JP7047405B2 - Organic light emission display device - Google Patents

Description

The present invention relates to an organic light emitting display device.

The organic light emitting display device is usually provided with various optical elements (Patent Documents 1 to 4). As one of such optical elements, there is a liquid crystal curing layer formed of a cured product obtained by orienting a liquid crystal composition containing a liquid crystal compound and curing the liquid crystal composition while maintaining the oriented state. Since the liquid crystal cured layer usually has birefringence depending on the liquid crystal compound, it can be used as an optical element such as a wave plate and a retardation plate.

Japanese Patent No. 5363022 Japanese Unexamined Patent Publication No. 2015-161714 Japanese Unexamined Patent Publication No. 2016-110153 Japanese Unexamined Patent Publication No. 2017-138608

The organic light emitting display device may be provided with a polarizing plate such as a circular polarizing plate and an elliptical polarizing plate as a reflection suppressing film for suppressing the reflection of external light on the display screen. This polarizing plate can be obtained, for example, by combining a polarizing element and a liquid crystal curing layer.

From the viewpoint of suppressing reflection and obtaining excellent viewing angle characteristics when the display screen is viewed from an inclined direction, it is preferable that the liquid crystal cured layer is adjusted for birefringence in the thickness direction. As a method for adjusting birefringence in the thickness method, for example, a method of inclining the molecules of the liquid crystal compound contained in the liquid crystal cured layer with respect to the in-plane direction of the liquid crystal cured layer can be mentioned. By appropriately adjusting the tilt angle of the molecules of the liquid crystal compound, the birefringence in the thickness direction of the liquid crystal cured layer can be adjusted. Therefore, conventionally, it has been expected that the reflection of external light can be effectively suppressed in the tilt direction. rice field.

However, in an actual organic light emitting display device, effective reflection suppression that is satisfactory in the tilt direction has not been achieved. Generally, an organic light emitting display device receives external light emitted by the sun or lighting from above in the vertical direction of the display screen. Further, although the reflection on the display screen is usually affected by optical phenomena such as scattering, diffraction, and refraction, most of the light is specularly reflected. "Specular reflection" refers to reflection in which the incident angle and the reflection angle of light are the same. Therefore, in order to effectively suppress the reflection of external light on the display screen, it is required to suppress the specular reflection of external light received from above. However, such suppression of specular reflection has been insufficient with conventional techniques.

The present invention has been devised in view of the above problems, and an object of the present invention is to provide an organic light emitting display device capable of effectively suppressing specular reflection of external light from above in the vertical direction of a display screen.

The present inventor has diligently studied to solve the above-mentioned problems. Conventionally, a polarizing plate as a reflection-suppressing film has been actively studied, whereas the present inventor has focused on an entire organic light-emitting display device including a reflection-suppressing film and an organic light-emitting display panel. Then, the present inventor has found that effective reflection suppression is possible by appropriately adjusting the relationship between the vertical direction of the display screen and the optical axis of the polarizing element and the liquid crystal curing layer. Completed.
That is, the present invention includes the following.

[1] An organic light emitting display device having a display screen.
The organic light-emitting display device comprises a liquid crystal cured layer formed of a polarizing element, a cured product of a liquid crystal composition containing a liquid crystal compound, and an organic light-emitting display panel in this order.
At least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the in-plane direction of the liquid crystal cured layer.
The polarizing element has an absorption axis having an angle of more than 45 ° and 90 ° or less with respect to the vertical direction of the display screen.
An organic light emission display device in which the liquid crystal cured layer has a slow phase axis at an angle of 45 ° ± 5 ° with respect to the absorption axis of the polarizing element.
[2] The organic light emitting display device according to [1], wherein the tilt direction of the molecule of the liquid crystal compound contained in the liquid crystal cured layer is upward in the vertical direction of the display screen.
[3] The organic light emitting display device according to [1] or [2], wherein the in-plane retardation of the liquid crystal cured layer at a measurement wavelength of 590 nm is 100 nm or more and 180 nm or less.

According to the present invention, it is possible to provide an organic light emitting display device capable of effectively suppressing specular reflection of external light from above in the vertical direction of the display screen.

FIG. 1 is a perspective view schematically showing an organic light emitting display device as an embodiment of the present invention. FIG. 2 is an exploded perspective view schematically showing an organic light emitting display device as an embodiment of the present invention in an exploded manner. FIG. 3 is a graph in which the retardation ratio Re (θ) / Re (0 °) of the liquid crystal cured layer according to a certain example is plotted against the incident angle θ. FIG. 4 is a cross section schematically showing a cross section of a liquid crystal cured layer provided in an organic light emitting display device according to an embodiment of the present invention cut by a plane parallel to both the slow axis and the thickness direction of the liquid crystal cured layer. It is a figure. FIG. 5 is a plan view schematically showing a liquid crystal cured layer included in the organic light emitting display device according to the embodiment of the present invention. FIG. 6 is a perspective view for explaining a measurement direction when measuring the retardation of the liquid crystal cured layer from an inclined direction. FIG. 7 is a perspective view schematically showing how to set the brightness L ^* measuring device in the examples and the comparative examples.

Hereinafter, the present invention will be described in detail with reference to examples and embodiments. However, the present invention is not limited to the examples and embodiments shown below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

In the following description, the "left-right direction" of the display screen of the organic light-emitting display device indicates the horizontal direction of the display screen when the user views the display screen of the organic light-emitting display device, unless otherwise specified. In a stationary organic light emitting display device such as a television, a display device for a personal computer, or an in-vehicle display device, the left-right direction is usually parallel to a horizontal plane when the organic light emitting display device is installed on a horizontal support base. Corresponds to the direction parallel to the display screen. Further, in a portable organic light emitting display device such as a mobile phone, a smartphone, or a tablet terminal, the left-right direction is usually when the display screen of the organic light emitting display device held by a user in an upright position is viewed. It corresponds to the direction parallel to the horizontal plane and parallel to the display screen. For example, when the display screen is a rectangle, the left-right direction of the display screen is generally parallel to the base of this rectangle. Further, for example, when a design having a vertical direction and a horizontal direction is attached to the surface of the organic light emitting display device parallel to the display screen, the direction parallel to the horizontal direction is usually the left and right of the display screen. Corresponds to the direction. To give a specific example, in an organic light emitting display device having a logotype of a horizontally written character string, the left-right direction of the display screen is usually parallel to the arrangement direction of the character string.

In the following description, the "vertical direction" of the display screen of the organic light emitting display device means the vertical direction of the display screen when the user views the display screen of the organic light emitting display device, unless otherwise specified. Therefore, unless otherwise specified, the vertical direction of the display screen of the organic light emitting display device represents a direction parallel to the display screen and perpendicular to the horizontal direction of the display screen. For example, when the display screen is a rectangle, the left-right direction of the display screen is generally perpendicular to the base of the rectangle. Further, for example, when a design having a vertical direction and a horizontal direction is attached to the surface of the organic light emitting display device parallel to the display screen, the direction perpendicular to the horizontal direction is usually the top and bottom of the display screen. Corresponds to the direction. To give a specific example, in an organic light emitting display device having a logotype of a horizontally written character string, the vertical direction of the display screen is usually perpendicular to the arrangement direction of the character string.

In the following description, the "in-plane direction" of a layer means a direction parallel to the layer plane unless otherwise specified.

In the following description, the "thickness direction" of a layer represents a direction perpendicular to the layer plane, unless otherwise specified. Therefore, unless otherwise specified, the in-plane direction and the thickness direction of a certain layer are perpendicular to each other.

In the following description, the "front direction" of a surface represents the normal direction of the surface, and specifically, the direction of the polar angle of the surface of 0 °, unless otherwise specified.

In the following description, the "tilt direction" of a surface represents a direction that is neither parallel nor perpendicular to the surface unless otherwise specified, and specifically, the polar angle of the surface is in the range of 5 ° or more and 85 ° or less. Point to the direction of.

In the following description, "tilting" an element with respect to the in-plane direction means that the element is neither parallel nor perpendicular to the in-plane direction. The angle formed by the element with respect to the in-plane direction is usually in the range of 5 ° or more and 85 ° or less.

In the following description, unless the direction of the element is "parallel" or "vertical", it is within a range that does not impair the effect of the present invention, for example, ± 4 °, preferably ± 3 °, more preferably ± 1. It may include errors within the range of °.

In the following description, unless otherwise specified, the birefringence Δn (450) at a wavelength of 450 nm and the birefringence Δn (550) at a wavelength of 550 nm satisfy the following equation (N1), unless otherwise specified. To say. A liquid crystal compound capable of exhibiting such a reverse wavelength dispersive birefringence can usually exhibit a larger birefringence as the measurement wavelength is longer.
Δn (450) <Δn (550) (N1)

In the following description, unless otherwise specified, birefringence Δn (450) at a wavelength of 450 nm and birefringence Δn (550) at a wavelength of 550 nm satisfy the following equation (N2), unless otherwise specified. To say. A liquid crystal compound capable of exhibiting such forward wavelength dispersive birefringence can usually exhibit smaller birefringence as the measurement wavelength is longer.
Δn (450)> Δn (550) (N2)

In the following description, the in-plane retardation Re of a certain layer is a value represented by 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) and in the direction giving the maximum refractive index. ny represents the refractive index in the in-plane direction of the layer and orthogonal to the direction of nx. d represents the thickness of the layer. The measurement wavelength of the retardation is 590 nm unless otherwise specified. The in-plane retardation Re can be measured using a phase difference meter (“AxoScan” manufactured by Axometrics).

In the following description, the slow phase axis of a certain layer means the slow phase axis in the in-plane direction unless otherwise specified.

In the following description, unless otherwise specified, the "tilt angle" of the molecules of the liquid crystal compound contained in a certain layer represents the angle formed by the molecules of the liquid crystal compound with respect to the layer plane, and is also referred to as "tilt angle". Sometimes called. This tilt angle corresponds to the maximum angle among the angles formed by the direction of the maximum refractive index with the layer plane in the refractive index ellipsoid of the molecule of the liquid crystal compound. Further, in the following description, unless otherwise specified, the "tilt angle" represents the tilt angle of the molecule of the liquid crystal compound with respect to the in-plane direction of the layer containing the liquid crystal compound.

In the following description, the resin having a positive intrinsic birefringence value means a resin in which the refractive index in the stretching direction is larger than the refractive index in the direction orthogonal to the refractive index. Further, the resin having a negative intrinsic birefringence value means a resin in which the refractive index in the stretching direction is smaller than the refractive index in the direction orthogonal to the refractive index. The intrinsic birefringence value can be calculated from the permittivity distribution.

In the following description, the number of carbon atoms of a group having a substituent does not include the number of carbon atoms of the substituent unless otherwise specified. Therefore, for example, in the description of "an alkyl group having 1 to 20 carbon atoms which may have a substituent", the number of carbon atoms of the alkyl group itself which does not include the carbon atom number of the substituent is 1 to 20. Represents that.

[1. Description of Embodiment of Organic Luminous Display Device]
(Explanation of outline of organic light emission display device)
FIG. 1 is a perspective view schematically showing an organic light emitting display device 10 as an embodiment of the present invention.
As shown in FIG. 1, the organic light emitting display device 10 as an embodiment of the present invention is an image display device having a display screen 10U for displaying an image. In the present embodiment, as shown in FIG. 1, the display screen 10U has two sides 11 and 12 parallel to the left- _right direction ALR of the display screen _10U , and two sides 13 parallel to the vertical direction AUD of the display screen 10U. An example of a rectangle having 14 and 14 will be described.

FIG. 2 is an exploded perspective view schematically showing an organic light emitting display device 10 as an embodiment of the present invention in an exploded manner. In FIG. 2, a virtual straight line A ₂₁₀ extending in the same direction as the absorption axis A ₁₀₀ of the polarizing element 100 is shown by a two-dot chain line on the liquid crystal cured layer 200.
As shown in FIG. 2, the organic light emitting display device 10 includes a polarizing element 100, a liquid crystal curing layer 200, and an organic light emitting display panel 300 in this order in a direction perpendicular to the display screen 10U.

