In addition, when the structure of the compound thus obtained was confirmed by NMR and IR measurement, it was 4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl represented by the following general formula (4). It was confirmed.

  The 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl thus obtained is a compound having a rigid cyanobiphenyl structure as a mesogen, as is clear from the above formula (4). Moreover, using a differential scanning calorimeter (DSC 6220 manufactured by DSC SII NanoTechnology), the temperature was raised and lowered at a rate of 1 ° C./min to give 4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl. As a result of confirming the behavior of the liquid crystal phase, the liquid crystal phase is not shown, and the phase transition from the crystal layer to the isotropic phase is 69 ° C. during the temperature rising process, and the phase is changed from isotropic phase to crystallinity at 53 ° C. during the temperature lowering process. Phase transition.

  After 15 mmol of 4- (6-acryloyloxyhexyloxy) -4′-cyanobiphenyl thus obtained was added to 35 mL of N, N-dimethylformamide (DMF), 0.75 mmol of azobenzene was further added. Bisisobutyronitrile (AIBN) was added as a thermal polymerization initiator and stirred at a temperature of 70 ° C. for 6 hours to allow the reaction to proceed to obtain a polymerization solution. Next, the polymerization solution after completion of the reaction was put into 0.5 L of methanol to precipitate a polymer, washed again in 0.5 L of methanol, and then filtered to obtain a solid content. Subsequently, the obtained solid content was vacuum-dried at room temperature (25 ° C.) for 24 hours to obtain 4.7 g of a polymer.

  When GPC measurement was performed on the polymer thus obtained, it was confirmed that the number average molecular weight Mn of the polymer was 8000 g / mol when converted to polystyrene standards. Further, when the polymer was subjected to differential scanning calorimetry using a differential scanning calorimeter (DSC), it exhibited a glass transition temperature at 38 ° C. in the temperature rising process, liquid crystallinity at 38 to 126 ° C., and 124 to 124 in the temperature decreasing process. The liquid crystallinity was exhibited up to 29 ° C., and the glass transition temperature was exhibited at 29 ° C. Thus, 4- (6-acryloyloxyhexyloxy) -4'-cyanobiphenyl was found to be a compound exhibiting liquid crystallinity after polymerization.

(Example 1)
First, as the first polymerizable compound (compound 1), the following general formula (5):

4- (6-acryloyl) obtained in Synthesis Example 1 as the second compound (compound 2) using 1,6-hexanediol dimethacrylate represented by the formula (HDDMA: manufactured by Tokyo Chemical Industry Co., Ltd .: bifunctional methacrylate). Using oxyhexyloxy) -4′-cyanobiphenyl (A6CB: 1 functional acrylate), the mixing ratio was 2:98 in a molar ratio ([first polymerizable compound]: [second compound]). After mixing in such a manner, Irgacure 651 (manufactured by BASF) as a photopolymerization initiator was added at a ratio of 1 mol% with respect to all the compounds, and once dissolved in dichloromethane, the solvent was distilled off. A polymerizable composition was prepared.

