JP2018162379A - Liquid crystal composition, liquid crystal cured film and method for producing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal composition that makes it possible to obtain a liquid crystal cured layer in which tilt angles of liquid crystalline compound molecules are discontinuously different in thickness direction, and orientation defects are suppressed.SOLUTION: A liquid crystal composition contains a first liquid crystalline compound that has inclined orientation properties and can express birefringence of normal wavelength dispersion, a second liquid crystalline compound that can express birefringence of reverse wavelength dispersion, and a surfactant. The surfactant contains a fluorine atom, and has 1-octanol/water partition coefficients of 4.8 or more and 6.7 or less.SELECTED DRAWING: Figure 1

Description

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

  Conventionally, a film including a liquid crystal cured layer obtained by curing a film of a liquid crystal composition containing a liquid crystal compound has been known. Usually, in such a film, the molecules of the liquid crystalline compound are uniformly oriented, and the tilt angle formed by the molecules of the liquid crystalline compound with respect to the layer plane is constant in the thickness direction.

  However, in recent years, a technique has been developed in which a specific liquid crystal composition is used to make the tilt angle of the molecules of the liquid crystal compound in the liquid crystal cured layer non-uniform in the thickness direction (see Patent Documents 1 to 3).

Japanese Patent No. 5363022 JP, 2015-161714, A JP 2016-110153 A

  In the liquid crystal cured layer obtained by the techniques described in Patent Documents 1 to 3, generally, the tilt angles of the molecules of the liquid crystalline compound are continuously different in the thickness direction of the liquid crystal cured layer. Specifically, in the conventional liquid crystal cured layer, the tilt angle is usually smaller as it is closer to one side of the liquid crystal cured layer, and the tilt angle is larger as it is closer to the other side. Therefore, a liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction has not been known conventionally.

  The liquid crystal cured layer is expected to be used in optical applications such as viewing angle compensation films for liquid crystal display devices. However, in order to enable various optical designs in optical applications, development of a liquid crystal cured layer having a structure different from the conventional one is required.

  The present invention was devised in view of the above problems, and a liquid crystal composition capable of obtaining a liquid crystal cured layer in which the tilt angle of molecules of a liquid crystal compound is discontinuously different in the thickness direction and alignment defects are suppressed. A liquid crystal cured film having a liquid crystal cured layer in which the tilt angle of the molecules of the liquid crystal compound differs discontinuously in the thickness direction and orientation defects are suppressed; and the tilt angle of the molecules of the liquid crystal compound is discontinuous in the thickness direction; It is an object of the present invention to provide a method for producing a cured liquid crystal film comprising a cured liquid crystal layer in which orientation defects are suppressed.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a first liquid crystalline compound having a tilt alignment property and capable of exhibiting birefringence with forward wavelength dispersion, and birefringence with reverse wavelength dispersion. It was found that a liquid crystal composition in which a second liquid crystalline compound capable of developing a compound and a surfactant containing a fluorine atom and having a predetermined 1-octanol / water partition coefficient can solve the above-mentioned problems, Completed.
That is, the present invention includes the following items.