(Explanation of Polarizer 100)
The splitter 100 is an optical element having an absorption axis A ₁₀₀ . The splitter 100 can absorb linearly polarized light having a vibration direction parallel to the absorption axis A ₁₀₀ , and can transmit other linearly polarized light. The vibration direction of linearly polarized light means the vibration direction of the electric field of linearly polarized light.

The absorption axis A ₁₀₀ of the polarizing element 100 forms an angle θ ₁₀₀ larger than 45 ° and 90 ° or less with respect to the vertical direction _AUD of the display screen 10U when the display screen 10U is viewed from the front direction. From the viewpoint of more effectively suppressing the reflection of external light, the angle θ ₁₀₀ is usually larger than 45 °, preferably larger than 50 °, more preferably larger than 55 °, and usually 90 ° or less. When the organic light emitting display device 10 is viewed from the polarizing element 100 side, the absorption axis A ₁₀₀ of the polarizing element 100 is described in either clockwise or counterclockwise direction with respect to the vertical _AUD of the display screen 10U. The angle θ ₁₀₀ of may be formed.

The polarizing element 100 is, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and then uniaxially stretching the film in a boric acid bath; adsorbing iodine or a dichroic dye on the polyvinyl alcohol film. Examples thereof include a film obtained by stretching and further modifying a part of polyvinyl alcohol units in the molecular chain to polyvinylene units. Of these, as the splitter 100, a splitter containing polyvinyl alcohol is preferable.

The degree of polarization of the polarizing element 100 is not particularly limited, but is preferably 98% or more, more preferably 99% or more.
The thickness of the splitter 100 is not particularly limited, but is preferably 5 μm to 80 μm.

(Explanation of LCD cured layer 200)
The liquid crystal cured layer 200 is a layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound. Since it is formed of a cured product of the liquid crystal composition, the liquid crystal cured layer 200 contains molecules of a liquid crystal compound. The molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 may have a fixed orientation. The term "liquid crystal compound having a fixed orientation state" includes a polymer of the liquid crystal compound. Normally, the liquid crystal property of the liquid crystal compound is lost by polymerization, but in the present application, the liquid crystal compound thus polymerized is also included in the term "liquid crystal compound contained in the liquid crystal cured layer".

The liquid crystal curing layer 200 has a slow axis A ₂₀₀ forming an angle θ ₂₀₀ of 45 ° ± 5 ° with respect to the absorption axis A ₁₀₀ of the polarizing element 100 when the display screen 10U is viewed from the front. From the viewpoint of more effectively suppressing the reflection of external light, the angle θ ₂₀₀ is usually 40 ° or more, preferably 42 ° or more, more preferably 44 ° or more, and usually 50 ° or less, preferably 48 °. Below, it is more preferably 46 ° or less. When the organic light emitting display device 10 is viewed from the polarizing element 100 side, the slow phase axis A ₂₀₀ of the liquid crystal curing layer 200 is oriented in either clockwise or counterclockwise direction with respect to the absorption axis A ₁₀₀ of the polarizing element 100. The angle θ ₂₀₀ may be set.

At least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction of the liquid crystal cured layer 200. The in-plane direction of the liquid crystal curing layer 200 is usually parallel to the display screen 10U. Therefore, the molecules of the liquid crystal compound inclined in this way are usually in a state of being neither parallel nor perpendicular to the display screen 10U.

In the liquid crystal cured layer 200, some of the molecules of the liquid crystal compound may be inclined with respect to the in-plane direction of the liquid crystal cured layer 200, and all of them may be inclined with respect to the in-plane direction of the liquid crystal cured layer 200. May be. For example, the inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 may be smaller as it is closer to one side and larger as it is farther from one side in the thickness direction. Therefore, in the vicinity of the surface on one side of the liquid crystal cured layer 200, the molecules of the liquid crystal compound may be parallel to the in-plane direction. Further, in the vicinity of the surface of the liquid crystal cured layer 200 opposite to one side, the molecules of the liquid crystal compound may be perpendicular to the in-plane direction. However, even when the molecules of the liquid crystal compound are parallel or perpendicular to the in-plane direction in the portion near the surface of the liquid crystal cured layer 200 as described above, usually, the portion near the surface of the liquid crystal cured layer 200 is excluded. In the above part, the molecules of the liquid crystal compound are inclined with respect to the in-plane direction.

The fact that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction of the liquid crystal cured layer 200 is a cross section of the liquid crystal cured layer 200 with a polarizing microscope having sufficient resolution. It can be confirmed by observing. This observation may be carried out by inserting a wave plate as an inspection plate between the observation sample and the objective lens of the polarizing microscope, if necessary, in order to make it easier to visually recognize the inclination of the molecules of the liquid crystal compound. ..

Alternatively, it can be confirmed as follows that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction of the liquid crystal cured layer 200. The retardation Re (θ) of the liquid crystal cured layer 200 at the incident angle θ is measured in the measurement direction perpendicular to the phase advance axis direction in the plane of the liquid crystal cured layer 200. Then, the retardation ratio Re (θ) / Re () obtained by dividing the retardation Re (θ) of the liquid crystal cured layer 200 at the incident angle θ by the retardation Re (0 °) of the liquid crystal cured layer 200 at the incident angle 0 °. 0 °) is calculated. When a graph is drawn with the retardation ratio Re (θ) / Re (0 °) obtained in this way on the vertical axis and the incident angle θ on the horizontal axis, the obtained graph should be asymmetric with respect to θ = 0 °. For example, it can be confirmed that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction of the liquid crystal cured layer 200.

Hereinafter, a more specific description will be given with an example. FIG. 3 is a graph in which the retardation ratio Re (θ) / Re (0 °) of the liquid crystal cured layer 200 according to a certain example is plotted with respect to the incident angle θ. When the inclination angle of all the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is 0 ° or 90 °, the retardation ratio Re (θ) / Re (0 °) is the example shown by the broken line in FIG. As shown above, it is line symmetric with respect to a straight line of θ = 0 ° (vertical axis passing through θ = 0 ° in FIG. 3). On the other hand, when at least some molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction of the liquid crystal cured layer 200, the retardation ratio Re (θ) / Re (0). °) is usually asymmetric with respect to a straight line of θ = 0 °, as shown in the example shown by the solid line in FIG. Therefore, when the retardation ratio Re (θ) / Re (0 °) is asymmetric with respect to θ = 0 °, at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is the liquid crystal cured. It can be determined that the layer 200 is inclined with respect to the in-plane direction.

FIG. 4 shows a cross section of the liquid crystal cured layer 200 included in the organic light emitting display device 10 as an embodiment of the present invention cut along a plane parallel to both the slow axis A200 and the thickness direction of the liquid crystal cured layer ₂₀₀ . It is sectional drawing which shows schematically.
As shown in FIG. 4, at least a part of the molecules 210 of the liquid crystal compound contained in the liquid crystal cured layer 200 are inclined with respect to the in-plane direction. Therefore, the tilt direction _AT can be conceived for the molecule 210 of the liquid crystal compound contained in the liquid crystal cured layer 200. The "tilt direction _AT " of the molecule 210 of the liquid crystal compound is a direction parallel to the in-plane direction of the liquid crystal cured layer 200, and indicates a direction in which the director D ₂₁₀ of the molecule 210 of the liquid crystal compound stands up. .. The “director D ₂₁₀ ” of the liquid crystal compound molecule 210 indicates a vector indicating the direction of the maximum refractive index in the refractive index ellipsoid of the liquid crystal compound molecule 210 as the average of the entire liquid crystal cured layer 200. Further, the “rise” of the director D ₂₁₀ means a rise based on the surface 200D of the liquid crystal cured layer 200, whichever has a smaller inclination angle of the molecule 210 of the liquid crystal compound, among the surface 200D and the surface 200U. Therefore, by writing the director D ₂₁₀ so that the start point is placed on the surface 200D side having the smaller inclination angle and the end point is placed on the surface 200U side having the larger inclination angle, the director D ₂₁₀ is parallel to the in-plane direction of the director D 210. As the direction of the vector indicated by the component, the tilt direction _AT as the direction in which the director D ₂₁₀ stands up can be specified.

Specifically, the tilt direction _AT can be measured by the following method.
A phase difference meter (“AxoScan” manufactured by Axometrics) is used to detect the slow axis A ₂₀₀ of the liquid crystal cured layer 200.
Further, among the surfaces 200D and 200U of the liquid crystal cured layer 200, the surface 200D having the smaller inclination angle of the molecule 210 of the liquid crystal compound is specified. The surface 200D is specified, for example, by cutting the liquid crystal cured layer 200 on a plane parallel to both the slow axis A ₂₀₀ of the liquid crystal cured layer 200 and the thickness direction, cutting out a section having a thickness of about 1 μm, and observing with a polarizing microscope. This can be done by observing the cross section of the section.
Then, the retardation of the liquid crystal cured layer 200 is measured using a phase difference meter (“AxoScan” manufactured by Axometrics) with the surface 200D having the smaller inclination angle facing down. The retardation is measured by gradually increasing the incident angle from 0 ° in the measurement direction perpendicular to the phase advance axis of the liquid crystal cured layer 200. When the retardation of the liquid crystal curing layer 200 gradually decreases as the incident angle gradually increases, it can be determined that the measurement direction approaches parallel to the tilt direction _AT . Therefore, the tilt direction can be specified by the measurement of the retardation.
If the slow axis A ₂₀₀ of the liquid crystal cured layer 200 and the surface 200D on which the tilt angle of the molecule 210 of the liquid crystal compound is smaller are known, the detection and tilt angle of the slow axis A ₂₀₀ is smaller. The specific operation of the surface 200D may be omitted.

FIG. 5 is a plan view schematically showing a liquid crystal curing layer 200 included in the organic light emitting display device 10 as an embodiment of the present invention.
The tilt direction _AT of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is preferably upward in the vertical direction _AUD of the display screen 10U. That is, as shown in FIG. 5, when the vector B _T representing the _tilt direction _AT is decomposed into the vector component _BY in the vertical direction A _UD and the vector component BX in the horizontal direction A _LR , the vertical direction A _UD It is preferable that the vector component _BY of is facing upward. Thereby, the reflection of the external light from the upper direction of the vertical direction _AUD of the display screen 10U on the display screen 10U can be suppressed particularly effectively.

Since the liquid crystal cured layer 200 contains the molecules of the liquid crystal compound inclined with respect to the in-plane direction of the liquid crystal cured layer 200, the substantially maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is usually set. It is 5 ° or more and 85 ° or less. The "substantially maximum tilt angle" of the molecule of the liquid crystal compound contained in a certain layer is that the tilt angle of the molecule on one surface of the layer is 0 ° and the tilt angle of the molecule is a constant ratio in the thickness direction. It is the maximum value of the inclination angle of the molecule of the liquid crystal compound when it is assumed that it is changing. Usually, in a layer containing a liquid crystal compound, the inclination angle of the molecule of the liquid crystal compound is smaller as it is closer to one side of the layer in the thickness direction and larger as it is farther from the one side. The effective maximum tilt angle is calculated on the assumption that the rate of change in the tilt angle in the thickness direction (that is, the rate of change that decreases as it is closer to one side and increases as it is farther from one side) is constant. Represents the maximum value of the tilt angle. For example, in the liquid crystal cured layer 200 obtained by curing the layer of the liquid crystal composition formed on the support surface, the substantially maximum inclination angle is the inclination angle of the molecule on the surface of the liquid crystal cured layer 200 on the support surface side. It represents the maximum value of the tilt angle of the molecule of the liquid crystal compound when it is 0 ° and the tilt angle of the molecule changes at a constant rate in the thickness direction.

