Phase difference film and method for manufacturing the same

Abstract

The present invention provides a three-dimensional phase difference film that can be easily manufactured at low cost and exhibits good inverse wavelength dispersion, as well as a method for manufacturing the same. [Solution] A phase difference film comprising an optically anisotropic layer containing a polymer of a photopolymerizable liquid crystal compound, wherein the photopolymerizable liquid crystal compound is a compound having an NN bond and having an Nz coefficient of less than 1. A method for manufacturing a phase difference film, comprising the steps of: (s1) preparing a substrate; (s2) providing a layer of a liquid crystal composition containing a photopolymerizable liquid crystal compound on the surface of the substrate, wherein the photopolymerizable liquid crystal compound is oriented in a certain orientation direction in the layer; and (s3) irradiating the layer of the liquid crystal composition with linearly polarized ultraviolet light, wherein the polarization direction of the linearly polarized ultraviolet light is perpendicular to the orientation direction.

Description

[Technical Field]

[0001] The present invention relates to a phase difference film and a method for manufacturing the same. [Background technology]

[0002] As a material for constructing optical components such as phase difference films, an optically anisotropic layer, that is, a layered structure having optical anisotropy, is used.

[0003] As an optically anisotropic layer, a so-called three-dimensional phase difference film, i.e., a film in which the principal refractive indices nx, ny, and nz have the relationship nx > nz > ny, is useful. When a three-dimensional phase difference film is used as a component of a display device such as a liquid crystal display device, advantageous functions such as viewing angle compensation can be realized. However, in normal operations to impart phase difference to a film, such as stretching, it is extremely difficult to make nz larger than ny when nx > ny. Therefore, three-dimensional phase difference films are manufactured by methods such as combining multiple types of materials with special properties, or by special processes such as film shrinkage. Consequently, the manufacture of three-dimensional phase difference films is relatively costly.

[0004] As a simpler and lower-cost method for manufacturing three-dimensional phase difference films, it has been proposed to produce a three-dimensional phase difference film by polymerizing a photopolymerizable liquid crystal compound by irradiating it with polarized ultraviolet light (Patent Documents 1-2). [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2008-164925 [Patent Document 2] Japanese Patent Publication No. 2023-023609 [Overview of the project] [Problems that the invention aims to solve]

[0006] When a three-dimensional phase difference film is used as a component of a display device such as a liquid crystal display device, it is preferable that it exhibits desired optical performance over a wide wavelength range, such as the entire visible region. To achieve this, it is required to be a so-called inverse wavelength dispersive film.

[0007] However, a three-dimensional phase difference film that can be easily manufactured at low cost and exhibits good inverse wavelength dispersion has not yet been obtained.

[0008] Therefore, the object of the present invention is to provide a three-dimensional phase difference film that can be easily manufactured at low cost and exhibits good inverse wavelength dispersion, as well as a method for manufacturing the same. [Means for solving the problem]

[0009] As a result of studies conducted to solve the aforementioned problems, the inventors of the present invention discovered that such a three-dimensional phase difference film can be constructed by an optically anisotropic layer containing a polymer of a specific photopolymerizable liquid crystal compound, and thus completed the present invention. In other words, the present invention provides the following:

[0010] (1) comprising an optically anisotropic layer containing a polymer of a photopolymerizable liquid crystal compound, The photopolymerizable liquid crystal compound is a compound having an NN bond, The Nz coefficient is less than 1. Phase difference film. (2) The phase difference film according to (1), wherein the photopolymerizable liquid crystal compound has one or more ultraviolet absorption peaks in the region less than 340 nm and in the region 340 nm or more. (3) The phase difference film according to (1) or (2), wherein the photopolymerizable liquid crystal compound is an inverse wavelength dispersive liquid crystal compound. (4) A method for manufacturing a phase difference film according to any one of items (1) to (3), Steps to prepare the base material (s1), Step (s2) is a step of providing a layer of liquid crystal composition containing a photopolymerizable liquid crystal compound on the surface of the substrate, wherein the photopolymerizable liquid crystal compound is oriented in a certain orientation direction in the layer, and A method for manufacturing a phase difference film, comprising step (s3) of irradiating a layer of the liquid crystal composition with linearly polarized ultraviolet light, wherein the polarization direction of the linearly polarized ultraviolet light is perpendicular to the orientation direction. (5) The method for manufacturing a phase difference film according to (4), wherein in step (s3), the in-plane phase difference Re(550) of the liquid crystal composition layer at a wavelength of 550 nm increases. [Effects of the Invention]

[0011] The present invention provides a three-dimensional phase difference film that can be easily manufactured at low cost and exhibits good inverse wavelength dispersion, as well as a method for manufacturing the same. [Modes for carrying out the invention]

[0012] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with modifications as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0013] In the following description, the orientation of the elements being "parallel," "perpendicular," and "orthogonal" may include errors within a range that does not impair the effects of the present invention, for example, within a range of ±3°, ±2°, or ±1°, unless otherwise specified.

[0014] In the following explanation, the in-plane phase difference Re of a layer is given by the value Re = (nx - ny) × d unless otherwise specified. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the layer (in-plane direction) that gives the maximum refractive index. ny represents the refractive index in the aforementioned in-plane direction of the layer that is perpendicular to the direction of nx. Also, nz represents the refractive index in the thickness direction of the layer. d represents the thickness of the layer. The measurement wavelength is 550 nm unless otherwise specified.

[0015] In the following explanation, when expressing phase difference, symbols combining the type of phase difference and the measurement wavelength, or symbols combining the type of phase difference, the measurement wavelength, and the symbol of the object being measured may be used. For example, for layer (L3), the symbol "Re(550)(L3)" may be used to refer to the in-plane phase difference Re measured at a measurement wavelength of 550 nm.

[0016] In the following explanation, unless otherwise specified, "reverse wavelength dispersion" of a layer refers to the property that the in-plane phase difference Re(450) at a wavelength of 450 nm, the in-plane phase difference Re(550) at a wavelength of 550 nm, and the in-plane phase difference Re(650) at a wavelength of 650 nm satisfy the following equation (e1). A layer of material having reverse wavelength dispersion preferably satisfies both equation (e1) and equation (e2) below. Furthermore, a layer with high reverse wavelength dispersion means a layer with a small value of Re(450) / Re(550). Re(450) / Re(550)<1.00 Equation (e1) Re(650) / Re(550)>1.00 Equation (e2)

[0017] In the following explanation, unless otherwise stated in the context, light that is not explicitly polarized is unpolarized, meaning it has no polarization component bias.

[0018] (Phase difference film) The phase difference film of the present invention comprises a specific optical anisotropic layer. The optical anisotropic layer may have various phase differences suitable for use as an optical film. The phase difference film of the present invention may exhibit a phase difference through a combination of the optical anisotropic layer and other layers, but preferably, the phase difference film of the present invention consists only of an optical anisotropic layer, or is a laminate of an optical anisotropic layer and an isotropic film, and exhibits a phase difference due to the optical properties of the optical anisotropic layer.

[0019] The phase difference film of the present invention may have multiple optical anisotropic layers stacked on top of each other, but it is preferable that the optical anisotropic layer be a single layer. As described below, the specific optical anisotropic layer in this application may have desirable optical properties as a single layer. A phase difference film having an optical anisotropic layer as a single layer can be manufactured easily and at low cost. Even if the optical anisotropic layer is a single layer, the phase difference film of the present invention can be a three-dimensional phase difference film that exhibits good inverse wavelength dispersion.

[0020] The phase difference film of the present invention preferably has an in-plane phase difference Re of a certain size that allows it to be used alone for applications such as λ / 2 wave plates and λ / 4 wave plates. Specifically, the Re of the phase difference film can preferably be 132 nm to 325 nm. However, the Re of the phase difference film is not limited to this range, and may be a larger or smaller value, and may be used in combination with other layers for applications such as λ / 2 wave plates and λ / 4 wave plates.

[0021] In particular, when used as a λ / 2 wave plate, the Re of the phase difference film is preferably 265 nm or more, more preferably 280 nm, while preferably 325 nm or less, and more preferably 310 nm or less. When used as a λ / 4 wave plate, the Re of the phase difference film is preferably 132 nm or more, more preferably 140 nm, while preferably 163 nm or less, and more preferably 155 nm or less. When the phase difference of the phase difference film of the present invention is manifested by an optically anisotropic layer, it is preferable that the in-plane phase difference Re of the optically anisotropic layer is within the range described above. In particular, when the phase difference of the phase difference film of the present invention is manifested by a single optically anisotropic layer, it is preferable that the in-plane phase difference Re of the single optically anisotropic layer is within the range described above.

[0022] The phase difference film of the present invention can be a film exhibiting inverse wavelength dispersion. Specifically, the Re(450) / Re(550) of the phase difference film of the present invention is preferably less than 1.00, more preferably 0.95 or less, and even more preferably 0.90 or less. The lower limit of Re(450) / Re(550) is not particularly limited, but can be, for example, 0.78 or more. Furthermore, the Re(650) / Re(550) of the phase difference film of the present invention is preferably greater than 1.00, more preferably 1.05 or more, and even more preferably 1.10 or more. The upper limit of Re(650) / Re(550) is not particularly limited, but can be, for example, 1.20 or less.

[0023] The phase difference film of the present invention has an Nz coefficient of less than 1. Therefore, the optical anisotropy itself may also have an Nz coefficient of less than 1. By having an Nz coefficient of less than 1, the phase difference film of the present invention can exhibit advantageous functions such as a field of view compensation function. Specifically, the Nz coefficient of the phase difference film of the present invention is preferably 0.98 or less, more preferably 0.95 or less. The lower limit of the Nz coefficient is not particularly limited, but can be, for example, 0.40 or more. When the phase difference of the phase difference film of the present invention is expressed by an optical anisotropy layer, it is preferable that the Nz coefficient of the optical anisotropy layer is within the range described above. In particular, when the phase difference of the phase difference film of the present invention is expressed by a single optical anisotropy layer, it is preferable that the Nz coefficient of the single optical anisotropy layer is within the range described above.