Further, the polymerization completion times of the first polymerizable compound and the second compound were measured as follows. Two soda glass substrates with a size of 25 mm square and a thickness of 1.1 mm are made with a polyimide tape with a thickness of 100 μm as a spacer, and the overlapping area of the planar portions of the upper and lower substrates is 15 mm long and 25 mm wide (spacer A glass cell having a cell thickness of 100 μm was produced by bonding the parallel surfaces so that the sides parallel to the long side direction overlap each other by 15 mm (in this cell, the spacers were formed by two parallel vertical two sides (left and right) of the glass substrate). The portions of the glass substrate that were formed at the locations and were not formed with spacers were openings, and the size inside the cell was 15 mm long, 10 mm wide, and 100 μm thick. Next, a mixture in which the photopolymerization initiator Irgacure 651 was mixed with the compound for measuring the polymerization completion time so as to have a content of 1 mol% was prepared. Next, after the glass cell was placed on a hot stage (trade names “FP-90, FP-82HT” manufactured by METTLER TOLEDO), the glass was obtained by capillary action while melting the mixture at a temperature of 100 ° C. After pouring the mixture (containing 1 mol% of photopolymerization initiator Irgacure 651) into the cell until the inside of the cell was filled, the temperature was lowered to 85 ° C. at a rate of 0.5 ° C./min, and held at 85 ° C. for 3 minutes. Thus, a film of the polymerizable composition (film size: length 1.5 cm, width 1.0 cm, thickness 100 μm) was obtained. Next, the film was photopolymerized by irradiating 366 nm light extracted from a high pressure mercury lamp with a filter at an intensity of 1.9 mW / cm ² . After starting photopolymerization, after irradiating with light for 5 seconds, 15 seconds, 30 seconds, and 60 seconds, the film was taken out from the glass cell and the surface was washed with chloroform to visually check the film formation state. Confirmed with. The first polymerizable compound (HDDMA) was confirmed to form a film with an irradiation time of 30 seconds, and the polymerization completion time was confirmed to be between 15 seconds and 30 seconds, and the second compound (A6CB). ), Film formation was confirmed at an irradiation time of 60 seconds, and polymerization completion time was confirmed to be between 30 seconds and 60 seconds or less.

  Next, two soda glass substrates each having a size of 25 mm square and a thickness of 1.1 mm are mixed with epoxy adhesive mixed with silica particles having a diameter of 2 μm on the left and right ends (two parallel sides) of the glass substrate. A glass cell having a cell thickness of 2 μm was applied by applying and adhering them with a length of 25 mm and a width of 2.5 mm (the adhesive also functions as a spacer. The portions not applied with the adhesive were used as openings). did. The soda glass substrate used was subjected to UV ozone treatment after ultrasonic cleaning in the order of neutral detergent, ion-exchanged water, acetone and isopropanol.

Next, after the glass cell was placed on a hot stage (trade names “FP-90, FP-82HT” manufactured by METTLER TOLEDO), the polymerizable composition was melted under a temperature condition of 150 ° C. From one opening, the polymerizable composition was injected into the glass cell by capillary action from the opening over 2 minutes, then cooled to 120 ° C., and then held at 120 ° C. for 3 minutes to maintain the polymerizable composition. A membrane (membrane size: 20 mm long, 20 mm wide, 2 μm thick) was obtained. Next, while maintaining the temperature condition of 120 ° C., a photomask having a square shape of 30 mm in length and 30 mm in width so as to cover the entire film in the glass cell (so that the film enters the light shielding portion) ) Arranged. Next, irradiation of light from the light source is started, and while the light is irradiated, the photomask is moved at 20 μm / s so that the film in the glass cell is irradiated with light, so that a partial region of the film Polymerization is started, and the photomask is continuously moved so that the boundary between the light irradiation region and the light non-irradiation region moves toward the non-irradiation region at 20 μm / s. Photopolymerization was carried out in (below). Here, the process of moving such a photomask will be described with reference to FIG. 8. The exposed portion A1 on the soda glass substrate 12 of the cell before the photomask is moved is a rectangle of 5 mm in length and 25 mm in width. (The region is a region of 5 mm vertically from the opening on the side where the polymerizable composition is not injected, and the film does not exist in the region. , And the direction of movement of the photomask is a direction perpendicular to the boundary S of the light irradiation area A1 (see FIG. 8). The direction indicated by the arrow A in the middle). FIG. 8 is a schematic plan view schematically showing a state in which the substrate and the photomask are viewed from the light source side (the optical axis direction of light to be irradiated). In such photopolymerization, a high pressure mercury lamp (trade name “SX-UI501HQ” manufactured by Ushio Inc.) was used as a light source, and ultraviolet light with an illuminance of 1.2 mW / cm ² (peak wavelength: 366 nm) was irradiated. In this way, polymerization is started from a part of the region, the polymerizable composition is polymerized while moving the boundary between the polymerized region and the unpolymerized region, and light is applied to the entire region of the film-like polymerizable composition. And photopolymerization was carried out. Thus, after carrying out photopolymerization by irradiating light while moving a photomask to the film-like polymerizable composition, the illuminance is 1.2 mW / cm ² (peak wavelength) at a temperature condition of 120 ° C. for 5 minutes. : After completion of polymerization of the film by irradiation with ultraviolet light of 366 nm). Next, after maintaining the temperature of the film after performing such post-polymerization from 120 ° C. to 150 ° C. and maintaining it for 3 minutes, the liquid crystalline compound is maintained at a temperature at which it becomes an isotropic phase, The temperature was lowered (cooled) from 150 ° C. to the same temperature (120 ° C.) as the heating temperature employed during the polymerization.