[1] Including a first liquid crystal compound that has tilt alignment and can exhibit forward wavelength dispersive birefringence, a second liquid crystal compound that can exhibit reverse wavelength dispersive birefringence, and a surfactant. A liquid crystal composition comprising:
The liquid crystal composition, wherein the surfactant contains a fluorine atom and has a 1-octanol / water partition coefficient of 4.8 or more and 6.7 or less.
[2] The liquid crystal composition according to [1], wherein the first liquid crystalline compound has a refractive index anisotropy Δn at a measurement wavelength of 550 nm of 0.11 or more.
[3] The amount of the first liquid crystalline compound with respect to a total of 100 parts by weight of the first liquid crystalline compound and the second liquid crystalline compound is 1 part by weight or more and 25 parts by weight or less, [1] or [2] The liquid crystal composition described.
[4] The amount of the surfactant with respect to a total of 100 parts by weight of the first liquid crystalline compound and the second liquid crystalline compound is 0.11 part by weight or more and 0.29 part by weight or less. [3] The liquid crystal composition according to any one of [3].
[5] A liquid crystal cured film comprising a liquid crystal cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound,
The liquid crystal cured layer includes a first layer, a second layer, and a third layer in this order, including the liquid crystalline compound in which the alignment state may be fixed,
A first tilt angle formed by molecules of the liquid crystalline compound contained in the first layer with respect to a layer plane is constant in the first layer;
The second tilt angle formed by the molecules of the liquid crystalline compound contained in the second layer with respect to the layer plane is constant in the second layer, and discontinuously differs from the first tilt angle,
The third tilt angle formed by the molecules of the liquid crystalline compound contained in the third layer with respect to the layer plane is constant in the third layer, and the first tilt angle and the second tilt angle are not. Continuously different liquid crystal cured film.
[6] The liquid crystal cured film according to [5], wherein the liquid crystal composition is the liquid crystal composition according to any one of [1] to [4].
[7] The ratio of the thickness of the first layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 14% or more and 66% or less,
The ratio of the thickness of the second layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 1% or more and 80% or less,
The liquid crystal according to [5] or [6], wherein the ratio of the thickness of the third layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 6% or more and 33% or less. Cured film.
[8] The first tilt angle is not less than 0 ° and not more than 20 °,
The second tilt angle is not less than 20 ° and not more than 70 °;
The liquid crystal cured film according to any one of [5] to [7], wherein the third tilt angle is not less than 70 ° and not more than 90 °.
[9] A step of forming a layer of the liquid crystal composition according to any one of [1] to [4] on a support surface;
Aligning the first liquid crystalline compound and the second liquid crystalline compound contained in the layer of the liquid crystal composition;
And a step of curing the liquid crystal composition layer.

  According to the present invention, the liquid crystal composition capable of obtaining a liquid crystal cured layer in which the tilt angle of the molecules of the liquid crystal compound is discontinuously different in the thickness direction and the alignment defect is suppressed; the tilt angle of the molecules of the liquid crystal compound is A liquid crystal cured film having a liquid crystal cured layer that is discontinuously different in the thickness direction and suppressed in alignment defects; and a liquid crystal in which the tilt angle of molecules of the liquid crystal compound is discontinuously different in the thickness direction and alignment defects are suppressed. The manufacturing method of the liquid crystal cured film provided with the cured layer can be provided.

FIG. 1 is a cross-sectional view schematically showing a cross section of a cured liquid crystal film according to an embodiment of the present invention, taken along a plane parallel to the thickness direction. FIG. 2 is a photograph of a cross section of the liquid crystal cured layer observed with a polarizing microscope in Example 1 of the present invention. FIG. 3 is an explanatory diagram for explaining each part of FIG.

  Hereinafter, the present invention will be described in detail with reference to examples and embodiments. However, the present invention is not limited to the following exemplifications and embodiments, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof.

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

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

  In the following description, the retardation of a certain layer represents in-plane retardation Re unless otherwise specified. This in-plane retardation Re is a value represented by Re = (nx−ny) × d unless otherwise specified. Here, nx represents a refractive index in a direction (in-plane direction) perpendicular to the thickness direction of the layer and giving the maximum refractive index. ny represents the refractive index in the in-plane direction of the layer and perpendicular to the nx direction. d represents the thickness of the layer. The measurement wavelength of retardation is 550 nm unless otherwise specified.

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

  In the following description, unless the direction of the element is “parallel” or “vertical”, the range is within a range that does not impair the effect of the present invention, for example, ± 5 °, preferably ± 3 °, more preferably ± 1. An error within the range of ° may be included.

  In the following description, unless otherwise specified, the “tilt angle” of a molecule of a liquid crystal compound contained in a certain layer represents an angle formed by the molecule of the liquid crystal compound with respect to the layer plane. This tilt angle corresponds to the maximum angle among the angles formed by the direction of the maximum refractive index in the refractive index ellipse of the molecules of the liquid crystalline compound and the layer plane.

[1. Outline of liquid crystal composition]
The liquid crystal composition of the present invention includes a first liquid crystal compound, a second liquid crystal compound, and a surfactant containing a fluorine atom. In the following description, a surfactant containing a fluorine atom may be referred to as a “fluorine surfactant” as appropriate.

[2. First liquid crystalline compound]
Since the first liquid crystalline compound is a compound having liquid crystallinity, it is usually a compound that can exhibit a liquid crystal phase when the first liquid crystalline compound is aligned. And as this 1st liquid crystalline compound, what has inclination orientation and can express birefringence of forward wavelength dispersion is used.