[0024] The optically anisotropic layer contains a polymer of a photopolymerizable liquid crystal compound. A photopolymerizable liquid crystal compound is a liquid crystal compound that has the property of being polymerizable by irradiation with light. Here, light includes visible light, infrared light, and ultraviolet light. From the viewpoint of ease of polymerization, it is preferable that the photopolymerizable liquid crystal compound is a compound that can be polymerized by ultraviolet light. A liquid crystal compound is a compound that can exhibit a liquid crystal phase, either on its own or in a composition with any optional components such as appropriate additives and solvents. A liquid crystal composition containing a photopolymerizable liquid crystal compound (in this application, for the sake of explanation, "liquid crystal composition" includes not only mixtures of a photopolymerizable liquid crystal compound and any optional components, but also those consisting only of a photopolymerizable liquid crystal compound) can be formed into a layer by operations such as coating it on the surface of a suitable substrate, the photopolymerizable liquid crystal compound in the layer can be oriented to exhibit a liquid crystal phase, and by irradiating the layer with light while maintaining this orientation, it can be made into a solid while exhibiting the liquid crystal phase, and as a result, a solid layer having optical anisotropy can be formed.

[0025] In this application, the photopolymerizable liquid crystal compound has an NN bond in its molecular structure. The inventors have found that an optically anisotropic layer formed from such a polymer of a photopolymerizable liquid crystal compound can be easily manufactured as a three-dimensional phase difference film exhibiting good inverse wavelength dispersion even as a single layer.

[0026] In a preferred example, the photopolymerizable liquid crystal compound has one or more ultraviolet absorption peaks below 340 nm and above 340 nm. By using a compound having such peaks as the photopolymerizable liquid crystal compound, an optically anisotropic layer exhibiting good inverse wavelength dispersion can be manufactured more easily, even as a single layer.

[0027] The peak of a photopolymerizable liquid crystal compound can be measured by dissolving the compound in a suitable solvent to form a solution and measuring the ultraviolet absorbance of the solution. Alternatively, if data for the ultraviolet absorbance peak of a specific photopolymerizable liquid crystal compound is known, that data may be referred to.

[0028] In a preferred example, the photopolymerizable liquid crystal compound is an inverse wavelength dispersive liquid crystal compound. By using an inverse wavelength dispersive liquid crystal compound as the photopolymerizable liquid crystal compound, an inverse wavelength dispersive phase difference film can be easily formed. An inverse wavelength dispersive liquid crystal compound is a liquid crystal compound capable of exhibiting inverse wavelength dispersive birefringence. Furthermore, a liquid crystal compound capable of exhibiting inverse wavelength dispersive birefringence refers to a liquid crystal compound that exhibits inverse wavelength dispersive birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in that layer. On the other hand, a forward-dispersive liquid crystal compound is a liquid crystal compound capable of exhibiting forward wavelength dispersive birefringence. Furthermore, a liquid crystal compound capable of exhibiting forward wavelength dispersive birefringence refers to a liquid crystal compound that exhibits forward wavelength dispersive birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in that layer.

[0029] Normally, the wavelength dispersion of birefringence exhibited by a liquid crystal compound can be confirmed by examining the wavelength dispersion of birefringence exhibited by a layer of liquid crystal compound when the liquid crystal compound is homogeneously oriented. Homogeneously oriented liquid crystal compound means forming a layer containing the liquid crystal compound and oriented the direction of the maximum refractive index in the refractive index ellipsoid of the liquid crystal compound molecules in that layer in a certain direction parallel to the plane of the layer.

[0030] Specifically, the fact that a photopolymerizable liquid crystal compound is inverse wavelength dispersive can be confirmed by the following method. (c1) Prepare a liquid crystal composition comprising a photopolymerizable liquid crystal compound, a surfactant, and a solvent. (c2) A liquid crystal composition is applied to a substrate on which an orientation-regulating force is applied to the surface to form a coating film, and the coating film is dried to form a layer of photopolymerizable liquid crystal compound. (c3) If necessary, the photopolymerizable liquid crystal compound layer is heated to orient the polymerizable liquid crystal compound in the photopolymerizable liquid crystal compound layer, and the in-plane retardations Re(450), Re(550), and Re(650) of the photopolymerizable liquid crystal compound layer at wavelengths of 450 nm, 550 nm, and 650 nm are measured to confirm that Re(450) / Re(550) < 1.00 (or that Re(450) / Re(550) < 1.00 and Re(650) / Re(550) > 1.00).

[0031] More specifically, the layer (L2) or layer (L3) obtained by step (s2) of the method for manufacturing the phase difference film of the present invention (described later) can be used as the layer of the photopolymerizable liquid crystal compound obtained in (2) above, and the presence or absence of inverse wavelength dispersion can be evaluated by performing (3) above on it.

[0032] The molecular structure of a reverse wavelength-dispersive liquid crystal compound may have a main chain mesogen and side chain mesogens that can be oriented in a direction different from that of the main chain mesogen. In this case, if there is an NN bond at the binding site between the main chain mesogen and the side chain mesogen, or within the side chain mesogen, good reverse wavelength dispersion can be observed, but the Re value is likely to increase due to the cleavage of such a bond upon irradiation with ultraviolet light. A reverse wavelength-dispersive liquid crystal compound having an NN bond at the binding site between the main chain mesogen and the side chain mesogen, or within the side chain mesogen, can be easily used to form a phase difference film with desired optical properties by step (s3) (described later) of the manufacturing method of the present invention, and can be used particularly useful as a photopolymerizable liquid crystal compound in the present invention. More specific examples of reverse wavelength-dispersive photopolymerizable liquid crystal compounds will be described later.

[0033] (Polymers of photopolymerizable liquid crystal compounds) In this application, the term "polymer of a photopolymerizable liquid crystal compound" includes not only the polymer itself formed solely by the polymerization reaction of a photopolymerizable liquid crystal compound, but also the substance obtained as a result of further processing of the polymer after the polymerization reaction.

[0034] The method for polymerizing a photopolymerizable liquid crystal compound and further processing it to obtain a polymer having a desired molecular structure and layered shape is not particularly limited, but for example, a polymer having a layered shape can be obtained by processing a liquid crystal composition containing a photopolymerizable liquid crystal compound by steps (s2) to (s3) (described later) of the method for manufacturing a phase difference film of the present invention.

[0035] (Optional components of the optically anisotropic layer) The optically anisotropic layer may contain optional components in addition to the polymer of the photopolymerizable liquid crystal compound. Examples of optional components include polymerization initiators, antioxidants, and trace amounts of solvents contained in the liquid crystal composition for polymerizing the photopolymerizable liquid crystal compound.

[0036] Another example of an optional component is a component generated by the decomposition of the polymer during post-polymerization processing of the photopolymerizable liquid crystal compound. Specifically, the optically anisotropic layer may contain fragments of side chains generated as a result of cleavage of side chains in the polymer of the photopolymerizable liquid crystal compound in step (s3) (described later) of the method for manufacturing the phase difference film of the present invention. Such fragments are amines, imines, or salts thereof generated as a result of cleavage of NN bonds. Since such fragments are usually non-volatile, they remain in the optically anisotropic layer. Therefore, the optically anisotropic layer in the phase difference film of the present invention may contain such amines or salts thereof. Specifically, if the photopolymerizable liquid crystal compound is a compound represented by formula (I) described later, HN(R g )R h HN=C(R g )R h HN=R i R represents a group selected from the group consisting of these salts. g , R h , and R i The meaning of these terms is the same as those in equation (I) described later.

[0037] (Any component of a phase difference film) The phase difference film of the present invention may include any component in addition to the optical anisotropy layer. The phase difference film of the present invention may comprise two or more of the specific optical anisotropy layers described above, or it may comprise layers having optical anisotropy other than the specific optical anisotropy layers of the present invention in addition to the optical anisotropy layers described above. However, in the present invention, the desired optical properties described above can be easily obtained with only a single optical anisotropy layer, so the phase difference film of the present invention may comprise only a single optical anisotropy layer as the layer that exhibits optical anisotropy.

[0038] Another example of an optional component of the present invention is a substrate for supporting the optically anisotropic layer. Specifically, the phase difference film of the present invention may be a laminate of an optically anisotropic layer and an isotropic film for mechanically supporting the optically anisotropic layer.

[0039] (Applications of phase difference film) The phase difference film of the present invention can be used as an optical film having a phase difference in display devices such as liquid crystal display devices and organic electroluminescent display devices. For example, it can be provided with optical anisotropy suitable for performing functions such as λ / 4 wave plates, λ / 2 wave plates, and optical compensation layers, and can be used in these applications.

[0040] (Method of manufacturing phase difference film) The phase difference film of the present invention can preferably be manufactured by a manufacturing method including the following steps (s1) to (s3). In the following, this manufacturing method will be described as a method for manufacturing the phase difference film of the present invention.

[0041] Process (s1): The process of preparing the base material. Step (s2): A step of providing a layer of liquid crystal composition containing a photopolymerizable liquid crystal compound on the surface of a substrate. Step (s3): A step of irradiating a layer of liquid crystal composition with linearly polarized ultraviolet light.

[0042] (Process (s1)) The substrate prepared in step (s1) can be appropriately selected from those commonly used in the relevant technical field. The substrate may have an orientation-regulating force on its surface. For example, it may have an orientation-regulating force that restricts the orientation direction of the photopolymerizable liquid crystal compound on its surface through stretching, rubbing, or the like.

[0043] (Process (s2)) Process (s2) can be carried out by performing the operations (2-1) to (2-3) below. (2-1) A liquid crystal composition containing a photopolymerizable liquid crystal compound is applied to form a layer of the liquid crystal composition. (2-2) Further, if necessary, the layers of the liquid crystal composition are subjected to orientation treatment. (2-3) If necessary, the liquid crystal composition layer is further cured.

[0044] In the following, for the sake of explanation, the layer obtained in step (s2-1) in which the liquid liquid crystal composition is unfolded may be referred to as "layer (L1)", the layer of liquid crystal composition in which the photopolymerizable liquid crystal compound is oriented but not yet cured may be referred to as "layer (L2)", and the layer of liquid crystal composition in which the photopolymerizable liquid crystal compound has been cured with the photopolymerizable liquid crystal compound oriented may be referred to as "layer (L3)". In layer (L3), some or all of the photopolymerizable liquid crystal compound in the layer of the liquid crystal composition may exist in a polymerized state.

[0045] Step (s2-1) can be carried out by applying a liquid crystal composition to the surface of the substrate prepared in step (s1) (or, if the orientation-restricting force of a surface having an orientation-restricting force is utilized, the surface having said orientation-restricting force), thereby obtaining a multilayer material including the substrate and layer (L1).