  After that, with the glass cell installed on the hot stage, the temperature of the hot stage is adjusted so that the polymer film in the glass cell has a cooling rate (temperature decrease rate: instantaneous cooling rate) of 1 ° C / min (almost constant). However, it was cooled to 120 ° C. to room temperature (25 ° C.), which is the same temperature as the heating temperature employed during polymerization (the temperature employed when photopolymerization was performed by irradiating light while moving the photomask). . The cooling rate from 120 ° C. to 60 ° C. (instantaneous rate) and the cooling rate from 120 ° C. to room temperature (25 ° C.) (instantaneous rate) are both made by attaching a thermocouple to a glass cell and manufactured by Keyence Corporation. The product name “Data Logger GR-3500” was 1 ° C./min (almost constant). It should be noted that the cooling rate from 120 ° C. to room temperature (25 ° C.) was always within a range of 0.1 to 30 ° C./min. After cooling to room temperature in this way, the glass cell was removed from the hot stage to obtain a film (color: white) formed in the glass cell. The photograph of the film (thin film) formed in the obtained glass cell is shown in FIG.

  In order to confirm the properties of the film thus obtained, the glass cell was inserted between two polarizing plates arranged orthogonally with a polarizing microscope (trade name “BX50” manufactured by Olympus), and the two sheets The measurement was carried out while rotating the polarizing plate in an orthogonal arrangement. As a result of such measurement, the film in the case where the angle between the vibration direction of the analyzer and the moving direction of the photomask when the two polarizing plates (analyzer and polarizer) are rotated while being orthogonally arranged is 45 °. FIG. 13 shows a polarizing microscope photograph of the above, and the two polarizing plates are rotated in an orthogonal arrangement, the focal point is changed in the film thickness direction, and the analyzer is set so that the vibration direction and the moving direction of the photomask are parallel to each other. FIG. 14 shows a polarizing microscope photograph of the film when the film is applied. Further, the two polarizing plates are rotated in an orthogonal arrangement, the focus is changed in the film thickness direction, and the vibration direction of the analyzer and the moving direction of the photomask are made. A polarizing micrograph of the film when the angle is 45 ° is shown in FIG. 13 to 15, AN indicates the vibration direction of the analyzer (analyzer), PO indicates the vibration direction of the polarizer (polarizer), and A indicates the moving direction of the photomask. Moreover, with respect to the obtained film, the state of the film was measured using a polarizing microscope by utilizing a test plate. As a result of such measurement, polarizing micrographs of the state of the film when the direction of the optical axis of the test plate is changed are shown in FIGS. The film shown in FIG. 13 and the film shown in FIG. 16 were measured by setting the film in the same direction with respect to the microscope. The film shown in FIG. 14 and the film shown in FIG. The film shown in FIG. 15 and the film shown in FIG. 18 were measured by setting the film in the same direction with respect to the microscope. . 16-18, O shows the direction of the optical axis of a test plate.

  As is clear from the polarization micrographs shown in FIGS. 13 to 18, bright and dark stripe-like patterns were confirmed in the direction perpendicular to the polymerization progress direction (moving direction of the photomask), and from the results shown in FIGS. 13 to 15. It was found that different textures can be confirmed by changing the focus in the film thickness direction. Also, as shown in FIGS. 16 to 18, when the orientation direction of the molecules in each layer was examined using a test plate, the molecules were oriented perpendicular to the layer in which the molecules were oriented parallel to the moving direction of the photomask. It was revealed that the layers were alternately formed, and in the intermediate layer, the molecules were oriented obliquely.

