TW201940562A - Liquid crystal cured film, polarization plate, and method for manufacturing organic electroluminescence display device - Google Patents

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

Liquid crystal cured film, polarizing plate and method for manufacturing organic electroluminescence display device

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

As one type of optical film, a liquid crystal cured film is known. The liquid crystal cured film generally includes a liquid crystal cured layer formed of a cured product that orients a liquid crystal composition containing a liquid crystalline compound and directly cures the liquid crystal composition while maintaining the alignment state. As such a liquid crystal cured film, those described in Patent Documents 1 to 3 have been proposed.

『Patent Literature』
"Patent Document 1": Japanese Patent No. 5363022 "Patent Document 2": International Patent Publication No. 2016/031853 "Patent Document 3": Japanese Patent Publication No. 2017-037193

The liquid crystal cured layer included in the liquid crystal cured film usually contains a liquid crystal compound. The molecules of the liquid crystalline compound may be inclined with respect to the plane of the layer of the liquid crystal cured layer. Such a liquid crystal cured layer containing a liquid crystal compound having a molecular tilt as described above generally has birefringence in the thickness direction depending on the magnitude of the tilt angle of the molecules of the liquid crystal compound. In addition, a liquid crystal cured film including a "liquid crystal cured layer with a moderately adjusted birefringence in the thickness direction" is provided on an image display device such as an organic electroluminescence display device (hereinafter referred to as an "organic EL display device" as appropriate) Various advantages such as improvement of viewing angle can be obtained.

The tilt angle of the molecules of the liquid crystalline compound contained in a certain layer can be evaluated by the substantial maximum tilt angle. The so-called "substantially maximum tilt angle" refers to a case where the tilt angle of a molecule on one surface of a layer body is 0 °, and the tilt angle of the molecule changes at a certain ratio in the thickness direction. The maximum tilt angle of the molecule. In a layered body containing a liquid crystal compound, the inclination angle of the molecules of the liquid crystal compound may be smaller toward one side of the layer body in the thickness direction and larger from the one side. The substantial maximum inclination angle indicates that the inclination angle calculated based on the assumption that the rate of change in the inclination angle in the thickness direction (that is, the rate of change that decreases toward the side and increases away from the side) is constant. The maximum value.

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 cumbersome to prepare liquid crystal compositions having different compositions each time the substantial maximum tilt angle is to be changed. Therefore, it is desired to develop a technology that can easily adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer.

The present invention was initiated in view of the foregoing problems, and an object thereof is to provide a method for manufacturing a liquid crystal cured film having a liquid crystal cured layer, and to easily adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. A method of manufacturing a polarizing plate using the aforementioned method of manufacturing a liquid crystal cured film; and a method of manufacturing an organic EL display device using the aforementioned method of manufacturing a liquid crystal cured film.

In order to solve the aforementioned problems, the present inventors devoted themselves to research. As a result, the inventors have found that a first cured layer is formed through the first liquid crystal composition, a layer of a second liquid crystal composition containing a liquid crystal compound is directly formed on the first cured layer, and the first 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 will increase with time. Then, based on this knowledge, the present inventors have completed the present invention.

That is, the present invention includes the following.

[1] A method for producing a liquid crystal cured film, which is a method for producing a liquid crystal cured film including a liquid crystal cured layer, the liquid crystal cured layer including a first cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound. And a second cured layer; wherein the substantial maximum tilt 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 sequentially includes a step (I) of forming a layer body of the first liquid crystal composition containing the liquid crystal compound; and a step of orienting the liquid crystal compound contained in the layer body of the first liquid crystal composition (II). ); Step (III) of curing the layer of the first liquid crystal composition to form the first cured layer; step (IV) of directly forming the layer of the second liquid crystal composition on the first cured layer, The second liquid crystal composition includes the liquid crystal compound that is the same as or different from the liquid crystal compound included in the first liquid crystal composition; orients the liquid crystal compound included in the layer of the second liquid crystal composition. Step (V); a step (VI) of increasing a substantial maximum tilt angle of a molecule of the liquid crystal compound contained in the layer of the second liquid crystal composition with time, and a step of forming the second liquid crystal composition The step (VII) of curing the laminated body to form the aforementioned second cured layer.

[2] The method for producing a liquid crystal cured film according to [1], which takes 60 seconds or more to perform the step (VI).

[3] The method for producing a liquid crystal cured film according to [1] or [2], which takes the time of 120 seconds or more and 600 seconds or less to perform the step (VI).

[4] The method for producing a liquid crystal cured film according to any one of [1] to [3], which is in a liquid crystal phase-solid phase transition of the liquid crystal compound that is not included in the second liquid crystal composition The step (VI) is performed under a temperature condition of a temperature.

[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 birefringent liquid crystal compound capable of exhibiting reverse wavelength dispersion.

[6] The method for producing a liquid crystal cured film according to any one of [1] to [5], wherein a substantial maximum tilt angle of a molecule of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° or more and 85 ° or less.

[7] The method for producing a liquid crystal cured film according to any one of [1] to [6], wherein a substantial maximum tilt angle of a molecule of the liquid crystal compound contained in the second cured layer is larger than that of the first The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the cured layer is also large.

[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 1/4 wavelength plate.

[9] A method for manufacturing a polarizing plate, which is a method for manufacturing a polarizing plate including a liquid crystal cured film, including:
The manufacturing method described in any one of [1] to [8], for producing the liquid crystal cured film.

[10] A method for manufacturing an organic electroluminescence display device, which is a method for manufacturing an organic electroluminescence display device including a polarizing plate, including:
The above-mentioned polarizing plate was manufactured by the manufacturing method described in [9].

According to the present invention, there can be provided a manufacturing method of a liquid crystal cured film having a liquid crystal cured layer, and a manufacturing method capable of easily adjusting a substantial maximum tilt angle of molecules of a liquid crystal compound contained in the liquid crystal cured layer; A manufacturing method of a polarizing plate in a manufacturing method; and a manufacturing method of an organic EL display device using the aforementioned manufacturing method of a liquid crystal cured film.

Examples and embodiments are disclosed below to explain the present invention in detail. However, the present invention is not limited to the examples and implementation modes disclosed below, and can be implemented with arbitrary changes without departing from the scope of the patent application of the present invention and its equivalent scope.

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

In the following description, the "thickness direction" of a layer body means a direction perpendicular to the plane of the layer body unless otherwise noted. Therefore, unless otherwise noted, the in-plane direction of a layer is perpendicular to the thickness direction.

In the following description, unless otherwise noted, the "frontal direction" of a certain surface indicates the normal direction of the surface, and specifically refers to the direction in which the polar angle of the aforementioned surface is 0 °.

In the following description, unless otherwise noted, the "tilt direction" of a surface means a direction that is neither parallel nor perpendicular to the surface, specifically the polar angle of the aforementioned surface is 5 ° or more and 85 ° or less Range of directions.

In the following description, unless otherwise noted, the birefringence of inverse wavelength dispersion refers to the birefringence Δn (450) at a wavelength of 450 nm and the birefringence Δn (550) at a wavelength of 550 nm to satisfy the following formula ( N1) birefringence. Liquid crystal compounds that exhibit such a birefringence of inverse wavelength dispersion, usually exhibit longer birefringence at longer wavelengths.
Δn (450) <Δn (550) (N1)

In the following description, unless otherwise noted, the birefringence of forward wavelength dispersion refers to the birefringence Δn (450) at a wavelength of 450 nm and the birefringence Δn (550) at a wavelength of 550 nm to satisfy the following formula ( N2) birefringence. Liquid crystal compounds that exhibit such a birefringence of forward wavelength dispersion are usually measured at a longer wavelength, and exhibit smaller birefringence.
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 noted. Here, nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the layer body and a direction giving the maximum refractive index. ny represents the refractive index of the layer in the aforementioned in-plane direction and a direction orthogonal to the direction of nx. d represents the thickness of the layer. The retardation measurement wavelength is 590 nm unless otherwise noted. The in-plane delay Re can be measured using a phase difference meter ("AxoScan" manufactured by Axometrics).

In the following description, a resin having a positive intrinsic birefringence value means a resin whose refractive index in the direction of extension becomes larger than the refractive index in a direction orthogonal to it. In addition, a resin having a negative intrinsic birefringence value means a resin having a refractive index in an extending direction that is smaller than a refractive index in a direction orthogonal to the extending direction. The intrinsic birefringence is worth calculating from the dielectric constant distribution.

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

In the following description, the directions of the elements are "parallel" and "vertical". Unless otherwise noted, within the range not impairing the effect of the present invention, for example, ± 4 °, preferably ± 3 ° The error is within the better range of ± 1 °.

In the following description, unless otherwise noted, the so-called "tilt angle" of the molecules of a liquid crystal compound contained in a layer indicates the angle between the molecules of the liquid crystal compound and the plane of the layer, and is sometimes called Is the "tilt angle". This tilt angle corresponds to the largest angle between the direction of the maximum refractive index on the refractive index ellipsoid of the molecules of the liquid crystal compound and the angle between the planes of the layer. In the following description, unless otherwise noted, the so-called "tilt angle" means the tilt angle of the molecules of the liquid crystal compound with respect to the plane of the layer body of the layer body included in the liquid crystal compound. The inclination angle with respect to the plane of the layer body is sometimes referred to as "the inclination angle with respect to the in-plane direction (parallel to this plane of the layer body)".

[1. Overview of Production Method of Liquid Crystal Cured Film]

FIG. 1 is a schematic cross-sectional view of a liquid crystal cured film 100 manufactured by a manufacturing method as an embodiment of the present invention.

As shown in FIG. 1, as a method for manufacturing a liquid crystal cured film 100 according to an embodiment of the present invention, the method is a method for manufacturing a liquid crystal cured film 100 including a liquid crystal cured layer 110. The liquid crystal cured layer 110 is composed of a liquid crystal compound. It is formed by the cured product of the liquid crystal composition. The liquid crystal cured layer 110 of the liquid crystal cured film 100 manufactured by this manufacturing 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 the liquid crystal composition is formed of a cured product of a liquid crystal composition, the liquid crystal cured layer 110 includes molecules of a liquid crystal compound (not shown). 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 having a fixed orientation state" includes a polymer of a liquid crystal compound. Although the liquid crystal property of a liquid crystal compound is usually lost due to polymerization, in the present application, such a polymerized liquid crystal compound is also included in the term "liquid crystal compound included in the liquid crystal cured layer".

The molecules of at least a part of the liquid crystal compound contained in the liquid crystal cured layer 110 are inclined with respect to the plane of the layer body of the liquid crystal cured layer 110 (that is, with respect to the in-plane direction). The so-called "tilt" of the molecules of a liquid crystalline compound with respect to the plane of the layer (that is, with respect to the in-plane direction) means that the tilt angle of the molecules with respect to the plane of the layer (that is, with respect to the in-plane direction) is 5 ° or more Range below 85 °. The molecules of the liquid crystalline compound thus inclined are usually in a state that they are neither parallel nor perpendicular to the plane of the layer body (that is, 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 a layer plane (ie, with respect to an in-plane direction) of the liquid crystal cured layer 110, The substantial maximum tilt angle of the molecule is usually 5 ° or more and 85 ° or less. This substantial maximum tilt angle is an index that reveals the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110. Generally, the liquid crystal cured layer 110 having a substantially large maximum tilt angle tends to have a larger tilt angle as a whole of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110. Therefore, if the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 can be adjusted, the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer 110 can be adjusted as a whole. In addition, the liquid crystal cured film 100 provided with the liquid crystal cured layer 110 with a substantially maximum substantially inclined angle can appropriately adjust the birefringence in the thickness direction, and thus can exhibit excellent viewing angle characteristics.

The manufacturing method of such a liquid crystal cured film 100 includes:
A step (I) of forming a layered body of the first liquid crystal composition containing a liquid crystalline compound;
A step (II) of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition;
A step (III) of curing the layer of the first liquid crystal composition to form the first cured layer 111;
Step (IV) of directly forming a layer body of a second liquid crystal composition on the first cured layer 111, the second liquid crystal composition including liquid crystals that are the same as or different from the liquid crystal compounds included in the first liquid crystal composition Sex compounds
A step (V) of orienting the liquid crystal compound contained in the layer of the second liquid crystal composition;
Step (VI) of increasing a substantial maximum tilt angle of molecules of a liquid crystal compound contained in a layer of the second liquid crystal composition with the passage of time; and curing the layer of the second liquid crystal composition to form a second Step (VII) of the cured layer 112.

[2. Step (I): Formation of Layer of First Liquid Crystal Composition]

In the step (I), a layered body of the first liquid crystal composition "which is 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 crystalline compound is a compound having liquid crystallinity, and is generally a compound that can exhibit a liquid crystal phase when the liquid crystalline compound is aligned. As the liquid crystalline compound, a reverse-dispersive liquid crystalline compound, a cis-dispersive liquid crystalline compound, or a combination of a reverse-dispersive liquid crystalline compound and a cis-dispersive liquid crystalline compound may be used.

