WO2019131662A1

WO2019131662A1 - Liquid crystal cured film, polarization plate, and method for manufacturing organic electroluminescence display device

Info

Publication number: WO2019131662A1
Application number: PCT/JP2018/047634
Authority: WO
Inventors: 菜津美藤原
Original assignee: 日本ゼオン株式会社
Priority date: 2017-12-28
Filing date: 2018-12-25
Publication date: 2019-07-04
Also published as: TW201940562A; JPWO2019131662A1; JP7306273B2

Abstract

A method for manufacturing a liquid crystal cured film provided with a liquid crystal cured layer including a first cured layer and a second cured layer, wherein the method includes, in the sequence listed: a step for forming a layer of a first liquid crystal composition; a step for aligning a liquid crystalline compound contained in the first liquid crystal composition; a step for curing the layer of the first liquid crystal composition and forming the first cured layer; a step for forming a layer of a second liquid crystal composition directly on the first cured layer; a step for aligning a liquid crystalline compound contained in the second liquid crystal composition; a step in which the actual maximum tilt angle of the molecules of the liquid crystalline compound contained in the second liquid crystal composition increases with the passage of time; and a step for curing the layer of the second liquid crystal composition and forming the second cured layer.

Description

Method of manufacturing liquid crystal cured film, polarizing plate and organic electroluminescence display device

The present invention relates to a liquid crystal cured film, a polarizing plate, and a method of manufacturing an organic electroluminescence display.

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

Patent No. 5363022 gazette International Publication No. 2016/031853 JP, 2017-037193, A

The liquid crystal cured layer included in the liquid crystal cured film usually contains a liquid crystal compound. The molecules of the liquid crystal compound may be inclined with respect to the layer plane of the liquid crystal cured layer. The liquid crystal cured layer containing the liquid crystal compound in which the molecules are inclined in this manner generally has birefringence in the thickness direction according to the size of the inclination angle of the molecules of the liquid crystal compound. A cured liquid crystal film including a cured liquid crystal layer whose birefringence in the thickness direction is appropriately adjusted is used as an image display device such as an organic electroluminescent display device (hereinafter sometimes referred to as “organic EL display device” as appropriate). By providing them, various advantages such as improvement of the viewing angle can be obtained.

The tilt angle of the molecules of the liquid crystal compound contained in a certain layer can be evaluated by the substantially maximum tilt angle. The “substantially maximum inclination angle” means that the inclination angle of the molecule on one surface of the layer is 0 ° and the inclination angle of the molecule changes at a constant rate in the thickness direction. The maximum value of the tilt angle of molecules of a liquid crystal compound. In a layer containing a liquid crystal compound, the inclination angle of the molecules of the liquid crystal compound may be smaller as it is closer to one side of the layer in the thickness direction, and larger as it is farther from the one side. The actual maximum inclination angle is calculated on the assumption that the ratio of the change of the inclination angle in the thickness direction (ie, the ratio of the change decreasing closer to one side and increasing increasing farther from one side) is constant. Represents the maximum value of the tilt angle.

The adjustment of the substantial maximum tilt angle of the molecules of the liquid crystal compound can usually be performed by adjusting the composition of the liquid crystal composition. However, it is troublesome to prepare liquid crystal compositions having different compositions each time the substantial maximum inclination angle is to be changed. Therefore, development of a technique capable of easily adjusting the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is desired.

The present invention has been made in view of the above problems, and is a method for producing a cured liquid crystal film having a cured liquid crystal layer, which facilitates the substantially maximum inclination angle of the molecules of the liquid crystal compound contained in the cured liquid crystal layer. Manufacturing method of the polarizing plate using the manufacturing method of the liquid crystal cured film described above; and a manufacturing method of an organic EL display device using the manufacturing method of the liquid crystal cured film described above; I assume.

The present inventors diligently studied to solve the above-mentioned problems. As a result, the inventor forms a first cured layer with the first liquid crystal composition, forms a layer of the second liquid crystal composition containing the liquid crystal compound directly on the first cured layer, and After the liquid crystal compound contained in the layer of the second liquid crystal composition is aligned, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition is increased with the passage of time. I found it to grow. And based on this knowledge, the present inventors completed the present invention.
That is, the present invention includes the following.

[1] A method for producing a cured liquid crystal film comprising a cured liquid crystal composition containing a liquid crystal compound, and a cured liquid crystal layer comprising a first cured layer and a second cured layer,
The substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is 5 ° or more and 85 ° or less,
The manufacturing method is
Step (I) of forming a layer of a first liquid crystal composition containing the liquid crystal compound
Aligning the liquid crystal compound contained in the layer of the first liquid crystal composition (II);
Curing the layer of the first liquid crystal composition to form the first cured layer (III);
Forming a layer of a second liquid crystal composition containing the liquid crystal compound which is the same as or different from the liquid crystal compound contained in the first liquid crystal composition directly on the first cured layer;
Aligning the liquid crystalline compound contained in the layer of the second liquid crystal composition (V);
Step (VI) in which the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition increases with the passage of time;
Curing the layer of the second liquid crystal composition to form the second cured layer (VII); in this order, a method for producing a liquid crystal cured film.
[2] The method for producing a liquid crystal cured film according to [1], wherein the step (VI) is performed for 60 seconds or more.
[3] The method for producing a liquid crystal cured film according to [1] or [2], wherein the step (VI) is performed for a time of 120 seconds to 600 seconds.
[4] Any one of [1] to [3], wherein the step (VI) is performed under a temperature condition lower than the liquid crystal phase-solid phase transition temperature of the liquid crystal compound contained in the second liquid crystal composition The manufacturing method of the liquid crystal hardening film as described in-.
[5] The method for producing a liquid crystal cured film according to any one of [1] to [4], wherein the liquid crystal compound is a liquid crystal compound capable of exhibiting reverse wavelength dispersive birefringence.
[6] The liquid crystal cured film according to any one of [1] to [5], wherein the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° to 85 °. Manufacturing method.
[7] The substantial maximum tilt angle of the molecules of the liquid crystalline compound contained in the second cured layer is larger than the substantial maximum tilt angle of the molecules of the liquid crystalline compound contained in the first cured layer, [1] The manufacturing method of the liquid crystal cured film as described in any one of [6].
[8] The method for producing a liquid crystal cured film according to any one of [1] to [7], wherein the liquid crystal cured layer can function as a quarter wavelength plate.
[9] A manufacturing method of a polarizing plate provided with a liquid crystal cured film,
A method for producing a polarizing plate, comprising producing the liquid crystal cured film by the method according to any one of [1] to [8].
[10] A method of manufacturing an organic electroluminescent display device comprising a polarizing plate,
The manufacturing method of the organic electroluminescent display apparatus including manufacturing the said polarizing plate by the manufacturing method of [9] description.

According to the present invention, there is provided a method of producing a cured liquid crystal film comprising a cured liquid crystal layer, wherein the substantially maximum inclination angle of the molecules of the liquid crystal compound contained in the cured liquid crystal layer can be easily adjusted; The manufacturing method of the polarizing plate using the manufacturing method of these; And the manufacturing method of the organic electroluminescence display using the manufacturing method of said liquid crystal cured film can be provided.

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

Hereinafter, the present invention will be described in detail by way of examples and embodiments. However, the present invention is not limited to the examples and embodiments shown below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents 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 certain layer indicates the direction perpendicular to the plane of the layer, unless otherwise specified. Therefore, unless otherwise specified, the in-plane direction and thickness direction of a given layer are perpendicular.

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

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

In the following description, the birefringence Δn (450) at a wavelength of 450 nm and the birefringence Δn (550) at a wavelength of 550 nm satisfy the following formula (N1) unless otherwise specified: Say Generally, a liquid crystal compound capable of expressing such reverse wavelength dispersive birefringence can exhibit greater birefringence as the measurement wavelength is longer.
Δn (450) <Δn (550) (N1)

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 formula (N2), unless otherwise specified. Say In general, a liquid crystal compound capable of expressing such normal wavelength dispersive birefringence can exhibit smaller birefringence as the measurement wavelength is longer.
Δn (450)> Δn (550) (N2)

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

In the following description, a resin having a positive intrinsic birefringence value means a resin in which the refractive index in the stretching direction is larger than the refractive index in the direction orthogonal thereto. In addition, a 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 thereto. The intrinsic birefringence value can be calculated from the dielectric constant distribution.

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

In the following description, unless the directions of the elements “parallel” and “vertical” are different from each other, they do not impair the effects of the present invention, for example, ± 4 °, preferably ± 3 °, more preferably ± 1. An error within the range of ° may be included.

In the following description, unless otherwise specified, the "tilt angle" of the molecules of the liquid crystal compound contained in a certain layer means the angle that the molecules of the liquid crystal compound form with respect to the layer plane, and "tilt angle" Sometimes called. This inclination angle corresponds to the largest angle among the angles that the direction of the largest refractive index makes with the layer plane in the refractive index ellipsoid of the molecules of the liquid crystal compound. In the following description, unless otherwise specified, the "tilt angle" refers to the tilt angle of the molecules of the liquid crystal compound relative to the layer plane of the layer in which the liquid crystal compound is contained. The tilt angle with respect to the layer plane may be referred to as “tilt angle with respect to the in-plane direction” parallel to the layer plane.

[1. Outline of production method of liquid crystal cured film]
FIG. 1 is a cross-sectional view schematically showing a liquid crystal cured film 100 produced by the production method according to an embodiment of the present invention.
As shown in FIG. 1, the method for producing a cured liquid crystal film 100 according to an embodiment of the present invention is a cured liquid crystal film 100 having a cured liquid crystal layer 110 formed of a cured product of a liquid crystal composition containing a liquid crystalline compound. Manufacturing method. The liquid crystal cured layer 110 of the liquid crystal cured film 100 produced by this production method includes a first cured layer 111 and a second cured layer 112 formed of a cured product of a liquid crystal composition containing a liquid crystal compound.

Since it is formed of a cured product of the liquid crystal composition, the liquid crystal cured layer 110 contains molecules (not shown) of the liquid crystal compound. The molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 may be fixed in the alignment state. The term "liquid crystal compound in which the alignment state is fixed" includes polymers of liquid crystal compounds. Usually, the liquid crystallinity of the liquid crystalline compound is lost by polymerization, but in the present application, the liquid crystalline compound thus polymerized is also included in the term “liquid crystalline compound contained in the liquid crystal cured layer”.

At least a part of molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 is inclined with respect to the layer plane of the liquid crystal cured layer 110 (that is, in the in-plane direction). When a molecule of a liquid crystal compound is "tilted" with respect to the layer plane (ie, with respect to the in-plane direction), the tilt angle of the molecule with respect to the layer plane (ie with respect to the in-plane direction) It represents that it is in the range below °. The molecules of the liquid crystal compound thus inclined are usually neither parallel nor perpendicular to the layer plane (ie, to the in-plane direction).

Since at least a part of molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 is inclined with respect to the layer plane of the liquid crystal cured layer 110 (that is, with respect to the in-plane direction), it is included in the liquid crystal cured layer 110 The substantial maximum tilt angle of the molecules of the liquid crystal compound is usually 5 ° or more and 85 ° or less. The substantial maximum tilt angle is an index indicating the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110. In general, as the liquid crystal cured layer 110 has a substantially larger maximum tilt angle, the tilt angle as a whole of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 tends to be larger. Therefore, if the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 can be adjusted, the inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 can be adjusted as a whole. And the liquid crystal cured film 100 provided with the liquid crystal cured layer 110 in which the substantial maximum inclination angle is appropriately adjusted can appropriately adjust the birefringence in the thickness direction, and therefore can exhibit excellent viewing angle characteristics.

The manufacturing method of such a liquid crystal hardening film 100 is
Forming a layer of a first liquid crystal composition containing a liquid crystal compound (I);
Aligning the liquid crystal compound contained in the layer of the first liquid crystal composition (II);
Curing the layer of the first liquid crystal composition to form a first cured layer 111 (III);
Forming a layer of a second liquid crystal composition containing a liquid crystal compound which is the same as or different from the liquid crystal compound contained in the first liquid crystal composition directly on the first cured layer 111;
Aligning the liquid crystal compound contained in the layer of the second liquid crystal composition (V);
Step (VI) in which the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition increases with the passage of time;
Curing the layer of the second liquid crystal composition to form a second cured layer 112 (VII);
In this order.

[2. Step (I): Formation of Layer of First Liquid Crystal Composition]
In the step (I), a layer of a first liquid crystal composition as a liquid crystal composition for forming a first cured layer is formed.

The first liquid crystal composition includes a liquid crystal compound for forming a first cured layer. The liquid crystal compound is a compound having liquid crystallinity, and is usually a compound capable of exhibiting a liquid crystal phase when the liquid crystal compound is aligned. As the liquid crystal compound, a reverse dispersion liquid crystal compound may be used, a forward dispersion liquid crystal compound may be used, or a combination of the reverse dispersion liquid crystal compound and the forward dispersion liquid crystal compound may be used.

