JP7081660B2 - Liquid crystal cured film and its manufacturing method, first cured layer, polarizing plate, and organic electroluminescence display device - Google Patents

Description

The present invention relates to a liquid crystal cured film and a method for producing the same, a first cured layer, a polarizing plate, and an organic electroluminescence display device.

A liquid crystal curing film is known as one of the optical films. The liquid crystal curing film generally includes a liquid crystal curing layer formed of a cured product obtained by orienting a liquid crystal composition containing a liquid crystal compound and curing the liquid crystal composition while maintaining the oriented state. As such a liquid crystal curing film, the one described in Patent Document 1 has been proposed.

Japanese Patent No. 5363022

The liquid crystal cured layer included in the liquid crystal cured film usually contains a liquid crystal compound. The molecules of this liquid crystal compound may be inclined with respect to the layer plane of the liquid crystal cured layer. When a liquid crystal curing film provided with a liquid crystal curing layer containing a liquid crystal compound having an inclined molecule is provided in an image display device, the inclination angle of the molecule of the liquid crystal compound is adjusted in order to adjust optical characteristics such as viewing angle characteristics. It is desirable to adjust properly.

For example, an organic electroluminescence display device (hereinafter, may be appropriately referred to as an "organic EL display device") has a circular polarizing plate and an elliptical plate as a reflection suppressing film for suppressing reflection of external light on the display surface thereof. A polarizing plate such as a polarizing plate may be provided. This polarizing plate usually includes a linear polarizing element and a retardation film in combination. From the viewpoint of suppressing reflection when the display surface is viewed from an inclined direction and obtaining excellent viewing angle characteristics, it is preferable to adjust birefringence in the thickness direction of the retardation film. Therefore, in order to realize a retardation film having appropriate birefringence in the thickness direction, the present inventors have developed a liquid crystal curing film provided with a liquid crystal curing layer in which the inclination angle of the molecules of the liquid crystal compound is appropriately adjusted. I tried.

Further, in order to exert a desired optical function in a wide wavelength range, it is desired that the retardation film has an in-plane retardation of anti-wavelength dispersibility. Therefore, when a liquid crystal cured layer is used as the retardation film, it is desirable to use a liquid crystal compound having a reverse wavelength dispersive birefringence (hereinafter, may be appropriately referred to as “reverse dispersion liquid crystal compound”). ..

However, with the conventional technique, it has been difficult to increase the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer.

The present invention has been devised in view of the above problems, and is a liquid crystal curing film provided with a liquid crystal curing layer capable of increasing the tilt angle of the molecules of the back-dispersed liquid crystal compound; a method for producing the same; molecules of the back-dispersed liquid crystal compound. A first cured layer capable of producing a liquid crystal cured layer capable of increasing the tilt angle of The purpose is to provide the device;

The present inventor has diligently studied to solve the above-mentioned problems. As a result, the present inventor uses a reverse-dispersion liquid crystal compound having a predetermined birefringence to form a first cured layer satisfying a predetermined requirement and a second cured layer in direct contact with the first cured layer. The present invention has been completed by finding that the tilt angle of the molecules of the back-dispersed liquid crystal compound can be increased as a whole of the liquid crystal cured layer when the liquid crystal cured layer containing the liquid crystal cured layer is formed. That is, the present invention includes the following.

[1] A liquid crystal cured layer containing a molecule of the liquid crystal compound which is formed of a cured product of a liquid crystal composition containing a liquid crystal compound having birefringence of reverse wavelength dispersibility and whose orientation state may be fixed may be provided. ,
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
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 liquid crystal cured layer includes a first cured layer and a second cured layer in direct contact with the first cured layer.
A liquid crystal curing film in which the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the first cured layer.
[2] The liquid crystal curing film according to [1], wherein the liquid crystal compound is represented by the following formula (I) or formula (II).

(In the above formulas (I) and (II),
Ga represents ^a divalent organic group having 1 to 30 carbon atoms which may have a substituent.
Y ^a is a chemical single bond, -O-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O). -O-, -C (= O) -S-, -SC (= O)-, -NR ¹² -C (= O)-, -C (= O) -NR ^12- , -OC (= O) -NR ^12- , -NR ¹² -C (= O) -O-, -S-, -N = N-, or -C≡C-. R ¹² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Fx ¹ and Fx ² each independently represent an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
^{RI, R II ,} R ^III and R ^IV each independently have a hydrogen atom; a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; at least one hydrogen atom is replaced with a halogen atom. An alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 6 carbon atoms; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ; show. Ra may have an alkyl group having 1 to 20 carbon atoms which may have ^a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It represents a cycloalkyl group having a number of 3 to 12, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. At least one of CR ^I , CR ^II , CR ^III and CR ^IV may be replaced with a nitrogen atom.
Each R ⁰ is independently a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is replaced with a halogen atom; 1 to 6 alkoxy groups; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ;.
p represents an integer of 0 to 3.
p1 represents an integer of 0 to 4.
p2 represents 0 or 1.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are independently chemically single bonds, -O-, -O-CH _2- , -CH ₂ respectively. -O-, -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹³ -C (= O)-, -C (= O) -NR ^13- , -CF ₂ -O-, -O-CF _2- , -CH ₂ -CH _2- , -CF ₂ -CF _2- , -O-CH ₂ -CH ₂ -O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _{2-, -CH 2 -} O- C (= O)-, -C (= O) -O-CH _2- , -CH ₂ -CH ₂ -C (= O) -O-, -OC (= O) -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC (= O)-, -C (= O) -O-CH ₂ -CH _2- , -CH = CH-, -N = CH-, -CH = N -, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C-. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ¹ , A ² , B ¹ and B ² each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
G ¹ and G ² are divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may independently have a substituent; and 3 carbon atoms which may have a substituent. At least one of -CH _2- contained in ~ 30 divalent aliphatic hydrocarbon groups is -O-, -S-, -OC (= O)-, -C (= O) -O-. , -OC (= O) -O-, -NR ¹⁴ -C (= O)-, -C (= O) -NR ^14- , -NR ^14- , or -C (= O)- Represents any organic group selected from the group consisting of substituted groups (except when two or more -O- or -S- are adjacent to each other and intervening); R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ¹ and P ² each represent an alkenyl group having 2 to 10 carbon atoms, which may be independently substituted with a halogen atom or a methyl group.
m and n independently represent 0 or 1, respectively. )
[3] A first cured layer containing a molecule of the liquid crystal compound which is formed of a cured product of a liquid crystal composition containing a liquid crystal compound having a birefringence of reverse wavelength dispersibility and whose orientation state may be fixed. There,
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
At least a part of the molecules of the liquid crystal compound contained in the first cured layer are inclined with respect to the layer plane of the first cured layer.
The first cured layer having an in-plane retardation of 20 nm or more and less than 80 nm at a measurement wavelength of 590 nm.
[4] The liquid crystal curing film according to [1] or [2], wherein the first cured layer can function as an alignment film for increasing the inclination angle of the molecules of the liquid crystal compound contained in the second cured layer.
[5] The item according to any one of [1], [2] and [4], wherein the substantially maximum inclination angle of the molecule of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° or more and 85 ° or less. LCD curable film.
[6] The liquid crystal curing film according to any one of [1], [2], [4] and [5], wherein the liquid crystal curing layer has a thickness of 10 μm or less.
[7] The liquid crystal curing film according to any one of [1], [2] and [4] to [6], wherein the liquid crystal curing layer can function as a 1/4 wave plate.
[8] The method for producing a liquid crystal cured film according to any one of [1], [2] and [4] to [7].
A step of forming a layer of the first liquid crystal composition containing the liquid crystal compound, and
A step of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition,
The step of curing the layer of the first liquid crystal composition to form the first cured layer,
A step of directly forming a layer of a second liquid crystal composition containing the same or different liquid crystal compound as the liquid crystal compound contained in the first liquid crystal composition on the first cured layer.
A step of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition,
A method for producing a liquid crystal cured film, which comprises a step of curing a layer of the second liquid crystal composition to form a second cured layer.
[9] A liquid crystal cured layer containing a molecule of the liquid crystal compound which is formed of a cured product of a liquid crystal composition containing a liquid crystal compound having birefringence of reverse wavelength dispersibility and whose orientation state may be fixed. Including with a linear deflector
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
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 liquid crystal cured layer includes a first cured layer and a second cured layer in direct contact with the first cured layer.
A polarizing plate in which the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the first cured layer.
[10] An organic electroluminescence display device including the polarizing plate according to [9].

According to the present invention, a liquid crystal curing film provided with a liquid crystal curing layer capable of increasing the tilt angle of the molecules of the back-dispersed liquid crystal compound and a method for producing the same; a liquid crystal cured layer capable of increasing the tilt angle of the molecules of the back-dispersed liquid crystal compound. It is possible to provide a first cured layer that can be produced; a polarizing plate having a liquid crystal cured layer capable of increasing the inclination angle of a molecule of a reverse-dispersed liquid crystal compound; and an organic EL display device including the above-mentioned polarizing plate.

FIG. 1 is a cross-sectional view schematically showing a liquid crystal cured film according to an embodiment of the present invention. FIG. 2 is a graph in which the retardation ratio R (θ) / R (0 °) of the liquid crystal cured layer according to a certain example is plotted against the incident angle θ. FIG. 3 is a cross-sectional view schematically showing a liquid crystal cured film according to another embodiment of the present invention. FIG. 4 is a perspective view for explaining the measurement direction when measuring the retardation of the first cured layer from the inclined direction.

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

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

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

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

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

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

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

In the following description, unless otherwise specified, "(meth) acrylic acid" is a term that includes "acrylic acid", "methacrylic acid" and combinations thereof, and "(meth) acryloyl group" is a term. A term that includes "acryloyl group", "methacrylic acid group" and combinations thereof.

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

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

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

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

In the following description, unless otherwise specified, the "tilt angle" of the molecules of the liquid crystal compound contained in a certain layer represents the angle formed by the molecules of the liquid crystal compound with respect to the layer plane of the layer, and is "tilt". 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 molecule of the liquid crystal compound. Further, in the following description, unless otherwise specified, the "tilt angle" represents the tilt angle of the molecule of the liquid crystal compound with respect to the layer plane of the layer containing the liquid crystal compound.

In the following description, the "substantially maximum tilt angle" of the molecule of the liquid crystal compound contained in a certain layer is that the tilt angle of the molecule on one surface of the layer is 0 ° and the tilt angle of the molecule is the thickness. It refers to the maximum value of the tilt angle of the molecule of the liquid crystal compound, assuming that it changes at a constant rate in the direction. Specifically, consider a case where the inclination angle of the molecule of the liquid crystal compound is smaller as it is closer to one side of the layer and larger as it is farther from the one side in the thickness direction of the layer containing the liquid crystal compound. The effective maximum tilt angle is calculated on the assumption that the rate of change in the tilt angle in the thickness direction (that is, the rate of change that decreases as it is closer to one side and increases as it is farther from one side) is constant. Represents the maximum value of the tilt angle.

[1. Overview of LCD curable film]
FIG. 1 is a cross-sectional view schematically showing a liquid crystal cured film 10 according to an embodiment of the present invention. As shown in FIG. 1, the liquid crystal cured film 10 according to the embodiment of the present invention is a film containing a liquid crystal cured layer 100 formed of a cured product of a liquid crystal composition containing a back-dispersed liquid crystal compound.

Since it is formed of a cured product of the liquid crystal composition, the liquid crystal cured layer 100 contains molecules of a reverse-dispersed liquid crystal compound. The molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer 100 may have a fixed orientation. The term "reverse-dispersed liquid crystal compound having a fixed orientation state" includes a polymer of the reverse-dispersed liquid crystal compound. Normally, the liquid crystal property of the back-dispersed liquid crystal compound is lost by polymerization, but in the present application, the back-dispersed liquid crystal compound thus polymerized is also included in the term “back-dispersed liquid crystal compound contained in the liquid crystal cured layer”.

At least a part of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer 100 are inclined with respect to the layer plane of the liquid crystal cured layer 100. When a molecule of a liquid crystal compound is "tilted" with respect to a layer plane, it means that the inclination angle of the molecule with respect to the layer plane is in the range of 5 ° or more and 85 ° or less. Molecules of such an inclined liquid crystal compound are usually in a state of being neither parallel nor perpendicular to the layer plane.

Further, the liquid crystal display cured layer 100 includes a first cured layer 110 and a second cured layer 120 that is in direct contact with the first cured layer 110. When two layers are in contact "directly", it means that there is no other layer between these two layers. The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer.

The substantially maximum tilt angle is an index indicating the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in a certain layer. Generally, the larger the substantially maximum tilt angle, the larger the tilt angle as a whole of the molecules of the liquid crystal compound contained in the layer tends to be. In the present embodiment, the first cured layer 110 can function as an alignment film that increases the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer 120. The fact that the first cured layer 110 functions as an alignment film in this way means that the first cured layer 110 contains the substantially maximum inclination angle of the molecules of the reverse-dispersed liquid crystal compound contained in the second cured layer 120. It appears to be larger than the effective maximum tilt angle of the molecule of the compound. By the action of the first cured layer 110, the inclination angle of the molecules of the back-dispersed liquid crystal compound contained in the second cured layer 120 can be increased, so that the first cured layer 110 and the second cured layer 120 are included. The tilt angle of the molecules of the back-dispersed liquid crystal compound as a whole of the liquid crystal cured layer 100 can be increased.

Further, in the present embodiment, as the back-dispersion liquid crystal compound for forming the liquid crystal curing layer 100 as described above, a back-dispersion liquid crystal compound having a birefringence Δn in a predetermined range is used. By using such a back-dispersed liquid crystal compound having birefringence Δn, the inclination angle of the molecule of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer 100 with respect to the layer plane is increased as a whole of the liquid crystal cured layer 100. be able to.

[2. Reverse dispersion liquid crystal compound]
The reverse-dispersed liquid crystal compound is a compound having a liquid crystal property, and is usually a compound capable of exhibiting a liquid crystal phase when the reverse-dispersed liquid crystal compound is oriented.

Further, the reverse dispersion liquid crystal compound is a liquid crystal compound having a reverse wavelength dispersive birefringence as described above. A liquid crystal compound having a reverse wavelength dispersible birefringence is a liquid crystal compound that exhibits a reverse wavelength dispersive birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. Refers to a compound. Usually, when the liquid crystal compound is homogenically oriented, the liquid crystal compound has the birefringence of the reverse wavelength dispersibility by examining whether the layer of the liquid crystal compound exhibits the birefringence of the reverse wavelength dispersibility. You can check if it is. To homogenize the liquid crystal compound means to form a layer containing the liquid crystal compound, and to set the direction of the maximum refractive index in the refractive index ellipse of the molecule of the liquid crystal compound in the layer to the layer plane of the layer. Orienting in one parallel direction.

The birefringence Δn of the inversely dispersed liquid crystal compound at a measurement wavelength of 590 nm is usually 0.065 or less, preferably 0.064 or less, more preferably 0.063 or less, preferably 0.035 or more, and more preferably 0. It is 040 or more, particularly preferably 0.045 or more. By adopting the birefringence Δn in such a range, the inclination angle of the molecule of the inversely dispersed liquid crystal compound with respect to the layer plane of the liquid crystal cured layer can be increased as a whole of the liquid crystal cured layer.

The birefringence of the inversely dispersed liquid crystal compound can be measured by the following method. A layer containing a reverse-dispersed liquid crystal compound is prepared, and the liquid crystal compound contained in the layer is homogenically oriented. Then, the in-plane retardation of the layer is measured. Then, the birefringence Δn of the inversely dispersed liquid crystal compound can be obtained from “(in-plane lettering of the layer) ÷ (thickness of the layer)”. At this time, in order to facilitate the in-plane retardation and the measurement of the thickness, the layer of the liquid crystal compound homogenically oriented may be cured.
A specific method for measuring birefringence Δn can be carried out by the procedure described in the examples.

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

The inversely dispersed liquid crystal compound may contain an ethylenically unsaturated bond and an aromatic ring in its molecular structure. When the inversely dispersed liquid crystal compound containing an ethylenically unsaturated bond and an aromatic ring is used as described above, it is possible to quantify the progress of the polymerization reaction in the first cured layer by using the measurement of the total reflection absorption spectrum of infrared rays. be.

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

As the back-dispersion liquid crystal compound, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

As the reverse dispersion liquid crystal compound, a compound represented by the following formula (I) or formula (II) is preferable.

(In the above formulas (I) and (II),
Ga represents ^a divalent organic group having 1 to 30 carbon atoms which may have a substituent.
Y ^a is a chemical single bond, -O-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O). -O-, -C (= O) -S-, -SC (= O)-, -NR ¹² -C (= O)-, -C (= O) -NR ^12- , -OC (= O) -NR ^12- , -NR ¹² -C (= O) -O-, -S-, -N = N-, or -C≡C-. R ¹² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Fx ¹ and Fx ² each independently represent an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
^{RI, R II ,} R ^III and R ^IV each independently have a hydrogen atom; a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; at least one hydrogen atom is replaced with a halogen atom. Alkoxy group with 1 to 6 carbon atoms; Alkoxy group with 1 to 6 carbon atoms; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ; show. Ra may have an alkyl group having 1 to 20 carbon atoms which may have ^a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It represents a cycloalkyl group having a number of 3 to 12, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. At least one of CR ^I , CR ^II , CR ^III and CR ^IV may be replaced with a nitrogen atom.
Each R ⁰ is independently a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is replaced with a halogen atom; 1 to 6 alkoxy groups; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ;.
p represents an integer of 0 to 3.
p1 represents an integer of 0 to 4.
p2 represents 0 or 1.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are independently chemically single bonds, -O-, -O-CH _2- , -CH ₂ respectively. -O-, -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹³ -C (= O)-, -C (= O) -NR ^13- , -CF ₂ -O-, -O-CF _2- , -CH ₂ -CH _2- , -CF ₂ -CF _2- , -O-CH ₂ -CH ₂ -O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _{2-, -CH 2 -} O- C (= O)-, -C (= O) -O-CH _2- , -CH ₂ -CH ₂ -C (= O) -O-, -OC (= O) -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC (= O)-, -C (= O) -O-CH ₂ -CH _2- , -CH = CH-, -N = CH-, -CH = N -, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C-. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ¹ , A ² , B ¹ and B ² each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
G ¹ and G ² are divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may independently have a substituent; and 3 carbon atoms which may have a substituent. At least one of -CH _2- contained in ~ 30 divalent aliphatic hydrocarbon groups is -O-, -S-, -OC (= O)-, -C (= O) -O-. , -OC (= O) -O-, -NR ¹⁴ -C (= O)-, -C (= O) -NR ^14- , -NR ^14- , or -C (= O)- Represents any organic group selected from the group consisting of substituted groups (except when two or more -O- or -S- are adjacent to each other and intervening); R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ¹ and P ² each represent an alkenyl group having 2 to 10 carbon atoms, which may be independently substituted with a halogen atom or a methyl group.
m and n independently represent 0 or 1, respectively. )

Hereinafter, the formula (I) and the formula (II) will be described in detail. In the following description of the formulas (I) and (II), the carbon number of the group having a substituent does not include the carbon number of the substituent unless otherwise specified. Therefore, for example, the description of "an alkyl group having 1 to 6 carbon atoms which may have a substituent" indicates that the alkyl group itself, which does not contain the carbon number of the substituent, has 1 to 6 carbon atoms. ..

(About ^Ga )
In the above formulas (I) and (II), Ga represents ^a divalent organic group having 1 to 30 carbon atoms which may have a substituent. Preferably, Ga represents ^a divalent organic group having 3 to 30 carbon atoms which may have a substituent.