The so-called inverse dispersion liquid crystalline compound is a liquid crystal compound which exhibits birefringence of inverse wavelength dispersion. In addition, the so-called birefringent liquid crystal compound exhibiting reverse wavelength dispersion refers to a birefringence exhibiting reverse wavelength dispersion when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. Liquid crystal compounds.

The cis-dispersing liquid crystalline compound is a birefringent liquid crystal compound that exhibits CW dispersion. In addition, the so-called birefringent liquid crystal compound exhibiting forward wavelength dispersion refers to a birefringence exhibiting forward wavelength dispersion when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer. Liquid crystal compounds.

In general, when the liquid crystal compound is uniformly aligned, the wavelength dispersion of the birefringence displayed by the layer of the liquid crystal compound can be checked by checking the wavelength dispersion of the birefringence displayed by the layer of the liquid crystal compound. Here, the so-called uniform orientation of the liquid crystal compound refers to forming a layer body including the liquid crystal compound, so that the direction of the maximum refractive index on the ellipsoid of the refractive index of the molecules of the liquid crystal compound in this layer body is along with The planes of the aforementioned layers are oriented in a certain direction in parallel. The birefringence of the layered body can be obtained from "(in-plane retardation of the layered body) ÷ (thickness of the layered body)".

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, the reverse dispersion liquid crystal compound is preferred. By using the reverse dispersion liquid crystalline compound, the substantial maximum tilt angle of the molecules of the reverse dispersion liquid crystalline compound contained in the layer body of the second liquid crystal composition can be effectively increased with the passage of time in the step (VI). Therefore, the tilt angle of the molecules of the liquid crystal compound in the step (VI) can be effectively adjusted. In addition, by using a reverse-dispersive liquid crystal compound, the first cured layer generally functions as a tilt alignment film that increases the tilt angle of the molecules of the reverse-dispersed liquid crystal compound contained in the second cured layer. Accordingly, when the second liquid crystal composition contains a 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 over a wide range.

The anisotropy of the refractive index of a liquid crystalline compound exhibiting reversed dispersion liquid crystallinity appears as follows: On the refractive index ellipsoid of the molecule of the liquid crystalline compound, the refractive index indicating the direction of the maximum refractive index and the direction intersecting with this The difference in refractive index in the other direction. In addition, the wavelength dispersion properties of the refractive indexes in the aforementioned directions differ depending on the molecular structure of the liquid crystal compound. According to this, for example, in a direction where the refractive index is relatively large, although the refractive index measured at a long wavelength is smaller than the refractive index measured at a short wavelength, 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 a long wavelength becomes smaller than the refractive index measured at a short wavelength, and the difference between them is large. In this example, the refractive index difference between the aforementioned directions becomes smaller if the measurement wavelength is short, and becomes larger if the measurement wavelength is long. As a result, birefringence with inverse wavelength dispersion can be exhibited.

The liquid crystalline compound is preferably polymerizable. Therefore, it is preferred that the liquid crystal compound contains a polymerizable group such as an acrylfluorenyl group, a methacrylfluorenyl group, and an epoxy group in its molecule. The polymerizable liquid crystal compound can be polymerized in a state showing a liquid crystal phase, and becomes a polymer while maintaining the orientation of molecules in the liquid crystal phase. Therefore, the alignment state of the liquid crystal compound can be fixed in the first cured layer, the degree of polymerization of the liquid crystal compound can be increased, and the mechanical strength of the first cured layer can be improved.

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

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, and more preferably 0.15 or less, and more preferably 0.10 or less. By using a liquid crystal compound having a birefringence Δn in such a range, a first cured layer having a substantial maximum tilt angle of a molecule of the liquid crystal compound can be easily obtained. In addition, by using a liquid crystal compound having birefringence Δn in such a range, it is usually easy to obtain a first cured layer with few alignment defects.

The birefringence of a liquid crystal compound can be measured by the following method, for example.

A layered body of the liquid crystal compound is prepared, and the liquid crystal compounds contained in the layered body are uniformly aligned. Then, the in-plane retardation of this layer was measured. Then, "(in-plane retardation of the layer body) ÷ (thickness of the layer body)" can be used to obtain the birefringence of the liquid crystal compound. In this case, in order to facilitate the measurement of the in-plane retardation and thickness, the layered body of the liquid crystal compound that has been uniformly aligned may be cured.

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

Specifically, the type of the liquid crystal compound is not limited. For example, as an example of a reverse-dispersion liquid crystal compound, the compound represented by following formula (I) is mentioned.

『Hua1』

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

『Hua 2』

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

In the aforementioned formulae (II-1) to (II-7), D ¹ to D ³ are each independently and represent an aromatic hydrocarbon ring group which may have a substituent or an aromatic heterocyclic group which may also have a substituent. The number of carbon atoms of the group represented by D ¹ to D ³ (the number of carbon atoms including a substituent) is independent, and is usually 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 the aromatic hydrocarbon ring group, a phenyl group is preferred.

Examples of the substituent possessed by the aromatic hydrocarbon ring group in D ¹ to D ³ include, for example, halogen atoms such as fluorine atom and chlorine atom; cyano group; Alkyl groups; alkenyl groups having 2 to 6 carbon atoms such as vinyl and allyl groups; halogenated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl groups; N having 1 to 12 carbon atoms such as dimethylamino groups , N-dialkylamino; alkoxy having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy; nitro; -OCF ₃ ; -C (= O) -R ^b ; -O-C (= O) -R b; -C (= O) -O-R b; -SO 2 R a; and the like. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

R ^a represents 6 to 20 carbon atoms selected from the group consisting of: 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. Aromatic ring groups; groups of groups.

R ^b represents a group selected from: an alkyl group having 1 to 20 carbon atoms which may have a substituent; an alkenyl group having 2 to 20 carbon atoms which may have a substituent; and 3 to 12 carbon atoms which may also have a substituent A cycloalkyl group; and an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent; a group of groups.

The carbon number of the alkyl group having 1 to 20 carbon atoms in R ^b is preferably 1 to 12, and more preferably 4 to 10. Examples of the alkyl group having 1 to 20 carbon atoms in R ^b include methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, 1-methylpentyl, and 1 -Ethylpentyl, secondary butyl, tertiary butyl, n-pentyl, isopentyl, neopentyl, n-hexyl, isohexyl, n-heptyl, n-octyl, n-nonyl, n-decyl, Regular eleven, regular twelve, regular thirteen, regular fourteen, regular fifteen, regular sixteen, regular seventeen, regular eighteen, regular nineteen and regular twenty .

Examples of the substituent having an alkyl group having 1 to 20 carbon atoms in R ^b include halogen atoms such as a fluorine atom and a chlorine atom; cyano groups; and carbon atoms having 2 to 12 carbon atoms such as a dimethylamino group. N, N-dialkylamino groups; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy; methoxymethoxy, methoxyethoxy, etc. Alkoxy groups having 1 to 12 carbon atoms substituted by alkoxy groups having 1 to 12 carbon atoms; nitro groups; aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups; triazolyl and pyrrolyl groups Aromatic heterocyclic groups having 2 to 20 carbon atoms, such as sulfonyl, furyl, thienyl, thiazolyl, benzothiazol-2-ylthio; cyclopropyl, cyclopentyl, and cyclohexyl Cycloalkyl; cycloalkoxy having 3 to 8 carbon atoms such as cyclopentyloxy and cyclohexyloxy; tetrahydrofuranyl, tetrahydropiperanyl, dioxy, dioxy, etc. having 2 to 12 carbon atoms Cyclic ether groups; aryloxy groups with 6 to 14 carbon atoms such as phenoxy and naphthyloxy; trifluoromethyl, pentafluoroethyl, -CH ₂ CF ₃ and more than one hydrogen atom substituted with fluorine atom Fluoroalkyl with 1 to 12 carbon atoms; benzofuranyl Benzopyran-yl; benzodioxin uh-yl; and benzodioxylmethine; and the like. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

The alkenyl group having 2 to 20 carbon atoms in R ^b preferably has 2 to 12 carbon atoms. Examples of the alkenyl group having 2 to 20 carbon atoms in R ^b include vinyl, propenyl, isopropenyl, butenyl, isobutenyl, pentenyl, hexenyl, heptenyl, and octyl Alkenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentaenyl, hexadecenyl, heptenyl, octadecenyl, undecenyl And eicosyl.

As the number of carbon atoms in the alkenyl R ^b in the group have 2 to 20 having the substituent group include an alkyl group with the number of carbon atoms in R ^b in the 1 to 20 to have the same substituent group of embodiments. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

Examples of the substituent having a cycloalkyl group having 3 to 12 carbon atoms in R ^b include halogen atoms such as a fluorine atom and a chlorine atom; cyano groups; and a carbon number of 2 to 12 such as a dimethylamino group. N, N-dialkylamino groups; alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl; those having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropyloxy Alkoxy; nitro; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl; and the like. Among them, as a substituent of a cycloalkyl group, a halogen atom such as a fluorine atom or a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; a methoxy group, an ethoxy group, Alkoxy groups having 1 to 6 carbon atoms such as isopropoxy; nitro groups; and aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl are preferred. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

Examples of the substituent having an aromatic hydrocarbon ring group having 6 to 12 carbon atoms in R ^b include halogen atoms such as fluorine atom and chlorine atom; cyano group; dimethylamino group having 2 to 12 carbon atoms N, N-dialkylamino groups; alkoxy groups having 1 to 20 carbon atoms, such as methoxy, ethoxy, isopropoxy, and butoxy; methoxymethoxy, methoxyethoxy Alkyl groups having 1 to 12 carbon atoms substituted by alkoxy groups having 1 to 12 carbon atoms; nitro groups; aromatics having 2 to 20 carbon atoms such as triazolyl, pyrrolyl, furyl, and thienyl groups Cycloyl groups; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl; cycloalkoxy groups having 3 to 8 carbon atoms such as cyclopentyloxy and cyclohexyloxy; tetrahydrofuranyl, Tetrahydropiperanyl, dioxy, dioxy, and other cyclic ether groups having 2 to 12 carbon atoms; phenoxy, naphthyloxy and other aryloxy groups having 6 to 14 carbon atoms; trifluoromethyl, A fluoroalkyl group having 1 to 12 carbon atoms, in which one or more hydrogen atoms are replaced by a fluorine atom, such as pentafluoroethyl group, -CH ₂ CF ₃ ; -OCF ₃ ; benzofuranyl group; Dioxyl; benzodioxy; etc. Among them, as the substituent of the aromatic hydrocarbon ring group, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkoxy group having 1 to 20 carbon atoms such as a methoxy group, an ethoxy group, an isopropoxy group, and a butoxy group; ; Nitro; furanyl, thienyl and other aromatic heterocyclic groups having 2 to 20 carbon atoms; cyclopropyl, cyclopentyl, cyclohexyl and other cycloalkyl groups having 3 to 8 carbon atoms; trifluoromethyl, penta A fluoroalkyl group having 1 to 12 carbon atoms in which at least one hydrogen atom such as fluoroethyl group, -CH ₂ CF _{3 is} replaced by a fluorine atom; -OCF _{3 is} preferred. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

The aromatic heterocyclic group in D ¹ to D ³ preferably has 2 to 30 carbon atoms. Examples of the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ include 1-benzofuranyl, 2-benzofuranyl, imidazolyl, indolyl, and furanyl , Oxazolyl, quinolinyl, thiadiazolyl, thiazolyl, thiazolopyryl, thiazolopyryl, thiazolopyryl, thiazolopyrimidyl, thienyl, triyl, triazolyl, pyridinyl , Pyryl, pyrazolyl, piperanyl, pyridyl, pyridyl, pyrimidinyl, pyrrolyl, fluorenyl, furyl, benzene [c] thienyl, benzene [b] thienyl, benzoisoxazolyl , Benzoisothiazolyl, benzimidazolyl, benzoxadiazolyl, benzoxazolyl, benzothiadiazolyl, benzothiazolyl, benzotriyl, benzotriazolyl, and benzo Pyrazolyl and the like. Among them, as the aromatic heterocyclic group, there are monocyclic aromatic heterocyclic groups such as furyl, piperanyl, thienyl, oxazolyl, furyl, thiazolyl, and thiadiazolyl; and benzothiazolyl and benzene Benzozolyl, quinolinyl, 1-benzofuranyl, 2-benzofuranyl, phthaloimino, benzo [c] thienyl, benzo [b] thienyl, thiazopyridyl, thiazolo Pyryl, benzoisoxazolyl, benzoxadiazolyl, and benzothiadiazolyl are more preferably aromatic heterocyclic groups.

As the aromatic heterocyclic ring in D ¹ ~ D ³ in the group to have the substituent group include the same groups as in the embodiment of the aromatic hydrocarbon ring group to have the substituent D ¹ ~ D ^3. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

In the formulae (II-1) to (II-7), D ⁴ to D ⁵ are each independently and represent a non-cyclic group which may have a substituent. D ⁴ and D ⁵ can also form a ring together. The number of carbon atoms of the group represented by D ⁴ to D ⁵ (the number of carbon atoms including the substituents) is independent, and is usually 1 to 100.

