WO2020116466A1

WO2020116466A1 - Liquid-crystal cured film and method for manufacturing same

Info

Publication number: WO2020116466A1
Application number: PCT/JP2019/047288
Authority: WO
Inventors: 俊平中島
Original assignee: 日本ゼオン株式会社
Priority date: 2018-12-06
Filing date: 2019-12-03
Publication date: 2020-06-11
Also published as: JPWO2020116466A1

Abstract

The present invention provides a liquid-crystal cured film provided with a liquid-crystal cured layer formed of a cured liquid-crystal composition containing a liquid-crystal compound and a chiral compound including asymmetric carbon atoms, the liquid-crystal cured layer containing molecules of the liquid-crystal compound, which may be in a fixed alignment state. At least some molecules of the liquid-crystal compound contained in the liquid-crystal cured layer are tilted with respect to the layer plane of the liquid-crystal cured layer, and the front linear-polarization retardation LRe and the front circular-polarization retardation CRe of the liquid-crystal cured layer at a measurement wavelength of 550 nm satisfy a prescribed relationship.

Description

Liquid crystal cured film and method for producing the same

The present invention relates to a liquid crystal cured film and a method for manufacturing the same.

Liquid crystal cured film is known as one of the optical films. The liquid crystal cured film generally includes a liquid crystal cured layer formed of a cured product obtained by aligning a liquid crystal composition containing a liquid crystal compound and curing the liquid crystal composition while maintaining the alignment state. As such a liquid crystal cured film, those described in Patent Documents 1 to 3 have been proposed.

Japanese Patent No. 5604774 Japanese Patent No. 5804991 JP, 2005-161714, A

The liquid crystal cured layer included in the liquid crystal cured film usually contains a liquid crystal compound. The molecules of the liquid crystal compound may tilt with respect to the layer plane of the liquid crystal cured layer. When an appropriate liquid crystal cured film having a liquid crystal cured layer containing a liquid crystal compound whose molecules are tilted in this way is provided in an image display device, optical characteristics such as viewing angle characteristics can be improved.

However, when a liquid crystal cured layer containing a liquid crystalline compound with tilted molecules was observed with a polarizing microscope, uneven alignment was sometimes observed. Specifically, the orientation direction of the molecules of the liquid crystal compound becomes non-uniform on the surface of the layer of the liquid crystal composition that was the air interface, so that the orientation component parallel to the layer plane of the orientation direction (in-plane component). The direction) becomes non-uniform, and variations may occur in the in-plane slow axis direction. In particular, such alignment unevenness was remarkable when the reverse dispersion liquid crystal compound was used.

When the present inventor examined the above-mentioned alignment unevenness, it was found that the alignment unevenness was caused by the twist of the alignment direction of the molecules of the liquid crystal compound. Specifically, paying attention to the direction component parallel to the layer plane of the alignment direction, the alignment direction of the molecules of the liquid crystalline compound may be different for each position in the thickness direction of the liquid crystal cured layer. When the orientation direction of molecules at a certain position in the thickness direction of the liquid crystal cured layer is used as a reference, the orientation direction of a molecule that is farther from the reference molecule in the thickness direction is parallel to the layer plane. Tend to be very different. Usually, the molecules of the liquid crystal compound are aligned in a certain alignment direction on a certain first plane in the liquid crystal cured layer. In the next second plane in the layer, which overlaps the first plane, the orientation direction of the molecules deviates slightly from the orientation direction in the first plane. In the next third plane, which further overlaps the second plane, the orientation direction of the molecules deviates further from the orientation direction in the second plane by an angle. In this way, in the planes that are arranged so as to overlap with each other, the angles of the orientation directions of the molecules in the planes are sequentially shifted, and the orientation directions of the molecules of the liquid crystal compound can be twisted in a spiral shape as a whole. In a conventional liquid crystal cured layer containing molecules of a liquid crystalline compound tilted with respect to the layer plane, the twisting directions (that is, rightward and leftward) may be non-uniform in the plane. Was non-uniform, resulting in uneven alignment. Hereinafter, the twist in which the alignment direction of the molecules of the liquid crystal compound included in the liquid crystal cured layer occurs in the thickness direction may be simply referred to as “twist in the alignment direction”.

Also, if the molecules of the liquid crystalline compound are twisted in the alignment direction as described above, the light passing through the liquid crystal cured layer containing the molecules of the liquid crystalline compound may cause optical rotation. However, in some cases, only a part of the light transmitted through the liquid crystal cured layer causes optical rotation, and the other part disturbs the polarization state. For example, when linearly polarized light is incident on the liquid crystal cured layer, the linearly polarized light may be partially depolarized or elliptically polarized by being transmitted through the liquid crystal cured layer. Since such a disorder of the polarization state may cause a deterioration in performance when the liquid crystal cured film is used as an optical film, it is desired to suppress it.

For example, in an organic electroluminescence display device (hereinafter sometimes referred to as an “organic EL display device” as appropriate), a circularly polarizing plate and an ellipse are used as a reflection suppressing film for suppressing reflection of external light on its display surface. A polarizing plate such as a polarizing plate may be provided. This polarizing plate usually includes a linear polarizer and a retardation film in combination. When a liquid crystal cured film is used as this retardation film, the disturbance of the polarization state as described above may reduce the ability to suppress reflection of external light.

The present invention was devised in view of the above-mentioned problems, and includes a liquid crystal compound in which molecules are inclined with respect to a layer plane, and liquid crystal curing capable of suppressing uneven alignment and disturbance of polarization state of transmitted light. An object of the present invention is to provide a liquid crystal cured film having a layer and a method for manufacturing the same.

The present inventor diligently studied to solve the above problems. As a result, the present inventor has found that the above problems can be solved by using a liquid crystal composition containing a chiral compound appropriately, and completed the present invention.
That is, the present invention includes the following.

[1] A liquid crystal cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound and a chiral compound containing an asymmetric carbon atom, the liquid crystal cured layer containing molecules of the liquid crystal compound which may have a fixed alignment state. Prepare,
At least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer,
A liquid crystal cured film in which the front linearly polarized light retardation LRe and the front circularly polarized light retardation CRe of the liquid crystal cured layer at a measurement wavelength of 550 nm satisfy the following formula (1).

[2] The ratio CRe/D between the front circularly polarized light phase difference CRe of the liquid crystal cured layer and the thickness D [nm] of the liquid crystal cured layer at a measurement wavelength of 550 nm is 0.0002 or more and 0.0133 or less. ] A liquid crystal cured film according to.
[3] The liquid crystal cured film according to [1] or [2], wherein the amount of the chiral compound relative to 100 parts by weight of the liquid crystal compound is 0.05 parts by weight or more and 0.5 parts by weight or less.
[4] The front linearly polarized light phase difference LRe of the liquid crystal cured layer at a measurement wavelength of 550 nm is in the range of 50 nm or more and 90 nm or less, or in the range of 120 nm or more and 160 nm or less, [1] to [3]. The liquid crystal cured film according to 1.
[5] The liquid crystal cured film according to any one of [1] to [4], in which the liquid crystal compound can exhibit birefringence of reverse wavelength dispersion.
[6] The liquid crystal cured film according to any one of [1] to [5], wherein the liquid crystalline compound has a benzothiazole ring.
[7] A method for producing a liquid crystal cured film according to any one of [1] to [6],
A step of forming a layer of the liquid crystal composition,
A step of orienting the liquid crystalline compound contained in the layer of the liquid crystal composition,
And a step of curing the layer of the liquid crystal composition to obtain the liquid crystal cured layer.

According to the present invention, a liquid crystal cured film including a liquid crystal compound whose molecules are inclined with respect to the plane of the layer and including a liquid crystal cured layer capable of suppressing alignment unevenness and disturbance of the polarization state of transmitted light, and a method for producing the same. Can be provided.

FIG. 1 is a graph in which the retardation ratio R(θ)/R(0°) of a liquid crystal cured layer according to an example is plotted against the incident angle θ. FIG. 2 is a perspective view schematically showing an optical system in which a pair of linear polarizers set to a para-Nicol are arranged on both sides of a certain liquid crystal layer. FIG. 3 is a graph showing the relationship between the transmittance I and the in-plane retardation Δn×d in Expression (3) when the wavelength λ=550 nm is substituted. FIG. 4 is a cross-sectional view schematically showing an example of a liquid crystal cured layer included in the liquid crystal cured film according to an embodiment of the present invention. FIG. 5: is sectional drawing which shows typically the example of the liquid crystal hardening layer with which the liquid crystal hardening film which concerns on one Embodiment of this invention is equipped. FIG. 6 is a perspective view for explaining the measurement direction when measuring the linearly polarized light phase difference R(θ) as the retardation of the liquid crystal cured layer from the tilt direction.

Hereinafter, the present invention will be described in detail by showing examples and embodiments. However, the present invention is not limited to the exemplifications and embodiments described below, and may be implemented by being arbitrarily modified within the scope of the claims of the present invention and the scope of equivalents thereof.

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

In the following description, the “thickness direction” of a layer means the 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 “frontal direction” of a surface refers to the normal direction of the surface, and specifically refers to the direction of the polar angle of 0° unless otherwise specified.

In the following description, the “inclination direction” of a surface represents a direction that is neither parallel nor perpendicular to the surface unless specifically stated otherwise, and specifically, the polar angle of the surface is in the range of 5° to 85°. Point in the direction of.

In the following description, the terms “polarizing plate” and “wave plate” include flexible films and sheets such as resin films unless otherwise specified.

In the following description, the birefringence reverse wavelength dispersion property means that the birefringence Δn(450) at a wavelength of 450 nm and the birefringence Δn(550) at a wavelength of 550 nm satisfy the following formula (N1) unless otherwise specified. Say. A liquid crystal compound capable of exhibiting such birefringence having an inverse wavelength dispersive property can generally exhibit greater birefringence as the measurement wavelength is longer.
Δn(450)<Δn(550) (N1)

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

In the following description, the front linearly polarized light phase difference LRe of a certain layer is a value represented by “LRe=(nx−ny)×d” unless otherwise specified. Further, the front circularly polarized light phase difference CRe of a certain layer is a value represented by “CRe=(φ/360°)×λ” unless otherwise specified. Here, nx represents the refractive index in the direction perpendicular to the thickness direction of the layer (in-plane direction) and giving the maximum refractive index. ny represents the refractive index in the in-plane direction of the layer and in the direction orthogonal to the nx direction. d represents the thickness of the layer. φ represents the optical rotation angle [°] of the linearly polarized light that passes through the layer in the thickness direction. λ represents the measurement wavelength. The measurement wavelength is 550 nm unless otherwise specified. The front linearly polarized light phase difference LRe and the front circularly polarized light phase difference CRe can be measured using a phase difference meter (“AxoScan” manufactured by Axometrics).

In the following description, a resin having a positive intrinsic birefringence value means a resin whose refractive index in the stretching direction is higher than that in the direction orthogonal to it. Further, a resin having a negative intrinsic birefringence value means a resin whose refractive index in the stretching direction is smaller than that in the direction orthogonal thereto. The intrinsic birefringence value can be calculated from the dielectric constant distribution.

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

In the following description, the directions of elements are “parallel” and “vertical” unless otherwise specified, within a range that does not impair the effects of the present invention, for example, ±4°, preferably ±3°, more preferably ±1. It may include an error within a range of °.

In the following description, unless otherwise specified, the “tilt angle” of a molecule of a liquid crystal compound included in a layer represents an angle formed by the molecule of the liquid crystal compound with respect to the layer plane of the layer, and “tilt angle”. It is sometimes called "horn". 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 molecules of the liquid crystal compound. In addition, in the following description, unless otherwise specified, the “tilt angle” refers to the tilt angle of the molecules of the liquid crystal compound with respect to the layer plane of the layer containing the liquid crystal compound.

In the following description, the “substantially maximum tilt angle” of the molecules of the liquid crystal compound contained in a layer means that the tilt angle of the molecule on one surface of the layer is 0° and the tilt angle of the molecule is the thickness. It means the maximum value of the tilt angle of the molecules of the liquid crystal compound when it is assumed that the liquid crystal compound changes at a constant ratio in the direction. Specifically, consider a case in which, in the thickness direction of a layer containing a liquid crystal compound, the tilt angle of the molecules of the liquid crystal compound is smaller as it is closer to one side of the layer and is larger as it is farther from the one side. The substantial maximum tilt angle is calculated by assuming that the ratio of the change of the tilt angle in the thickness direction (that is, the ratio of the change that decreases toward one side and increases toward the one side) is constant. Represents the maximum value of the tilt angle. To give a specific example, in the liquid crystal cured layer obtained by curing the layer of the liquid crystal composition formed on the supporting surface, the substantially maximum tilt angle is usually the molecule on the surface on the supporting surface side of the liquid crystal cured layer. Represents the maximum value of the tilt angle of the molecules of the liquid crystal compound when it is assumed that the tilt angle is 0° and the tilt angle of the molecules changes at a constant ratio in the thickness direction. Further, as will be described later, in a liquid crystal cured layer having a multi-layer structure including a first cured layer and a second cured layer, the substantially maximum inclination angle is usually 0 when the inclination angle of the molecule on the surface on the first cured layer side is 0. And represents the maximum value of the tilt angle of the molecules of the liquid crystal compound under the assumption that the tilt angle of the molecules changes at a constant ratio in the thickness direction.