Examples of the substituent that the organic group of Ga may have include an alkyl group having 1 to 5 carbon atoms such as ^a methyl group, an ethyl group and a propyl group; a methoxy group, an ethoxy group, a propoxy group and the like. , An alkoxy group having 1 to 5 carbon atoms; a cyano group; a halogen atom such as a fluorine atom and a chlorine atom; The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other. Further, the total number of carbon atoms of ^Ga including the substituent is preferably 1 to 50.

^A preferred first example of Ga is a divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms which may have a substituent.

As ^a preferred second example of Ga, at least one of -CH _2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms which may have a substituent is -O-,. -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹¹ -C (= O)-, -C ( = O) -NR ^11- , -NR ^11- , or a group substituted with -C (= O)-. R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. At least one of these "-CH _2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms is -O-, -S-, -OC (= O)-, -C ( = O) -O-, -OC (= O) -O-, -NR ¹¹ -C (= O)-, -C (= O) -NR ^11- , -NR ^11- , or -C The "group substituted with ( ⁼ O)-" may be appropriately referred to as "substituted aliphatic group (Ga -1)". In this substituted aliphatic group ( ^Ga -1), it is preferable that —O— and —S— do not replace the continuous —CH ₂ − in the aliphatic hydrocarbon group. That is, the substituted aliphatic group (Ga-1) preferably does not contain the structures of —O— and ^—SS— . Therefore, it is preferable to exclude the case where two or more of -O- or -S- are adjacent to each other from the substituted aliphatic group ( ^Ga -1). Further, in the substituted aliphatic group (Ga -1), it is preferable that —C ( ⁼ O) — does not replace the continuous —CH ₂ − in the aliphatic hydrocarbon group. That is, it is preferable that the substituted aliphatic group (Ga-1) does not contain the structure of —C ( ⁼ O) —C (= O) −.

In the preferred first and second examples of Ga, the "divalent aliphatic hydrocarbon group" is preferably ^a divalent chain aliphatic hydrocarbon group, and is preferably an alkylene group. Is more preferable.

In the preferred first example and second example of Ga, the substituent which the divalent aliphatic hydrocarbon group may have includes, for example, ^a methyl group, an ethyl group, a propyl group and the like, and has a carbon number of carbon atoms. Examples thereof include an alkyl group of 1 to 5; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and an isopropoxy group; a cyano group; and a halogen atom such as a fluorine atom and a chlorine atom. The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other.

When the number of carbon atoms of ^Ga is 3 or more, it is preferable that both ends of Ga are ^−CH ₂ −. Therefore, it is preferable that the hydrogen atom bonded to the carbon atom at both ends of Ga is not substituted with ^a substituent.

(About ^Ya )
In the above formulas (I) and (II), Ya is ^a chemical single bond, -O-, -C (= O)-, -C (= O) -O-, -OC ( = O)-, -OC (= O) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹² -C (= O)-, -C (= O) -NR ^12- , -OC (= O) -NR ^12- , -NR ¹² -C (= O) -O-, -S-, -N = N-, or -C≡ Represents C-. R ¹² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(About Fx ¹ and Fx ² )
In the above formulas (I) and (II), Fx ¹ and Fx ² each independently represent an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. The organic groups of Fx ¹ and Fx ² preferably have 2 to 30 carbon atoms, preferably 7 or more, more preferably 8 or more, and particularly preferably 10 or more.

A preferred first example of Fx ¹ and Fx ² is a cyclic group having 2 to 20 carbon atoms, which may have a substituent and has at least one of an aromatic hydrocarbon ring and an aromatic heterocycle. Can be mentioned. When the cyclic group has two or more aromatic hydrocarbon rings, the aromatic hydrocarbon rings may be the same or different. Further, when the cyclic group has two or more aromatic heterocycles, the aromatic heterocycles may be the same or different.

Examples of the aromatic hydrocarbon ring include an aromatic hydrocarbon ring having 6 to 30 carbon atoms such as a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring, and a fluorene ring.

Examples of the aromatic heterocycle include 1H-isoindole-1,3 (2H) -dione ring, 1-benzofuran ring, 2-benzofuran ring, aclydin ring, isoquinoline ring, imidazole ring, indole ring, and oxadiazole ring. , Oxadiazole ring, oxazolopyrazine ring, oxazolopyridine ring, oxazolopyridazine ring, oxazolopyrimidine ring, quinazoline ring, quinoxalin ring, quinoline ring, cinnoline ring, thiadiazole ring, thiazole ring, thiazolopyrazine ring, thiazolopyridine Ring, thiazolopyridazine ring, thiazolopyrimidine ring, thiophene ring, triazine ring, triazole ring, naphthylidine ring, pyrazine ring, pyrazole ring, pyranone ring, pyrane ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrrole ring, phenant Lydin ring, phthalazine ring, furan ring, benzo [b] thiophene ring, benzo [c] thiophene ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazole ring, benzoxadiazole ring, benzoxadiazole ring, benzothiadiazole ring , Benzothiazole ring, dibenzothiophene ring, benzotriazine ring, benzotriazole ring, benzopyrazole ring, benzopyranone ring, xanthene ring and the like, and examples thereof include aromatic heterocycles having 2 to 30 carbon atoms.

Examples of the substituent that the cyclic group may have 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; An alkenyl group having 2 to 6 carbon atoms such as a vinyl group and an allyl group; an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom such as a trifluoromethyl group and a pentafluoroethyl group; N, N-dialkylamino group having 2 to 12 carbon atoms such as dimethylamino group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group and isopropoxy group; nitro group; -OCF ₃ ; -C (= O) -R ^a ; -C (= O) -OR ^a ; -OC (= O) -R ^a ; and the like. These substituents are usually attached to the carbon atoms that make up the aromatic hydrocarbon ring or aromatic heterocycle. Ra may have an alkyl group having 1 to 20 carbon atoms which may have ^a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It represents a cycloalkyl group having a number of 3 to 12, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. The total number of carbon atoms of ^Ra including the substituent is preferably 1 to 50.

The number of substituents contained in the cyclic group may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other.

Examples of the cyclic group include, firstly, a hydrocarbon ring group having at least one aromatic hydrocarbon ring having 6 to 18 carbon atoms and optionally having a substituent having 6 to 20 carbon atoms. .. Specific examples thereof 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), and a fluorenyl group (carbon carbon atoms). Aromatic hydrocarbon ring groups having 6 to 18 carbon atoms, such as number 13); indanyl groups (9 carbon atoms); 1,2,3,4-tetrahydronaphthyl groups (10 carbon atoms); 1,4-dihydronaphthyl Group (10 carbon atoms); Among them, the groups represented by the following formulas (2-1) to (2-21) are preferable. Further, the groups represented by the following formulas (2-1) to (2-21) may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

As an example of the cyclic group, secondly, a substituent having 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 is used. Examples thereof include a heterocyclic group having 2 to 20 carbon atoms which may be possessed. The "aromatic ring" represents a cyclic structure having aromaticity in a broad sense according to Huckel's rule. Therefore, the "aromatic ring" is a cyclic conjugated structure having (4n + 2) π electrons; and a cyclic structure in which isolated electron pairs of heteroatoms such as sulfur, oxygen, and nitrogen are involved in the π-electron system to exhibit aromaticity. (Thiophene ring, furan ring, benzothiazole ring, etc.); Specific examples thereof include a phthalimide group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a frazanyl group, an oxazolyl group, an oxazolopyrazinyl group and an oxazolopyridinyl group. , Oxazolopyridadinyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiadiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridinyl group, thiazolopyrida Ginyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyldinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phenanthridinyl group , Phtalazinyl group, furanyl group, benzo [c] thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzoimidazolyl group, benzoxazolyl group, benzothiasiazolyl group, benzothiazolyl group, benzothiophenyl group, Aromatic heterocyclic groups having 2 to 18 carbon atoms such as benzotriazinyl group, benzotriazolyl group, benzopyrazolyl group, benzopyranonyl group; xanthenyl group; 2,3-dihydroindolyl group; 9,10-dihydro Acridinyl group; 1,2,3,4-tetrahydroquinolyl group; dihydropyranyl group; tetrahydropyranyl group; dihydrofuranyl group; tetrahydrofuranyl group; Among them, the groups represented by the following formulas (3-1) to (3-51) are preferable. The groups represented by the following formulas (3-1) to (3-51) may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

In the above formula, E represents NR ¹⁵ , oxygen atom or sulfur atom. Further, in the above formula, X, Y and Z independently represent NR ¹⁵ , oxygen atom, sulfur atom, -SO- or -SO _2- (where, oxygen atom, sulfur atom,-. Except when SO- and -SO _2- are adjacent to each other). R ¹⁵ 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.

All of the cyclic groups exemplified above may have a substituent. The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other. Examples of these substituents include the same examples as those described above as substituents that the cyclic group may have.

As a preferred second example of Fx ¹ and Fx ² , the above-mentioned cyclic group is substituted with one or more hydrogen atoms and may have a substituent other than the cyclic group, having 1 to 18 carbon atoms. Alkyl group of. That is, as a preferred second example of Fx ¹ and Fx ² , at least one hydrogen atom may have a substituent having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, carbon. Examples thereof include an alkyl group having 1 to 18 carbon atoms, which is substituted with a "cyclic group having a number of 2 to 20" and may have a substituent other than the cyclic group. The above-mentioned substituted alkyl group as a preferable second example of Fx ¹ and Fx ² may be appropriately referred to as "substituted alkyl group (Fx-1)".

In the substituted alkyl group (Fx-1), examples of the alkyl group having 1 to 18 carbon atoms include a methyl group, an ethyl group, a propyl group and an isopropyl group.

In the substituted alkyl group (Fx-1), the aromatic hydrocarbon ring and the aromatic heterocycle contained in the cyclic group substituted with the alkyl group may be directly bonded to the carbon atom of the alkyl group, and may form a linking group. It may be bonded via. Examples of the linking group include -S-, -O-, -C (= O)-, -C (= O) -O-, -OC (= O)-, and -OC (= O). ) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹¹ -C (= O)-, -C (= O) -NR ¹¹ and the like.

Therefore, the cyclic group of the substituted alkyl group (Fx-1) is a group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle, such as a fluorenyl group and a benzothiazolyl group; an aromatic that may be substituted. Group Hydrocarbon Ring Group; Aromatic Complex Ring Group May Be Substituted; A Group Consisting with an Aromatic Hydrocarbon Ring May Be Substituted with a Linking Group; A group consisting of a ring; is included.

Examples of the group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle include the cyclic group described as a preferable first example of Fx ¹ and Fx ² .

Examples of the aromatic hydrocarbon ring group include an aromatic hydrocarbon ring group having 6 to 30 carbon atoms such as a phenyl group, a naphthyl group, an anthrasenyl group, a phenanthrenyl group, a pyrenyl group and a fluorenyl group. The aromatic hydrocarbon ring group exemplified here may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

Examples of the aromatic heterocyclic group include a phthalimide group, a 1-benzofuranyl group, a 2-benzofuranyl group, an acridinyl group, an isoquinolinyl group, an imidazolyl group, an indolinyl group, a frazanyl group, an oxazolyl group, an oxazolopyrazinyl group and an oxazolo. Pyrizinyl group, oxazolopyridadynyl group, oxazolopyrimidinyl group, quinazolinyl group, quinoxalinyl group, quinolyl group, cinnolinyl group, thiathiazolyl group, thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group, thiazolo Pyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyldinyl group, pyrazinyl group, pyrazolyl group, pyranonyl group, pyranyl group, pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phenanthridini Lu group, phthalazinyl group, furanyl group, benzo [c] thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzoimidazolyl group, benzoxadiazolyl group, benzoxazolyl group, benzothia Asiazolyl group, Examples thereof include aromatic heterocyclic groups having 2 to 30 carbon atoms such as a benzothiazolyl group, a benzothienyl group, a benzotriazinyl group, a benzotriazolyl group, a benzopyrazolyl group and a benzopyranonyl group. The aromatic heterocyclic group exemplified here may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

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 include a phenylthio group, a naphthylthio group, an anthrasenylthio group, a phenanthrenylthio group and a pyrenylthio group. , Fluolenylthio group, phenyloxy group, naphthyloxy group, anthrasenyloxy group, phenanthrenyloxy group, pyrenyloxy group, fluorenyloxy group, benzoisoxazolylthio group, benzoisothiazolylthio group, benzooxa Diazolylthio group, benzoxazolylthio group, benzothia zolylthio group, benzothiazolylthio group, benzothienylthio group, benzoisoxazolyloxy group, benzoisothiazolyloxy group, benzoxadiazolyloxy group , Benzoxazolyloxy group, benzothia zolyloxy group, benzothiazolyloxy group, benzothienyloxy group, and the like. The group consisting of an aromatic hydrocarbon ring having a linking group and the group consisting of an aromatic heterocycle having a linking group may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

Preferred examples of the substituted alkyl group (Fx-1) include groups represented by the following formulas (4-1) to (4-11). However, the present invention is not limited to the examples shown below. In the following equation, "-" represents ^a bond with Ya that extends from any position on the ring. The groups represented by the following formulas (4-1) to (4-11) may have a substituent. Examples of the substituent include the same examples as those described above as the substituent that the cyclic group may have.

The total number of π electrons contained in the ring structure in Fx ¹ is preferably 8 or more, more preferably 10 or more, preferably 20 or less, and even more preferably 18 or less. In particular, it is particularly preferable that the total number of π electrons contained in the aromatic hydrocarbon ring and the aromatic heterocycle in Fx ¹ falls within the above range.
The total number of π electrons contained in the ring structure in Fx ² is preferably 4 or more, more preferably 6 or more, preferably 20 or less, and more preferably 18 or less. .. In particular, it is particularly preferable that the total number of π electrons contained in the aromatic hydrocarbon ring and the aromatic heterocycle in Fx ² falls within the above range.

Fx ¹ is preferably any of the following formulas (i-1) to (i-9). Further, Fx ² is preferably any of the following (i-1) to (i-13). The groups represented by the following formulas (i-1) to (i-13) may have a substituent.

Further, it is particularly preferable that Fx ¹ is any of the following formulas (ii-1) to (ii-20). Further, it is particularly preferable that Fx ² is any of the following (ii-1) to (ii-26). The groups represented by the following formulas (ii-1) to (ii-26) may have a substituent.

(About Q)
In the above formulas (I) and (II), Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of the alkyl group having 1 to 6 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group and the like. Examples of the substituent include aromatic hydrocarbon groups having 6 to 18 carbon atoms, such as a phenyl group and a naphthalene group. The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other. The carbon number of Q including the substituent is preferably 50 or less.

(About R ^I to R ^IV )
In the above formulas (I) and (II), ^{RI, R II ,} R ^III and R ^IV are independently hydrogen atoms; halogen atoms such as fluorine atom and chlorine atom; methyl group and ethyl group. , An alkyl group having 1 to 6 carbon atoms such as a propyl group; a cyano group; a nitro group; a trifluoromethyl group, a pentafluoroethyl group, etc. Alkyl group; alkoxy group having 1 to 6 carbon atoms such as methoxy group, ethoxy group, isopropoxy group; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) ) -R ^a ;. ^{RI to RIV may} all be the same or different.

In the above formulas (I) and (II), at least one of CR ^I , CR ^II , CR ^III and CR ^IV constituting the ring is replaced with a nitrogen atom. May be. Specific examples of groups in which at least one of CR ^I to CR ^IV is replaced with a nitrogen atom are shown below. However, the group in which at least one of CR ^I to CR ^IV is replaced with a nitrogen atom is not limited to these.

(About R ⁰ )
In the above formulas (I) and (II), R ⁰ is independently a halogen atom; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, and a propyl group; a cyano group; a nitro group. An alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted with a halogen atom such as a trifluoromethyl group and a pentafluoroethyl group; and an alkyl group having 1 to 6 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group. Alkoxy group; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ;. When there are a plurality of R ^0s , the R ^0s may be the same or different.

(About p, p1 and p2)
In the above equations (I) and (II), p represents an integer of 0 to 3.
In the above formulas (I) and (II), p1 represents an integer of 0 to 4.
In the above formulas (I) and (II), p2 represents 0 or 1.
It is preferable that p, p1 and p2 are all 0.

(About Y ¹ to Y ⁸ )
In the above formulas (I) and (II), Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are independently chemically single bonds, −. O-, -O-CH _2- , -CH ₂ -O-, -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-, -C (= O) -O-, -O- C (= O)-, -OC (= O) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹³ -C (= O)-, -C (= O) -NR ^13- , -CF ₂ -O-, -O-CF _2- , -CH ₂ -CH _2- , -CF ₂ -CF _2- , -O-CH ₂ -CH _2- O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _{2-, -CH 2 -OC (= O)-, -C (= O) -O-CH 2-, -CH 2 -CH 2 - C} (= O) -O-,- OC (= O) -CH ₂ -CH _2- , -CH ₂ -CH ₂ -OC (= O)-, -C (= O) -O-CH ₂ -CH _2- , -CH = Represents CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C- .. Here, R ¹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

(About A ¹ , A ² , B ¹ and B ² )
In the above formulas (I) and (II), A ¹ , A ² , B ¹ and B ² each independently have a cyclic aliphatic group or a substituent which may have a substituent. Represents an aromatic group that may have.

A ¹ , A ² , B ¹ and B ² independently have a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent and a carbon which may have a substituent. Aromatic groups of number 2 to 20 are preferred.

Examples of the cyclic aliphatic group include cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, cycloheptane-1,4-diyl group, cyclooctane-1,5-diyl group and the like. Cycloalkandyl groups having 5 to 20 carbon atoms; bicycloalkandyl groups having 5 to 20 carbon atoms such as decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl group; and the like can be mentioned. .. The cyclic aliphatic group may be a trans form, a cis form, or a mixture of a cis form and a trans form, but a trans form is more preferable.

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

Examples of the substituent that the cyclic aliphatic group and the aromatic group may have include a halogen atom; an alkyl group having 1 to 6 carbon atoms; an alkoxy group having 1 to 5 carbon atoms; a nitro group; a cyano group; and the like. Can be mentioned. The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other. The carbon number of each of A ¹ , A ² , B ¹ and B ² including the substituent is preferably 2 to 50 independently.

(About G ¹ and G ² )
In the above formulas (I) and (II), G ¹ and G ² are independent of each other.
A divalent aliphatic hydrocarbon group having 1 to 30 carbon atoms, which may have a substituent;
At least one of -CH _2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms, which may have a substituent, is -O-, -S-, -OC (=). O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁴ -C (= O)-, -C (= O) -NR ^14- , -NR Group substituted with ¹⁴ -or -C (= O)-(except when two or more -O- or -S- are adjacent to each other);
Represents any organic group selected from the group consisting of. R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

The above-mentioned "at least one of -CH _2- contained in a divalent aliphatic hydrocarbon group having 3 to 30 carbon atoms is -O-, -S-, -OC (= O)-, -C ( = O) -O-, -OC (= O) -O-, -NR ¹⁴ -C (= O)-, -C (= O) -NR ^14- , -NR ^14- , or -C The "group substituted with (= O)-" may be appropriately referred to as "substituted aliphatic group (G-2)". However, in this substituted aliphatic group (G-2), —O— and —S— do not replace the contiguous —CH ₂ − in the aliphatic hydrocarbon group. That is, the substituted aliphatic group (G-2) does not contain the structures of —O— and —SS—. Therefore, from the substituted aliphatic group (G-2), the case where two or more -O- or -S- are adjacent to each other is excluded. Further, in the substituted aliphatic group (G-2), it is preferable that —C (= O) — does not replace the continuous —CH ₂ − in the aliphatic hydrocarbon group. That is, it is preferable that the substituted aliphatic group (G-2) does not contain the structure of —C (= O) —C (= O) −.