The number of carbon atoms of the non-cyclic group in D ⁴ to D ⁵ is preferably 1 to 13. Examples of the acyclic group in D ⁴ to D ⁵ include: an alkyl group having 1 to 6 carbon atoms; a cyano group; a carboxyl group; a fluoroalkyl group having 1 to 6 carbon atoms; and 1 to 6 carbon atoms _{alkoxy; -C (= O) -CH 3} ; -C (= O) NHPh; -C (= O) -OR x. Wherein, as a non-cyclic groups, cyano groups, _{carboxy, -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 aforementioned Ph represents a phenyl group. In addition, the aforementioned R ^x represents an organic group having 1 to 12 carbon atoms. Specific examples of R ^x include an alkoxy group having 1 to 12 carbon atoms or an alkyl group having 1 to 12 carbon atoms which may be substituted with a hydroxyl group.

Examples of the substituent having a non-cyclic group in D ⁴ to D ⁵ include the same examples as the substituents having an aromatic hydrocarbon ring group in D ¹ to D ³ . The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

When D ⁴ and D ⁵ form a ring together, a ring-containing organic group is formed by the aforementioned D ⁴ and D ⁵ . Examples of the organic group include a group represented by the following formula. In the following formula, * indicates the position of the carbon to which D ⁴ and D ⁵ are bonded in each organic group.

『Hua 3』

R ^* represents an alkyl group having 1 to 3 carbon atoms.

R ^** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.

R ^** represents a group selected from the group consisting of an alkyl group having 1 to 3 carbon atoms and a phenyl group which may have a substituent.

R ^{** * *} represents a group selected from the group consisting of a hydrogen atom, an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, and -COOR ¹³ . R ¹³ represents an alkyl group having 1 to 3 carbon atoms.

Examples of the substituent having a phenyl group include a halogen atom, an alkyl group, an alkenyl group, an aryl group, a heterocyclic group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, a fluorenyl group, a cyano group, and an amine group. . Among these, a halogen atom, an alkyl group, a cyano group, and an alkoxy group are preferred as the substituent. The number of substituents in the phenyl group may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

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

Examples of the organic group having 1 to 30 carbon atoms which may have a substituent in R ^g include, for example, an alkyl group having 1 to 20 carbon atoms which may have a substituent; an alkane having 1 to 20 carbon atoms. At least one of -CH ₂ -substituted by -O-, -S-, -O-C (= O)-, -C (= O) -O-, or -C (= O)- However, it excludes the case where two or more -O- or -S- are adjacent and intermediary respectively; an alkenyl group having 2 to 20 carbon atoms which may have a substituent; an alkyne 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; an aromatic hydrocarbon ring group having 6 to 30 carbon atoms, which may have a substituent; an aromatic group having 2 to 30 carbon atoms, which may have a substituent Heterocyclyl; -SO ₂ R ^a ; -C (= O) -R ^b ; -CS-NH-R ^b . The meaning of R ^a and R ^b is as described above.

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

Examples of the substituent having an alkyl group having 1 to 20 carbon atoms in R ^g include halogen atoms such as a fluorine atom and a chlorine atom; cyano groups; and carbon atoms having 2 to 12 carbon atoms such as a dimethylamino group. N, N-dialkylamino groups; alkoxy groups having 1 to 20 carbon atoms such as methoxy, ethoxy, isopropoxy, and butoxy; methoxymethoxy, methoxyethoxy, etc. Alkoxy groups having 1 to 12 carbon atoms substituted by alkoxy groups having 1 to 12 carbon atoms; nitro groups; aromatic hydrocarbon ring groups having 6 to 20 carbon atoms such as phenyl and naphthyl groups; triazolyl and pyrrolyl groups Aromatic heterocyclic groups having 2 to 20 carbon atoms, such as phenyl, furyl, and thienyl; cycloalkyl groups having 3 to 8 carbon atoms such as cyclopropyl, cyclopentyl, and cyclohexyl; cyclopentyloxy, cyclohexyloxy Cycloalkoxy groups having 3 to 8 carbon atoms; cyclic ether groups having 2 to 12 carbon atoms such as tetrahydrofuranyl, tetrahydropiperanyl, dioxy, and dioxy; phenoxy, naphthyloxy, etc. Aryloxy groups with 6 to 14 carbon atoms; Fluoroalkyl groups with 1 to 12 carbon atoms with one or more hydrogen atoms replaced by fluorine atoms; benzofuranyl; benzopiperanyl; benzodioxyl ; benzodioxylmethine; -SO ₂ R ^a; -SR ^b Carbon atoms substituted by the -SR ^b group having 1 to 12 alkoxy; hydroxy; and the like. The meaning of R ^a and R ^b is as described above. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

As the number of the alkenyl carbon atoms and R ^g groups have 2 to 20 having the substituent group include the same group of embodiments and to have numbers of the alkyl R ^g of 1 to 20 carbon atoms, substituted. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

Examples of the alkynyl group having 2 to 20 carbon atoms in R ^g include ethynyl, propynyl, 2-propynyl (propargyl), butynyl, 2-butynyl, 3- Butynyl, pentynyl, 2-pentynyl, hexynyl, 5-hexynyl, heptynyl, octynyl, 2-octynyl, nonynyl, decynyl, 7-decynyl Base etc.

As the group to have the substituent R ^g alkynyl numbers of 2 to 20 carbon atoms, and examples thereof include the same group of embodiments and to have numbers of the alkyl R ^g of 1 to 20 carbon atoms, substituted. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

As the alkyl group to have the substituent group in the ring of numbers R ^g 3 to 12 carbon atoms include, for example, the same group of embodiments and to have numbers of the alkyl R ^g of 1 to 20 carbon atoms, substituted. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

Examples of the aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g include 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 having an aromatic hydrocarbon ring group having 6 to 30 carbon atoms in R ^g include the same examples as the substituents having an aromatic hydrocarbon ring group in D ¹ to D ³ . The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

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

In the above, R ^g is an alkyl group having 1 to 20 carbon atoms which may have a substituent; at least one of the alkyl groups having 1 to 20 carbon atoms -CH ₂ -via -O-,- S-, -O-C (= O)-, -C (= O) -O-, or -C (= O)-substituted groups (except that more than 2 -O- or -S- are adjacent and intermediary respectively Case); cycloalkyl having 3 to 12 carbon atoms which may have a substituent; aromatic hydrocarbon ring having 6 to 30 carbon atoms which may have a substituent; and 2 carbon atoms which may have substituent A ~ 30 aromatic heterocyclic group is preferred. Among them, R ^g is an alkyl group having 1 to 20 carbon atoms which may have a substituent; and at least one of -CH ₂ -via -O-, -S included in the alkyl group having 1 to 20 carbon atoms. -, -O-C (= O)-, -C (= O) -O- or -C (= O)-substituted groups (but excluding 2 or more -O- or -S- are adjacent and intermediary respectively Situation) is particularly preferred.

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

Preferable examples of ^Rh include (1) a cyclic hydrocarbon group having 6 to 40 carbon atoms and an aromatic hydrocarbon ring having 6 to 30 carbon atoms. Hereinafter, this cyclic hydrocarbon group having an aromatic hydrocarbon ring is referred to as "(1) cyclic hydrocarbon group" as appropriate. Specific examples of the (1) cyclic hydrocarbon group include the following groups.

『Hua 4』

(1) The cyclic hydrocarbon group may have a substituent. Examples of the substituents that (1) a cyclic hydrocarbon group has include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; a vinyl group, Alkenyl groups having 2 to 6 carbon atoms such as allyl groups; halogenated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl groups; N, N-dialkyl groups having 2 to 12 carbon atoms such as dimethylamino groups Amine groups; alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, and isopropoxy; nitro groups; aromatic hydrocarbon ring groups having 6 to 20 carbon atoms, such as phenyl and naphthyl; -OCF ₃ ^{; -C (= O) -R b} ; -O-C (= O) -R b; -C (= O) -O-R b; -SO 2 R a; and the like. The meaning of R ^a and R ^b is 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 preferred. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

As another preferred example of ^Rh , (2) one or more aromatic rings 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 A heterocyclic group having 2 to 40 carbon atoms. Hereinafter, this heterocyclic group having an aromatic ring is referred to as "(2) heterocyclic group" as appropriate. Specific examples of the (2) heterocyclic group include the following groups. R each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

『Hua 5』

『Hua 6』

『Hua 7』

『Hua 8』

『Hua 9』

『Hua 10』

『Hua 11』

『Hua 12』

(2) The heterocyclic group may have a substituent. As a substituent which the (2) heterocyclic group has, the same thing as the substituent which a (1) cycloalkyl group has is mentioned, for example. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

As another another good example of R ^h , (3) One or more 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. Alkyl having 1 to 12 carbon atoms. This substituted alkyl group is hereinafter referred to as "(3) substituted alkyl group" as appropriate.

Examples of the "alkyl group having 1 to 12 carbon atoms" in the substituted alkyl group (3) include methyl, ethyl, propyl, and isopropyl.

Examples of the "arene ring group having 6 to 30 carbon atoms" in the substituted alkyl group (3) include the same examples as the aromatic ring group having 6 to 30 carbon atoms in D ¹ to D ³ .

Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the substituted alkyl group (3) include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ .

(3) The substituted alkyl group may further have a substituent. Examples of the substituent which the (3) alkyl group has include the same examples as those of the (1) cycloalkyl group. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

As another another good example of R ^h , (4) One or more 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. Alkenyl group having 2 to 12 carbon atoms substituted by a carbon group. Hereinafter, this substituted alkenyl group is appropriately referred to as "(4) substituted alkenyl group".

Examples of the "alkenyl group having 2 to 12 carbon atoms" in the (4) substituted alkenyl group include a vinyl group and an allyl group.

Examples of the "arene ring group having 6 to 30 carbon atoms" in the (4) substituted alkenyl group include the same examples as the aromatic ring group having 6 to 30 carbon atoms in D ¹ to D ³ .

Examples of the "aromatic heterocyclic group having 2 to 30 carbon atoms" in the (4) substituted alkenyl group include the same examples as the aromatic heterocyclic group having 2 to 30 carbon atoms in D ¹ to D ³ .

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

As another another good example of R ^h , (5) One or more 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. Alkynyl having 2 to 12 carbon atoms. Hereinafter, this substituted alkynyl group is appropriately referred to as "(5) substituted alkynyl group".

Examples of the "alkynyl group having 2 to 12 carbon atoms" in the (5) substituted alkynyl group include an ethynyl group and a propynyl group.

Examples of the "arene ring group having 6 to 30 carbon atoms" in the (5) substituted alkynyl group include the same examples as the aromatic ring group having 6 to 30 carbon atoms in D ¹ to D ³ .

Examples of the "aryl heterocyclic group having 2 to 30 carbon atoms" in the (5) 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 possessed by (5) substituted alkynyl include the same examples as those substituted by (1) cycloalkyl. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

As a good specific example of ^Rh , the following groups are mentioned.

『Hua 13』

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

『Hua 14』

As a particularly preferable specific example of R ^h , the following groups may be mentioned.

『Hua 15』

The above-mentioned specific examples of R ^h may further have a substituent. Examples of the substituent include a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group; and a carbon atom number such as a vinyl group or an allyl group. Alkenyl groups of 2 to 6; halogenated alkyl groups having 1 to 6 carbon atoms such as trifluoromethyl; N, N-dialkylamino groups having 2 to 12 carbon atoms such as dimethylamino; methoxy, Alkoxy having 1 to 6 carbon atoms such as ethoxy and isopropoxy; nitro; -OCF ₃ ; -C (= O) -R ^b ; -O-C (= O) -R ^b ;- C (= O) -O-R ^b ; -SO ₂ R ^a ; etc. The meaning of R ^a and R ^b is 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 preferred. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

Preferable examples of R ⁱ include cyclic hydrocarbon groups having 6 to 40 carbon atoms and one or more aromatic hydrocarbon rings having 6 to 30 carbon atoms.

In addition, as another preferable example of R ⁱ , one having one or more aromatic rings selected from the group consisting of an aromatic hydrocarbon ring having 6 to 30 carbon atoms and an aromatic heterocyclic ring having 2 to 30 carbon atoms can be cited. Heterocyclic group having 2 to 40 carbon atoms.

As a particularly preferable specific example of R ⁱ , the following groups may be mentioned. The meaning of R is as described above.

『Hua 16』

The group represented by any one of formulae (II-1) to (II-7) may 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-alkyl group having 1 to 6 carbon atoms. Amine group, N, N-dialkylamino group with 2 to 12 carbon atoms, alkoxy group with 1 to 6 carbon atoms, alkylsulfinyl sulfonyl group with 1 to 6 carbon atoms, carboxyl group, carbon number A sulfanyl group of 1 to 6, an N-alkylaminesulfonyl group having 1 to 6 carbon atoms, and an N, N-dialkylaminesulfonyl group having 2 to 12 carbon atoms. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

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

『Hua 17』

As particularly preferable specific examples of the formula (III-1) and the formula (III-4), the following groups may be mentioned. In the following formula, * indicates a bonding position.