  Further, as is apparent from the results of the polarizing micrographs shown in FIGS. 13 to 18, when viewed from the direction perpendicular to the glass cell surface, the results shown in FIGS. The liquid crystal molecules arranged in the direction) are confirmed (FIG. 19 conceptually shows the alignment direction of the liquid crystal molecules confirmed by the measurement results shown in FIGS. 13 and 16), and shown in FIGS. From the results, liquid crystal molecules arranged such that the angle formed with respect to the polymerization progress direction (moving direction of the photomask) is 45 ° were confirmed (the alignment direction of the liquid crystal molecules confirmed by the measurement results shown in FIGS. FIG. 20 is a diagram conceptually showing the above.) From the results shown in FIGS. 15 and 18, liquid crystal molecules arranged in a direction perpendicular to the polymerization progress direction (moving direction of the photomask) were confirmed (FIG. 15 and The drawings conceptually showing the arrangement direction of liquid crystal molecules was confirmed by the measurement results shown in FIG. 18 is shown in FIG. 21.). From these results, it can be seen that in the obtained film, a structure in which the alignment direction of the liquid crystal molecules adjacent in the polymerization progress direction is changed stepwise is formed. The result considered that the cylindrical alignment structure as shown in 7 was formed was obtained.

  Further, with respect to any three measurement points on the film thus obtained, a helium neon laser having a wavelength of 633 nm (He-Ne laser, trade name “05-LHR-151 manufactured by MELLES GRIOT Co., Ltd.) was used. )), Diffracted light was projected onto a screen arranged in parallel with the glass cell, and the projected diffracted light was measured. In such a measurement, a condensing lens (a single convex lens having a diameter of 30 mm and a focal length of 40 mm) was installed between the glass cell and the screen, and the diffracted light was condensed on the detector. FIG. 22 shows a photograph of the pattern of diffracted light projected on the screen at an arbitrary one of the measurement points on the glass cell. From the pattern (diffracted image) of the diffracted light projected on such a screen, it was confirmed that the light was diffracted in the vertical direction and the horizontal direction (movement direction of the boundary between the superposed region and the unpolymerized region).

In addition, the product name “Optical Power Meter 3664” and the product name “Optical Sensor 9742” manufactured by Hioki Electric Co., Ltd. are used as light intensity measuring devices, and the peak of the intensity of the first-order diffracted light is obtained at each of the three measurement points. When measured, the average peak of the diffracted light intensity was 0.90 mW. In addition, the transmitted light measurement film (with uniform orientation) obtained by adopting the same manufacturing method as the above optical film except that the method of cooling after polymerization was changed to a method of quenching by immersing in liquid nitrogen for 5 seconds. In the same manner as the method of measuring the intensity peak of the first-order diffracted light using a transparent sample in which no periodic structure is generated by fixing: a transparent film obtained in Comparative Example 1 described later) When the average value of the transmitted light intensity of the measurement film was measured, the average value of the transmitted light intensity was 5.72 mW. From the results of the average value of the peak of the intensity of the first-order diffracted light and the average value of the transmitted light intensity, the diffraction efficiency (%) is determined based on the above-described formula (1). It was 7%. Since such a high diffraction efficiency was confirmed, it was found that a periodic structure having a sufficiently high periodicity was formed in the obtained film. When the intensity of the diffracted light was measured, the grating period was also calculated as described above, and the grating period was 1.14 μm. As is clear from the photograph of the film (thin film) shown in FIG. 12, it was confirmed that light scattering was seen over the entire surface. From the above results, it was obtained in Example 1. It was confirmed that the film had a sufficient diffraction efficiency and a periodic structure having a sufficiently high periodicity was formed. From these results, it was found that the film obtained in Example 1 was an optical film having a periodic structure. The obtained results are shown in Table 1.