When the number of carbon atoms of G ¹ is 3 or more, it is preferable that both ends of G ¹ are −CH ₂ −. Further, when the number of carbon atoms of G ² is 3 or more, it is preferable that both ends of G ² are −CH ₂ −. Therefore, when G ¹ and G ² each have 3 or more carbon atoms independently, the hydrogen atom bonded to the carbon atom at both ends of G ¹ and G ² is not substituted with a substituent. preferable.

G ¹ and G ² are independently contained in a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms; and a divalent aliphatic hydrocarbon group having 3 to 18 carbon atoms-CH _2- . At least one of is -O-, -S-, -OC (= O)-, -C (= O) -O-, -OC (= O) -O-, -NR ¹⁴ -C. Any organic group selected from the group consisting of (= O)-, -C (= O) -NR ^14- , -NR ^14- , or -C (= O)-substituted group; Is preferable.

G ¹ and G ² are independently contained in a divalent aliphatic hydrocarbon group having 1 to 18 carbon atoms; and a divalent aliphatic hydrocarbon group having 3 to 18 carbon atoms-CH _2- . At least one of the groups substituted with -O-, -S-, -OC (= O)-, -C (= O) -O-, or -C (= O)-); It is more preferable that it is any organic group selected from the group.

It is particularly preferable that G ¹ and G ² are independently alkylene groups having 1 to 18 carbon atoms.

As described above, the divalent aliphatic hydrocarbon group and the substituted aliphatic group (G-2) may have a substituent. Therefore, the hydrogen atom contained in the divalent aliphatic hydrocarbon group and the substituted aliphatic group (G-2) may be substituted with the substituent. Examples of the substituent include an alkyl group having 1 to 5 carbon atoms such as a methyl group, an ethyl group and a propyl group; an alkoxy group having 1 to 5 carbon atoms such as a methoxy group, an ethoxy group and a propoxy group; a cyano group. Halogen atoms such as fluorine atom and chlorine atom; The number of substituents may be 1 or 2 or more. Further, the two or more substituents may be the same or different from each other. The carbon number of each of G ¹ and G ² including the substituent is preferably 1 to 50 independently.

(About P ¹ and P ² )
In the above formulas (I) and (II), P ¹ and P ² each represent an alkenyl group having 2 to 10 carbon atoms, which may be independently substituted with a halogen atom or a methyl group. Examples of the alkenyl group having 2 to 10 carbon atoms include a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, an isobutenyl group, a pentanyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group and a decenyl group. ..

(About m and n)
In the above formulas (I) and (II), m and n independently represent 0 or 1, respectively. It is preferable that m and n are independently and 1 respectively.

When both m and n are 1, it is preferable that B ¹ and B ² in the above-mentioned formula (I) are cyclic aliphatic groups which may independently have a substituent. It is more preferably a cyclic aliphatic group having 5 to 20 carbon atoms which may have a substituent.

The compound represented by the above formula (I) or formula (II) can be synthesized by combining known synthetic reactions. That is, various documents (for example, International Publication No. 2012/141245, International Publication No. 2012/147904, International Publication No. 2014/010325, International Publication No. 2013/046781, International Publication No. 2014/061709, International Publication No. 2014/126113, International Publication 2015/06498, International Publication No. 2015-140302, International Publication No. 2015/129654, International Publication No. 2015/141784, International Publication No. 2016/159193, International Publication No. 2012 It can be synthesized by referring to the method described in / 169424, International Publication No. 2012/176679, International Publication No. 2015/122385, etc.).

[3. Liquid crystal composition]
The liquid crystal composition is a material containing the above-mentioned inversely dispersed liquid crystal compound. Here, the material referred to as a "liquid crystal composition" for convenience includes not only a mixture of two or more substances but also a material composed of a single substance. The liquid crystal composition may contain any component other than the above-mentioned inversely dispersed liquid crystal compound. Any component may be used alone or in combination of two or more at any ratio.

Optional components include, for example, a polymerization initiator. Of these, a photopolymerization initiator is preferable. The type of the polymerization initiator can be selected according to the type of the polymerizable compound contained in the liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator can be used. Further, for example, if the polymerizable compound is anionic polymerizable, an anionic polymerization initiator may be used. Further, for example, if the polymerizable compound is cationically polymerizable, a cationic polymerization initiator can be used.

Among them, as the polymerization initiator, a radical polymerization initiator is preferable, and an oxime ester-based polymerization initiator is more preferable. The oxime ester-based polymerization initiator is a polymerization initiator containing an oxime ester group. By using the oxime ester-based polymerization initiator, the solubility resistance of the cured product of the liquid crystal composition can be effectively enhanced.

Examples of the oxime ester-based polymerization initiator include 1,2-octanedione, 1- (4- (phenylthio) -2- (O-benzoyloxime)), etanone, 1- (9-ethyl-6 (2-). Methylbenzoyl) -9H-carbazole-3-yl) -1- (O-acetyloxime), an oxime ester-based polymerization initiator described in JP-A-2001-233842, and the like can be mentioned. Examples of the oxime ester-based polymerization initiator by trade name include IrgacureOXE01, IrgacureOXE02, and IrgacureOXE04 manufactured by BASF; Adeka Arkuru's N-1919T and Adeka Arkuru's NCI730 manufactured by ADEKA.

As the polymerization initiator, one type may be used alone, or two or more types may be used in combination at any ratio.

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

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 desired liquid crystal cured layer. In the following description, a surfactant containing a fluorine atom in the molecule may be appropriately referred to as a "fluorine-based surfactant".

The fluorosurfactant preferably has a predetermined range of logP. “LogP” refers to the 1-octanol / water partition coefficient. The preferable range of logP of the fluorine-based surfactant is usually 3.5 or more, and usually 7.5 or less. By using a fluorine-based surfactant having a log P in such a range, the inclination angle of the molecule of the back-dispersed 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. Can be done.

The logP of the fluorine-based surfactant can be measured by the following measuring method.
A sample solution containing 1% by weight of a fluorine-based surfactant was prepared, and HPLC / ELSD was prepared by a method generally compliant with JIS 7260-117: 2006 {Measurement of distribution coefficient (1-octanol / water) -high performance liquid chromatography}. Analysis (high performance liquid chromatography / evaporation light scattering detection analysis) is performed to measure the elution time (rt). On the other hand, the labeled compound having a known logP value described in JIS 7260-117: 2006 is subjected to HPLC / ELSD analysis in the same manner as the above-mentioned fluorine-based surfactant, and the elution time (rt) is measured. .. Based on the measurement results of the labeled compound, a calibration curve showing the relationship between the elution time and logP is prepared. Then, the elution time measured for the fluorine-based surfactant is applied to the calibration curve to determine the logP of the fluorine-based surfactant.

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

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

The amount of the surfactant is preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, and preferably 0.50 parts by weight or less, based on 100 parts by weight of the reverse dispersion liquid crystal compound. It is preferably 0.40 parts by weight or less, more preferably 0.30 parts by weight or less. When the amount of the surfactant is in the above range, a desired liquid crystal cured layer can be stably obtained.

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

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

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

Yet another optional component includes, for example, a tilting component capable of exerting an action of increasing the substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound. When the tilting component is used, the tilting of the molecules of the back-dispersed liquid crystal compound can be promoted, and a liquid crystal cured layer having a large tilt angle of the molecules of the back-dispersed liquid crystal compound can be easily obtained. However, since it is possible to promote the tilting of the molecules of the back-dispersed liquid crystal compound by adjusting the operation or conditions in the process of producing the liquid crystal cured layer, it is not always necessary to use the tilting action component.

Examples of the tilting action component include liquid crystal compounds having magnetic field responsiveness. Here, the "liquid crystal compound having magnetic field responsiveness" is a liquid crystal compound whose orientation state can be changed by the magnetic field when a magnetic field is applied at the liquefaction temperature. A liquid crystal composition containing a liquid crystal compound having magnetic field responsiveness can be appropriately applied with a magnetic field during its orientation treatment to obtain a substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer. It can exert the effect of increasing.

Whether or not the liquid crystal compound has magnetic field responsiveness is difficult to determine from its molecular structure, but it can be determined by the following method.
The liquid crystal compound as a sample is heated in a non-oriented state to form a liquid crystal phase. This heated liquid crystal compound is placed on the stage of a polarizing microscope, and observation is performed under a cross Nicol to observe an image. Then, while continuing heating, a horizontal magnetic field parallel to the stage is applied to the liquid crystal compound. The magnetic flux density of the magnetic field at this time is set to be the same as the magnetic flux density of the magnetic field applied to the layer of the liquid crystal composition in the step of orienting the inversely dispersed liquid crystal compound in the method for producing a liquid crystal cured film. Then, the liquid crystal compound is observed while the application of the magnetic field is continued. When the image of the liquid crystal compound observed after the application of the magnetic field is different from the image of the non-oriented state before the application of the magnetic field, it can be determined that the image has magnetic field responsiveness. Further, when the image of the liquid crystal compound observed after the application of the magnetic field is the same as the image of the non-oriented state before the application of the magnetic field, it can be determined that there is no magnetic field response.

The liquid crystal compound having magnetic field responsiveness may have a birefringence having a reverse wavelength dispersion and may have a birefringence having a forward wavelength dispersion. A liquid crystal compound having a forward wavelength-dispersible birefringence may be appropriately referred to as a "forward-dispersion liquid crystal compound". A liquid crystal compound having forward wavelength dispersive birefringence is a liquid crystal compound that exhibits forward wavelength dispersive birefringence when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. Refers to a compound. Usually, when a liquid crystal compound is homogenically oriented, the liquid crystal compound has a forward wavelength dispersive birefringence by examining whether the layer of the liquid crystal compound exhibits forward wavelength dispersive birefringence. You can check if it is.

The molecular weight of the liquid crystal compound having magnetic field responsiveness is preferably 1000 or less, more preferably 800 or less, and particularly preferably 600 or less. Since the molecular weight of the liquid crystal compound having magnetic field responsiveness is small as described above, a desired liquid crystal cured layer can be stably obtained. The lower limit of the molecular weight is not particularly limited, but is preferably 100 or more.

As the liquid crystal compound having magnetic field responsiveness, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

Examples of the liquid crystal compound having magnetic field responsiveness include the following. Further, for the liquid crystal compound having magnetic field responsiveness, the description of JP-A-2018-163218 (or the specification of Japanese Patent Application No. 2017-059327) may be referred to.

The amount of the liquid crystal compound having magnetic field responsiveness is preferably 0.1 part by weight or more, more preferably 1 part by weight, based on 100 parts by weight of the total of the liquid crystal compound having magnetic field responsiveness and the inversely dispersed liquid crystal compound. More than parts, particularly preferably 3 parts by weight or more, preferably 40 parts by weight or less, more preferably 30 parts by weight or less, and particularly preferably 20 parts by weight or less. By keeping the amount of the liquid crystal compound having magnetic field responsiveness within the above range, the inclination angle of the molecule of the back-dispersed liquid crystal compound with respect to the layer plane of the liquid crystal cured layer is effectively increased as a whole of the liquid crystal cured layer. be able to.

As another tilting action component, for example, a forward-dispersed liquid crystal compound having a tilting orientation can be mentioned. By using the forward-dispersed liquid crystal compound having a gradient orientation, the inclination angle of the molecule of the reverse-dispersed 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. Above all, when a forward-dispersed liquid crystal compound having a gradient orientation and a fluorine-based surfactant having a log P in the above-mentioned preferable range are used in combination, the molecule of the back-dispersed liquid crystal compound as a whole of the liquid crystal cured layer is used. It is possible to significantly increase the tilt angle.

The "forward-dispersed liquid crystal compound having a gradient orientation" is a test composition containing a forward-dispersed liquid crystal compound alone as a liquid crystal compound on the rubbing-treated surface of a resin film and subjected to an orientation treatment. A forward-dispersed liquid crystal compound in which, when a test layer is obtained, the substantially maximum tilt angle formed by the molecules of the forward-dispersed liquid crystal compound contained in the test layer with respect to the layer plane can be within a predetermined range. Specifically, the range of the substantially maximum inclination angle is usually 30 ° or more, preferably 40 ° or more, more preferably 45 ° or more, and usually 90 ° or less. The test layer can be formed by the same method as in Example 1 described later, except that a forward-dispersed liquid crystal compound having a gradient orientation is used instead of the reverse-dispersed liquid crystal compound.

As the forward-dispersed liquid crystal compound having a gradient orientation, a compound having a large birefringence Δn at a measurement wavelength of 590 nm is particularly preferable. The specific birefringence Δn of the forward-dispersed liquid crystal compound having a gradient orientation at a measurement wavelength of 590 nm is preferably 0.11 or more, more preferably 0.18 or more, and particularly preferably 0.21 or more, preferably 0.21 or more. It is 0.4 or less, more preferably 0.35 or less, and particularly preferably 0.3 or less. A desired liquid crystal cured layer can be easily obtained by using a forward-dispersed liquid crystal compound having a gradient orientation having a birefringence Δn in such a range.

The forward-dispersed liquid crystal compound having a gradient orientation is preferably polymerizable. Therefore, it is preferable that the molecule of the forward-dispersed liquid crystal compound having a gradient orientation contains a polymerizable group.

The molecular weight of the forward-dispersed liquid crystal compound having a gradient orientation is preferably 200 or more, more preferably 300 or more, preferably 1500 or less, and more preferably 1100 or less. By using a forward-dispersed liquid crystal compound having a gradient orientation having a molecular weight in such a range, the coatability of the liquid crystal composition can be particularly improved.

As the forward-dispersed liquid crystal compound having a gradient orientation, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

Examples of the forward-dispersed liquid crystal compound having a gradient orientation include the following compounds. Further, for the forward-dispersed liquid crystal compound having a gradient orientation, the description in JP-A-2018-162379 (or the specification of Japanese Patent Application No. 2017-060154) may be referred to.

The amount of the forward-dispersed liquid crystal compound having a gradient orientation is preferably 1 part by weight or more, more preferably 1 part by weight, based on 100 parts by weight of the total of the reverse-dispersed liquid crystal compound and the forward-dispersed liquid crystal compound having a gradient orientation. It is 5 parts by weight or more, more preferably 10 parts by weight or more, preferably 25 parts by weight or less, and more preferably 20 parts by weight or less. By using the forward-dispersed liquid crystal compound having a gradient orientation in such an amount, it is possible to significantly increase the tilt angle of the molecule of the reverse-dispersed liquid crystal compound as a whole of the liquid crystal cured layer.

As yet another inclined action component, for example, the ratio Mw / Np of the molecular weight Mw of the (meth) acrylic acid ester compound to the π electron number Np per molecule of the (meth) acrylic acid ester compound is predetermined. Examples include (meth) acrylic acid ester compounds in the range of. Specifically, the range of the ratio Mw / Np is usually 17 or more, preferably 23 or more, and usually 70 or less, preferably 50 or less. By using such a (meth) acrylic acid ester compound, the inclination angle of the molecule of the inversely dispersed 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. Above all, when the above-mentioned (meth) acrylic acid ester compound is used in combination with a fluorine-based surfactant, it is possible to remarkably increase the inclination angle of the molecule of the back-dispersed liquid crystal compound as a whole of the liquid crystal cured layer. Is.

The number of π electrons per molecule of a compound is determined based on the type and number of unsaturated bonds contained in the compound. To give an example of the number of π electrons contained in each unsaturated bond, the number of π electrons contained in an aliphatic or aromatic carbon-carbon double bond (C = C) is two, and a carbon-carbon triple bond is used. The number of π electrons contained in (C≡C) is 4, the number of π electrons contained in a carbon-nitrogen double bond (C = N) is 2, and the number of π electrons contained in a carbon-nitrogen triple bond (C≡N) is π. The number of electrons is 4, and the number of π electrons contained in a nitrogen-nitrogen double bond (N = N) is 2.

The molecular weight Mw of the (meth) acrylic acid ester compound is preferably 900 or less, more preferably 850 or less. Since the molecular weight Mw of the (meth) acrylic acid ester compound is small as described above, a desired liquid crystal cured layer can be stably obtained. The lower limit of the molecular weight Mw is not particularly limited, but is preferably 100 or more, more preferably 300 or more.

Since the (meth) acrylic acid ester compound has a (meth) acryloyl group as a polymerizable group, it is polymerizable. Since the (meth) acrylic acid ester compound having such polymerizable properties can be polymerized in the step of curing the layer of the liquid crystal composition, it is usually contained in a part of the molecule of the polymer in the liquid crystal cured layer.

The number of (meth) acryloyl groups per molecule of the (meth) acrylic acid ester compound is preferably two or more. By having two or more (meth) acryloyl groups per molecule, the degree of polymerization can be increased when the liquid crystal composition is cured, and the mechanical strength of the liquid crystal cured layer can be increased.

The (meth) acrylic acid ester compound may be a non-liquid crystal compound having no liquid crystal property, or may be a liquid crystal compound. For example, the (meth) acrylic acid ester compound may be a forward-dispersed liquid crystal compound.

When the (meth) acrylic acid ester compound is a liquid crystal compound, the (meth) acrylic acid ester compound can exhibit a liquid crystal phase when oriented. The (meth) acrylic acid ester compound as a liquid crystal compound usually has birefringence Δn. The birefringence Δn of the (meth) acrylic acid ester compound as a liquid crystal compound at a measurement wavelength of 590 nm is preferably 0.11 or more, more preferably 0.14 or more, preferably 0.4 or less, and more preferably 0. It is 0.3 or less. By using a liquid crystal compound having a birefringence Δn in such a range as a (meth) acrylic acid ester compound, a desired liquid crystal cured layer can be easily obtained.

As the (meth) acrylic acid ester compound, one kind may be used alone, or two or more kinds may be used in combination at an arbitrary ratio.

Examples of the (meth) acrylic acid ester compound include the following. Further, regarding the above-mentioned (meth) acrylic acid ester compound, the description of International Publication No. 2018/173778 (or the specification of Japanese Patent Application No. 2017-060122) may be referred to.

The amount of the (meth) acrylic acid ester compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more, based on 100 parts by weight of the total of the reverse dispersion liquid crystal compound and the (meth) acrylic acid ester compound. Yes, preferably 30 parts by weight or less, more preferably 20 parts by weight or less. By keeping the amount of the (meth) acrylic acid ester compound within the above range, it is possible to significantly increase the inclination angle of the molecule of the back-dispersed liquid crystal compound as a whole of the liquid crystal cured layer.

Further, when a fluorine-based surfactant is used in combination with the (meth) acrylic acid ester compound, it is preferable that the amount of the fluorine-based surfactant is within a predetermined range. Specifically, the amount of the fluorosurfactant is preferably 0.03 part by weight or more, more preferably 0, based on 100 parts by weight of the total of the back-dispersed liquid crystal compound and the (meth) acrylic acid ester compound. It is 05 parts by weight or more, preferably 0.50 parts by weight or less, more preferably 0.40 parts by weight or less, and particularly preferably 0.30 parts by weight or less. When the amount of the fluorine-based surfactant is in the above range, it is possible to significantly increase the inclination angle of the molecule of the inversely dispersed liquid crystal compound as a whole of the liquid crystal cured layer.