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, the description "an alkyl group having 1 to 20 carbon atoms which may have a substituent" has 1 to 20 carbon atoms in the alkyl group itself which does not include the number of carbon atoms of the substituent. It means that.

[1. Outline of liquid crystal cured film]
A liquid crystal cured film according to an embodiment of the present invention includes a liquid crystal cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound and a chiral compound. The chiral compound refers to a compound containing an asymmetric carbon atom.

Since it is formed of a cured product of a liquid crystal composition, the liquid crystal cured layer contains molecules of a liquid crystal compound. The alignment state of the molecules of the liquid crystal compound contained in the liquid crystal cured layer may be fixed. The term "a liquid crystal compound having a fixed alignment state" includes a polymer of a liquid crystal compound. Usually, the liquid crystallinity of the liquid crystalline compound is lost by polymerization, but in the present application, the liquid crystalline compound thus polymerized is also included in the term “liquid crystalline compound contained in the liquid crystal cured layer”.

At least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are tilted with respect to the layer plane of the liquid crystal cured layer. The term “inclined” with respect to the layer plane of a liquid crystal compound means that the inclination angle of the molecule with respect to the layer plane is in the range of 5° to 85°. The molecules of the liquid crystal compound tilted in this manner are usually neither parallel nor perpendicular to the layer plane.

The front linear polarization phase difference LRe and the front circular polarization phase difference CRe of the liquid crystal cured layer at the measurement wavelength of 550 nm satisfy the following formula (1). Hereinafter, the front linearly polarized light phase difference LRe may be referred to as “in-plane retardation” LRe. Further, hereinafter, the front circularly polarized light phase difference CRe may be referred to as “optical rotation phase difference” CRe.

According to the liquid crystal cured layer having the above-mentioned configuration, it is possible to suppress the alignment unevenness of the liquid crystal cured layer, and it is possible to suppress the disturbance of the polarization state of the light transmitted through the liquid crystal cured layer.

[2. Liquid crystalline compound]
The liquid crystal compound is a compound having liquid crystallinity, and usually can exhibit a liquid crystal phase when the liquid crystal compound is aligned.

As the liquid crystal compound, a reverse dispersion liquid crystal compound may be used, a forward dispersion liquid crystal compound may be used, or a combination of the reverse dispersion liquid crystal compound and the forward dispersion liquid crystal compound may be used. The reverse dispersion liquid crystal compound is a liquid crystal compound capable of exhibiting reverse wavelength dispersion birefringence. In addition, a liquid crystal compound capable of exhibiting birefringence of reverse wavelength dispersion exhibits a birefringence of reverse wavelength dispersion when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. A liquid crystal compound that On the other hand, the forward dispersion liquid crystal compound is a liquid crystal compound capable of exhibiting forward wavelength dispersion birefringence. Further, a liquid crystal compound capable of exhibiting forward wavelength dispersive birefringence means that when a layer of the liquid crystalline compound is formed and the liquid crystal compound is oriented in the layer, forward wavelength dispersive birefringence is exhibited. A liquid crystal compound that

Usually, when the liquid crystal compound is homogeneously aligned, the wavelength dispersion property of the birefringence exhibited by the liquid crystal compound can be confirmed by examining the wavelength dispersion property of the birefringence exhibited by the layer of the liquid crystal compound. Aligning the liquid crystal compound homogeneously means forming a layer containing the liquid crystal compound, and the direction of the maximum refractive index in the refractive index ellipsoid of the molecules of the liquid crystal compound in the layer is parallel to the surface of the layer. It means to orient in one certain direction. Further, the birefringence of the layer is calculated from "(in-plane retardation of layer)/(layer thickness)".

As the liquid crystal compound, it is preferable to use a reverse dispersion liquid crystal compound. When a reverse dispersion liquid crystalline compound is used, a liquid crystal cured layer having a reverse wavelength dispersion in-plane retardation LRe can be usually obtained, so that a liquid crystal cured film capable of exhibiting a desired optical function in a wide wavelength range is obtained. be able to. In addition, since the alignment unevenness was remarkably generated in the conventional liquid crystal cured layer using the reverse dispersion liquid crystalline compound, the reverse dispersion liquid crystallinity in the present embodiment is also used from the viewpoint of effectively utilizing the effect of suppressing the alignment unevenness. Preference is given to using compounds.

The birefringence of the inverse dispersion liquid crystalline compound is the difference between the refractive index in the direction showing the maximum refractive index and the refractive index in another direction perpendicular to this direction in the refractive index ellipsoid of the molecule of the inverse dispersion liquid crystalline compound. It can appear as a difference. Further, the wavelength dispersibility of the refractive index in each direction may be different depending on the molecular structure of the reverse dispersion liquid crystalline compound. For example, in a certain reverse-dispersion liquid crystalline compound, the refractive index measured at a long wavelength is smaller than the refractive index measured at a short wavelength in a certain direction, but the difference between them is small. On the other hand, in another direction where the index of refraction is relatively small, the index of refraction measured at long wavelengths is less than the index of refraction measured at short wavelengths, and the difference between them is large. In the liquid crystal compound of such an example, the difference in refractive index between the directions is small when the measurement wavelength is short, and is large when the measurement wavelength is long. As a result, this reverse dispersion liquid crystalline compound can exhibit birefringence with reverse wavelength dispersion.

The liquid crystal compound preferably has polymerizability. Therefore, the liquid crystal compound preferably has a molecule containing a polymerizable group such as an acryloyl group, a methacryloyl group, and an epoxy group. The number of polymerizable groups per molecule of the liquid crystal compound may be one, but is preferably two or more. 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 alignment state of molecules in the liquid crystal phase. Therefore, it is possible to fix the alignment state of the liquid crystal compound in the liquid crystal cured layer or increase the degree of polymerization of the liquid crystal compound to enhance 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. When a liquid crystal compound having a molecular weight in such a range is used, the coatability of the liquid crystal composition can be made particularly good.

The birefringence Δn of the liquid crystal compound at a measurement wavelength of 590 nm is preferably 0.01 or more, more preferably 0.03 or more, preferably 0.15 or less, more preferably 0.10 or less. When a liquid crystal compound having a birefringence Δn in such a range is used, it is easy to obtain a liquid crystal cured layer with few alignment defects.

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

The liquid crystal compound may be used alone or in combination of two or more kinds at an arbitrary ratio.

Examples of liquid crystal compounds include liquid crystal compounds represented by the following formula (I). The liquid crystal compound represented by the formula (I) can usually exhibit reverse wavelength dispersion birefringence.

In the formula (I), Ar has at least one of an aromatic heterocycle, a heterocycle, and an aromatic hydrocarbon ring, and is an optionally substituted divalent organic group having 6 to 67 carbon atoms. Represents. Examples of the aromatic heterocycle include 1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring and oxadiazole ring. , Oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thia Zolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring, Phenanthridine ring, phthalazine ring, furan ring, benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, benzooxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzothiazole ring, Examples thereof include a benzothiophene ring, a benzotriazine ring, a benzotriazole ring, a benzopyrazole ring, and a benzopyranone ring. Examples of the heterocycle include 1,3-dithiolane ring, pyrrolidine, piperazine and the like. Examples of the aromatic hydrocarbon ring include a phenyl ring and a naphthalene ring.

Preferred examples of Ar include groups represented by any of the following formulas (II-1) to (II-4). In formulas (II-1) to (II-4), * represents a bonding position with Z ¹ or Z ² . Further, Ar preferably has a benzothiazole ring.

In the above formulas (II-1) to (II-4), E ¹ and E ² are each independently -CR ¹¹ R ¹² -, -S-, -NR ¹¹ -, -CO- and -. It represents a group selected from the group consisting of O-. Further, R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among them, it is preferable that E ¹ and E ² are each independently -S-.

In the above formulas (II-1) to (II-4), D ¹ and D ² each independently represent an acyclic group which may have a substituent. D ¹ and D ² may be joined together to form a ring. The number of carbon atoms of the group represented by D ¹ to D ² (including the number of carbon atoms of the substituent) is, independently of each other, usually 1 to 100.

The number of carbon atoms of the acyclic group in D ¹ to D ² is preferably 1 to 13. Examples of the non-cyclic group for D ¹ to D ² 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; an alkoxy group having 1 to 6 carbon atoms. -C(=O)-CH ₃ ; -C(=O)NHPh; -C(=O)-OR ^x ; Among them, as the non-cyclic group, 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 preferred. The above Ph represents a phenyl group. In addition, 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 which the non-cyclic group in D ¹ to D ² may 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, 6 alkyl group; vinyl group, allyl group, etc., alkenyl group having 2 to 6 carbon atoms; trifluoromethyl group, etc., halogenated alkyl group having 1 to 6 carbon atoms; carbon atom, such as dimethylamino group N,N-dialkylamino group having 1 to 12; alkoxy group having 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 or different from each other.

R ^a represents an alkyl group having 1 to 6 carbon atoms; and an optionally substituted alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms, which has 6 carbon atoms. To 20 aromatic hydrocarbon ring groups;

R ^b is 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; A 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 R ^b is preferably 1 to 12, and more preferably 4 to 10. Examples of the alkyl group having 1 to 20 carbon atoms for R ^b include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group. , Sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group Groups and the like.

Examples of the substituent that the alkyl group having 1 to 20 carbon atoms in R ^b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like having 2 to 12 carbon atoms. N,N-dialkylamino group; methoxy group, ethoxy group, isopropoxy group, butoxy group, etc., alkoxy group having 1 to 20 carbon atoms; 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 benzothiazol-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; phenoxy group, naphthoxy group, etc., aryloxy group having 6 to 14 carbon atoms; trifluoromethyl group, pentafluoroethyl group, --CH ₂ CF _3, etc., at least one hydrogen atom being replaced by a fluorine atom 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 or different from each other.

The alkenyl group having 2 to 20 carbon atoms in R ^b preferably has 2 to 12 carbon atoms. Examples of the alkenyl group having 2 to 20 carbon atoms for R ^b include, for example, vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group. , Dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, and icosenyl group.

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

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

Examples of the substituent that the cycloalkyl group having 3 to 12 carbon atoms in R ^b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like having 2 to 12 carbon atoms. An N,N-dialkylamino group; an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group, propyl group; an alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group 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. Among them, as the substituent of the cycloalkyl group, 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 Groups, an alkoxy group having 1 to 6 carbon atoms such as 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; The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms for R ^b 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 R ^b may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like. 2 to 12 N,N-dialkylamino group; methoxy group, ethoxy group, isopropoxy group, butoxy group, etc., alkoxy group having 1 to 20 carbon atoms; methoxymethoxy group, methoxyethoxy group, etc., carbon atom number An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12; a nitro group; an aromatic heterocyclic group having 2 to 20 carbon atoms, such as a triazolyl group, a pyrrolyl group, a furanyl group or a thiophenyl group; Cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group, cyclohexyl group; cycloalkyloxy group having 3 to 8 carbon atoms such as cyclopentyloxy group, cyclohexyloxy group; tetrahydrofuranyl group, 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, pentafluoroethyl group Group, a —CH ₂ CF ₃ etc. fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom; —OCF ₃ ; benzofuryl group; benzopyranyl group; benzodioxolyl group; A benzodioxanyl group; and the like. Among them, as the substituent of the aromatic hydrocarbon ring group, 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 having 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 or different from each other.

When D ¹ and D ² together form a ring, the aforementioned D ¹ and D ² form an organic group containing a ring. Examples of this organic group include groups represented by the following formula. In the following formula, * represents carbon to which each organic group is bonded to D ¹ and D ² .

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 may 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. Is mentioned. Among them, the substituent is preferably a halogen atom, an alkyl group, a cyano group or an alkoxy group. The phenyl group may have one or more substituents. Further, the plurality of substituents may be the same as or different from each other.

In the above formulas (II-1) to (II-4), D ³ is -C(R ^f )=NN(R ^g )R ^h , -C(R ^f )=NN=C (R ^g )R ^h and a group selected from the group consisting of —C(R ^f )═N—N═R ⁱ . The number of carbon atoms of the group represented by D ³ (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, for example, an alkyl group having 1 to 20 carbon atoms which may have a substituent; At least one of —CH ₂ — contained in the alkyl group of 20 is —O—, —S—, —O—C(═O)—, —C(═O)—O—, or —C(= O)-substituted group (provided that 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 Aromatic hydrocarbon ring group having 6 to 30 atoms; Aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent; -G ^x -Y ^x -F ^x ; -SO ₂ R ^a -C(=O)-R ^b ; -CS-NH-R ^b ; The meanings of R ^a and R ^b are as described above.

The preferable range of the number of carbon atoms of the alkyl group having 1 to 20 carbon atoms in R ^g and the exemplified substances are the same as 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 R ^g may have include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a dimethylamino group and the like having 2 to 12 carbon atoms. N,N-dialkylamino group; methoxy group, ethoxy group, isopropoxy group, butoxy group, etc., alkoxy group having 1 to 20 carbon atoms; methoxymethoxy group, methoxyethoxy group, etc., having 1 to 12 carbon atoms An alkoxy group substituted with an alkoxy group having 1 to 12 carbon atoms; 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, cyclohexyl group; cyclopentyloxy group, cyclohexyloxy group A cycloalkyloxy group having 3 to 8 carbon atoms; a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, a dioxanyl group, a cyclic ether group having 2 to 12 carbon atoms, a carbon group such as a phenoxy group or a naphthoxy group Aryloxy group having 6 to 14 atoms; Fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with fluorine atoms; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl Group; —SO ₂ R ^a ; —SR ^b ; —SR ^b substituted alkoxy group having 1 to 12 carbon atoms; hydroxyl group; 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 or different from each other.