[0046] The liquid crystal composition may contain optional components in addition to the photopolymerizable liquid crystal compound. The type and proportion of the optional components can be appropriately selected within a range that does not significantly impair the effects of the present invention. Examples of such optional components include surfactants, antioxidants, solvents such as various organic solvents, and polymerization initiators. As polymerization initiators, photopolymerization initiators such as ultraviolet polymerization initiators are preferred from the viewpoint of facilitating polymerization operations. Examples of polymerization initiators include "NCI-730," "NCI-831," and "NCI-930" from ADEKA, and "Irgacure Oxe03," "Irgacure Oxe04," and "Irgacure379" from BASF.

[0047] Step (s2-2) can be performed, for example, by forming layer (L1) and then adjusting its temperature to orient the photopolymerizable liquid crystal compound in the liquid crystal composition, thereby obtaining layer (L2) exhibiting the desired liquid crystal phase. However, in cases where the photopolymerizable liquid crystal compound has the property of orienting at room temperature, step (s2-2) may be achieved and layer (L2) obtained without any special operation.

[0048] When layer (L1) is heated in step (s2-2), the solvent in the liquid crystal composition may volatilize due to the heating, and drying of layer (L1) may also be achieved. However, in cases where the solvent is highly volatile, such drying may be achieved without any special operation. The heating temperature and time are not particularly limited, and a temperature suitable for the photopolymerizable liquid crystal compound and liquid crystal composition used can be appropriately selected. In most cases, the heating temperature may be in the range of 50 to 170°C, and the heating time may be 30 seconds to 10 minutes.

[0049] In step (s2-2), the photopolymerizable liquid crystal compound is oriented in a certain orientation direction within layer (L2). The orientation direction is the direction in which the principal refractive index nx is observed when the refractive index of layer (L2) or the layer (L3) obtained by curing layer (L2) is measured. The orientation direction is usually the direction in which the principal axis of the molecules of the photopolymerizable liquid crystal compound is oriented.

[0050] Such an alignment direction is defined as the in-plane direction of the layer (L2), that is, the direction along the plane of the layer (L2). For example, when the liquid crystal compound molecules are tilted, if the direction showing the maximum refractive index in the layer (L2) is inclined with respect to the in-plane direction, the direction obtained by projecting the said direction onto the plane is defined as the "alignment direction" in the step (s2).

[0051] The alignment direction is usually controlled by the alignment regulating force of the substrate prepared in the step (s1). For example, when the surface of the substrate is subjected to a stretching treatment or a rubbing treatment, usually, the substrate exhibits an alignment regulating force along the treatment direction (that is, the stretching direction or the rubbing direction), and as a result, the alignment direction becomes a direction parallel to the treatment direction.

[0052] The step (s2-3) can be achieved by promoting the polymerization of the photopolymerizable liquid crystal compound in the liquid crystal composition. For example, as the liquid crystal composition, one containing a photoinitiator if necessary is adopted, and by irradiating the layer (L2) with light, curing can be achieved. By such curing, the polymerization of the photopolymerizable liquid crystal compound in the layer (L2) can be achieved, and the layer (L3) can be formed. However, when the layer (L2) has the property of curing by drying and a certain degree of polymerization even when left in a working space at room temperature, etc., the step (s2-3) may be achieved and the layer (L3) may be obtained without performing special operations.

[0053] Light irradiation can be performed from either one side of the multilayer including the substrate and the coating film. It is preferable to perform the irradiation in an inert gas atmosphere such as nitrogen from the viewpoint of performing polymerization with a high degree of polymerization. From the viewpoint of ease of operation, etc., as the photopolymerizable liquid crystal compound, a compound that can be polymerized by ultraviolet rays alone or in cooperation with a photoinitiator is adopted, and it is preferable to irradiate ultraviolet rays in the step (s2-3). The irradiation amount of the ultraviolet rays in that case can be, for example, 400 to 1000 mJ / cm 2 and so on.

[0054] After the completion of step (s2), the multilayer material having the obtained layer (L3) (for example, a multilayer material having a base material and layer (L3)) can be subjected to step (s3) as is. Alternatively, the multilayer material having layer (L3) may be subjected to any step before being subjected to step (s3). Examples of any step include peeling layer (L3) from the multilayer material having layer (L3) and laminating the peeled layer (L3) to another base material. For example, in various cases such as when the base material prepared in step (s1) is a film with a phase difference, such as a stretched film, a film with low transparency, or does not have sufficient strength for handling, peeling the base material before being subjected to step (s3) and laminating layer (L3) to another base material to create a new multilayer material makes it easier to measure the phase difference and perform subsequent operations.

[0055] (Process (s3)) In step (s3), the layer (L3) obtained in step (s2) is irradiated with linearly polarized ultraviolet light. For the sake of explanation, the layer after step (s3) will be referred to as "layer (L4)" below.

[0056] Such irradiation is performed by adjusting the polarization direction of the linearly polarized ultraviolet light so that its polarization direction is perpendicular to the orientation regulation direction. Here, the polarization direction refers to the direction of the electric field oscillation. The angle between the polarization direction of the linearly polarized ultraviolet light and the orientation regulation direction is the angle between these directions when observed from a direction perpendicular to the irradiated surface. These "orthogonal" directions in this process may include errors within a range that does not significantly impair the effects of the present invention. For example, they may include errors of about ±10° from the 90° direction.

[0057] Such linearly polarized ultraviolet irradiation can be performed by placing an ultraviolet linear polarizer capable of polarizing ultraviolet light on the surface of layer (L3) and irradiating unpolarized ultraviolet light through this polarizer. When placing the polarizer, the orientation can be adjusted so that the direction of the transmission axis of the linear polarizer is perpendicular to the orientation direction of layer (L3) (i.e., the direction of the principal refractive index nx, usually the direction corresponding to the orientation regulation direction of the substrate). By performing ultraviolet irradiation through a polarizer with such an adjusted arrangement, it is possible to achieve irradiation with polarization such that the polarization direction of the linearly polarized ultraviolet light is perpendicular to the orientation direction of the liquid crystal compound, and layer (L4) can be obtained.

[0058] The wavelength of ultraviolet light irradiated in step (s3) can be appropriately selected to obtain the desired optical properties for layer (L4). The optimal wavelength may differ depending on the photopolymerizable liquid crystal compound used. Therefore, prior to manufacturing a commercially usable product, preliminary manufacturing may be performed by irradiating with light of various wavelengths to determine the optimal wavelength. Specifically, using a suitable spectroscopic device (e.g., a spectroscopic aging tester SPX, manufactured by Suga Test Instruments Co., Ltd.), light with a wide range of wavelengths, such as 250 nm to 420 nm, distributed across the irradiation surface can be irradiated through an ultraviolet linear polarizer. Among the various regions within the plane of layer (L4) obtained by such irradiation, the wavelength irradiated in the region that yields the most useful optical properties (low Re(450) / Re(550) value, low Nz coefficient, etc.) can be adopted as the wavelength used in subsequent product manufacturing. When light of various wavelengths is distributed across an irradiated surface and then spectrally separated by a prism, the regions irradiated by each wavelength of light become narrow, slit-like regions, making it difficult to determine the nz coefficient. In such cases where it is difficult to individually determine all the values ​​of nx, ny, and nz for some reason, the Nz coefficient and other parameters can be calculated by assuming that the average refractive index (i.e., (nx + ny + nz) / 3) typically exhibited by the polymer of a photopolymerizable liquid crystal compound is a specific, representative value for the material used.

[0059] The inventors have found that by employing the specific compounds described above as photopolymerizable liquid crystal compounds and performing such a process (s3), a three-dimensional phase difference film exhibiting good inverse wavelength dispersion can be easily manufactured. Specifically, by performing process (s3), the in-plane phase difference Re(550) of the layers of the liquid crystal composition can be increased. That is, the Re(550) of layer (L4) will be higher than that of layer (L3). Specifically, the fluctuation rate of Re(550), ΔRe(550), i.e., {Re(550)(L4)-Re(550)(L3)} / Re(550)(L3), is greater than 0.00, preferably 0.03 or higher, and more preferably 0.05 or higher. On the other hand, the value of the Nz coefficient of layer (L4) obtained as a result of process (s3) can be a small value of less than 1.0. Furthermore, while the Re(450) / Re(550) value tends to be larger in layer (L4) compared to layer (L3), it can be kept within a favorable range of less than 1.0. Although not bound by any particular theory, the reason is presumed to be as follows.

[0060] In other words, when a specific photopolymerizable liquid crystal compound used in this invention is oriented, the side chains may be oriented in a direction different from the orientation direction of the main chain (i.e., usually the nx direction), separate from the orientation of the main chain. In this case, side chains oriented in a direction close to the thickness direction can often contribute significantly to the expression of nz. On the other hand, side chains oriented in a direction close to the plane direction of the layer can often contribute significantly to the expression of ny. Here, if the photopolymerizable liquid crystal compound has an NN bond, in particular if the photopolymerizable liquid crystal compound has a main chain and side chains, and the side chains are linked to the main chain via an NN bond, the photopolymerizable liquid crystal compound or its polymer may be cleaved by step (s3), and as a result, the refractive index in the layer (L4) in directions other than the nx direction may change from that of the layer (L3).

[0061] Here, the inventors have found that when the ultraviolet light irradiated in step (s3) is linearly polarized ultraviolet light of the specific form described above, the refractive index in the ny direction decreases significantly, while the refractive index in the nz direction also decreases, but the amount of decrease is small. This is thought to be because, when irradiated with such specific linearly polarized ultraviolet light, the side chains oriented in a direction close to the plane direction of the layer are more likely to be cleaved at the NN bond, while the side chains oriented in a direction close to the thickness direction are less likely to be cleaved at the NN bond. By utilizing this phenomenon, it is thought that a three-dimensional phase difference film exhibiting good inverse wavelength dispersion can be easily manufactured.

[0062] The layer (L4) or the multilayer material containing layer (L4) obtained in step (s3) can be used as is, or after being subjected to any further step, as the phase difference film of the present invention. Examples of any further steps include peeling off the substrate and transferring it to another substrate.

[0063] (Specific examples of photopolymerizable liquid crystal compounds) A more specific example of a photopolymerizable liquid crystal compound, specifically an inverse wavelength dispersive liquid crystal compound, is a liquid crystal compound represented by the following formula (I). Liquid crystal compounds represented by formula (I) can typically exhibit inverse wavelength dispersive birefringence.