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『Hua 19』

『Hua20』

『Chem 21』

『Hua22』

In Formula (I), Z ¹ and Z ² are each independently selected from 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- , -CH ₂ -CH ₂ -O-C (= O)-, -C (= O) -O- CH ₂ -CH _2- , -CH = CH-, -N = CH-, -CH = N-, -N = C (CH ₃ )-, -C (CH ₃ ) = N-, -N = N- And -C≡C-any one of the group. R ^{21 is} each independently and represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In Formula (I), A ¹ , A ² , B ^1, and B ² are each independently and represent a group selected from the group consisting of an alicyclic group which may have a substituent and an aryl group which may also have a substituent. The number of carbon atoms (including the number of carbon atoms of the substituents) of the groups represented by A ¹ , A ² , B ¹ and B ² are independent, and are usually 3 to 100. Among them, A ¹ , A ² , B ^1, and B ² are each independently, and an alicyclic group having 5 to 20 carbon atoms which may have a substituent or an aryl group having 2 to 20 carbon atoms which may also have a substituent is good.

Examples of the alicyclic group in A ¹ , A ² , B ^1, and B ² include cyclopentane-1,3-diyl, cyclohexane-1,4-diyl, and cycloheptane-1. 4,4-diyl, cyclooctane-1,5-diyl, and other cycloalkanediyl groups having 5 to 20 carbon atoms; decalin-1,5-diyl, decalin-2,6-diyl Bicycloalkanediyl with 5 to 20 carbon atoms; etc. Among them, a cycloalkanediyl group having 5 to 20 carbon atoms which can also be substituted is preferred, a cyclohexanediyl group is more preferred, and a cyclohexane-1,4-diyl group is particularly preferred. The alicyclic group may be a trans-isomer, a cis-isomer, or a mixture of a cis-isomer and a trans-isomer. Among them, trans isomers are preferred.

Examples of the substituent which the alicyclic group in A ¹ , A ² , B ¹ and B ² has include a halogen atom, an alkyl group having 1 to 6 carbon atoms, and an alkoxy group having 1 to 5 carbon atoms. Group, nitro, cyano and the like. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

Examples of the aryl group in A ¹ , A ² , B ¹ and B ² include 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 1,4- Aromatic ring groups having 6 to 20 carbon atoms, such as, for example, naphthyl, 1,5-naphthyl, 2,6-naphthyl, 4,4'-biphenyl; furan-2,5-diyl, Aromatic heterocyclic groups having 2 to 20 carbon atoms such as thiophene-2,5-diyl, pyridine-2,5-diyl, and pyr-2,5-diyl; etc. Among them, an aromatic hydrocarbon ring group having 6 to 20 carbon atoms is preferable, a phenylene group is more preferable, and a 1,4-phenylene group is particularly preferable.

For example, as mentioned in A ^1, A ^2, B ^2, and in the obtained alicyclic group having a substituent group of the same B ¹ A ^1, A ^2, B ¹ and B ² in the group to have the substituent aryl group, Example. The number of substituents may be one or plural. Moreover, a plurality of substituents may be the same as or different from each other.

In the formula (I), Y ¹ to Y ⁴ are each independently selected from a single bond, -O-, -C (= O)-, -C (= O) -O-, -O-C (= O )-, -NR ²² -C (= O)-, -C (= O) -NR ^22- , -O-C (= O) -O-, -NR ^22- C (= O) -O-, -O-C (= O) -NR ²² -and -NR ²² -C (= O) -NR ^23- . R ²² and R ²³ are each independently and represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In Formula (I), G ¹ and G ² are each independently selected from the group consisting of an aliphatic hydrocarbon group having 1 to 20 carbon atoms; and one or more methylene groups contained in the aliphatic hydrocarbon group having 3 to 20 carbon atoms. A group (-CH _2- ) substituted by -O- or -C (= O)-; an organic group of the group. The hydrogen atom contained in the organic group of G ¹ and G ² may be substituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen atom. However, the methylene groups (-CH _2- ) at both ends of G ¹ and G ^{2 are} not 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 are each independently and represent a polymerizable group. Examples of the polymerizable group in P ¹ and P ² include a group represented by CH ₂ = CR ³¹ -C (= O) -O-, such as acryloxy and methacryloxy; and ethylene; Groups; vinyl ether groups; p-distyryl groups; acrylfluorenyl groups; methacrylfluorenyl groups; carboxyl groups; methylcarbonyl groups; hydroxyl groups; amidoamino groups; Oxy; oxo; aldehyde; isocyanate; thioisocyanate; etc. R ³¹ represents a hydrogen atom, a methyl group or a chlorine atom. Among them, a base represented by CH ₂ = CR ³¹ -C (= O) -O- is preferable, and CH ₂ = CH-C (= O) -O- (propylene alkoxy), and CH ₂ = C (CH ₃ ) -C (= O) -O- (methacryloxy) is more preferred, and acryloxy is particularly preferred.

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

The reverse dispersion liquid crystalline compound represented by the formula (I) can be produced by, for example, a reaction of a hydrazine compound and a carbonyl compound described in International Patent Publication No. 2012/147904.

The first liquid crystal composition may further include an optional component in combination with a liquid crystal compound as required. An arbitrary component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

Generally, since the first liquid crystal composition can be cured by polymerization, the first liquid crystal composition includes a polymerization initiator as an arbitrary component. The type of the polymerization initiator must be selected in accordance with the type of the polymerizable compound included in the first liquid crystal composition. For example, if the polymerizable compound is radical polymerizable, a radical polymerization initiator may be used. If the polymerizable compound is anionic polymerizable, an anionic polymerization initiator can be used. Furthermore, if the polymerizable compound is cationic polymerizable, a cationic polymerization initiator may be used. A polymerization initiator may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

The amount of the polymerization initiator is preferably 0.1 parts by weight or more, more preferably 0.5 parts by weight or more, more preferably 30 parts by weight or less, and preferably 10 parts by weight or less with respect to 100 parts by weight of the liquid crystal compound. . When the amount of the polymerization initiator falls within the aforementioned range, the polymerization can be performed efficiently.

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

The surfactant is preferably a nonionic surfactant. When the surfactant is a nonionic surfactant having no ionic group, the surface state and orientation of the liquid crystal cured layer can be optimized in particular.

The surfactant may be non-polymerizable or polymerizable. Since a polymerizable surfactant can be polymerized in the step of curing the layer of the first liquid crystal composition, it is usually contained in the liquid crystal cured layer as part of the molecules of the polymer.

Examples of the surfactant include Surflon series (S420, etc.) manufactured by AGC Seimi Chemical Co., Ltd., FTERGENT series (251, FTX-212M, FTX-215M, FTX-209, etc.) manufactured by NEOS, and DIC. Company-made MEGAFAC series (F-444, etc.), etc. The surfactant may be used singly or in combination of two or more at any ratio.

The amount of the surfactant is preferably 0.03 parts by weight or more, more preferably 0.05 parts by weight or more, more preferably 0.50 parts by weight or less, and 0.30 parts by weight or less with respect to 100 parts by weight of the liquid crystal compound. When the amount of the surfactant is in the aforementioned range, the substantial maximum tilt 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 include a solvent as an optional component. The solvent is preferably one that can dissolve the liquid crystal compound. As such a solvent, an organic solvent is usually used. Examples of the organic solvent include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone, and methyl isobutyl ketone; acetate solvents such as butyl acetate and amyl acetate; chloroform, Halogenated hydrocarbon solvents such as dichloromethane and dichloroethane; 1,4-dioxy, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropiran, 1,3-dioxy, 1,2-dimethoxyethyl Ether solvents such as alkane; and aromatic solvents such as toluene, xylene, and 1,3,5-trimethylbenzene. The solvents may be used singly or in combination of two or more at any ratio.

From the viewpoint of excellent workability, the boiling point of the solvent is preferably 60 ° C to 250 ° C, and more preferably 60 ° C to 150 ° C.

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

In addition, in order to further increase the inclination angle of the molecules of the liquid crystal compound contained in the first cured layer, the first liquid crystal composition may further include an inclination function component that can increase the substantial maximum inclination angle of the molecules of the liquid crystal compound. As an arbitrary ingredient. As the type and amount of the tilt action component, for example, Japanese Patent Publication No. 2018-162379 (or the specification of Japanese Patent Application No. 2017-060154), International Patent Publication No. 2018/173778 (or Japanese Patent Application No. 2017-060122), Japanese Patent Publication No. 2018-163218 (or Japanese Patent Application No. 2017-059327). However, by adjusting the operation or conditions in the process of manufacturing the first cured layer, the substantial maximum tilt angle of the molecules of the liquid crystal compound can also be increased, so it is not impossible without using the tilt-action component.

Examples of any other components included in the first liquid crystal composition 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; level dyeing Thixotropic agents; gelling agents; polysaccharides; ultraviolet absorbers; infrared absorbers; antioxidants; ion exchange resins; etc. The amounts of these components are each 0.1 to 20 parts by weight based on 100 parts by weight of the total of the liquid crystal compound.

In the step (I), a layered body of the first liquid crystal composition is usually formed on a suitable support surface. As the supporting surface, an arbitrary surface that can support a layer of the first liquid crystal composition may be used. As this support surface, from the viewpoint of optimizing the surface state of the liquid crystal cured layer, a flat surface without a concave portion and a convex portion is generally used. Furthermore, from the viewpoint of improving the productivity of the liquid crystal cured layer, it is preferable to use a surface of a long substrate as the support surface. Here, the so-called “long strip” refers to a shape having a length of 5 times or more with respect to the width, and preferably a length of 10 times or more, and specifically refers to a roll that can be rolled or stored. The length of the shape of the film.

As the substrate, a resin film or a glass plate is usually used. In particular, when performing an orientation treatment at a high temperature, it is better to select a substrate that can withstand this temperature. As the resin, a thermoplastic resin is usually used. Among these, from the viewpoints of high orientation restraining force, high mechanical strength, and low cost, as the resin, a resin having a positive intrinsic birefringence value is preferred. Furthermore, in terms of excellent transparency, low hygroscopicity, dimensional stability, and light weight, a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin is preferably used. To give a suitable example of the resin contained in the base material under a trade name, "ZEONOR" manufactured by Japan's Rui On Co., Ltd. can be cited as the norylene resin.

The glass transition temperature of the material forming the support surface is preferably 90 ° C or higher, more preferably 100 ° C or higher, and particularly preferably 120 ° C or higher. Step (II) and step (V) may be performed in a high-temperature environment in order 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 orientation. The glass transition temperature of the material forming the support surface is as high as described above, and the deformation of the support surface due to heat in a high-temperature environment can be suppressed. 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 lower.

In order to promote the orientation of the liquid crystalline compound in the layer of the first liquid crystal composition on the surface of the substrate serving as the supporting surface, it is preferable to apply a treatment for imparting an orientation restricting force. The so-called "orientation limiting force" refers to the "property of a supporting surface" that can orient the liquid crystal compound contained in the liquid crystal composition. Examples of the process for applying an orientation restricting force to the support surface include a light orientation process, a rubbing process, an ion beam orientation process, and an extension process.

In the step (I) of forming a layered body 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. Examples of the method for applying the first liquid crystal composition include a curtain coating method, an extrusion coating method, a roll coating method, a spin coating method, a dip coating method, a bar coating method, a spray coating method, a slant plate coating method, and a printing coating method. , Gravure coating method, mold coating method, gap coating method and dipping method.

[3. Step (II): Orientation Treatment of Layer of First Liquid Crystal Composition]

After the layer body of the first liquid crystal composition is formed in the step (I), a step (II) of orienting the liquid crystal compound contained in the layer body of the first liquid crystal composition is performed. When the orientation is performed, the layer of the first liquid crystal composition is generally maintained for as long as specified under the specified temperature conditions. Thereby, the liquid crystal compound can be aligned in the layered body of the first liquid crystal composition.

Specifically, in the in-plane direction, the liquid crystalline compound is usually oriented in a direction corresponding to the orientation restricting force of the support surface.

On the other hand, in the thickness direction, the liquid crystalline compound is preferably oriented so that at least a portion thereof is inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction). Thereby, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer can be increased. In addition, by this, it is possible to effectively adjust the substantially maximum tilt angle of the molecules of the liquid crystal compound in the step (VI).

The method for orienting the liquid crystal compound contained in the layer of the first liquid crystal composition such that at least a part of the liquid crystal compound is inclined with respect to the plane of the layer (that is, with respect to the in-plane direction) is arbitrary. Among them, a method of orienting the liquid crystal compound so as to obtain a first cured layer having a substantial maximum tilt angle of the molecules of the liquid crystal compound is preferred.

For example, step (II) is preferably performed in such a manner that the temperature condition of the layer of the first liquid crystal composition satisfies specified requirements. Specifically, it is preferable that the temperature condition of the layered body of the first liquid crystal composition in the step (II) is the same as the temperature condition that the viscosity of the residual component of the test composition is usually 800 cP or less. The aforementioned test composition is a composition having a composition in which a polymerization initiator has been excluded from the first liquid crystal composition. The residual component viscosity of the test composition refers to the viscosity of the residual component of the test composition under the same temperature conditions as the layer of the first liquid crystal composition in the step (II). In addition, the residual component of the test composition is a component that remains without being vaporized under the same temperature condition as the layer of the first liquid crystal composition in the step (II) among the components included in the test composition. By performing the step (II) in a manner satisfying such requirements, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer can be increased.