The preferable range of the number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms in R ^g and the exemplified substances are the same as the alkenyl group having 2 to 20 carbon atoms in R ^b .

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

Examples of the alkynyl group having 2 to 20 carbon atoms in R ^g include ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl group, 2-butynyl group, 3-butynyl group, pentynyl group, 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 which may have an alkynyl group having 2 to 20 carbon atoms in R ^g, for example, include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R ^g. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or 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 which may have a cycloalkyl group having 3 to 12 carbon atoms in R ^g, for example, include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R ^g. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g include a phenyl group and a naphthyl group. Among them, a phenyl group is more preferable as the aromatic hydrocarbon ring group.

Examples of the substituent which the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g may have include the same examples as the substituent which the acyclic group in D ¹ to D ² may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in R ^g include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, flazanyl group, oxazolyl group, quinolyl group, thiadiazolyl group, thiazolyl group. , Thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl 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, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxazodiazolyl group , A benzoxazolyl group, a benzothiadiazolyl group, a benzothiazolyl group, a benzotriazinyl group, a benzotriazolyl group, and a benzopyrazolyl group. Among them, as the aromatic heterocyclic group, a monocyclic aromatic heterocyclic group such as a furanyl group, a pyranyl group, a thienyl group, an oxazolyl group, a flazanyl group, a thiazolyl group, and a thiadiazolyl group; and a benzothiazolyl group, benzoxazol group Zolyl group, quinolyl group, 1-benzofuranyl group, 2-benzofuranyl group, phthalimido group, benzo[c]thienyl group, benzo[b]thienyl group, thiazolopyridyl group, thiazolopyrazinyl group, benzisoxazoli And a benzoxiadiazolyl group and a benzothiadiazolyl group;

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

G ^x is a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent; and a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent. At least one of —CH ₂ — contained in the aliphatic hydrocarbon group is —O—, —S—, —O—C(═O)—, —C(═O)—O—, —O—C( =O)-O-, -NR ¹⁴ -C(=O)-, -C(=O)-NR ¹⁴ -, -NR ¹⁴ -, or a group substituted with -C(=O)- (provided that , -O- or -S- are each adjacent to each other except for two or more). R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. The "divalent aliphatic hydrocarbon group" is preferably a divalent chain aliphatic hydrocarbon group, and more preferably an alkylene group.

Y ^x is -O-, -C(=O)-, -S-, -C(=O)-O-, -OC(=O)-, -OC(=O)-O. -, - C (= O) -S -, - S-C (= O) -, - NR 15 -C (= O) -, - C (= O) -NR 15 -, - O-C (= O)—NR ¹⁵ —, —NR ¹⁵ —C(═O)—O—, —N═N—, and —C≡C—. R ¹⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Of these, Y ^x is preferably —O—, —O—C(═O)—O— and —C(═O)—O—.

F ^x represents an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. The number of carbon atoms in this organic group is preferably 2 or more, more preferably 7 or more, further preferably 8 or more, particularly preferably 10 or more, and preferably 30 or less. The number of carbon atoms of the organic group does not include the carbon atoms of the substituent.

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

The aromatic hydrocarbon ring in F ^x may have a substituent. Examples of the substituent that the aromatic hydrocarbon ring in F ^x may have include 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 groups; vinyl groups, allyl groups, etc., alkenyl groups having 2 to 6 carbon atoms; trifluoromethyl groups, pentafluoroethyl groups, etc., halogenated alkyl groups having 1 to 6 carbon atoms; dimethylamino groups, etc. An N,N-dialkylamino group having 2 to 12 carbon atoms; an alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group, an isopropoxy group; a nitro group; -OCF ₃ ; O)-R ^b ; -C(=O)-O-R ^b ; -OC(=O)-R ^b ; and the like. The meaning of R ^b is as described above. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the aromatic heterocycle in F ^x include 1H-isoindole-1,3(2H)-dione ring, 1-benzofuran ring, 2-benzofuran ring, acridine ring, isoquinoline ring, imidazole ring, indole ring, oxa Diazole ring, oxazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazyl ring, oxazolopyrimidine ring, quinazoline ring, quinoxaline ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine Ring, thiazolopyridine ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthyridine ring, pyrazine ring, pyrazole ring, pyranone ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring, Pyrrole ring, phenanthridine ring, phthalazine ring, furan ring, benzo[c]thiophene ring, benzisoxazole ring, benzisothiazole ring, benzimidazole ring, benzooxadiazole ring, benzoxazole ring, benzothiadiazole ring, benzo Examples thereof include aromatic heterocycles having 2 to 30 carbon atoms such as thiazole ring, benzothiophene ring, benzotriazine ring, benzotriazole ring, benzopyrazole ring and benzopyranone ring. When F ^x has a plurality of aromatic heterocycles, the plurality of aromatic heterocycles may be the same as or different from each other.

The aromatic heterocycle in F ^x may have a substituent. Examples of the substituent which the aromatic heterocyclic ring in the F ^x may have, for example, include the same examples as the substituent group which may have an aromatic hydrocarbon ring in F ^x. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Preferred examples of F ^x include “a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent and has 2 to 20 carbon atoms”. Hereinafter, this cyclic group may be appropriately referred to as “cyclic group (a)”.

Examples of the substituent that the cyclic group (a) may have include the same examples as the substituent that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Preferred examples of the cyclic group (a) include a hydrocarbon ring group having 6 to 20 carbon atoms which may have a substituent and which has at least one aromatic hydrocarbon ring having 6 to 18 carbon atoms. Can be mentioned. Hereinafter, this hydrocarbon ring group may be appropriately referred to as “hydrocarbon ring group (a1)”.

Examples of the hydrocarbon ring group (a1) include a phenyl group (6 carbon atoms), a naphthyl group (10 carbon atoms), an anthracenyl group (14 carbon atoms), a phenanthrenyl group (14 carbon atoms), a pyrenyl group. (16 carbon atoms), fluorenyl group (13 carbon atoms), indanyl group (9 carbon atoms), 1,2,3,4-tetrahydronaphthyl group (10 carbon atoms), 1,4-dihydronaphthyl group Examples thereof include aromatic hydrocarbon ring groups having 6 to 18 carbon atoms such as (having 10 carbon atoms).

Specific examples of the hydrocarbon ring group (a1) include groups represented by the following formulas (1-1) to (1-21). Moreover, these groups may have a substituent. In the following formula, “−” represents a bond with Y ^x extending from any position of the ring.

Another preferable example of the cyclic group (a) has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 18 carbon atoms and an aromatic heterocycle having 2 to 18 carbon atoms. And a heterocyclic group having 2 to 20 carbon atoms which may have a substituent. Hereinafter, this heterocyclic group may be referred to as “heterocyclic group (a2)” as appropriate.

Examples of the heterocyclic group (a2) include a phthalimido group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a flazanyl group, an oxazolyl group, an oxazolopyrazinyl group and an oxaxyl group. Zolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazlopyrazinyl group, thiazolopyridinyl group , Thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, Phenanthridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxazolyl group, benzothiadiazolyl group, benzothiazolyl group, Aromatic heterocyclic groups having 2 to 18 carbon atoms, such as benzothiophenyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group; xanthenyl group; 2,3-dihydroindolyl group 1,10-dihydroacridinyl group; 1,2,3,4-tetrahydroquinolyl group; dihydropyranyl group; tetrahydropyranyl group; dihydrofuranyl group; and tetrahydrofuranyl group.

Specific examples of the heterocyclic group (a2) include groups represented by the following formulas (2-1) to (2-51). Moreover, these groups may have a substituent. In the following formula, “−” represents a bond with Y ^x extending from any position of the ring. In the following formula, X represents —CH ₂ —, —NR ^c —, an oxygen atom, a sulfur atom, —SO— or —SO ₂ —. Y and Z each independently represent -NR ^c -, an oxygen atom, a sulfur atom, -SO- or -SO ₂ -. E represents —NR ^c —, an oxygen atom or a sulfur atom. Here, R ^c represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group and a propyl group. (However, in each formula, an oxygen atom, a sulfur atom, —SO—, and —SO ₂ — are not adjacent to each other.).

Another preferable example of F ^x is “a cyclic group having 2 to 20 carbon atoms, which has at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, and which may have a substituent, And an alkyl group having 1 to 18 carbon atoms, which is substituted with a hydrogen atom and may have a substituent other than the above cyclic group. Hereinafter, this substituted alkyl group may be appropriately referred to as a “substituted alkyl group (b)”.

Examples of the alkyl group having 1 to 18 carbon atoms in the substituted alkyl group (b) include a methyl group, an ethyl group, a propyl group and an isopropyl group.

In the substituted alkyl group (b), “a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent and has 2 to 20 carbon atoms” is, for example, a cyclic group. The group of the range demonstrated as group (a) is mentioned.

In the substituted alkyl group (b), “at least one of an aromatic hydrocarbon ring and an aromatic heterocycle” may be directly bonded to a carbon atom of an alkyl group having 1 to 18 carbon atoms, and may be a linking group. It may be bound via. Examples of the linking group include -S-, -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-, -OC(=O). ) -O-, -C(=O)-S-, -SC(=O)-, -NR ¹⁵ -C(=O)-, -C(=O)-NR ^{15 and the} like. The meaning of R ¹⁵ is as described above. Therefore, in the "substituted alkyl group (b) "a cyclic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, which may have a substituent and has 2 to 20 carbon atoms"," is a fluorenyl group. , A group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle such as a benzothiazolyl group; an optionally substituted aromatic hydrocarbon ring group; an optionally substituted aromatic heterocyclic group; a linking group A group consisting of an optionally substituted aromatic hydrocarbon ring having a group; and a group consisting of an optionally substituted aromatic heterocycle having a linking group.

Preferred examples of the aromatic hydrocarbon ring group in the substituted alkyl group (b) include phenyl group, naphthyl group, anthracenyl group, phenanthrenyl group, pyrenyl group, fluorenyl group and the like aromatic carbon ring having 6 to 20 carbon atoms. A hydrogen ring group is mentioned.

The aromatic hydrocarbon ring group in the substituted alkyl group (b) may have a substituent. Examples of this substituent include the same examples as the substituent that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Preferred examples of the aromatic heterocyclic group in the substituted alkyl group (b) include a phthalimido group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a flazanyl group, an oxazolyl group and an oxaxyl group. Zolopyrazinyl group, oxazolopyridinyl group, oxazolopyridazinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group , Thiazolopyridyl group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl Group, pyrrolyl group, phenanthridinyl group, phthalazinyl group, furanyl group, benzo[c]thienyl group, benzisoxazolyl group, benzisothiazolyl group, benzimidazolyl group, benzoxazodiazolyl group, benzoxazolyl Group, benzothiadiazolyl group, benzothiazolyl group, benzothienyl group, benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group and the like, and aromatic heterocyclic group having 2 to 20 carbon atoms. Be done.

The aromatic heterocyclic group in the substituted alkyl group (b) may have a substituent. Examples of this substituent include the same examples as the substituent that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the “group consisting of an aromatic hydrocarbon ring having a linking group” and the “group consisting of an aromatic heterocycle having a linking group” in the substituted alkyl group (b) include, for example, a phenylthio group, a naphthylthio group and an anthracenylthio group. , Phenanthrenylthio group, pyrenylthio group, fluorenylthio group, phenyloxy group, naphthyloxy group, anthracenyloxy group, phenanthrenyloxy group, pyrenyloxy group, fluorenyloxy group, benzisoxazolylthio group, Benzisothiazolylthio group, benzoxazodiazolylthio group, benzoxazolylthio group, benzothiadiazolylthio group, benzothiazolylthio group, benzothienylthio group, benzisoxazolyloxy group, benzisothiazolyl Examples thereof include an oxy group, a benzoxazodiazolyloxy group, a benzoxazolyloxy group, a benzothiadiazolyloxy group, a benzothiazolyloxy group and a benzothienyloxy group.

The "group consisting of an aromatic hydrocarbon ring having a linking group" and the "group consisting of an aromatic heterocycle having a linking group" in the substituted alkyl group (b) may each have a substituent. Examples of this substituent include the same examples as the substituent that the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Examples of the substituent other than the cyclic group which the substituted alkyl group (b) may have include the same examples as the substituent which the aromatic hydrocarbon ring in F ^x may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Specific examples of the substituted alkyl group (b) include groups represented by the following formulas (3-1) to (3-11). Moreover, these groups may have a substituent. In the following formula, “−” represents a bond with Y ^x extending from any position of the ring. Moreover, in the following formula, * represents a bonding position.

In particular, when Ar is represented by the formula (II-2), F ^x is preferably a group represented by any of the following formulas (i-1) to (i-9). Further, particularly when Ar is represented by the formula (II-3) or the formula (II-4), F ^x is a group represented by any one of the following formulas (i-1) to (i-13). Is preferred. The groups represented by the following formulas (i-1) to (i-13) may have a substituent. Moreover, in the following formula, * represents a bonding position.

Further, when Ar is represented by the formula (II-2), F ^x is particularly preferably a group represented by any of the following formulas (ii-1) to (ii-18). When Ar is represented by the formula (II-3) or the formula (II-4), F ^x is a group represented by any of the following formulas (ii-1) to (ii-24). Is particularly preferable. The groups represented by the following formulas (ii-1) to (ii-24) may have a substituent. In the following formula, the meaning of Y is as described above. Moreover, in the following formula, * represents a bonding position.