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

[4. Characteristics of LCD cured layer]
The liquid crystal cured layer is a layer of a cured product obtained by curing the above-mentioned liquid crystal composition. Curing of the liquid crystal composition is usually achieved by polymerization of the 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 contained in the liquid crystal composition. For example, when the back-dispersed liquid crystal compound has polymerizability, the back-dispersed liquid crystal compound polymerizes when the liquid crystal composition is cured, so that the liquid crystal cured layer is polymerized while maintaining the orientation state before polymerization. It can be a layer containing a polymer of a sex compound. As described above, this polymerized reverse-dispersed liquid crystal compound is also included in the term "back-dispersed 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 that the orientation state of the inversely dispersed liquid crystal compound is usually fixed in the orientation state before curing. Then, at least a part of the molecules of the back-dispersed 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 back-dispersed 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. good. Therefore, when a layer containing molecules of a reverse-dispersed liquid crystal compound inclined with respect to the layer plane of the liquid crystal cured layer is referred to as a "tilted oriented layer", the liquid crystal cured layer may include a inclined oriented layer as a part thereof. , The entire liquid crystal cured layer may be a gradient alignment layer. Further, in the liquid crystal cured layer, whether the molecules of the inversely dispersed liquid crystal compound contained in the layer portion other than the inclined alignment layer are usually parallel to the layer plane of the liquid crystal cured layer (inclination angle is 0 °). Alternatively, it is perpendicular to the layer plane of the liquid crystal cured layer (inclination angle is 90 °).

Observing the cross section of the liquid crystal cured layer with a polarizing microscope having sufficient resolution that at least a part of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer. It can be confirmed by doing. 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 inclination of the molecule of the inversely dispersed liquid crystal compound.

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

Hereinafter, a more specific description will be given with an example. FIG. 2 is a graph in which the retardation ratio R (θ) / R (0 °) of the liquid crystal cured layer according to a certain example is plotted against the incident angle θ. When the inclination angle of all the molecules of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer is 0 ° or 90 °, the retardation ratio R (θ) / R (0 °) is an example shown by a broken line in FIG. As shown above, it is line-symmetric with respect to a straight line of θ = 0 ° (vertical axis passing through θ = 0 ° in FIG. 2). On the other hand, when at least a part of the molecules of the back-dispersed 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 °). ) Is usually asymmetric with respect to a straight line of θ = 0 °, as shown in the example shown by the solid line in FIG. Therefore, when the retardation ratio R (θ) / R (0 °) is asymmetric with respect to θ = 0 °, at least a part of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer is the liquid crystal. It can be determined that the cured layer is inclined with respect to the layer plane.

The liquid crystal cured layer included in the liquid crystal cured film according to the present embodiment can increase the inclination angle of the molecule of the back-dispersed liquid crystal compound as a whole of the liquid crystal cured layer. The magnitude of this tilt angle can be expressed by the substantially maximum tilt angle. In the liquid crystal cured layer, the substantially maximum inclination angle is assumed that the inclination angle of the molecule on the surface on the first cured layer side is 0 ° and the inclination angle of the molecule changes at a constant ratio in the thickness direction. Represents the maximum value of the tilt angle of the molecule of the inversely dispersed liquid crystal compound in the case. The specific substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer is not particularly limited, but is preferably 40 ° or more, more preferably 46 ° or more, and particularly preferably 56 ° or more. It is preferably 85 ° or less, more preferably 83 ° or less, and particularly preferably 80 ° or less.

The fact that the substantially maximum tilt angle of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer is large as described above means that the tilt angle of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer is large as a whole. show. Therefore, since the liquid crystal cured layer having a large substantially maximum tilt angle can appropriately adjust the birefringence in the thickness direction, the liquid crystal cured layer is provided in the organic EL display device as a reflection suppression film in combination with a linear polarizing element. In this case, the reflection can be effectively suppressed in the tilting direction of the display surface. Therefore, it is possible to realize a polarizing plate that can achieve high viewing angle characteristics.

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

In the in-plane direction of the liquid crystal cured layer, the orientation direction of the molecules of the inversely dispersed liquid crystal compound is usually uniform. Therefore, the liquid crystal cured layer usually has an in-plane slow phase axis parallel to the orientation direction of the molecules of the inversely dispersed liquid crystal compound when the liquid crystal cured layer is viewed from the thickness direction. Since the reverse-dispersed liquid crystal compound is oriented in a certain orientation direction in the in-plane direction in this way, the liquid crystal cured layer usually has an in-plane retardation of a predetermined size.

The specific range of the in-plane retardation of the liquid crystal cured layer can be arbitrarily set according to the use of the liquid crystal cured layer. In particular, in order to obtain a polarizing plate as a reflection-suppressing film for an organic EL display device in combination with a linear polarizing element, it is desirable that the liquid crystal cured layer has an in-plane retardation that can function as a 1/4 wave plate. .. Here, the in-plane retardation that can function as a 1/4 wave plate is usually 80 nm or more, preferably 100 nm or more, particularly preferably 120 nm or more, and usually less than 190 nm, preferably 170 nm or less, at a measurement wavelength of 590 nm. It is particularly preferably 160 nm or less.

Since it contains a reverse-dispersed liquid crystal compound, the in-plane retardation of the liquid crystal cured layer usually exhibits reverse wavelength dispersibility. Therefore, the in-plane retardations Re (450) and Re (550) of the liquid crystal cured layer at a wavelength of 450 nm and a wavelength of 550 nm usually satisfy the following formula (N3), and preferably the following formula (N4). Such a liquid crystal cured layer can uniformly exhibit its function in a wide wavelength band in optical applications such as a 1/4 wave plate. Therefore, by using such a liquid crystal cured layer, it is possible to realize a reflection suppression film capable of suppressing reflection of external light in a wide wavelength range.
Re (450) / Re (550) <1.00 (N3)
Re (450) / Re (550) <0.90 (N4)

Since the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer can achieve 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 reflection suppressing film, it is possible to obtain an excellent viewing angle characteristic that the reflection can be effectively suppressed in the tilting direction of the display surface.

From the viewpoint of realizing excellent viewing angle characteristics, the average retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is preferably 0.90 or more, more preferably 0.93 or more, and particularly preferably. Is 0.95 or more, preferably 1.15 or less, more preferably 1.10 or less, and particularly preferably 1.05 or less. Here, R (± 50 °) is a letter of the liquid crystal cured layer at an incident angle θ of −50 ° and + 50 ° measured in a measurement direction perpendicular to the in-plane phase advancing axis of the liquid crystal cured layer. Represents the average value of the ground R (-50 °) and R (+ 50 °). Further, R (0 °) represents the lettering of the liquid crystal cured layer at an incident angle of 0 °, and thus represents the in-plane lettering.

Generally, external light incident on the display surface of an image display device at an incident angle of “+ φ” is reflected at an emitted angle of “−φ”. Therefore, when the reflection suppression film provided on the display surface includes a liquid crystal curing layer, the external light is transmitted in the inclined direction of the display surface on the path including the outward path at the incident angle “+ φ” and the return path at the exit angle “−φ”. It passes through the liquid crystal curing layer. From the viewpoint of effectively suppressing the reflection of light passing through this path, the retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is preferably close to 1.00. When the retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is in the above range close to 1.00, the polarizing plate including the liquid crystal cured layer reflects external light in the tilt direction. Can be effectively suppressed. Specifically, it is possible to appropriately convert the polarization state while the external light passes through the liquid crystal cured layer twice, when it is incident and when it is reflected, and to realize effective blocking by the linear polarizing element of the polarizing plate. It will be possible. Therefore, when such a liquid crystal cured layer is combined with a linear polarizing element to obtain a polarizing plate, the reflection suppressing ability of the polarizing plate can be exhibited in a wide angle of view range, so that particularly excellent viewing angle characteristics can be obtained. Can be done.

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. Haze can also be measured using a haze meter.

[5. Layer structure of LCD cured layer]
The liquid crystal cured layer has a multi-layer structure including a first cured layer and a second cured layer. In the following description, layers such as the first cured layer and the second cured layer as portions contained in the liquid crystal cured layer may be appropriately referred to as "unit cured layer". Such a multi-layer structure usually results from a method of manufacturing a liquid crystal cured layer.

Each unit cured layer contained in the liquid crystal cured layer can be distinguished by the following method. The liquid crystal hardened 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 in-plane slow phase axis of the liquid crystal cured layer is parallel to the cross section. Then, the cross section revealed by the slice is observed using a polarizing microscope. This observation is performed by inserting a wave plate between the observation sample and the objective lens of the polarizing microscope so that an image having a color corresponding to the retardation of the observation sample can be seen. At this time, the portion having a different color can be confirmed as a boundary between the unit cured layers, and each unit cured layer can be distinguished.

The liquid crystal cured layer is included in a part of the unit cured layer because at least a part of the molecules of the back-dispersed 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 molecules of the inversely dispersed liquid crystal compound may not be inclined with respect to the layer plane of the liquid crystal cured layer. Therefore, for example, the molecules of the inversely dispersed liquid crystal compound contained in a part of the unit cured layer may be parallel or perpendicular to the layer plane of the liquid crystal cured layer. However, normally, the molecules of the inversely dispersed liquid crystal compound contained in any of the unit cured layers are inclined with respect to the layer plane of the liquid crystal cured layer. Therefore, normally, the molecules of the back-dispersed liquid crystal compound contained in the first cured layer are inclined with respect to the layer plane of the liquid crystal cured layer, and the molecules of the back-dispersed liquid crystal compound contained in the second hardened layer. Is inclined with respect to the layer plane of the liquid crystal cured layer.

Further, in the liquid crystal cured layer, the unit cured layer closer to the first cured layer usually has a smaller substantial maximum inclination angle of the molecules of the back-dispersed liquid crystal compound contained in the unit cured layer, and the unit cured layer is farther from the first cured layer. The more the molecule of the back-dispersed liquid crystal compound contained in the unit cured layer tends to have a larger substantial maximum inclination angle. Therefore, usually, the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer. There is. In such a liquid crystal cured layer, the unit cured layer having a small substantial maximum inclination angle of the molecule of the back-dispersed liquid crystal compound is usually the previously formed unit cured layer, and is the substantially maximum of the molecule of the back-dispersed liquid crystal compound. The unit-cured layer having a large inclination angle is a unit-cured layer formed later.

The range of the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in each unit cured layer can be appropriately set according to the use of the liquid crystal cured film. Specific examples of a range suitable from the viewpoint of obtaining excellent viewing angle characteristics include the following range.

The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer is preferably 15 ° or more, more preferably 20 ° or more, and particularly preferably 30 ° or more. The upper limit is not particularly limited, but is preferably 60 ° or less.
The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer can be measured in the process of forming the liquid crystal cured layer.

The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer is preferably 45 ° or more, more preferably 50 ° or more, particularly preferably 57 ° or more, and preferably 85 ° or less. ..
The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer is the substantially maximum of the molecule of the back-dispersed liquid crystal compound contained in the entire liquid crystal cured layer including the first cured layer and the second cured layer. It can be calculated using the tilt angle, the substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound contained in the first cured layer, the thickness of the first cured layer, and the thickness of the second cured layer.

The difference between the substantially maximum tilt angle of the molecule of the dedispersed liquid crystal compound contained in the first cured layer and the substantially maximum tilt angle of the molecule of the dedispersed liquid crystal compound contained in the second cured layer is preferably 5 ° or more. , More preferably 8 ° or more, particularly preferably 10 ° or more, preferably 70 ° or less, more preferably 65 ° or less, and particularly preferably 55 ° or less.

The liquid crystal display cured layer may further include any unit cured layer in combination with the first cured layer and the second cured layer.
FIG. 3 is a cross-sectional view schematically showing the liquid crystal curing film 20 according to another embodiment of the present invention. For example, as shown in FIG. 3, the liquid crystal cured layer 200 included in the liquid crystal cured film 20 includes a first cured layer 110, a second cured layer 120 in direct contact with the first cured layer 110, and the second cured layer. The third cured layer 230 that is in direct contact with the 120 may be included in this order in the thickness direction of the liquid crystal cured layer 200.

In such a liquid crystal cured layer 200, the substantially maximum inclination angle of the molecule of the back-dispersed liquid crystal compound contained in the third cured layer 230 is usually the substance of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer 120. Greater than the maximum tilt angle. Further, preferably, the substantially maximum inclination angle of the molecule of the back-dispersed liquid crystal compound contained in the third cured layer 230 is the layer portion formed before the third cured layer 230 (that is, the first cured layer 110). And the layer portion composed of the second cured layer 120) 240, which is larger than the substantially maximum inclination angle of the molecule of the back-dispersed liquid crystal compound.

To show a specific example in a range suitable from the viewpoint of obtaining excellent viewing angle characteristics, the substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound contained in the third cured layer is preferably 50 ° or more, more preferably 55. ° or more, particularly preferably 60 ° or more, and preferably 85 ° or less.

The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the third cured layer is the back-dispersed liquid crystal compound contained in the entire liquid crystal cured layer including the first cured layer, the second cured layer and the third cured layer. The real maximum tilt angle of the molecule of the , The thickness of the first cured layer, the thickness of the second cured layer, and the thickness of the third cured layer can be used for calculation. At this time, the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer 110 and the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer 120 are liquid crystal cured. It can be measured during the layer formation process.

[6. Thickness of LCD cured layer]
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, and more preferably 7.0 μm or less. When the thickness of the liquid crystal cured layer is within the above range, the characteristics such as in-plane retardation can be easily adjusted to a desired range. Further, since the liquid crystal cured layer having such a thickness is thinner than the conventional retardation film used for the reflection suppression film of the organic EL display device, it can contribute to the thinning of the organic EL display device.

[7. Any layer]
The liquid crystal curing film may be a film containing only a liquid crystal curing layer, or may be a film containing an arbitrary layer in combination with the liquid crystal curing layer. Optional layers include a substrate used for manufacturing a liquid crystal cured layer; a retardation film; an adhesive layer for adhering to other members; a matte layer for improving the slipperiness of the film; an impact-resistant polymethacrylate resin layer and the like. Hard coat layer; antireflection layer; antifouling layer; etc.

[8. Outline of manufacturing method of liquid crystal curing film]
The method for producing a liquid crystal cured film described above is arbitrary as long as a desired liquid crystal cured film can be obtained. In one embodiment, the method for producing a liquid crystal cured film is
(S1) The process of preparing the first cured layer and
(S2) A step of directly forming the second cured layer on the first cured layer, and
including. The aspect of forming another layer on one layer "directly" means that there is no other layer between these two layers.

The unit-cured layer such as the first cured layer can function as an alignment film that increases the inclination angle of the molecules of the reverse-dispersed liquid crystal compound contained in another unit-cured layer directly formed on the unit-cured layer. Therefore, usually, another unit structure layer formed after that than the substantially maximum inclination angle of the molecule of the inversely dispersed liquid crystal compound contained in the unit structure layer (for example, the first cured layer) formed first (for example, the first cured layer). For example, the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer) is large. Therefore, by repeating the formation of the unit cured layer, it is possible to obtain a liquid crystal cured layer having a large inclination angle of the reverse dispersion liquid crystal compound as a whole. In the liquid crystal cured layer thus obtained, the unit cured layer formed later tends to be able to obtain a substantially maximum inclination angle. Hereinafter, a manufacturing method including such a step (S1) and a step (S2) will be described in detail.

[9. Preparation of the first hardened layer]
In the step (S1), the first cured layer is prepared. As described above, the first cured layer is a layer formed of a cured product of a liquid crystal composition containing a reverse-dispersed liquid crystal compound having a birefringence Δn in a predetermined range. In the following description, the liquid crystal composition used for forming the first cured layer may be appropriately referred to as "first liquid crystal composition". Since it is formed of a cured product of the first liquid crystal composition, the first cured layer contains molecules of a reverse-dispersed liquid crystal compound whose orientation may be fixed.

It is preferable that at least a part of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer are inclined with respect to the layer plane of the first cured layer. The surface of the first cured layer containing the molecules of the inversely dispersed liquid crystal compound having such an inclination is included in the layer of the second liquid crystal composition when the layer of the second liquid crystal composition is formed on the surface. It has the effect of tilting the molecules of the inversely dispersed liquid crystal compound with respect to the layer plane. In the following description, the surface of the first cured layer having such an action may be appropriately referred to as a “specific surface”. Explaining with the example of the liquid crystal curing film 10 shown in FIG. 1 described above, the surface 110U of the first cured layer 110 on the second cured layer 120 side corresponds to a specific surface. Further, the second liquid crystal composition represents a liquid crystal composition used for forming the second cured layer.

In the first cured layer, some of the molecules of the inversely dispersed liquid crystal compound may be inclined with respect to the layer plane of the first cured layer, and all of them may be inclined with respect to the layer plane of the first cured layer. May be. Usually, in the first cured layer, the inclination angle of the molecule of the inversely dispersed liquid crystal compound is larger as it is closer to the specific surface and smaller as it is farther from the specific surface in the thickness direction. Therefore, in the vicinity of the specific surface of the first cured layer, the molecules of the inversely dispersed liquid crystal compound may be perpendicular to the layer plane. Further, in the vicinity of the surface of the first cured layer opposite to the specific surface, the molecules of the inversely dispersed liquid crystal compound may be parallel to the layer plane. However, even when the molecules of the inversely dispersed liquid crystal compound are parallel or perpendicular to the layer plane in the portion near the surface of the first cured layer as described above, usually, the portion near the surface of the first cured layer is formed. In the removed portion, the molecules of the inversely dispersed liquid crystal compound are inclined with respect to the layer plane.
It can be confirmed by the same method as that of the liquid crystal cured layer that at least a part of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer are inclined.

When at least a part of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer are inclined, the molecules of the back-dispersed liquid crystal compound contained in the first cured layer are usually 5 ° or more and 85 ° or less. It has a substantially maximum tilt angle. In the first cured layer, the substantially maximum inclination angle is such that the inclination angle of the molecule on the surface opposite to the specific surface of the first cured layer is 0 °, and the inclination angle of the molecule is a constant ratio in the thickness direction. Represents the maximum value of the inclination angle of the molecule of the inversely dispersed liquid crystal compound, assuming that it changes in.

Generally, the larger the substantially maximum tilt angle of the molecule of the dedispersed liquid crystal compound contained in the first cured layer, the larger the substantially maximum tilt angle of the molecule of the dedispersed liquid crystal compound contained in the second cured layer can be. , The substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the entire liquid crystal cured layer can be increased. Therefore, the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer is preferably in a large range so that a liquid crystal cured layer having a desired substantially maximum tilt angle can be obtained. The specific range of the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer is as described above.

In the in-plane direction of the first cured layer, the orientation direction of the molecules of the inversely dispersed liquid crystal compound is usually uniform. Therefore, the first cured layer usually has an in-plane slow phase axis parallel to the orientation direction of the molecules of the inversely dispersed liquid crystal compound when the first cured layer is viewed from the thickness direction. Since the inversely dispersed liquid crystal compound is oriented in a certain orientation direction in the in-plane direction in this way, the first cured layer usually has an in-plane retardation of a predetermined size.

The specific range of the in-plane retardation of the first cured layer prepared in the step (S1) can be arbitrarily set according to the use of the liquid crystal cured layer. In particular, from the viewpoint of increasing the tilt angle of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer, the tilt angle of the molecules of the back-dispersed liquid crystal compound contained in the entire liquid crystal cured layer is increased. The in-plane retardation of the cured layer at a measurement wavelength of 590 nm is preferably 20 nm or more, more preferably 25 nm or more, particularly preferably 30 nm or more, usually less than 80 nm, preferably 75 nm or less, and particularly preferably 70 nm or less.

Since the first cured layer contains a reverse dispersion liquid crystal compound, the in-plane retardation of the first cured layer usually exhibits reverse wavelength dispersibility. Therefore, the in-plane retardations Re (450) and Re (550) of the first cured layer at a wavelength of 450 nm and a wavelength of 550 nm usually satisfy the above formula (N3), and preferably satisfy the above formula (N4).

The specific surface of the first cured layer prepared in the step (S1) preferably has a predetermined range of surface free energy. The specific surface free energy of the specific surface is usually 40 mJ / m ² or more, preferably 40.5 mJ / m ² or more. Since the specific surface has such a large surface free energy, the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer can be effectively increased. Further, usually, when the layer of the second liquid crystal composition is formed on the specific surface, the generation of cissing can be suppressed. The upper limit of the surface free energy of a specific surface is not particularly limited, but is usually 45 mJ / m ² or less.