The reverse dispersion liquid crystal compound is a liquid crystal compound capable of expressing reverse wavelength dispersive birefringence. In addition, a liquid crystal compound capable of expressing reverse wavelength dispersive birefringence forms a layer of the liquid crystal compound, and when the liquid crystal compound is aligned in that layer, it exhibits reverse wavelength dispersive birefringence. Liquid crystal compound.

The normal dispersion liquid crystal compound is a liquid crystal compound capable of expressing birefringence with normal wavelength dispersion. In addition, a liquid crystal compound capable of expressing forward wavelength dispersive birefringence forms a layer of the liquid crystal compound, and when the liquid crystal compound is aligned in the layer, it exhibits birefringence of forward wavelength dispersion. Liquid crystal compound.

Usually, when the liquid crystalline compound is homogeneously aligned, the wavelength dispersion of birefringence exhibited by the liquid crystalline compound can be confirmed by examining the wavelength dispersion of birefringence exhibited by the layer of the liquid crystalline compound. Here, the liquid crystal compound is homogeneously aligned by forming a layer containing the liquid crystal compound, and the direction of the maximum refractive index in the refractive index ellipsoid of the molecules of the liquid crystal compound in the layer is It refers to orienting in one direction parallel to the plane. The birefringence of the layer is determined from "(in-plane retardation of layer) / (thickness of layer)".

In particular, as the liquid crystal compound contained in the first liquid crystal composition, when the second liquid crystal composition contains a reverse dispersion liquid crystal compound, a reverse dispersion liquid crystal compound is preferable. By using the reverse dispersion liquid crystal compound, in the step (VI), the substantial maximum tilt angle of the molecules of the reverse dispersion liquid crystal compound contained in the layer of the second liquid crystal composition can be effectively enlarged with the passage of time. Therefore, adjustment of the tilt angle of the molecules of the liquid crystal compound in the step (VI) can be effectively performed. Furthermore, by using the reverse dispersion liquid crystal compound, in general, the first cured layer can function as a tilted alignment film that increases the tilt angle of the molecules of the reverse dispersion liquid crystal compound contained in the second cured layer. Therefore, when the second liquid crystal composition contains the reverse dispersion liquid crystal compound, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be adjusted in a wide range.

The refractive index anisotropy of the liquid crystal compound exhibiting reverse wavelength dispersion is the refractive index of the direction showing the maximum refractive index and the refractive index of the molecule of the liquid crystal compound, and the other direction intersecting this direction It expresses as a difference with the refractive index of Further, depending on the molecular structure of the liquid crystal compound, the wavelength dispersion of the refractive index in each direction may differ. Thus, for example, in a direction in which the refractive index is relatively large, the refractive index measured at the long wavelength is smaller than the refractive index measured at the short wavelength, but the difference between them is small. On the other hand, in the other direction where the refractive index is relatively small, the refractive index measured at the long wavelength is smaller than the refractive index measured at the short wavelength, and the difference between them is large. The refractive index difference between the directions in such an example is small when the measurement wavelength is short, and is large when the measurement wavelength is long. As a result, it is possible to express reverse wavelength dispersive birefringence.

The liquid crystal compound preferably has a polymerizability. Therefore, in the liquid crystal compound, the molecule preferably contains a polymerizable group such as an acryloyl group, a methacryloyl group, and an epoxy group. A polymerizable liquid crystal compound can be polymerized in a liquid crystal phase, and can be a polymer while maintaining the alignment state of molecules in the liquid crystal phase. Therefore, it is possible to fix the alignment state of the liquid crystalline compound in the first cured layer, or to increase the degree of polymerization of the liquid crystalline compound to increase the mechanical strength of the first cured layer.

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

The birefringence Δn of the liquid crystal compound at a measurement wavelength of 550 nm is preferably 0.01 or more, more preferably 0.03 or more, preferably 0.15 or less, more preferably 0.10 or less. By using a liquid crystal compound having a birefringence Δn in such a range, it is possible to easily obtain a first cured layer in which the substantial maximum tilt angle of the molecules of the liquid crystal compound is large. Furthermore, usually, by using a liquid crystal compound having a birefringence Δn in such a range, it is easy to obtain a first cured layer with few alignment defects.

The birefringence of the liquid crystal compound can be measured, for example, by the following method.
A layer of liquid crystal compound is produced, and the liquid crystal compound contained in the layer is homogeneously aligned. Thereafter, the in-plane retardation of the layer is measured. Then, the birefringence of the liquid crystal compound can be determined from “(in-plane retardation of layer) / (thickness of layer)”. Under the present circumstances, in order to make measurement of in-plane retardation and thickness easy, you may harden the layer of the liquid crystal compound which carried out homogeneous orientation.

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

There is no restriction | limiting in the kind of concrete liquid crystalline compound. For example, as an example of the reverse dispersion liquid crystal compound, those represented by the following formula (I) can be mentioned.

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

In formulas (II-1) to (II-7) above, E ¹ and E ² are each independently —CR ¹¹ R ¹² —, —S—, —NR ¹¹ —, —CO— and — It represents a group selected from the group consisting of O-. R ¹¹ and R ¹² each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. Among them, E ¹ and E ² are preferably each independently —S—.

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

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

As a substituent which the aromatic hydrocarbon ring group in D ¹ to D ³ may have, for example, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a carbon atom such as a methyl group, an ethyl group and a propyl group An alkyl group having 1 to 6 carbons; an alkenyl group having 2 to 6 carbon atoms such as a vinyl group or an allyl group; a halogenated alkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group; a dimethylamino group And an alkoxy group having 1 to 6 carbon atoms, such as an N, N-dialkylamino group having 1 to 12 carbon atoms; a methoxy group, an ethoxy group and an isopropoxy group; a nitro group; -OCF ₃ ; -C (= O —R ^b ; —O—C (= O) —R ^b ; —C (= O) —O—R ^b ; —SO ₂ R ^a ; The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

R ^a represents an alkyl group having 1 to 6 carbon atoms; and an alkyl group having 1 to 6 carbon atoms or an alkoxy group having 1 to 6 carbon atoms as a substituent, having 6 carbon atoms And a group selected from the group consisting of -20 aromatic hydrocarbon ring groups;

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

The number of carbon atoms of the alkyl group having 1 to 20 carbon atoms for R ^b is preferably 1 to 12, and more preferably 4 to 10. As a C1-C20 alkyl group in R ^b , for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group , Sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group , N-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, and n-icosyl group And the like.

The substituent which the alkyl group having 1 to 20 carbon atoms for R ^b may have is, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a dimethylamino group or the like; N, N-dialkylamino group; an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy; and C 1 to 12 having carbon atoms such as methoxymethoxy and methoxyethoxy An alkoxy group substituted with an alkoxy group, an alkoxy group having 1 to 12 carbon atoms, a nitro group, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, Aromatic heterocyclic groups having 2 to 20 carbon atoms such as thienyl group, thiazolyl group and benzothiazol-2-ylthio group; cyclopropyl group, cyclopentyl group A cycloalkyl group having 3 to 8 carbon atoms, such as clohexyl group; a cycloalkyloxy group having 3 to 8 carbon atoms, such as cyclopentyloxy group and cyclohexyloxy group; a tetrahydrofuranyl group, a tetrahydropyranyl group, a dioxolanyl group, Cyclic ether group having 2 to 12 carbon atoms such as dioxanyl group; aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF ₃ And the like, fluoroalkyl groups having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted by fluorine atoms; benzofuryl groups; benzopyranyl groups; benzodioxolyl groups; and benzodioxanyl groups; Be The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

The number of carbon atoms of the alkenyl group having 2 to 20 carbon atoms for R ^b is preferably 2 to 12. As a C2-C20 alkenyl group in R ^b , for example, a vinyl group, propenyl group, isopropenyl group, butenyl group, isobutenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group And dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icosenyl group and the like.

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

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

The substituent that the cycloalkyl group having 3 to 12 carbon atoms for R ^b may have is, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a cyano group; a dimethylamino group or the like N, N-dialkylamino groups; alkyl groups having 1 to 6 carbon atoms, such as methyl, ethyl and propyl; and alkoxy having 1 to 6 carbon atoms, such as methoxy, ethoxy and isopropoxy. And nitro aromatic group, and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as phenyl group and naphthyl group. Among them, as a substituent of the cycloalkyl group, a halogen atom such as fluorine atom and chlorine atom; cyano group; an alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; methoxy group, ethoxy An alkoxy group having 1 to 6 carbon atoms such as a group and isopropoxy group; a nitro group; and an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group are preferable. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms as R ^b include a phenyl group, a 1-naphthyl group and a 2-naphthyl group. Among them, as an aromatic hydrocarbon ring group, a phenyl group is preferable.

The substituent that the aromatic hydrocarbon ring group having 6 to 12 carbon atoms for R ^b may have is, for example, a halogen atom such as a fluorine atom or a chlorine atom; a carbon atom number such as a cyano group; a dimethylamino group 2 to 12 N, N-dialkylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group and butoxy group; carbon atom number such as methoxymethoxy group and methoxyethoxy group An alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group of 1 to 12; nitro group; an aromatic heterocyclic group having 2 to 20 carbon atoms such as triazolyl group, pyrrolyl group, furanyl group, thiophenyl group, etc .; A cycloalkyl group having 3 to 8 carbon atoms, such as cyclopropyl group, cyclopentyl group and cyclohexyl group; cyclopentyloxy group, cyclohexyloxy group and the like Of C 3-8 cycloalkyloxy groups; tetrahydrofuranyl groups, tetrahydropyranyl groups, dioxolanyl groups, dioxanyl groups, cyclic ether groups of 2 to 12 carbon atoms, phenoxy groups, naphthoxy groups, etc. An aryloxy group having 6 to 14 carbon atoms; a fluorocarbon having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom, such as trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF ₃ alkyl group; -OCF _3; benzofuryl; benzopyranyl group; benzodioxolyl group; benzodioxanyl group; and the like. Among them, as a substituent of the aromatic hydrocarbon ring group, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a cyano group; a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, etc. Alkoxy group; nitro group; aromatic heterocyclic group having 2 to 20 carbon atoms such as furanyl group and thiophenyl group; cycloalkyl group having 3 to 8 carbon atoms such as cyclopropyl group, cyclopentyl group and cyclohexyl group; A fluoroalkyl group having 1 to 12 carbon atoms, in which one or more hydrogen atoms are substituted with a fluorine atom, such as trifluoromethyl group, pentafluoroethyl group, -CH ₂ CF _{3 and the} like; -OCF ₃ ; is preferable. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

The number of carbon atoms of the aromatic heterocyclic group in D ¹ to D ³ is preferably 2 to 30. Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ include 1-benzofuranyl group, 2-benzofuranyl group, imidazolyl group, indolinyl group, furazanyl group, oxazolyl group, quinolyl group, and thiadiazolyl group. , Thiazolyl group, thiazolopyrazinyl group, thiazolopyridyl group, thiazolopyridazinyl group, thiazolopyridazinyl group, thiazolopyrimidinyl group, thienyl group, triazinyl group, triazolyl group, naphthyridinyl group, pyrazinyl group, pyrazolyl group, pyranyl group, Pyridyl group, pyridazinyl group, pyrimidinyl group, pyrrolyl group, phthalazinyl group, furanyl group, benzo [c] thienyl group, benzo [b] thienyl group, benzoisoxazolyl group, benzoisothiazolyl group, benzoimidazolyl group, benzooxa Diazolyl group, benzoxazolyl group, Down zone thiadiazolyl group, benzothiazolyl group, triazinyl group, benzotriazolyl group, and benzo pyrazolyl group and the like. Among them, as the aromatic heterocyclic group, monocyclic aromatic heterocyclic groups such as furanyl group, pyranyl group, thienyl group, oxazolyl group, furazanyl group, thiazolyl group, and thiadiazolyl group; and benzothiazolyl group, benzooxa group Zoryl group, quinolyl group, 1-benzofuranyl group, 2-benzofuranyl group, phthalimido group, benzo [c] thienyl group, benzo [b] thienyl group, thiazolopyridyl group, thiazolopyrazinyl group, benzisoxazolate And aromatic heterocyclic groups such as fused rings, such as a ring group, a benzoxadiazolyl group, and a benzothiadiazolyl group.

Examples of the substituent which the aromatic heterocyclic group may have the D 1 ^~ D ^3, for example, include the same examples as the substituent group which may have an aromatic hydrocarbon ring group of D 1 ^~ D ^3. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

In the above formulas (II-1) to (II-7), D ⁴ to D ⁵ each independently represent an acyclic group which may have a substituent. D ⁴ and D ⁵ may together form a ring. The carbon atom number (including the carbon atom number of the substituent) of the group represented by D ⁴ to D ⁵ is generally independently 1 to 100.