When Ar is represented by the formula (II-2), the total number of π electrons contained in the ring structure in F ^x is preferably 8 or more, more preferably 10 or more, and 20 or less. It is preferably 18 or less, and more preferably 18 or less. When Ar is represented by the formula (II-3) or the formula (II-4), the total number of π electrons contained in the ring structure in F ^x is preferably 4 or more, and 6 or more. More preferably, it is preferably 20 or less, and more preferably 18 or less.

Among the above, as R ^g , at least one of —CH ₂ — contained in the alkyl group having 1 to 20 carbon atoms which may have a substituent; and the alkyl group having 1 to 20 carbon atoms, -O-, -S-, -OC(=O)-, -C(=O)-O-, or a group substituted with -C(=O)- (provided that -O- or- (Except when two or more S- groups are adjacently intervening each other); a cycloalkyl group having a carbon number of 3 to 12 which may have a substituent; a carbon atom having a carbon number of 6 to which a substituent may have 6 to An aromatic hydrocarbon ring group having 30; an aromatic heterocyclic group having 2 to 30 carbon atoms which may have a substituent; and -G ^x -Y ^x -F ^x ; are preferable. Among them, as R ^g , at least one of —CH ₂ — contained in the alkyl group having 1 to 20 carbon atoms which may have a substituent; and the alkyl group having 1 to 20 carbon atoms is —O. Groups substituted with -, -S-, -OC(=O)-, -C(=O)-O-, or -C(=O)- (provided that -O- or -S- Each of which is adjacent to each other by 2 or more); an aromatic hydrocarbon ring group having 6 to 30 carbon atoms which may have a substituent; and -G ^x -Y ^x -F ^x ; Particularly preferred.

R ^h represents an organic group having at least one aromatic ring 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, which has at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms. Hereinafter, the hydrocarbon ring group having the aromatic hydrocarbon ring may be appropriately referred to as "(1) hydrocarbon ring group". Specific examples of the (1) hydrocarbon ring group include the following groups.

(1) The hydrocarbon ring group may have a substituent. (1) The substituent which the hydrocarbon ring group may have includes, for example, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a C 1 to 6 carbon atom such as a methyl group, an ethyl group and a propyl group. Alkyl group; vinyl group, allyl group, etc., alkenyl group having 2 to 6 carbon atoms; trifluoromethyl group, etc., halogenated alkyl group having 1 to 6 carbon atoms; dimethylamino group, etc., 2 carbon atoms To 12 N,N-dialkylamino groups; methoxy groups, ethoxy groups, isopropoxy groups, and other alkoxy groups having 1 to 6 carbon atoms; nitro groups; phenyl groups, naphthyl groups, and other C6 to 20 carbon atoms An aromatic hydrocarbon ring group; -OCF ₃ ; -C(=O)-R ^b ; -OC(=O)-R ^b ; -C(=O)-O-R ^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 or different from each other.

Another preferable example of R ^h has (2) at least one aromatic ring 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. And a heterocyclic group having 2 to 40 carbon atoms. Hereinafter, the heterocyclic group having this aromatic ring may be appropriately referred to as "(2) heterocyclic group". (2) Specific examples of the heterocyclic group include the following groups. Each 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 (1) substituent that the hydrocarbon ring group may have. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

Yet another preferred example of R ^h is (3) one or more groups selected from the group consisting of aromatic hydrocarbon ring groups having 6 to 30 carbon atoms and aromatic heterocyclic groups having 2 to 30 carbon atoms. And an alkyl group having 1 to 12 carbon atoms, which is 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, an isopropyl group and the like.
(3) Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g .
(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 R ^g .

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

Still another preferable example of R ^h 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. And an alkenyl group having 2 to 12 carbon atoms, which is substituted with. Hereinafter, the substituted alkenyl group may be 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 vinyl group and allyl group.
(4) Examples of the "aromatic hydrocarbon ring group having 6 to 30 carbon atoms" in the substituted alkenyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g .
(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 R ^g .

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

Still another preferable example of R ^h is (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. And an alkynyl group having 2 to 12 carbon atoms, which is substituted with. Hereinafter, the substituted alkynyl group may be 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 ethynyl group and propynyl group.
(5) Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkynyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g .
(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 R ^g .

(5) The substituted alkynyl group may further have a substituent. Examples of the substituent that the substituted alkynyl group may have (5) 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 or different from each other.

Specific examples of R ^h include the following groups.

More preferable specific examples of R ^h include the following groups.

The following groups are mentioned as particularly preferable specific examples of R ^h .

The specific examples of R ^h 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; a vinyl group, an allyl group and the like. An alkenyl group having 2 to 6 carbon atoms; a halogenated alkyl 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, an isopropoxy group; a nitro group; -OCF ₃ ; -C(=O)-R ^b ; -OC(=O)-R ^{^{b; -C (= O) -O}} -R 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 or different from each other.

R ⁱ represents an organic group having at least one aromatic ring 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 ⁱ include a hydrocarbon ring group having 6 to 40 carbon atoms, which has at least one aromatic hydrocarbon ring having 6 to 30 carbon atoms.
Another preferable example of R ⁱ has at least one aromatic ring 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 particularly preferable specific examples of R ⁱ . The meaning of R is as described above.

The group represented by any of the formulas (II-1) to (II-4) may further have a substituent in addition to D ¹ to D ³ . Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 6 carbon atoms, a halogenated alkyl group having 1 to 6 carbon atoms, and an N-alkylamino group having 1 to 6 carbon atoms. Group, N,N-dialkylamino group having 2 to 12 carbon atoms, alkoxy group having 1 to 6 carbon atoms, alkylsulfinyl group having 1 to 6 carbon atoms, carboxyl group, thioalkyl group having 1 to 6 carbon atoms , N-alkylsulfamoyl groups having 1 to 6 carbon atoms and N,N-dialkylsulfamoyl groups 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 or different from each other.

Preferred examples of Ar in the formula (I) include groups represented by the following formulas (III-1) to (III-7). The groups represented by formulas (III-1) to (III-7) may have an alkyl group having 1 to 6 carbon atoms as a substituent. In the following formula, * represents a bonding position.

Particularly preferred specific examples of the formula (III-1) include the following groups. In the following formula, * represents a bonding position.

In formula (I), Z ¹ and Z ² are each independently a single bond, —O—, —O—CH ₂ —, —CH ₂ —O—, —O—CH ₂ —CH ₂ —, — 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 -, - O-C (}} = O) -CH 2 -, - CH 2 -O-C (= O) -, - C (= O) -O-CH 2 -, - CH 2 -CH 2 - _{_{C (= O) -O -,}} - O-C (= O) -CH 2 -CH 2 -, - CH 2 -CH 2 -O-C (= 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-. R ^21's each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formula (I), A ¹ , A ² , B ¹ and B ² are each independently 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 a group. 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 each independently. Among them, A ¹ , A ² , B ¹ and B ² each independently have a cycloaliphatic group having 5 to 20 carbon atoms which may have a substituent, or a substituent. Aromatic groups having 2 to 20 carbon atoms are preferable.

Examples of the cycloaliphatic group in A ¹ , A ² , B ¹ and B ² include a cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane-1,4-diyl group, A cycloalkanediyl group having 5 to 20 carbon atoms such as cyclooctane-1,5-diyl group; a carbon atom such as decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl group A bicycloalkanediyl group of the number 5 to 20; and the like. Of these, an optionally substituted cycloalkanediyl group having 5 to 20 carbon atoms is preferable, a cyclohexanediyl group is more preferable, and a cyclohexane-1,4-diyl group is particularly preferable. The cycloaliphatic group may be in the trans form, the cis form, or a mixture of the cis form and the trans form. Among them, the trans form is more preferable.

Examples of the substituent that the cycloaliphatic group in A ¹ , A ² , B ¹ and B ² may have include a halogen atom, an alkyl group having 1 to 6 carbon atoms, 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 or different from each other.

Examples of the aromatic group for 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 group having 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 -Diyl group, pyridine-2,5-diyl group, pyrazine-2,5-diyl group and the like; and aromatic heterocyclic groups having 2 to 20 carbon atoms; and the like. 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 substituent which the aromatic group in A ¹ , A ² , B ¹ and B ² may have is, for example, the same as the substituent which the cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² may have. An example is given. The number of substituents may be one or plural. Further, the plurality of substituents may be the same as or different from each other.

In formula (I), Y ¹ to Y ⁴ are each independently a single bond, —O—, —C(═O)—, —C(═O)—O—, —O—C(═O )-, -NR ²² -C(=O)-, -C(=O)-NR ²² -, -OC(=O)-O-, -NR ²² -C(=O)-O-, ^{-O-C (= O) -NR} 22 -, ^{and, -NR 22 -C (= O)} -NR 23 -, represents any one selected from the group consisting of. 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 each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms. Represents an organic group selected from the group consisting of one or more of (—CH ₂ —) 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 for P ¹ and P ² include a group represented by CH ₂ ═CR ³¹ —C(═O)—O— such as an acryloyloxy group and a methacryloyloxy group; a vinyl group; a vinyl ether group; p-stilbene group; acryloyl group; methacryloyl group; carboxyl group; methylcarbonyl group; hydroxyl group; amide group; alkylamino group having 1 to 4 carbon atoms; amino group; epoxy group; oxetanyl group; aldehyde group; isocyanate group; thio Isocyanate group; and the like. R ³¹ represents a hydrogen atom, a methyl group, or a chlorine atom. Of these, a group represented by CH ₂ ═CR ³¹ —C(═O)—O— is preferable, and CH ₂ ═CH—C(═O)—O—(acryloyloxy group) and CH ₂ ═C(CH ₃ )-C(=O)-O-(methacryloyloxy group) is more preferable, and acryloyloxy group is particularly preferable.

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

Among the above-mentioned liquid crystal compounds, those containing a benzothiazole ring in the molecule of the liquid crystal compound are preferable from the viewpoint of remarkably exerting the desired effect of the present invention. Here, the benzothiazole ring means a ring structure having a structure represented by the following formula (II).

The liquid crystal compound represented by the formula (I) can be produced, for example, by reacting a hydrazine compound with a carbonyl compound described in International Publication No. 2012/147904 and International Publication No. 2018/173954.

Specific examples of the liquid crystal compound represented by the formula (I) include compounds represented by the following formulas.

[3. Chiral compound]
As the chiral compound, a compound containing an asymmetric carbon atom can be used. The chiral compound can positively cause the molecules of the liquid crystal compound contained in the liquid crystal composition to twist in one direction. Therefore, it is possible to prevent the twist direction of the alignment direction from becoming non-uniform, and thus it is possible to suppress the uneven alignment of the liquid crystal cured layer.

Examples of the chiral compound include JP-A-2005-289881, JP-A-2004-115414, JP-A-2003-66214, JP-A-2003-313187, JP-A-2003-342219, and JP-A-2000. -290315, JP-A-6-072962, JP-A-6468444, WO98/00428, JP-A-2007-176870, and the like. Further, as the chiral compound, a commercially available product can be used, and for example, it can be obtained as BASF's Palio Color LC756.

The chiral compound may be used alone or in combination of two or more kinds at any ratio.

The helical twisting power (HTP) of the chiral compound is arbitrary. However, the HTP is preferably large from the viewpoint of positively causing the twist of the alignment direction of the molecules of the liquid crystal compound. Specifically, the HTP of the chiral compound is preferably 9.0 or higher, and more preferably 20.0 or higher at 25°C. On the other hand, the upper limit of HTP is not particularly limited and may be 200 or less, for example.
Here, HTP is calculated by HTP=1/(P _L ×0.01C _C ). In the formula, C _C represents the content ratio (% by weight) of the chiral compound in the liquid crystal composition during alignment, and P _L represents the twist pitch (nm) in the alignment direction of the molecules of the liquid crystal compound. The pitch P _L can be obtained by actual measurement of electron micrographs.

The amount of the chiral compound can be arbitrarily adjusted within the range where a desired liquid crystal cured film can be obtained. Specifically, the amount of the chiral compound is preferably 0.05 parts by weight or more, more preferably 0.07 parts by weight or more, particularly preferably 0.10 parts by weight or more, based on 100 parts by weight of the liquid crystal compound. It is preferably 0.5 parts by weight or less, more preferably 0.4 parts by weight or less, and particularly preferably 0.3 parts by weight or less. When the amount of the chiral compound is equal to or more than the lower limit value of the above range, twist in the alignment direction of the molecules of the liquid crystal compound can be effectively caused, and thus the alignment unevenness of the liquid crystal cured layer can be effectively suppressed. On the other hand, when the amount of the chiral compound is less than or equal to the upper limit value of the above range, the pitch of twist can be made sufficiently long, so that the disturbance of the polarization state of the light passing through the liquid crystal cured layer can be effectively suppressed.

[4. Liquid crystal composition]
The liquid crystal composition contains the liquid crystal compound and the chiral compound described above. Further, the liquid crystal composition may contain an arbitrary component in combination with the liquid crystal compound and the chiral compound. As the optional component, one type may be used alone, or two or more types may be used in combination at any ratio.

The optional components include, for example, a polymerization initiator. Among them, the photopolymerization initiator is preferable. The type of polymerization initiator can be selected according to the type of polymerizable compound contained in the liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator may be used. Further, for example, if the polymerizable compound is anionically polymerizable, an anionic polymerization initiator can be used. Furthermore, for example, 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 an arbitrary ratio.