The substantially maximum tilt angle is an index indicating the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200. Usually, the liquid crystal cured layer 200 having a substantially maximum tilt angle tends to have a larger tilt angle as a whole of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200. Therefore, it is possible to adjust the birefringence in the thickness direction of the liquid crystal cured layer 200 by adjusting the substantially maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200.

It is desirable that the range of the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is appropriately set so as to enable efficient suppression of reflection of external light. From the viewpoint of more effectively suppressing the reflection of external light, the range of the substantially maximum tilt angle is preferably 40 ° or more, more preferably 45 ° or more, particularly preferably 50 ° or more, and preferably 85 °. Below, it is more preferably 80 ° or less, and particularly preferably 75 ° or less.

The substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the liquid crystal cured layer 200 can be measured by the measuring method described in Examples described later.

The liquid crystal cured layer 200 may have a single-layer structure including only one layer formed of the cured product of the liquid crystal composition, and may include two or more layers formed of the cured product of the liquid crystal composition. It may have a layered structure. In the following description, each of the plurality of layers contained in the liquid crystal cured layer 200 having a multi-layer structure may be appropriately referred to as a "partial layer" in order to distinguish it from the liquid crystal cured layer 200. When the liquid crystal cured layer 200 has a multi-layer structure, the slow axis of each of the plurality of partial layers contained in the liquid crystal cured layer 200 may be the same or different. When the liquid crystal cured layer 200 has a multi-layer structure as described above, the slow axis A200 of the liquid crystal cured layer ₂₀₀ is not the slow axis of each of the partial layers, but the liquid crystal cured layer including the plurality of partial layers. It represents a slow-phase axis obtained by viewing the entire 200 as one retardation film.

When the liquid crystal cured layer 200 has a single layer structure, the orientation direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is usually the slow axis of the liquid crystal cured layer 200 in the in-plane direction of the liquid crystal cured layer 200. It is parallel to A ₂₀₀ .
On the other hand, when the liquid crystal cured layer 200 has a multi-layer structure, the orientation direction of the molecules of the liquid crystal compound contained in each of the partial layers is usually the slow axis of each of the partial layers in the in-plane direction of the liquid crystal cured layer 200. It is parallel. Therefore, when the liquid crystal cured layer 200 has a multi-layer structure, the orientation direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 200 is the slow axis of the liquid crystal cured layer 200 in the in-plane direction of the liquid crystal cured layer 200. It can be parallel to or non-parallel to the _A200 .
In either case, the liquid crystal cured layer 200 has an in-plane retardation of a predetermined size because the molecules of the liquid crystal compound are usually oriented in the in-plane direction.

The specific range of the in-plane retardation of the liquid crystal cured layer 200 can be set so that the combination of the polarizing element 100 and the liquid crystal cured layer 200 can function as a polarizing plate such as a circular polarizing plate and an elliptical polarizing plate. desirable. Specifically, the in-plane retardation Re of the liquid crystal cured layer 200 is preferably 100 nm or more, more preferably 110 nm or more, particularly preferably 120 nm or more, preferably 180 nm or less, and more preferably 170 nm or less at a measurement wavelength of 590 nm. Particularly preferably, it is 160 nm or less.

The liquid crystal cured layer 200 preferably has an in-plane retardation having a reverse wavelength dispersibility. Here, the reverse wavelength dispersibility in-plane retardation is an in-plane letter in which the in-plane retardation Re (450) at a wavelength of 450 nm and the in-plane retardation Re (550) at a wavelength of 550 nm satisfy the following formula (N3). Refers to the ground. Above all, it is particularly preferable that the in-plane retardation of the liquid crystal cured layer 200 satisfies the following formula (N4). As described above, the liquid crystal cured layer 200 having the in-plane retardation having the reverse wavelength dispersibility can uniformly exhibit the function in a wide wavelength band, so that the reflection of external light can be effectively suppressed in a wide wavelength range.
Re (450) / Re (550) <1.00 (N3)
Re (450) / Re (550) <0.90 (N4)

The thickness of the liquid crystal cured layer 200 is preferably 0.5 μm or more, more preferably 1.0 μm or more, particularly preferably 2.0 μm or more, preferably 10.0 μm or less, more preferably 7.0 μm or less, and particularly preferably. Is 5.0 μm or less.

(Explanation of the organic light emitting display panel 300)
The organic light emitting display panel 300 is a device capable of emitting light for displaying an image on the display screen 10U of the organic light emitting display device 10. As the organic light emitting display panel 300, for example, a panel provided with an organic electroluminescence element (hereinafter, may be appropriately referred to as an “organic EL element”) can be used. Normally, the light emitted from the organic EL element is visually recognized through the liquid crystal curing layer 200 and the polarizing element 100, so that the user visually recognizes the image displayed on the display screen 10U.

The organic EL element usually includes a transparent electrode layer, a light emitting layer, and an electrode layer in this order, and the light emitting layer can generate light by applying a voltage from the transparent electrode layer and the electrode layer. Examples of the materials constituting the organic light emitting layer include polyparaphenylene vinylene-based materials, polyfluorene-based materials, and polyvinylcarbazole-based materials. Further, the light emitting layer may have a laminate of a plurality of layers having different emission colors, or a mixed layer in which a layer of a certain dye is doped with different dyes. Further, the organic EL element may include functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface forming layer, and a charge generation layer.

(Explanation of reflex suppression effect)
In a normal usage mode, the organic light emitting display device 10 is irradiated with light from a light source in the upward direction of the vertical _UD . The light irradiated in this way is normally incident on the display screen 10U in the tilting direction of the incident angle _φi . Most of the light thus incident is specularly reflected at a reflection angle _φr having the same magnitude as the incident angle _φi . The organic light emitting display device 10 described above can achieve such effective suppression of specular reflection.

The mechanism of reflection suppression will be described below. The light incident on the display screen 10U becomes circularly polarized light or elliptically polarized light when only a part of the linearly polarized light passes through the polarizing element 100 and then passes through the liquid crystal curing layer 200. This circularly polarized light or elliptically polarized light is reflected on or inside the surface or inside of the organic light emitting display panel 300, and when it passes through the liquid crystal curing layer 200 again, it becomes linearly polarized light having a vibration direction orthogonal to the vibration direction of the incident linearly polarized light. It does not pass through the splitter 100. As a result, the function of suppressing reflection is achieved. For the principle of such reflection suppression, Japanese Patent Application Laid-Open No. 9-127885 may be referred to.

When the external light emitted from the upward light source of the vertical direction _AUD is transmitted through the polarizing element 100 and the liquid crystal curing layer 200 in this order, it is normally transmitted in an inclined direction inclined with respect to the display screen 10U. On the other hand, the reflected light reflected by the organic light emitting display panel 300 is also transmitted in the inclined direction inclined with respect to the display screen 10U when the liquid crystal curing layer 200 and the polarizing element 100 are transmitted in this order. In general, the change in the polarization state caused by transmitting the polarizing element and the liquid crystal curing layer in the tilting direction differs depending on the orientation in the tilting direction. Here, the orientation in the tilt direction means a component parallel to the display screen in the tilt direction. Therefore, in the conventional organic light emitting display device, it is difficult to precisely control the change in the polarization state due to the transmission through the polarizing element and the liquid crystal curing layer. Therefore, in the past, it was difficult to convert the light transmitted through the polarizing element into ideal linear polarization that cannot be transmitted through the polarizing element by the time the light is reflected and then incident on the polarizing element again, so that a sufficient reflection suppressing effect can be obtained. Not obtained. On the other hand, in the organic light emitting display device 10 according to the above-described embodiment, the angle θ ₁₀₀ of the absorption axis A ₁₀₀ of the polarizing element 100 with respect to the vertical direction AUD of the display screen _10U and the absorption axis A ₁₀₀ of the polarizing element 100. Effective suppression of specular reflection can be achieved by appropriately adjusting the angle θ ₂₀₀ of the slow axis A ₂₀₀ of the liquid crystal cured layer 200.

(Explanation of modification)
Although one embodiment of the present invention has been described above, the present invention may be further modified and carried out.
For example, the organic light emitting display device 10 may further include any member in combination with the polarizing element 100, the liquid crystal curing layer 200, and the organic light emitting display panel 300.

[2. Description of liquid crystal composition]
The liquid crystal composition as a material of the liquid crystal curing layer is a material containing a liquid crystal compound. This liquid crystal composition includes not only a material containing two or more kinds of components but also a material containing only one kind of liquid crystal compound.

The liquid crystal compound is a compound having a liquid crystal property, and usually, when the liquid crystal compound is oriented, it can exhibit a liquid crystal phase. As the liquid crystal compound, a reverse-dispersed liquid crystal compound may be used, a forward-dispersed liquid crystal compound may be used, or a combination of a reverse-dispersed liquid crystal compound and a forward-dispersed liquid crystal compound may be used.

The reverse-dispersed liquid crystal compound is a liquid crystal compound capable of exhibiting birefringence of reverse wavelength dispersibility. Further, the liquid crystal compound capable of expressing the birefringence of the reverse wavelength dispersibility is a layer of the liquid crystal compound, and when the liquid crystal compound is oriented in the layer, the birefringence of the reverse wavelength dispersibility is expressed. A liquid crystal compound.

The forward-dispersed liquid crystal compound is a liquid crystal compound capable of exhibiting birefringence of forward wavelength dispersibility. Further, the liquid crystal compound capable of exhibiting forward wavelength dispersible birefringence expresses forward wavelength dispersive birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. A liquid crystal compound.

Usually, when the liquid crystal compound is homogenically oriented, the wavelength dispersibility of the birefringence exhibited by the layer of the liquid crystal compound can be confirmed by examining the wavelength dispersibility of the birefringence exhibited by the liquid crystal compound. To homogenically orient a liquid crystal compound means to form a layer containing the liquid crystal compound, and the direction of the maximum refractive index in the refractive index ellipse of the molecule of the liquid crystal compound in the layer is parallel to the plane of the layer. It means orienting in one direction. Further, the birefringence of the layer is obtained from "(in-plane retardation of the layer) ÷ (thickness of the layer)".

Among them, the reverse dispersion liquid crystal compound is preferable as the liquid crystal compound from the viewpoint of suppressing the reflection of external light in a wide wavelength range.

The liquid crystal compound is preferably polymerizable. Therefore, it is preferable that the molecule of the liquid crystal compound contains a polymerizable group such as an acryloyl group, a methacryloyl group, and an epoxy group. The polymerizable liquid crystal compound can be polymerized in a state of exhibiting a liquid crystal phase, and can be a polymer while maintaining the molecular orientation state in the liquid crystal phase. Therefore, it is possible to fix the orientation state of the liquid crystal compound in the cured product of the liquid crystal composition, or to increase the degree of polymerization of the liquid crystal compound to increase the mechanical strength of the liquid crystal cured layer.

The molecular weight of the liquid crystal compound is preferably 300 or more, more preferably 500 or more, particularly preferably 800 or more, preferably 2000 or less, more preferably 1700 or less, and particularly preferably 1500 or less. By using a liquid crystal compound having a molecular weight in such a range, the coatability of the liquid crystal composition can be particularly improved.

The birefringence Δn of the liquid crystal compound at the measurement wavelength of 550 nm is preferably 0.01 or more, more preferably 0.03 or more, preferably 0.15 or less, and more preferably 0.10 or less. By using a liquid crystal compound having a birefringence Δn in such a range, it is usually easy to obtain a liquid crystal cured layer having few orientation defects.

The birefringence of the liquid crystal compound can be measured, for example, by the following method.
A layer of the liquid crystal compound is prepared, and the liquid crystal compound contained in the layer is homogenically oriented. Then, the in-plane retardation of the layer is measured. Then, the birefringence of the liquid crystal compound can be obtained from "(in-plane retardation of the layer) ÷ (thickness of the layer)". At this time, in order to facilitate the measurement of the in-plane retardation and the optical thickness, the layer of the liquid crystal compound homogenically oriented may be cured.