The number of carbon atoms of the noncyclic group in D ⁴ to D ⁵ is preferably 1 to 13. As the non-cyclic group in D ⁴ to D ⁵ , for example, alkyl group having 1 to 6 carbon atoms; cyano group; carboxyl group; fluoroalkyl group having 1 to 6 carbon atoms; alkoxy group having 1 to 6 carbon atoms _{; -C (= O) -CH 3} ; -C (= O) NHPh; -C (= O) -OR x; and the like. Among them, as the non-cyclic group, a cyano group, a carboxyl _{group, -C (= O) -CH 3} , -C (= O) NHPh, -C (= O) -OC 2 H 5, -C (= O) _{_{_{_{-OC 4 H 9, -C (=}}}} O) -OCH (CH 3) 2, -C (= O) -OCH 2 CH 2 CH (CH 3) -OCH 3, -C (= O) -OCH 2 CH ₂ C (CH ₃ ) ₂ —OH and —C (= O) —OCH ₂ CH (CH ₂ CH ₃ ) —C ₄ H ₉ are preferred. The above Ph represents a phenyl group. Further, R ^x represents an organic group having 1 to 12 carbon atoms. Specific examples of R ^x include an alkoxy group having 1 to 12 carbon atoms, and an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group.

Examples of the substituent that the noncyclic group in D ⁴ to D ⁵ may have include the same examples as the substituents that the aromatic hydrocarbon ring group in D ¹ to D ³ may have. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

When D ⁴ and D ⁵ are taken together to form a ring, the above-mentioned D ⁴ and D ⁵ form an organic group containing a ring. As this organic group, the group represented by a following formula is mentioned, for example. In the following formula, * represents the position where each organic group is bonded to the carbon to which D ⁴ and D ⁵ are bonded.

R ^* represents an alkyl group having 1 to 3 carbon atoms.
R ^** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^*** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.
R ^**** is a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, hydroxyl group, and represents a group selected from the group consisting of -COOR ^13. R ¹³ represents an alkyl group having 1 to 3 carbon atoms.
As a substituent which a phenyl group may have, for example, a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an acyloxy group, a cyano group and an amino group Can be mentioned. Among them, as a substituent, a halogen atom, an alkyl group, a cyano group and an alkoxy group are preferable. The number of substituents which a phenyl group has may be one or more. The plurality of substituents may be identical to or different from each other.

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

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

R ^g represents a group selected from the group consisting of a hydrogen atom; and an organic group having 1 to 30 carbon atoms which may have a substituent.

As the organic group having 1 to 30 carbon atoms which may have a substituent in R ^g , for example, an alkyl group having 1 to 20 carbon atoms which may have a substituent; At least one of —CH ₂ — contained in the 20 alkyl groups is —O—, —S—, —O—C (= O) —, —C (= O) —O—, or —C (= O)-substituted group (provided that two or more adjacent groups each other except -O- or -S- are interposed); alkenyl group having 2 to 20 carbon atoms which may have a substituent An alkynyl group having 2 to 20 carbon atoms which may have a substituent; a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; carbon which may have a substituent An aromatic hydrocarbon ring group having 6 to 30 atoms; an aromatic compound having 2 to 30 carbon atoms which may have a substituent Ring _{^{^{group; -SO 2 R a; -C (}}} = O) -R b; -CS-NH-R b; and the like. The meanings of R ^a and R ^b are as described above.

The preferable carbon atom number range and examples of the alkyl group having 1 to 20 carbon atoms in R ^g are the same as the alkyl group having 1 to 20 carbon atoms in R ^b .

The substituent which the alkyl group having 1 to 20 carbon atoms in R ^g may have is, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a dimethylamino group or the like, and the like. N, N-dialkylamino group; an alkoxy group having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy and butoxy; and C 1 to 12 having carbon atoms such as methoxymethoxy and methoxyethoxy An alkoxy group substituted with an alkoxy group, an alkoxy group having 1 to 12 carbon atoms, a nitro group, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms such as a phenyl group and a naphthyl group; a triazolyl group, a pyrrolyl group, a furanyl group, Aromatic heterocyclic groups having 2 to 20 carbon atoms, such as thiophenyl; and cyclos having 3 to 8 carbons, such as cyclopropyl, cyclopentyl and cyclohexyl. Alkyl group: cycloalkyloxy group having 3 to 8 carbon atoms such as cyclopentyloxy group and cyclohexyloxy group; cyclic having 2 to 12 carbon atoms such as tetrahydrofuranyl group, tetrahydropyranyl group, dioxolanyl group, dioxanyl group and the like An ether group; an aryloxy group having 6 to 14 carbon atoms such as phenoxy group and naphthoxy group; a fluoroalkyl group having 1 to 12 carbon atoms in which one or more hydrogen atoms are substituted with a fluorine atom; benzofuryl group; benzopyranyl A benzodioxolyl group; a benzodioxanyl group; -SO ₂ R ^a ; -SR ^b ; an alkoxy group having 1 to 12 carbon atoms substituted with -SR ^b ; a hydroxyl group; and the like. The meanings of R ^a and R ^b are as described above. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

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

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

As an alkynyl group having 2 to 20 carbon atoms for R ^g , for example, ethynyl group, propynyl group, 2-propynyl group (propargyl group), butynyl group, 2-butynyl group, 3-butynyl group, 3-butynyl group, pentynyl group, 2- And pentynyl group, hexynyl group, 5-hexynyl group, heptynyl group, octynyl group, 2-octynyl group, nonanyl group, decanyl group, 7-decanyl group and the like.

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

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

Examples of the substituent which may have a cycloalkyl group having 3 to 12 carbon atoms in R ^g, for example, include the same examples as the substituent group which may have an alkyl group having 1 to 20 carbon atoms in R ^g. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

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

Examples of the substituent that the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g may have include the same examples as the substituents that the aromatic hydrocarbon ring group in D ¹ to D ³ may have. Be The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

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

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

Among the above-mentioned, as R ^g , at least one of an alkyl group having 1 to 20 carbon atoms which may have a substituent; and —CH ₂ — contained in an alkyl group having 1 to 20 carbon atoms is -O-, -S-, -O-C (= O)-, -C (= O) -O-, or a group substituted with -C (= O)-, provided that -O- or- Two or more adjacent to each other and intervening S)); a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent; 6 to 6 carbon atom which may have a substituent 30 aromatic hydrocarbon ring groups; and an optionally substituted aromatic heterocyclic group having 2 to 30 carbon atoms are preferable. Among them, as R ^g , at least one of —C ₂ -C 20 alkyl groups which may have a substituent; and —CH ₂ — contained in C 1 -C 20 alkyl groups is -O-, -S-, -O-C (= O)-, -C (= O) -O-, or a group substituted with -C (= O)-, provided that -O- or- Particularly preferred is the case where two or more S-s are adjacent to each other.

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

Preferred examples of R ^h include (1) a hydrocarbon ring group having 6 to 40 carbon atoms, which has one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms. Hereinafter, the hydrocarbon ring group having an aromatic hydrocarbon ring may be appropriately referred to as “(1) hydrocarbon ring group”. (1) Specific examples of the hydrocarbon ring group include the following groups.

(1) The hydrocarbon ring group may have a substituent. (1) As a substituent which a hydrocarbon ring group may have, for example, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; a methyl group, an ethyl group, a propyl group, etc. Alkyl group; alkenyl group having 2 to 6 carbon atoms such as vinyl group and allyl group; halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; and 2 carbon atoms such as dimethylamino group -12 N, N-dialkylamino groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy and isopropoxy groups; nitro groups; 6 to 20 carbon atoms such as phenyl and naphthyl groups aromatic hydrocarbon ring _{^{^{group; -OCF 3; -C (= O}}} ) -R b; -O-C (= O) -R b; -C (= O) -O-R b; -SO 2 R ^a ; etc. The meanings of R ^a and R ^b are as described above. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

Another preferable example of R ^h includes (2) at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms. And heterocyclic groups having 2 to 40 carbon atoms. Hereinafter, the heterocyclic group having an aromatic ring may be appropriately referred to as "(2) heterocyclic group". (2) The following groups may be mentioned as specific examples of the heterocyclic group. Each R independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

As still another preferable example of R ^h , (3) at least one group selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms And an alkyl group having 1 to 12 carbon atoms substituted by Hereinafter, this substituted alkyl group may be appropriately referred to as "(3) substituted alkyl group".

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

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

As still another preferable example of R ^h , (4) at least one group selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms And an alkenyl group having 2 to 12 carbon atoms which is substituted by Hereinafter, this substituted alkenyl group may be referred to as “(4) substituted alkenyl group” as appropriate.

(4) Examples of the “alkenyl group having 2 to 12 carbon atoms” in the substituted alkenyl group include a vinyl group and an allyl group.
(4) Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkenyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ . It can be mentioned.
(4) Examples of the “aromatic heterocyclic group having 2 to 30 carbon atoms” in the substituted alkenyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ . .

(4) The substituted alkenyl group may further have a substituent. (4) As a substituent which a substituted alkenyl group may have, the same example as a substituent which (1) hydrocarbon ring group may have is mentioned, for example. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

As still another preferable example of R ^h , (5) at least one group selected from the group consisting of an aromatic hydrocarbon ring group having 6 to 30 carbon atoms and an aromatic heterocyclic group having 2 to 30 carbon atoms And an alkynyl group having 2 to 12 carbon atoms which is substituted by Hereinafter, this substituted alkynyl group may be referred to as “(5) substituted alkynyl group” as appropriate.

(5) Examples of the “C 2-12 alkynyl group” in the substituted alkynyl group include ethynyl group and propynyl group.
(5) Examples of the “aromatic hydrocarbon ring group having 6 to 30 carbon atoms” in the substituted alkynyl group include the same examples as the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in D ¹ to D ³ . It can be mentioned.
(5) Examples of the “aromatic heterocyclic group having 2 to 30 carbon atoms” in the substituted alkynyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ . .

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

The following group is mentioned as a preferable specific example of R ^h .

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

Particularly preferred specific examples of R ^h include the following groups.

The specific examples of R ^h described above may further have a substituent. Examples of this substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; vinyl group, allyl group and the like An alkenyl group having 2 to 6 carbon atoms; a halogenated alkyl group having 1 to 6 carbon atoms such as trifluoromethyl group; an N, N-dialkylamino group having 2 to 12 carbon atoms such as dimethylamino group An alkoxy group having 1 to 6 carbon atoms, such as a methoxy group, an ethoxy group and an isopropoxy group; a nitro group; -OCF ₃ ; -C (= O) -R ^b ; -O-C (= O) -R ^b ; -C (= O) -O-R ^b ; -SO ₂ R ^a ; and the like. The meanings of R ^a and R ^b are as described above. Among these, a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 6 carbon atoms are preferable. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

R ⁱ represents an organic group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms.

Preferred examples of R ⁱ include hydrocarbon ring groups having 6 to 40 carbon atoms, which have one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms.
In addition, another preferable example of R ⁱ has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms, And heterocyclic groups having 2 to 40 carbon atoms.

Particularly preferred specific examples of R ⁱ include the following groups. The meaning of R is as described above.

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

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

Specific preferred examples of the formula (III-1) and the formula (III-4) include the following groups. In the following formula, * represents a bonding position.

In formula (I), Z ¹ and Z ² are each independently a single bond, -O-, -O-CH _2- , -CH ₂ -O-, -O-CH ₂ -CH ₂ -,- CH ₂ -CH ₂ -O-, -C (= O) -O-, -O-C (= O)-, -C (= O) -S-, -S-C (= O)-,- ^{^{_{NR 21 -C (= O) -}}} , - C (= O) -NR 21 -, - CF 2 -O -, - O-CF 2 -, - CH 2 -CH 2 -, - CF 2 -CF 2 - _{_{, -O-CH 2 -CH 2 -O}} -, - CH = CH-C (= O) -O -, - O-C (= O) -CH = CH -, - CH 2 -C (= O) _{_{-O -, - O-C (}} = O) -CH 2 -, - CH 2 -O-C (= O) -, - C (= O) -O-CH 2 -, - CH 2 -CH 2 - C (= O) -O -, - O-C (= O) -CH 2 -CH 2 -, - C _{_{_{2 -CH 2 -O-C (=}}} O) -, - C (= O) -O-CH 2 -CH 2 -, - CH = CH -, - N = CH -, - CH = N -, - N It represents any one selected from the group consisting of CC (CH ₃ ) —, —C (CH ₃ ) = N—, —N = N—, and —C≡C—. Each R ²¹ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

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

As a cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² , for example, cyclopentane-1,3-diyl group, cyclohexane-1,4-diyl group, 1,4-cycloheptane-1,4 Cycloalkanediyl group having 5 to 20 carbon atoms, such as -diyl group, cyclooctane-1,5-diyl group; decahydronaphthalene-1,5-diyl group, decahydronaphthalene-2,6-diyl group, etc. And a bicycloalkanediyl group having 5 to 20 carbon atoms; and the like. Among them, a cycloalkanediyl group having 5 to 20 carbon atoms which may be substituted is preferable, a cyclohexanediyl group is more preferable, and a cyclohexane-1,4-diyl group is particularly preferable. The cyclic aliphatic group may be trans, cis or a mixture of cis and trans. Among them, the trans form is more preferable.