This is explained in more detail. When the step (II) of orienting the liquid crystal compound is performed so as to satisfy the aforementioned requirements, the step (II) is to adjust the layer of the first liquid crystal composition to have a viscosity drop from the residual component of the test composition. The temperature conditions in the specified range are performed under the same temperature conditions. The specific range of the viscosity of the residual component is generally 800 cP (centipoise) or less, preferably 600 cP or less, more preferably 400 cP or less, and even more preferably 200 cP or less. By using the same temperature conditions as the temperature conditions at which the viscosity of the residual components of the test composition is lowered, the liquid crystal compounds in the layer of the first liquid crystal composition are aligned, thereby increasing the liquid crystal contained in the first cured layer. Substantial maximum tilt angle of the molecule of the sex compound. From the viewpoint of obtaining a first cured layer having a desired thickness, the lower limit of the viscosity of the residual component is preferably 5 cP or more, and more preferably 10 cP or more.

Under the same temperature conditions as the layer of the first liquid crystal composition in the step (II), the residual component viscosity of the test composition can be measured by the following method.

A test composition having a polymerization initiator removed from the first liquid crystal composition was prepared. This test composition was concentrated under reduced pressure on a rotary evaporator to remove the solvent, and a residual component was obtained. The viscosity of the residual component is measured in advance while changing the measurement temperature to obtain information about the measurement temperature and the viscosity at the measurement temperature. This information is hereinafter referred to as "temperature-viscosity information" as appropriate. From this "temperature-viscosity information", the viscosity at the temperature of the layer of the first liquid crystal composition in the step (II) is understood as the viscosity of the residual component.

As a method of making the viscosity of the residual component of the test composition fall within the above-mentioned range under the same temperature conditions as the layer of the first liquid crystal composition in the step (II), for example, the following method.
(A) The temperature of the layered body of the first liquid crystal composition in the step (II) of orienting the liquid crystal compound is appropriately adjusted. In this method, it is usually adjusted by reducing the viscosity of the residual component of the test composition under the same temperature condition by making the temperature of the layer of the first liquid crystal composition sufficiently high to make it the above range.
(B) Moderately adjust the composition of the first liquid crystal composition. In this method, it is usually adjusted by reducing the viscosity of the residual components of the test composition containing the additive by combining appropriate types and amounts of additives into the liquid crystal compound as components contained in the first liquid crystal composition. To make it into the above range.

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

In addition, the liquid crystal can also be obtained by, for example, a method of using a first liquid crystal composition containing a tilt-action component, or a method of using a liquid crystal compound having a property of tilting with respect to a plane of a layer body (that is, with respect to an in-plane direction). The substantial maximum tilt angle of the molecule of the sexual compound is a large first cured layer.

The specific temperature at the time of the orientation treatment can be appropriately set within a range of the liquid crystal phase-solid phase transition temperature of the liquid crystal compound, and a temperature lower than the glass transition temperature of the resin contained in the substrate is preferred. This makes it possible to suppress the occurrence of strain on the substrate due to the alignment treatment.

The step (II) of orienting the liquid crystalline 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 better to measure and record in advance: at a plurality of oven set temperatures, the temperature of the layer of the first liquid crystal composition placed in the oven at this set temperature is better. Hereinafter, the information of the recorded set temperature of the oven and the temperature of the layer of the first liquid crystal composition placed in the oven at the set temperature is appropriately referred to as "set temperature-layer temperature information". If this "set temperature-layer temperature information" is used, 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 maintaining the temperature of the layer of the first liquid crystal composition at the aforementioned temperature can be arbitrarily set within a range in which a desired first cured layer can be obtained, for example: 30 seconds to 5 minutes.

[4. Step (III): Curing the layer of the first liquid crystal composition]

After orienting the liquid crystal compound contained in the layer of the first liquid crystal composition in the step (II), the step (III) of curing the layer of the first liquid crystal composition is performed.

In the step (III), the layered body of the first liquid crystal composition is usually cured by polymerizing a polymerizable compound contained in the first liquid crystal composition. According to this, for example, when the liquid crystal compound has polymerizability, the liquid crystal compound usually directly polymerizes while maintaining the molecular orientation. By the aforementioned polymerization, the alignment state of the liquid crystal compound contained in the first liquid crystal composition before the polymerization is fixed.

As a polymerization method, a method suitable for selecting the properties of the components included in the first liquid crystal composition may be selected. Examples of the polymerization method include a method of irradiating an active energy ray and a thermal polymerization method. Among them, since the polymerization reaction can be performed at room temperature without heating, a method of irradiating active energy rays is preferable. Here, the irradiated active energy rays may include light rays such as visible light, ultraviolet rays and infrared rays, and arbitrary energy rays such as electron beams.

Among them, a method of irradiating light such as ultraviolet rays is preferable for easy operation. The temperature at the time of ultraviolet irradiation is preferably below the glass transition temperature of the substrate, more preferably 150 ° C or lower, more preferably 100 ° C or lower, and even more preferably 80 ° C or lower. The lower limit of the temperature at the time of ultraviolet irradiation is set to 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, and more preferably 10,000 mW / cm ² or less, and more preferably 5000 mW / cm ² or less. The amount of ultraviolet radiation is preferably 0.1 mJ / cm ² or more, more preferably 0.5 mJ / cm ² or more, and more preferably 10,000 mJ / cm ² or less, and more preferably 5,000 mJ / cm ² or less.

Through the aforementioned step (III), a first cured layer formed from a cured product of the first liquid crystal composition can be obtained. This first curing layer is a layer that cures the cured product of the first liquid crystal composition. The curing of the first liquid crystal composition is usually achieved by polymerizing a polymerizable compound contained in the first liquid crystal composition, as described above. Accordingly, the first cured layer usually includes a polymer of a part or all of the components included in the first liquid crystal composition. Therefore, when the liquid crystal compound has polymerizability, the liquid crystal compound is polymerized, so the first cured layer is a layered body including a polymer of a liquid crystal compound that is directly polymerized while maintaining an alignment state before polymerization. The polymerized liquid crystal compound is included in the term "liquid crystal compound included in the first cured layer".

In the cured product of the first liquid crystal composition, the fluidity before curing is lost. Therefore, in the first cured layer, the alignment state of the liquid crystal compound is usually directly fixed in the alignment state before curing. Moreover, it is preferable that at least a part of molecules of the liquid crystal compound contained in the first cured layer is inclined with respect to a plane of the layer body of the first cured layer (that is, with respect to an in-plane direction). This makes it possible to effectively adjust the tilt angle of the molecules of the liquid crystal compound in the step (VI).

In the first cured layer, a part of the molecules of the liquid crystal compound may be inclined with respect to the plane of the layer body of the first cured layer (that is, with respect to the in-plane direction), or may be all with respect to the first cured layer. The plane of the layer body (that is, relative to the in-plane direction) is inclined. Generally, in the first cured layer, the inclination angle of the molecules of the liquid crystalline compound decreases as it approaches the support surface in the thickness direction, and increases as it moves away from the support surface. According to this, in the adjacent portion of the surface on the support surface side of the first cured layer, the molecules of the liquid crystal compound may be parallel with respect to the plane of the layer body (that is, with respect to the in-plane direction). Moreover, in the adjacent portion of the surface of the first cured layer on the side opposite to the support surface, the molecules of the liquid crystal compound may be perpendicular to the plane of the layer body (that is, to the in-plane direction). However, it is preferable that even if a part of the molecules of the liquid crystalline compound adjacent to the surface of the first cured layer is so parallel or perpendicular to the plane of the layer (that is, relative to the in-plane direction), the first In the part of the surface adjacent to the cured layer, the molecules of the liquid crystal compound are still inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction).

When the molecules of at least a part of the liquid crystal compound contained in the first cured layer are inclined with respect to the plane of the layer body of the first cured layer (that is, with respect to the in-plane direction), a polarization microscope having a sufficient resolution can be used. The cross section of the first cured layer was observed to confirm. In order to make the tilt of the molecules of the liquid crystalline compound easier to see, this observation can also be implemented by inserting a wavelength plate between the observation sample and the objective lens of the polarizing microscope as a test plate.

Alternatively, the fact that at least a part of the molecules of the liquid crystalline compound included in the first cured layer is inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction) of the first cured layer can be confirmed as follows. The retardation R (θ) of the first cured layer at an incident angle θ is measured in a measurement direction perpendicular to the fast axis direction in the plane of the first cured layer. Then, the retardation R (θ) of the first cured layer at the incident angle θ is divided by the retardation R (0 °) of the first cured layer at the incident angle 0 °, and the retardation ratio R (θ) / R (0 °). In the case of plotting a graph with the retardation ratio R (θ) / R (0 °) thus obtained as the vertical axis and the incident angle θ as the horizontal axis, as long as the graph obtained is not valid for θ = 0 ° Symmetrically, it can be confirmed that the molecules of at least a part of the liquid crystal compound contained in the first cured layer are inclined with respect to the plane of the layer body of the first cured layer (that is, with respect to the in-plane direction).

The following examples illustrate this in more detail. FIG. 2 is a graph plotting the retardation ratio R (θ) / R (0 °) of a related example of the first cured layer against the incident angle θ. If all the molecules of the liquid crystal compound contained in the first cured layer have an inclination angle of 0 ° or 90 °, the retardation ratio R (θ) / R (0 °), as shown by the dotted line in FIG. 2, It is linearly symmetric with respect to a straight line of θ = 0 ° (through the vertical axis of θ = 0 ° in FIG. 2). In contrast, if at least a part of the molecules of the liquid crystal compound contained in the first cured layer is inclined with respect to the plane of the layer body of the first cured layer (that is, relative to the in-plane direction), the retardation ratio R (θ) / R (0 °), as shown by the solid line in FIG. 2, is generally asymmetric with respect to a straight line of θ = 0 °. Therefore, when the retardation ratio R (θ) / R (0 °) is asymmetrical with respect to θ = 0 °, it can be determined that at least a part of the molecules of the liquid crystal compound included in the first cured layer is relative to the first The layer plane of the cured layer (ie, relative to the in-plane direction) is inclined.

In the case where the first cured layer includes molecules of a liquid crystalline compound that is inclined with respect to the plane of the layer body of the first cured layer (that is, with respect to the in-plane direction), the substantial maximum tilt angle of the first cured layer indicates: Assuming that the inclination angle of the molecules on the side of the support surface side of the first cured layer is 0 °, and the inclination angle of the molecules changes at a certain ratio in the thickness direction, the maximum inclination angle of the molecules of the liquid crystal compound. This substantial maximum tilt angle is an index that reveals the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the first cured layer. Generally, the more the first solidified layer having a larger maximum inclination angle, the larger the inclination angle as seen by the entire molecules of the liquid crystal compound contained in the first cured layer.

Generally, the larger the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer, the larger the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be increased. According to this, the maximum value of the range of the substantial maximum tilt angle that can be adjusted in the process (VI) can be increased, and therefore the range of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the finally obtained liquid crystal cured layer can be increased. Adjustable range.

The range of the substantial maximum tilt angle of the molecules of the liquid crystalline compound included in the first cured layer is set to conform to the range in which the substantial maximum tilt angle of the molecules of the liquid crystalline compound included in the liquid crystal cured layer can be adjusted to an appropriate range. Expect. 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 60 ° or less Better. Since the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the first cured layer is in the aforementioned range, the adjustment of the inclination angle of the molecules of the liquid crystal compound in the step (VI) can be effectively performed. Furthermore, it is generally easy to produce a liquid crystal cured film having particularly excellent viewing angle characteristics.

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

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

Generally, the surface of the first cured layer (refer to the surface 111U in FIG. 1) has an alignment restricting force that orients the molecules of the liquid crystal compound contained in the second cured layer formed on the surface. This orientation limiting force will orient the molecules of the liquid crystal compound contained in the second cured layer in the same direction as the orientation direction of the molecules of the liquid crystal compound contained in the first cured layer in the in-plane direction.

In addition, the orientation restricting force on the surface of the first cured layer meets expectations so that the molecules of the liquid crystal compound contained in the second cured layer are oriented such that the inclination angle of the molecules becomes larger in the thickness direction. In this case, the first cured layer can function as a tilt alignment film that increases the tilt angle of the molecules of the liquid crystalline compound contained in the second cured layer. The aforementioned function as an oblique alignment film can be significantly exhibited when, for example, both the first liquid crystal composition and the second liquid crystal composition include a reverse dispersion liquid crystal compound.

In a certain thickness range, the thinner the first cured layer, the greater the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer. 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 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 angle, 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, and more preferably 5.0 μm or less, and more preferably 4.0 μm or less. It is particularly preferred to be 3.0 μm or less.