(Example 2)
When the polymer film in the glass cell is cooled, a cooling rate from 120 ° C. to room temperature (25 ° C.) and a cooling rate from 120 ° C. to 60 ° C. (thermoelectricity is applied to the glass cell while adjusting the temperature of the hot stage. Aside from changing the value measured with the Keyence Corporation product name “Data Logger GR-3500: instantaneous speed” from 1 ° C./min (almost constant) to 10 ° C./min (almost constant). Obtained the film (color: white) formed in the glass cell like Example 1. FIG. It should be noted that the cooling rate from 120 ° C. to room temperature (25 ° C.) was always within a range of 0.1 to 30 ° C./min. A photograph of the film (thin film) formed in the glass cell thus obtained is shown in FIG.

  Further, diffracted light was measured in the same manner as in Example 1 at any three measurement points on the film thus obtained. FIG. 24 shows a photograph of the pattern of diffracted light projected on the screen at any one of the measurement points on the film. From such a diffracted light pattern (diffraction image) projected on the screen, particularly strong diffraction was confirmed in the lateral direction (polymerization movement direction: movement direction of the boundary between the polymerized region and the unpolymerized region), and the obtained film It was found that a lattice-like periodic structure was formed in. Further, when the product name “Optical Power Meter 3664” and the product name “Optical Sensor 9742” manufactured by Hioki Electric Co., Ltd. were used as measuring devices, the peak of the diffracted light intensity was measured at each measurement point. The value was confirmed to be 0.522 mW, and when the diffraction efficiency (%) was determined in the same manner as in Example 1, it was found that the diffraction efficiency was 9.1%. Since such a high diffraction efficiency was confirmed, it was found that a periodic structure having a sufficiently high periodicity was formed in the obtained film. Further, when the grating period was calculated as described above, the grating period was 1.14 μm.

  Moreover, the structure of the obtained film was confirmed by observing using a polarizing microscope (The brand name "BX50" by Olympus). The obtained polarizing microscope photograph is shown in FIG. As is clear from the polarization micrograph shown in FIG. 25, the length of 2 μm in the moving direction of the photomask (the direction from the left to the right in FIG. 25 and perpendicular to the arrow PO in FIG. 25). Two grating-like periodic structures were confirmed, and the grating period confirmed by a polarizing microscope was 1.0 μm, which was almost in agreement with the above calculated value. Measurement by such a polarizing microscope also confirmed that a lattice-like periodic structure (a so-called cylindrical periodic structure) was formed in the obtained film. As is clear from the photograph of the film (thin film) shown in FIG. 23, it was confirmed that light scattering was observed over the entire surface of the obtained film.

  From the above results, it was confirmed that the periodic structure having a sufficiently high periodicity was formed in the film obtained in Example 2. From these results, it was found that the film obtained in Example 2 was an optical film having a periodic structure. The obtained results are shown in Table 1.

(Comparative Example 1)
When cooling the polymer film in the glass cell, the glass cell is taken out of the hot stage in liquid nitrogen instead of cooling to room temperature (25 ° C.) at a cooling rate (temperature decrease rate) of 1 ° C./min (almost constant). Example 1 except that the film in the glass cell was rapidly cooled with liquid nitrogen, the glass cell after cooling was taken out of the liquid nitrogen, and the temperature of the film was set to room temperature (25 ° C.). In the same manner as above, a film (color: colorless and transparent) formed in the glass cell was obtained. The photograph of the film (thin film) formed in the obtained glass cell is shown in FIG.

  In order to confirm the characteristics of the film thus obtained, the glass cell was inserted between two orthogonally arranged polarizing plates and observed while rotating the glass cell. And it was confirmed that the obtained film was an orientation film oriented almost uniformly in an area of about 20 mm square. The dark field direction was parallel or perpendicular to the photomask movement direction with respect to the absorption axes of the two polarizing plates arranged orthogonally.