The surface free energy of the specific surface of the first cured layer is obtained from the contact angle of pure water (H ₂ O) and the contact angle of diiodomethane (CH ₂ I ₂ ) on the specific surface based on the theory of Owns-Wendt.

In the Owens-Wendt theory, the surface free energy is assumed to be divided into a dispersion component d and a hydrogen bond component h. Therefore, the surface free energy γ _L of the liquid is expressed as the sum of the dispersion component γ _L ^d and the hydrogen bond component γ _L ^h , as represented by the following formula (X1). Further, the surface free energy γ _S of a solid is expressed as the sum of its dispersion component γ _S ^d and its hydrogen bond component γ _S ^h , as represented by the following formula (X2). The adhesion work _WLS when the liquid adheres to the solid is expressed by the following formula (X3). According to the formula of Young-Dupre, the adhesion work _WLS is expressed by the following formula (X4) using the contact angle θc of the liquid with respect to the solid. Therefore, the following equation (X5) holds. Therefore, by applying the contact angle θc of pure water and diiodomethane, which are liquids in which the dispersion component γ _L ^d and the hydrogen bond component γ _L ^h of the surface free energy γ _L are known, to the equation (X5), the simultaneous equations can be solved. The surface free energy of a specific surface corresponding to the surface free energy γ _S of a solid can be obtained.
For the above-mentioned Owens-Wendt theory, "DK Owns, RC Wendt, J. Appl. Polym. Sci., 13, 1741, (1969)" can be referred to.

Examples of the method for adjusting the surface free energy of the specific surface of the first cured layer include the type and amount of the inversely dispersed liquid crystal compound contained in the first liquid crystal composition, and the interface which may be contained in the first liquid crystal composition. Examples thereof include a method for appropriately adjusting the type and amount of the activator and the thickness of the first liquid crystal composition.

Further, when the inversely dispersed liquid crystal compound contained in the first liquid crystal composition contains an ethylenically unsaturated bond and an aromatic ring in its molecular structure, the specific surface of the first cured layer prepared in the step (S1) is It is preferable to satisfy the formula (X6).
0.450> X (S) / X (A) (X6)
(In the above equation (X6),
X (S) represents the peak ratio X of the specific surface of the first cured layer.
X (A) represents the peak ratio X of the non-polymerized reverse-dispersed liquid crystal compound.
The peak ratio X represents the ratio represented by X = I (1) / I (2).
I (1) represents the peak intensity derived from the in-plane variable angle vibration of the ethylenically unsaturated bond by infrared total reflection absorption spectrum measurement.
I (2) represents the peak intensity derived from the expansion and contraction vibration of the unsaturated bond of the aromatic ring measured by infrared total internal reflection absorption spectrum measurement. )
In the following description, the "infrared total reflection absorption spectrum" may be appropriately referred to as an "IR spectrum".

More specifically, X (S) / X (A) is usually less than 0.450, preferably 0.370 or less, and more preferably 0.320 or less. Since X (S) / X (A) is small as described above, the solubility resistance of a specific surface of the first cured layer can be improved. The lower limit of X (S) / X (A) is ideally 0, but is usually 0.100 or more.

The significance of the equation (X6) will be explained. The cured product of the first liquid crystal composition contained in the first cured layer is usually cured by polymerizing the reverse-dispersed liquid crystal compound contained in the first liquid crystal composition to fix the orientation state. be. Further, since it is generally difficult to completely proceed with the polymerization reaction of the polymerizable liquid crystal compound, the cured product may contain a back-dispersed liquid crystal compound that has not been polymerized as a residual monomer. When the first liquid crystal composition is cured, the ethylenically unsaturated bond of the inversely dispersed liquid crystal compound disappears by the polymerization reaction, but the unsaturated bond of the aromatic ring does not react, so that it does not disappear. Therefore, the ratio X (A) of the peak intensity I (1) and the peak intensity I (2) of the non-polymerized inversely dispersed liquid crystal compound is the inverse dispersed liquid crystal compound contained in the first liquid crystal composition before curing. The ratio of ethylenically unsaturated bonds is shown. Further, the ratio X (S) of the peak intensity I (1) and the peak intensity I (2) of the specific surface of the first cured layer is the identification of the first cured layer obtained by curing the first liquid crystal composition. The residual ratio of the ethylenically unsaturated bond of the inversely dispersed liquid crystal compound on the surface is shown. Therefore, according to these ratios X (S) / X (A), the degree of progress of the polymerization reaction on a specific surface of the first cured layer can be quantitatively expressed.

Therefore, the formula (X6) indicates that the polymerization reaction is largely proceeding on the specific surface of the first cured layer. This improves the solubility resistance of the specific surface of the first cured layer. Therefore, even if the second liquid crystal composition is coated on the specific surface, the specific surface of the first cured layer can be difficult to melt depending on the components contained in the second liquid crystal composition.

The peak ratio X (S) of the specific surface of the first cured layer can be measured from the IR spectrum of the specific surface. Specifically, it can be measured by the following method.
The IR spectrum of a specific surface of the first cured layer is measured using a Fourier transform infrared spectrophotometer (“FTIR4100” manufactured by JASCO Corporation). This measurement is performed at an incident angle of 45 ° using a jig (“ATR-PRO450-S” manufactured by JASCO Corporation) attached to the Fourier transform infrared spectrophotometer. From the measured IR spectra, the peak intensity I (1) of 1408 cm ^-1 derived from the in-plane variable vibration of the ethylenically unsaturated bond and the peak of 1505 cm ^-1 derived from the expansion and contraction vibration of the unsaturated bond of the aromatic ring. Find the strength I (2). Then, the peak ratio X (S) of the specific surface can be calculated from the obtained peak intensities I (1) and peak intensities I (2).

Further, the peak ratio X (A) of the non-polymerized reverse-dispersed liquid crystal compound can be measured from the IR spectrum of the reverse-dispersed liquid crystal compound. Specifically, it can be measured by the following method.
The IR spectrum of the non-polymerized inversely dispersed liquid crystal compound is measured using a Fourier transform infrared spectrophotometer (“FTIR4100” manufactured by JASCO Corporation). This measurement is performed at an incident angle of 45 ° using a jig (“ATR-PRO450-S” manufactured by JASCO Corporation) attached to the Fourier transform infrared spectrophotometer. From the measured IR spectra, the peak intensity I (1) of 1408 cm ^-1 derived from the in-plane variable vibration of the ethylenically unsaturated bond and the peak of 1505 cm ^-1 derived from the expansion and contraction vibration of the unsaturated bond of the aromatic ring. Find the strength I (2). Then, from the obtained peak intensity I (1) and peak intensity I (2), the peak ratio X (A) of the non-polymerized reverse-dispersed liquid crystal compound can be calculated.

Examples of the method for adjusting the ratio X (S) / X (A) include an irradiation amount of active energy rays such as ultraviolet rays that may be irradiated when the first liquid crystal composition is cured, and a type of inversely dispersed liquid crystal compound. , A method of appropriately selecting conditions such as the type of photopolymerization initiator, the amount of photopolymerization initiator, and the temperature at the time of irradiation with active energy rays such as ultraviolet rays.

Further, when the first liquid crystal composition contains a reverse dispersion liquid crystal compound and a fluorine-based surfactant, the surface _fluorine atomic weight MF [mol%] of the specific surface of the first cured layer measured by X-ray photoelectron spectroscopy. It is preferable that the ratio MF / _T of the first cured layer and the thickness T [μm] of the first cured layer is within a predetermined range. The specific range of the ratio MF / _T is usually 0.1 or more and usually 100.0 or less. When the ratio MF / _T falls within the above range, the specific surface can effectively increase the inclination angle of the molecule of the inversely dispersed liquid crystal compound contained in the second cured layer.

The surface fluorine atomic weight MF on the specific surface of the first cured layer is the fluorine ( _F ) atom contained in all the atoms except hydrogen (H) present on the specific surface of the first cured layer by X-ray photoelectron spectroscopy. It can be measured as the molar content of. X-ray photoelectron spectroscopy can be performed using the following X-ray photoelectron spectroscopy analysis system.
System: "AXIS ULTRA" manufactured by Kratos Analytical
Excited X-ray: Al Kα ray Filament Emission: 10 mA
Analog HT: 15kV
Neutralizing gun: Electron Neutralizer
Neutralization conditions Filment Current: 1.55A
Charge Balance: 3.3V
Filment Bias: 1.5V
Analysis area: Approximately 700 μm x 300 μm
Photoelectron detection angle: 0 ° (angle between sample surface and detector: 90 °)

Examples of the method for adjusting the ratio MF / _T include a method for adjusting the surface _fluorine atomic weight MF and the thickness T of the specific surface of the first cured layer. Further, as a method for adjusting the surface _fluorine atomic weight MF of the specific surface of the first cured layer, for example, the type of the fluorine-based surfactant, the combination of the reverse dispersion liquid crystal compound and the fluorine-based surfactant, and the first. Examples thereof include a method of appropriately adjusting the concentration of the fluorine-based surfactant in the liquid crystal composition.

The thickness of the first cured layer is usually 2.5 μm or less, preferably less than 2.0 μm, more preferably 1.8 μm or less, still more preferably 1.6 μm or less, and particularly preferably 1.5 μm or less, particularly preferably 1. It is 0 μm or less. Within a certain thickness range, the thinner the first cured layer, the larger the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the first cured layer. Therefore, in a certain predetermined thickness range, the thinner the first cured layer, the more effectively the substantially maximum inclination angle of the second cured layer formed directly on the first cured layer can be increased. Therefore, since the substantially maximum tilt angle can be effectively increased in the entire liquid crystal cured layer, the viewing angle characteristics can be greatly improved. Above all, this effect is remarkable when the thickness of the first cured layer is less than 2.0 μm. The lower limit of the thickness of the first cured layer is not particularly limited, but is preferably 0.1 μm or more, more preferably 0.2 μm or more, and particularly preferably 0.3 μm or more.

The first cured layer is, for example,
(S1-1) A step of forming a layer of the first liquid crystal composition;
(S1-2) A step of orienting the inversely dispersed liquid crystal compound contained in the layer of the first liquid crystal composition;
(S1-3) A step of curing the layer of the first liquid crystal composition to form the first cured layer;
It can be manufactured by a manufacturing method including.

In the step (S1-1), a layer of the first liquid crystal composition is usually formed on a suitable support surface. As the support surface, any surface that can support the layer of the first liquid crystal composition can be used. As the support surface, it is preferable to use a flat surface without recesses and protrusions from the viewpoint of improving the surface condition of the first cured layer. Further, from the viewpoint of increasing the productivity of the first cured layer, it is preferable to use the surface of a long base material as the support surface. Here, "long" means a shape having a length of 5 times or more with respect to the width, preferably having a length of 10 times or more, and specifically being wound into a roll shape. The shape of the film that has a length that can be stored or transported.

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

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

In the step of forming the layer of the first liquid crystal composition (S1-1), the first liquid crystal composition is usually prepared in a fluid state. Therefore, usually, the first liquid crystal composition is applied to the support surface to form a layer of the first liquid crystal composition. Examples of the method for coating the first 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, and a print coating method. , Gravure coating method, die coating method, gap coating method, and dipping method.

After the step of forming the layer of the first liquid crystal composition (S1-1), the step of orienting the inversely dispersed liquid crystal compound contained in the layer of the first liquid crystal composition (S1-2) is performed. In this step, usually, the layer of the first liquid crystal composition is subjected to an orientation treatment to orient the inversely dispersed liquid crystal compound in a direction corresponding to the orientation restricting force of the support surface.

The alignment treatment is usually performed by adjusting the temperature of the layer of the first liquid crystal composition to a predetermined orientation temperature. The orientation temperature can be a temperature equal to or higher than the liquid crystal display temperature of the first liquid crystal composition. At this time, the orientation temperature is preferably a temperature 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 orientation treatment.

Normally, in the in-plane direction, the inversely dispersed liquid crystal compound is oriented in a direction corresponding to the orientation restricting force of the support surface. Further, in the thickness direction, the inversely dispersed liquid crystal compound is usually oriented so that at least a part thereof is greatly inclined with respect to the layer plane. As a result, the inclination angle of the inversely dispersed liquid crystal compound with respect to the layer plane can be effectively increased.

Further, it is preferable that the step (S1-2) is performed by adjusting the operation or conditions so that the first cured layer having a large inclination angle of the molecule of the back-dispersion liquid crystal compound can be obtained.

For example, the step (S1-2) is preferably performed so that the temperature condition of the layer of the first liquid crystal composition satisfies a predetermined requirement. Specifically, it is preferable that the temperature condition of the layer of the first liquid crystal composition in the step (S1-2) is the same as the temperature condition in 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 first liquid crystal composition. The residual viscosity of the test composition is the viscosity of the residual component of the test composition under the same temperature conditions as the layer of the first liquid crystal composition in the step (S1-2). The residual component of the test composition is a component contained in the test composition that remains without being vaporized under the same temperature conditions as the layer of the first liquid crystal composition in the step (S1-2). By performing the step (S1-2) so as to satisfy such a requirement, it is possible to increase the inclination angle of the molecule of the inversely dispersed liquid crystal compound contained in the first cured layer.

This will be described in more detail. When the step (S1-2) for orienting the back-dispersed liquid crystal compound is performed so as to satisfy the above-mentioned requirements, the step (S1-2) is set to a temperature condition in which the residual viscosity of the test composition is within a predetermined range. The layer of the first liquid crystal composition is adjusted to the same temperature condition. The specific range of the residual viscosity is usually 800 cP (centipores) or less, preferably 600 cP or less, more preferably 400 cP or less, still more preferably 200 cP or less. By orienting the liquid crystal compound in the layer of the first liquid crystal composition under the same temperature condition as the temperature condition at which the residual component viscosity of the test composition becomes low in this way, the inversely dispersed liquid crystal compound contained in the first cured layer. The tilt angle of the molecule 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 first cured layer having a desired thickness.

The residual viscosity of the test composition under the same temperature conditions as the layer of the first liquid crystal composition in the step (S1-2) can be measured by the following method.
A test composition obtained by removing the polymerization initiator from the first liquid crystal composition is prepared. The test composition is concentrated under reduced pressure on a rotary evaporator to remove the solvent to obtain residual components. The viscosity of this residual component is measured in advance while changing the measurement temperature, and information on the measurement temperature and the viscosity at the measurement temperature is obtained. This information is hereinafter appropriately referred to as "temperature-viscosity information". From this "temperature-viscosity information", the viscosity at the temperature of the layer of the first liquid crystal composition in the step (S1-2) is read as the residual component viscosity.

Examples of the method for keeping the residual viscosity of the test composition within the above-mentioned range under the same temperature conditions as the layer of the first liquid crystal composition in the step (S1-2) include the following methods (A) and (B). Be done.
(A) The temperature of the layer of the first liquid crystal composition in the step (S1-2) of orienting the reverse dispersion liquid crystal compound is appropriately adjusted. In this method, usually, the temperature of the layer of the first liquid crystal composition is sufficiently high enough to reduce the residual viscosity of the test composition under the same temperature conditions as the above temperature so as to be within the above range. Adjust to.
(B) The composition of the first liquid crystal composition is appropriately adjusted. In this method, the residual viscosity of the test composition containing the additive is usually lowered by combining the reverse-dispersed liquid crystal compound with an appropriate type and amount of the additive as a component contained in the first liquid crystal composition. Then, the adjustment is made so as to be within the above-mentioned range.

For the adjustment of the temperature condition of the layer of the first liquid crystal composition in the step (S1-2), the description of International Publication No. 2018/173773 (or the specification of Japanese Patent Application No. 2017-060159) may be referred to.

Further, for example, when a first liquid crystal composition containing a liquid crystal compound having magnetic field responsiveness is used, the step (S1-2) may be performed in a state where a magnetic field is applied to the layer of the first liquid crystal composition. preferable. As a result, the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the first cured layer can be effectively increased.

The direction of the magnetic field applied to the layer of the first liquid crystal composition is usually not perpendicular to the thickness direction of the layer of the first liquid crystal composition, preferably the thickness direction of the layer of the first liquid crystal composition. The direction is parallel to. By applying a magnetic field in such a direction, the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the first cured layer can be effectively increased.

The magnetic flux density of the magnetic field applied to the layer of the first liquid crystal composition is preferably 0.2 tesla or more, more preferably 0.5 tesla or more, and particularly preferably 0.8 tesla or more. By applying a magnetic field of such a magnitude, the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the first cured layer can be effectively increased. There is no limit to the upper limit of the magnetic flux density of the magnetic field, which may be, for example, 20.0 tesla or less. Regarding the application of the magnetic field, the description of JP-A-2018-163218 (or the specification of Japanese Patent Application No. 2017-059327) may be referred to.

The step of orienting the back-dispersed liquid crystal compound (S1-2) is usually performed in an oven. At this time, the set temperature of the oven and the temperature of the layer of the first liquid crystal composition placed in the oven may be different. In this case, it is preferable to measure and record the temperature of the layer of the first liquid crystal composition placed in the oven at the set temperature in advance at a large number of oven set temperatures. The recorded information on the set temperature of the oven and the temperature of the layer of the first liquid crystal composition placed in the oven at the set temperature is hereinafter appropriately referred to as "set temperature-layer temperature information". By using this "set temperature-layer temperature information", the temperature of the layer of the first liquid crystal composition placed in the oven can be easily known from the oven set temperature.

In the step of orienting the back-dispersed liquid crystal compound (S1-2), the time for holding the temperature of the layer of the first liquid crystal composition at the above temperature can be arbitrarily set within a range in which a desired first cured layer can be obtained. For example, it can be 30 seconds to 5 minutes.

After the step of orienting the back-dispersed liquid crystal compound (S1-2), the step of curing the layer of the first liquid crystal composition to obtain the first cured layer (S1-3) is performed. Curing of the first liquid crystal composition in this step (S1-3) is usually achieved by polymerization of the polymerizable compound contained in the first liquid crystal composition. For example, when the back-dispersion liquid crystal compound has polymerizability, the layer of the first liquid crystal composition is cured by polymerizing a part or all of the back-dispersion liquid crystal compound. Polymerization usually proceeds while maintaining the molecular orientation of the liquid crystal compound. Therefore, by the above-mentioned polymerization, the orientation state of the reverse-dispersed liquid crystal compound contained in the first liquid crystal composition before the polymerization is fixed.

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

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

The first cured layer can be manufactured by the above-mentioned manufacturing method. In this manufacturing method, a first cured layer formed on a support surface of a base material is usually obtained. In this case, the surface of the first cured layer opposite to the support surface may be a specific surface.

[10. Formation of second hardened layer]
After preparing the first cured layer, the step (S2) of directly forming the second cured layer on the first cured layer is performed. The second cured layer is, for example,
(S2-1) A step of directly forming a layer of the second liquid crystal composition on the first cured layer;
(S2-2) A step of orienting the inversely dispersed liquid crystal compound contained in the layer of the second liquid crystal composition;
(S2-3) A step of curing the layer of the second liquid crystal composition to form the second cured layer,
It can be manufactured by a manufacturing method including.

In the step (S2-1), a layer of the second liquid crystal composition is directly formed on the surface of the first cured layer such as a specific surface. The second liquid crystal composition is a liquid crystal composition for forming a second cured layer, and as described above, contains a reverse-dispersion liquid crystal compound having a birefringence Δn in a predetermined range. The reverse-dispersion liquid crystal compound contained in the second liquid crystal composition may be the same as or different from the reverse-dispersion liquid crystal compound contained in the first liquid crystal composition. Furthermore, the second liquid crystal composition may be different from or the same as the first liquid crystal composition.