  Here, the “first liquid crystalline compound having tilted orientation” means that the first test composition containing the first liquid crystalline compound alone as the liquid crystalline compound is applied to the rubbing-treated surface of the resin film and aligned. When the first test layer is obtained by performing the treatment, the average tilt angle formed by the molecules of the first liquid crystal compound in the first test layer with respect to the layer plane can be 30 ° or more. Say. Here, the composition for a 1st test is the same composition as Example 1 mentioned later except not using the 2nd liquid crystalline compound and using 100 weight part of 1st liquid crystalline compounds independently as a liquid crystalline compound. Is a composition. The average tilt angle refers to the average tilt angle in the layer thickness direction.

Specifically, the tilt orientation of the liquid crystal compound can be confirmed by conducting the following evaluation test.
Similarly to Example 1 described later, a resin film made of norbornene resin is prepared, and the surface is subjected to rubbing treatment. Further, as the liquid crystalline compound, a test composition having the same composition as that of Example 1 described later is prepared except for 100 parts by weight of the liquid crystalline compound to be evaluated and the liquid crystalline compound. The test composition is applied to the rubbing-treated surface of the resin film in the same manner as in Example 1 described later to obtain a layer of the test composition. Thereafter, the same orientation treatment as in Example 1 described later is performed to align the molecules of the liquid crystalline compound in the test composition, thereby obtaining a test layer having the same thickness as in Example 1 described later. Then, the average tilt angle of the molecules of the liquid crystal compound contained in this test layer is measured. If the measured average tilt angle is 30 ° or more and 90 ° or less, the liquid crystal compound is determined to have tilt alignment. Moreover, if the measured average tilt angle is 0 ° or more and less than 30 °, it is determined that the liquid crystalline compound does not have a tilt alignment property.

The average tilt angle of the liquid crystal compound molecules contained in the test layer can be measured by the following method.
Using a phase difference meter, the retardation of the test layer is measured at a measurement wavelength of 590 nm and in an incident angle range of −50 ° to 50 °. Then, from the measured retardation, the average tilt angle of the liquid crystal compound molecules contained in the test layer is analyzed by assuming that the test layer is a set of layers having a thickness of about 0.1 μm. Can be obtained. The analysis can be performed using, for example, analysis software “Malti-Layer Analysis” manufactured by AxsoMetrics.

  In particular, from the viewpoint of easily obtaining a desired liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction, the first liquid crystal properties measured by the evaluation test of the tilt orientation of the liquid crystal compound are described. The average tilt angle of the compound molecules is preferably in a predetermined range larger than 30 °. Specifically, the average tilt angle of the molecules of the first liquid crystalline compound measured in the evaluation test of the tilt orientation of the liquid crystalline compound is usually 30 ° or more, preferably 40 ° or more, more preferably 45 ° or more. Yes, usually 90 ° or less.

  Usually, it is difficult to specify whether or not a certain liquid crystalline compound has tilt alignment from the structure of the liquid crystalline compound. Therefore, when selecting the first liquid crystal compound from the group of liquid crystal compounds as candidates, an evaluation test of the tilt alignment of the liquid crystal compounds is conducted, and the average tilt angle of the liquid crystal compounds as candidates is actually measured. It is desirable to measure to.

  In addition, as the first liquid crystal compound, a liquid crystal compound capable of expressing forward wavelength dispersive birefringence is used from the viewpoint of obtaining a desired liquid crystal cured layer. Here, a liquid crystal compound capable of developing forward wavelength dispersive birefringence means that when a layer of the liquid crystal compound is formed and the liquid crystal compound is oriented in the layer, the forward wavelength dispersive birefringence is increased. It refers to a liquid crystal compound that develops. Normally, when a liquid crystal compound is homogeneously oriented, the liquid crystal compound exhibits forward wavelength dispersive birefringence by examining whether the liquid crystal compound layer exhibits forward wavelength dispersive birefringence. You can check if you want to. Here, the liquid crystal compound is homogeneously aligned means that a layer containing the liquid crystal compound is formed, and the major axis direction of the mesogenic skeleton of the molecule of the liquid crystal compound in the layer is parallel to the plane of the layer. Alignment in one direction. When the liquid crystalline compound includes a plurality of types of mesogenic skeletons having different alignment directions, the direction in which the longest type of mesogen is aligned is the alignment direction. In the following description, a liquid crystalline compound capable of developing forward wavelength dispersive birefringence may be referred to as a “forward dispersed liquid crystalline compound” as appropriate.