[5. Step (IV): Formation of Layer of Second Liquid Crystal Composition]

After the first cured layer is obtained in the step (III), a step (IV) of directly forming a layer body of the second liquid crystal composition as the liquid crystal composition for forming the second cured layer on the first cured layer is performed. Here, the so-called state of forming another layer body on a certain layer body is "direct", which means that there is no other layer body between these two layer bodies.

The second liquid crystal composition includes a liquid crystal compound for forming a second cured layer. As the liquid crystal compound included in the second liquid crystal composition, any liquid crystal compound can be selected and used from the range described as the liquid crystal compound included in the first liquid crystal composition. Thereby, in the second liquid crystal composition and the second cured layer, the same advantages as those obtained in the first liquid crystal composition and the first cured layer can also be obtained. In particular, when both the first liquid crystal composition and the second liquid crystal composition include a reverse-dispersion liquid crystal compound, the liquid crystal compound contained in the layer of the second liquid crystal composition can be increased in the step (V). The inclination angle of the molecules of the liquid crystal compound is effectively adjusted in the step (VI). 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 have the same or similar The structure is better. Furthermore, as the liquid crystal compound contained in the second liquid crystal composition, one kind may be used alone, or two or more kinds may be used in combination at any ratio.

In addition, the second liquid crystal composition may further include an arbitrary component combined with the liquid crystal compound as required. An arbitrary component may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios. As an arbitrary component, the component other than the liquid crystal compound contained in a 1st liquid crystal composition can be used for the range of the quantity of the said component in a 1st liquid crystal composition, for example. Thereby, in the second liquid crystal composition and the second cured layer, the same advantages as those obtained in the first liquid crystal composition and the first cured layer can also be obtained.

The second liquid crystal composition may be different from or the same as the first liquid crystal composition.

In the step (IV) of forming a layered body 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 body of the second liquid crystal composition. Examples of the method for applying the second liquid crystal composition include the same examples as those described as the method for applying the first liquid crystal composition. Since the first cured layer is formed of a cured product containing a liquid crystal compound, the first cured layer generally has a high affinity for a second liquid crystal composition containing a liquid crystal compound. Accordingly, the surface of the first cured layer generally has a good affinity for the second liquid crystal composition. Therefore, the surface state of the layer of the second liquid crystal composition can be optimized, and the surface state of the second cured layer can be optimized.

[6. Step (V): Orientation treatment of layered body of second liquid crystal composition]

After the layer body of the second liquid crystal composition is formed in the step (IV), a step (V) of orienting the liquid crystal compound contained in the layer body of the second liquid crystal composition is performed. Thereby, the liquid crystal compound can be aligned in the layered body of the second liquid crystal composition.

Specifically, in the in-plane direction, the liquid crystal compounds included in the layer body of the second liquid crystal composition are usually aligned with the liquid crystal properties included in the first cured layer by the orientation limiting force of the surface of the first cured layer. The compounds are oriented in the same direction.

On the other hand, in the thickness direction, the liquid crystal compound contained in the layer body of the second liquid crystal composition is generally oriented such that at least a portion thereof is inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction). The method for orienting the liquid crystal compound contained in the layer body of the second liquid crystal composition such that at least a part of the liquid crystal compound is inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction) is arbitrary. For example, according to a method in which both the first liquid crystal composition and the second liquid crystal composition include a reverse-dispersing liquid crystal compound, the function as a tilted alignment film of the first cured layer can be greatly exerted, so that the second The molecules of the liquid crystal compound contained in the layer body of the liquid crystal composition are oriented in such a manner that they are largely inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction). According to this, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer body of the second liquid crystal composition can be particularly increased. When the first cured layer is used as an oblique alignment film, a second cured layer containing molecules of a liquid crystalline compound having a higher molecular weight than that of the liquid crystal compounds contained in the first cured layer is usually obtained. The substantial maximum tilt angle of the molecule is also large.

The specific operation in the step (V) of orienting the liquid crystal compound included in the layer of the second liquid crystal composition may be the same as the step of orienting the liquid crystal compound included in the layer of the first liquid crystal composition (II) )the same. Thereby, in the second liquid crystal composition and the second cured layer, the same advantages as those obtained in the first liquid crystal composition and the first cured layer can also be obtained. In particular, in the step (V), the same as the step (II), it is preferable that the temperature conditions of the layer of the second liquid crystal composition in the step (V) be equal to and correspond to the second liquid crystal. Test of composition The viscosity of the residual component of the test composition is usually carried out in the same manner under the temperature condition of 800 cP or less.

As described above, the first cured layer has high affinity for the second liquid crystal composition. Therefore, the second liquid crystal composition is compatible with the first cured layer, and the orientation of the molecules is not easily confused. In addition, in the first cured layer, the occurrence of alignment defects is generally suppressed. Therefore, the occurrence of the alignment defects in the layer of the second liquid crystal composition due to the alignment defects in the first cured layer is also suppressed. Accordingly, in the layered body of the second liquid crystal composition, the alignment state can be made uniform in the in-plane direction, and the occurrence of alignment defects can be suppressed.

[7. Process (VI): Adjustment of Substantially Maximum Inclination Angle]

After orienting the liquid crystal compound contained in the layer of the second liquid crystal composition in step (V), in order to adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition, Operation (VI). In operation (VI). The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer body of the second liquid crystal composition is increased with time.

Specifically, in the step (VI), a period of time is allowed from the time when the liquid crystal compound is aligned in the step (V) until the layer of the second liquid crystal composition is cured in the step (VII). . Within this vacant time, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer body of the second liquid crystal composition becomes larger. Since the substantial maximum tilt angle will increase with time, usually the longer the time vacated from step (V) to step (VII), the liquid crystal contained in the layer of the second liquid crystal composition The substantial maximum tilt angle of the molecule of the sex compound becomes larger. Therefore, by adjusting the time vacated from the step (V) to the step (VII), the substantial maximum tilt angle of the molecules of the liquid crystalline compound contained in the second cured layer can be adjusted, so as a result, the The substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer of the first cured layer and the second cured layer.

The temperature condition of the layer of the second liquid crystal composition in the step (VI) is not particularly limited. The step (V) is generally performed in a temperature adjustment device such as an oven in order to adjust the temperature of the layer of the second liquid crystal composition, and the step (VI) is performed outside the temperature adjustment device. Accordingly, the temperature conditions of the layered body of the second liquid crystal composition in the step (VI) are often different from those in the step (V). Specific temperature conditions are not particularly limited, but a temperature below the glass transition temperature of the resin contained in the substrate is preferred. Among them, from the viewpoint of saving heating energy to reduce manufacturing costs, the temperature conditions below the liquid crystal phase-solid phase transition temperature of the liquid crystal compound contained in the second liquid crystal composition are preferably, and the temperature range is from 20 ° C to 30 ° C. Room temperature is particularly preferred.

The time taken in the step (VI) is appropriately set to meet expectations based on the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer for the purpose. Here, the time taken in the step (VI) refers to the time period from the orientation 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 consumed in the step (VI) is preferably 60 seconds or more, more preferably 120 seconds or more, and more preferably 600 seconds or less. Since the time spent in the step (VI) is equal to or more than the lower limit of the aforementioned range, the substantial maximum tilt angle of the liquid crystal compound contained in the layer body of the second liquid crystal composition can be greatly increased, so that the step ( VI). In addition, since the time consumed in the step (VI) is equal to or less than the upper limit of the aforementioned range, the time required for manufacturing the liquid crystal cured film can be shortened.

The magnitude of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer of the second liquid crystal composition through the process (VI) is preferably 1 ° or more, more preferably 5 ° or more, and 15 ° or more More preferably, it is more preferably 20 ° or more, more preferably 45 ° or less, and even more preferably 40 ° or less.

[8. Step (VII): Curing the Layer of the Second Liquid Crystal Composition]

After adjusting the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the layer body of the second liquid crystal composition in step (VI), a step of curing the layer body of the second liquid crystal composition to obtain a second cured layer is performed ( VII). Thereby, a liquid crystal cured film including a liquid crystal cured layer including a first cured layer and a second cured layer can be obtained. The specific operation in the step (VII) of curing the layer of the second liquid crystal composition may be the same as the step (III) of curing the layer of the first liquid crystal composition. Thereby, in the second liquid crystal composition and the second cured layer, the same advantages as those obtained in the first liquid crystal composition and the first cured layer can also be obtained.

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 the same as the curing of the first liquid crystal composition, and is usually achieved by polymerizing a polymerizable compound contained in the second liquid crystal composition. Accordingly, the second cured layer usually includes a polymer of a part or all of the components included in the second liquid crystal composition. For example, in the case where the liquid crystal compound has polymerizability, the liquid crystal compound is polymerized, so the second cured layer may be a layer body including a polymer of the liquid crystal compound that is directly polymerized while maintaining the orientation state before polymerization. The polymerized liquid crystal compound is included in the term "liquid crystal compound included in the second cured layer".

In the cured product of the second liquid crystal composition, since the fluidity before curing is lost, the alignment state of the liquid crystal compound is usually directly fixed in the alignment state before curing. At least a part of the liquid crystalline compound included in the second cured layer is inclined with respect to a layer body plane (that is, with respect to an in-plane direction) of the second cured layer. The tilt angle of the liquid crystal compound contained in the second cured layer has been adjusted to a size corresponding to the adjustment in the step (VI). Therefore, the magnitude of the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer has been adjusted appropriately. In the second cured layer, this substantial maximum inclination angle indicates that, if the inclination angle of the molecules on the side of the first cured layer is 0 °, and the inclination angle of the molecules changes at a certain rate in the thickness direction, The maximum value of the tilt angle of the molecules of the liquid crystal compound. This substantial maximum tilt angle is an index that reveals the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the second cured layer. Generally, the second cured layer having a substantially larger maximum inclination angle tends to have a larger inclination angle as a whole of the molecules of the liquid crystal compound contained in the second cured layer.

The substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the second cured layer is set to be within a desired range as the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is in line with expectations. 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 between the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer and the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be increased. Accordingly, 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 over a wide range. As a method for increasing the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer to be larger than the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer, examples include: A method in which both the first liquid crystal composition and the second liquid crystal composition include a reverse dispersion liquid crystal compound.

In the foregoing 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. 8 ° or more is preferable, 10 ° or more is particularly preferable, 70 ° or less is preferable, 65 ° or less is preferable, and 55 ° or less is more preferable.

The substantial maximum tilt 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, and 50 ° or more from the viewpoint of obtaining a liquid crystal cured film having excellent viewing angle characteristics. More preferably, it is more preferably 57 ° or more, and more preferably 85 ° or less.

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

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

In addition, since orientation defects are suppressed in the first cured layer, the occurrence of orientation defects can also be suppressed in the second cured layer formed on the first cured layer.

Furthermore, the surface of the second cured layer is usually good.

The thickness of the second cured layer is not particularly limited, but it is preferably thicker than the first cured layer. Thereby, the correlation between the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer and the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be increased. Accordingly, by adjusting the substantial maximum tilt angle in the step (VI), it becomes possible to adjust the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer over 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 further preferably 10.0 μm or less, more preferably 7.5 μm or less, and more preferably 5.0 μm or less. Particularly preferred is 3.0 μm or less.

[9. Arbitrary process]

The method for producing a liquid crystal cured film may further include an arbitrary step in combination with the above steps.

For example, in the case of using a substrate, a liquid crystal cured film having a liquid crystal cured layer formed on a support surface of the substrate can be obtained by the aforementioned manufacturing method. Therefore, the manufacturing method of the said liquid crystal hardened film may include the process of peeling a liquid crystal hardened layer from a support surface.

The method for producing a liquid crystal cured film may include, for example, a step of further forming a layered body from a cured product of a liquid crystal compound on the second cured layer.

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

The method for producing a liquid crystal cured film may include, for example, a step of transferring a liquid crystal cured layer formed on a substrate to an arbitrary film layer. Therefore, for example, the method for manufacturing a liquid crystal cured film may also include: after laminating the liquid crystal cured layer formed on the substrate with an arbitrary film layer, peeling off the substrate as required to obtain a liquid crystal cured layer and an arbitrary film layer The process of liquid crystal curing film. In this case, an appropriate adhesive or bonding agent may be used for bonding.

Furthermore, for example, before the surface of the first cured layer is formed into a layer body of the second liquid crystal composition, the surface of the first cured layer may be subjected to a treatment such as rubbing treatment to impart an orientation restricting force. However, even if the surface of the first cured layer is not subjected to a special treatment, it usually has an alignment restricting force for appropriately aligning the liquid crystal compound contained in the layer body of the second liquid crystal composition formed on the surface. According to this, from the viewpoint of reducing the number of steps to efficiently manufacture a liquid crystal cured film, step (IV) includes forming a second liquid crystal on the surface of the first cured layer without including a rubbing treatment on the surface of the first cured layer. The matter of the layer of the composition is better.

[10. Main advantages of manufacturing method of liquid crystal cured film]

As described above, according to a method for manufacturing a liquid crystal cured film according to an embodiment of the present invention, a liquid crystal cured film including a liquid crystal cured layer including a first cured layer and a second cured layer can be manufactured. In this manufacturing method, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be adjusted by adjusting the time consumed in the step (VI). Accordingly, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be adjusted without changing the composition of the liquid crystal composition. Therefore, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be easily adjusted.