Before forming the layer of the second liquid crystal composition on the surface of the first cured layer, the surface may be subjected to a treatment for imparting an orientation restricting force such as a rubbing treatment. However, the surface of the first cured layer has an orientation restricting force that appropriately orients the reverse-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition formed on the surface without any special treatment. Have. Therefore, from the viewpoint of reducing the number of steps and efficiently advancing the production of the liquid crystal cured film, in the step (S2-1), the surface of the first cured layer is not subjected to the rubbing treatment, and the second liquid crystal composition is directly prepared. It preferably involves forming a layer.

In the step of forming the layer of the second liquid crystal composition (S2-1), the second liquid crystal composition is usually prepared in a fluid state. Therefore, usually, the second liquid crystal composition is applied on the first cured layer to form a layer of the second liquid crystal composition. Examples of the method for applying the second liquid crystal composition include the same examples as those described for the method for applying the first liquid crystal composition.

After the step of forming the layer of the second liquid crystal composition (S2-1), the step of orienting the inversely dispersed liquid crystal compound contained in the layer of the second liquid crystal composition (S2-2) is performed. As a result, the liquid crystal compound such as the back-dispersed liquid crystal compound is oriented in the layer of the second liquid crystal composition.

The first cured layer prepared in the step (S1) has an orientation regulating force for orienting the molecules of the reverse-dispersed liquid crystal compound contained in the second cured layer formed on the surface of the first cured layer. In the in-plane direction, this orientation regulating force orients the molecules of the back-dispersed liquid crystal compound contained in the second cured layer in the same direction as the orientation direction of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer. Try to make it. Therefore, normally, in the in-plane direction, the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition is the back-dispersed liquid crystal compound contained in the first cured layer due to the orientation restricting force of the first cured layer. Orients in the same direction as the orientation direction.

Further, the orientation restricting force attempts to orient the molecule of the inversely dispersed liquid crystal compound contained in the second cured layer so that the inclination angle of the molecule becomes large in the thickness direction. Therefore, in the thickness direction, at least a part of the inversely dispersed liquid crystal compound contained in the layer of the second liquid crystal composition is oriented so as to be inclined with respect to the layer plane. At this time, the molecules of the inversely dispersed liquid crystal compound contained in the layer of the second liquid crystal composition are greatly inclined with respect to the layer plane by the action of the first cured layer. Therefore, the inclination angle of the molecule of the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition is large. Usually, the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition is larger than the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer. ,growing.

The specific operation in the step of orienting the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition (S2-2) is the step of orienting the back-dispersed liquid crystal compound contained in the layer of the first liquid crystal composition. It can be the same as (S1-2). Thereby, the same advantages obtained in the first liquid crystal composition and the first cured layer can be obtained in the second liquid crystal composition and the second cured layer. In particular, in the step (S2-2), as in the step (S1-2), the temperature condition of the layer of the second liquid crystal composition in the step (S2-2) corresponds to the test composition corresponding to the second liquid crystal composition. It is preferable to carry out the process so that the residual viscosity of the liquid crystal display is usually the same as the temperature condition of 800 cP or less. Further, in the step (S2-2), a magnetic field may be applied as in the step (S1-2).

After the step of orienting the back-dispersed liquid crystal compound (S2-2), the step of curing the layer of the second liquid crystal composition to form the second cured layer (S2-3) is performed. The specific operation in the step of curing the layer of the second liquid crystal composition (S2-3) can be the same as the step of curing the layer of the first liquid crystal composition (S1-3). Thereby, the same advantages obtained in the first liquid crystal composition and the first cured layer can be obtained in the second liquid crystal composition and the second cured layer.

Curing of the second liquid crystal composition in the step (S2-3) is usually achieved by the polymerization of the polymerizable compound contained in the second liquid crystal composition, as in the case of curing the first liquid crystal composition. Therefore, by the above-mentioned polymerization, a second cured layer containing a reverse-dispersed liquid crystal compound having a fixed orientation state in the second liquid crystal composition before polymerization can be obtained.

At least a part of the molecules of the back-dispersed liquid crystal compound contained in the obtained second cured layer are usually inclined with respect to the layer plane of the second cured layer. The molecules of the inversely dispersed liquid crystal compound contained in the second cured layer are greatly inclined with respect to the layer plane of the second cured layer due to the action of the first cured layer. Therefore, the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer can be increased. The substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound contained in the second cured layer is such that the tilt angle of the molecule on the surface on the first cured layer side is 0 ° and the tilt angle of the molecule is in the thickness direction. It represents the maximum value of the inclination angle of the molecule of the inversely dispersed liquid crystal compound, assuming that it changes at a constant rate.

Further, the orientation direction of the molecules of the inversely dispersed liquid crystal compound in the in-plane direction of the second cured layer is usually the same as the orientation direction of the molecules of the inverse dispersed liquid crystal compound in the in-plane direction of the first cured liquid crystal layer. Therefore, normally, in the in-plane direction, the molecules of the back-dispersed liquid crystal compound contained in the obtained liquid crystal cured layer are on the same plane as the orientation direction of the molecules of the back-dispersed liquid crystal compound contained in the first cured layer as a whole. Oriented inward. Therefore, the in-plane slow phase axis of the liquid crystal cured layer obtained by the above-mentioned manufacturing method is usually parallel to the in-plane slow phase axis of the first cured layer.

The thickness of the second cured layer is not particularly limited and is preferably 0.3 μm or more, more preferably 0.5 μm or more, preferably 10.0 μm or less, more preferably 7.5 μm or less, still more preferable. Is 5.0 μm or less, particularly preferably 3.0 μm or less.

As described above, according to the manufacturing method including forming the second cured layer directly on the first cured layer, the liquid crystal cured layer including the first cured layer and the second cured layer can be obtained. In the above-mentioned manufacturing method, since the first cured layer functions as an alignment film, the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer can be increased, so that the entire liquid crystal cured layer has a reverse dispersed liquid crystal display. The tilt angle of the molecule of the sex compound can be increased.

Further, in the above-mentioned manufacturing method, since a desired liquid crystal cured layer can be obtained by repeating the formation of the unit structure layer, it is not necessary to form a layer other than the unit structure layer, so that the efficiency of the manufacturing process can be improved. It is possible. Furthermore, if it is not necessary to form a layer other than the unit structure layer in this way, it is possible to reduce the manufacturing cost by the amount that it is not necessary to prepare a layer (alignment film, etc.) different from the liquid crystal cured layer. be.

In the above-mentioned production method, as described above, the substance of the molecule of the back-dispersed liquid crystal compound contained in the second cured layer is larger than the substantially maximum inclination angle of the molecule of the back-dispersed liquid crystal compound contained in the first cured layer. The maximum tilt angle can be increased, and as a result, the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the entire liquid crystal cured layer is increased. The present inventors presume that such a phenomenon is caused by the mechanism described below. However, the technical scope of the present invention is not limited by the mechanism described below.

When a layer of the second liquid crystal composition is formed on the first cured layer, the orientation of the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition affects the orientation of the back-dispersed liquid crystal compound in the first cured layer. Will be done. Therefore, when the molecules of the dedisperse liquid crystal compound are inclined with respect to the layer plane in the first cured layer, the molecules of the dedisperse liquid crystal compound thus inclined are contained in the layer of the second liquid crystal composition. It works to increase the inclination of the molecule of the inversely dispersed liquid crystal compound with respect to the layer plane. Therefore, in the second cured layer, the substantially maximum inclination angle of the molecule of the inversely dispersed liquid crystal compound can be increased.
Further, since the surface of the first cured layer corresponds to the air interface of the layer of the first liquid crystal composition, specific chemical species are likely to concentrate. In addition, some of these chemical species have a small affinity for the inversely dispersed liquid crystal compound. Then, when the layer of the second liquid crystal composition is formed on the first cured layer, the molecules of the inversely dispersed liquid crystal compound contained in the second liquid crystal composition do not adapt to the above chemical species and should be separated as much as possible. And. Therefore, the molecules of the back-dispersed liquid crystal compound contained in the layer of the second liquid crystal composition tend to be greatly inclined so as to be repelled by the surface of the first cured layer, and therefore, the back-dispersed liquid crystal property in the second cured layer. The substantially maximum tilt angle of the molecule of the compound can be increased.
By these actions, the substantially maximum tilt angle of the molecules of the back-dispersed liquid crystal compound contained in the second cured layer can be increased, so that the substantially maximum tilt angle of the molecules of the liquid crystal compound in the entire liquid crystal cured layer can be increased. ing.

[11. Arbitrary process]
The method for producing a liquid crystal cured film according to the above-mentioned example may further include an arbitrary step in combination with the above-mentioned steps.
For example, in the case of producing a liquid crystal cured layer including an arbitrary unit cured layer in combination with the first cured layer and the second cured layer, the method for producing a liquid crystal cured film is to form an arbitrary unit cured layer on the second cured layer. It may include a step of forming.

For example, a liquid crystal cured layer including a first cured layer, a second cured layer in direct contact with the first cured layer, and a third cured layer in direct contact with the second cured layer (liquid crystal curing in FIG. 3). Layer 200) is formed after the first cured layer and the second cured layer are formed by the manufacturing method described above.
A step of directly forming a layer of a third liquid crystal composition containing a back-dispersed liquid crystal compound on the second cured layer,
A step of orienting the reverse-dispersed liquid crystal compound contained in the layer of the third liquid crystal composition,
The step of curing the layer of the third liquid crystal composition to form the third cured layer,
It can be manufactured by a manufacturing method including.

The third liquid crystal composition represents a liquid crystal composition used for forming the third cured layer. The reverse-dispersion liquid crystal compound contained in the third liquid crystal composition may be the same as or different from the reverse-dispersion liquid crystal compound contained in the first liquid crystal composition and the second liquid crystal composition. Furthermore, the third liquid crystal composition may be different from or the same as the first liquid crystal composition and the second liquid crystal composition. Further, the thickness of the third cured layer may be different or the same as that of the first cured layer and the second cured layer. The above-mentioned step for forming the third cured layer can be carried out by the same operation as the step for forming the second cured layer, and the same advantages as the step for forming the second cured layer can be obtained.

The method for producing a liquid crystal cured film may include, for example, a step of forming an arbitrary layer on the second cured layer. Further, the method for producing a liquid crystal cured film may include a step of forming an arbitrary layer on the side of the first cured layer opposite to the second cured layer.

When a liquid crystal cured layer formed on the support surface of the base material is obtained, the film containing the base material and the liquid crystal cured layer may be used as the liquid crystal cured film. Further, the method for producing the liquid crystal cured film may include a step of peeling off the base material. In this case, the liquid crystal cured layer itself can be used as the liquid crystal cured film. Further, the base material may be peeled off from the first cured layer before forming the layer of the second liquid crystal composition on the first cured layer.

Further, the method for producing a liquid crystal cured film may include, for example, a step of transferring the liquid crystal cured layer formed on the substrate to an arbitrary film layer. Therefore, for example, in the method for producing a liquid crystal cured film, after the liquid crystal cured layer formed on the substrate and an arbitrary film layer are bonded together, the substrate is peeled off as necessary to form the liquid crystal cured layer and the liquid crystal cured layer. It may include a step of obtaining a liquid crystal cured film containing an arbitrary film layer. At this time, an appropriate adhesive or adhesive may be used for bonding.

According to the manufacturing method as described above, a long liquid crystal cured film can be obtained by using a long base material. Such a long liquid crystal cured film can be continuously manufactured and is excellent in productivity. Further, since the film can be bonded to another film by roll-to-roll, the productivity is excellent in this respect as well. Normally, a long liquid crystal cured film is rolled up and stored and transported in a roll state.

[12. Polarizer]
The polarizing plate according to the embodiment of the present invention includes the above-mentioned liquid crystal curing layer and a linear polarizing element. It is preferable that this polarizing plate can function as a circular polarizing plate or an elliptical polarizing plate. By providing such a polarizing plate in the organic EL display device, it is possible to suppress reflection of external light in the front direction of the display surface of the organic EL display device. At this time, since the liquid crystal cured layer contains the reverse dispersion liquid crystal compound, it is possible to suppress the reflection of external light in a wide wavelength range. Further, as can be seen from the fact that the substantially maximum tilt angle of the molecule of the back-dispersed liquid crystal compound is large in the above-mentioned liquid crystal cured layer, the tilt angle of the molecule of the back-dispersed liquid crystal compound is large as a whole layer, so that the in-plane direction thereof. Not only that, the birefringence can be appropriately adjusted in the thickness direction as well. Therefore, the polarizing plate including the liquid crystal curing layer can suppress the reflection of external light not only in the front direction of the display surface of the organic EL display device but also in the inclined direction. Therefore, by using this polarizing plate, it is possible to realize an organic EL display device having a wide viewing angle.

As the linear deflector, for example, a film obtained by adsorbing iodine or a dichroic dye on a polyvinyl alcohol film and then uniaxially stretching in a boric acid bath; adsorbing iodine or a dichroic dye on the polyvinyl alcohol film. Examples thereof include a film obtained by stretching and further modifying a part of polyvinyl alcohol units in the molecular chain to polyvinylene units. Further, as another example of the linear polarizing element, there is a polarizing element having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizing element and a multilayer polarizing element. Of these, as the linear splitter, a splitter containing polyvinyl alcohol is preferable.

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

When it is desired to make the polarizing plate function as a circular 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 polarizing element is preferably 45 ° or an angle close to it. Specifically, the angle is preferably 45 ° ± 5 ° (that is, 40 ° to 50 °), more preferably 45 ° ± 4 ° (that is, 41 ° to 49 °), and particularly preferably 45 °. It is ± 3 ° (that is, 42 ° to 48 °).

The polarizing plate may further include any layer in combination with the linear polarizing element and the liquid crystal curing layer. Examples of the optional layer include an adhesive layer for adhering a linear polarizing element and a liquid crystal curing layer; a polarizing element protective film layer for protecting the linear polarizing element; and the like.

[13. Organic EL display device]
The organic EL display device according to an embodiment of the present invention 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 visual side of the organic EL element. Further, the polarizing plate includes the liquid crystal curing layer and the linear polarizing element in this order from the organic EL element side. In such a configuration, the polarizing plate can function as a reflection suppression film.

Hereinafter, the mechanism of reflection suppression will be described by taking as an example the case where the polarizing plate functions as a circular polarizing plate. The light incident from the outside of the device is circularly polarized by passing only a part of the linearly polarized light through the linearly polarized light and then passing through the liquid crystal curing layer. Circularly polarized light is reflected by a component (reflective electrode of an organic EL element, etc.) that reflects light in the display device, and passes through the liquid crystal curing layer again to change the vibration direction orthogonal to the vibration direction of the incident linearly polarized light. It becomes linearly polarized light and does not pass through the linearly polarizing element. Here, the vibration direction of linearly polarized light means the vibration direction of the electric field of linearly polarized light. As a result, the function of suppressing reflection is achieved. For the principle of such reflection suppression, Japanese Patent Application Laid-Open No. 9-127885 may be referred to.

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

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the examples shown below, and may be arbitrarily modified and implemented without departing from the scope of claims of the present invention and the equivalent scope thereof. In the following description, "%" and "part" representing quantities are based on weight unless otherwise specified. In addition, the operations described below were performed in the air at normal temperature and pressure unless otherwise specified.

[Reverse dispersion liquid crystal compound]
The molecular structures of the inversely dispersed liquid crystal compounds (LA) to (LC) used in the following Examples and Comparative Examples are as follows.

[Synthesis Example 1: Synthesis of Reverse Dispersion Liquid Crystal Compound (LA) (Another Example of the Compound Represented by Formula (I))]

<Step 1: Synthesis of Intermediate A>

In a three-port reactor equipped with a thermometer, 83.05 g (0.40 mol) of trans-1,4-cyclohexanedicarboxylic acid dichloride was added to 600 g of cyclopentyl methyl ether in a nitrogen stream to 5 ° C. under an ice bath. Cooled. To this solution, 100 g (0.38 mol) of 4- (6-acryloyloxy-hex-1-yloxy) phenol (manufactured by DKSH), 1.67 g of 2,6-diter Shirley butyl-4-methylphenol, and tetrahydrofuran. 230 g of (THF) was added. To there, 40.2 g (0.40 mol) of triethylamine was slowly added dropwise under strong stirring. After completion of the dropping, the reaction was carried out at 5 ° C. for 1 hour. After completion of the reaction, 250 g of water was added, the temperature was raised to 50 ° C., and the mixture was stirred for 4 hours. Then, 416 g of a 1 mol / L concentration acetic acid / sodium acetate buffered aqueous solution was added to the organic layer obtained by extracting the aqueous layer, and the mixture was stirred for 30 minutes, and then the aqueous layer was extracted. Further, the organic layer obtained by washing the organic layer with 250 g of water was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue is purified by silica gel column chromatography (THF: toluene = 1: 9 (volume ratio)) to obtain 75 g of the intermediate A as a white solid. Obtained. The yield was 47.4 mol%. The structure of Intermediate A was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 12.12 (s, 1H), 6.99 (d, 2H, J = 9.0 Hz), 6.92 (d, 2H, J) = 9.0Hz), 6.32 (dd, 1H, J = 1.5Hz, 17.5Hz), 6.17 (dd, 1H, J = 10.0Hz, 17.5Hz), 5.93 (dd, 1H, J = 1.5Hz, 10.0Hz), 4.11 (t, 2H, J = 6.5Hz), 3.94 (t, 2H, J = 6.5Hz), 2.48-2.56 (M, 1H), 2.18-2.26 (m, 1H), 2.04-2.10 (m, 2H), 1.93-2.00 (m, 2H), 1.59-1 .75 (m, 4H), 1.35-1.52 (m, 8H).

<Step 2: Synthesis of Intermediate B>

Intermediate A: 10.00 g (23.90 mmol), 2,5-dihydroxybenzaldehyde 1.32 g (9.56 mmol), and 2.5-dihydroxybenzaldehyde synthesized in step 1 above in a nitrogen stream in a three-port reactor equipped with a thermometer. 234 mg (1.92 mmol) of 4- (dimethylamino) pyridine was added to 80 mL of chloroform. At room temperature, 3.2 g (25.36 mmol) of N, N'-diisopropylcarbodiimide was slowly added dropwise. After completion of the dropping, the mixture was stirred at 23 ° C. for 3 hours. After completion of the reaction, the reaction solution was directly purified by silica gel column chromatography (diient from chloroform only to chloroform: THF = 9: 1 (volume ratio)) to obtain 6.80 g of intermediate B as a white solid. The yield was 75.7 mol%. The structure of Intermediate B was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, DMSO-d ₆ , TMS, δ ppm): 10.02 (s, 1H), 7.67 (d, 1H, J = 3.0 Hz), 7.55 (dd, 1H, J) = 3.0Hz, 8.5Hz), 7.38 (d, 1H, J = 8.5Hz), 6.99-7.04 (m, 4H), 6.91-6.96 (m, 4H) , 6.32 (dd, 2H, J = 1.5Hz, 17.5Hz), 6.17 (dd, 2H, J = 10.0Hz, 17.5Hz), 5.93 (dd, 2H, J = 1) .5Hz, 10.0Hz), 4.11 (t, 4H, J = 6.5Hz), 3.95 (t, 4H, J = 6.5Hz), 2.56-2.81 (m, 4H) , 2.10-2.26 (m, 8H), 1.50-1.76 (m, 16H), 1.33-1.49 (m, 8H).