As the liquid crystal compound, one type may be used alone, or two or more types may be used in combination at any ratio.

There is no limitation on the specific type of liquid crystal compound. For example, examples of the inversely dispersed liquid crystal compound include those represented by the following formula (I).

In the formula (I), Ar represents a group represented by any of the following formulas (II-1) to (II-7). In equations (II-1) to (II-7), * represents the bonding position with Z ¹ or Z ² .

In the above equations (II-1) to (II-7), E ¹ and E ² are independently -CR ¹¹ R ^12- , -S-, -NR ^11- , -CO- and-, respectively. Represents a group selected from the group consisting of O-. Further, R ¹¹ and R ¹² independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Above all, it is preferable that E ¹ and E ² are independently of —S—.

In the above formulas (II-1) to (II-7), D ¹ to D ³ each independently have an aromatic hydrocarbon ring group or a substituent which may have a substituent. Represents an aromatic heterocyclic group that may have. The number of carbon atoms of the group represented by D ¹ to D ³ (including the number of carbon atoms of the substituent) is usually 2 to 100 independently of each other.

The number of carbon atoms of the aromatic hydrocarbon ring group in D ¹ to D ³ is preferably 6 to 30. Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ include a phenyl group and a naphthyl group. Among them, the phenyl group is more preferable as the aromatic hydrocarbon ring group.

Examples of the substituent that the aromatic hydrocarbon ring group in D ¹ to D ³ can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom such as a methyl group, an ethyl group and a propyl group. Alkyl group of number 1 to 6; alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; alkyl halide group having 1 to 6 carbon atoms such as trifluoromethyl group; dimethylamino group and the like , N, N-dialkylamino group with 1 to 12 carbon atoms; alkoxy group with 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; nitro group; -OCF ₃ ; -C (= O) ) -R ^b ; -OC (= O) -R ^b ; -C (= O) -OR ^b ; -SO ₂ R ^a ; and the like. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Ra may have an alkyl group having 1 to 6 carbon atoms; an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as ^a substituent, and has 6 carbon atoms. Represents a group selected from the group consisting of ~ 20 aromatic hydrocarbon ring groups;

R ^b may have an alkyl group having 1 to 20 carbon atoms which may have a substituent; an alkenyl group having 2 to 20 carbon atoms which may have a substituent; even if it has a substituent. It represents a group selected from the group consisting of a good cycloalkyl group having 3 to 12 carbon atoms; and an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent.

The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms in ^Rb is preferably 1 to 12, more preferably 4 to 10. Examples of the alkyl group having 1 to 20 carbon atoms in ^Rb include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a 1-methylpentyl group and a 1-ethylpentyl group. , Se-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 etc. can be mentioned.

Examples of the substituent that the alkyl group having 1 to 20 carbon atoms in ^Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a dimethylamino group having 2 to 12 carbon atoms. N, N-dialkylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; methoxymethoxy group, methoxyethoxy group, etc., having 1 to 12 carbon atoms. An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, Aromatic heterocyclic group having 2 to 20 carbon atoms such as thienyl group, thiazolyl group and benzothiazole-2-ylthio group; cycloalkyl having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group. Group; Cycloalkyloxy group having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; Cyclic ether having 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group and dioxanyl group. Group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; one or more hydrogen atoms such as trifluoromethyl group, pentafluoroethyl group and -CH ₂ CF ₃ are replaced with fluorine atom. Examples thereof include a fluoroalkyl group having 1 to 12 carbon atoms; a benzofuryl group; a benzopyranyl group; a benzodioxolyl group; and a benzodioxanyl group; The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

The number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms in ^Rb is preferably 2 to 12. Examples of the alkenyl group having 2 to 20 carbon atoms in ^Rb include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a decenyl group and an undecenyl group. , Dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadesenyl group, icosenyl group and the like.

Examples of the substituent that the alkenyl group having 2 to 20 carbon atoms in ^{Rb can have include the same examples as the substituent that the alkyl group having 1 to 20 carbon atoms in R b can} have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the cycloalkyl group having 3 to 12 carbon atoms in ^Rb include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group and the like. Of these, as the cycloalkyl group, a cyclopentyl group and a cyclohexyl group are preferable.

Examples of the substituent that the cycloalkyl group having 3 to 12 carbon atoms in ^Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a dimethylamino group having 2 to 12 carbon atoms. N, N-dialkylamino group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkoxy having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group. Examples thereof include an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a group; a nitro group; and a phenyl group and a naphthyl group; Among them, the substituent of the cycloalkyl group includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; a methoxy group and an ethoxy group. An alkoxy group having 1 to 6 carbon atoms such as a group and an isopropoxy group; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; are preferable. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms in ^Rb include a phenyl group, a 1-naphthyl group, a 2-naphthyl group and the like. Of these, a phenyl group is preferable as the aromatic hydrocarbon ring group.

Examples of the substituent that the aromatic hydrocarbon ring group having 6 to 12 carbon atoms in ^Rb can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a dimethylamino group and the like. 2 to 12 N, N-dialkylamino groups; alkoxy groups with 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; number of carbon atoms such as methoxymethoxy group and methoxyethoxy group. An alkoxy group having 1 to 12 carbon atoms substituted with 1 to 12 alkoxy groups; a nitro group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as a triazolyl group, a pyrrolyl group, a furanyl group and a thiophenyl group; Cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cycloalkyloxy group having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; tetrahydrofuranyl group and tetrahydro Cyclic ether group having 2 to 12 carbon atoms such as pyranyl group, dioxolanyl group and dioxanyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; trifluoromethyl group and pentafluoroethyl A fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, such as a group, -CH ₂ CF ₃ , etc .;-OCF ₃ ; benzofuryl group; benzopyranyl group; benzodioxoryl group; Benzodioxanyl groups; and the like. Among them, the substituent of the aromatic hydrocarbon ring group includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group and the like, and has 1 to 20 carbon atoms. Alkoxy group; nitro group; aromatic heterocyclic group having 2 to 20 carbon atoms such as furanyl group and thiophenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; A fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, such as a trifluoromethyl group, a pentafluoroethyl group, and -CH ₂ CF ₃ , -OCF ₃ ; is preferable. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

The number of carbon atoms of the aromatic heterocyclic group in D ¹ to D ³ is preferably 2 to 30. Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, frazanyl group, oxazolyl group, quinolyl group and thiadiazolyl group. , Thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridadinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyldinyl group, pyrazinyl group, pyrazolyl group, pyranyl group, Pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phthalazinyl group, furanyl group, benzo [c] thienyl group, benzo [b] thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzoimidazolyl group, benzoxa Examples thereof include a diazolyl group, a benzoxazolyl group, a benzothiadiazolyl group, a benzothiazolyl group, a benzotriazinyl group, a benzotriazolyl group, a benzopyrazolyl group and the like. Among them, the aromatic heterocyclic group includes a monocyclic aromatic heterocyclic group such as a furanyl group, a pyranyl group, a thienyl group, an oxazolyl group, a frazanyl group, a thiazolyl group, and a thiadiazolyl group; and a benzothiazolyl group and a benzoxa. Zoryl group, quinolyl group, 1-benzofuranyl group, 2-benzofuranyl group, phthalimide group, benzo [c] thienyl group, benzo [b] thienyl group, thiazolopyridyl group, thiazolopyrazinyl group, benzoisooxazoli More preferably, an aromatic heterocyclic group of the fused ring, such as a ru group, a benzoxaziazolyl group, and a benzothiadiazolyl group.

Examples of the substituent that the aromatic heterocyclic group in D ¹ to D ³ can have include the same example as the substituent that the aromatic hydrocarbon ring group in D ¹ to D ³ can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

In the above formulas (II-1) to (II-7), D ⁴ to D ⁵ each independently represent a non-cyclic group which may have a substituent. D ⁴ and D ⁵ may be combined to form a ring. The number of carbon atoms of the group represented by D ⁴ to D ⁵ (including the number of carbon atoms of the substituent) is usually 1 to 100 independently of each other.

The number of carbon atoms of the acyclic group in D ⁴ to D ⁵ is preferably 1 to 13. Examples of the acyclic group in D ⁴ to D ⁵ include an alkyl group having 1 to 6 carbon atoms; a cyano group; a carboxyl group; a fluoroalkyl group having 1 to 6 carbon atoms; and an alkoxy group having 1 to 6 carbon atoms. -C (= O) -CH ₃ ; -C (= O) NHPh; -C (= O) -OR ^x ; Among them, the acyclic groups include a cyano group, a carboxyl group, -C (= O) -CH ₃ , -C (= O) NHPh, -C (= O) -OC ₂ H ₅ , -C (= O). -OC ₄ H ₉ , -C (= O) -OCH (CH ₃ ) ₂ , -C (= O) -OCH ₂ CH ₂ CH (CH ₃ ) -OCH ₃ , -C (= O) -OCH ₂ CH ₂ C (CH ₃ ) ₂ -OH and -C (= O) -OCH ₂ CH (CH ₂ CH ₃ ) -C ₄ H ₉ are preferable. The Ph represents a phenyl group. Further, the above-mentioned R ^x represents an organic group having 1 to 12 carbon atoms. Specific examples of R ^x include an alkoxy group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group.

Examples of the substituent that the acyclic group in D ⁴ to D ⁵ can have include the same example as the substituent that the aromatic hydrocarbon ring group in D ¹ to D ³ can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

When D ⁴ and D ⁵ are combined to form a ring, the above D ⁴ and D ⁵ form an organic group containing a ring. Examples of this organic group include a group represented by the following formula. In the following formula, * represents the position where each organic group is bonded to the carbon to which D ⁴ and D ⁵ are bonded.

R ^* represents an alkyl group having 1 to 3 carbon atoms.
R ^** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^*** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^*** represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, and -COOR ¹³ . R ¹³ represents an alkyl group having 1 to 3 carbon atoms.
Examples of the substituent that the phenyl group can have include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group and an amino group. Can be mentioned. Of these, as the substituent, a halogen atom, an alkyl group, a cyano group and an alkoxy group are preferable. The number of substituents of the phenyl group may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

In the above equations (II-1) to (II-7), D ⁶ is -C (R ^f ) = N-N (R ^g ) R ^h , -C (R ^f ) = N-N = C. Represents a group selected from the group consisting of (R ^g ) R ^h and —C (R ^f ) = NN = ^Ri . The number of carbon atoms of the group represented by D ⁶ (including the number of carbon atoms of the substituent) is usually 3 to 100.

R ^f represents a group selected from the group consisting of a hydrogen atom; and an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, a propyl group, and an isopropyl group;

R ^g 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 a substituent.

Examples of the organic group having 1 to 30 carbon atoms which may have a substituent in R ^g include an alkyl group having 1 to 20 carbon atoms which may have a substituent; and 1 to 20 carbon atoms. At least one of -CH _2- contained in the alkyl group of 20 is -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (=). O) -Substituent group (except when two or more -O- or -S- are adjacent to each other); an alkenyl group having 2 to 20 carbon atoms which may have a substituent. An alkynyl group having 2 to 20 carbon atoms which may have a substituent; a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; a carbon which may have a substituent. An aromatic hydrocarbon ring group having 6 to 30 atoms; an aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent; -SO ₂ Ra; -C (= O ^{) -R b .} ; -CS-NH-R ^b ; may be mentioned. The meanings of R ^a and R ^b are as described above.

The preferred range and examples of the number of carbon atoms of the alkyl group having 1 to 20 carbon atoms in R ^g is the same as that of the alkyl group having 1 to 20 carbon atoms in R ^b .