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

As an aromatic group in A ¹ , A ² , B ¹ and B ² , for example, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 1,4-naphthylene group, 1, Aromatic hydrocarbon ring group having 6 to 20 carbon atoms, such as 5-naphthylene group, 2,6-naphthylene group, 4,4′-biphenylene group, etc .; furan-2,5-diyl group, thiophene-2,5 -Aromatic heterocyclic groups having 2 to 20 carbon atoms, such as -diyl, pyridine-2, 5-diyl and pyrazine-2, 5-diyl; and the like. Among them, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is particularly preferable.

As a substituent which the aromatic group in A ¹ , A ² , B ¹ and B ² may have, for example, the same as the substituents which the cyclic aliphatic group in A ¹ , A ² , B ¹ and B ² may have An example is given. The number of substituents may be one or more. The plurality of substituents may be identical to or different from each other.

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

In formula (I), G ¹ and G ² are each independently an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and a methylene group contained in an aliphatic hydrocarbon group having 3 to 20 carbon atoms 1 or more of (—CH ₂ —) represents an organic group selected from the group consisting of a group substituted by —O— or —C (= O) —. The hydrogen atom contained in the organic group of G ¹ and G ² may be substituted by an alkyl group of 1 to 5 carbon atoms, an alkoxy group of 1 to 5 carbon atoms, or a halogen atom. However, methylene groups (-CH _2- ) at both ends of G ¹ and G ² are not substituted with -O- or -C (= O)-.

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

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

In formula (I), P ¹ and P ² each independently represent a polymerizable group. As a polymerizable group in P ¹ and P ² , for example, a group represented by CH ₂ CRCR ³¹ —C (= O) —O— such as an acryloyloxy group, a methacryloyloxy group, etc .; a vinyl group; a vinyl ether group; Acryloyl: methacryloyl group; carboxyl group: methyl carbonyl group: hydroxyl group: amide group: alkylamino group having 1 to 4 carbon atoms; amino group: epoxy group: oxetanyl group: aldehyde group: isocyanate group: thio Isocyanate group; and the like. R ³¹ represents a hydrogen atom, a methyl group or a chlorine atom. Among them, a group represented by CH ₂ CRCR ³¹ —C (= O) —O— is preferable, and CH ₂ CHCH—C (= O) —O— (acryloyloxy group), CH ₂ CC (CH ₃₎ More preferred is —C (= O) —O— (methacryloyloxy group), and the acryloyloxy group is particularly preferred.

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

The reverse dispersed liquid crystalline compound represented by the formula (I) can be produced, for example, by the reaction of a hydrazine compound and a carbonyl compound described in WO 2012/147904.

The first liquid crystal composition may further contain an optional component in combination with the liquid crystal compound, if necessary. As the optional components, one type may be used alone, or two or more types may be used in combination in an optional ratio.

Usually, since the first liquid crystal composition can be cured by polymerization, the first liquid crystal composition contains a polymerization initiator as an optional component. The type of polymerization initiator may be selected according to the type of polymerizable compound contained in the first liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator may be used. In addition, if the polymerizable compound is anionically polymerizable, an anionic polymerization initiator may be used. Furthermore, if the polymerizable compound is cationically polymerizable, a cationic polymerization initiator may be used. As the polymerization initiator, one type may be used alone, or two or more types may be used in combination in an arbitrary ratio.

The amount of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, preferably 30 parts by weight or less, more preferably 10 parts by weight, based on 100 parts by weight of the liquid crystal compound. Part or less. When the amount of the polymerization initiator falls within the above range, the polymerization can be efficiently advanced.

The first liquid crystal composition may contain a surfactant as an optional component. In particular, from the viewpoint of stably obtaining a desired liquid crystal cured layer, as the surfactant, a surfactant containing a fluorine atom in the molecule is preferable.

The surfactant is preferably a nonionic surfactant. When the surfactant is a nonionic surfactant which does not contain an ionic group, the surface state and the orientation of the liquid crystal cured layer can be made particularly good.

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

As the surfactant, for example, Surfron series (S420 etc.) manufactured by AGC Seimi Chemical Co., Ltd., Ftergent series manufactured by Neos (251, FTX-212M, FTX-215M, FTX-209 etc.), manufactured by DIC Megafuck series (F-444 etc.) etc. may be mentioned. Moreover, surfactant may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The amount of the surfactant is preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, preferably 0.50 parts by weight or less, more preferably 100 parts by weight of the liquid crystal compound. It is 0.30 parts by weight or less. When the amount of surfactant is in the above range, the substantial maximum inclination angle of the molecules of the liquid crystal compound in the liquid crystal cured layer can be effectively increased.

The first liquid crystal composition may contain a solvent as an optional component. As the solvent, those capable of dissolving the liquid crystal compound are preferable. An organic solvent is usually used as such a solvent. Examples of the organic solvent include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetic acid ester solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; And ether solvents such as 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane and 1,2-dimethoxyethane; and aromatic hydrocarbon solvents such as toluene, xylene and mesitylene. Moreover, a solvent may be used individually by 1 type, and may be used combining 2 or more types by arbitrary ratios.

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, preferably 650 parts by weight or less, more preferably 100 parts by weight of the liquid crystalline compound. It is at most 550 parts by weight, particularly preferably at most 450 parts by weight. By setting the amount of the solvent to the lower limit value or more of the range, the generation of foreign matter can be suppressed, and by setting the amount to the upper limit value or less of the range, the drying load can be reduced.

In addition, the first liquid crystal composition has an effect of increasing the substantial maximum tilt angle of the molecules of the liquid crystal compound as an optional component in order to increase the tilt angle of the molecules of the liquid crystal compound contained in the first cured layer. It may contain a gradient action component capable of exerting As a kind and quantity of a gradient action component, the specification of Unexamined-Japanese-Patent No. 2018-262379 (or specification of Japanese Patent Application No. 2017-060154), the specification of International Publication No. 2018/173778 (or Japanese Patent Application No. 2017-060122) is mentioned, for example. And JP-A No. 2018-163218 (or the specification of Japanese Patent Application No. 2017-059327). However, since it is possible to increase the substantial maximum inclination angle of the molecules of the liquid crystal compound also by adjusting the operation or conditions in the process of producing the first cured layer, the inclination action component is not necessarily used. I do not care.

Examples of optional other components that the first liquid crystal composition may contain include 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; Agents, thixotropic agents, gelling agents, polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and the like. The amount of these components may be 0.1 parts by weight to 20 parts by weight with respect to a total of 100 parts by weight of the liquid crystal compound.

In step (I), a layer of the first liquid crystal composition is usually formed on a suitable support surface. As the support surface, any surface capable of supporting the layer of the first liquid crystal composition can be used. From the viewpoint of improving the surface condition of the cured liquid crystal layer, it is preferable to use a flat surface free of concave and convex portions as the support surface. In addition, from the viewpoint of enhancing the productivity of the liquid crystal cured layer, it is preferable to use the surface of a long base as the support surface. Here, "long" refers to a shape having a length of 5 or more times the width, preferably 10 or more times the length, and specifically wound in a roll. It refers to the shape of a film having a length that can be stored or transported.

As a base material, usually, a resin film or a glass plate is used. In particular, when the orientation treatment is performed at a high temperature, it is preferable to select a substrate that can withstand the temperature. As the resin, usually, a thermoplastic resin is used. Among them, a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoint of the height of alignment control force, the height of mechanical strength, and the cost reduction. Furthermore, it is preferable to use a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin because it is excellent in transparency, low hygroscopicity, dimensional stability and lightness. When the suitable example of resin contained in a base material is mentioned by a brand name, "Zeonor" by Nippon Zeon Co., Ltd. can be mentioned as norbornene-type resin.

The glass transition temperature of the material forming the support surface is preferably 90 ° C. or more, more preferably 100 ° C. or more, and particularly preferably 120 ° C. or more. Steps (II) and (V) may be performed in a high temperature environment to adjust the temperature of the layer of the first liquid crystal composition and the temperature of the layer of the second liquid crystal composition to a temperature suitable for alignment. . The high glass transition temperature of the material forming the support surface as described above can suppress deformation of the support surface due to heat in a high temperature environment. The upper limit of the glass transition temperature of the material forming the support surface is not particularly limited, and may be, for example, 250 ° C. or less.

In order to promote the alignment of the liquid crystal compound in the layer of the first liquid crystal composition, the surface of the base material as the support surface is preferably subjected to a treatment for imparting an alignment regulating force. The alignment control force refers to the property of the support surface which can align the liquid crystal compound contained in the liquid crystal composition. Examples of the treatment for applying the alignment control force to the support surface include a photoalignment treatment, a rubbing treatment, an ion beam alignment treatment, and an extension treatment.

In the step (I) of forming the layer of the first liquid crystal composition, the first liquid crystal composition is usually prepared in a fluid state. Therefore, the first liquid crystal composition is usually coated on the support surface to form a layer of the first liquid crystal composition. As a method of applying the first liquid crystal composition, for example, curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, printing coating method , Gravure coating method, die coating method, gap coating method, and dipping method.

[3. Step (II): Alignment Treatment of Layer of First Liquid Crystal Composition]
After the layer of the first liquid crystal composition is formed in the step (I), the step (II) of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition is performed. In orientation, usually, the layer of the first liquid crystal composition is kept at a predetermined temperature condition for a predetermined time. Thereby, in the layer of the first liquid crystal composition, the liquid crystal compound can be aligned.

Specifically, in the in-plane direction, the liquid crystal compound is usually oriented in a direction according to the alignment regulating force of the support surface.
On the other hand, in the thickness direction, it is preferable to align the liquid crystal compound so that at least a part thereof is inclined with respect to the layer plane (that is, with respect to the in-plane direction). Thereby, the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the first cured layer can be increased. And thereby, the adjustment of the substantial maximum inclination angle of the molecules of the liquid crystal compound in the step (VI) can be effectively performed.

A method for orienting the liquid crystal compound contained in the layer of the first liquid crystal composition so that at least a part thereof is inclined with respect to the layer plane (that is, with respect to the in-plane direction) is optional. Among them, it is preferable to select a method of aligning the liquid crystal compound so as to obtain a first cured layer in which the substantial maximum inclination angle of the molecules of the liquid crystal compound is large.

For example, the step (II) is preferably performed such that the temperature condition of the layer of the first liquid crystal composition satisfies a predetermined requirement. Specifically, the temperature condition of the layer of the first liquid crystal composition in step (II) is preferably the same as the temperature condition at which the residual viscosity of the test composition is usually 800 cP or less. The above-mentioned 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 step (II). Further, the residual component of the test composition is a component of the components contained in the test composition which remains without being vaporized under the same temperature conditions as the layer of the first liquid crystal composition of step (II). By performing the step (II) so as to satisfy such requirements, it is possible to increase the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer.

It will be described in more detail. When the step (II) of orienting the liquid crystal compound is performed so as to satisfy the above requirements, the step (II) is performed under the same temperature condition as the temperature condition in which the residual viscosity of the test composition falls within the predetermined range. It is carried out by adjusting the layer of one liquid crystal composition. The specific range of the residual viscosity is usually 800 cP (centipoise) or less, preferably 600 cP or less, more preferably 400 cP or less, still more preferably 200 cP or less. Thus, the molecules of the liquid crystal compound contained in the first cured layer are oriented by orienting the liquid crystal compound in the layer of the first liquid crystal composition under the same temperature conditions as the temperature conditions at which the residual viscosity of the test composition decreases. The real maximum inclination angle of 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 of step (II) can be measured by the following method.
A test composition is prepared by removing the polymerization initiator from the first liquid crystal composition. The test composition is concentrated under reduced pressure on a rotary evaporator to remove the solvent and obtain the remaining 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. Hereinafter, this information is 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 step (II) is read as the residual viscosity.

Examples of the method for keeping the residual viscosity of the test composition in the above-mentioned range under the same temperature conditions as the layer of the first liquid crystal composition of the step (II) include the following methods (A) and (B).
(A) The temperature of the layer of the first liquid crystal composition in the step (II) of orienting the liquid crystal compound is appropriately adjusted. In this method, usually, the temperature of the layer of the first liquid crystal composition is sufficiently raised to lower the residual viscosity of the test composition under the same temperature condition as this temperature, and the above-mentioned range is achieved. Adjust to
(B) The composition of the first liquid crystal composition is appropriately adjusted. In this method, as a component contained in the first liquid crystal composition, the residual viscosity of the test composition containing the additive is reduced by combining the liquid crystal compound with an additive of an appropriate type and amount. , Adjust to be in the range described above.