In addition, according to the aforementioned manufacturing method, a long liquid crystal cured film can be obtained by using a long substrate. Such a long liquid crystal cured film can be continuously produced and has excellent productivity. In addition, since it can be bonded to another film by a roller, it is excellent in productivity at this point. Usually long liquid crystal cured films are rolled up, stored and transported in a roll state.

[11. Obtained liquid crystal cured film]

The liquid crystal cured film manufactured by the manufacturing method related to the above embodiment mode includes a liquid crystal cured layer, and the liquid crystal cured layer includes a first cured layer and a second cured layer directly connected to a surface of the first cured layer. The so-called "directly" contacting another layer body means that there is no other layer body between these two layer bodies.

The molecules of at least a part of the liquid crystal compound contained in the liquid crystal cured layer are inclined with respect to the plane of the layer body of the liquid crystal cured layer (that is, with respect to the in-plane direction). In the liquid crystal cured layer, a part of the molecules of the liquid crystal compound may be inclined with respect to the plane of the layer of the liquid crystal cured layer (that is, with respect to the in-plane direction), or may be all plane of the layer with respect to the liquid crystal cured layer. (Ie, relative to the in-plane direction). The fact that at least a part of the molecules of the liquid crystal compound contained in the liquid crystal cured layer is inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction) can be performed by the same method as that described in the item of the first cured layer To confirm. Moreover, by including molecules of liquid crystal compounds that are inclined with respect to the plane of the layer body (that is, with respect to the in-plane direction), the substantial maximum tilt angle of the molecules of the liquid crystal compounds contained in the liquid crystal cured layer is usually 5 ° or more and Below 85 °.

In the liquid crystal cured layer, the substantially maximum tilt angle indicates that liquid crystallinity is assumed in a case where the tilt angle of a molecule on the side of the first cured layer is 0 °, and the tilt angle of the molecule changes at a certain rate in the thickness direction. The maximum value of the tilt angle of a molecule of a compound. This substantial maximum tilt angle is an index that reveals the magnitude of the tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. Generally, as the liquid crystal cured layer having a substantial maximum tilt angle becomes larger, the tilt angle as seen by the entire molecules of the liquid crystal compound contained in the liquid crystal cured layer tends to be larger. Accordingly, by increasing the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer, the birefringence of the liquid crystal cured layer in the thickness direction can be increased. Therefore, the birefringence of the liquid crystal cured layer can be appropriately adjusted by adjusting the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. Therefore, when the liquid crystal cured film is provided on a polarizing plate as a reflection suppression film It is possible to obtain excellent viewing angle characteristics in which reflection can be effectively suppressed in the oblique 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 may 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 tilt angle of the molecules of the liquid crystalline compound contained in the liquid crystal cured layer is preferably 40 ° or more, more preferably 46 ° or more, and 56 ° or more It is particularly preferred, and is preferably 85 ° or less, more preferably 83 ° or less, and even more preferably 80 ° or less.

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

In the in-plane direction, the molecules of the liquid crystal compound included in the liquid crystal cured layer are aligned in the same plane direction as the orientation direction of the molecules of the liquid crystal compound included in the first cured layer as a whole. Accordingly, the in-plane slow axis of the liquid crystal cured layer is generally parallel to the in-plane slow axis of the first cured layer.

The in-plane retardation range 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 combine a liquid crystal cured film with a linear polarizer to obtain a polarizing plate as a reflection suppressing film for an organic EL display panel, the liquid crystal cured layer is expected to have an in-plane retardation capable of functioning as a 1/4 wavelength plate. Here, the in-plane retardation function as a 1/4 wavelength plate can be exerted. Specifically, in the measurement wavelength of 590 nm, it is preferably 80 nm or more, more preferably 100 nm or more, and more preferably 110 nm or more. Above 120 nm is particularly preferred, below 190 nm is preferred, below 180 nm is preferred, below 170 nm is more preferred, below 160 nm is particularly preferred.

The in-plane retardation of the liquid crystal cured layer is preferred to exhibit inverse wavelength dispersion. Based on this, it is better to measure the in-plane retardation Re (450) and Re (550) of the cured liquid crystal layer with a wavelength of 450 nm and 550 nm to satisfy the following formula (N3), and to satisfy the following formula (N4). good.
Re (450) / Re (550) <1.00 (N3)
Re (450) / Re (550) <0.90 (N4)

Such a liquid crystal cured layer having an in-plane retardation exhibiting inverse wavelength dispersion properties can uniformly exhibit a function in a wide wavelength bandwidth for optical applications such as a 1/4 wavelength plate or a 1/2 wavelength plate. Therefore, when a liquid crystal cured film including this liquid crystal cured layer is used for a polarizing plate as a reflection suppression film, reflection can be suppressed in a wide wavelength range.

From the viewpoint of achieving 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 even more preferably 0.95 or more. In addition, it is preferably 1.10 or less, more preferably 1.08 or less, and even more preferably 1.05 or less. Here, the so-called R (± 50 °) means that in a measurement direction perpendicular to the fast axis direction in the plane of the liquid crystal cured layer, the measured liquid crystal is cured at an incidence angle θ of −50 ° and + 50 °. The average of the retardation of the layer R (-50 °) and R (+ 50 °). In addition, R (0 °) represents a retardation of the liquid crystal cured layer at an incident angle of 0 °.

Generally, external light incident on a display surface of an image display device at an incident angle "+ ϕ" is reflected at an exit angle "-ϕ". Therefore, in the case where the reflection suppressing film provided on the display surface includes a liquid crystal cured film, in the oblique direction of the display surface, external light will be included in the distance of the incident angle "+ ϕ" and the exit angle "-ϕ". The way back, through the liquid crystal cured layer. From the viewpoint of effectively suppressing the reflection of light passing through this distance, the retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is preferably close to 1.00. Since the retardation ratio R (± 50 °) / R (0 °) of the liquid crystal cured layer is in the aforementioned range close to 1.00, a polarizing plate including the liquid crystal cured layer can be used to effectively suppress the reflection of external light in the oblique direction. Specifically, when external light passes through the liquid crystal curing layer twice when it is incident and when it is reflected, the polarization state is appropriately converted, thereby making it possible to effectively shield the linear polarizer using the polarizing plate. Therefore, when a liquid crystal cured film containing such a liquid crystal cured layer is used in combination with a linear polarizer to obtain a polarizing plate, it can exhibit the reflection suppression ability using this polarizing plate over a wide range of incident angles, so it is particularly excellent in obtaining Perspective characteristics.

As described above, in the first cured layer and the second cured layer, the occurrence of orientation defects is generally suppressed. Accordingly, the entire liquid crystal cured layer including the first cured layer and the second cured layer can also suppress the occurrence of alignment defects.

As described above, the first cured layer and the second cured layer generally have good surface conditions. Accordingly, the entire surface of the liquid crystal cured layer including the first cured layer and the second cured layer is good. Therefore, the unevenness of the thickness of the liquid crystal cured layer is generally small, so the unevenness of the in-plane retardation is small.

The thickness of the liquid crystal cured layer is preferably 0.5 μm or more, more preferably 1.0 μm or more, and more preferably 15.0 μm or less, more preferably less than 11.5 μm, more preferably 8.0 μm, and more preferably 6.0 μm. good. Since the thickness of the liquid crystal cured layer is in the aforementioned range, characteristics such as in-plane retardation can be easily adjusted to a desired range. In addition, since the liquid crystal cured layer having such a thickness is thinner than a conventional retardation film used in a reflection suppressing film for an organic EL display panel, it can contribute to a reduction in thickness of the organic EL display panel.

In the liquid crystal cured layer, the first cured layer and the second cured layer can generally be distinguished by the following methods.

The cured liquid crystal layer was embedded with epoxy resin to obtain a test piece. Using a slicer, slice this test piece in parallel along the thickness direction of the liquid crystal cured layer to obtain an observation sample. At this time, the slicing is performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer become parallel. Then, a cross section showing the section was observed using a polarizing microscope. This observation is performed by inserting a wavelength plate as a test plate between the observation sample and the objective lens of the polarizing microscope, and performing the method such that an image showing a color corresponding to the retardation of the observation sample is seen. At this time, the part with different colors can be distinguished as the boundary between the first cured layer and the second cured layer.

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

The liquid crystal cured film may be a film including only a liquid crystal cured layer, or may be a film including an arbitrary layer combination in a liquid crystal cured layer. Examples of the arbitrary layer body include: a base material used in the production of a liquid crystal cured layer; a retardation film; a bonding agent layer for bonding with other components; a base layer for optimizing the smoothness of the film; and an impact-resistant polymethyl Hard coatings such as acrylic resin layers; anti-reflection layers; antifouling layers; etc.

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. In addition, the haze of the liquid crystal cured film is preferably 5% or less, more preferably 3% or less, and even more preferably 1% or less. The total light transmittance can be measured in the range of wavelengths from 400 nm to 700 nm using an ultraviolet-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, and more preferably 300 μm or less, and more preferably 200 μm or less.

[12. Polarizer]

The aforementioned liquid crystal cured film can be applied to a polarizing plate. This polarizing plate includes the above-mentioned liquid crystal cured film, and usually further includes a linear polarizer. The polarizing plate preferably functions as a circular polarizing plate or an elliptical polarizing plate. Such a polarizing plate can suppress reflection of external light in the front direction of the display surface by being provided in a display device such as an organic EL display device.

In addition, since the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer can be appropriately adjusted, the liquid crystal cured layer has birefringence that can be adjusted appropriately not only in the in-plane direction but also in the thickness direction. According to this, the polarizing plate suppresses reflection of external light not only in the front direction of the display surface of the display device but also in the oblique direction. Therefore, by using this polarizing plate, a display device with a wide viewing angle can be realized.

Examples of the linear polarizer include a film obtained by uniaxially stretching in a boric acid bath after adsorbing iodine or a dichroic dye on a polyvinyl alcohol film; and by adsorbing iodine or a dichroic dye on A film obtained by extending a polyvinyl alcohol film and further modifying a part of the polyvinyl alcohol unit in the molecular chain to a polyvinylidene unit. In addition, as another example of the linear polarizer, a polarizer having a function of separating polarized light into reflected light and transmitted light, such as a grid polarizer and a multilayer polarizer, may be mentioned. Among these, as the linear polarizer, a polarizer containing polyvinyl alcohol is preferred.

If natural light is incident on the linear polarizer, only a single direction of polarized light is transmitted. The degree of polarization of the linear polarizer is not particularly limited, but it is preferably 98% or more, and more preferably 99% or more.

The thickness of the linear polarizer is preferably 5 μm to 80 μm.

In the case where the polarizing plate is intended to function as a circular polarizing plate, the angle between the slow axis of the liquid crystal cured layer and the angle near the polarizing light absorption axis of the linear polarizer is preferably 45 ° or close to it. The aforementioned angle, specifically, is preferably 45 ° ± 5 ° (that is, 40 ° to 50 °), more preferably 45 ° ± 4 ° (that is, 41 ° to 49 °), and 45 ° ± 3 ° (That is, 42 ° to 48 °) is particularly preferred.

The polarizing plate may include any layer other than the linear polarizer and the liquid crystal cured film. Examples of the arbitrary layer body include: a bonding layer for bonding a linear polarizer and a liquid crystal cured film; a polarizer protective film layer for protecting the linear polarizer; and the like.

The said polarizing plate can be manufactured by the manufacturing method including "the thing which manufactures a liquid-crystal hardened film by the manufacturing method related to the said embodiment." For example, the aforementioned polarizing plate can be manufactured by a manufacturing method including "the manufacturing of a liquid crystal cured film through the manufacturing method related to the above-mentioned embodiment" and "the bonding of the manufactured liquid crystal cured film with a linear polarizer". For bonding, a bonding agent can also be used as required.

[13. Organic EL display device]

The aforementioned polarizing plate is applicable to an organic EL display device. This organic EL display device includes the above-mentioned polarizing plate, and usually further includes an organic electroluminescence element (hereinafter referred to as an “organic EL element” as appropriate). The organic EL display device generally includes a polarizing plate on the viewing side of the organic EL element. The polarizing plate includes a liquid crystal cured film and a linear polarizer in this order from the organic EL element side. In this configuration, the polarizing plate can function as a reflection suppressing film.

In the following, a case where a polarizing plate functions as a circular polarizing plate is taken as an example to explain the mechanism of suppressing reflection. Only a part of the linearly polarized light entering from the outside of the device passes through the linear polarizer, and then passes through the liquid crystal curing film, thereby becoming circularly polarized light. The circularly polarized light is reflected by constituent elements (reflective electrodes of the organic EL element, etc.) that reflect light in the organic EL element and passes through the liquid crystal curing film again, thereby becoming a vibration direction orthogonal to the vibration direction of the incident linearly polarized light The polarized light does not pass through the linear polarizer. Here, the vibration direction of the linearly polarized light means the vibration direction of the electric field of the linearly polarized light. Thereby, the function of suppressing reflection is achieved. The principle of such reflection suppression can be referred to Japanese Patent Laid-Open No. H9-127885.