Examples of the substituent that the alkyl group having 1 to 20 carbon atoms in ^Rg can have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; and a dimethylamino group having 2 to 12 carbon atoms. N, N-dialkylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; methoxymethoxy group, methoxyethoxy group, etc., having 1 to 12 carbon atoms. An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group; a nitro group; an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, Aromatic heterocyclic group having 2 to 20 carbon atoms such as thiophenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cyclopentyloxy group, cyclohexyloxy group and the like. , Cycloalkyloxy group with 3 to 8 carbon atoms; cyclic ether group with 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group, dioxanyl group; carbon such as phenoxy group and naphthoxy group. An aryloxy group having 6 to 14 atoms; a fluoroacyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom; a benzofuryl group; a benzopyranyl group; a benzodioxolyl group; a benzodioxanyl Groups; -SO ₂ Ra; -SR ^b ; alkoxy groups having 1 to 12 carbon atoms substituted with ^{-SR b ;} hydroxyl groups; and the like. The meanings of R ^a and R ^b are as described above. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

The preferred range and examples of carbon atoms of the alkenyl group having 2 to 20 carbon atoms in R ^g is the same as that of the alkenyl group having 2 to 20 carbon atoms in R ^b .

Examples of the substituent that the alkenyl group having 2 to 20 carbon atoms in ^Rg can have include the same examples as the substituent that the alkyl group having 1 to 20 carbon atoms in ^Rg can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the alkynyl group having 2 to 20 carbon atoms in ^Rg include an ethynyl group, a propynyl group, a 2-propynyl group (propargyl group), a butynyl group, a 2-butynyl group, a 3-butynyl group, a pentynyl group, and 2-. Examples thereof include a pentynyl group, a hexynyl group, a 5-hexynyl group, a heptynyl group, an octynyl group, a 2-octynyl group, a nonanyl group, a decanyl group and a 7-decanyl group.

Examples of the substituent that the alkynyl group having 2 to 20 carbon atoms in R ^g can have include the same examples as the substituent that the alkyl group having 1 to 20 carbon atoms in R ^g can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the cycloalkyl group having 3 to 12 carbon atoms in R ^g include the same examples as the cycloalkyl group having 3 to 12 carbon atoms in R ^b .

Examples of the substituent that the cycloalkyl group having 3 to 12 carbon atoms in R ^g can have include the same examples as the substituent that the alkyl group having 1 to 20 carbon atoms in R ^g can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ .

Examples of the substituents that the aromatic hydrocarbon ring group having 6 to ³⁰ carbon atoms in ^Rg can have include the same examples as the substituents that the aromatic hydrocarbon ring groups in D1 to ^D3 can have. Be done. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in R ^g include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ .

Examples of the substituent that the aromatic heterocyclic group having 2 to 30 carbon atoms in ^Rg can have include the same examples as the substituent that the aromatic hydrocarbon ring group in D ¹ to D ³ can have. .. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Among the above-mentioned ones, as R ^g , at least one of an alkyl group having 1 to 20 carbon atoms which may have a substituent; and -CH _2- contained in the alkyl group having 1 to 20 carbon atoms is used. A group substituted with -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (= O)-(however, -O- or- (Except when two or more S- are adjacent to each other); Cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; 6 to 6 carbon atoms which may have a substituent. 30 aromatic hydrocarbon ring groups; and aromatic heterocyclic groups having 2 to 30 carbon atoms which may have a substituent; are preferable. Among them, as R ^g , at least one of an alkyl group having 1 to 20 carbon atoms which may have a substituent; and -CH _2- contained in the alkyl group having 1 to 20 carbon atoms is included. A group substituted with -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (= O)-(however, -O- or- (Except when two or more S- are adjacent to each other); is particularly preferable.

R ^h represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms.

Preferred examples of R ^h include (1) a hydrocarbon ring group having 6 to 40 carbon atoms and having an aromatic hydrocarbon ring having 1 or more carbon atoms and 6 to 30 carbon atoms. The hydrocarbon ring group having this aromatic hydrocarbon ring may be appropriately referred to as "(1) hydrocarbon ring group" below. (1) Specific examples of the hydrocarbon ring group include the following groups.

(1) The hydrocarbon ring group may have a substituent. (1) Substituents that the hydrocarbon ring group can have include, for example, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a methyl group, an ethyl group, a propyl group and the like, having 1 to 6 carbon atoms. Alkyl group; alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; alkyl halide group having 1 to 6 carbon atoms such as trifluoromethyl group; dimethylamino group having 2 carbon atoms ~ 12 N, N-dialkylamino groups; alkoxy groups with 1-6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; nitro group; 6-20 carbon atoms such as phenyl group, naphthyl group, etc. Aromatic hydrocarbon ring group of; -OCF ₃ ; -C (= O) -R ^b ; -OC (= O) -R ^b ; -C (= O) -OR ^b ; -SO ₂ R ^a ; and the like. The meanings of R ^a and R ^b are as described above. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Another preferred example of ^Rh is (2) having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms. , A heterocyclic group having 2 to 40 carbon atoms can be mentioned. The heterocyclic group having this aromatic ring may be appropriately referred to as "(2) heterocyclic group" below. (2) Specific examples of the heterocyclic group include the following groups. R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(2) The heterocyclic group may have a substituent. Examples of the substituent that the (2) heterocyclic group may have include the same examples as the substituent that the (1) hydrocarbon ring group may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

As yet another preferable example of R ^h , (3) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples thereof include an alkyl group having 1 to 12 carbon atoms substituted with. Hereinafter, the substituted alkyl group may be appropriately referred to as "(3) substituted alkyl group".

(3) Examples of the "alkyl group having 1 to 12 carbon atoms" in the substituted alkyl group include a methyl group, an ethyl group, a propyl group and an isopropyl group.
(3) As the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkyl group, for example, the same example as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ can be used. Can be mentioned.
(3) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ . ..

(3) The substituted alkyl group may further have a substituent. Examples of the substituent that the (3) substituted alkyl group can have include the same examples as the substituent that the (1) hydrocarbon ring group can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Still another preferable example of ^Rh is (4) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples thereof include an alkenyl group having 2 to 12 carbon atoms substituted with. The substituted alkenyl group may be hereinafter appropriately referred to as "(4) substituted alkenyl group".

(4) Examples of the "alkenyl group having 2 to 12 carbon atoms" in the substituted alkenyl group include a vinyl group and an allyl group.
(4) As the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkenyl group, for example, the same example as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ can be used. Can be mentioned.
(4) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkenyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ . ..

(4) The substituted alkenyl group may further have a substituent. Examples of the substituent that the (4) substituted alkenyl group can have include the same examples as the substituent that the (1) hydrocarbon ring group can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

As yet another preferable example of R ^h , (5) one or more groups selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms. Examples thereof include an alkynyl group having 2 to 12 carbon atoms substituted with. The substituted alkynyl group may be hereinafter appropriately referred to as "(5) substituted alkynyl group".

(5) Examples of the "alkynyl group having 2 to 12 carbon atoms" in the substituted alkynyl group include an ethynyl group and a propynyl group.
(5) As the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkynyl group, for example, the same example as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ can be used. Can be mentioned.
(5) Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkynyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ . ..

(5) The substituted alkynyl group may further have a substituent. (5) Examples of the substituent that the substituted alkynyl group can have include the same examples as those of (1) the substituent that the hydrocarbon ring group can have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Preferred specific examples of R ^h include the following groups.

Further preferable specific examples of ^Rh include the following groups.

^Particularly preferable specific examples of Rh include the following groups.

The specific example of ^Rh described above may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group; and a vinyl group and an allyl group. , An alkenyl group having 2 to 6 carbon atoms; an alkyl halide group having 1 to 6 carbon atoms such as a trifluoromethyl 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, and an isopropoxy group; a nitro group; -OCF ₃ ; -C (= O) -R ^b ; -OC (= O) -R ^b ; -C (= O) -OR ^b ; -SO ₂ R ^a ; and the like. The meanings of R ^a and R ^b are as described above. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

^Ri represents an organic group having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms.

Preferred examples of ^Ri include a hydrocarbon ring group having 6 to 40 carbon atoms and having one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms.
Further, as another preferable example of ^Ri , it has one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocycle having 2 to 30 carbon atoms. Examples thereof include heterocyclic groups having 2 to 40 carbon atoms.

The following groups are mentioned as a particularly preferable specific example of ^Ri . The meaning of R is as described above.

The group represented by any of the formulas (II-1) to (II-7) may further have a substituent other than D ¹ to D ⁶ . Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, an alkyl halide group having 1 to 6 carbon atoms, and an N-alkylamino having 1 to 6 carbon atoms. Group, N, N-dialkylamino group with 2 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkylsulfinyl group with 1 to 6 carbon atoms, carboxyl group, thioalkyl group with 1 to 6 carbon atoms , N-alkylsulfamoyl group having 1 to 6 carbon atoms and N, N-dialkylsulfamoyl group having 2 to 12 carbon atoms. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Preferred examples of Ar in the formula (I) include groups represented by the following formulas (III-1) to (III-10). Further, the groups represented by the formulas (III-1) to (III-10) may have an alkyl group having 1 to 6 carbon atoms as a substituent. In the following formula, * represents the bond position.

Particularly preferable specific examples of the formula (III-1) and the formula (III-4) include the following groups. In the following formula, * represents the bond position.

In formula (I), Z ¹ and Z ² are independently single-bonded, -O-, -O-CH _{2-, -CH 2-O-, -O-CH 2 -CH 2 - ,} -, respectively. CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -C (= O) -S-, -SC (= O)-,- NR ²¹ -C (= O)-, -C (= O) -NR ^21- , -CF _{2-O-, -O-CF 2-, -CH 2 - CH 2-} , -CF ₂ -CF _2- , -O-CH ₂ -CH ₂ -O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _2- , -CH _{2-OC (= O)-, -C (= O) -O-CH 2-, -CH 2 - CH 2-} C (= O) -O-, -OC (= O) -CH ₂ -CH _{2-, -CH 2 -} CH ₂ -OC (= O)-, -C (= O) -O- CH ₂ -CH _2- , -CH = CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- , And -C≡C-, which is selected from the group consisting of. R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (I), A ¹ , A ² , B ¹ and B ² independently have a cyclic aliphatic group which may have a substituent and an aromatic group which may have a substituent. Represents a group selected from the group consisting of family groups. The number of carbon atoms of the group represented by A ¹ , A ² , B ¹ and B ² (including the number of carbon atoms of the substituent) is usually 3 to 100 independently of each other. Among them, A ¹ , A ² , B ¹ and B ² each independently have a cyclic aliphatic group having 5 to 20 carbon atoms or a substituent which may have a substituent. An aromatic group having 2 to 20 carbon atoms is preferable.

Examples of the cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² include cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, and 1,4-cycloheptane-1,4. -Cycloalkanediyl group having 5 to 20 carbon atoms such as diyl group, cyclooctane-1,5-diyl group; decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl group, etc. , A bicycloalkandyl group having 5 to 20 carbon atoms; and the like. Of these, a cycloalkandyl 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 cyclic aliphatic group may be a trans form, a cis form, or a mixture of a cis form and a trans form. Among them, the transformer body is more preferable.

Examples of the substituent that the cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² can have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Examples thereof include a nitro group and a cyano group. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

Examples of the aromatic group in A ¹ , A ² , B ¹ and B ² include 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1, Aromatic hydrocarbon ring groups with 6 to 20 carbon atoms such as 5-naphthylene group, 2,6-naphthylene group, 4,4'-biphenylene group; furan-2,5-diyl group, thiophene-2,5 -Aromatic heterocyclic groups having 2 to 20 carbon atoms such as a diyl group, a pyridine-2,5-diyl group, a pyrazine-2,5-diyl group; and the like can be mentioned. 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.

The substituents that the aromatic group in A ¹ , A ² , B ¹ and B ² can have are the same as the substituents that the cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² can have, for example. An example is given. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as each other or may be different from each other.