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

Also, for example, a liquid crystal compound can be obtained by a method using a first liquid crystal composition containing a tilt action component, or a method using a liquid crystal compound having a property of being inclined with respect to a layer plane (that is, with respect to the in-plane direction) It is possible to obtain a first cured layer having a substantial maximum inclination angle of the molecule of.

The specific temperature at the time of alignment treatment is appropriately set in the range above the liquid crystal phase-solid phase transition temperature of the liquid crystal compound, and is preferably a temperature below the glass transition temperature of the resin contained in the substrate. . Thereby, generation | occurrence | production of distortion of the base material by orientation processing can be suppressed.

The step (II) of orienting the liquid crystal compound 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 in advance the temperature of the layer of the first liquid crystal composition placed in the oven at a number of oven setting temperatures. The information on the recorded set temperature of the oven and the temperature of the layer of the first liquid crystal composition placed in the set temperature is hereinafter referred to as "set temperature-layer temperature information" as appropriate. By using this "set temperature-layer temperature information", the temperature of the layer of the first liquid crystal composition placed in the oven can be easily known from the oven set temperature.

In the step (II) of orienting the liquid crystal compound, the time for which the temperature of the layer of the first liquid crystal composition is kept at the above temperature can be arbitrarily set within a range where the desired first cured layer can be obtained. It may be ~ 5 minutes.

[4. Step (III): Curing of Layer of First Liquid Crystal Composition]
After the liquid crystal compound contained in the layer of the first liquid crystal composition is oriented in the step (II), the step (III) of curing the layer of the first liquid crystal composition is performed.

In the step (III), usually, the layer of the first liquid crystal composition is cured by polymerization of the polymerizable compound contained in the first liquid crystal composition. Therefore, for example, when the liquid crystal compound has a polymerizability, the liquid crystal compound is usually polymerized while maintaining the alignment of its molecules. The alignment state of the liquid crystal compound contained in the first liquid crystal composition before polymerization is fixed by the polymerization described above.

As the polymerization method, a method may be selected that is adapted to the nature of the components contained in the first liquid crystal composition. Examples of the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among them, the method of irradiating active energy rays is preferable because heating is unnecessary and the polymerization reaction can be allowed to proceed at room temperature. Here, the active energy ray to be irradiated may include light such as visible light, ultraviolet light and infrared light, and any energy ray such as electron beam.

Among them, a method of irradiating light such as ultraviolet light is preferable because the operation is simple. The temperature at the time of ultraviolet irradiation is preferably below the glass transition temperature of the substrate, preferably 150 ° C. or less, more preferably 100 ° C. or less, and particularly preferably 80 ° C. or less. The lower limit of the temperature during ultraviolet irradiation may be 15 ° C. or higher. The irradiation intensity of ultraviolet rays is preferably 0.1 mW / cm ² or more, more preferably 0.5 mW / cm ² or more, preferably 10000 mW / cm ² or less, more preferably 5000 mW / cm ² or less. The dose of ultraviolet rays is preferably 0.1 mJ / cm ² or more, more preferably 0.5 mJ / cm ² or more, preferably 10000 mJ / cm ² or less, more preferably 5000 mJ / cm ² or less.

The first cured layer formed of the cured product of the first liquid crystal composition is obtained by the above-mentioned step (III). The first cured layer is a layer of a cured product obtained by curing the first liquid crystal composition described above. The curing of the first liquid crystal composition is usually achieved by the polymerization of the polymerizable compound contained in the first liquid crystal composition, as described above. Thus, the first cured layer usually contains a polymer of part or all of the components contained in the first liquid crystal composition. Therefore, when the liquid crystal compound has a polymerizability, the liquid crystal compound is polymerized, so the first cured layer may be a layer containing a polymer of the liquid crystal compound polymerized while maintaining the alignment state before polymerization. . The polymerized liquid crystal compound is included in the term "liquid crystal compound contained in the first cured layer".

In the cured product of the first liquid crystal composition, the flowability before curing is lost. Therefore, in the first cured layer, the alignment state of the liquid crystal compound is usually fixed in the alignment state before curing. And it is preferable that at least a part of molecules of the liquid crystal compound contained in the first cured layer be inclined with respect to the layer plane of the first cured layer (that is, with respect to the in-plane direction). Thereby, adjustment of the tilt angle of the molecules of the liquid crystal compound in the step (VI) can be effectively performed.

In the first cured layer, some of the molecules of the liquid crystal compound may be inclined with respect to the layer plane of the first cured layer (that is, with respect to the in-plane direction). It may be inclined with respect to the layer plane (ie, with respect to the in-plane direction). Usually, in the first cured layer, the inclination angle of the molecules of the liquid crystal compound is smaller as it is closer to the support surface in the thickness direction, and larger as it is farther from the support surface. Therefore, in the vicinity of the surface on the support surface side of the first cured layer, the molecules of the liquid crystal compound may be parallel to the layer plane (that is, in the in-plane direction). In addition, in the vicinity of the surface opposite to the support surface of the first cured layer, the molecules of the liquid crystal compound may be perpendicular to the layer plane (that is, in the in-plane direction). However, even if the molecules of the liquid crystal compound are parallel or perpendicular to the layer plane (in the in-plane direction) in the vicinity of the surface of the first hardened layer, the surface of the first hardened layer It is preferable that the molecules of the liquid crystal compound be inclined with respect to the plane of the layer (i.e., with respect to the in-plane direction) in the portions other than the vicinity.

That at least a part of the molecules of the liquid crystal compound contained in the first cured layer is inclined with respect to the layer plane of the first cured layer (that is, with respect to the in-plane direction) is polarized light with sufficient resolution. It can confirm by observing the cross section of a 1st hardened layer with a microscope. This observation may be carried out by inserting a wave plate as an inspection plate between the observation sample and the objective lens of the polarization microscope, if necessary, in order to make the inclination of the molecules of the liquid crystal compound more visible. .

Alternatively, at least some 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 (that is, with respect to the in-plane direction) as follows: Can check. The retardation R (θ) of the first cured layer at an incident angle θ is measured in a measurement direction perpendicular to the in-plane fast axis direction of the first cured layer. And retardation ratio R ((theta)) / R ((theta) which divided the retardation R ((theta)) of the 1st cured layer in incident angle (theta) by the retardation R (0 degree) of the 1st cured layer in 0 angle of incidence Find 0 °). If a graph is drawn with the thus obtained retardation ratio R (θ) / R (0 °) as the vertical axis and the incident angle θ as the horizontal axis, the obtained graph may be asymmetric with respect to θ = 0 °. For example, it can be confirmed that at least a part of molecules of the liquid crystal compound contained in the first cured layer is inclined with respect to the layer plane of the first cured layer (that is, with respect to the in-plane direction).

Hereinafter, the present invention will be described in more detail by way of examples. FIG. 2 is a graph in which the retardation ratio R (θ) / R (0 °) of the first cured layer according to an example is plotted against the incident angle θ. The retardation ratio R (θ) / R (0 °) is an example shown by a broken line in FIG. 2 when the tilt angle of all the molecules of the liquid crystal compound contained in the first cured layer is 0 ° or 90 °. As described above, line symmetry is made with respect to a line of θ = 0 ° (in FIG. 2, a vertical axis passing θ = 0 °). On the other hand, when at least a part of the molecules of the liquid crystal compound contained in the first cured layer is inclined with respect to the layer plane of the first cured layer (with respect to the in-plane direction), the retardation ratio R is As in the example shown by the solid line in FIG. 2, (θ) / R (0 °) is usually asymmetric with respect to the straight line of θ = 0 °. Therefore, when the retardation ratio R (θ) / R (0 °) is asymmetrical with respect to θ = 0 °, at least a part of the molecules of the liquid crystal compound contained in the first cured layer is the first one. It can be determined that it is inclined with respect to the layer plane of the hardened layer (that is, with respect to the in-plane direction).

When the first cured layer contains molecules of the liquid crystal compound inclined with respect to the layer plane of the first cured layer (that is, with respect to the in-plane direction), the substantial maximum tilt angle of the first cured layer is The tilt angle of the molecule on the surface on the support surface side of one cured layer is 0 °, and the tilt angle of the molecule is assumed to change at a constant ratio in the thickness direction, and the molecules of the liquid crystal compound Represents the maximum value of the tilt angle. The substantial maximum inclination angle is an index indicating the size of the inclination angle of the molecules of the liquid crystal compound contained in the first cured layer. In general, as the first cured layer having a substantially larger maximum tilt angle, the tilt angle as a whole of the molecules of the liquid crystal compound contained in the first cured layer tends to be larger.

Generally, as the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer is larger, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be increased. Therefore, since the maximum value of the range of the substantially maximum tilt angle adjustable in step (VI) can be increased, the adjustable range of the substantially maximum tilt angle of the liquid crystal compound molecules contained in the finally obtained liquid crystal cured layer Can be

The range of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer should be set so that the substantial maximum tilt angle of the molecules of the liquid crystalline compound contained in the liquid crystal cured layer can be adjusted to an appropriate range. Is desirable. The specific range of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer is preferably 15 ° or more, more preferably 20 ° or more, particularly preferably 30 ° or more, and preferably 60 ° It is below. When the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the first cured layer is in the above range, adjustment of the inclination angle of the molecules of the liquid crystal compound in the step (VI) can be effectively performed. . Furthermore, it is usually easy to produce a liquid crystal cured film having particularly excellent viewing angle characteristics.

The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer can be measured by the measurement method described in the examples described later.

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

Usually, the surface of the first cured layer (see the surface 111U in FIG. 1) has an alignment regulating force that aligns the molecules of the liquid crystal compound contained in the second cured layer formed on the surface. This alignment control force tends to align the molecules of the liquid crystal compound contained in the second cured layer in the same direction as the alignment direction of the molecules of the liquid crystal compound contained in the first cured layer in the in-plane direction. .

Moreover, as for the orientation control force of the surface of a 1st hardened layer, it is desirable to orientate the molecule | numerator of the liquid crystalline compound contained in a 2nd hardened layer in the thickness direction so that the inclination angle of the said molecule may become large. In this case, the first cured layer can function as a tilted alignment film that increases the tilt angle of the molecules of the liquid crystal compound contained in the second cured layer. The function as the above-mentioned gradient alignment film is remarkably exhibited, for example, when both of the first liquid crystal composition and the second liquid crystal composition contain the reverse dispersion liquid crystal compound.

In a certain predetermined thickness range, as the first cured layer is thinner, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer can be increased. Therefore, the substantial maximum tilt angle of the molecules of the liquid crystal compound in the liquid crystal cured layer including the first cured layer can be increased, and the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be adjusted in a wide range. From the viewpoint of achieving this, the thickness of the first cured layer is preferably 0.1 μm or more, more preferably 0.2 μm or more, particularly preferably 0.3 μm or more, preferably 5.0 μm or less, more preferably 4 0.1 μm or less, particularly preferably 3.0 μm or less.

[5. Step (IV): Formation of Layer of Second Liquid Crystal Composition]
After obtaining the first cured layer in step (III), a layer of a second liquid crystal composition as a liquid crystal composition for forming a second cured layer is formed directly on the first cured layer Perform step (IV). Here, the aspect of forming another layer on a certain layer "directly" means that there is no other layer between these two layers.

The second liquid crystal composition includes a liquid crystal compound for forming a second cured layer. As the liquid crystal compound contained in the second liquid crystal composition, any liquid crystal compound can be selected and used from the range described as the liquid crystal compound contained in the first liquid crystal composition. Thereby, the same advantage as obtained in the first liquid crystal composition and the first cured layer can be obtained also in the second liquid crystal composition and the second cured layer. In particular, when both of the first liquid crystal composition and the second liquid crystal composition contain the reverse dispersion liquid crystal compound, the tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition in the step (V) Of the liquid crystal compound in step (VI) can be effectively adjusted. The liquid crystal compound contained in the second liquid crystal composition may be the same as or different from the liquid crystal compound contained in the first liquid crystal composition. In order to effectively adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer, the liquid crystal compound contained in the first liquid crystal composition and the liquid crystal compound contained in the second liquid crystal composition And preferably have the same or similar structure. Furthermore, as the liquid crystal compound contained in the second liquid crystal composition, one type may be used alone, or two or more types may be used in combination in an arbitrary ratio.

Furthermore, the second liquid crystal composition may further contain an optional component in combination with the liquid crystal compound, if necessary. One of the optional components may be used alone, or two or more of the optional components may be used in combination at an optional ratio. As an optional component, for example, a component other than the liquid crystal compound which can be contained in the first liquid crystal composition can be used in the range of the amount of the component in the first liquid crystal composition. Thereby, the same advantage as obtained in the first liquid crystal composition and the first cured layer can be obtained also in the second liquid crystal composition and the second cured layer.

The second liquid crystal composition may be different from or identical to the first liquid crystal composition.