The amount of the polymerization initiator is preferably 0.1 part by weight or more, more preferably 0.5 part 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. Below the section. When the amount of the polymerization initiator falls within the above range, the polymerization can proceed efficiently.

Another optional ingredient is, for example, a surfactant. Among the surfactants, a surfactant containing a fluorine atom in the molecule is preferable from the viewpoint of improving the coatability of the liquid crystal composition and stably obtaining a liquid crystal cured layer having excellent orientation. In the following description, the surfactant containing a fluorine atom in the molecule may be appropriately referred to as a “fluorine-based surfactant”.

The fluorosurfactant preferably has a log P within a predetermined range. "LogP" refers to the 1-octanol/water partition coefficient. The preferable range of logP of the fluorosurfactant is preferably 3.5 or more and 7.5 or less. By using a fluorine-based surfactant having a logP in such a range, the tilt angle of the molecules of the liquid crystal compound with respect to the layer plane of the liquid crystal cured layer can be effectively increased as a whole of the liquid crystal cured layer.

The logP of the fluorosurfactant can be measured by the following measuring method.
A sample solution containing 1% by weight of a fluorosurfactant was prepared, and HPLC/ELSD was carried out by a method substantially conforming to JIS 7260-117:2006 {Partition coefficient (1-octanol/water) measurement-high performance liquid chromatography}. An analysis (high performance liquid chromatography/evaporative light scattering detection analysis) is performed to measure the elution time (rt). On the other hand, a standard compound having a known logP value described in JIS 7260-117:2006 was subjected to HPLC/ELSD analysis in the same manner as the above-mentioned fluorosurfactant, and the elution time (rt) was determined. taking measurement. Based on the measurement results of the standard compound, a calibration curve showing the relationship between the elution time and logP is created. Then, the elution time measured for the fluorosurfactant is applied to the above calibration curve to determine the logP of the fluorosurfactant.

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 made particularly good.

Examples of the surfactant include Surflon series (S420 etc.) manufactured by AGC Seimi Chemical Co., Futgent series (251, FTX-212M, FTX-215M, FTX-209 etc.) manufactured by Neos, manufactured by DIC. Fluorosurfactants such as Megafac series (F-444, etc.) can be mentioned. Further, one kind of the surfactant may be used alone, or two or more kinds thereof may be used in combination at an arbitrary 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 100 parts by weight of the liquid crystal compound. It is 0.40 parts by weight or less, more preferably 0.30 parts by weight or less. By setting the amount of the surfactant within the above range, a desired liquid crystal cured layer can be stably obtained.

As another optional component, for example, a solvent can be mentioned. As the solvent, those capable of dissolving the liquid crystal compound are preferable. An organic solvent is usually used as such a solvent. Examples of organic solvents include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetic acid ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; 1 , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,2-dimethoxyethane and the like; and aromatic hydrocarbon solvents such as toluene, xylene and mesitylene. Further, the solvent may be used alone or in combination of two or more kinds at an arbitrary 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 easy handling.

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, preferably 650 parts by weight or less, and more preferably 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. When the amount of the solvent is equal to or more than the lower limit value of the above range, generation of foreign matter can be suppressed, and when the amount of the solvent is less than or equal to the upper limit value of the range, the drying load can be reduced.

As yet another optional component, for example, a tilt acting component capable of exerting an effect of increasing the substantially maximum tilt angle of the molecules of the liquid crystal compound can be mentioned. When the tilting component is used, the tilting of the molecules of the liquid crystalline compound can be promoted, and a liquid crystal cured layer having a large tilt angle of the molecules of the liquid crystalline compound can be easily obtained. However, since the inclination of the molecules of the liquid crystal compound can be promoted by adjusting the operation or the conditions in the process of producing the liquid crystal cured layer, the inclination acting component may not necessarily be used. As such a gradient action component, for example, the components described in JP-A-2018-163218, JP-A-2018-162379, and International Publication No. 2018/173778 can be used.

Other optional components that the liquid crystal composition may include include, for example, metals; metal complexes; metal oxides such as titanium oxide; coloring agents such as dyes and pigments; luminescent materials such as fluorescent materials and phosphorescent materials; antioxidants. Leveling agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and the like. The amounts of these components may each be 0.1 to 20 parts by weight based on 100 parts by weight of the liquid crystal compound.

[5. Characteristics of liquid crystal cured layer]
The liquid crystal cured layer is a layer of a cured product obtained by curing the above liquid crystal composition. Curing of the liquid crystal composition is usually achieved by polymerizing a polymerizable compound contained in the liquid crystal composition. Therefore, the liquid crystal cured layer usually contains a polymer of a part or all of the components included in the liquid crystal composition. For example, when the liquid crystal compound has a polymerizability, the liquid crystal compound can be polymerized during curing of the liquid crystal composition. Therefore, the liquid crystal cured layer is a polymer of the liquid crystal compound polymerized while maintaining the alignment state before the polymerization. Can be a layer containing. As described above, this polymerized liquid crystal compound is also 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, so the alignment state of the liquid crystal compound is usually fixed in the alignment state before curing. Then, at least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer.

In the liquid crystal cured layer, some of the molecules of the liquid crystal compound may be inclined with respect to the layer plane of the liquid crystal cured layer, or all of them may be inclined with respect to the layer plane of the liquid crystal cured layer. Therefore, when the layer containing the molecules of the liquid crystalline compound tilted with respect to the layer plane of the liquid crystal cured layer is referred to as the “tilted alignment layer”, the liquid crystal cured layer may include the tilted alignment layer as a part thereof. The entire cured layer may be an inclined alignment layer. In the liquid crystal cured layer, the molecules of the liquid crystalline compound contained in the layer portion other than the tilt alignment layer are usually parallel to the layer plane of the liquid crystal cured layer (the tilt angle is 0°), or It is perpendicular to the layer plane of the liquid crystal cured layer (inclination angle is 90°).

The fact that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are tilted with respect to the layer plane of the liquid crystal cured layer means that the cross section of the liquid crystal cured layer is observed with a polarization microscope having sufficient resolution. Can be confirmed by This observation may be carried out by inserting a wave 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 tilt of the molecules of the liquid crystal compound.

Alternatively, it can be confirmed as described below that 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 layer plane of the liquid crystal cured layer. The linear polarization phase difference R(θ) as the retardation of the liquid crystal cured layer at the incident angle θ is measured in the measurement direction perpendicular to the in-plane fast axis of the liquid crystal cured layer. The retardation ratio R(θ)/the linear polarization phase difference R(θ) of the liquid crystal cured layer at the incident angle θ is divided by the linear polarization phase difference R(0°) of the liquid crystal cured layer at the incident angle 0°. Find R (0°). Here, the linear polarization phase difference R(0°) of the liquid crystal cured layer at an incident angle of 0° represents the in-plane retardation LRe of the liquid crystal cured layer. When a graph is drawn with the retardation ratio R(θ)/R(0°) thus obtained as the vertical axis and the incident angle θ as the horizontal axis, the obtained graph must be asymmetric with respect to θ=0°. For example, it can be confirmed that at least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer.

The following is a more specific explanation using an example. FIG. 1 is a graph in which the retardation ratio R(θ)/R(0°) of a liquid crystal cured layer according to an example is plotted against the incident angle θ. When the tilt angle of all the molecules of the liquid crystal compound contained in the liquid crystal cured layer is 0° or 90°, the retardation ratio R(θ)/R(0°) is as shown by the example shown by the broken line in FIG. In addition, it is line-symmetric with respect to a straight line of θ=0° (in FIG. 1, a vertical axis passing through θ=0°). On the other hand, when 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 layer plane of the liquid crystal cured layer, the retardation ratio R(θ)/R(0°) becomes As in the example shown by the solid line in FIG. 1, it is usually asymmetric with respect to a straight line at θ=0°. Therefore, when the retardation ratio R(θ)/R(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 is the liquid crystal cured layer. It can be determined that it is inclined with respect to the layer plane.

The molecules of the liquid crystal compound tilted with respect to the plane of the layer may be oriented in one direction (tilted orientation). In this case, the tilt angle formed by the molecules of the liquid crystalline compound with respect to the plane of the layer may be constant. The molecules of the liquid crystalline compound tilted with respect to the plane of the layer are oriented such that the tilt angle formed with respect to the plane of the layer is smaller as it is closer to one side of the liquid crystal cured layer and larger as it is farther from the one side. Good (hybrid orientation).

Since the liquid crystal composition contains a chiral compound, due to the action of the chiral compound, the alignment direction of the molecules of the liquid crystalline compound in the liquid crystal cured layer is twisted in one direction (that is, one of rightward and leftward). .. As described above, since the chiral compound causes a positive twist in one direction, in the liquid crystal cured layer, the unevenness of the twist direction in the alignment direction of the molecules of the liquid crystal compound is suppressed. Therefore, in the liquid crystal cured layer included in the liquid crystal cured film according to the embodiment of the present invention, it is possible to prevent the orientation directions of molecules from becoming non-uniform. In particular, it is possible to prevent the components parallel to the layer plane in the orientation direction from becoming non-uniform. Therefore, alignment unevenness can be suppressed.

The in-plane retardation LRe and the optical rotation retardation CRe of the liquid crystal cured layer at the measurement wavelength of 550 nm satisfy the above formula (1). More specifically, the parameter XRe defined by the following formula (2) is usually 500 nm or more, preferably 1000 nm or more, particularly preferably 1500 nm or more, usually 20000 nm or less, preferably 10000 nm or less, particularly preferably 5000 nm or less. .. By setting the parameter XRe within the above range, it is possible to suppress the disturbance of the polarization state of the light passing through the liquid crystal cured layer.

The fact that the parameter XRe represented by the formula (2) is within the above range satisfying the formula (1) means that the twist of the alignment direction of the molecules of the liquid crystal compound is gentle in the thickness direction. Here, the term “gentle” in the twist in the orientation direction means that the pitch of the twist in the orientation direction of the molecule (period of the helical structure) is long. That is, the twist in the orientation direction is "gradual" means that the difference in the orientation direction per unit thickness is small.

In general, when light passes through a liquid crystal layer containing molecules of a liquid crystalline compound whose orientation direction is twisted in a spiral, a twist pitch is required to be sufficiently long to generate optical rotation (Morgan condition; SEMI color Revised edition of TFT liquid crystal display editorial committee, "Revised edition of color TFT liquid crystal display", Kyoritsu Shuppan, October 30, 2005, p.36). If the pitch of the twist is short, the light passing through the liquid crystal layer has a light component that cannot be rotated according to the twist, and the polarization state of the light component is disturbed, resulting in elliptically polarized light or depolarization. Sometimes. Expression (1) indicates that the twist in the alignment direction is gentle enough to suppress such a disorder of the polarization state.

The significance of the formula (1) will be described in more detail. FIG. 2 is a perspective view schematically showing an optical system in which a pair of

linear polarizers

110 and 120 set in a para-Nicol are arranged on both sides of a certain liquid crystal layer 100. Paranicol refers to a state in which the polarization transmission axis A ₁₁₀ of one linear polarizer ₁₁₀ and the polarization transmission axis A _{120 of} the other linear polarizer ₁₂₀ are parallel to each other. When natural light L1 enters one of the linear polarizers 110, linearly polarized light L2 having a vibration direction parallel to the polarization transmission axis A ₁₁₀ of the linear polarizer 110 is transmitted. The vibration direction of linearly polarized light means the vibration direction of the electric field of linearly polarized light. The linearly polarized light L2 is transmitted through the liquid crystal layer 100, and the transmitted light L3 is incident on the other linear polarizer 120. Of the transmitted light L3, only the component having the vibration direction parallel to the polarization transmission axis A ₁₂₀ of the linear polarizer 120 is transmitted and becomes the transmitted light L4, and the other components are blocked by the linear polarizer 120.

Regarding the above optical system, the Gucci-Terry formula of the following formula (3) is known as the formula of the TN liquid crystal panel (SEMI color TFT liquid crystal display revised edition, “Edited color TFT liquid crystal display revised edition”). , Kyoritsu Shuppan, October 30, 2005, p.42-43). In this formula (3), the orientation direction of the molecules of the liquid crystal compound included in the liquid crystal layer 100 is twisted by 90°. Therefore, the linearly polarized light L2 is rotated by the liquid crystal layer 100 by the optical rotation angle φ=90°. In this case, the ratio (transmittance) I of light that can be transmitted through the linear polarizer 120 is represented. In Expression (3), Δn represents the birefringence of the liquid crystal layer 100, d represents the thickness of the liquid crystal layer 100, and λ represents the wavelength of light. Therefore, in the formula (3), Δn×d represents the in-plane retardation of the liquid crystal layer 100.

Substituting the wavelength of light λ=550 nm into the formula (3) and displaying the transmittance I on the vertical axis and the in-plane retardation Δn×d on the horizontal axis, a graph shown in FIG. 3 is obtained. .. As can be seen from FIG. 3, the transmittance I takes a minimum point (about 476 nm) near the in-plane retardation Δn×d=500 nm, and the transmittance I is within a range where the in-plane retardation Δn×d is smaller than this minimum point. Is big. As a result, in the range where the in-plane retardation Δn×d is smaller than the above-mentioned minimum point, the twist in the alignment direction of the molecules included in the liquid crystal layer 100 is not sufficiently “gradual”, and thus the polarization state is disturbed. It means that. On the other hand, in the range where the in-plane retardation Δn×d is equal to or more than the above-mentioned minimum point, the twist in the orientation direction of the molecules is sufficiently “gradual”, which means that the disorder of the polarization state can be suppressed. Since the liquid crystal layer 100 can change the polarization state of the transmitted light not only by optical rotation but also by the action of the in-plane retardation Δn×d, the in-plane retardation Δn×d is not less than the above-mentioned minimum point. In some cases, the transmittance I does not reach 0.0. As described above, when the optical rotation angle φ is 90°, it can be expressed by using the formula (3) that the twist in the alignment direction is “gradual”.