The forward wavelength dispersive birefringence refers to birefringence in which birefringence ΔN (450) at a wavelength of 450 nm and birefringence ΔN (550) at a wavelength of 550 nm satisfy the following formula (N1). Such a liquid crystalline compound capable of exhibiting forward wavelength dispersive birefringence can usually exhibit smaller birefringence as the measurement wavelength is longer.
ΔN (450)> ΔN (550) (N1)

  As the first liquid crystal compound, those having a large refractive index anisotropy Δn at a measurement wavelength of 550 nm are particularly preferable. The specific refractive index anisotropy Δn of the first liquid crystal compound at a measurement wavelength of 550 nm is preferably 0.11 or more, more preferably 0.18 or more, and particularly preferably 0.21 or more. By using the first liquid crystalline compound having a large refractive index anisotropy Δn, a desired liquid crystal cured layer can be easily obtained. The upper limit of the refractive index anisotropy Δn of the first liquid crystalline compound is not particularly limited, but is preferably 0.4 or less, more preferably 0.8, from the viewpoint of easy availability of the first liquid crystalline compound. 35 or less, particularly preferably 0.3 or less.

The refractive index anisotropy of the liquid crystal compound can be measured, for example, by the following method.
A liquid crystal compound film is prepared, and the liquid crystal compound contained in the film is homogeneously aligned. Thereafter, the retardation of the film is measured. The refractive index anisotropy of the liquid crystalline compound can be determined from “(film retardation) ÷ (film optical thickness)”. At this time, in order to facilitate the measurement of the retardation and the optical thickness, the film of the homogeneously aligned liquid crystal compound may be cured.

  The first liquid crystalline compound preferably has polymerizability. Therefore, it is preferable that the molecule | numerator of 1st liquid crystalline compounds contains polymeric groups, such as an acryloyl group, a methacryloyl group, and an epoxy group. The first liquid crystalline compound having polymerizability can be polymerized in a state exhibiting a liquid crystal phase, and can be a polymer while maintaining the alignment state of molecules in the liquid crystal phase. Therefore, it is possible to fix the alignment state of the first liquid crystalline compound in the liquid crystal cured layer or to increase the degree of polymerization of the liquid crystalline compound to increase the mechanical strength of the liquid crystal cured layer.

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

  Examples of the first liquid crystalline compound include the following compounds. A 1st liquid crystalline compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the first liquid crystalline compound relative to the total of 100 parts by weight of the first liquid crystalline compound and the second liquid crystalline compound is preferably 1 part by weight or more, more preferably 5 parts by weight or more, and even more preferably 10 parts by weight or more. , Preferably 25 parts by weight or less, more preferably 20 parts by weight or less. By keeping the amount of the first liquid crystal compound within the above range, a liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction and the alignment defects are few can be easily obtained. .

[3. Second liquid crystalline compound]
The second liquid crystalline compound is a compound having liquid crystallinity, and is usually a compound that can exhibit a liquid crystal phase when the second liquid crystalline compound is aligned.

  The second liquid crystalline compound is a liquid crystalline compound capable of developing reverse wavelength dispersive birefringence. Here, the liquid crystalline compound capable of exhibiting reverse wavelength dispersive birefringence means that when a liquid crystal compound layer is formed and the liquid crystal compound is aligned in the layer, the reverse wavelength dispersive birefringence is exhibited. It refers to a liquid crystal compound that develops. Normally, when a liquid crystal compound is homogeneously aligned, the liquid crystal compound exhibits reverse wavelength dispersive birefringence by investigating whether the liquid crystal compound layer exhibits reverse wavelength dispersive birefringence. You can check if you want to. In the following description, a liquid crystal compound capable of developing reverse wavelength dispersive birefringence may be referred to as “reverse disperse liquid crystal compound” as appropriate.

The reverse wavelength dispersive birefringence refers to birefringence in which the birefringence ΔN (450) at a wavelength of 450 nm and the birefringence ΔN (550) at a wavelength of 550 nm satisfy the following formula (N2). Such a liquid crystalline compound capable of exhibiting reverse wavelength dispersive birefringence can usually exhibit greater birefringence as the measurement wavelength is longer.
ΔN (450) <ΔN (550) (N2)

  The reverse dispersion liquid crystal compound such as the second liquid crystal compound may be a compound containing a main chain mesogen and a side chain mesogen bonded to the main chain mesogen in the molecule of the reverse dispersion liquid crystal compound. In the reverse dispersion liquid crystal compound containing a main chain mesogen and a side chain mesogen, the side chain mesogen can be aligned in a direction different from the main chain mesogen in a state where the reverse dispersion liquid crystal compound is aligned. Therefore, in the layer of the reverse dispersion liquid crystal compound thus aligned, the main chain mesogen and the side chain mesogen can be aligned in different directions. In such a case, the birefringence of the layer is expressed as a difference between the refractive index corresponding to the main chain mesogen and the refractive index corresponding to the side chain mesogen, and as a result, reverse wavelength dispersive birefringence can be expressed.