[0064] [ka]

[0065] In equation (I), Ar is a group represented by any of the following equations (II-2) to (II-4). In equations (II-2) to (II-4), * is Z 1 or Z 2 This indicates the bonding position with [the other group]. Furthermore, it is preferable that Ar has a benzothiazole ring. In this example, group D 3 This corresponds to the side chain mesogen, and the group Y in formula (I) 3 From Y 4 Of the parts up to base D 3 The portion excluding that part corresponds to the main chain mesogen.

[0066] [ka]

[0067] In equations (II-2) to (II-4) above, D 3 -C(R f )=NN(R g )R h , -C(R f )=NN=C(R g )R h , and -C(R f )=NN=R i This represents a group selected from the group consisting of D. 3 -C(R f )=NN(R g )R h It is especially preferable that this be the case. D 3 The number of carbon atoms in the group represented by (including the number of carbon atoms in substituents) is usually between 3 and 100.

[0068] R f Rf represents a hydrogen atom; and a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, and isopropyl groups. Rf is particularly preferably a hydrogen atom.

[0069] R g This represents a group selected from the group consisting of a hydrogen atom and an organic group having 1 to 30 carbon atoms, which may have substituents.

[0070] R gExamples of optionally substituted organic groups having 1 to 30 carbon atoms include: optionally substituted alkyl groups having 1 to 20 carbon atoms; groups in which at least one of the -CH2- groups in an optionally substituted alkyl group having 1 to 20 carbon atoms is substituted with -O-, -S-, -OC(=O)-, -C(=O)-O-, or -C(=O)- (except when two or more -O- or -S- groups are adjacent to each other); optionally substituted alkenyl groups having 2 to 20 carbon atoms; optionally substituted alkynyl groups having 2 to 20 carbon atoms; optionally substituted cycloalkyl groups having 3 to 12 carbon atoms; optionally substituted aromatic hydrocarbon ring groups having 6 to 30 carbon atoms; optionally substituted aromatic heterocyclic groups having 2 to 30 carbon atoms; -G x -Y x -F x ;-SO2R a ;-C(=O)-R b ;-CS-NH-R b ; is one example.

[0071] R a This represents a group selected from the group consisting of alkyl groups having 1 to 6 carbon atoms, and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, which may have an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent.

[0072] R b This represents a group selected from the group consisting of alkyl groups having 1 to 20 carbon atoms that may have substituents; alkenyl groups having 2 to 20 carbon atoms that may have substituents; cycloalkyl groups having 3 to 12 carbon atoms that may have substituents; and aromatic hydrocarbon ring groups having 6 to 12 carbon atoms that may have substituents.

[0073] R b The number of carbon atoms in the alkyl group having 1 to 20 carbon atoms is preferably 1 to 12, more preferably 4 to 10. bExamples of alkyl groups having 1 to 20 carbon atoms in this context include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group.

[0074] R bThe substituents that a C1-C20 alkyl group in this can have include, for example, halogen atoms such as fluorine and chlorine atoms; cyano groups; N,N-dialkylamino groups with 2-12 carbon atoms such as dimethylamino groups; alkoxy groups with 1-20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy groups; alkoxy groups with 1-12 carbon atoms substituted with alkoxy groups with 1-12 carbon atoms such as methoxymethoxy and methoxyethoxy groups; nitro groups; aromatic hydrocarbon ring groups with 6-20 carbon atoms such as phenyl and naphthyl groups; aromatic heterocyclic groups with 2-20 carbon atoms such as triazolyl, pyrrolyl, furanyl, thienyl, thiazolyl, and benzothiazole-2-ylthio groups; and Examples include cycloalkyl groups with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups; cycloalkyloxy groups with 3 to 8 carbon atoms, such as cyclopentyloxy and cyclohexyloxy groups; cyclic ether groups with 2 to 12 carbon atoms, such as tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, and dioxanyl groups; aryloxy groups with 6 to 14 carbon atoms, such as phenoxy and naphthoxy groups; fluoroalkyl groups with 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, such as trifluoromethyl, pentafluoroethyl, and -CH2CF3; benzofuryl, benzopyranyl, benzodioxolyl, and benzodioxanyl groups. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0075] R b The number of carbon atoms in the alkenyl group having 2 to 20 carbon atoms is preferably 2 to 12. b Examples of alkenyl groups having 2 to 20 carbon atoms include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, octenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl, nonadecenyl, and icocenyl groups.

[0076] R b Examples of substituents that an alkenyl group with 2 to 20 carbon atoms in this compound may have include R b Examples of substituents that alkyl groups having 1 to 20 carbon atoms can have are the same as those shown in [reference]. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0077] R b Examples of cycloalkyl groups having 3 to 12 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and cyclooctyl groups. Among these, cyclopentyl and cyclohexyl groups are preferred as cycloalkyl groups.

[0078] R b Examples of substituents that a cycloalkyl group having 3 to 12 carbon atoms may have include halogen atoms such as fluorine and chlorine atoms; cyano groups; N,N-dialkylamino groups having 2 to 12 carbon atoms such as dimethylamino groups; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy groups; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups. In particular, preferred substituents for cycloalkyl groups are halogen atoms such as fluorine and chlorine atoms; cyano groups; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy groups; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups. The number of substituents may be one or multiple. Furthermore, the substituents may be identical or different from one another.

[0079] R b Examples of aromatic hydrocarbon ring groups having 6 to 12 carbon atoms include phenyl groups, 1-naphthyl groups, and 2-naphthyl groups. Among these, phenyl groups are preferred as aromatic hydrocarbon ring groups.

[0080] R b The substituents that a C6-C12 aromatic hydrocarbon ring group in this context may have include, for example, halogen atoms such as fluorine and chlorine; cyano groups; N,N-dialkylamino groups with 2-12 carbon atoms such as dimethylamino groups; alkoxy groups with 1-20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy groups; alkoxy groups with 1-12 carbon atoms substituted with alkoxy groups with 1-12 carbon atoms such as methoxymethoxy and methoxyethoxy groups; nitro groups; aromatic heterocyclic groups with 2-20 carbon atoms such as triazolyl, pyrrolyl, furanyl, and thiophenyl groups; and cyclopropyl, cyclopentyl, and cyclohexyl groups. Examples include cycloalkyl groups having 3 to 8 carbon atoms; cycloalkyloxy groups having 3 to 8 carbon atoms such as cyclopentyloxy and cyclohexyloxy groups; cyclic ether groups having 2 to 12 carbon atoms such as tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, and dioxanyl groups; aryloxy groups having 6 to 14 carbon atoms such as phenoxy and naphthoxy groups; fluoroalkyl groups having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, such as trifluoromethyl, pentafluoroethyl, and -CH2CF3; -OCF3; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl group; and so on. In particular, preferred substituents for aromatic hydrocarbon ring groups include halogen atoms such as fluorine and chlorine atoms; cyano groups; alkoxy groups with 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy groups; nitro groups; aromatic heterocyclic groups with 2 to 20 carbon atoms such as furanyl and thiophenyl groups; cycloalkyl groups with 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl groups; fluoroalkyl groups with 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms, such as trifluoromethyl, pentafluoroethyl, and -CH2CF3; and -OCF3. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0081] R gThe preferred range of carbon atoms and examples of alkyl groups having 1 to 20 carbon atoms in R b This is the same as an alkyl group with 1 to 20 carbon atoms.

[0082] R g The substituents that a C1-C20 alkyl group in this can have include, for example, halogen atoms such as fluorine and chlorine atoms; cyano groups; N,N-dialkylamino groups with 2-12 carbon atoms such as dimethylamino groups; alkoxy groups with 1-20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy groups; alkoxy groups with 1-12 carbon atoms substituted with alkoxy groups with 1-12 carbon atoms such as methoxymethoxy and methoxyethoxy groups; nitro groups; aromatic hydrocarbon ring groups with 6-20 carbon atoms such as phenyl and naphthyl groups; and triazolyl, pyrrolyl, furanyl, and thiophenyl groups. Aromatic heterocyclic groups; cycloalkyl groups with 3 to 8 carbon atoms, such as cyclopropyl, cyclopentyl, and cyclohexyl groups; cycloalkyloxy groups with 3 to 8 carbon atoms, such as cyclopentyloxy and cyclohexyloxy groups; cyclic ether groups with 2 to 12 carbon atoms, such as tetrahydrofuranyl, tetrahydropyranyl, dioxolanyl, and dioxanyl groups; aryloxy groups with 6 to 14 carbon atoms, such as phenoxy and naphthoxy groups; fluoroalkyl groups with 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms; benzofuryl groups; benzopyranyl groups; benzodioxolyl groups; benzodioxanyl groups; -SO2R a ;-SR b ;-SR b Examples include alkoxy groups with 1 to 12 carbon atoms substituted with R; hydroxyl groups; etc. a and R b The meaning is as described above. The number of substituents may be one or multiple. Furthermore, the substituents may be identical or different from one another.

[0083] R g The preferred range of carbon atoms and examples of alkenyl groups with 2 to 20 carbon atoms in R bThis is the same as the alkenyl group with 2 to 20 carbon atoms in [the relevant compound].

[0084] R g Examples of substituents that an alkenyl group with 2 to 20 carbon atoms in this compound may have include R g Examples of substituents that alkyl groups having 1 to 20 carbon atoms can have are the same as those shown in [reference]. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0085] R g Examples of alkynyl groups having 2 to 20 carbon atoms include ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 2-pentynyl group, hexynyl group, 5-hexynyl group, heptynyl group, octinyl group, 2-octinyl group, nonanyl group, decanyl group, and 7-decanyl group.

[0086] R g Examples of substituents that an alkynyl group with 2 to 20 carbon atoms in this compound may have include R g Examples of substituents that alkyl groups having 1 to 20 carbon atoms can have are the same as those shown in [reference]. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0087] R g Examples of cycloalkyl groups with 3 to 12 carbon atoms in R b Similar examples include cycloalkyl groups with 3 to 12 carbon atoms.

[0088] R g Examples of substituents that a cycloalkyl group having 3 to 12 carbon atoms may have include R g Examples of substituents that alkyl groups having 1 to 20 carbon atoms can have are the same as those shown in [reference]. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0089] R g Examples of aromatic hydrocarbon ring groups having 6 to 30 carbon atoms include phenyl groups and naphthyl groups. Among these, phenyl groups are more preferred as aromatic hydrocarbon ring groups.