However, the optical rotation angle of the liquid crystal cured layer according to the above-described embodiment is not necessarily 90°, and is usually a smaller value. Therefore, in the present embodiment, when it is assumed that the thickness of the liquid crystal cured layer is adjusted so that the liquid crystal cured layer has an optical rotation angle of 90°, the in-plane retardation that the liquid crystal cured layer will have is expressed by It is obtained as the parameter XRe represented by (2). The parameter XRe thus obtained corresponds to the in-plane retardation Δn×d in the Gucci-Terry equation of the equation (3). Therefore, by using this parameter XRe and the Gucci-Terry equation of the equation (3), the condition that the twist in the orientation direction is "gradual" is specified, and this condition is defined in the equation (1).

The parameter XRe can be adjusted by, for example, the type of liquid crystal compound; the type and amount of chiral compound; and the thickness of the liquid crystal cured layer.

The ratio CRe/D between the optical rotation retardation CRe of the liquid crystal cured layer and the thickness D of the liquid crystal cured layer at a measurement wavelength of 550 nm is preferably 0.0002 or more, more preferably 0.0005 or more, and particularly preferably 0.0010 or more. It is preferably 0.0133 or less, more preferably 0.0100 or less, and particularly preferably 0.0050 or less. When the ratio CRe/D is equal to or more than the lower limit value of the above range, the alignment direction of the molecules of the liquid crystal compound is effectively twisted, and thus the alignment unevenness can be effectively suppressed. Further, when the ratio CRe/D is equal to or less than the upper limit value of the above range, the twist of the alignment direction is gentle, so that the disturbance of the polarization state of the light passing through the liquid crystal cured layer can be effectively suppressed.

The optical retardation CRe of the liquid crystal cured layer at the measurement wavelength of 550 nm is preferably 1.0 nm or more, more preferably 1.2 nm or more, particularly preferably 1.5 nm or more, preferably 20 nm or less, more preferably 10 nm or less, Particularly preferably, it is 7 nm or less. When the optical rotation phase difference CRe is equal to or more than the lower limit value of the above range, the alignment unevenness can be effectively suppressed. Further, when the optical rotation retardation CRe is equal to or less than the upper limit value of the range, it is possible to effectively suppress the disorder of the polarization state of the light passing through the liquid crystal cured layer.

The optical rotation retardation CRe can be adjusted by, for example, the type of liquid crystal compound; the type and amount of chiral compound; and the thickness of the liquid crystal cured layer.

The specific in-plane retardation LRe of the liquid crystal cured layer at the measurement wavelength of 550 nm can be arbitrarily set according to the application of the liquid crystal cured film. Among the preferred ranges, the in-plane retardation LRe is preferably 50 nm or more, more preferably 55 nm or more, particularly preferably 60 nm or more, and preferably 90 nm or less, more preferably 85 nm or less, particularly preferably Is in the first range of 80 nm or less. Alternatively, the in-plane retardation LRe is preferably 120 nm or more, more preferably 125 nm or more, particularly preferably 130 nm or more, and preferably 160 nm or less, more preferably 155 nm or less, particularly preferably 150 nm or less. It is in the second range. When the in-plane retardation LRe is in the first range, the liquid crystal cured layer can be used as a λ/8 wave plate. When the in-plane retardation LRe is in the second range, the liquid crystal cured layer can be used as a λ/4 wavelength plate.

The in-plane retardation LRe of the liquid crystal cured layer preferably exhibits reverse wavelength dispersion. Therefore, the in-plane retardations LRe(450) and LRe(550) of the liquid crystal cured layer at wavelengths of 450 nm and 550 nm preferably satisfy the following formula (N3), more preferably the following formula (N4).
LRe(450)/LRe(550)<1.00 (N3)
LRe(450)/LRe(550)<0.90 (N4)
As described above, the liquid crystal cured layer having the in-plane retardation LRe having the reverse wavelength dispersion property can uniformly exhibit a function in a wide wavelength band in optical applications such as a quarter-wave plate or a half-wave plate. The liquid crystal cured layer having the in-plane retardation LRe having the reverse wavelength dispersion property can be realized by using the reverse dispersion liquid crystal compound as the liquid crystal compound.

The size of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer as a whole layer can be represented by the substantially maximum tilt angle. The substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is usually 5° or more and 85° or less. Among them, the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is preferably 40° or more, more preferably 46° or more, particularly preferably 56° or more, and preferably 85° or less, more preferably Is 83° or less, particularly preferably 80° or less.

The actual maximum tilt angle is an index showing the size of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. A large substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer generally means that the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is large as a whole. Since a liquid crystal cured layer having a large substantially maximum tilt angle can appropriately adjust the birefringence in the thickness direction, when the liquid crystal cured layer is combined with a linear polarizer and provided as an antireflection film in an organic EL display device. In addition, reflection can be effectively suppressed in the tilt direction of the display surface. Therefore, it is possible to realize a polarizing plate that can achieve high viewing angle characteristics.

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

When the molecules of the liquid crystal compound contained in the liquid crystal cured layer have a large tilt angle as a whole of the liquid crystal cured layer, the birefringence in the thickness direction of the liquid crystal cured layer can be appropriately adjusted. Therefore, when the liquid crystal cured layer is provided on the polarizing plate as the antireflection film, it is possible to obtain excellent viewing angle characteristics that reflection can be effectively suppressed in the tilt direction of the display surface.

In the in-plane direction of the liquid crystal cured layer, the orientation direction of the molecules of the liquid crystal compound is usually uniform. Therefore, the liquid crystal cured layer can usually have a slow axis parallel to the alignment direction of the molecules of the liquid crystal compound when the liquid crystal cured layer is viewed from the thickness direction.

The liquid crystal cured layer preferably has excellent transparency. Specifically, the total light transmittance of the liquid crystal cured layer is preferably 75% or more, more preferably 80% or more, and particularly preferably 84% or more. The haze of the liquid crystal cured layer is preferably 5% or less, more preferably 3% or less, and particularly preferably 1% or less. The total light transmittance can be measured in the wavelength range of 400 nm to 700 nm using an ultraviolet/visible spectrometer. Moreover, haze can be measured using a haze meter.

[6. Layer configuration of liquid crystal cured layer]
4 and 5 are cross-sectional views schematically showing examples of the liquid crystal cured

layers

200 and 300 included in the liquid crystal cured film according to the embodiment of the present invention, respectively.
As in the example shown in FIG. 4, the liquid crystal cured layer 200 may have a single-layer structure including only one layer. Further, as in the example shown in FIG. 5, the liquid crystal cured layer 300 may have a multilayer structure including a plurality of layers such as the first cured layer 310 and the second cured layer 320. In the following description, the layers such as the first cured layer and the second cured layer which are included in the liquid crystal cured layer may be appropriately referred to as “unit cured layer”.

In the liquid crystal cured layer 300 having a multilayer structure including a plurality of unit structure layers, it is preferable that there is no other layer between the adjacent unit structure layers. Therefore, in the liquid crystal cured layer 300 including the first cured layer 310 and the second cured layer 320, it is preferable that there is no other layer between the first cured layer 310 and the second cured layer 320. The contact between two layers without sandwiching another layer between them in this manner is sometimes referred to as “direct” contact.

The multi-layer structure as shown in FIG. 5 usually occurs due to the manufacturing method of the liquid crystal cured layer 300. For example, when the reverse dispersion liquid crystal compound is used, the surface 310U of the unit curing layer such as the first curing layer 310 containing the molecules of the reverse dispersion liquid crystal compound tilted with respect to the plane of the layer is usually formed on the surface 310U. It can function as an alignment film for increasing the tilt angle of the molecules of the reverse dispersion liquid crystalline compound contained in another unit cured layer such as the second cured layer 320 formed. Therefore, when it is desired to increase the tilt angle of the molecules of the reverse dispersion liquid crystal compound included in the liquid crystal cured layer 300 as a whole layer, a production including forming another unit cured layer on the previously formed unit cured layer. It is preferable to adopt the method. In the liquid crystal cured layer 300 including the first cured layer 310 and the second cured layer 320, when the first cured layer 310 functions as an alignment film in this manner, the reverse dispersion liquid crystal compound included in the second cured layer 320 The substantially maximum tilt angle of the molecule may be greater than the substantially maximum tilt angle of the molecule of the inverse dispersion liquid crystal compound included in the first curable layer 310.

Each unit curing layer included in the liquid crystal curing layer can be distinguished by the following method. The liquid crystal cured layer is embedded with an epoxy resin to obtain a sample piece. This sample piece is sliced in parallel with the thickness direction of the liquid crystal cured layer using a microtome to obtain an observation sample. At this time, slicing is performed so that the slow axis of the liquid crystal cured layer and the cross section are parallel to each other. After that, the cross section exposed by the slice is observed using a polarization microscope. This observation is performed by inserting a wave plate between the observation sample and the objective lens of the polarization microscope so that an image showing a color corresponding to the phase difference of the observation sample can be seen. At this time, the portions having different colors are confirmed as boundaries between the unit cured layers, and each unit cured layer can be distinguished.

In the liquid crystal cured layer, at least some of the molecules of the liquid crystalline compound contained in the liquid crystal cured layer are tilted with respect to the layer plane of the liquid crystal cured layer. The molecules of the compound may not be tilted with respect to the layer plane of the liquid crystal cured layer. Therefore, for example, the molecules of the liquid crystal compound contained in some unit cured layers may be parallel or perpendicular to the layer plane of the liquid crystal cured layer. However, normally, the molecules of the liquid crystalline compound contained in any of the unit cured layers are inclined with respect to the layer plane of the liquid crystal cured layer. Therefore, in the liquid crystal cured layer 300 including the first cured layer 310 and the second cured layer 320 as in the example shown in FIG. 5, the molecules of the liquid crystalline compound contained in the first cured layer 310 are usually relative to the layer plane. The molecules of the liquid crystal compound included in the second cured layer 320 are inclined and inclined with respect to the layer plane.

[7. Liquid crystal cured layer thickness]
The thickness of the liquid crystal cured layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 10.0 μm or less, more preferably 7.0 μm or less. When the thickness of the liquid crystal cured layer is within the above range, properties such as in-plane retardation LRe and optical rotation retardation CRe can be easily adjusted to desired ranges. Further, since the liquid crystal cured layer having such a thickness is thinner than the conventional retardation film used for the reflection suppressing film of the organic EL display device, it can contribute to the thinning of the organic EL display device.

[8. Any layer]
The liquid crystal cured film may be a film containing only the liquid crystal cured layer, or may be a film containing any layer in combination with the liquid crystal cured layer. As an optional layer, a base material used for producing a liquid crystal cured layer; a retardation film; an adhesive layer for adhering to other members; a mat layer for improving the slipperiness of the film; an impact-resistant polymethacrylate resin layer, etc. Hard coat layer; antireflection layer; antifouling layer;

[9. Manufacturing method of liquid crystal cured film]
The method for producing the liquid crystal cured film is not particularly limited. For example, a liquid crystal cured film
(I) a step of forming a layer of the liquid crystal composition,
(Ii) a step of aligning a liquid crystalline compound contained in the layer of the liquid crystal composition,
(Iii) curing a layer of the liquid crystal composition to obtain a liquid crystal cured layer,
Can be manufactured by a manufacturing method including.

In the step (i) of forming the layer of the liquid crystal composition, the layer of the liquid crystal composition is usually formed on an appropriate supporting surface. As the supporting surface, any surface that can support the layer of the liquid crystal composition can be used. From the viewpoint of improving the surface condition of the liquid crystal cured layer, it is preferable to use a flat surface having no concave portions or convex portions as the supporting surface. Further, from the viewpoint of enhancing the productivity of the liquid crystal cured layer, it is preferable to use the surface of a long base material as the supporting surface. Here, the "long length" means a shape having a length of 5 times or more the width, preferably 10 times or more, and specifically, wound into a roll shape. The shape of the film is long enough to be stored or transported. The upper limit of the length is not particularly limited and may be 10,000 times or less the width.

 Normally, a resin film or glass plate is used as the base material. In particular, when the orientation treatment is performed at a high temperature, it is preferable to select a substrate that can withstand the temperature. A thermoplastic resin is usually used as the resin. Among them, a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoints of high orientation regulation force, high mechanical strength, and low cost. Furthermore, it is preferable to use a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin because it is excellent in transparency, low hygroscopicity, dimensional stability and light weight. A preferred example of the resin contained in the base material is a norbornene-based resin, which includes "Zeonor" manufactured by Nippon Zeon Co., Ltd.

The surface of the base material as a supporting surface is preferably subjected to a treatment for imparting an alignment regulating force in order to promote the alignment of the liquid crystal compound in the liquid crystal composition layer. The alignment regulating force refers to a property of a surface that can align the liquid crystal compound contained in the liquid crystal composition. Examples of the treatment for imparting the alignment regulating force to the support surface include a photo-alignment treatment, a rubbing treatment, an ion beam alignment treatment, and a stretching treatment.