  As described above, the three-dimensional shape of a compound having a main chain mesogen and a side chain mesogen is a specific shape different from the three-dimensional shape of a general forward-dispersed liquid crystal compound. Since the reverse-dispersed liquid crystalline compound has such a specific three-dimensional shape, generally, the liquid crystal composition containing the reverse-dispersed liquid crystalline compound exhibits different properties from the liquid crystal composition containing only the forward-dispersed liquid crystalline compound. There is. According to the study by the present inventors, the second liquid crystal compound as the reverse dispersion liquid crystal compound has a specific three-dimensional shape as described above, for example, the second liquid crystal property having no tilt alignment property. Even when a compound is used, it is presumed that this is one of the reasons why a specific structure of the liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound differ discontinuously in the thickness direction can be realized. However, the technical scope of the present invention is not limited by the above estimation.

  Furthermore, as the second liquid crystalline compound, a compound having tilt alignment may be used, or a compound having no tilt alignment may be used. Here, “second liquid crystalline compound having no tilt orientation” means that a second test composition containing a second liquid crystalline compound alone as a liquid crystalline compound is applied to the rubbing-treated surface of the resin film. When the second test layer is obtained by performing the alignment treatment, the average tilt angle formed by the molecules of the second liquid crystal compound in the second test layer with respect to the layer plane cannot be 30 ° or more. Refers to a chemical compound. Here, the composition for a second test is the same composition as Example 1 described later except that the first liquid crystalline compound is not used and 100 parts by weight of the second liquid crystalline compound is used alone as the liquid crystalline compound. Is a composition. The presence or absence of the tilt alignment of the second liquid crystalline compound can be specifically determined by the evaluation test of the tilt alignment of the liquid crystal compound described in the section of the first liquid crystal compound.

  The refractive index anisotropy Δn of the second liquid crystalline compound at a measurement wavelength of 550 nm is preferably 0.01 or more, more preferably 0.05 or more, preferably 0.15 or less, more preferably 0.10 or less. is there. By using the second liquid crystalline compound having a refractive index anisotropy Δn in such a range, a desired liquid crystal cured layer can be easily obtained. Furthermore, usually, by using a second liquid crystal compound having a refractive index anisotropy Δn in such a range, it is easy to obtain a liquid crystal cured layer having high reverse wavelength dispersion.

  The second liquid crystal compound preferably has polymerizability. Therefore, it is preferable that the molecule | numerator of 2nd liquid crystalline compounds contains polymeric groups, such as an acryloyl group, a methacryloyl group, and an epoxy group. The second liquid crystalline compound having polymerizability can be polymerized in a state exhibiting a liquid crystal phase, and can be a polymer while maintaining the molecular alignment state in the liquid crystal phase. Therefore, it is possible to fix the orientation state of the second liquid crystalline compound in the liquid crystal cured layer or increase the degree of polymerization of the liquid crystalline compound to increase the mechanical strength of the liquid crystal cured layer.

  The molecular weight of the second liquid crystalline compound is preferably 300 or more, more preferably 700 or more, particularly preferably 1000 or more, preferably 2000 or less, more preferably 1700 or less, and particularly preferably 1500 or less. By using the second liquid crystalline compound having a molecular weight in such a range, the coating property of the liquid crystal composition can be made particularly good.

  A 2nd liquid crystalline compound may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  Examples of the reverse dispersion liquid crystalline compound include compounds represented by the following formula (Ia). In the following description, the compound represented by the formula (Ia) may be referred to as “compound (Ia)” as appropriate. Therefore, these compounds (Ia) can be used as the second liquid crystalline compound.

In the formula (Ia), A ^1a is an aromatic carbon atom having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring and having an organic group having 1 to 67 carbon atoms as a substituent. A hydrogen ring group; or an aromatic heterocyclic group having, as a substituent, an organic group having 1 to 67 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; .