[0090] R g The substituents that a C6-C30 aromatic hydrocarbon ring group in this compound may have include, for example, halogen atoms such as fluorine and chlorine atoms; cyano groups; C1-C6 alkyl groups such as methyl, ethyl, and propyl groups; C2-C6 alkenyl groups such as vinyl and allyl groups; C1-C6 halogenated alkyl groups such as trifluoromethyl groups; C1-C12 N,N-dialkylamino groups such as dimethylamino groups; C1-C6 alkoxy groups such as methoxy, ethoxy, and isopropoxy groups; nitro groups; -OCF3; -C(=O)-R b ;-OC(=O)-R b ;-C(=O)-OR b ;-SO2R a Examples include: R a and R b The meaning is as described above. The number of substituents may be one or multiple. Furthermore, the substituents may be identical or different from one another.

[0091] R gExamples of aromatic heterocyclic groups with 2 to 30 carbon atoms in this context include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, furazanyl group, oxazolyl group, quinolyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridadinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthylidinyl group, pyrazinyl group, pyrazolyl group, Examples include pyranyl group, pyridyl group, pyridadinyl group, pyrimidinyl group, pyrrolyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzo[b]thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzimidazolyl group, benzoxadiazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, benzotriazinyl group, benzotriazolyl group, and benzopyrazolyl group. Among these, monocyclic aromatic heterocyclic groups such as furanyl, pyranyl, thienyl, oxazolyl, furazanyl, thiazolyl, and thiadiazolyl groups; and fused aromatic heterocyclic groups such as benzothiazolyl, benzoxazolyl, quinolyl, 1-benzofuranyl, 2-benzofuranyl, phthalimide, benzo[c]thienyl, benzo[b]thienyl, thiazolopyridyl, thiazolopyrazinyl, benzoisoxazolyl, benzoxadiazolyl, and benzothiadiazolyl groups are more preferred as aromatic heterocyclic groups.

[0092] R g Examples of substituents that an aromatic heterocyclic group with 2 to 30 carbon atoms in this compound may have include, g Examples of substituents that can be present on an aromatic hydrocarbon ring group having 6 to 30 carbon atoms are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0093] G xis a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and at least one of -CH2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent is -O-, -S-, -O-C(=O)-, -C(=O)-O-, -O-C(=O)-O-, -NR 14 -C(=O)-, -C(=O)-NR 14 -, -NR 14 -, or a group substituted with -C(=O)- (however, excluding the case where two or more -O- or -S- are adjacent to each other); represents an organic group selected from the group consisting of. R 14 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The "divalent aliphatic hydrocarbon group" is preferably a divalent chain aliphatic hydrocarbon group, and more preferably an alkylene group.

[0094] Y x is -O-, -C(=O)-, -S-, -C(=O)-O-, -O-C(=O)-, -O-C(=O)-O-, -C(=O)-S-, -S-C(=O)-, -NR 15 -C(=O)-, -C(=O)-NR 15 -, -O-C(=O)-NR 15 -, -NR 15 -C(=O)-O-, -N=N-, and -C≡C-, represents a group selected from the group consisting of. R 15 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Among them, Y x is preferably -O-, -O-C(=O)-O- and -C(=O)-O-.

[0095] F x represents an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The number of carbon atoms of this organic group is preferably 2 or more, more preferably 7 or more, still more preferably 8 or more, particularly preferably 10 or more, and preferably 30 or less. The number of carbon atoms of the above organic group does not include the carbon atoms of the substituent.

[0096] F xExamples of the aromatic hydrocarbon ring in [X] include aromatic hydrocarbon rings having 6 to 30 carbon atoms, such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring. F x When [X] has a plurality of aromatic hydrocarbon rings, the plurality of aromatic hydrocarbon rings may be the same as or different from each other.

[0097] F x The aromatic hydrocarbon ring in [X] may have a substituent. F x Examples of the substituent that the aromatic hydrocarbon ring in [X] may have include, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group or an allyl group; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group or a pentafluoroethyl group; an N,N-dialkylamino group having 2 to 12 carbon atoms such as a dimethylamino group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group, or an isopropoxy group; a nitro group; -OCF3; -C(=O)-R b ;-C(=O)-O-R b ;-O-C(=O)-R b ; and the like. The meaning of R b is as described above. The number of substituents may be one or more than one. Also, the plurality of substituents may be the same as or different from each other.

[0098] F xExamples of aromatic heterocycles in this context include the 1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, oxadiazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, sinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, Examples include aromatic heterocycles with 2 to 30 carbon atoms, such as triazole rings, naphthyridine rings, pyrazine rings, pyrazole rings, pyran rings, pyridine rings, pyridazine rings, pyrimidine rings, pyrrole rings, phenanthridine rings, phthalazine rings, furan rings, benzo[c]thiophene rings, benzoisoxazole rings, benzoisothiazole rings, benzimidazole rings, benzoxadiazole rings, benzoxazole rings, benzothiadiazole rings, benzothiazole rings, benzothiophene rings, benzotriazine rings, benzotriazole rings, benzopyrazole rings, and benzopyranone rings. x However, if there are multiple aromatic heterocycles, the multiple aromatic heterocycles may be the same as or different from each other.

[0099] F x The aromatic heterocycle in F may have substituents. x Examples of substituents that an aromatic heterocycle in this can have include F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0100] F x A preferred example is a "cyclic group having 2 to 20 carbon atoms, which may have substituents, and which has at least one of an aromatic hydrocarbon ring and an aromatic heterocycle." Hereinafter, this cyclic group may be referred to as "cyclic group (a)" as appropriate.

[0101] Possible substituents of the cyclic group (a) include, for example, F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0102] A preferred example of the cyclic group (a) is a hydrocarbon ring group having 6 to 20 carbon atoms, which may have substituents and possess at least one aromatic hydrocarbon ring having 6 to 18 carbon atoms. This hydrocarbon ring group may hereafter be referred to as "hydrocarbon ring group (a1)" as appropriate.

[0103] Examples of hydrocarbon ring groups (a1) include aromatic hydrocarbon ring groups having 6 to 18 carbon atoms, such as phenyl group (6 carbon atoms), naphthyl group (10 carbon atoms), anthracenyl group (14 carbon atoms), phenantrenyl group (14 carbon atoms), pyrenyl group (16 carbon atoms), fluorenyl group (13 carbon atoms), indanyl group (9 carbon atoms), 1,2,3,4-tetrahydronaphthyl group (10 carbon atoms), and 1,4-dihydronaphthyl group (10 carbon atoms).

[0104] Specific examples of the hydrocarbon ring group (a1) mentioned above include the groups represented by the following formulas (1-1) to (1-21). These groups may also have substituents. In the following formulas, "-" represents a Y extending from any position on the ring. x This represents a combination of two things.

[0105] [ka]

[0106] Another preferred example of the cyclic group (a) is a heterocyclic group having 2 to 20 carbon atoms, which may have substituents, and which has one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 18 carbon atoms and aromatic heterocyclic rings having 2 to 18 carbon atoms. This heterocyclic group may be referred to as "heterocyclic group (a2)" below as appropriate.

[0107] Examples of heterocyclic groups (a2) include phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, indolinyl group, flazanyl group, oxazolyl group, oxazolopyridinyl group, oxazolopyridinyl group, oxazolopyridadinyl group, oxazolopyridinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, synnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyrazinyl group, thiazolopyridadinyl group, thiazolopyridadinyl group, thienyl group, triazinyl group, triazolyl group, naphthylidinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl Examples include aromatic heterocyclic groups having 2 to 18 carbon atoms, such as pyrimidinyl group, pyrrolyl group, phenantridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, benzothiophenyl group, benzotriazinyl group, benzotriazolyl group, benzopyranonyl group, etc.; xanthenyl group; 2,3-dihydroindolyl group; 9,10-dihydroacridinyl group; 1,2,3,4-tetrahydroquinolyl group; dihydropyranyl group; tetrahydropyranyl group; dihydrofuranyl group; and tetrahydrofuranyl group.

[0108] Specific examples of the heterocyclic group (a2) mentioned above include the groups represented by the following formulas (2-1) to (2-51). These groups may also have substituents. In the following formulas, "-" represents a Y extending from any position on the ring. x This represents a bond between -CH2- and -NR. In the following equation, X is -CH2-, -NR c - represents an oxygen atom, a sulfur atom, -SO- or -SO2-. Y and Z are independently -NR c - represents an oxygen atom, a sulfur atom, -SO- or -SO2-. E is -NR c - represents an oxygen atom or a sulfur atom. Here, R crepresents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms, such as a methyl group, ethyl group, or propyl group. (However, oxygen atoms, sulfur atoms, -SO-, and -SO2- are not adjacent to each other in each formula.)

[0109] [ka]

[0110] F x Another preferred example is a cyclic group having 2 to 20 carbon atoms, which may have substituents, having at least one aromatic hydrocarbon ring and / or aromatic heterocycle, and in which at least one hydrogen atom is substituted, and which may have substituents other than the cyclic group, and which has 1 to 18 carbon atoms. This substituted alkyl group may hereafter be referred to as "substituted alkyl group (b)" as appropriate.

[0111] Examples of alkyl groups with 1 to 18 carbon atoms in the substituted alkyl group (b) include methyl, ethyl, propyl, and isopropyl groups.

[0112] In the substituted alkyl group (b), "a cyclic group having 2 to 20 carbon atoms, which may have substituents, having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" is, for example, a group within the range described as cyclic group (a).

[0113] In the substituted alkyl group (b), "at least one of the aromatic hydrocarbon ring and the aromatic heterocycle" may be directly bonded to the carbon atoms of the alkyl group having 1 to 18 carbon atoms, or it may be bonded via a linking group. Examples of linking groups include -S-, -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O-, -C(=O)-S-, -SC(=O)-, and -NR. 15 -C(=O)-, -C(=O)-NR 15 These are some examples. 15The meaning is as described above. Therefore, the "cyclic group having 2 to 20 carbon atoms, which may have substituents, having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle" in substituted alkyl(b) includes groups having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, such as fluorenyl groups and benzothiazolyl groups; optionally substituted aromatic hydrocarbon ring groups; optionally substituted aromatic heterocycle groups; groups consisting of optionally substituted aromatic hydrocarbon rings having linking groups; and groups consisting of optionally substituted aromatic heterocycles having linking groups.