  Further, diffracted light was measured in the same manner as in Example 1 at any three measurement points on the film thus obtained. FIG. 27 shows a photograph of the light pattern projected on the screen for any one of the measurement points on the film. From the light pattern projected on the screen (light projection image), no light diffraction was confirmed, and it was found that no periodic structure was formed on the obtained film. In addition, the product name “Optical Power Meter 3664” and the product name “Optical Sensor 9742” manufactured by Hioki Electric Co., Ltd. were used as measurement devices, and the average value of the intensity of transmitted light at any three measurement points of the film was obtained. However, the average value of the transmitted light intensity of the film was 5.72 mW.

  From the above results, it was confirmed that in the film obtained in Comparative Example 1, although a compound having liquid crystallinity (polymer having a structural unit derived from A6CB) is oriented, no periodic structure is formed. The obtained results are shown in Table 1.

(Comparative Example 2)
When cooling the polymer film in the glass cell, instead of cooling to room temperature (25 ° C.) with a cooling rate (temperature decrease rate) of 1 ° C./min (almost constant), the glass cell is taken out of the hot stage and 5 ° C. The glass cell is hung in the refrigerator so that the entire surface of the cell can come into contact with the cold air (atmosphere gas in the refrigerator), the film after photopolymerization is cooled in the cold air (in air), and then A film (color: white and partially transparent) formed in the glass cell was obtained in the same manner as in Example 1 except that the solution was cooled to room temperature (25 ° C.) in the refrigerator under the same conditions. In addition, the time until the temperature of the film | membrane in a glass cell becomes 120 to 60 degreeC was measured, and the average cooling calculated | required by dividing the temperature difference 60 degreeC (120 degreeC-60 degreeC) by the measured time The speed was 37 ° C./minute (note that the temperature of the film itself was measured by attaching a thermocouple to a glass cell and using a trade name “Data Logger GR-3500” manufactured by Keyence Corporation). A photograph of the film (thin film) formed in the glass cell thus obtained is shown in FIG.

  In order to confirm the characteristics of the film thus obtained, the glass cell was inserted between two polarizing plates arranged orthogonally and observed while rotating the glass cell. It was found that the obtained film was partially oriented in a region of about 20 mm square and had some periodicity in some regions. The dark field direction was parallel or perpendicular to the absorption axes of the two polarizing plates arranged orthogonally.

  Further, diffracted light was measured in the same manner as in Example 1 at any three measurement points on the film thus obtained. FIG. 29 shows a photograph of the pattern of diffracted light projected on the screen at any one of the measurement points on the film. Although the diffracted light can be confirmed in the vertical direction and the horizontal direction (polymerization movement direction) from the pattern (diffracted image) of the diffracted light projected on such a screen, the product name “optical power” manufactured by Hioki Electric Co., Ltd. is used as a measuring device. When the peak of the first-order diffracted light intensity was measured at each measurement point using the “Meter 3664” and the trade name “Optical Sensor 9742”, the average peak of the first-order diffracted light intensity was 0.025 mW, which was the same as in Example 1. The diffraction efficiency was calculated as described above, and the diffraction efficiency (%) of the obtained film was 0.4%. From these results, it was found that the periodicity was not sufficiently confirmed in the obtained film, and a periodic structure having a diffraction efficiency of 5% or more was not formed. In addition, although the periodic structure which has sufficient periodicity was not formed, when the grating period of the film was calculated from the confirmed diffracted light, the grating period was 1.14 μm. Further, as is apparent from the photograph of the film (thin film) shown in FIG. 28, no light scattering (white) was observed on the entire surface of the obtained film.

  From the above results, in the film obtained in Comparative Example 2, although the compound having liquid crystallinity (polymer having a structural unit derived from A6CB) is oriented, the periodic structure such that the diffraction efficiency is 5% or more. It was confirmed that was not formed. The obtained results are shown in Table 1.

  As is clear from the results as described above, in the films obtained in Examples 1 and 2, it was confirmed that an optical film in which a periodic structure having a sufficiently high periodicity was formed was formed. According to the method for producing an optical film of the present invention, when producing an optical film having a periodic structure formed in the film, a method of mechanically engraving a micron-order linear groove on the film, photolithography, It was found that an optical film having a periodic structure can be more easily produced without employing an optical method such as the above.