In formula (I), Y ¹ to Y ⁴ are independently single-bonded, -O-, -C (= O)-, -C (= O) -O-, -OC (= O). )-, -NR ²² -C (= O)-, -C (= O) -NR ^{22-, -OC (= O) -O-, -NR 22 -} C (= O) -O-, It represents any one selected from the group consisting of -OC (= O) -NR ^{22- and -NR 22 -} C (= O) -NR ^23- . R ²² and R ²³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (I), G ¹ and G ² are independently aliphatic hydrocarbon groups having 1 to 20 carbon atoms; and methylene groups contained in the aliphatic hydrocarbon groups having 3 to 20 carbon atoms. Represents an organic group selected from the group consisting of a group in which one or more of (-CH _2- ) is substituted with -O- or -C (= O)-. The hydrogen atom contained in the organic group of G ¹ and G ² 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 (-CH _2- ) at both ends of G ¹ and G ² are not replaced with -O- or -C (= O)-.

Specific examples of the aliphatic hydrocarbon group having 1 to 20 carbon atoms in G ¹ and G ² include an alkylene group having 1 to 20 carbon atoms.

Specific examples of the aliphatic hydrocarbon group having 3 to 20 carbon atoms in G ¹ and G ² include an alkylene group having 3 to 20 carbon atoms.

In formula (I), P ¹ and P ² each independently represent a polymerizable group. Examples of the polymerizable group in P ¹ and P ² include acryloyloxy group, methacryloyloxy group and the like represented by CH ₂ = CR ³¹ -C (= O) -O-; vinyl group; vinyl ether group; p-Stilben group; acryloyl group; methacryloyl group; carboxyl group; methylcarbonyl group; hydroxyl group; amide group; alkylamino group with 1 to 4 carbon atoms; amino group; epoxy group; oxetanyl group; aldehyde group; isocyanate group; thio An isocyanate group; and the like. R ³¹ represents a hydrogen atom, a methyl group, or a chlorine atom. Among them, the group represented by CH ₂ = CR ³¹ -C (= O) -O- is preferable, CH ₂ = CH-C (= O) -O- (acryloyloxy group), CH ₂ = C (CH ₃ ). )-C (= O) -O- (methacryloyloxy group) is more preferable, and acryloyloxy group is particularly preferable.

In formula (I), p and q independently represent 0 or 1, respectively.

The liquid crystal composition may further contain any component in combination with the liquid crystal compound, if necessary. Any component may be used alone or in combination of two or more at any ratio.

Since the liquid crystal composition can usually be cured by polymerization, the liquid crystal composition contains a polymerization initiator as an arbitrary component. The type of the polymerization initiator can be selected according to the type of the polymerizable compound contained in the liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator can be used. Further, if the polymerizable compound is anionic polymerizable, an anionic polymerization initiator can be used. Further, if the polymerizable compound is cationically polymerizable, a cationic polymerization initiator can be used. As the polymerization initiator, one type may be used alone, or two or more types may be used in combination at any ratio.

The amount of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 30 parts by weight or less, and more preferably 10 parts by weight with respect to 100 parts by weight of the liquid crystal compound. It is less than a part. When the amount of the polymerization initiator is within the above range, the polymerization can be efficiently promoted.

The liquid crystal composition may contain a surfactant as an arbitrary component. In particular, from the viewpoint of stably obtaining a liquid crystal cured layer having excellent orientation, a surfactant containing a fluorine atom in the molecule is preferable as the surfactant. In the following description, a surfactant containing a fluorine atom in the molecule may be appropriately referred to as a "fluorine-based surfactant".

The surfactant is preferably a nonionic surfactant. When the surfactant is a nonionic surfactant containing no ionic group, the surface state and orientation of the liquid crystal cured layer can be particularly improved.

The surfactant does not have to have polymerizability and may have polymerizability. Since the polymerizable surfactant can be polymerized in the step of curing the layer of the liquid crystal composition, it is usually contained in a part of the molecule of the polymer in the liquid crystal cured layer.

Examples of the surfactant include AGC Seimi Chemical's Surflon series (S420, etc.), Neos's Futergent series (251, FTX-212M, FTX-215M, FTX-209, etc.), and DIC's. Examples include the Mega Fuck series (F-444, etc.). In addition, one type of surfactant may be used alone, or two or more types may be used in combination at any ratio.

The amount of the surfactant is preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 0.50 parts by weight or less, and more preferably more preferably 0.50 parts by weight or more with respect to 100 parts by weight of the liquid crystal compound. It is 0.30 parts by weight or less. When the amount of the surfactant is in the above range, a liquid crystal cured layer having excellent orientation can be obtained.

The liquid crystal composition may contain a solvent as an arbitrary component. As the solvent, a solvent capable of dissolving a liquid crystal compound is preferable. As such a solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as cyclopentanone, cyclohexanone, methylethylketone, acetone and methylisobutylketone; acetate solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; 1 , 4-Dioxane, cyclopentylmethyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,2-dimethoxyethane and other ether solvents; and aromatic hydrocarbon solvents such as toluene, xylene and mesitylene; In addition, one type of solvent may be used alone, or two or more types may be used in combination at any ratio.

The boiling point of the solvent is preferably 60 ° C. to 250 ° C., more preferably 60 ° C. to 150 ° C. from the viewpoint of excellent handleability.

The amount of the solvent is preferably 200 parts by weight or more, more preferably 250 parts by weight or more, particularly preferably 300 parts by weight or more, and preferably 650 parts by weight or less, more preferably 650 parts by weight or more, based on 100 parts by weight of the liquid crystal compound. It is 550 parts by weight or less, particularly preferably 450 parts by weight or less. By setting the amount of the solvent to the lower limit of the above range or more, the generation of foreign matter can be suppressed, and by setting the amount to the upper limit of the range or less, the drying load can be reduced.

Further, the liquid crystal composition can exert an action of increasing the substantially maximum inclination angle of the molecule of the liquid crystal compound as an arbitrary component in order to increase the inclination angle of the molecule of the liquid crystal compound contained in the liquid crystal cured layer. It may contain a tilting component. As the type and amount of the inclined action component, for example, those described in the specification of Japanese Patent Application No. 2017-060154, the specification of Japanese Patent Application No. 2017-060122, and the specification of Japanese Patent Application No. 2017-059327 may be adopted. .. However, since it is possible to increase the substantially maximum tilt angle of the molecule of the liquid crystal compound by adjusting the operation or conditions in the process of manufacturing the liquid crystal cured layer, it is not always necessary to use the tilting action component. not.

Any other components that the liquid crystal composition may contain include, for example, metals; metal complexes; metal oxides such as titanium oxide; colorants such as dyes and pigments; light emitting materials such as fluorescent materials and phosphorescent materials; leveling agents; Examples thereof include thixo agents; gelling agents; polysaccharides; ultraviolet absorbers; infrared absorbers; antioxidants; ion exchange resins; and the like. The amount of these components may be 0.1 part by weight to 20 parts by weight, respectively, with respect to 100 parts by weight of the total amount of the liquid crystal compound.

[3. Explanation of an example of a method for manufacturing a liquid crystal cured layer]
Next, a method for manufacturing the liquid crystal cured layer will be described. The method for manufacturing the liquid crystal cured layer is not particularly limited. For example, the liquid crystal cured layer is
(I) A step of forming a layer of the liquid crystal composition and
(Ii) A step of orienting a liquid crystal compound contained in a layer of a liquid crystal composition,
(Iii) A step of curing the layer of the liquid crystal composition and
Can be manufactured by the first manufacturing method containing the above in this order.

In step (i), a layer of the liquid crystal composition is usually formed on a suitable support surface. As the support surface, any surface that can support the layer of the liquid crystal composition can be used. As the support surface, it is preferable to use a flat surface without recesses and protrusions from the viewpoint of improving the surface condition of the liquid crystal cured layer. Further, from the viewpoint of increasing the productivity of the liquid crystal cured layer, it is preferable to use the surface of a long base material as the support surface. Here, "long" means a shape having a length of 5 times or more with respect to the width, preferably having a length of 10 times or more, and specifically being wound into a roll shape. The shape of the film that has a length that can be stored or transported.

As the base material, a resin film or a glass plate is usually used. In particular, when the orientation treatment is performed at a high temperature, it is preferable to select a base material that can withstand the temperature. As the resin, a thermoplastic resin is usually used. Among them, a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoints of high orientation control force, high mechanical strength, and low cost. Further, since it is excellent in transparency, low hygroscopicity, dimensional stability and light weight, it is preferable to use a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin. To give a suitable example of the resin contained in the base material by trade name, as a norbornene-based resin, "Zeonoa" manufactured by Nippon Zeon Corporation can be mentioned.

In order to promote the orientation of the molecules of the liquid crystal compound in the layer of the liquid crystal composition, the surface of the base material as the support surface is preferably treated to impart an orientation restricting force. The orientation regulating force refers to the property of a surface capable of orienting a liquid crystal compound contained in a liquid crystal composition. Examples of the treatment for imparting an orientation restricting force to the support surface include a photoalignment treatment, a rubbing treatment, an alignment film forming treatment, an ion beam orientation treatment, and a stretching treatment.

In the step (i) of forming the layer of the liquid crystal composition, the liquid crystal composition is usually prepared in a fluid state. Therefore, usually, the liquid crystal composition is applied to the support surface to form a layer of the liquid crystal composition. Examples of the method for coating the liquid crystal composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, and gravure. Examples include a coating method, a die coating method, a gap coating method, and a dipping method.

After the step (i) of forming the layer of the liquid crystal composition, the step (ii) of orienting the liquid crystal compound contained in the layer of the liquid crystal composition is performed. When the orientation is performed, the layer of the liquid crystal composition is usually held in a predetermined temperature condition for a predetermined time. As a result, the molecules of the liquid crystal compound are oriented in the layer of the liquid crystal composition.

Normally, in the in-plane direction, the molecules of the liquid crystal compound are oriented in a direction corresponding to the orientation restricting force of the support surface. Further, when the conditions are appropriate, in the thickness direction, the molecules of the liquid crystal compound are oriented so that at least a part thereof is inclined with respect to the in-plane direction. As a method for appropriately adjusting the above conditions, a method for appropriately preparing the composition of the liquid crystal composition and a support surface having an orientation-regulating force for orienting the molecules of the liquid crystal compound so as to be inclined with respect to the in-plane direction are used. Examples thereof include a method to be used, a method of applying a magnetic field, a method of appropriately adjusting the temperature condition at the time of orientation, and the like. Examples of these methods include Patent No. 5363022, Japanese Patent Application No. 2017-060122, Japanese Patent Application No. 2017-059327, Japanese Patent Application No. 2017-060154, and Japanese Patent Application No. 2017-060159. The method described in the specification of the above may be applied.

Above all, a method of appropriately adjusting the temperature condition at the time of orientation is preferable. In this method, the orientation is performed so that the temperature condition of the layer of the liquid crystal composition is the same as the temperature condition of the residual viscosity of the test composition of 800 cp (centipores) or less. The test composition is a composition having a composition obtained by removing the polymerization initiator from the liquid crystal composition. The residual viscosity of the test composition is the viscosity of the residual component of the test composition under the same temperature conditions as the layer of the liquid crystal composition at the time of orientation. The residual component of the test composition is a component contained in the test composition that remains without being vaporized under the same temperature conditions as the layer of the liquid crystal composition at the time of orientation. By orienting so as to satisfy such a requirement, the molecules of the liquid crystal compound contained in the layer of the liquid crystal composition can be oriented so as to be greatly inclined with respect to the in-plane direction.

The residual viscosity of the test composition under the same temperature conditions as the layer of the liquid crystal composition at the time of orientation can be measured by the following method.
A test composition obtained by removing the polymerization initiator from the liquid crystal composition is prepared. The test composition is concentrated under reduced pressure on a rotary evaporator to remove the solvent to obtain residual components. The viscosity of this residual component is measured in advance while changing the measurement temperature, and information on the measurement temperature and the viscosity at the measurement temperature is obtained. This information is hereinafter appropriately referred to as "temperature-viscosity information". From this "temperature-viscosity information", the viscosity at the temperature of the layer of the liquid crystal composition at the time of orientation is read as the residual viscosity.