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

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 may be performed. In this step (ii), the liquid crystal compound is usually aligned in a direction according to the alignment control force of the supporting surface by subjecting the layer of the liquid crystal composition to alignment treatment.

Alignment treatment is usually performed by adjusting the temperature of the liquid crystal composition layer to a predetermined alignment temperature. The orientation temperature can be a temperature equal to or higher than the liquid crystallizing temperature of the liquid crystal composition. At this time, the orientation temperature is preferably lower than the glass transition temperature of the resin contained in the substrate. As a result, it is possible to suppress the occurrence of distortion of the base material due to the alignment treatment.

Normally, in the in-plane direction, the liquid crystal compound is aligned in the direction according to the alignment control force of the supporting surface. Further, in the thickness direction, the liquid crystal compound is usually oriented so that at least a part thereof is largely inclined with respect to the layer plane. Thereby, the tilt angle of the liquid crystal compound with respect to the layer plane can be effectively increased.

Further, it is preferable that the step (ii) is performed by adjusting the operation or conditions so that a liquid crystal cured layer having a large tilt angle of the molecules of the liquid crystal compound can be obtained.

For example, when an inverse dispersion liquid crystal compound is used as the liquid crystal compound, step (ii) is preferably performed so that the temperature condition of the layer of the liquid crystal composition satisfies predetermined requirements. Specifically, it is preferable that the temperature condition of the layer of the liquid crystal composition in the step (ii) is the same as the temperature condition under which the residual viscosity of the test composition is usually 800 cP 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 components of the test composition under the same temperature conditions as the layer of the liquid crystal composition in step (ii). In addition, the residual component of the test composition is a component that remains in the test composition without vaporizing under the same temperature condition as the layer of the liquid crystal composition of step (ii). By performing the step (ii) so as to satisfy such requirements, it is possible to increase the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer.

Explain further. When the step (ii) of orienting the liquid crystal compound is performed so as to satisfy the above-mentioned requirements, the step (ii) is performed under the same temperature condition that the residual viscosity of the test composition falls within a predetermined range. This is done by adjusting the layer of the composition. The specific range of the residual viscosity is usually 800 cP (centipoise) or less, preferably 600 cP or less, more preferably 400 cP or less, and further preferably 200 cP or less. In this way, by aligning the liquid crystal compound in the layer of the liquid crystal composition under the same temperature condition that the residual viscosity of the test composition becomes low, the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer Can be increased. The lower limit of the residual viscosity is preferably 5 cP or more, more preferably 10 cP or more from the viewpoint of obtaining a liquid crystal cured layer having a desired thickness.

The residual viscosity of the test composition under the same temperature conditions as the layer of the liquid crystal composition of step (ii) can be measured by the following method.
A test composition is prepared by removing the polymerization initiator from the liquid crystal composition. The test composition is concentrated under reduced pressure with a rotary evaporator to remove the solvent and obtain a residual component. 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. Hereinafter, this information will be referred to as “temperature-viscosity information” as appropriate. From this "temperature-viscosity information", the viscosity at the temperature of the layer of the liquid crystal composition in step (ii) is read as the residual viscosity.

Examples of the method of keeping the residual viscosity of the test composition within the above range under the same temperature condition as the layer of the liquid crystal composition in step (ii) include the following methods (A) and (B).
The temperature of the layer of the liquid crystal composition in the step (ii) of orienting the liquid crystal compound (A) is appropriately adjusted. In this method, usually, the temperature of the layer of the liquid crystal composition is sufficiently high to reduce the residual viscosity of the test composition under the same temperature condition as this temperature, and the viscosity is adjusted to fall within the above range. To do.
(B) The composition of the liquid crystal composition is appropriately adjusted. In this method, usually, as a component contained in the liquid crystal composition, a liquid crystal compound is combined with an additive of an appropriate type and amount to reduce the residual viscosity of the test composition containing the additive, Adjust so that it is within the specified range.

Regarding the adjustment of the temperature condition of the layer of the liquid crystal composition in the step (ii), the description in International Publication No. 2018/1737773 may be referred to.

Further, for example, when using a liquid crystal composition containing an inverse dispersion liquid crystal compound and a liquid crystal compound having a magnetic field responsiveness, the step (ii) is performed in a state in which a magnetic field is applied to a layer of the liquid crystal composition. Is preferred. Thereby, the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be effectively increased. Regarding the application of the magnetic field, the description in JP-A-2018-163218 may be referred to.

The step (ii) of orienting the liquid crystal compound is usually performed in an oven. At this time, the set temperature of the oven may be different from the temperature of the layer of the liquid crystal composition placed in the oven. In this case, it is preferable to measure and record the temperature of the layer of the liquid crystal composition placed in the oven at the preset temperatures at a number of preset temperatures. The information on the recorded set temperature of the oven and the temperature of the layer of the liquid crystal composition placed in the oven at the set temperature is hereinafter referred to as "set temperature-layer temperature information" as appropriate. By using this "set temperature-layer temperature information", the temperature of the layer of the liquid crystal composition placed in the oven can be easily known from the oven set temperature.

In the step (ii) of orienting the liquid crystal compound, the time for maintaining the temperature of the layer of the liquid crystal composition at the above temperature can be arbitrarily set within the range where a desired liquid crystal cured layer can be obtained, and for example, 30 seconds to 5 minutes. Can be

After the step (ii) of orienting the liquid crystal compound, the step (iii) of curing the layer of the liquid crystal composition to obtain a liquid crystal cured layer is performed. The curing of the liquid crystal composition in step (iii) is usually achieved by polymerizing the polymerizable compound contained in the liquid crystal composition. For example, when the liquid crystal compound is polymerizable, the layer of the liquid crystal composition is cured by polymerizing a part or all of the liquid crystal compound. The polymerization usually proceeds while maintaining the alignment of the molecules of the liquid crystal compound. Therefore, the alignment state of the liquid crystal compound contained in the liquid crystal composition before the polymerization is fixed by the above-mentioned polymerization.

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. Among them, the method of irradiating with active energy rays is preferable because heating is not necessary and the polymerization reaction can proceed at room temperature. Here, the active 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, the method of irradiating light such as ultraviolet rays is preferable because the operation is simple. The temperature at the time of ultraviolet irradiation is preferably not more than the glass transition temperature of the substrate, preferably 150° C. or less, more preferably 100° C. or less, particularly preferably 80° C., from the viewpoint of not affecting the substrate. It is below. The lower limit of the temperature during UV irradiation is preferably 15° C. or higher, and more preferably 20° 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 10000 mW / cm ² or less, more preferably 5000 mW / cm ² or less. The dose 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, more preferably 5000 mJ / cm ² or less.

The liquid crystal cured layer can be obtained by performing the above steps. The above-described manufacturing method may include a step of further forming a liquid crystal cured layer on the thus obtained liquid crystal cured layer. In this case, a liquid crystal cured layer having a multilayer structure including a first cured layer corresponding to the liquid crystal cured layer formed as described above and a second cured layer further formed on the first cured layer is obtained. Be done.

The second cured layer is preferably formed directly on the first cured layer. Here, the term “directly” as a mode of forming another layer on a certain layer means that there is no other layer between these two layers. When a reverse-dispersed liquid crystalline compound is used, a unit cured layer such as a first cured layer containing the reverse-dispersed liquid crystalline compound is contained in another unit cured layer directly formed on the unit cured layer. It can function as an alignment film for increasing the tilt angle of the molecules of the liquid crystal compound. Therefore, in general, a unit structure layer (for example, a first cured layer) formed earlier than a substantially maximum tilt angle of the molecules of the reverse dispersion liquid crystal compound included in another unit structure layer (hereinafter referred to as a unit structure layer) is formed. For example, the substantially maximum tilt angle of the molecules of the reverse dispersion liquid crystal compound contained in the second cured layer) can be increased. Therefore, by repeating the formation of the unit cured layer, a liquid crystal cured layer having a large tilt angle of the reverse dispersion liquid crystalline compound can be obtained as a whole. In the liquid crystal cured layer thus obtained, the unit cured layer formed later tends to have a substantially larger maximum tilt angle.

The second cured layer can be formed, for example, by performing the steps (i) to (iii) described above. At this time, the liquid crystal compound contained in the liquid crystal composition used to form the second cured layer may be the same as or different from the liquid crystal compound contained in the liquid crystal composition used to form the first cured layer. May be. Furthermore, the liquid crystal composition used to form the second cured layer and the liquid crystal composition used to form the first cured layer may be different or the same.

Before the layer of the liquid crystal composition is formed, the surface of the first cured layer may be subjected to a treatment such as a rubbing treatment for giving an alignment regulating force. However, the surface of the first cured layer has an alignment regulating force for appropriately aligning the reverse dispersion liquid crystalline compound contained in the layer of the liquid crystal composition formed on the surface without any special treatment. Therefore, from the viewpoint of reducing the number of steps and efficiently advancing the production of the liquid crystal cured film, it is preferable not to rub the surface of the first cured layer.

After forming the second cured layer, a step of further forming an arbitrary unit cured layer on the second cured layer may be performed.

The liquid crystal cured film including the liquid crystal cured layer can be manufactured by the manufacturing method described above. In this manufacturing method, usually, a liquid crystal cured film including a substrate and a liquid crystal cured layer formed on the supporting surface of the substrate is obtained.

The above-mentioned manufacturing method may include a step of peeling the base material. In this case, the liquid crystal cured layer itself can be used as a liquid crystal cured film.

Furthermore, the method for producing a liquid crystal cured film may include, for example, a step of transferring a liquid crystal cured layer formed on a base material to an arbitrary film layer. Therefore, for example, the method for producing a liquid crystal cured film, after laminating the liquid crystal cured layer formed on the substrate and any film layer, the substrate is peeled off if necessary, and the liquid crystal cured layer and It may include a step of obtaining a liquid crystal cured film including an optional film layer. At this time, an appropriate pressure-sensitive adhesive or adhesive may be used for bonding.

Further, the method for producing a liquid crystal cured film may include a step of further forming an arbitrary layer on the liquid crystal cured layer, for example.

Further, the method for producing a liquid crystal cured film may include, for example, a step of drying the liquid crystal composition layer before the step (iii) of curing the liquid crystal composition layer. Such drying can be achieved by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying. By such drying, the solvent can be removed from the layer of the liquid crystal composition.

According to the manufacturing method as described above, a long liquid crystal cured film can be obtained using a long substrate. Such a long-sized liquid crystal cured film can be continuously manufactured and is excellent in productivity. In addition, since the long liquid crystal cured film can be attached to another film by roll-to-roll, the productivity is excellent also in this respect. Usually, a long liquid crystal cured film is wound up and stored and transported in a roll state.

[10. Polarizer]
A polarizing plate can be manufactured by using the above-mentioned liquid crystal cured film. This polarizing plate can be usually manufactured by a manufacturing method including a step of manufacturing a liquid crystal cured film by the manufacturing method described above and a step of laminating the liquid crystal cured film and a linear polarizer.

The polarizing plate thus obtained contains a liquid crystal cured film and a linear polarizer. It is preferable that this polarizing plate can function as a circular polarizing plate or an elliptically polarizing plate. By providing such a polarizing plate in the organic EL display device, reflection of external light can be suppressed on the display surface of the organic EL display device. In particular, in the above-mentioned liquid crystal cured layer, the birefringence can be appropriately adjusted not only in the in-plane direction but also in the thickness direction by appropriately adjusting the tilt angle of the molecules of the liquid crystal compound. Therefore, the polarizing plate including the liquid crystal cured layer can suppress reflection of external light not only in the front direction of the display surface of the organic EL display device but also in the tilt direction. Therefore, by using this polarizing plate, an organic EL display device having a wide viewing angle can be realized. Further, since the above-mentioned liquid crystal cured layer can suppress the alignment unevenness and the disturbance of the polarization state of transmitted light, the polarizing plate provided with the liquid crystal cured film including the liquid crystal cured layer is effective in both the front direction and the tilt direction. It is possible to suppress reflection.

As the linear polarizer, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and then uniaxially stretching it in a boric acid bath; adsorbing the iodine or dichroic dye on the polyvinyl alcohol film And a film obtained by modifying a part of polyvinyl alcohol units in the molecular chain into polyvinylene units. Further, other examples of the linear polarizer include a polarizer having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer and a multilayer polarizer. Among these, as the linear polarizer, a polarizer containing polyvinyl alcohol is preferable.

When natural light is incident on the linear polarizer, only one polarized light is transmitted. The degree of polarization of this linear polarizer is not particularly limited, but is preferably 98% or more, more preferably 99% or more.
The thickness of the linear polarizer is preferably 5 μm to 80 μm.

When the polarizing plate is desired to function as a circularly polarizing plate, the angle formed by the slow axis of the liquid crystal cured layer with respect to the polarization absorption axis of the linear polarizer is preferably 45° or close thereto. The angle is specifically preferably 45°±5° (ie preferably 40°-50°), more preferably 45°±4° (ie more preferably 41°-49°), It is particularly preferably 45°±3° (that is, particularly preferably 42° to 48°).

The polarizing plate may include an arbitrary layer in combination with the linear polarizer and the liquid crystal cured layer. Examples of the optional layer include an adhesive layer for bonding the linear polarizer and the liquid crystal cured layer; a polarizer protective film layer for protecting the linear polarizer.