  As described above, according to the present invention, there is provided a method for producing an optical film having a periodic structure, which can more easily produce an optical film in which a periodic structure having a sufficiently high periodicity is formed. It becomes possible to do. As described above, the method for producing an optical film having a periodic structure according to the present invention can form a periodic structure uniformly over the entire surface. For example, a template for growing a diffraction grating or a photonic crystal is used. It is particularly useful as a method for producing an optical film having a periodic structure for use in, for example.

  11: light source, 12: substrate, 13: film made of polymerizable composition, 14: photomask, 14A: opening, X: length of short side of opening 14A, Y: length of long side of opening 14A S: boundary of overlapping region, A: arrow conceptually indicating a direction in which the boundary S of overlapping region is moved, P: arrow conceptually indicating a direction perpendicular to the boundary S of overlapping region, L: irradiation from a light source Light, A1: region irradiated with light (polymerized region: exposed portion), A2: unpolymerized region not irradiated with light (unpolymerized region: light-shielding portion), A3: orientation formed A4: a region in which one spiral array is formed, D: a grating period of a periodic structure (width of one period), AN: vibration direction of an analyzer (analyzer), PO: polarizer (polarizer) ) Vibration direction, O: direction of the optical axis of the test plate.

Claims (8)

Containing a first polymerizable compound and a second compound having a polymerization completion time longer than that of the first polymerizable compound when polymerized under the same conditions, and the first polymerizable compound, Using a film made of a polymerizable composition, wherein at least one of the second compound and the compound obtained after polymerization is a compound exhibiting liquid crystallinity,
Polymerization of the polymerizable composition is started from a partial region of the film, and the boundary of the region is continuously moved toward an unpolymerized region at such a speed that the compound exhibiting liquid crystallinity is aligned. After polymerization, the step of cooling the polymerized film to obtain an optical film having a periodic structure,
Polymerizing the film while heating at a heating temperature of 80 to 150 ° C. during the polymerization; and
During the cooling, the film is cooled at a cooling rate of 0.1 to 30 ° C./min until the temperature of the film reaches at least 60 ° C. from the same heating temperature employed during the polymerization,
A method for producing an optical film having a periodic structure. An optical film having the periodic structure,
An average value of diffraction intensities of the first-order diffracted light measured when a helium neon laser having a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of the optical film;
2. The method according to claim 1, except that a method of cooling the film by immersing the polymerized film in liquid nitrogen for 5 seconds without using a method of cooling at the cooling rate is adopted at the time of cooling. When a helium neon laser having a wavelength of 633 nm is irradiated from a perpendicular direction to any three or more measurement points of a transmitted light measurement film obtained by adopting the same method as the optical film manufacturing method of An average value of the intensity of transmitted light to be measured;
Based on the following formula (1):
[E] = ([Is] / [Ir]) × 100 (1)
[In the formula (1), Is represents the average value (unit: mW) of the diffraction intensity of the first-order diffracted light of the optical film, and Ir represents the average value (unit: mW) of the transmitted light intensity of the transmitted light measurement film. ) And E represents diffraction efficiency (unit:%). ]
2. The method for producing an optical film having a periodic structure according to claim 1, wherein the optical film has a diffraction efficiency of 5% or more obtained by calculating.   The method for producing an optical film having a periodic structure according to claim 1, wherein the cooling rate is a cooling rate of 0.8 to 12 ° C./min.   The first polymerizable 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 of the polymerizable functional groups of the second compound. The manufacturing method of the optical film which has the periodic structure as described in any one of Claims 1-3 characterized by the above-mentioned.   