As a method for keeping the residual viscosity of the test composition within the above-mentioned range under the same temperature conditions as the layer of the liquid crystal composition at the time of orientation, for example, a method of appropriately adjusting the temperature of the layer of the liquid crystal composition at the time of orientation is used. Can be mentioned. In this method, usually, the temperature of the layer of the liquid crystal composition is sufficiently high enough to reduce the residual viscosity of the test composition under the same temperature conditions as this temperature, and adjust the viscosity so as to be within the above range. do.

In the step (ii) of orienting the liquid crystal compound, the time for holding the temperature of the layer of the liquid crystal composition at a predetermined temperature condition can be arbitrarily set within a range in which a desired liquid crystal cured layer can be obtained, for example, from 30 seconds to 5 seconds. It can be a minute.

After the step (ii) of orienting the liquid crystal compound, the step (iii) of curing the layer of the liquid crystal composition to obtain the liquid crystal cured layer is performed. In this step (iii), the layer of the liquid crystal composition is usually cured by polymerizing the polymerizable compound contained in the liquid crystal composition. Therefore, for example, when the liquid crystal compound has polymerizability, the liquid crystal compound is usually polymerized while maintaining the orientation of the molecule. By the above-mentioned polymerization, the orientation state of the liquid crystal compound contained in the liquid crystal composition before the polymerization is fixed.

As the polymerization method, a method suitable for the properties of the components contained in the liquid crystal composition can be selected. Examples of the polymerization method include a method of irradiating with active energy rays and a thermal polymerization method. Above all, the method of irradiating with active energy rays is preferable because heating is not required and the polymerization reaction can proceed at room temperature. Here, the activated energy rays to be irradiated may include light such as visible light, ultraviolet rays, and infrared rays, and arbitrary energy rays such as electron beams.

Among them, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple. The temperature at the time of irradiation with ultraviolet rays is preferably not more than the glass transition temperature of the base material, preferably 150 ° C. or less, more preferably 100 ° C. or less, and particularly preferably 80 ° C. or less. The lower limit of the temperature at the time of irradiation with ultraviolet rays may be 15 ° C. or higher. The irradiation intensity of ultraviolet rays is preferably 0.1 mW / cm ² or more, more preferably 0.5 mW / cm ² or more, preferably 10,000 mW / cm ² or less, and more preferably 5000 mW / cm ² or less. The irradiation amount of ultraviolet rays is preferably 0.1 mJ / cm ² or more, more preferably 0.5 mJ / cm ² or more, preferably 10000 mJ / cm ² or less, and more preferably 5000 mJ / cm ² or less.

By the above step (iii), a liquid crystal cured layer formed of a cured product of the liquid crystal composition is obtained. Since the curing of the liquid crystal composition is usually achieved by the polymerization of the polymerizable compound contained in the liquid crystal composition, the liquid crystal cured layer contains a polymer of a part or all of the components contained in the liquid crystal composition. Therefore, when the liquid crystal compound has polymerizability, the liquid crystal compound polymerizes, so that the liquid crystal cured layer can be a layer containing a polymer of the liquid crystal compound polymerized while maintaining the orientation state before the polymerization. This polymerized liquid crystal compound is included in the term "liquid crystal compound contained in the liquid crystal cured layer".

In the cured product of the liquid crystal composition, the fluidity before curing is lost. Therefore, in the liquid crystal cured layer, the orientation state of the liquid crystal compound is usually fixed in the orientation state before curing. In this way, a liquid crystal cured layer containing a liquid crystal compound in which at least a part of the molecules are inclined with respect to the in-plane direction can be obtained.

In the first production method according to the above example, the layer of the liquid crystal composition contained in the liquid crystal cured layer is cured at one time, but the mode of curing is not limited to this example. For example, a portion of the layer of the liquid crystal composition may be cured in advance. Hereinafter, a manufacturing method for obtaining a liquid crystal cured layer by preliminarily curing a part of the layer of the liquid crystal composition in this way will be described.

For example, the liquid crystal cured layer is
(I) A step of forming a layer of the first liquid crystal composition and
(Ii) A step of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition,
(Iii) A step of curing the layer of the first liquid crystal composition to obtain a first unit cured layer,
(Iv) A step of forming a layer of the second liquid crystal composition directly on the surface of the first unit cured layer, and
(V) A step of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition,
(Vi) A step of curing the layer of the second liquid crystal composition to obtain a second unit cured layer,
It can be manufactured by the second manufacturing method including. In the description of the second production method, the "first unit cured layer" refers to a portion of the liquid crystal cured layer obtained by first curing the liquid crystal composition. Further, the "first liquid crystal composition" refers to a liquid crystal composition as a material for the first unit cured layer. Further, the "second unit cured layer" refers to a portion of the liquid crystal cured layer obtained by later curing the liquid crystal composition. Further, the "second liquid crystal composition" refers to a liquid crystal composition as a material for the second unit cured layer.

Steps (i) to (iii) can be carried out in the same manner as in the first manufacturing method described above. As a result, the first unit cured layer formed by the cured product of the first liquid crystal composition is obtained. The molecules of the liquid crystal compound contained in the first unit cured layer are usually oriented in one direction in the in-plane direction. Further, the molecules of the liquid crystal compound contained in the first unit cured layer are usually oriented so that at least a part thereof is inclined with respect to the in-plane direction in the thickness direction thereof.

After preparing the first unit cured layer, the step (iv) of forming the layer of the second liquid crystal composition directly on the surface of the first unit cured layer is performed. Here, the aspect of forming another layer on one layer "directly" means that there is no other layer between these two layers. Further, the second liquid crystal composition may be the same as or different from the first liquid crystal composition. Therefore, the liquid crystal compound contained in the first liquid crystal composition and the liquid crystal compound contained in the second liquid crystal composition may be the same or different.

The formation of the layer of the second liquid crystal composition is usually carried out by applying the liquid crystal composition to the surface of the first unit cured layer. As the coating method, the same method as described in the section of step (i) may be used. Before applying the second liquid crystal composition, the surface of the first unit cured layer may be subjected to a treatment for imparting an orientation restricting force such as a rubbing treatment. However, the surface of the first unit cured layer has an orientation regulating force that appropriately orients the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition formed on the surface without any special treatment. Has. Therefore, from the viewpoint of reducing the number of steps and efficiently advancing the production, it is preferable that the surface of the first unit cured layer is not subjected to the rubbing treatment in the step (iv).

After the step (iv) of forming the layer of the second liquid crystal composition on the surface of the first unit cured layer, the step (v) of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition is performed. The specific operation in this step (v) can be the same as that in step (ii) described above. As a result, the liquid crystal compound is oriented in the layer of the second liquid crystal composition. Normally, in the in-plane direction, the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition are the liquid crystal compounds contained in the first unit cured layer due to the orientation restricting force of the surface of the first unit cured layer. Orients in the same direction as the orientation direction. On the other hand, in the thickness direction, the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition are oriented so that at least a part thereof is inclined with respect to the in-plane direction. In particular, when both the first liquid crystal composition and the second liquid crystal composition contain a back-dispersed liquid crystal compound, the first unit cured layer is a layer of the second liquid crystal composition formed on the surface of the first unit cured layer. It can function as an alignment film that greatly tilts the molecules of the reverse-dispersed liquid crystal compound contained in the above in the in-plane direction. Therefore, the molecules of the liquid crystal compound can be oriented so as to be greatly inclined with respect to the in-plane direction as the whole of the liquid crystal cured layer.

After the step (v) of orienting the liquid crystal compound, the step (vi) of curing the layer of the second liquid crystal composition to obtain the liquid crystal cured layer is performed. The specific operation in this step (vi) can be the same as that in step (iii) described above. As a result, a second unit cured layer in which the layer of the second liquid crystal composition is cured is obtained on the first unit cured layer. Therefore, it is possible to obtain a liquid crystal cured layer as a layer including the first unit cured layer and the second unit cured layer.

A liquid crystal cured layer can be obtained by the above-mentioned manufacturing method. According to the above-mentioned manufacturing method, a long liquid crystal cured layer can be obtained by using a long base material. Such a long liquid crystal cured layer can be continuously manufactured and is excellent in productivity. Further, since it can be bonded to other members such as a film by roll-to-roll, it is also excellent in productivity in this respect.

The method for producing a liquid crystal cured layer may further include an arbitrary step in combination with the above-mentioned steps.
For example, when a base material is used, a liquid crystal cured layer can be obtained on the support surface of the base material by the above-mentioned manufacturing method. Therefore, the method for manufacturing the liquid crystal cured layer may include a step of peeling the liquid crystal cured layer from the support surface.

Further, the above-mentioned manufacturing method may include, for example, a step of transferring the liquid crystal curable layer provided on the substrate to an arbitrary film layer. Therefore, for example, in the method for producing a liquid crystal curable layer, the liquid crystal curable layer formed on the base material may be bonded to an arbitrary film layer, and then the base material may be peeled off as necessary. At this time, an appropriate adhesive or adhesive may be used for bonding.

Further, the above-mentioned production method may include, for example, a step of forming a layer of the cured product of the liquid crystal composition on the second unit cured layer by further using the liquid crystal composition. Such a layer can be formed, for example, by the same method as the second unit cured layer.

Further, the above-mentioned manufacturing method may include, for example, a step of further providing an arbitrary layer on the obtained liquid crystal cured layer.

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples shown below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof.

In the following description, "%" and "part" representing quantities are based on weight unless otherwise specified. Further, the operations described below were performed in the air at normal temperature and pressure unless otherwise specified.

Since the supporting base material contained in the optical films produced in the examples and comparative examples described below has optical isotropic properties, it does not affect the measurement result of the retardation. Therefore, the measurement of the retardation of the liquid crystal cured layer in the examples and comparative examples described below was carried out using an optical film as a sample.

[Thickness measurement method]
The thickness of the layer was measured using a film thickness meter (“F20-EXR” manufactured by Filmometry Co., Ltd.).

[Measurement method of in-plane retardation Re]
The in-plane retardation of the liquid crystal cured layer was measured using a phase difference meter (“AxsoScan” manufactured by Axsometrics). The measurement wavelength was 590 nm.

[Method of confirming that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined]
Using a phase difference meter (“AxoScan” manufactured by Axometrics), the retardation of the liquid crystal cured layer was measured in the range of an incident angle θ of −50 ° to 50 °. At this time, the measurement direction was set perpendicular to the in-plane phase advance axis direction of the liquid crystal cured layer. The measurement wavelength was 590 nm.

The retardation Re (θ) of the liquid crystal cured layer at the measured incident angle θ is divided by the retardation Re (0 °) of the liquid crystal cured layer at the incident angle 0 °, and the retardation ratio Re (θ) / Re. (0 °) was calculated. A graph was drawn with the obtained retardation ratio Re (θ) / Re (0 °) as the vertical axis and the incident angle θ as the horizontal axis. When the obtained graph is asymmetric with respect to θ = 0 °, it is said that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined or oriented with respect to the in-plane direction of the liquid crystal cured layer. Judged.

[Method for measuring the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer]
FIG. 6 is a perspective view for explaining a measurement direction when measuring the retardation of the liquid crystal cured layer 400 from an inclined direction. In FIG. 6, arrow A ₄₁₀ indicates the in-plane slow phase axial direction of the liquid crystal cured layer 400, arrow A ₄₂₀ indicates the in-plane phase advancing axial direction of the liquid crystal cured layer 400, and arrow A ₄₃₀ indicates the liquid crystal cured layer 400. Represents the thickness direction of.

As shown in FIG. 6, the retardation of the liquid crystal cured layer 400 was measured using a phase difference meter (“AxoScan” manufactured by Axometrics) in a range of an incident angle θ of −50 ° to + 50 °. At this time, the measurement direction A ₄₄₀ was set perpendicular to the in-plane phase advance axis direction A ₄₂₀ of the liquid crystal curing layer 400. The measurement wavelength was 590 nm.