[11. Organic EL display device]
An organic EL display device can be manufactured by using the above-mentioned polarizing plate. This organic EL display device can be usually manufactured by a manufacturing method including manufacturing a polarizing plate by the above-described manufacturing method.

This organic EL display device includes the above-mentioned polarizing plate. An organic EL display device usually includes an organic EL element as a display element, and a polarizing plate is provided on the viewing side of this organic EL element. The polarizing plate includes a liquid crystal cured film and a linear polarizer in this order from the organic EL element side. And in such a structure, the said polarizing plate can function as an antireflection film.

Below, the mechanism of reflection suppression will be explained by taking the case where the polarizing plate functions as a circularly polarizing plate as an example. Light incident from the outside of the device becomes circularly polarized light because only part of the linearly polarized light passes through the linear polarizer and then it passes through the liquid crystal curing layer. Circularly polarized light is reflected by a component that reflects light in the display device (a reflective electrode of an organic EL element, etc.) and passes through the liquid crystal cured layer again, so that the vibration direction orthogonal to the vibration direction of the incident linearly polarized light is changed. It becomes the linearly polarized light that it has and does not pass through the linear polarizer. Thereby, the function of suppressing reflection is achieved. For the principle of such reflection suppression, refer to Japanese Patent Application Laid-Open No. 9-127885.

The organic EL element is usually provided with a transparent electrode layer, a light emitting layer and an electrode layer in this order, and the light emitting layer can generate light when a voltage is applied from the transparent electrode layer and the electrode layer. Examples of the material forming 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 certain dye layer is doped with different dyes. Furthermore, the organic EL device 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.

The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples shown below, and may be implemented by being arbitrarily modified within the scope of the claims of the present invention and the scope of equivalents thereof. In the following description, "%" and "parts" representing amounts are by weight unless otherwise specified. Unless otherwise specified, the operations described below were performed in normal temperature and normal pressure atmosphere.

[Method of measuring thickness]
In the following examples and comparative examples, the layer thickness was measured using a film thickness meter (“F-20” manufactured by Filmetrix).

[Explanation of Liquid Crystalline Compound]
The molecular structures of the reverse dispersion liquid crystalline compounds (LA) to (LC) used in the following Examples and Comparative Examples are as follows.

[Explanation of chiral compounds]
In the following examples and comparative examples, "LC756" manufactured by BASF Corporation was used as the chiral compound (C-X).
A compound having the following molecular structure was used as the chiral compound (CY). In the formula below, Me represents a methyl group. The HLC of the chiral compound (C—X) “LC756” manufactured by BASF and the chiral compound (C—Y) are 20 or more and 200 or less, respectively.

[Examples and Comparative Examples]
(Preparation of liquid crystal composition)
100 parts by weight of a reverse dispersion liquid crystalline compound of the type shown in Table 1 below, 0.15 parts by weight of a fluorosurfactant ("S420" manufactured by AGC Seimi Chemical Co., log P=5.3), and shown in Table 1 below. Type and amount of chiral compound, 4.0 parts by weight of photopolymerization initiator (“NCI-730” manufactured by ADEKA), 162.3 parts by weight of cyclopentanone as a solvent, and 243.5 parts by weight of 1,3-dioxolane. And parts were mixed to obtain a liquid crystal composition.

(Preparation of base film)
As a base film, a resin film (“Zeonor film” manufactured by Nippon Zeon Co., Ltd.; thickness 100 μm) made of a thermoplastic norbornene resin having a masking film attached to one surface was prepared. Since this substrate film was an optically isotropic film, it does not affect the measurement results of the retardations LRe, CRe and R(θ) of the liquid crystal cured layer described later. The masking film was peeled off from this substrate film, and the masking peeled surface was subjected to corona treatment. Then, the corona-treated surface was subjected to rubbing treatment.

(Formation of first cured layer)
The liquid crystal composition was applied to the rubbing-treated surface of the base film using a #2 or #3 wire bar to form a layer of the liquid crystal composition.
Then, the layer of the liquid crystal composition was heated at 110° C. for 4 minutes to perform alignment treatment. The alignment temperature in this alignment treatment was the same as the temperature condition under which the residual viscosity of the test compositions corresponding to the liquid crystal compositions of the respective Examples and Comparative Examples was 800 cP or less. By this alignment treatment, the reverse dispersion liquid crystal compound contained in the layer of the liquid crystal composition was aligned.
The layer of the liquid crystal composition that has been subjected to the alignment treatment is irradiated with 500 mJ/cm ² of ultraviolet rays in a nitrogen atmosphere to cure the layer of the liquid crystal composition, and the first cured layer having the thickness shown in Table 1 below. Formed. Thereby, an intermediate film having a layer structure of the first cured layer/base film was obtained.

(Formation of liquid crystal cured layer)
The liquid crystal composition was further applied to the surface of the first cured layer of the intermediate film using a #3 or #6 wire bar to form a layer of the liquid crystal composition.
Then, the layer of the liquid crystal composition was heated at 110° C. for 4 minutes to perform alignment treatment. By this alignment treatment, the reverse dispersion liquid crystal compound contained in the layer of the liquid crystal composition was aligned.
The liquid crystal composition layer that had been subjected to the alignment treatment was irradiated with 1000 mJ/cm ² of ultraviolet light in a nitrogen atmosphere to cure the liquid crystal composition layer to form a second cured layer. Thus, a liquid crystal cured layer having a thickness shown in Table 1 was obtained as a layer including the first cured layer and the second cured layer. Thus, a liquid crystal cured film having a layer structure of liquid crystal cured layer/base film was obtained.

(Confirmation of tilt orientation of the reverse dispersion liquid crystalline compound contained in the liquid crystal cured layer)
FIG. 6 is a perspective view for explaining the measurement direction when measuring the linearly polarized light phase difference R(θ) as the retardation of the liquid crystal cured layer 400 from the tilt direction. In FIG. 6, an arrow A1 represents an in-plane slow axis of the liquid crystal cured layer 400, an arrow A2 represents an in-plane fast axis of the liquid crystal cured layer 400, and an arrow A3 represents a thickness direction of the liquid crystal cured layer 400. ..

The liquid crystal cured film was set on a retarder ("AxoScan" manufactured by Axometrics). The liquid crystal cured film is rotated about the fast axis A2 of the liquid crystal cured layer 400 as a rotation axis, and as shown in FIG. 6, the linear polarization phase difference R(θ) of the liquid crystal cured layer 400 is measured at an incident angle θ of −50°. It was measured in the range of ˜50°. Therefore, the measurement direction A4 is set to be perpendicular to the fast axis A2 of the liquid crystal cured layer 400. The measurement wavelength was 590 nm.

The linear polarization phase difference R(θ) of the liquid crystal cured layer measured at an incident angle θ of −50° to 50° is defined as the linear polarization phase difference R(0°) of the liquid crystal cured layer at an incident angle of 0°. It was divided to obtain the retardation ratio R(θ)/R(0°). A graph was drawn with the determined retardation ratio R(θ)/R(0°) as the vertical axis and the incident angle θ as the horizontal axis.
When the obtained graph of retardation ratio R(θ)/R(0°) is asymmetric with respect to θ=0°, at least some of the molecules of the reverse dispersion liquid crystalline compound contained in the liquid crystal cured layer are liquid crystals. It can be determined that the layer is inclined with respect to the layer plane of the hardened layer. When the graph of retardation ratio R(θ)/R(0°) is symmetric with respect to θ=0°, all the molecules of the reverse dispersion liquid crystalline compound contained in the liquid crystal cured layer are in the liquid crystal cured layer. It can be determined to be parallel or perpendicular to the layer plane.

As a result of the measurement, the graph of the retardation ratio R(θ)/R(0°) was asymmetric with respect to θ=0° in any of the examples and the comparative examples. Therefore, it was determined that at least some of the molecules of the reverse dispersion liquid crystalline compound contained in the liquid crystal cured layer were tilted with respect to the layer plane of the liquid crystal cured layer.

(Measurement of actual maximum tilt angle)
From the linearly polarized light phase difference R(θ) measured in the above (confirmation of the tilt orientation of the inverse dispersion liquid crystalline compound contained in the liquid crystal cured layer), the analysis software attached to the above retarder (Axometrics The analysis software “Multi-Layer Analysis”; analysis conditions were an analysis wavelength of 590 nm and the number of layer divisions was 20).

(Measurement of in-plane retardation LRe and optical retardation CRe)
An in-plane retardation LRe and an optical rotation retardation CRe of the liquid crystal cured layer were measured using a retardation meter (“Axoscan” manufactured by Axometrix). The measurement wavelength was 550 nm.

(Confirmation of reverse wavelength dispersion)
The in-plane retardations LRe (450) and LRe (550) at the measurement wavelengths of 450 nm and 550 nm of the liquid crystal cured layer of the liquid crystal cured film were measured using a retardation meter (“AxoScan” manufactured by Axometrics). As a result of the measurement, LRe(450)/LRe(550)<0.9 was established in all Examples and Comparative Examples.

(Evaluation of surface condition of liquid crystal cured layer)
The liquid crystal cured layer of the liquid crystal cured film was observed using a polarization microscope. In the observed image, the amount of alignment unevenness was evaluated. In the above Examples and Comparative Examples, the alignment unevenness is usually caused by the formation of a portion in which the orientation directions of the molecules of the reverse dispersion liquid crystalline compound are non-uniform. Therefore, it can be determined that the smaller the orientation unevenness, the more uniform the orientation directions of the molecules of the reverse dispersion liquid crystalline compound and the better the surface state. Therefore, the surface condition of the liquid crystal cured layer was evaluated on the basis of the amount of alignment unevenness according to the following criteria.
“Good”: No alignment unevenness or slight alignment unevenness.
"Poor": uneven alignment.

(Evaluation of extinction)
Two sheets of linearly polarizing film were prepared and laminated so as to form a crossed Nicol. Then, a liquid crystal cured film was placed between the linearly polarized films. The liquid crystal cured film was rotated around the axis in the thickness direction, and the orientation of the liquid crystal cured film was adjusted to the extinction position. Here, the extinction position refers to the orientation of the liquid crystal cured film that minimizes the amount of transmitted light that is transmitted through the one linearly polarized film, the liquid crystal cured film, and the other linearly polarized film in this order in the thickness direction.

In this state, the transmitted light was observed, and "light leakage" as a phenomenon in which the transmitted light was visually recognized was evaluated. In the above Examples and Comparative Examples, light leakage is usually caused by linearly polarized light transmitted through the liquid crystal cured layer due to the twist pitch in the orientation direction of the molecules of the reverse dispersion liquid crystalline compound contained in the liquid crystal cured layer being too short. It is caused by the disordered polarization state. That is, when light is incident on the liquid crystal cured layer, some of the polarized light becomes elliptically polarized light or depolarized light when polarized light is incident on the liquid crystal cured layer, and part or all of it is linear. It is generated by passing through a polarizing film. The light leakage was evaluated according to the following criteria.
“Good”: No light leakage.
"OK": There is a slight light leakage.
"Poor": There is light leakage.

[result]
The results of the above Examples and Comparative Examples are shown in Table 1 below. In the table below, the meanings of the abbreviations are as follows.
Θ: Substantially maximum tilt angle of the liquid crystal cured layer.
LRe: In-plane retardation of the liquid crystal cured layer.
CRe: Optical retardation of the cured liquid crystal layer.
XRe: Parameter defined by equation (2).

100 Liquid Crystal Layer 110 Linear Polarizer 120 Linear Polarizer 200 Liquid Crystal Curing Layer 300 Liquid Crystal Curing Layer 310 First Curing Layer 320 Second Curing Layer 400 Liquid Crystal Curing Layer

Claims

A liquid crystal compound, and, formed of a cured product of a liquid crystal composition containing a chiral compound containing an asymmetric carbon atom, a liquid crystal cured layer containing a molecule of the liquid crystal compound which may have a fixed alignment state,
At least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer,
A liquid crystal cured film in which the front linearly polarized light retardation LRe and the front circularly polarized light retardation CRe of the liquid crystal cured layer at a measurement wavelength of 550 nm satisfy the following formula (1).
The ratio CRe/D between the front circularly polarized light phase difference CRe of the liquid crystal cured layer and the thickness D [nm] of the liquid crystal cured layer at a measurement wavelength of 550 nm is 0.0002 or more and 0.0133 or less. Liquid crystal cured film.
The liquid crystal cured film according to claim 1 or 2, wherein the amount of the chiral compound is 0.05 parts by weight or more and 0.5 parts by weight or less based on 100 parts by weight of the liquid crystal compound.
The liquid crystal cure according to any one of claims 1 to 3, wherein a front linear polarization phase difference LRe of the liquid crystal cured layer at a measurement wavelength of 550 nm is in a range of 50 nm to 90 nm, or 120 nm to 160 nm. the film.
The liquid crystal cured film according to any one of claims 1 to 4, wherein the liquid crystal compound is capable of exhibiting birefringence of reverse wavelength dispersion.
The liquid crystal cured film according to any one of claims 1 to 5, wherein the liquid crystalline compound has a benzothiazole ring.
The method for producing a liquid crystal cured film according to any one of claims 1 to 6, comprising:
A step of forming a layer of the liquid crystal composition,
A step of orienting the liquid crystalline compound contained in the layer of the liquid crystal composition,
And a step of curing the layer of the liquid crystal composition to obtain the liquid crystal cured layer.