In order to perform polymerization of the polymerizable composition by photopolymerization and continuously move the boundary toward the unpolymerized region, the boundary of the light irradiation region is continuously directed toward the unirradiated region. The method for producing an optical film having a periodic structure according to any one of claims 1 to 4, wherein the optical film has a periodic structure.   A photomask is used during the photopolymerization, and the photomask is continuously moved so that the boundary of the light irradiation region is continuously moved toward an unirradiated region of light. The manufacturing method of the optical film which has a periodic structure of Claim 5. The speed of moving the boundary is 1 × 10 ⁻⁷ to 4 × 10 ⁻¹ m / s, The optical film having a periodic structure according to claim 1. Production method. The first polymerizable compound is represented by the following general formula (1):
^{Z 1 p-M 1 -L 1} - (M 2 -L 2) q-M 3 -Z 2 r (1)
And each of Z ¹ , Z ² , M ¹ , M ² , M ³ , L ¹ , L ² , p, q, and r in the formula is represented by the following compounds C11 to C13 [in the compound C11: Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is an acryl group and a methacryl group. Any one of the groups, S ¹ is any ^one of a single bond and a linear alkylene group having 1 to 12 carbon atoms, and L ³ is any one of an ether group, an ester group, and a carbonate group. Yes, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is either a single bond or —COO—, q is 0, and M ³ is 1,4- A phenylene group and r is 1,
In the compound C12, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is acrylic Any one of a group and a methacryl group, S ¹ is any ^one of a single bond and a linear alkylene group having 1 to 12 carbon atoms, and L ³ is an ether group, an ester group or a carbonate group. Any one, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is —COO—, M ² is a 1,4-phenylene group, and L ² is —OCO—. Q is 1, M ³ is a 1,4-phenylene group, and r is 1.
In the compound C13, Z ¹ and Z ² in the formula (1) may be the same or different, and each is a group represented by the formula: -L ³ -S ¹ -F ¹ , and F ¹ is acrylic Or a methacryl group, S ¹ is a group represented by the formula: (CH ₂ CH ₂ O) z (z is any one of 2 and 3), and L ³ is A single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is either a single bond or an ester group, q is 0, and M ³ is 1,4- A phenylene group and r is 1. ], The following general formula (2):
(In the formula, R ⁵ is either hydrogen or a methyl group, and x is 2 or 3.)
And a compound C14 represented by the following general formula (3):
(In the formula, R ⁵ is either hydrogen or a methyl group, and y is an integer of 2 to 12.)
And at least one compound selected from the group consisting of compound C15 represented by:
The second compound is represented by the following general formula (1):
^{Z 1 p-M 1 -L 1} - (M 2 -L 2) q-M 3 -Z 2 r (1)
And each of Z ¹ , Z ² , M ¹ , M ² , M ³ , L ¹ , L ² , p, q, and r in the formula is represented by the following compounds C21 to C24 [in the compound C21: Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is ^one of an acrylic group and a methacryl group, and S ¹ is a single bond And L ³ is a single bond, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, q is 0, and M ³ is 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, and r Is 1,
In Compound C22, Z ¹ in Formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is A linear alkylene group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is a single bond, and q is 0 M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. One selected, and r is 1,
In compound C23, Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is any one of an acryl group and a methacryl group, and S ¹ is A group represented by the formula: (CH ₂ CH ₂ O) z (z is any one of 2 and 3), L ³ is a single bond, p is 1, M ¹ is 1 , 4-phenylene group, L ¹ is a single bond, q is 0, M ³ is a 1,4-phenylene group, Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, carbon One selected from an alkyl group having 1 to 12 carbon atoms and an alkoxy group having 1 to 12 carbon atoms, and r is 1.
In compound C24, Z ¹ in formula (1) is a group represented by the formula: -L ³ -S ¹ -F ¹ , F ¹ is ^one of an acryl group and a methacryl group, and S ¹ is A linear alkylene group having 1 to 12 carbon atoms, L ³ is an ether group, p is 1, M ¹ is a 1,4-phenylene group, L ¹ is —COO—, and q is 0, M ³ is a 1,4-phenylene group, and Z ² is a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 12 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms. And r is 1. ]
Being at least one compound selected from the group consisting of:
The manufacturing method of the optical film which has the periodic structure as described in any one of Claims 1-7 characterized by these.