From the measured retardation, the liquid crystal cured layer was used with the analysis software attached to the phase difference meter (analysis software "Malti-Layer Analysis" manufactured by AxoMetics; the analysis conditions were an analysis wavelength of 590 nm and a number of layer divisions of 20 layers). The substantially maximum tilt angle of the molecule of the liquid crystal compound contained in 400 was analyzed.

[Method of specifying the tilt direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer]
The letterage of the liquid crystal cured layer was measured using a phase difference meter (“AxoScan” manufactured by Axometrics) with the side having the smaller inclination angle facing down. The retardation was measured by gradually increasing the incident angle from 0 ° in the measurement direction perpendicular to the phase advance axis of the liquid crystal cured layer 200. When the retardation of the liquid crystal curing layer 200 gradually decreases as the incident angle gradually increases, it can be determined that the measurement direction approaches parallel to the tilt direction _AT . Therefore, the tilt direction was specified by the measurement of the retardation.
In Examples and Comparative Examples described later, from the method for producing the liquid crystal cured layer, the tilt angle of the molecule of the liquid crystal compound among the slow axis of the liquid crystal cured layer and the surface (front surface and back surface) of the liquid crystal cured layer. The smaller side was known. Therefore, in the method for specifying the tilt angle, the detection of the slow axis of the liquid crystal cured layer and the specific operation of the surface having the smaller inclination angle of the molecule of the liquid crystal compound are omitted.

[Examples 1 to 6 and Comparative Examples 1 to 2]
(Manufacturing of liquid crystal composition)
100 parts by weight of the polymerizable reverse-dispersed liquid crystal compound A represented by the following formula, 0.15 parts by weight of a fluorosurfactant (“S420” manufactured by AGC Seimi Chemical Co., Ltd.), and a photopolymerization initiator (manufactured by BASF). "IrgacureOXE04") 4.3 parts by weight, cyclopentanone 148.5 parts by weight as a solvent, and 1,3-dioxolane 222.8 parts by weight as a solvent were mixed to obtain a liquid crystal composition.

(Preparation of support base material)
As a supporting base material, a resin film made of a thermoplastic norbornene resin having a masking film bonded to one side (“Zeonoa Film ZF16” manufactured by Zeon Corporation; thickness 100 μm) was prepared. This supporting substrate was an optically isotropic film without lettering. The masking film was peeled off from this supporting base material, and the masking peeled surface was subjected to corona treatment. Next, the corona-treated surface of the support substrate was subjected to a rubbing treatment.

(Formation of LCD cured layer)
The liquid crystal composition was applied to the rubbing-treated surface of the support substrate using a wire bar to form a layer of the liquid crystal composition.
The layer of the liquid crystal composition was heated in an oven set at 145 ° C. for 4 minutes to orient the liquid crystal compounds in the layer. The temperature condition at the time of this orientation was a temperature condition in which the residual viscosity of the test composition corresponding to the liquid crystal composition used was 800 cP or less.
Then, the layer of the liquid crystal composition was irradiated with ultraviolet rays of 500 mJ / cm ² under a nitrogen atmosphere to cure the layer of the liquid crystal composition to form a first unit cured layer having a thickness of about 1.2 μm.

The surface of the first unit cured layer is coated with the remaining liquid crystal composition used for forming the first unit cured layer using a wire bar without applying a rubbing treatment to the liquid crystal composition. Formed a layer.
The layer of the liquid crystal composition was heated in an oven set at 145 ° C. for 4 minutes in the same manner as in the step of forming the first unit cured layer to orient the liquid crystal compound in the layer.
Then, the layer of the liquid crystal composition was irradiated with ultraviolet rays of 500 mJ / cm ² under a nitrogen atmosphere to cure the layer of the liquid crystal composition to form a second unit cured layer having a thickness of about 2.4 μm.

As a result, an optical film including a supporting base material and a liquid crystal cured layer including a first unit cured layer and a second unit cured layer was obtained. The liquid crystal cured layer of the obtained optical film had a thickness of 3.4 μm and an in-plane retardation of 147 nm. With respect to this liquid crystal cured layer, it was confirmed by the above-mentioned method that the molecules of the back-dispersed liquid crystal compound A contained in the liquid crystal cured layer were inclined with respect to the in-plane direction of the liquid crystal cured layer. The substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer was 65 °. Further, the tilt direction of the molecule of the inversely dispersed liquid crystal compound A contained in the liquid crystal cured layer was measured by the above-mentioned method.

(Manufacturing of circularly polarizing plate)
The liquid crystal cured layer of the optical film and the polarizing element were bonded together using an adhesive (“CS9621T” manufactured by Nitto Denko Corporation). Then, the supporting substrate was peeled off to obtain a circularly polarizing plate having a liquid crystal cured layer and a polarizing element.
In the above bonding, the slow axis of the liquid crystal cured layer is clockwise at the angle θ (P / L) shown in Table 1 with respect to the absorption axis of the polarizing element when looking at the polarizing element side of the circular polarizing plate. Went to. This angle θ (P / L) corresponds to the angle formed by the slow axis of the liquid crystal cured layer clockwise with respect to the absorption axis of the polarizing element when the polarizing element side of the test member described later is viewed from the front direction. ..

(Manufacturing of simulated organic liquid crystal display device)
A metal plate was prepared as a member imitating an organic light emitting display panel. The circular polarizing plate was attached to the surface of this metal plate using an adhesive (“CS9621T” manufactured by Nitto Denko Corporation). As a result, a test member including a polarizing element, a pressure-sensitive adhesive layer, a liquid crystal curing layer, a pressure-sensitive adhesive layer, and a metal plate imitating an organic light-emitting display panel was obtained in this order. The above-mentioned bonding was performed so as to satisfy the following requirements (a1) and (a2).
(A1) When the polarizing element side of the test member is viewed from the front direction, the absorption axis of the polarizing element is clockwise at an angle θ (D / P) shown in Table 1 with respect to the vertical direction of the display screen of the test member. Make.
(A2) The tilt direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is the direction shown in Table 1 in the vertical direction of the display screen.

(Measurement test of brightness L ^* )
FIG. 7 is a perspective view schematically showing how to set the brightness L ^* measuring device in the examples and the comparative examples.
The brightness L ^* was measured using "GCMS-4" manufactured by Murakami Color Technology Research Institute as a measuring device. As shown in FIG. 7, this measuring device measures the brightness L ^* of the display screen 510U of the test member 510 illuminated by the light L ₅₂₀ from the light source 520 at an arbitrary position by the detector 530 at an arbitrary position. It is a device that can measure. The position of the light source 520 was adjusted so that the light L ₅₂₀ emitted from the light source 520 was incident on the display screen _510U perpendicularly to the left-right direction ALR of the display screen 510U and at an incident angle φi ₌ 60 °. .. Further, the position of the light source 520 was set so that the light L ₅₂₀ emitted from the light source 520 was incident on the display screen _510U from the upper direction in the vertical direction AUD. Further, the position of the detector 530 is adjusted so that the light L ₅₂₀ that is specularly reflected by the display screen 510U can be measured perpendicularly to the left- _right direction ALR of the display screen 510U and with a reflection angle _φr = 60 °. bottom. Then, in order to eliminate the light reflected on the surface of the circularly polarizing plate without passing through the circularly polarizing plate, the test member 510 is parallel to the vertical AUD of the display screen _510U as shown by the arrow A7. It was rotated 5 ° around the axis of rotation (not shown). The above rotation was performed clockwise when viewed from above in the vertical direction _UD .

The brightness L ^* of the display screen 510U was measured by the detector 530 while illuminating the display screen 510U of the test member 510 with the light L ₅₂₀ emitted from the light source 520. Then, based on the measured brightness L ^* , the determination was made as follows. The smaller the brightness L ^* , the better the effect of suppressing reflection.
"○○": L ^* <45.
"○": 45 ≤ L ^* <60.
"X": 60≤L ^* .

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1, the values of the angle θ (D / P) and the angle θ (P / L) represent the angles formed in the clockwise direction. Therefore, by subtracting the values shown in Table 1 from 180 °, the angle θ (D / P) and the angle θ (P / L) can be converted into the values of the angles forming counterclockwise, respectively. For example, in Example 6, the angle θ (P / L) is 45 ° when converted into a counterclockwise angle.

In Table 1, the meanings of the abbreviations are as follows.
"Θ (D / P)": An angle formed by the absorption axis of the splitter in a clockwise direction with respect to the vertical direction of the display screen of the test member when looking at the polarizing element side of the test member.
"Θ (P / L)": The angle formed by the slow axis of the liquid crystal cured layer clockwise with respect to the absorption axis of the polarizing element when looking at the polarizing element side of the circular polarizing plate.
"Tilt direction": The tilt direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer.
"Up" in the tilt direction column: Upward in the vertical direction of the display screen.
"Down" in the tilt direction column: Downward in the vertical direction of the display screen.
"-" In the tilt direction column: The direction perpendicular to the vertical direction of the display screen.

[Consideration]
As can be seen from Table 1, in each of the examples, the measured brightness L ^* is small. From this result, it was confirmed that the organic light emitting display device of the present invention can effectively suppress the specular reflection of external light from above in the vertical direction of the display screen.
In particular, when Example 3 and Example 6 are compared, it can be seen that Comparative Example 6 shows a smaller value of brightness L ^* . From this result, when the tilt direction of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is upward in the vertical direction of the display screen, the positive reflection of external light is particularly effective as compared with the case where it is in the downward direction. It was confirmed that it can be suppressed.

10 Organic light emission display device.
11-14 The side of the display screen.
10U display screen.
100 Polarizer.
200 LCD cured layer.
The surface of the 200D LCD cured layer.
The surface of the 200U LCD cured layer.
210 Molecules of liquid crystal compounds.
300 Organic light emitting display panel.
400 LCD cured layer.
510 Test member.
510U display screen.
520 light source.
530 detector.
A _UD display screen up and down.
A _LR display screen left-right direction.
The tilt direction of the molecule of the _AT liquid crystal compound.
Absorption axis of A ₁₀₀ modulator.
A ₂₀₀ Slow axis of the liquid crystal cured layer.
A ₂₁₀ A virtual straight line extending in the same direction as the absorption axis of the stator.
A vector indicating the _BT tilt direction.
_BX Vertical component of the vector indicating the tilt direction.
A component in the left-right direction of a vector indicating the _BY tilt direction.
D ₂₁₀ Molecule director of liquid crystal compounds.
L ₅₂₀ light.
θ ₁₀₀ The angle formed by the absorber's absorption axis with respect to the vertical direction of the display screen.
θ The angle formed by the slow axis of the liquid crystal cured layer with respect to the absorption axis of the ₂₀₀ -polarizer.

Claims (3)

An organic light emitting display device comprising a display screen and a design having a vertical direction and a horizontal direction attached to a surface parallel to the display screen .
The organic light-emitting display device comprises a liquid crystal cured layer formed of a polarizing element, a cured product of a liquid crystal composition containing a liquid crystal compound, and an organic light-emitting display panel in this order.
At least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the in-plane direction of the liquid crystal cured layer.
The polarizing element has an absorption axis having an angle of more than 45 ° and 90 ° or less with respect to the vertical direction of the display screen.
The liquid crystal cured layer has a slow phase axis at an angle of 45 ° ± 5 ° with respect to the absorption axis of the polarizing element.
An organic light emitting display device in which the vertical direction of the display screen is perpendicular to the horizontal direction of the design . The organic light emitting display device according to claim 1, wherein the tilt direction of the molecule of the liquid crystal compound contained in the liquid crystal cured layer is upward in the vertical direction of the display screen. The organic light emitting display device according to claim 1 or 2, wherein the in-plane retardation of the liquid crystal cured layer at a measurement wavelength of 590 nm is 100 nm or more and 180 nm or less.

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