An organic EL element generally includes a transparent electrode layer, a light emitting layer, and an electrode layer in order, and light must be generated from the light emitting layer by applying a voltage from the transparent electrode layer and the electrode layer. Examples of the material constituting the organic light-emitting layer include materials of a polyparastyrene type, a polyfluorene type, and a polyvinyl carbazole type. In addition, the light emitting layer may include a stack of a plurality of layers having different emission colors, or a mixed layer in which a layer of a certain pigment is doped with a different pigment. 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 generating layer.

The organic EL display device can be manufactured by a manufacturing method including "the manufacture of a polarizing plate by the above-mentioned manufacturing method".

『Examples』

The following examples are disclosed to illustrate the present invention in detail. However, the present invention is not limited to the embodiments disclosed below, and can be implemented with arbitrary changes without departing from the scope of the patent application of the present invention and its equivalent scope.

In the following description, the "%" and "part" of the amount are based on weight unless otherwise noted. In addition, the operations described below are performed in normal temperature and pressure atmosphere unless otherwise noted.

In addition, since the supporting substrate included in the liquid crystal cured film manufactured in the examples and comparative examples described below has optical isotropy, it does not affect the measurement result of the delay. Therefore, the measurement of the retardation of the liquid crystal cured layer in the examples and comparative examples described below was performed using a liquid crystal cured film as a sample.

[Evaluation method]

(Liquid Crystal Phase of Liquid Crystalline Compounds-Measurement Method of Solid Phase Transition Temperature)

Weigh 10 mg of liquid crystalline compound. The weighed liquid crystal compound was sandwiched between two glass substrates subjected to a rubbing treatment with the liquid crystal compound in a solid state. This substrate was carried on a hot plate, and after the temperature was raised from 40 ° C to 200 ° C, the temperature was lowered to 40 ° C. A change in the microstructure of the liquid crystalline compound was observed with a polarizing microscope during the aforementioned temperature increase and temperature decrease.

In this way, the measurement of the liquid crystal phase-solid phase transition temperature of the liquid crystal compound is performed in a temperature range of 40 ° C to 200 ° C.

(Measurement method of the substantial maximum tilt angle of the molecules of the liquid crystal cured layer and the molecules of the liquid crystal compound contained in the first cured layer to the second cured layer thereof)

FIG. 3 is a perspective view illustrating a measurement direction when the retardation of the liquid crystal cured layer 200 is measured from an oblique direction. In FIG. 3, the arrow A1 indicates the slow axis direction in the plane of the liquid crystal cured layer 200, the arrow A2 indicates the fast axis direction in the plane of the liquid crystal cured layer 200, and the arrow A3 indicates the thickness direction of the liquid crystal cured layer 200.

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

From the measured delay, the analysis software (Axometrics' analysis software "Multi-Layer Analysis") attached to the aforementioned phase difference meter was used to analyze the analysis conditions at an analysis wavelength of 590 nm and a number of layer divisions of 20 layers. The substantial maximum tilt angle of the molecules of the liquid crystal compound in the liquid crystal cured layer 200.

In addition, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the first cured layer is measured by the following method.

Except that the first cured layer is used instead of the liquid crystal cured layer, the liquid crystal contained in the first cured layer is measured by the same method as the method for measuring the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer. Substantial maximum tilt angle of the molecule of the sex compound. This measurement is performed at the time point "in the manufacturing process of the liquid crystal cured layer, after the first cured layer is obtained and before the surface of the first cured layer is further coated with the liquid crystal composition for forming the second cured layer".

Furthermore, the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer is measured by the following method.

Measure 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. Then, using the measured maximum inclination angles and the thicknesses of the first cured layer and the second cured layer, the substantial maximum inclination angle of the molecules of the liquid crystal compound contained in the second cured layer is analyzed.

(Evaluation method of viewing angle characteristics)

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

Calculate the average R (± 50 °) of the retardation R (-50 °) at the angle of incidence θ of −50 ° and the retardation R (+ 50 °) at the angle of incidence θ of + 50 °. Then, this average value R (± 50 °) is divided by the in-plane retardation R (0 °) with an incident angle θ of 0 °, and the average retardation ratio R (± 50 °) / R (0 °) is obtained. The closer the average retardation ratio R (± 50 °) / R (0 °) is to 1.00, the more excellent the viewing angle characteristics can be achieved in the organic EL display device. Then, the viewing angle characteristics of the liquid crystal cured layer were evaluated on the basis of the following average retardation ratio R (± 50 °) / R (0 °).
"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 obtained by using the average retardation ratio R (± 50 °) / R (0 °).

[Explanation of liquid crystal compounds]

The structures of the reverse dispersion liquid crystalline compound 1 (liquid crystal phase-solid phase transition temperature = 96 ° C) and reverse dispersion liquid crystalline compound 2 (liquid crystal phase-solid phase transition temperature = 125 ° C) used in the following examples are as follows .

『Hua23』

Inverse dispersion liquid crystalline compound 1

『Hua 24』

Inverse dispersion liquid crystalline compound 2

[Examples 1 to 21]

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.), and a polymerization initiator ("Irgacure OXE04" manufactured by BASF) were mixed. 4.3 parts by weight and "148.5 parts by weight of cyclopentanone and 222.8 parts by weight of 1,3-dioxo" as a solvent to produce a liquid crystal composition.

(Preparation of supporting substrate)

A resin film ("ZeonorFilm ZF16" manufactured by Japan's Rui On Co., Ltd .; thickness: 100 μm; glass transition temperature of the resin: 160 ° C) was prepared as a supporting substrate. Corona treatment is applied to one side of the supporting substrate. Subsequently, the corona-treated surface of the supporting substrate is subjected to a rubbing treatment.

(Formation of the first cured layer)

On the friction-treated surface of the supporting substrate, a liquid crystal composition is applied using a wire rod to form a layered body of the liquid crystal composition (step (I)).

Subsequently, the layered body of the liquid crystal composition was heated in an oven set at 160 ° C. for 2 minutes to orient the liquid crystal compound in the layered body (step (II)). The aforementioned heating condition is a temperature condition in which the viscosity of the residual component of the test composition corresponding to the liquid crystal composition used is 140 cP in the example using the liquid crystal compound 1. In addition, in the example using the liquid crystal compound 2, the above heating conditions are temperature conditions in which the viscosity of the residual component of the test composition corresponding to the liquid crystal composition used is 209 cP.

Thereafter, the layered body of the liquid crystal composition was irradiated with 500 mJ / cm ² of ultraviolet rays in a nitrogen atmosphere to cure the layered body of the liquid crystal composition to form a first cured layer having a thickness of 1 μm (step (III)).

Measure 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.

(Formation of the second cured layer)

On the surface of the first cured layer, a wire rod was used to directly apply the remaining liquid crystal composition used in forming the first cured layer to form a layered body of the liquid crystal composition (step (IV)). Thus, a semi-finished product having a support substrate, a first cured layer, and a layered body of the liquid crystal composition in this order is obtained.

Subsequently, this semi-finished product was placed in an oven set at 160 ° C. and heated for 2 minutes to orient the liquid crystal compound in the layer body of the liquid crystal composition (step (V)). After that, the semi-finished product is taken out of the oven.

Thereafter, at the temperature shown in Table 1, the semi-finished product was left standing as long as the time shown in Table 1 (Step (VI)). At this time, standing at a temperature of 23 ° C was performed by placing a semi-finished product on a stainless steel plate. In addition, standing at other temperatures is performed by placing a semi-finished product on a temperature-adjusted hot plate.

Thereafter, the layered body of the liquid crystal composition was irradiated with 500 mJ / cm ² of ultraviolet rays in a nitrogen atmosphere to cure the layered body of the liquid crystal composition to form a second cured layer having a thickness of 2 μm (step (VII)). Thus, a liquid crystal cured film including a liquid crystal cured layer including a supporting substrate, a first cured layer and a second cured layer is obtained.

Perform: measurement of the substantial maximum tilt 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 tilt angle of the molecules of the liquid crystal compound contained in the second cured layer, and Evaluation of the viewing angle characteristics of the liquid crystal cured layer.

[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 semi-finished product standing is not performed, and the liquid crystal is irradiated with ultraviolet rays. Step (VII) of curing the layer of the composition.

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", and before the step (III) of curing the layer of the liquid crystal composition by irradiating ultraviolet rays, A step (VIII) of leaving the layered body of the liquid crystal composition at a room temperature of 23 ° C for 240 seconds is performed. The standing under the temperature condition of 23 ° C. was performed by placing a semi-finished product including a support 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 semi-finished product standing is not performed, and the liquid crystal is irradiated with ultraviolet rays Step (VII) of curing the layer of the composition.

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 foregoing examples and comparative examples are shown in Table 1 below. In Table 1, the meaning of the abbreviations is as follows.
Θ: substantial maximum tilt angle.
Re ratio: R (± 50 °) / R (0 °).

"Table 1"
[Table 1. Results of Examples and Comparative Examples]

[discuss]

Compared with the comparative example in which the step (VI) is not performed, in the examples in which the step (VI) is performed, the substantial tilt angle of the molecules of the liquid crystal compound contained in the second cured layer can be increased, and as a result, the The substantial tilt angle 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 is increased. In addition, in the examples, it was confirmed that the longer the time spent in the step (VI), the larger the substantial maximum tilt angle tends to be. Accordingly, it can be confirmed from the foregoing examples 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 according to the manufacturing method including the step (VI). In addition, it was confirmed that by adjusting the substantial tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal cured layer, the birefringence in the thickness direction of the liquid crystal cured layer can be appropriately adjusted, so that the improvement of viewing angle characteristics can be achieved.

100‧‧‧LCD curing film

110‧‧‧LCD curing layer

111‧‧‧The first curing layer

112‧‧‧Second curing layer

200‧‧‧LCD curing layer

<FIG. 1> FIG. 1 is a schematic cross-sectional view of a liquid crystal cured film manufactured by a manufacturing method as an embodiment of the present invention.

<Fig. 2> Fig. 2 is a graph plotting the retardation ratio R (θ) / R (0 °) of a related example of the first cured layer against the incident angle θ.

<Fig. 3> Fig. 3 is a perspective view for explaining the measurement direction when measuring the retardation of the liquid crystal cured layer from the oblique direction.

Claims (10)

A method for manufacturing a liquid crystal cured film, which is a method for manufacturing a liquid crystal cured film including a liquid crystal cured layer. The liquid crystal cured layer includes a first cured layer and a first cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound. Two curing layers; wherein the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the liquid crystal curing layer is 5 ° or more and 85 ° or less; the manufacturing method sequentially includes: forming a first liquid crystal composition containing the liquid crystal compound Step (I) of the layer of the object; step (II) of orienting the liquid crystal compound contained in the layer of the first liquid crystal composition; curing the layer of the first liquid crystal composition to form the first Step (III) of a cured layer; step (IV) of directly forming a layer body of a second liquid crystal composition on the first cured layer, the second liquid crystal composition comprising the same as the first liquid crystal composition The liquid crystal compounds having the same or different liquid crystal compounds; and the liquid crystal compounds included in the layer of the second liquid crystal composition are determined Step (V); a step (VI) of increasing a substantial maximum tilt angle of a molecule of the liquid crystal compound contained in the layer of the second liquid crystal composition with time, and a step of forming the second liquid crystal composition The step (VII) of curing the laminated body to form the aforementioned second cured layer. The method for manufacturing a liquid crystal cured film according to claim 1, wherein it takes 60 seconds or more to perform the step (VI). The method for manufacturing a liquid crystal cured film according to claim 1, wherein the step (VI) is performed in a time of 120 seconds or more and 600 seconds or less. The method for manufacturing a liquid crystal cured film according to claim 1, wherein the step (VI) is performed under a temperature condition that does not reach a liquid crystal phase-solid phase transition temperature of the liquid crystal compound contained in the second liquid crystal composition. By. The method for producing a liquid crystal cured film according to claim 1, wherein the liquid crystal compound is a birefringent liquid crystal compound capable of exhibiting reverse wavelength dispersion. The method for manufacturing a liquid crystal cured film according to claim 1, wherein a substantial maximum tilt angle of a molecule of the liquid crystal compound contained in the liquid crystal cured layer is 40 ° or more and 85 ° or less. The method for manufacturing a liquid crystal cured film according to claim 1, wherein the substantial maximum tilt angle of the molecules of the liquid crystal compound contained in the second cured layer is larger than the molecules of the liquid crystal compound contained in the first cured layer. The substantial maximum tilt angle is still large. The method for manufacturing a liquid crystal cured film according to claim 1, wherein the liquid crystal cured layer can function as a 1/4 wavelength plate. The manufacturing method of a polarizing plate is a manufacturing method of the polarizing plate provided with a liquid crystal hardened film, Comprising: The said liquid crystal hardened film is manufactured by the manufacturing method as described in any one of Claims 1-8. A method for manufacturing an organic electroluminescence display device, which is a method for manufacturing an organic electroluminescence display device including a polarizing plate, and includes the step of manufacturing the polarizing plate by the manufacturing method according to claim 9.