<Step 3: Synthesis of Intermediate C>

To a three-port reactor equipped with a thermometer, 50 g (268.5 mmol) of 1-naphthylacetic acid was added to 110 g of toluene in a nitrogen stream. Further, 34.8 g (255 mol) of 6-chloro-1-hexanol and 4.09 g (21.5 mmol) of p-toluenesulfonic acid monohydrate were added to prepare a solution. Using a Dean-Stark apparatus, the prepared solution was heated, and azeotropic dehydration (internal temperature of about 95 ° C.) was performed for 5 hours while discharging the generated water to the outside of the reaction system. After completion of the reaction, 75 g of 6 wt% sodium bicarbonate water was added to the reaction solution cooled to 25 ° C., and the mixture was separated and washed. After the liquid separation, the organic layer was further washed with 80 g of water. After washing, the organic layer was filtered. The solvent was distilled off from the organic layer with a rotary evaporator to obtain 75 g of a light brown oil containing Intermediate C. This light brown oil was not refined and was used as it was in the next reaction (step 4: synthesis of intermediate D). The structure of Intermediate C was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.00 (dd, 1H, J = 1.0 Hz, 8.5 Hz), 7.86 (dd, 1H, J = 1.5 Hz, 8. 5Hz), 7.79 (dd, 1H, J = 1.5Hz, 7.5Hz), 7.54-7.47 (m, 2H), 7.45-7.41 (m, 2H), 4. 09-4.06 (m, 4H), 3.43 (t, 2H, J = 7.0Hz), 1.67-1.61 (m, 2H), 1.58-1.53 (m, 2H) ), 1.35-1.29 (m, 2H), 1.22-1.15 (m, 2H).

<Step 4: Synthesis of Intermediate D>

In a three-port reactor equipped with a thermometer, 6.00 g (36.32 mmol) of 2-hydrazinobenzothiazole was dissolved in 65 mL of N, N-dimethylformamide in a nitrogen stream. To this solution, 23.67 g (72.63 mmol) of cesium carbonate and 20 g of brown oil containing the intermediate C synthesized in step 3 were added, and the whole volume was stirred at 25 ° C. for 15 hours. After completion of the reaction, 250 mL of distilled water was added to the reaction solution, and the mixture was extracted twice with 250 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off. The organic layer was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue is purified by silica gel column chromatography (hexane: THF = 80: 20 (volume ratio)) to make the intermediate D a white solid8. I got 0.0g. The yield was 51.0 mol%. The structure of Intermediate D was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 8.00 (d, 1H, J = 8.5 Hz), 7.85 (dd, 1H, J = 1.0 Hz, 8.0 Hz), 7 .78 (dd, 1H, J = 1.5Hz, 7.5Hz), 7.60 (dd, 1H, J = 1.0Hz, 7.5Hz), 7.54-7.51 (m, 2H), 7.49-7.40 (m, 3H), 7.28 (ddd, 1H, J = 1.0Hz, 7.5Hz, 7.5Hz), 7.07 (ddd, 1H, J = 1.0Hz, 7.5Hz, 7.5Hz), 4.16 (br, 2H), 4.08 (t, 2H, J = 6.5Hz), 4.06 (s, 2H), 3.66 (t, 2H, J = 7.0 Hz), 1.63-1.54 (m, 4H), 1.32-1.22 (m, 4H).

<Step 5: Synthesis of inversely dispersed liquid crystal compound (LA) (an example of the compound represented by the formula (I))>
To a three-port reactor equipped with a thermometer, add 3 g (7.17 mmol) of the intermediate A synthesized in step 1, 30 g of chloroform, and 1.0 g (13.7 mmol) of N, N-dimethylformamide in a nitrogen stream. It was cooled to 10 ° C. or lower. Then, 0.98 g (8.24 mmol) of thionyl chloride was added dropwise while maintaining the reaction temperature at 10 ° C. or lower. After completion of the dropping, the reaction solution was returned to 25 ° C. and stirred for 1 hour. After completion of the reaction, 20 g of chloroform was extracted by an evaporator and concentrated to synthesize a chloroform solution (1).
In a three-port reactor equipped with a separately prepared thermometer, in a nitrogen stream, 0.45 g (3.26 mmol) of 2,5-dihydroxybenzaldehyde and 2.09 g (19.5 mmol) of 2,6-lutidine were added to 20 g. It was dissolved in chloroform and the obtained solution was cooled to 10 ° C. or lower. The entire amount of the chloroform solution (1) was slowly added dropwise to this solution while keeping the reaction temperature at 10 ° C. or lower. After completion of the dropping, the whole volume was further stirred at 5 to 10 ° C. for 1 hour. After completion of the reaction, 12 g of a 1.0N hydrochloric acid aqueous solution and 1.84 g (4.24 mmol) of the intermediate D synthesized in Step 4 were added to the reaction solution while keeping the temperature below 10 ° C. Then, the temperature of the reaction solution was raised to 40 ° C., and the reaction was carried out for 3 hours. After completion of the reaction, the aqueous layer was extracted. Further, 10 g of distilled water was added to the organic layer to wash the organic layer. The obtained organic layer was dried over anhydrous sodium sulfate, and then the sodium sulfate was filtered off. Chloroform was distilled off from the filtrate under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (chloroform: THF = 95: 5) to obtain 3.0 g of a reverse dispersion liquid crystal compound (LA) as a yellow solid. The yield was 67.9%. The structure of the inversely dispersed liquid crystal compound (LA) was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.97 (dd, 1H, J = 0.5 Hz, 8.5 Hz), 7.80 (ddd, 1H, J = 0.5 Hz, 0. 5Hz, 8.0Hz), 773-7.76 (m, 2H), 7.67-7.71 (m, 2H), 7.61 (s, 1H), 7.49 (ddd, 1H, J = 1.0Hz, 6.5Hz, 8.5Hz), 7.42 (ddd, 1H, J = 1.5Hz, 7.0Hz, 7.0Hz), 7.33-7.39 (m, 3H) , 7.18 (ddd, 1H, J = 1.0Hz, 7.5Hz, 8.0Hz), 7.10-7.14 (m, 2H), 6.95-7.01 (m, 4H), 6.85-6.90 (m, 4H), 6.405 (dd, 1H, J = 1.5Hz, 17.5Hz), 6.402 (dd, 1H, J = 1.5Hz, 17.5Hz) , 6.127 (dd, 1H, J = 10.5Hz, 17.5Hz), 6.124 (dd, 1H, J = 10.5Hz, 17.5Hz), 5.822 (dd, 1H, J = 1) .5Hz, 10.5Hz) 5.819 (dd, 1H, J = 1.5Hz, 10.5Hz) 4.16-4.22 (m, 6H) 4.08 (t, 2H, J =) 6.5Hz), 4.03 (s, 2H), 3.95 (t, 2H, J = 6.5Hz), 3.93 (t, 2H, J = 6.5Hz), 2.56-2. 67 (m, 4H), 2.28-2.36 (m, 8H), 1.59-1.83 (m, 20H), 1.42-1.56 (m, 8H), 1.24- 1.36 (m, 4H).

[Synthesis Example 2: Synthesis of Reverse Dispersion Liquid Crystal Compound (LB) (Another Example of the Compound Represented by Formula (I))]

<Step 1: Synthesis of Intermediate E>

In a three-port reactor equipped with a thermometer, 6.00 g (36.32 mmol) of 2-hydrazinobenzothiazole was dissolved in 60.0 mL of N, N-dimethylformamide in a nitrogen stream. To this solution, 23.67 g (72.63 mmol) of cesium carbonate and 5.95 g (43.58 mmol) of 6-chloro-1-hexanol were added, and the whole volume was stirred at 25 ° C. for 14 hours. After completion of the reaction, 250 mL of distilled water was added to the reaction solution, and the mixture was extracted twice with 250 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off. The organic layer was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue is purified by silica gel column chromatography (hexane: THF = 40: 60 (volume ratio)) to make the intermediate E a gray solid 3 Obtained .89 g. The yield was 40.4 mol%. The structure of Intermediate E was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1H, J = 1.0 Hz, 8.0 Hz), 7.53 (d, 1H, J = 8.0 Hz), 7 .28 (ddd, 1H, J = 1.0Hz, 7.5Hz, 8.0Hz), 7.07 (ddd, 1H, J = 1.0Hz, 7.5Hz, 8.0Hz), 4.23 (br) , 2H), 3.77 (t, 2H, J = 7.5Hz), 3.65 (t, 2H, J = 6.5Hz), 1.76 (tt, 2H, J = 7.0Hz, 7. 5Hz), 1.56-1.61 (m, 2H), 1.39-1.50 (m, 5H).

<Step 2: Synthesis of Intermediate F>

In a three-port reactor equipped with a thermometer, the intermediate E synthesized in step 1 was 2.20 g (8.31 mmol) in a nitrogen stream, and the intermediate B synthesized in step 2 of synthesis example 1 was: 6.00 g (6.39 mmol) was dissolved in 12.0 mL of ethanol and 120 mL of THF. To this solution was added 0.30 g (1.28 mmol) of (±) -10-camphormonosulfonic acid, and the whole volume was stirred at 50 ° C. for 4 hours. After completion of the reaction, the reaction solution was put into 200 mL of distilled water and extracted twice with 200 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate, and then sodium sulfate was filtered off. Ethyl acetate was distilled off from the filtrate under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatographic (chloroform: THF = 95: 5) to obtain 6.73 g of Intermediate F as a yellow solid. The yield was 88.7 mol%. The structure of Intermediate F was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.74 (d, 1H, J = 3.0 Hz), 7.67-7.69 (m, 3H), 7.34 (ddd, 1H) , J = 1.0Hz, 7.5Hz, 8.0Hz), 7.17 (ddd, 1H, J = 1.0Hz, 7.5Hz, 8.0Hz), 7.09-7.14 (m, 2H) ), 6.96-7.00 (m, 4H), 6.87-6.90 (m, 4H), 6.42 (dd, 2H, J = 1.5Hz, 17.5Hz), 6.13 (Dd, 2H, J = 10.5Hz, 17.5Hz), 5.82 (dd, 2H, J = 1.5Hz, 10.5Hz), 4.32 (t, 2H, J = 7.5Hz), 4.18 (t, 4H, J = 7.0Hz), 3.95 (t, 2H, J = 6.5Hz), 3.94 (t, 2H, J = 6.5Hz), 3.61-3 .64 (m, 2H), 2.60-2.72 (m, 4H), 2.28-2.35 (m, 8H), 1.66-1.82 (m, 18H), 1.42 -1.62 (m, 15H).

<Step 3: Synthesis of inversely dispersed liquid crystal compound (LB) (another example of the compound represented by the formula (I))>
Intermediate F: 6.00 g (5.06 mmol) synthesized in step 2 and 120 mL of chloroform were added to a three-port reactor equipped with a thermometer in a nitrogen stream to prepare a uniform solution. To there, 1.29 g (6.07 mmol) of diphenylacetic acid was added. Then 0.148 g (1.21 mmol) of N, N-dimethyl-4-aminopyridine was added. Then, 0.842 g (6.68 mmol) of N, N'-diisopropylcarbodiimide was added over 5 minutes while maintaining the internal temperature of the reaction solution at 20 to 30 ° C., and then the whole volume was stirred at 25 ° C. for another 4 hours. did. After completion of the reaction, 250 mL of saturated brine was added to the reaction solution, and the mixture was extracted twice with 250 mL of chloroform. The organic layer was collected, dried over anhydrous sodium sulfate, and the sodium sulfate was filtered off. After evaporating and removing the solvent from the filtrate with a rotary evaporator, the obtained residue is purified by silica gel column chromatography (chloroform: THF = 95: 5), and the inversely dispersed liquid crystal compound (LB) is used as a yellow solid. 6.14 g was obtained. The yield was 87.9 mol%. The structure of the target product (reverse dispersion liquid crystal compound (LB)) was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.75 (dd, 1H, J = 0.5 Hz, 2.0 Hz), 7.69 (dd, 1H, J = 0.5 Hz, 8. 0Hz), 7.67 (d, 1H, J = 8.0Hz), 7.64 (s, 1H), 7.34 (ddd, 1H, J = 1.0Hz, 8.0Hz, 8.0Hz), 7.27-7.30 (m, 7H), 7.16-7.24 (m, 4H), 7.09-7.13 (m, 2H), 6.96-7.00 (m, 4H) ), 6.86-6.90 (m, 4H), 6.404 (dd, 1H, J = 1.5Hz, 17.5Hz), 6.402 (dd, 1H, J = 1.5Hz, 17. 5Hz), 6.12 (dd, 1H, J = 10.5Hz, 17.5Hz), 6.126 (dd, 1H, J = 10.5Hz, 17.5Hz), 5.823 (dd, 1H, J) = 1.5Hz, 10.5Hz) 5.821 (dd, 1H, J = 1.5Hz, 10.5Hz) 4.99 (s, 1H) 4.26 (t, 2H, J = 7. 5Hz), 4.18 (t, 4H, J = 6.5Hz), 4.14 (t, 2H, J = 6.5Hz), 3.95 (t, 2H, J = 6.5Hz), 3. 94 (t, 2H, J = 6.5Hz), 2.58-2.67 (m, 4H), 2.29-2.35 (m, 8H), 1.59-1.82 (m, 20H) ), 1.27-1.53 (m, 12H).

[Synthesis Example 3: Synthesis of Reverse Dispersion Liquid Crystal Compound (LC)]

<Step 1: Synthesis of intermediate α>

In a four-mouth reactor equipped with a thermometer, 2.00 g (12.1 mmol) of 2-hydrazinobenzothiazole was dissolved in 20 mL of dimethylformamide in a nitrogen stream. To this solution, 8.36 g (60.5 mmol) of potassium carbonate and 3.08 g (14.5 mmol) of 1-iodohexane were added, and the mixture was stirred at 50 ° C. for 7 hours. After completion of the reaction, the reaction solution was cooled to 20 ° C., the reaction solution was added to 200 mL of water, and the mixture was extracted with 300 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a yellow solid. This yellow solid was purified by silica gel column chromatography (hexane: ethyl acetate = 75: 25 (volume ratio)) to obtain 2.10 g of intermediate α as a white solid. The yield was 69.6 mol%. The structure of intermediate α was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

^{1 1} H-NMR (500 MHz, CDCl ₃ , TMS, δ ppm): 7.60 (dd, 1H, J = 1.0, 8.0 Hz), 7.53 (dd, 1H, J = 1.0, 8. 0Hz), 7.27 (ddd, 1H, J = 1.0,8.0,8.0Hz), 7.06 (ddd, 1H, J = 1.0,8.0,8.0Hz), 4 .22 (s, 2H), 3.74 (t, 2H, J = 7.5Hz), 1.69-1.76 (m, 2H), 1.29-1.42 (m, 6H), 0 .89 (t, 3H, J = 7.0Hz).

<Step 2: Synthesis of inversely dispersed liquid crystal compound (LC)>
In a four-mouth reactor equipped with a thermometer, the intermediate α: 697 mg (2.37 mmol) synthesized in the above step 1 and the intermediate B: 2.00 g synthesized in the step 2 of the synthesis example 1 were synthesized in a nitrogen stream. (2.13 mmol) was dissolved in 50 mL of chloroform. To this solution, 49 mg (0.21 mmol) of (±) -10-camphorsulfonic acid was added, and the mixture was stirred at 50 ° C. for 3 hours. After completion of the reaction, the reaction solution was put into a mixed water of 100 mL of water and 50 mL of a 5% aqueous sodium hydrogen carbonate solution, and extracted with 250 mL of ethyl acetate. The ethyl acetate layer was dried over anhydrous sodium sulfate. After sodium sulfate was filtered off, ethyl acetate was distilled off under reduced pressure using a rotary evaporator to obtain a white solid. This white solid was purified by silica gel column chromatography (toluene: ethyl acetate = 88: 12 (volume ratio)) to obtain 2.33 g of a reverse-dispersed liquid crystal compound (LC) as a white solid. The yield was 93.5 mol%. The structure of the target product (reverse dispersion liquid crystal compound (LC)) was identified by ¹ H-NMR. ^{1 1} H-NMR spectrum data is shown below.

¹ H-NMR (400MHz, CDCl ₃ , TMS, δppm): 7.75 (d, 1H, J = 2.5Hz), 7.67-7.70 (m, 3H), 7.34 (ddd, 1H) , J = 1.0Hz, 7.0Hz, 7.5Hz), 7.17 (ddd, 1H, J = 1.0Hz, 7.5Hz, 7.5Hz), 7.12 (d, 1H, J = 9) .0Hz), 7.10 (dd, 1H, J = 2.5Hz, 9.0Hz), 6.99 (d, 2H, J = 9.0Hz), 6.98 (d, 2H, J = 9. 0Hz), 6.88 (d, 4H, J = 9.0Hz), 6.40 (dd, 2H, J = 1.5Hz, 17.0Hz), 6.13 (dd, 2H, J = 10.5Hz) , 17.5Hz), 5.82 (dd, 2H, J = 1.5Hz, 10.5Hz), 4.30 (t, 2H, J = 8.0Hz), 4.18 (t, 4H, J =) 6.5Hz), 3.95 (t, 4H, J = 6.5Hz), 2.58-2.70 (m, 4H), 2.31-2.35 (m, 8H), 1.66- 1.82 (m, 18H), 1.31-1.54 (m, 14H), 0.90 (t, 3H, J = 7.0Hz).

[Measuring method of birefringence of liquid crystal compounds]
(Preparation of liquid crystal composition)
100 parts by weight of liquid crystal compound as a sample, 0.30 parts by weight of a fluorosurfactant (“F562” manufactured by DIC Corporation), 4.3 parts by weight of a photopolymerization initiator (“IrgacureOXE04” manufactured by BASF), as a solvent. A liquid crystal composition was obtained by mixing 162.3 parts by weight of cyclopentanone (manufactured by Nippon Zeon) and 243.5 parts by weight of 1,3-dioxolane (manufactured by Toho Kagaku Co., Ltd.) as a solvent.

(Preparation of base film)
As a base film, a diagonally stretched film (Zeonoa film ZD series manufactured by Zeon Corporation, made by Nippon Zeon Corporation) made of a thermoplastic norbornene resin having a masking film bonded to one side was prepared. The masking film was peeled off from this base film.

(Formation of sample liquid crystal layer)
The liquid crystal composition was applied to the masking peeled surface of the base film using the wire bar of # 7 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 an orientation treatment. As a result, the liquid crystal compound contained in the layer of the liquid crystal composition was oriented.
The oriented liquid crystal composition layer was irradiated with ultraviolet rays of 500 mJ / cm ² under a nitrogen atmosphere to cure the liquid crystal composition layer to form a sample liquid crystal layer having a thickness of about 2 μm. As a result, a multi-layer film having a layer structure of a sample liquid crystal layer / base film was obtained.

(Transfer of sample liquid crystal layer)
A slide glass with an adhesive on the surface was prepared. The surface of the double glazing on the sample liquid crystal layer side was attached to this slide glass. Then, the base film was peeled off to obtain a multilayer body having a layer structure of a sample liquid crystal layer / adhesive layer / slide glass.

(Confirmation of homogenius orientation)
The multi-layer body was set in a phase difference meter (“AxoScan” manufactured by Axometrix). The multi-layer body was rotated around the phase-advancing axis of the sample liquid crystal layer as the rotation axis, and the retardation of the sample liquid crystal layer was measured at the incident angles θ of + 50 ° and −50 °, respectively. Since the retardation at the incident angle θ = + 50 ° and the retardation at the incident angle θ = -50 ° are the same, the liquid crystal compound contained in the sample liquid crystal layer has a homogenic orientation parallel to the layer plane. I confirmed that I was doing it.

(Measurement of in-plane retardation of sample liquid crystal layer)
The multi-layer body was set in a phase difference meter (“AxoScan” manufactured by Axometrix), and the in-plane retardation of the sample liquid crystal layer was measured at a measurement wavelength of 590 nm.