[0114] Preferred examples of aromatic hydrocarbon ring groups in the substituted alkyl group (b) include aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, such as phenyl, naphthyl, anthracenyl, phenantrenyl, pyrenyl, and fluorenyl groups.

[0115] The aromatic hydrocarbon ring group in the substituted alkyl group (b) may have substituents. For example, F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0116] Preferred examples of aromatic heterocyclic groups in the substituted alkyl group (b) include phthalimide group, 1-benzofuranyl group, 2-benzofuranyl group, acridinyl group, isoquinolinyl group, imidazolyl group, indolinyl group, fluzanyl group, oxazolyl group, oxazolopyridinyl group, oxazolopyridanyl group, oxazolopyridinyl group, oxazolopyridinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, synnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridinyl group, thiazolopyridinyl group, thienyl group, triazinyl group, and Examples include aromatic heterocyclic groups having 2 to 20 carbon atoms, such as riazolyl group, naphthilidinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyrylyl group, pyridadinyl group, pyrimidinyl group, pyrrolyl group, phenantridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzimidazolyl group, benzoxadiazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothienyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, and benzopyranonyl group.

[0117] The aromatic heterocyclic group in the substituted alkyl group (b) may have substituents. For example, F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0118] Examples of "groups consisting of an aromatic hydrocarbon ring having a linking group" and "groups consisting of an aromatic heterocycle having a linking group" in the substituted alkyl group (b) include phenylthio group, naphthylthio group, anthracenylthio group, phenantrenylthio group, pyrenylthio group, fluorenylthio group, phenyloxy group, naphthyloxy group, anthracenyloxy group, phenantrenyloxy group, pyrenyloxy group, fluorenyloxy group, benzoisoxazolylthio group, benzoisothiazolylthio group, benzoxadiazolylthio group, benzoxazolylthio group, benzothiazolylthio group, benzothienylthio group, benzoisoxazolyloxy group, benzoisothiazolyloxy group, benzoxadiazolyloxy group, benzothiazolyloxy group, benzothiazolyloxy group, benzothienyloxy group, etc.

[0119] In the substituted alkyl group (b), the "group consisting of an aromatic hydrocarbon ring having a linking group" and the "group consisting of an aromatic heterocycle having a linking group" may each have substituents. Examples of such substituents include F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0120] Other substituents that the substituted alkyl group (b) may have include, for example, F x Examples of substituents that can be present on an aromatic hydrocarbon ring are the same as those shown. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from one another.

[0121] Specific examples of substituted alkyl groups (b) include the groups represented by the following formulas (3-1) to (3-11). These groups may also have substituents. In the following formulas, "-" represents a Y extending from any position on the ring. x This represents a bond between two elements. In the following equations, * indicates a bond position.

[0122] [ka]

[0123] In particular, when Ar is expressed by equation (II-2), F x It is preferable that the group is represented by any of the following formulas (i-1) to (i-9). In particular, when Ar is represented by formula (II-3) or formula (II-4), F x It is preferable that the group is represented by any of the following formulas (i-1) to (i-13). The group represented by the following formulas (i-1) to (i-13) may have substituents. In the following formulas, * represents a bond position.

[0124] [ka]

[0125] Furthermore, if Ar is expressed by equation (II-2), then F x It is particularly preferable that the group is represented by any of the following formulas (ii-1) to (ii-18). Also, if Ar is represented by formula (II-3) or formula (II-4), F x It is particularly preferable that the group is represented by any of the following formulas (ii-1) to (ii-24). The group represented by the following formulas (ii-1) to (ii-24) may have substituents. In the following formulas, the meaning of Y is as described above. Also, in the following formulas, * represents the bond position.

[0126] [ka]

[0127] [ka]

[0128] If Ar is expressed by equation (II-2), then F xThe total number of π electrons contained in the ring structure is preferably 8 or more, more preferably 10 or more, preferably 20 or less, and more preferably 18 or less. Also, when Ar is represented by formula (II-3) or formula (II-4), F x The total number of π electrons contained in the ring structure is preferably 4 or more, more preferably 6 or more, preferably 20 or less, and more preferably 18 or less.

[0129] Among those mentioned above, R g These include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents; groups in which at least one of the -CH2- groups in an alkyl group having 1 to 20 carbon atoms is substituted with -O-, -S-, -OC(=O)-, -C(=O)-O-, or -C(=O)- (except when two or more -O- or -S- groups are adjacent to each other); cycloalkyl groups having 3 to 12 carbon atoms which may have substituents; aromatic hydrocarbon ring groups having 6 to 30 carbon atoms which may have substituents; aromatic heterocyclic ring groups having 2 to 30 carbon atoms which may have substituents; and -G x -Y x -F x ; is preferable. Among them, R g These include hydrogen atoms, alkyl groups having 1 to 20 carbon atoms which may have substituents; groups in which at least one of the -CH2- groups in the alkyl group having 1 to 20 carbon atoms is substituted with -O-, -S-, -OC(=O)-, -C(=O)-O-, or -C(=O)- (except when two or more -O- or -S- groups are adjacent to each other); aromatic hydrocarbon ring groups having 6 to 30 carbon atoms which may have substituents; and -G x -Y x -F x ; is particularly preferable. Furthermore, among them, R g As such, hydrogen atoms, alkyl groups having 1 to 10 carbon atoms, phenyl groups, and naphthyl groups are particularly preferred. Furthermore, among these, R g Hydrogen atoms, C4-C8 alkyl groups, phenyl groups, and naphthyl groups are particularly preferred.

[0130] R h This represents an organic group having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings with 6 to 30 carbon atoms and aromatic heterocycles with 2 to 30 carbon atoms.

[0131] R h A preferred example of this is a hydrocarbon ring group having 6 to 40 carbon atoms and having one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms. This hydrocarbon ring group having an aromatic hydrocarbon ring may be referred to as "(1) hydrocarbon ring group" as appropriate below. Specific examples of (1) hydrocarbon ring groups include the following groups.

[0132] [ka]

[0133] (1) The hydrocarbon ring group may have substituents. (1) Substituents that the hydrocarbon ring group may have include, for example, halogen atoms such as fluorine and chlorine atoms; cyano groups; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups; alkenyl groups having 2 to 6 carbon atoms such as vinyl and allyl groups; halogenated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl groups; N,N-dialkylamino groups having 2 to 12 carbon atoms such as dimethylamino groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy groups; nitro groups; aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups; -OCF3; -C(=O)-R b ;-OC(=O)-R b ;-C(=O)-OR b ;-SO2R a Examples include: R a and R b The meaning is as described above. Among these, halogen atoms, cyano groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred. The number of substituents may be one or more. Furthermore, the substituents may be the same or different from each other.

[0134] R h Another preferred example of (2) is a heterocyclic group having 2 to 40 carbon atoms, having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocyclic rings having 2 to 30 carbon atoms. This heterocyclic group having an aromatic ring may hereafter be referred to as "(2) heterocyclic group" as appropriate. Specific examples of (2) heterocyclic groups include the following groups. Each R independently represents either a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0135] [ka]

[0136] [ka]

[0137] [ka]

[0138] [ka]

[0139] [ka]

[0140] [ka]

[0141] [ka]

[0142] [ka]

[0143] (2) The heterocyclic group may have substituents. (2) Examples of substituents that the heterocyclic group may have are the same as those that the hydrocarbon ring group may have. The number of substituents may be one or more. Also, the substituents may be the same or different from each other.

[0144] R h A further preferred example of this is an alkyl group having 1 to 12 carbon atoms that is substituted with one or more groups selected from the group consisting of (3) aromatic hydrocarbon ring groups having 6 to 30 carbon atoms and aromatic heterocyclic groups having 2 to 30 carbon atoms. This substituted alkyl group may hereafter be referred to as "(3) substituted alkyl group" as appropriate.

[0145] (3) Examples of "alkyl groups having 1 to 12 carbon atoms" in substituted alkyl groups include methyl groups, ethyl groups, propyl groups, isopropyl groups, etc. (3) Examples of "aromatic hydrocarbon ring groups having 6 to 30 carbon atoms" in substituted alkyl groups include R g An example of this is the aromatic hydrocarbon ring group with 6 to 30 carbon atoms in [the relevant context]. (3) Examples of "aromatic heterocyclic groups having 2 to 30 carbon atoms" in substituted alkyl groups include R g Similar examples include aromatic heterocyclic groups with 2 to 30 carbon atoms.

[0146] (3) The substituted alkyl group may have further substituents. (3) Examples of substituents that the substituted alkyl group may have are the same as those that the hydrocarbon ring group may have. The number of substituents may be one or more. The substituents may be the same or different from each other.

[0147] R hA further preferred example of this is an alkenyl group having 2 to 12 carbon atoms that is substituted with one or more groups selected from the group consisting of (4) aromatic hydrocarbon ring groups having 6 to 30 carbon atoms and aromatic heterocyclic groups having 2 to 30 carbon atoms. This substituted alkenyl group may hereafter be referred to as "(4) substituted alkenyl group" as appropriate.

[0148] (4) Examples of "alkenyl groups having 2 to 12 carbon atoms" in substituted alkenyl groups include vinyl groups and allyl groups. (4) Examples of "aromatic hydrocarbon ring groups having 6 to 30 carbon atoms" in substituted alkenyl groups include R g An example of this is the aromatic hydrocarbon ring group with 6 to 30 carbon atoms in [the relevant context]. (4) Examples of "aromatic heterocyclic groups having 2 to 30 carbon atoms" in substituted alkenyl groups include R g Similar examples include aromatic heterocyclic groups with 2 to 30 carbon atoms.

[0149] (4) The substituted alkenyl group may have further substituents. (4) Examples of substituents that the substituted alkenyl group may have are the same as those that the hydrocarbon ring group (1) may have. The number of substituents may be one or more. The substituents may be the same or different from each other.

[0150] R h A further preferred example of this is an alkynyl group having 2 to 12 carbon atoms that is substituted with one or more groups selected from the group consisting of (5) aromatic hydrocarbon ring groups having 6 to 30 carbon atoms and aromatic heterocyclic groups having 2 to 30 carbon atoms. This substituted alkynyl group may hereafter be referred to as "(5) substituted alkynyl group" as appropriate.