Specific examples of A ^1a include a group represented by the formula: —R ^f C (═N—NR ^g R ^h ), or a group represented by the formula: —R ^f C (═N— ^{N═R f1} R ^h ). A phenylene group; a benzothiazol-4,7-diyl group substituted with a 1-benzofuran-2-yl group; a benzothiazole-4 substituted with a 5- (2-butyl) -1-benzofuran-2-yl group , 7-diyl group; benzothiazol-4,7-diyl group substituted with 4,6-dimethyl-1-benzofuran-2-yl group; substituted with 6-methyl-1-benzofuran-2-yl group Benzothiazole-4,7-diyl group; benzothiazole-4,7-diyl group substituted with 4,6,7-trimethyl-1-benzofuran-2-yl group; 4,5,6-trimethyl-1- Substituted with benzofuran-2-yl group Benzothiazol-4,7-diyl group; benzothiazol-4,7-diyl group substituted with 5-methyl-1-benzofuran-2-yl group; substituted with 5-propyl-1-benzofuran-2-yl group Benzothiazol-4,7-diyl group; a benzothiazol-4,7-diyl group substituted with a 7-propyl-1-benzofuran-2-yl group; a 5-fluoro-1-benzofuran-2-yl group Benzothiazole-4,7-diyl group substituted with phenyl; benzothiazole-4,7-diyl group substituted with phenyl group; benzothiazole-4,7-diyl group substituted with 4-fluorophenyl group; 4 A benzothiazole-4,7-diyl group substituted with a nitrophenyl group; a benzothiazole-4,7-diyl group substituted with a 4-trifluoromethylphenyl group Benzothiazole-4,7-diyl group substituted with 4-cyanophenyl group; benzothiazole-4,7-diyl group substituted with 4-methanesulfonylphenyl group; substituted with thiophen-2-yl group; Benzothiazole-4,7-diyl group; benzothiazole-4,7-diyl group substituted with thiophen-3-yl group; benzothiazole-4,7- substituted with 5-methylthiophen-2-yl group Benzothiazol-4,7-diyl group substituted with 5-chlorothiophen-2-yl group; benzothiazole-4,7 substituted with thieno [3,2-b] thiophen-2-yl group A benzothiazole-4,7-diyl group substituted with a 2-benzothiazolyl group; a benzothiazole-4,7-disubstituted with a 4-biphenyl group A benzothiazole-4,7-diyl group substituted with a 4-propylbiphenyl group; a benzothiazole-4,7-diyl group substituted with a 4-thiazolyl group; a 1-phenylethylene-2-yl group Substituted benzothiazole-4,7-diyl group; benzothiazole-4,7-diyl group substituted with 4-pyridyl group; benzothiazole-4,7-diyl group substituted with 2-furyl group; [1,2-b] benzothiazole-4,7-diyl group substituted with furan-2-yl group; 1H-isoindole-1,3 (2H) substituted with 5-methoxy-2-benzothiazolyl group -Dione-4,7-diyl group; 1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with phenyl group; 1H- substituted with 4-nitrophenyl group Isoindole-1,3 (2H) -dione-4,7-diyl group; or 1H-isoindole-1,3 (2H) -dione-4,7-diyl group substituted with 2-thiazolyl group; Etc. Here, R ^f and R ^f1 each independently represent the same meaning as Q ¹ described later. R ^g represents the same meaning as A ^y described later, and R ^h represents the same meaning as A ^x described later.

In the formula (Ia), Y ^{1a to} Y ^8a each independently represent a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —. O—, —O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented. Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In the formula (Ia), G ^1a and G ^2a each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent. The aliphatic group includes one or more —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C per one aliphatic group. Even if (═O) —O—, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — are present. Good. However, the case where two or more of -O- or -S- are adjacent to each other is excluded. Here, R < ² > represents a hydrogen atom or a C1-C6 alkyl group.

In the formula (Ia), Z ^1a and Z ^2a each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.

In the formula (Ia), A ^2a and A ^3a each independently represent a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent.

In the formula (Ia), A ^4a and A ^5a each independently represent a divalent aromatic group having 6 to 30 carbon atoms, which may have a substituent.

  In the formula (Ia), k and l each independently represents 0 or 1.

  Among these, preferred specific examples include compounds represented by the following formula (I). In the following description, the compound represented by the formula (I) may be referred to as “compound (I)” as appropriate.