(Measurement of sample liquid crystal layer thickness)
The multi-layer body was set in a film thickness measuring meter (“F-20” manufactured by Filmtrix), and the thickness of the sample liquid crystal layer was measured.

(Calculation of birefringence Δn)
The in-plane retardation of the sample liquid crystal layer measured as described above was divided by the thickness of the sample liquid crystal layer to obtain the birefringence Δn of the liquid crystal compound.

In the above-mentioned measuring method, the fluorine-based surfactant and the photopolymerization initiator used in the preparation of the liquid crystal composition do not have birefringence, and the amount thereof is small. In addition, the solvent used to prepare the liquid crystal composition volatilizes prior to the formation of the sample liquid crystal layer. Therefore, the influence of the fluorine-based surfactant, the photopolymerization initiator and the solvent contained in the liquid crystal composition on the birefringence Δn of the sample liquid crystal layer is negligibly small. Therefore, the birefringence Δn of the liquid crystal compound can be obtained by the measurement method using the sample liquid crystal layer.

[Examples 1 to 4]
(Preparation of liquid crystal composition)
3. 100 parts by weight of the inversely dispersed liquid crystal compound shown in Table 1 below, 0.2 parts by weight of the fluorosurfactant (“S420” manufactured by AGC Seimi Chemical Co., Ltd.), and the photopolymerization initiator (“Irgacure OXE04” manufactured by BASF). Liquid crystal composition by mixing 3 parts by weight, 162.3 parts by weight of cyclopentanone (manufactured by Nippon Zeon) as a solvent, and 243.5 parts by weight of 1,3-dioxolane (manufactured by Toho Kagaku Co., Ltd.) as a solvent. I got something.

(Preparation of base film)
As a base film, a resin film made of a thermoplastic norbornene resin having a masking film bonded to one side (“Zeonoa film” manufactured by Zeon Corporation; thickness 100 μm) was prepared. Since this base film was an optically isotropic film, it does not affect the measurement results of the retardation of the first cured layer, the second cured layer and the liquid crystal cured layer, which will be described later. The masking film was peeled off from this base film, and the masking peeled surface was subjected to corona treatment. Next, the corona-treated surface was subjected to a rubbing treatment.

(Formation of the first hardened layer)
A liquid crystal composition was applied to the rubbing-treated surface of the base film using a wire bar to form a layer of the liquid crystal composition.
Then, the layer of the liquid crystal composition was heated at 145 ° C. for 4 minutes to perform an orientation treatment. The orientation temperature in this alignment treatment was the same as the temperature condition in which the residual viscosity of the test composition corresponding to the liquid crystal composition of each Example and Comparative Example was 800 cP or less. By this alignment treatment, the inversely dispersed liquid crystal compound contained in the layer of the liquid crystal composition foreign substance was oriented.
The oriented liquid crystal composition layer was irradiated with ultraviolet rays of 500 mJ / cm ² under a nitrogen atmosphere to cure the liquid crystal composition layer, and the first cured layer having the thickness shown in Table 1 was obtained. Formed. As a result, an intermediate film having a layer structure of the first cured layer / base film was obtained.

(Measurement of the thickness of the first cured layer)
The intermediate film was set in a film thickness measuring meter (“F-20” manufactured by Filmtrix), and the thickness of the first cured layer was measured.

(Measurement of in-plane retardation Re of the first cured layer)
The in-plane retardation Re of the first cured layer of the intermediate film at a measurement wavelength of 590 nm was measured using a retardation meter (“AxoScan” manufactured by Axometrics).

(Measurement of the substantial maximum inclination angle Θ of the molecule of the inversely dispersed liquid crystal compound contained in the first cured layer)
FIG. 4 is a perspective view for explaining a measurement direction when measuring the retardation of the first cured layer 300 from an inclined direction. In FIG. 4, the arrow A1 represents the in-plane slow-phase axis of the first cured layer 300, the arrow A2 represents the in-plane phase-advancing axis of the first cured layer 300, and the arrow A3 represents the thickness of the first cured layer 300. Represents the direction.

The intermediate film was set in a phase difference meter (“AxoScan” manufactured by Axometrics). The intermediate film is rotated around the phase-advancing axis A2 of the first cured layer 300 as the rotation axis, and as shown in FIG. 4, the retardation of the first cured layer 300 is applied in the range of an incident angle θ of −50 ° to 50 °. Measured at. Therefore, the measurement direction A4 is set perpendicular to the phase advance axis A2 of the first cured layer 300. The measurement wavelength was 590 nm.

From the measured retardation R (θ), the analysis software attached to the phase difference meter (analysis software "Multi-Layer Analysis" manufactured by Axometrics; analysis conditions are analysis wavelength 590 nm, number of layer divisions 20 layers). , The substantial maximum inclination angle Θ of the molecule of the inversely dispersed liquid crystal compound contained in the first cured layer was calculated.

(Evaluation of the gradient orientation of the inversely dispersed liquid crystal compound contained in the first cured layer)
The retardation R (θ) of the first cured layer measured at an incident angle θ in the range of −50 ° to 50 ° is divided by the retardation R (0 °) of the first cured layer at an incident angle of 0 °. The retardation ratio R (θ) / R (0 °) was determined. A graph was drawn with the obtained retardation ratio R (θ) / R (0 °) as the vertical axis and the incident angle θ as the horizontal axis.
When the graph of the obtained retardation ratio R (θ) / R (0 °) was asymmetric with respect to θ = 0 °, the gradient orientation was judged to be “good”. In this case, it can be determined that at least a part of the molecules of the inversely dispersed liquid crystal compound contained in the first cured layer are inclined with respect to the layer plane of the first cured layer.
Further, when the graph of the obtained retardation ratio R (θ) / R (0 °) was symmetric with respect to θ = 0 °, the gradient orientation was determined to be “poor”.

(Formation of LCD cured layer by formation of second cured layer)
A wire bar is used to directly coat the surface of the first cured layer of the intermediate film with the same liquid crystal composition used for forming the first cured layer to form a layer of the liquid crystal composition. did.
Then, the layer of the liquid crystal composition was heated at 145 ° C. for 4 minutes to perform an orientation treatment. By this alignment treatment, the inversely dispersed liquid crystal compound contained in the layer of the liquid crystal composition was oriented.
The oriented liquid crystal composition layer was irradiated with ultraviolet rays of 500 mJ / cm ² under a nitrogen atmosphere to cure the liquid crystal composition layer, and a second cured layer having the thickness shown in Table 1 was obtained. Formed. As a result, a liquid crystal cured film having a layer structure of a second cured layer / a first cured layer / a base film was obtained. In this liquid crystal cured film, the combination of the first cured layer and the second cured layer corresponds to the liquid crystal cured layer.

(Measurement of thickness of second cured layer and LCD cured layer)
The liquid crystal cured film was set in a film thickness measuring meter (“F-20” manufactured by Filmtrix), and the thickness of the liquid crystal cured layer was measured. Further, the thickness of the second cured layer was obtained by subtracting the thickness of the first cured layer from the thickness of the liquid crystal cured layer.

(Measurement of in-plane retardation Re of the second cured layer and the liquid crystal cured layer)
The in-plane retardation Re of the liquid crystal cured layer of the liquid crystal cured film at a measurement wavelength of 590 nm was measured using a phase difference meter (“AxoScan” manufactured by Axometrics). In addition, the in-plane retardation of the second cured layer was calculated from the in-plane retardation of the liquid crystal cured layer and the in-plane retardation of the first cured layer.

(Measurement of the substantially maximum tilt angle of the molecules of the inversely dispersed liquid crystal compound contained in the second cured layer and the liquid crystal cured layer)
The liquid crystal cured film was set in a phase difference meter (“AxoScan” manufactured by Axometrics). The liquid crystal cured film was rotated around the phase advance axis of the liquid crystal cured layer as a rotation axis, and the retardation of the liquid crystal cured layer was measured in the range of an incident angle θ of −50 ° to 50 °. Therefore, the measurement direction is set perpendicular to the phase advance axis of the liquid crystal cured layer. The measurement wavelength was 590 nm.

From the measured retardation R (θ), the analysis software attached to the phase difference meter (analysis software "Multi-Layer Analysis" manufactured by Axometrics; analysis conditions are analysis wavelength 590 nm, number of layer divisions 20 layers). , The substantial maximum tilt angle Θ of the molecule of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer was calculated. The larger the substantially maximum inclination angle Θ is, the larger the inclination angle of the molecules of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer is.

Further, the substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound in the entire liquid crystal cured layer, the substantially maximum tilt angle of the molecule of the dedispersed liquid crystal compound contained in the first cured layer, the first cured layer and the second. Using the thickness of the cured layer, the substantially maximum tilt angle of the molecule of the inversely dispersed liquid crystal compound contained in the second cured layer was calculated.

(Evaluation of the gradient orientation of the inversely dispersed liquid crystal compound contained in the liquid crystal cured layer)
The reflection R (θ) of the liquid crystal cured layer measured in the range of the incident angle θ in the range of −50 ° to 50 ° is divided by the retardation R (0 °) of the liquid crystal cured layer at the incident angle of 0 °. The lettering ratio R (θ) / R (0 °) was determined. A graph was drawn with the obtained retardation ratio R (θ) / R (0 °) as the vertical axis and the incident angle θ as the horizontal axis.
When the graph of the obtained retardation ratio R (θ) / R (0 °) was asymmetric with respect to θ = 0 °, the gradient orientation was judged to be “good”. In this case, it can be determined that at least a part of the molecules of the back-dispersed liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane of the liquid crystal cured layer.
Further, when the graph of the obtained retardation ratio R (θ) / R (0 °) was symmetric with respect to θ = 0 °, the gradient orientation was determined to be “poor”.

(Evaluation of reverse wavelength dispersibility of liquid crystal cured layer)
The in-plane retardations Re (450) and Re (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 phase difference meter (“AxoScan” manufactured by Axometrics). Based on this measurement result, the inverse wavelength dispersibility was evaluated according to the following criteria.
"Yu": Re (450) / Re (550) <0.9
"Good": Re (450) / Re (550) <1.0
"Defective": Re (450) / Re (550)> 1.0

(Evaluation of viewing angle characteristics of liquid crystal cured layer)
The liquid crystal cured film was set in a phase difference meter (“AxoScan” manufactured by Axometrics). The liquid crystal cured film was rotated around the phase advance axis of the liquid crystal cured layer as a rotation axis, and the retardation of the liquid crystal cured layer was measured in the range of an incident angle θ of −50 ° to 50 °. Therefore, the measurement direction is set perpendicular to the phase advance axis of the liquid crystal cured layer. The measurement wavelength was 590 nm.

Lettering R (+ 50 °) at incident angle θ = + 50 °, Lettering R (-50 °) at incident angle θ = -50 °, and Lettering R (0 °) at incident angle 0 ° (0 °) That is, the average retardation ratio T (= R (± 50 °) / R (0 °)) was calculated from the in-plane retardation) by the following formula. The closer the T value is to 1.00, the better the viewing angle characteristic can be obtained.
T = [{R (50 °) + R (-50 °)} / 2] / R (0 °)

[Comparative Examples 1 to 4]
The thickness of the first cured layer was adjusted as shown in Table 1. Moreover, the formation of the second hardened layer was not performed. Therefore, in Comparative Examples 1 to 4, the first cured layer and the intermediate film were treated as the liquid crystal cured layer and the liquid crystal cured film. Except for the above items, the liquid crystal cured film was manufactured and evaluated by the same operation as in Examples 1 to 4.

[Comparative Example 5]
The type of the inversely dispersed liquid crystal compound, the thickness of the first cured layer, and the thickness of the second cured layer were adjusted as shown in Table 1. Except for the above items, the liquid crystal cured film was manufactured and evaluated by the same operation as in Examples 1 to 4.

[result]
The results of the above-mentioned Examples and Comparative Examples are shown in Table 1 below. In Table 1, the meanings of the abbreviations are as follows.
Δn: Birefringence of the inversely dispersed liquid crystal compound.
Re: In-plane lettering.
Θ: Effective maximum tilt angle.

10 Liquid crystal cured film 20 Liquid crystal cured film 100 Liquid crystal cured layer 110 First cured layer 120 Second cured layer 200 Liquid crystal cured layer 230 Third cured layer 240 Layer portion consisting of first cured layer and second cured layer 300 First cured layer

Claims (10)

It is provided with a liquid crystal cured layer containing a molecule of the liquid crystal compound which is formed of a cured product of a liquid crystal composition containing a liquid crystal compound having birefringence of reverse wavelength dispersibility and may have a fixed orientation state.
The liquid crystal compound is a value calculated by forming a layer containing the liquid crystal compound and dividing the in-plane retardation in the layer in which the molecules of the liquid crystal compound contained in the layer are homogenically oriented by the thickness of the layer. When the birefringence of
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
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 liquid crystal cured layer includes a first cured layer and a second cured layer in direct contact with the first cured layer.
A liquid crystal curing film in which the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the first cured layer. The liquid crystal curing film according to claim 1, wherein the liquid crystal compound is represented by the following formula (I) or formula (II).

(In the above formulas (I) and (II),
Ga represents ^a divalent organic group having 1 to 30 carbon atoms which may have a substituent.
Y ^a is a chemical single bond, -O-, -C (= O)-, -C (= O) -O-, -OC (= O)-, -OC (= O). -O-, -C (= O) -S-, -SC (= O)-, -NR ¹² -C (= O)-, -C (= O) -NR ^12- , -OC (= O) -NR ^12- , -NR ¹² -C (= O) -O-, -S-, -N = N-, or -C≡C-. R ¹² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Fx ¹ and Fx ² each independently represent an organic group having at least one of an aromatic hydrocarbon ring and an aromatic heterocycle.
Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
^{RI, R II ,} R ^III and R ^IV each independently have a hydrogen atom; a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; at least one hydrogen atom is replaced with a halogen atom. Alkoxy group with 1 to 6 carbon atoms; Alkoxy group with 1 to 6 carbon atoms; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ; show. Ra may have an alkyl group having 1 to 20 carbon atoms which may have ^a substituent, an alkenyl group having 2 to 20 carbon atoms which may have a substituent, and carbon which may have a substituent. It represents a cycloalkyl group having a number of 3 to 12, or an aromatic hydrocarbon ring group having 6 to 18 carbon atoms which may have a substituent. At least one of CR ^I , CR ^II , CR ^III and CR ^IV may be replaced with a nitrogen atom.
R ⁰ is independently a halogen atom; an alkyl group having 1 to 6 carbon atoms; a cyano group; a nitro group; an alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is replaced with a halogen atom; Represents 1 to 6 alkoxy groups; -OCF ₃ ; -C (= O) -OR ^a ; or -OC (= O) -R ^a ;.
p represents an integer of 0 to 3.
p1 represents an integer of 0 to 4.
p2 represents 0 or 1.
Y ¹ , Y ² , Y ³ , Y ⁴ , Y ⁵ , Y ⁶ , Y ⁷ and Y ⁸ are independently chemically single bonds, -O-, -O-CH _2- , -CH ₂ respectively. -O-, -O-CH ₂ -CH _2- , -CH ₂ -CH ₂ -O-, -C (= O) -O-, -OC (= O)-, -OC (= O) -O-, -C (= O) -S-, -SC (= O)-, -NR ¹³ -C (= O)-, -C (= O) -NR ^13- , -CF ₂ -O-, -O-CF _2- , -CH ₂ -CH _2- , -CF ₂ -CF _2- , -O-CH ₂ -CH ₂ -O-, -CH = CH-C (= O) -O-, -OC (= O) -CH = CH-, -CH ₂ -C (= O) -O-, -OC (= O) -CH _{2-, -CH 2 -} O- C (= O)-, -C (= O) -O-CH _2- , -CH ₂ -CH ₂ -C (= O) -O-, -OC (= O) -CH ₂ -CH ₂ -, -CH ₂ -CH ₂ -OC (= O)-, -C (= O) -O-CH ₂ -CH _2- , -CH = CH-, -N = CH-, -CH = N -, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N-, or -C≡C-. R ¹³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
A ¹ , A ² , B ¹ and B ² each independently represent a cyclic aliphatic group which may have a substituent or an aromatic group which may have a substituent.
G ¹ and G ² are divalent aliphatic hydrocarbon groups having 1 to 30 carbon atoms which may independently have a substituent; and 3 carbon atoms which may have a substituent. At least one of -CH _2- contained in ~ 30 divalent aliphatic hydrocarbon groups is -O-, -S-, -OC (= O)-, -C (= O) -O-. , -OC (= O) -O-, -NR ¹⁴ -C (= O)-, -C (= O) -NR ^14- , -NR ^14- , or -C (= O)- Represents any organic group selected from the group consisting of substituted groups (except when two or more -O- or -S- are adjacent to each other and intervening); R ¹⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
P ¹ and P ² each represent an alkenyl group having 2 to 10 carbon atoms, which may be independently substituted with a halogen atom or a methyl group.
m and n independently represent 0 or 1, respectively. ) A first cured layer used for the liquid crystal curable film according to claim 1 or 2.
The first cured layer is formed of a cured product of a liquid crystal composition containing the liquid crystal compound having the reverse wavelength dispersive birefringence, and contains molecules of the liquid crystal compound whose orientation state may be fixed. See,
The liquid crystal compound is a value calculated by forming a layer containing the liquid crystal compound and dividing the in-plane retardation in the layer in which the molecules of the liquid crystal compound contained in the layer are homogenically oriented by the thickness of the layer. When the birefringence of
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
At least a part of the molecules of the liquid crystal compound contained in the first cured layer are inclined with respect to the layer plane of the first cured layer.
The first cured layer having an in-plane retardation of 20 nm or more and less than 80 nm at a measurement wavelength of 590 nm. The liquid crystal curing film according to claim 1 or 2, wherein the first cured layer can function as an alignment film for increasing the inclination angle of the molecules of the liquid crystal compound contained in the second cured layer. The liquid crystal curing film according to any one of claims 1, 2 and 4, wherein the substantially maximum inclination angle of the molecule of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° or more and 85 ° or less. The liquid crystal curing film according to any one of claims 1, 2, 4 and 5, wherein the thickness of the liquid crystal curing layer is 10 μm or less. The liquid crystal curing film according to any one of claims 1, 2 and 4 to 6, wherein the liquid crystal curing layer can function as a 1/4 wave plate. The method for producing a liquid crystal cured film according to any one of claims 1, 2 and 4 to 7.
A step of forming a layer of the first liquid crystal composition containing the liquid crystal compound, and
A step of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition,
The step of curing the layer of the first liquid crystal composition to form the first cured layer,
A step of directly forming a layer of a second liquid crystal composition containing the same or different liquid crystal compound as the liquid crystal compound contained in the first liquid crystal composition on the first cured layer.
A step of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition,
A method for producing a liquid crystal cured film, which comprises a step of curing a layer of the second liquid crystal composition to form a second cured layer. A liquid crystal cured layer containing a molecule of the liquid crystal compound which is formed of a cured product of a liquid crystal composition containing a liquid crystal compound having birefringence of reverse wavelength dispersibility and may have a fixed orientation state, and a linear polarizing element. Including and
The liquid crystal compound is a value calculated by forming a layer containing the liquid crystal compound and dividing the in-plane retardation in the layer in which the molecules of the liquid crystal compound contained in the layer are homogenically oriented by the thickness of the layer. When the birefringence of
The birefringence of the liquid crystal compound at the measurement wavelength of 590 nm is 0.065 or less.
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 liquid crystal cured layer includes a first cured layer and a second cured layer in direct contact with the first cured layer.
A polarizing plate in which the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the second cured layer is larger than the substantially maximum tilt angle of the molecule of the liquid crystal compound contained in the first cured layer. An organic electroluminescence display device including the polarizing plate according to claim 9.

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