In the step (IV) of forming the layer of the second liquid crystal composition, the second liquid crystal composition is usually prepared in a fluid state. Therefore, the second liquid crystal composition is usually coated on the surface of the first cured layer to form a layer of the second liquid crystal composition. As a method of coating a 2nd liquid crystal composition, the same example as the method demonstrated as a method of coating a 1st liquid crystal composition is mentioned, for example. Since the first cured layer is formed of a cured product containing a liquid crystalline compound, the first cured layer usually has high affinity to the second liquid crystal composition containing a liquid crystalline compound. Therefore, usually, the second liquid crystal composition conforms well to the surface of the first cured layer. Therefore, the surface condition of the layer of the second liquid crystal composition can be improved, and hence the surface condition of the second cured layer can be improved.

[6. Step (V): Alignment Treatment of Layer of Second Liquid Crystal Composition]
After forming the layer of the second liquid crystal composition in the step (IV), the step (V) of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition is performed. Thereby, in the layer of the second liquid crystal composition, the liquid crystal compound can be aligned.

Specifically, in the in-plane direction, the liquid crystalline compound contained in the layer of the second liquid crystal composition is generally contained in the first cured layer by the alignment regulating force of the surface of the first cured layer. Align in the same direction as the orientation direction of.
On the other hand, in the thickness direction, usually, the liquid crystal compound contained in the layer of the second liquid crystal composition is oriented such that at least a part thereof is inclined with respect to the layer plane (that is, with respect to the in-plane direction). The method for orienting the liquid crystal compound contained in the layer of the second liquid crystal composition so that at least a part thereof is inclined with respect to the layer plane (that is, with respect to the in-plane direction) is optional. For example, according to the method in which the reverse dispersion liquid crystal compound is contained in both the first liquid crystal composition and the second liquid crystal composition, the function of the first cured layer as a tilted alignment film can be exhibited largely. The molecules of the liquid crystal compound contained in the layer of the two liquid crystal composition can be aligned so as to be greatly inclined with respect to the layer plane (that is, with respect to the in-plane direction). Therefore, the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition can be particularly increased. When the first cured layer is allowed to act as the inclined alignment film, generally, molecules of the liquid crystal compound having a substantially maximum tilt angle larger than the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer A second cured layer can be obtained.

The specific operation in the step (V) of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition is the same as the step (II) of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition it can. Thereby, the same advantage as obtained in the first liquid crystal composition and the first cured layer can be obtained also in the second liquid crystal composition and the second cured layer. In particular, in the step (V), as in the step (II), the temperature conditions of the layer of the second liquid crystal composition in the step (V) are generally the residual viscosity of the test composition corresponding to the second liquid crystal composition. It is preferable to carry out so that it may become the same as the temperature conditions used as 800 cP or less.

Also, as described above, the first cured layer has high affinity to the second liquid crystal composition. Therefore, the second liquid crystal composition conforms to the first cured layer, and the orientation of molecules is less likely to be disturbed. Further, in general, in the first cured layer, the occurrence of alignment defects is suppressed, so that the occurrence of alignment defects in the layer of the second liquid crystal composition caused by the alignment defects of the first cured layer is also suppressed. Therefore, in the layer of the second liquid crystal composition, the alignment state can be made uniform in the in-plane direction, so the generation of alignment defects is suppressed.

[7. Step (VI): Adjustment of the substantially maximum inclination angle]
After aligning the liquid crystal compound contained in the layer of the second liquid crystal composition in the step (V), in order to adjust the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition Perform step (VI). In step (VI), the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition is increased with the passage of time.

Specifically, in the step (VI), time is allowed between the alignment of the liquid crystal compound in the step (V) and the curing of the layer of the second liquid crystal composition in the step (VII). At this idle time, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition is increased. Since the substantial maximum inclination angle increases with the passage of time, generally, the longer the time left between step (V) and step (VII), the more the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition The substantial maximum inclination angle is larger. Therefore, by adjusting the time interval from step (V) to step (VII), the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be adjusted, as a result, The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer including the cured layer and the second cured layer can be adjusted.

The temperature conditions of the layer of the second liquid crystal composition in step (VI) are not particularly limited. Usually, step (V) is performed within a temperature control device such as an oven to adjust the temperature of the layer of the second liquid crystal composition, while step (VI) is performed outside the temperature control device. . Therefore, the temperature conditions of the layer of the second liquid crystal composition in step (VI) are often different from the temperature conditions in step (V). The specific temperature condition is not particularly limited, but is preferably a temperature lower than the glass transition temperature of the resin contained in the substrate. Among them, from the viewpoint of omitting the energy for heating and lowering the manufacturing cost, temperature conditions lower than the liquid crystal phase-solid phase transition temperature of the liquid crystal compound contained in the second liquid crystal composition are preferable, and the normal temperature of 20 ° C to 30 ° C. Is particularly preferred.

It is desirable that the time taken for the step (VI) be appropriately set in accordance with the intended substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. Here, the time taken for the step (VI) refers to the time from the alignment of the liquid crystal compound in the step (V) to the curing of the layer of the second liquid crystal composition in the step (VII). The specific time taken for step (VI) is preferably 60 seconds or more, more preferably 120 seconds or more, and preferably 600 seconds or less. Since the substantially maximum inclination angle of the liquid crystal compound contained in the layer of the second liquid crystal composition can be greatly increased by setting the time for step (VI) to be at least the lower limit of the above range, the action of step (VI) Can be used effectively. Moreover, the time which manufacture of a liquid crystal cured film can be shortened because time to apply to process (VI) is below the upper limit of the said range.

The magnitude at which the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition changes according to step (VI) is preferably 1 ° or more, more preferably 5 ° or more, still more preferably 15 ° The angle is more preferably 20 ° or more, preferably 45 ° or less, more preferably 40 ° or less.

[8. Step (VII): Curing of Layer of Second Liquid Crystal Composition]
After adjusting the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition in step (VI), the layer of the second liquid crystal composition is cured to obtain a second cured layer Do (VII). Thereby, a liquid crystal cured film provided with a liquid crystal cured layer including the first cured layer and the second cured layer can be obtained. The specific operation in the step (VII) of curing the layer of the second liquid crystal composition can be the same as the step (III) of curing the layer of the first liquid crystal composition. Thereby, the same advantage as obtained in the first liquid crystal composition and the first cured layer can be obtained also in the second liquid crystal composition and the second cured layer.

The second cured layer is a layer formed of a cured product of a second composition containing a liquid crystal compound. The curing of the second liquid crystal composition is generally achieved by the polymerization of the polymerizable compound contained in the second liquid crystal composition, as with the curing of the first liquid crystal composition. Therefore, the second cured layer usually contains a polymer of part or all of the components contained in the second liquid crystal composition. For example, when the liquid crystal compound has a polymerizability, the liquid crystal compound is polymerized, so the second cured layer may be a layer containing a polymer of the liquid crystal compound polymerized while maintaining the alignment state before polymerization. . The polymerized liquid crystal compound is included in the term "liquid crystal compound contained in the second cured layer".

In the cured product of the second liquid crystal composition, since the flowability before curing is lost, the alignment state of the liquid crystal compound is usually fixed with the alignment state before curing. At least a part of the liquid crystal compound contained in the second hardened layer is inclined with respect to the layer plane of the second hardened layer (that is, in the in-plane direction). And the inclination angle of the liquid crystal compound contained in the second cured layer is adjusted to a size according to the adjustment in the step (VI). Therefore, the size of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer is properly adjusted. In the second hardened layer, when the inclination angle of the molecule on the surface on the first hardened layer side is 0 ° and the inclination angle of the molecule changes at a constant ratio in the thickness direction, the substantially maximum inclination angle is It represents the maximum value of the tilt angles of the molecules of the liquid crystal compound under the assumption. The substantial maximum tilt angle is an index indicating the size of the tilt angle of the molecules of the liquid crystal compound contained in the second cured layer. In general, as the second cured layer has a larger substantial maximum tilt angle, the tilt angle viewed as a whole of the molecules of the liquid crystal compound contained in the second cured layer tends to be larger.

The substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the second cured layer is preferably set so that the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer falls within a desired range. . At this time, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer is preferably larger than the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer. Thereby, the correlation of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer with respect to the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be increased. Therefore, by adjusting the substantial maximum tilt angle in the step (VI), it is possible to adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer in a wide range. As a method of making the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer larger than the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer, for example, And the second liquid crystal composition may include a reverse dispersion liquid crystal compound.

In the above case, the difference between the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer and the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer is preferably 5 ° or more More preferably, it is 8 ° or more, particularly preferably 10 ° or more, preferably 70 ° or less, more preferably 65 ° or less, particularly preferably 55 ° or less.

The substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the second cured layer is preferably 40 ° or more, more preferably 45 ° or more, still more preferably 50, from the viewpoint of obtaining a liquid crystal cured film excellent in viewing angle characteristics. Or more, particularly preferably 57 or more, preferably 85 or less.

The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be measured by the measurement method described in the examples described later.

Usually, the alignment direction of the molecules of the liquid crystal compound in the in-plane direction of the second cured layer is the same as the alignment direction of the molecules of the liquid crystal compound in the in-plane direction of the first cured layer.

In addition, since the orientation defect is suppressed in the first hardened layer, the generation of the orientation defect can be suppressed also in the second hardened layer formed on the first hardened layer.
Furthermore, the second cured layer usually has a good surface condition.

The thickness of the second cured layer is not particularly limited, but is preferably thicker than the first cured layer. Thereby, the correlation of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer with respect to the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be increased. Therefore, by adjusting the substantial maximum tilt angle in the step (VI), it is possible to adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer in a wide range. The specific thickness of the second cured layer is preferably 0.3 μm or more, more preferably 0.5 μm or more, and preferably 10.0 μm or less, more preferably 7.5 μm or less, still more preferably 5. It is 0 μm or less, particularly preferably 3.0 μm or less.

[9. Optional process]
The method for producing a liquid crystal cured film may further include an optional step in combination with the above-described step.
For example, when a base material is used, a liquid crystal cured film provided with the liquid crystal cured layer formed on the support surface of the base material can be obtained by the above-described manufacturing method. Therefore, the method for producing a cured liquid crystal film may include the step of peeling the cured liquid crystal layer from the support surface.
Moreover, the manufacturing method of a liquid crystal cured film may include the process of further forming a layer by the hardened | cured material of a liquid crystalline compound on a 2nd cured layer, for example.
Furthermore, the manufacturing method of a liquid crystal hardening film may be combined with a liquid crystal hardening layer, for example, and may include the process of forming an arbitrary layer further.

Moreover, the manufacturing method of a liquid-crystal cured film may include the process of transcribe | transferring the liquid-crystal cured layer formed on the base material to arbitrary film layers, for example. Therefore, for example, in the method for producing a cured liquid crystal film, after the liquid crystal cured layer formed on the substrate and the optional film layer are attached to each other, the substrate is peeled if necessary, and the cured liquid crystal layer You may include the process of obtaining the liquid-crystal cured film containing an arbitrary film layer. At this time, a suitable pressure-sensitive adhesive or adhesive may be used for bonding.

Furthermore, for example, before forming the layer of the second liquid crystal composition on the surface of the first cured layer, the surface of the first cured layer may be subjected to a treatment for applying an alignment regulating force such as rubbing treatment. Good. However, even if the surface of the first cured layer is not subjected to any special treatment, the alignment regulating force for appropriately aligning the liquid crystal compound contained in the layer of the second liquid crystal composition formed on the surface is usually performed. Have. Therefore, in order to reduce the number of steps and efficiently advance the production of a cured liquid crystal film, in the step (IV), the surface of the first cured layer is not subjected to rubbing treatment, and the second liquid crystal is applied to the surface of the first cured layer It is preferred to include forming a layer of the composition.

[10. Main advantages of liquid crystal cured film manufacturing method]
As described above, according to the method of manufacturing a cured liquid crystal film according to an embodiment of the present invention, it is possible to manufacture a cured liquid crystal film provided with a cured liquid crystal layer including the first cured layer and the second cured layer. In this production method, the maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be adjusted by adjusting the time applied to step (VI). Therefore, it is possible to adjust the substantially maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer without changing the composition of the liquid crystal composition. Therefore, the adjustment of the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be easily performed.

Moreover, according to said manufacturing method, a long liquid crystal cured film can be obtained using a long base material. Such a long liquid crystal cured film can be manufactured continuously and is excellent in productivity. Moreover, since bonding with another film can be performed by roll to roll, productivity is excellent in this point as well. Usually, a long liquid crystal cured film is wound and stored and transported in the form of a roll.

[11. Liquid crystal cured film obtained]
The liquid crystal cured film produced by the production method according to the embodiment described above includes a liquid crystal cured layer including a first cured layer and a second cured layer directly in contact with the surface of the first cured layer. The “direct” contact of another layer with the surface of one layer means that there is no other layer between the two layers.