[0151] (5) Examples of "alkynyl groups having 2 to 12 carbon atoms" in substituted alkynyl groups include the ethynyl group and the propynyl group. (5) Examples of "aromatic hydrocarbon ring groups having 6 to 30 carbon atoms" in substituted alkynyl groups include R gAn example of this is the aromatic hydrocarbon ring group with 6 to 30 carbon atoms in [the relevant context]. (5) Examples of "aromatic heterocyclic groups having 2 to 30 carbon atoms" in substituted alkynyl groups include R g Similar examples include aromatic heterocyclic groups with 2 to 30 carbon atoms.

[0152] (5) The substituted alkynyl group may have further substituents. Examples of substituents that the (5) substituted alkynyl group may have are the same as those that the (1) hydrocarbon ring group may have. The number of substituents may be one or more. The substituents may be the same or different from each other.

[0153] R h The following are some preferred examples of this.

[0154] [ka]

[0155] R h Further preferred examples include the following bases.

[0156] [ka]

[0157] R h Particularly preferred examples include the following bases.

[0158] [ka]

[0159] The above R hSpecific examples of these may have further substituents. Examples of these substituents include halogen atoms such as fluorine atoms and chlorine atoms; cyano groups; C1-C6 alkyl groups such as methyl groups, ethyl groups, and propyl groups; C2-C6 alkenyl groups such as vinyl groups and allyl groups; C1-C6 halogenated alkyl groups such as trifluoromethyl groups; C2-C12 N,N-dialkylamino groups such as dimethylamino groups; C1-C6 alkoxy groups such as methoxy groups, ethoxy groups, and isopropoxy groups; nitro groups; -OCF3; -C(=O)-R b ;-OC(=O)-R b ;-C(=O)-OR b ;-SO2R a Examples include: R a and R b The meaning is as described above. Among these, halogen atoms, cyano groups, alkyl groups having 1 to 6 carbon atoms, and alkoxy groups having 1 to 6 carbon atoms are preferred. The number of substituents may be one or more. Furthermore, the substituents may be the same or different from each other.

[0160] R i This represents an organic group having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings with 6 to 30 carbon atoms and aromatic heterocycles with 2 to 30 carbon atoms.

[0161] R i A preferred example of this is a hydrocarbon ring group having 6 to 40 carbon atoms, which has one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms. Also, R i Another preferred example is a heterocyclic group having 2 to 40 carbon atoms, having one or more aromatic rings selected from the group consisting of aromatic hydrocarbon rings having 6 to 30 carbon atoms and aromatic heterocyclic rings having 2 to 30 carbon atoms.

[0162] R i Particularly preferred examples include the following base. The meaning of R is as described above.

[0163] [ka]

[0164] The base represented by any of equations (II-2) to (II-4) is D 3 The molecule may have further substituents. Examples of these substituents include halogen atoms, cyano groups, nitro groups, C1-C6 alkyl groups, C1-C6 halogenated alkyl groups, C1-C6 N-alkylamino groups, C2-C12 N,N-dialkylamino groups, C1-C6 alkoxy groups, C1-C6 alkylsulfinyl groups, carboxyl groups, C1-C6 thioalkyl groups, C1-C6 N-alkylsulfamoyl groups, and C2-C12 N,N-dialkylsulfamoyl groups. The number of substituents may be one or more. Furthermore, the substituents may be identical or different from each other.

[0165] Preferred examples of Ar in formula (I) include the groups represented by formulas (III-2) to (III-7) below. Furthermore, the groups represented by formulas (III-2) to (III-7) may have alkyl groups having 1 to 6 carbon atoms as substituents. In the following formulas, * represents the bond position. Among these, the group represented by formula (III-2) is preferred for Ar.

[0166] [ka]

[0167] In equation (I), Z 1 and Z 2 These are, independently, single bonds, -O-, -O-CH2-, -CH2-O-, -O-CH2-CH2-, -CH2-CH2-O-, -C(=O)-O-, -OC(=O)-, -C(=O)-S-, -SC(=O)-, and -NR. 21 -C(=O)-, -C(=O)-NR 21This represents one of the following selected from the group consisting of -, -CF2-O-, -O-CF2-, -CH2-CH2-, -CF2-CF2-, -O-CH2-CH2-O-, -CH=CH-C(=O)-O-, -OC(=O)-CH=CH-, -CH2-C(=O)-O-, -OC(=O)-CH2-, -CH2-OC(=O)-, -C(=O)-O-CH2-, -CH2-CH2-C(=O)-O-, -OC(=O)-CH2-CH2-, -CH2-CH2-OC(=O)-, -C(=O)-O-CH2-CH2-, -CH=CH-, -N=CH-, -CH=N-, -N=C(CH3)-, -C(CH3)=N-, -N=N-, and -C≡C-. 21 Each of these independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0168] In equation (I), A 1 , A 2 B 1 and B 2 Each of these independently represents a group selected from the group consisting of optionally substituted cyclic aliphatic groups and optionally substituted aromatic groups. 1 , A 2 B 1 and B 2 The number of carbon atoms in the group represented by (including the number of carbon atoms in substituents) is usually 3 to 100, independently of each other. Among them, A 1 , A 2 B 1 and B 2 Each of these is preferably an independently cyclic aliphatic group having 5 to 20 carbon atoms, which may have substituents, or an aromatic group having 2 to 20 carbon atoms, which may have substituents.

[0169] A 1 , A 2 B 1 and B 2Examples of the cycloaliphatic group in [the compound] include cycloalkanediyl groups having 5 to 20 carbon atoms such as a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane-1,4-diyl group, a cyclooctane-1,5-diyl group; bicycloalkanediyl groups having 5 to 20 carbon atoms such as a decahydronaphthalene-1,5-diyl group, a decahydronaphthalene-2,6-diyl group; etc. Among them, a cycloalkanediyl group having 5 to 20 carbon atoms which may be substituted is preferable, a cyclohexanediyl group is more preferable, and a cyclohexane-1,4-diyl group is particularly preferable. The cycloaliphatic group may be a trans form, a cis form, or a mixture of a cis form and a trans form. Among them, the trans form is more preferable.

[0170] A 1 、A 2 、B 1 及びB 2 Examples of the substituent that the cycloaliphatic group in [the compound] may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, a nitro group, a cyano group, etc. The number of substituents may be one or plural. Further, the plural substituents may be the same as each other or different from each other.

[0171] A 1 、A 2 、B 1 及びB 2 Examples of the aromatic group in [the compound] include aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as a 1,2-phenylene group, a 1,3-phenylene group, a 1,4-phenylene group, a 1,4-naphthylene group, a 1,5-naphthylene group, a 2,6-naphthylene group, a 4,4'-biphenylene group; aromatic heterocyclic groups having 2 to 20 carbon atoms such as a furan-2,5-diyl group, a thiophene-2,5-diyl group, a pyridine-2,5-diyl group, a pyrazine-2,5-diyl group; etc. Among them, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is particularly preferable. [[ID=二十六]]

[0172] A 1 、A2 and B 1 and B 2 Examples of the substituents that the aromatic group in may have include, for example, A 1 and A 2 and B 1 and B 2 The same examples as the substituents that the cycloaliphatic group in may have can be cited. The number of substituents may be one or more. Also, the plurality of substituents may be the same as each other or different from each other.

[0173] In formula (I), Y 1 to Y 4 each independently represents a single bond, -O-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -NR 22 -C(=O)-, -C(=O)-NR 22 -, -O-C(=O)-O-, -NR 22 -C(=O)-O-, -O-C(=O)-NR 22 -, and -NR 22 -C(=O)-NR 23 -, and represents any one selected from the group consisting of. R 22 and R 23 each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

[0174] In formula (I), G 1 and G 2 each independently represents an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a group in which one or more of the methylene groups (-CH2-) contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms are substituted with -O- or -C(=O)-; represents an organic group selected from the group consisting of. G 1 and G 2 The hydrogen atom contained in the organic group of may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. However, the methylene groups (-CH2-) at both ends of G 1 and G 2 are not substituted with -O- or -C(=O)-.

[0175] G 1 and G2 A specific example of an aliphatic hydrocarbon group having 1 to 20 carbon atoms is an alkylene group having 1 to 20 carbon atoms.

[0176] G 1 and G 2 A specific example of an aliphatic hydrocarbon group having 3 to 20 carbon atoms is an alkylene group having 3 to 20 carbon atoms.

[0177] In equation (I), P 1 and P 2 Each of these independently represents a polymerizable group. 1 and P 2 Examples of polymerizable groups in this compound include CH2=CR groups such as acryloyloxy groups and methacryloyloxy groups. 31 Groups represented by -C(=O)-O- include vinyl groups, vinyl ether groups, p-stilbene groups, acryloyl groups, methacryloyl groups, carboxyl groups, methylcarbonyl groups, hydroxyl groups, amide groups, alkylamino groups with 1 to 4 carbon atoms, amino groups, epoxy groups, oxetanyl groups, aldehyde groups, isocyanate groups, thioisocyanate groups, etc. 31 The group represents a hydrogen atom, a methyl group, or a chlorine atom. In particular, CH2=CR 31 A group represented by -C(=O)-O- is preferred, CH2=CH-C(=O)-O- (acryloyloxy group) is more preferred, CH2=C(CH3)-C(=O)-O- (methacryloyloxy group) is more preferred, and the acryloyloxy group is particularly preferred.

[0178] In equation (I), p and q each independently represent either 0 or 1.

[0179] The liquid crystal compound represented by formula (I) can be produced, for example, by the reaction of a hydrazine compound with a carbonyl compound, as described in International Publication No. 2012 / 147904.

[0180] Examples of liquid crystal compounds represented by formula (I) include, for example, compounds represented by the following formula. Compound (A1-1) is particularly preferred because it can provide good inverse wavelength dispersion and optical anisotropy layer properties.

[0181] [ka] [Examples]

[0182] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and equivalents of the present invention.

[0183] In the following explanation, "%" and "parts" used to express quantities refer to weight unless otherwise specified. Furthermore, the operations described below were performed in the atmosphere under normal temperature and pressure conditions, unless otherwise specified.

[0184] (Measurement of optical properties) Using a phase difference meter (Axometrics), the in-plane phase differences Re(450) and Re(550) of the target object at wavelengths of 450 nm and 550 nm were measured. From the values ​​of Re(450) and Re(550), the chromatic dispersion Re(450) / Re(550) was calculated. Furthermore, for the multilayer material (M4), assuming that the thickness of layer (L4) was 2.6 μm and the average refractive index n (i.e., (nx+ny+nz) / 3) was 1.60, the Nz coefficient was calculated based on the values ​​obtained from the above measurements. Furthermore, the rate of change of Re(550) ΔRe(550) (i.e., {Re(550)(L4)-Re(550)(L3)} / Re(550)(L3)) was calculated from Re(550)(L3) (the value of Re(550) for the multi-layered structure (M3-2)) and Re(550)(L4) (the value of Re(550) for the multi-layered structure (M4)).

[0185] (Example 1) (1-1. Preparation of liquid crystal composition) 100 parts by weight of a photopolymerizable liquid crystal compound (A1-1) having a structure represented by the following formula (A1), 4.0 parts by weight of a photopolymerization initiator (“NCI-730” manufactured by ADEKA), 0.3 parts by weight of a surfactant (“Megafac F-562” manufactured by DIC), and 0.1 part by weight of an antioxidant (2,6-di-t-butyl-p-cresol; BHT) were weighed. To these, a diluting solvent (cyclopentanone: 1,3-dioxolane = 4:6) was added so that the solid content became 22 wt%, and the mixture was heated to 50 °C to dissolve the solid content, obtaining a solution. It was confirmed by visual observation that there was no precipitate in the solution. Then, the obtained solution was filtered through a 0.45 μm membrane filter to prepare a liquid crystal composition.

[0186] [Chemical formula]

[0187] The value of the ultraviolet absorption peak of the photopolymerizable liquid crystal compound (A1-1) is as shown in Table 1.

[0188] (1-2. Formation of layer (L3)) As a substrate, a long substrate film (product name “Obliquely Stretched Zeonoa Film”, Tg 126 °C (catalog value), manufactured by Nippon Zeon Co., Ltd., thickness 77 μm, in-plane retardation Re 141 nm at a wavelength of 550 nm, stretching direction is 45° with respect to the width direction) of a resin containing an alicyclic structure-containing polymer was prepared.

[0189] The liquid crystal composition obtained in (1-1) was applied onto the substrate film with a bar coater to form a layer (L1) of the liquid crystal composition. The thickness of the layer (L1) was adjusted so that the thickness of the resulting optically anisotropic layer would be about 2.6 μm. Then, the layer (L1) was dried in an oven at 110 °C for about 4 minutes to evaporate the solvent in the liquid crystal composition and dry the layer (L1), and at the same time, the photopolymerizable liquid crystal compound was aligned to form a layer (L2) of the liquid crystal composition that had been subjected to drying and alignment treatment. As a result, a multilayer product (M2) composed of the substrate film and the layer (L2) provided on its surface was obtained.

[0190] Under a nitrogen atmosphere, the substrate film side of the multilayer material (M2) was brought into close contact with a SUS plate, and the temperature of the SUS plate was monitored and heated to maintain a temperature of 50°C. In this atmosphere and temperature, the layer (L2) was irradiated with unpolarized ultraviolet light using an ultraviolet irradiation device. The cumulative illuminance was 700 mJ / cm². 2 (Irradiation intensity 350mW / cm 2 The irradiation time was set to 2 seconds. This irradiation cured the photopolymerizable liquid crystal compound in layer (L2), forming a cured layer (L3). As a result, a multilayer material (M3) consisting of a base film and a layer (L3) provided on its surface was obtained.

[0191] The surface of the layer (L3) side of the obtained multilayer (M3) was subjected to corona treatment. Subsequently, the surface of the layer (L3) side of the multilayer (M3) was bonded to the adhesive layer of a glass plate with an adhesive layer (the adhesive layer was "CS9861US" manufactured by Nitto Denko Corporation). Then, the base film was peeled off from layer (L3). As a result, a multilayer (M3-2) with a layer structure of (glass plate) / (adhesive layer) / layer (L3) was obtained. The optical properties of the multilayer (M3-2) were measured and Re(550) was determined. The direction of the principal refractive index nx of layer (L3) was in the direction corresponding to the stretched direction of the base film.

[0192] (1-3. Formation of the optically anisotropic layer (layer (L4))) A UV linear polarizer (product name "20LP-UV", a high-precision linear polarizer manufactured by Newport) was placed on the surface of the layer (L3) side of the multilayer material (M3-2) obtained in (1-2). During placement, the placement direction was adjusted so that the direction of the transmission axis of the linear polarizer made a 90° angle with the direction of the principal refractive index nx of the layer (L3) (i.e., the direction corresponding to the stretched direction of the base film).

[0193] These samples were placed in a spectroscopic aging tester SPX (manufactured by Suga Test Instruments Co., Ltd.). The layer (L3) was irradiated with light of various wavelengths distributed across the irradiation surface via an ultraviolet linear polarizer. The wavelengths of the irradiated light were distributed in the range of 250 nm to 520 nm. The irradiation time was 24 hours, and the irradiation intensity was 100 W / m². 2As a result, a layer (L4) of linearly polarized ultraviolet treated cured material was formed as an optically anisotropic layer, and a multilayer material (M4) having a layer structure of (glass plate) / (adhesive layer) / layer (L4) was obtained. Optical properties of the multilayer material (M4) were measured, and Re(550), Re(450), Re(450) / Re(550), ΔRe(550), and the Nz coefficient were determined.

[0194] Among the surfaces irradiated with polarized ultraviolet light of various wavelengths, the region irradiated with polarized ultraviolet light at wavelengths of 380-400 nm yielded low Nz coefficients of 0.93-0.94 and low Re(450) / Re(550) values ​​of 0.88-0.89. Therefore, the values ​​for the variability ΔRe(550) and Nz coefficient from the region irradiated with polarized ultraviolet light at wavelength 390 nm were adopted and are shown in Table 1.

[0195] (Comparative Example 1) Aside from the changes described below, the multilayer material was obtained and evaluated using the same procedure as in Example 1. In (1-3), the mounting direction was adjusted so that the direction of the transmission axis of the ultraviolet linear polarizer was at an angle of 0° with the direction of the principal refractive index nx of layer (L3). The direction of the principal refractive index nx of the layer (L3) obtained in (1-3) was the direction corresponding to the stretched direction of the substrate film.

[0196] In all regions irradiated with polarized ultraviolet light of various wavelengths, the Nz coefficient was 1 or greater in all areas irradiated with polarized ultraviolet light at wavelengths of 380-400 nm, and there were no regions where the Nz coefficient was less than 1, making it suitable for use as a phase difference film. For comparison with Example 1, the values ​​for the variation rate ΔRe(550) and Nz coefficient used in the region irradiated with polarized ultraviolet light at a wavelength of 390 nm were adopted and are shown in Table 1.

[0197] (Examples 2-3 and Comparative Example 2) Except for the changes described below, the multilayer material is obtained and evaluated using the same procedure as in Example 1. In the preparation of the liquid crystal composition of (1-1), instead of the photopolymerizable liquid crystal compound (A1-1), the photopolymerizable liquid crystal compound (A1-2) (Example 2), the photopolymerizable liquid crystal compound (A1-3) (Example 3), or the photopolymerizable liquid crystal compound (A1-4) (Comparative Example 2) is used.

[0198] [ka]

[0199] The ultraviolet absorption peaks of the photopolymerizable liquid crystal compounds (A1-2) to (A1-4) are shown in Table 1. In all examples, the direction of the principal refractive index nx of layer (L3) can correspond to the direction in which the substrate film is stretched. In Examples 2 and 3, desirable properties such as an Nz coefficient of less than 1.0 and a Re(450) / Re(550) value of less than 1.0 are expected to be obtained in the region irradiated with polarized ultraviolet light at a wavelength of 390 nm and in the vicinity thereof. On the other hand, in Comparative Example 2, it is expected that phenomena such as a decrease in the Nz coefficient due to the ultraviolet linear polarizer in steps (1-3) will not occur.

[0200] Table 1 shows an overview and evaluation results of Example 1 and Comparative Example 1, as well as the expected results for Examples 2-3 and Comparative Example 2.

[0201] [Table 1]

[0202] Polarization direction: The direction of polarization adjusted by the ultraviolet linear polarizer in process (1-3). The angle with respect to the direction of the principal refractive index nx of layer (L3).

[0203] The results from Example 1 and Comparative Example 1 show that the phase difference film of the present invention, manufactured by the manufacturing method of the present invention which includes a step of irradiating with specific polarized ultraviolet light, can be a three-dimensional phase difference film exhibiting good inverse wavelength dispersion. Furthermore, since the photopolymerizable liquid crystal compounds (A1-2) and (A1-3) used in Examples 2 and 3 are compounds having an NN bond in their molecules, similar to the photopolymerizable liquid crystal compound (A1-1), it is expected that in Examples 2 and 3, a three-dimensional phase difference film exhibiting good inverse wavelength dispersion will be obtained, similar to Example 1.

Claims

1. The optically anisotropic layer comprises a polymer of a photopolymerizable liquid crystal compound, The photopolymerizable liquid crystal compound is a compound having an N-N bond, The Nz coefficient is less than 1. Phase difference film.

2. The phase difference film according to claim 1, wherein the photopolymerizable liquid crystal compound has one or more ultraviolet absorption peaks in the region less than 340 nm and in the region 340 nm or more.

3. The phase difference film according to claim 1, wherein the photopolymerizable liquid crystal compound is an inverse wavelength dispersive liquid crystal compound.

4. A method for manufacturing a phase difference film according to any one of claims 1 to 3, Steps to prepare the base material (s1), Step (s2) is a step of providing a layer of liquid crystal composition containing a photopolymerizable liquid crystal compound on the surface of the substrate, wherein the photopolymerizable liquid crystal compound is oriented in a certain orientation direction in the layer, and A method for manufacturing a phase difference film, comprising step (s3) of irradiating a layer of the liquid crystal composition with linearly polarized ultraviolet light, wherein the polarization direction of the linearly polarized ultraviolet light is perpendicular to the orientation direction.

5. The method for manufacturing a phase difference film according to claim 4, wherein in step (s3), the in-plane phase difference Re(550) at a wavelength of 550 nm of the layer of the liquid crystal composition increases.

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