At least a part of molecules of the liquid crystal compound contained in the liquid crystal cured layer is inclined with respect to the layer plane of the liquid crystal cured layer (that is, in the in-plane direction). In the liquid crystal cured layer, some of the molecules of the liquid crystal compound may be inclined with respect to the layer plane of the liquid crystal cured layer (that is, with respect to the in-plane direction). It may be inclined with respect to (that is, with respect to the in-plane direction). The fact that at least some of the molecules of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the layer plane (that is, with respect to the in-plane direction) is the same method as the method described in the section of the first cured layer It can confirm by. Then, by including the molecules of the liquid crystal compound inclined with respect to the layer plane (that is, with respect to the in-plane direction) in this way, the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is usually , 5 ° or more and 85 ° or less.

In the liquid crystal cured layer, it is assumed that the substantially maximum tilt angle is 0 ° of the tilt angle of the molecule on the surface on the first cured layer side, and that the tilt angle of the molecule changes at a constant ratio in the thickness direction In this case, the maximum value of the tilt angle of the molecules of the liquid crystal compound is represented. The substantial maximum inclination angle is an index indicating the size of the inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. In general, as the liquid crystal cured layer has a substantially larger maximum tilt angle, the tilt angle as a whole of the molecules of the liquid crystal compound contained in the liquid crystal cured layer tends to be larger. Therefore, the birefringence of the liquid crystal cured layer in the thickness direction can be increased by increasing the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. Therefore, the birefringence of the liquid crystal cured layer can be appropriately adjusted by adjusting the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer, so the liquid crystal cured film is provided on the polarizing plate as the reflection suppressing film. In this case, it is possible to obtain excellent viewing angle characteristics that reflection can be effectively suppressed in the inclination direction of the display surface.

The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be arbitrarily set according to the application of the liquid crystal cured film. For example, from the viewpoint of achieving excellent viewing angle characteristics, the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is preferably 40 ° or more, more preferably 46 ° or more, particularly preferably 56 ° or more Preferably it is 85 degrees or less, More preferably, it is 83 degrees or less, More preferably, it is 80 degrees or less.

The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be measured by the measurement method described in the examples described later.

In the in-plane direction, the molecules of the liquid crystal compound contained in the liquid crystal cured layer are aligned in the same in-plane direction as the alignment direction of the molecules of the liquid crystal compound contained in the first cured layer as a whole. Therefore, the in-plane slow axis of the liquid crystal hardened layer is usually parallel to the in-plane slow axis of the first hardened layer.

The range of the in-plane retardation of the liquid crystal cured layer can be arbitrarily set according to the application of the liquid crystal cured film. In particular, in order to obtain a polarizing plate as a reflection suppression film for an organic EL display panel by combining a liquid crystal cured film and a linear polarizer, the liquid crystal cured layer can function as a quarter wavelength plate in-plane retardation. It is desirable to have Here, specifically, the in-plane retardation which can function as a quarter-wave plate is preferably 80 nm or more, more preferably 100 nm or more, still more preferably 110 nm or more, particularly preferably 120 nm or more at a measurement wavelength of 590 nm. Preferably it is 190 nm or less, More preferably, it is 180 nm or less, More preferably, it is 170 nm or less, Especially preferably, it is 160 nm or less.

The in-plane retardation of the liquid crystal cured layer preferably exhibits reverse wavelength dispersion. Therefore, the in-plane retardations Re (450) and Re (550) of the liquid crystal cured layer at the measurement wavelengths of 450 nm and 550 nm preferably satisfy the following formula (N3), and more preferably the following formula (N4).
Re (450) / Re (550) <1.00 (N3)
Re (450) / Re (550) <0.90 (N4)
Thus, the liquid crystal cured layer having in-plane retardation exhibiting reverse wavelength dispersion can uniformly exhibit functions in a wide wavelength band in optical applications such as a quarter wavelength plate or a half wavelength plate. Therefore, when the liquid crystal cured film including the liquid crystal cured layer is used for a polarizing plate as a reflection suppression film, it is possible to suppress reflection in a wide wavelength range.

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 greater than 0.91, more preferably 0.93 or more, and particularly preferably Preferably it is 0.95 or more, Moreover, Preferably it is 1.10 or less, More preferably, it is 1.08 or less, Especially preferably, it is 1.05 or less. Here, R (± 50 °) is the value of the liquid crystal cured layer measured at a measurement direction perpendicular to the in-plane fast axis direction of the liquid crystal cured layer at an incident angle θ of −50 ° and + 50 °. It represents the average of retardations R (−50 °) and R (+ 50 °). Further, R (0 °) represents the retardation of the liquid crystal cured layer at an incident angle of 0 °.

Generally, external light incident on the display surface of the image display device at an incident angle "+ φ" is reflected at an emission angle "-φ". Therefore, when the reflection suppression film provided on the display surface includes the liquid crystal cured film, the external light is in a path including the outward path at the incident angle "+ .PHI." And the return path at the emission angle "-.PHI." Pass through the liquid crystal curing layer. The retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is preferably close to 1.00 from the viewpoint of effectively suppressing the reflection of light passing through this path. When the retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is in the above-mentioned range close to 1.00, reflection of external light in the tilt direction by the polarizing plate including the liquid crystal cured layer Can be effectively suppressed. Specifically, while external light passes through the liquid crystal cured layer twice during incident and reflection, the polarization state is appropriately converted to realize effective blocking by the linear polarizer of the polarizing plate. It becomes possible. Therefore, when a liquid crystal cured film including such a liquid crystal cured layer is obtained in combination with a linear polarizer to obtain a polarizing plate, the reflection suppressing ability by the polarizing plate can be exhibited in a wide incident angle range, so a particularly excellent visual field Angular characteristics can be obtained.

As described above, in the first and second cured layers, the occurrence of alignment defects is usually suppressed. Therefore, the occurrence of alignment defects can be suppressed even in the entire liquid crystal cured layer including the first cured layer and the second cured layer.

As described above, the first cured layer and the second cured layer generally have good surface condition. Therefore, the surface condition is good also as the whole liquid crystal cured layer including the first cured layer and the second cured layer. Therefore, the cured liquid crystal layer usually has small unevenness in thickness and therefore small unevenness in in-plane retardation.

The thickness of the liquid crystal cured layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 15.0 μm or less, more preferably less than 11.5 μm, still more preferably 8.0 μm or less, particularly preferably 6.0 μm or less. When the thickness of the liquid crystal cured layer is in the above range, characteristics such as in-plane retardation can be easily adjusted to a desired range. Moreover, since the liquid crystal cured layer of such a thickness is thinner than the conventional retardation film used for the reflection suppression film of the organic EL display panel, it can contribute to thinning of the organic EL display panel.

In the liquid crystal cured layer, the first cured layer and the second cured layer can usually be distinguished by the following method.
The liquid crystal cured layer is embedded in epoxy resin to obtain a sample piece. The sample piece is sliced in parallel to 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 axis direction of the liquid crystal hardened layer and the cross section become parallel. Then, the cross section which appeared by slicing is observed using a polarization microscope. This observation is performed by inserting a wave plate as an inspection plate between the observation sample and the objective lens of the polarization microscope so that an image exhibiting a color according to the retardation of the observation sample can be seen. At this time, portions with different colors can be distinguished as boundaries between the first cured layer and the second cured layer.

The liquid crystal cured layer may be a layer having a two-layer structure including only the first cured layer and the second cured layer, but may include three or more layers.

The liquid crystal cured film may be a film including only the liquid crystal cured layer, or may be a film including any layer in combination with the liquid crystal cured layer. As an optional layer, a base material used for producing a liquid crystal cured layer, a retardation film, an adhesive layer for bonding to other members, a mat layer for improving the sliding property of the film, an impact resistant polymethacrylate resin layer, etc. Hard coat layer; antireflective layer; antifouling layer; and the like.

The liquid crystal cured film is preferably excellent in transparency. Specifically, the total light transmittance of the liquid crystal cured film is preferably 75% or more, more preferably 80% or more, and particularly preferably 84% or more. The haze of the liquid crystal cured film 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 and visible spectrometer. In addition, the haze can be measured using a haze meter.

The thickness of the liquid crystal cured film is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 300 μm or less, more preferably 200 μm or less.

[12. Polarizer]
The liquid crystal cured film described above can be applied to a polarizing plate. This polarizing plate comprises the liquid crystal cured film described above, and usually comprises a linear polarizer. It is preferable that the polarizing plate can function as a circularly polarizing plate or an elliptically polarizing plate. By providing such a polarizing plate in a display device such as an organic EL display device, reflection of external light can be suppressed in the front direction of the display surface.

In addition, since the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is properly adjusted, the liquid crystal cured layer has a birefringence appropriately adjusted not only in the in-plane direction but also in the thickness direction. Have. Therefore, the polarizing plate can suppress the reflection of outside light not only in the front direction of the display surface of the display device but also in the inclination direction. Therefore, by using this polarizing plate, a display device with a wide viewing angle can be realized.

As a linear polarizer, for example, a film obtained by adsorbing iodine or a dichroic dye to a polyvinyl alcohol film and uniaxially stretching in a boric acid bath; iodine or a dichroic dye is adsorbed to a polyvinyl alcohol film And a film obtained by further stretching and further modifying a part of polyvinyl alcohol units in the molecular chain into polyvinylene units. Moreover, as another example of a linear polarizer, the polarizer which has the function to isolate | separate polarization | polarized-light into reflected light and transmitted light, such as a grid polarizer and a multilayer polarizer, is mentioned. Among these, as the linear polarizer, a polarizer containing polyvinyl alcohol is preferable.

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

When it is desired to make the polarizing plate function as a circularly polarizing plate, the angle formed by the slow axis of the liquid crystal cured layer with the polarization absorption axis of the linear polarizer is preferably 45 ° or near. Specifically, the above angle is preferably 45 ° ± 5 ° (ie, 40 ° to 50 °), more preferably 45 ° ± 4 ° (ie, 41 ° to 49 °), and particularly preferably 45 ° ± 3. ° (ie 42 ° to 48 °).

The polarizing plate may further contain any layer in addition to the linear polarizer and the liquid crystal cured film. As an optional layer, for example, an adhesive layer for bonding a linear polarizer and a liquid crystal cured film; a polarizer protective film layer for protecting a linear polarizer; and the like can be mentioned.

The polarizing plate can be manufactured by a manufacturing method including manufacturing a liquid crystal cured film by the manufacturing method according to the embodiment described above. For example, the polarizing plate is manufactured by a manufacturing method including manufacturing a liquid crystal cured film by the manufacturing method according to the above-described embodiment, and laminating the manufactured liquid crystal cured film and a linear polarizer. it can. For bonding, an adhesive may be used as necessary.

[13. Organic EL Display Device]
The above polarizing plate can be applied to an organic EL display device. The organic EL display device includes the above-described polarizing plate, and further usually includes an organic electroluminescent element (hereinafter sometimes referred to as “organic EL element” as appropriate). The organic EL display device usually has a polarizing plate on the viewing side of the organic EL element. Moreover, a polarizing plate is equipped with a liquid crystal cured film and a linear polarizer 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 the case where the polarizing plate functions as a circularly polarizing plate as an example. The light incident from the outside of the device becomes circularly polarized light when only a part of the linearly polarized light passes through the linear polarizer and then passes through the liquid crystal cured film. Circularly polarized light is reflected by a component (such as a reflective electrode of the organic EL element) that reflects light in the organic EL element, and passes through the liquid crystal cured film again, so that the vibration direction is orthogonal to the vibration direction of incident linearly polarized light. Become linearly polarized light, and does not pass through the linear polarizer. Here, the vibration direction of linearly polarized light means the vibration direction of an electric field of linearly polarized light. Thereby, the function of reflection suppression is achieved. For the principle of such reflection suppression, reference may be made to JP-A-9-127885.

The organic EL device generally includes a transparent electrode layer, a light emitting layer and an electrode layer in this order, and the light emitting layer can generate light when voltage is applied from the transparent electrode layer and the electrode layer. As an example of the material which comprises an organic light emitting layer, the material of a polypara phenylene vinylene type | system | group, a poly fluorene type | system | group, and a polyvinyl carbazole type can be mentioned. In addition, the light emitting layer may have a stack of a plurality of layers having different emission colors, or a mixed layer in which layers of certain dyes are doped with different dyes. Furthermore, the organic EL element may be provided with functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface forming layer, and a charge generation layer.

The organic EL display device can be manufactured by a manufacturing method including manufacturing a polarizing plate by the above-described manufacturing method.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the embodiments shown below, and can be implemented with arbitrary modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

In the following description, "%" and "parts" representing amounts are by weight unless otherwise stated. Moreover, unless otherwise indicated, the operation described below was performed in a normal temperature and pressure atmosphere.

Moreover, since the support base material contained in the liquid-crystal cured film manufactured by the Example and comparative example which are demonstrated below has optical isotropy, it does not affect the measurement result of retardation. Then, the measurement of the retardation of the liquid-crystal cured layer in the Example and comparative example which are demonstrated below was implemented using the liquid-crystal cured film as a sample.

[Evaluation method]
(Method of measuring liquid crystal phase-solid phase transition temperature of liquid crystal compound)
10 mg of the liquid crystal compound was weighed. The measured liquid crystal compound was sandwiched between two glass substrates subjected to rubbing treatment while the liquid crystal compound was in a solid state. The substrate was placed on a hot plate, heated from 40 ° C. to 200 ° C., and then cooled to 40 ° C. At the time of temperature rise and temperature drop, the change in the structure of the liquid crystal compound was observed with a polarizing optical microscope.
Thus, the liquid crystal phase-solid phase transition temperature of the liquid crystal compound was measured at a temperature of 40 ° C. to 200 ° C.

(Method of measuring substantially maximum tilt angle of molecules of liquid crystal compound in liquid crystal cured layer and first to second cured layers contained therein)
FIG. 3 is a perspective view for explaining the measurement direction when measuring the retardation of the liquid crystal cured layer 200 from the tilt direction. In FIG. 3, the arrow A 1 represents the in-plane slow axis direction of the liquid crystal hardened layer 200, the arrow A 2 represents the in-plane fast axis direction of the liquid crystal hardened layer 200, and the arrow A 3 represents the thickness direction of the liquid crystal hardened layer 200. Represents

The retardation of the cured liquid crystal layer 200 was measured in the range of an incident angle θ of −50 ° to 50 °, as shown in FIG. 3, using a retardation meter (“AxoScan” manufactured by Axometrics). At this time, the measurement direction A4 was set to be perpendicular to the in-plane fast axis direction A2 of the liquid crystal cured layer 200. In addition, the measurement wavelength was 590 nm.

Based on the measured retardation, the liquid crystal cured layer was analyzed by the analysis software (analysis software "Multi-Layer Analysis" manufactured by AxoMetrics; analysis conditions: analysis wavelength 590 nm, 20 layer division number) attached to the above-mentioned retardation meter The substantial maximum tilt angles of the molecules of the liquid crystal compound contained in 200 were analyzed.

Further, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer was measured by the following method.
The liquid crystal contained in the first cured layer by the same method as the method for measuring the substantially maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer except using the first cured layer instead of the liquid crystal cured layer Maximum tilt angle of the molecule of the sex compound was measured. This measurement is carried out at a time before the liquid crystal composition for forming a second cured layer is further coated on the surface of the first cured layer after obtaining the first cured layer during the production of the liquid crystal cured layer. The

Furthermore, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer was measured by the following method.
The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer and the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer were measured. Then, the maximum tilt angles of the molecules of the liquid crystal compound contained in the second cured layer were analyzed using these measured maximum tilt angles and the thicknesses of the first cured layer and the second cured layer.

(Evaluation method of viewing angle characteristics)
The retardation of the cured liquid crystal layer 200 was measured in the range of an incident angle θ of −50 ° to 50 °, as shown in FIG. 3, using a retardation meter (“AxoScan” manufactured by Axometrics). At this time, the measurement direction A4 was set to be perpendicular to the in-plane fast axis direction A2 of the liquid crystal cured layer 200. In addition, the measurement wavelength was 590 nm.

The average value R (± 50 °) of the retardation R (−50 °) at an incident angle θ of −50 ° and the retardation R (+ 50 °) at an incident angle θ of + 50 ° was calculated. Then, the average value R (± 50 °) is divided by the in-plane retardation R (0 °) at an incident angle θ of 0 ° to obtain an average retardation ratio R (± 50 °) / R (0 °). I asked. The closer the average retardation ratio R (± 50 °) / R (0 °) to 1.00, the better the viewing angle characteristics can be realized in the organic EL display device. Therefore, the viewing angle characteristics of the liquid crystal cured layer were evaluated based on the value of the average retardation ratio R (± 50 °) / R (0 °) according to the following criteria.
"Good": R (± 50 °) / R (0 °)> 0.91
“Bad”: R (± 50 °) / R (0 °) ≦ 0.91

In addition, the average retardation ratio R (± 50 °) / R (0 °) of the first cured layer is the average retardation of the liquid crystal cured layer except that the first cured layer is used instead of the liquid crystal cured layer. It was determined by the same method as the ratio R (± 50 °) / R (0 °).

[Description of Liquid Crystalline Compound]
The structures of the reverse dispersed liquid crystal compound 1 (liquid crystal phase-solid phase transition temperature = 96 ° C.) and the reverse dispersed liquid crystal compound 2 (liquid crystal phase-solid phase transition temperature = 125 ° C.) used in the following examples are as follows: It is street.

[Examples 1 to 21]
(Preparation of liquid crystal composition)
100 parts by weight of a liquid crystal compound of the type shown in Table 1, 0.15 parts by weight of a surfactant ("S420" manufactured by AGC Seimi Chemical Co., Ltd.), 4.3 parts by weight of a polymerization initiator ("Irgacure OXE04" manufactured by BASF Corp.), Also, 148.5 parts by weight of cyclopentanone and 222.8 parts by weight of 1,3-dioxolane were mixed as a solvent to prepare a liquid crystal composition.

(Preparation of support base material)
As a supporting substrate, a resin film ("Zeonor film ZF16" manufactured by Nippon Zeon Co., Ltd .; thickness 100 μm; glass transition temperature of resin: 160 ° C.) made of thermoplastic norbornene resin was prepared. One side of this support base was subjected to corona treatment. Next, the corona-treated surface of the support substrate was subjected to rubbing treatment.

(Formation of first hardened layer)
The liquid crystal composition was coated on the rubbing-treated surface of the supporting substrate using a bar coater to form a layer of the liquid crystal composition (step (I)).
Then, the layer of the liquid crystal composition was heated for 2 minutes in an oven set at 160 ° C. to align the liquid crystal compound in the layer (step (II)). In the example using the liquid crystal compound 1, the heating condition was a temperature condition at which the residual viscosity of the test composition corresponding to the liquid crystal composition used is 140 cP. Further, in the example using the liquid crystal compound 2, the heating condition was such a temperature condition that the residual viscosity of the test composition corresponding to the used liquid crystal composition is 209 cP.
Thereafter, the layer of the liquid crystal composition was irradiated with ultraviolet light of 500 mJ / cm ² in a nitrogen atmosphere to cure the layer of the liquid crystal composition to form a first cured layer having a thickness of about 1 μm (step (III)) ).
The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer, and the average retardation ratio R (± 50 °) / R (0 °) of the first cured layer were measured.

(Formation of second hardened layer)
The remaining liquid crystal composition used for forming the first cured layer was directly coated on the surface of the first cured layer using a bar coater to form a layer of the liquid crystal composition (step (IV)) ). Thus, a work-in-process having the supporting substrate, the first cured layer, and the layer of the liquid crystal composition in this order was obtained.
Next, this work-in-process was placed in an oven set at 160 ° C. and heated for 2 minutes to orient the liquid crystal compound in the layer of the liquid crystal composition (step (V)). Thereafter, the work in process was removed from the oven.
Thereafter, the work-in-process was allowed to stand at the temperature shown in Table 1 for the time shown in Table 1 (Step (VI)). At this time, the standing at a temperature of 23 ° C. was performed by placing the work-in-process on a stainless steel plate. In addition, standing at other temperatures was carried out by placing the work-in-process on a temperature-controlled hot plate.
Thereafter, the layer of the liquid crystal composition was irradiated with ultraviolet light of 500 mJ / cm ² in a nitrogen atmosphere to cure the layer of the liquid crystal composition, thereby forming a second cured layer having a thickness of about 2 μm (step (VII) ). Thus, a liquid crystal cured film provided with a support base and a liquid crystal cured layer including the first cured layer and the second cured layer was obtained.
Measurement of the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer of the liquid crystal cured film thus obtained, measurement of the substantial maximum inclination angle of the molecules of the liquid crystalline compound contained in the second cured layer, and liquid crystal curing The viewing angle characteristics of the layer were evaluated.

Comparative Example 1
After the step (V) of orienting the liquid crystal compound in the layer of the liquid crystal composition for forming the second cured layer, the step (VI) of leaving the work in place is not performed, and the liquid crystal composition is irradiated with ultraviolet light. The step (VII) of curing the layer of matter was performed.
Except for the above matters, the same operation as in Example 1 was performed to manufacture and evaluate a liquid crystal cured film.

Example 22
After the step (II) of orienting the liquid crystal compound in the layer of the liquid crystal composition for forming the first cured layer, before the step (III) of curing the layer of the liquid crystal composition by irradiation of ultraviolet light A step (VIII) was performed in which the layer of the composition was allowed to stand at room temperature of 23 ° C. for 240 seconds. The standing under the temperature condition of 23 ° C. was carried out by placing a work-in-progress provided with a supporting substrate and a layer of a liquid crystal composition on a stainless steel plate.
Except for the above matters, the same operation as in Example 4 was performed to manufacture and evaluate a liquid crystal cured film.

Comparative Example 2
After the step (V) of orienting the liquid crystal compound in the layer of the liquid crystal composition for forming the second cured layer, the step (VI) of leaving the work in place is not performed, and the liquid crystal composition is irradiated with ultraviolet light. The step (VII) of curing the layer of matter was performed.
Except for the above matters, the same operation as in Example 22 was performed to manufacture and evaluate a liquid crystal cured film.

[result]
The results of the above Examples and Comparative Examples are shown in Table 1 below. In Table 1, the meanings of the abbreviations are as follows.
Θ: Real maximum tilt angle.
Re ratio: R (± 50 °) / R (0 °).

[Consideration]
As compared with the comparative example in which the step (VI) was not performed, in the example in which the step (VI) was performed, the substantial tilt angle of the molecules of the liquid crystal compound contained in the second cured layer could be increased. The substantial tilt angles of the molecules of the liquid crystal compound contained in the liquid crystal cured layer including the first cured layer and the second cured layer are also increased. Moreover, in the example, it can be confirmed that the substantial maximum inclination angle tends to be larger as the time taken to the step (VI) is longer. Therefore, according to the manufacturing method including the step (VI), it can be confirmed from the above example that the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be easily adjusted. Furthermore, by adjusting the substantial tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer, it is possible to appropriately adjust the birefringence in the thickness direction of the liquid crystal cured layer, so improvement in viewing angle characteristics can be achieved. Can be confirmed.

100 liquid crystal cured film 110 liquid crystal cured layer 111 first cured layer 112 second cured layer 200 liquid crystal cured layer

Claims

A method for producing a cured liquid crystal film comprising a cured liquid crystal composition containing a liquid crystal compound and comprising a cured liquid crystal layer comprising a first cured layer and a second cured layer,
The substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is 5 ° or more and 85 ° or less,
The manufacturing method is
Step (I) of forming a layer of a first liquid crystal composition containing the liquid crystal compound
Aligning the liquid crystal compound contained in the layer of the first liquid crystal composition (II);
Curing the layer of the first liquid crystal composition to form the first cured layer (III);
Forming a layer of a second liquid crystal composition containing the liquid crystal compound which is the same as or different from the liquid crystal compound contained in the first liquid crystal composition directly on the first cured layer;
Aligning the liquid crystalline compound contained in the layer of the second liquid crystal composition (V);
Step (VI) in which the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition increases with the passage of time;
Curing the layer of the second liquid crystal composition to form the second cured layer (VII); in this order, a method for producing a liquid crystal cured film.
The method for producing a liquid crystal cured film according to claim 1, wherein the step (VI) is performed for 60 seconds or more.
The manufacturing method of the liquid-crystal cured film of Claim 1 or 2 which performs said process (VI) over the time of 120 to 600 second.
The liquid crystal curing according to any one of claims 1 to 3, wherein the step (VI) is performed under a temperature condition lower than the liquid crystal phase-solid phase transition temperature of the liquid crystal compound contained in the second liquid crystal composition. How to make a film.
The method for producing a liquid crystal cured film according to any one of claims 1 to 4, wherein the liquid crystal compound is a liquid crystal compound capable of expressing reverse wavelength dispersive birefringence.
The method for producing a liquid crystal cured film according to any one of claims 1 to 5, wherein the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° or more and 85 ° or less.
The substantial maximum inclination angle of the molecule of the liquid crystal compound contained in the second hardened layer is larger than the substantial maximum inclination angle of the molecule of the liquid crystal compound contained in the first hardened layer. The manufacturing method of the liquid crystal hardening film as described in any one.
The method for producing a liquid crystal cured film according to any one of claims 1 to 7, wherein the liquid crystal cured layer can function as a quarter wavelength plate.
It is a manufacturing method of a polarizing plate provided with a liquid crystal hardening film,
A method for producing a polarizing plate, comprising producing the liquid crystal cured film by the method according to any one of claims 1 to 8.
A method of manufacturing an organic electroluminescent display device comprising a polarizing plate, comprising:
The manufacturing method of the organic electroluminescent display apparatus including manufacturing the said polarizing plate by the manufacturing method of Claim 9.