Compound (I) is usually, as represented by the following formula, based ^{-Y 5 -A 4 - (Y 3} -A 2) n -Y 1 -A 1 -Y 2 - (A 3 -Y 4) m - It includes two mesogenic skeletons of a main chain mesogen 1a composed of A ⁵ -Y ^6- and a side chain mesogen 1b composed of a group> A ¹ -C (Q ¹ ) = NN (A ^x ) A ^y . The main chain mesogen 1a and the side chain mesogen 1b cross each other. Although the main chain mesogen 1a and the side chain mesogen 1b can be combined into one mesogen, in the present invention, they are divided into two mesogens.

  The refractive index in the major axis direction of the main chain mesogen 1a is n1, and the refractive index in the major axis direction of the side chain mesogen 1b is n2. At this time, the absolute value and the wavelength dispersion of the refractive index n1 usually depend on the molecular structure of the main chain mesogen 1a. Further, the absolute value and wavelength dispersion of the refractive index n2 usually depend on the molecular structure of the side chain mesogen 1b. Here, since the molecules of the liquid crystal compound in the liquid crystal phase perform a rotational movement with the major axis direction of the main chain mesogen 1a as the rotation axis, the refractive indexes n1 and n2 here represent the refractive index as a rotating body. ing.

  Due to the molecular structure of the main chain mesogen 1a and the side chain mesogen 1b, the absolute value of the refractive index n1 is larger than the absolute value of the refractive index n2. Furthermore, the refractive indexes n1 and n2 usually show forward wavelength dispersion. Here, the forward wavelength dispersive refractive index represents a refractive index in which the absolute value of the refractive index decreases as the measurement wavelength increases. The refractive index n1 of the main chain mesogen 1a exhibits a small degree of forward wavelength dispersion. Therefore, the refractive index n1 measured at the long wavelength is smaller than the refractive index n1 measured at the short wavelength, but the difference between them is small. On the other hand, the refractive index n2 of the side chain mesogen 1b exhibits a large degree of forward wavelength dispersion. Therefore, the refractive index n2 measured at the long wavelength is smaller than the refractive index n2 measured at the short wavelength, and the difference between them is large. Therefore, when the measurement wavelength is short, the difference Δn between the refractive index n1 and the refractive index n2 is small, and when the measurement wavelength is long, the difference Δn between the refractive index n1 and the refractive index n2 is large. In this manner, the reverse wavelength dispersive birefringence can be expressed from the main chain mesogen 1a and the side chain mesogen 1b.

In the formula (I), Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —S—, —O—C (═O) —, —C (═O) —. O—, —O—C (═O) —O—, —NR ¹ —C (═O) —, —C (═O) —NR ¹ —, —O—C (═O) —NR ¹ —, —NR ¹ —C (═O) —O—, —NR ¹ —C (═O) —NR ¹ —, —O—NR ¹ —, or —NR ¹ —O— is represented.

Here, R ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Examples of the alkyl group having 1 to 6 carbon atoms of R ¹ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a t-butyl group, an n-pentyl group, An n-hexyl group may be mentioned.
R ¹ is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In the compound (I), Y ^{1 to} Y ⁸ are each independently a chemical single bond, —O—, —O—C (═O) —, —C (═O) —O—, or , —O—C (═O) —O— is preferable.

In the formula (I), G ¹ and G ² each independently represent a divalent aliphatic group having 1 to 20 carbon atoms, which may have a substituent.
Examples of the divalent aliphatic group having 1 to 20 carbon atoms include a divalent aliphatic group having a chain structure such as an alkylene group having 1 to 20 carbon atoms and an alkenylene group having 2 to 20 carbon atoms; And divalent aliphatic groups such as a cycloalkanediyl group having 3 to 20 carbon atoms, a cycloalkenediyl group having 4 to 20 carbon atoms, and a divalent alicyclic fused ring group having 10 to 30 carbon atoms.

Examples of the substituent for the divalent aliphatic group represented by G ¹ and G ² include halogen atoms such as fluorine atom, chlorine atom, bromine atom and iodine atom; methoxy group, ethoxy group, n-propoxy group, isopropoxy group , An n-butoxy group, a sec-butoxy group, a t-butoxy group, an n-pentyloxy group, an n-hexyloxy group, or the like, or an alkoxy group having 1 to 6 carbon atoms. Of these, a fluorine atom, a methoxy group, and an ethoxy group are preferable.

The aliphatic group includes one or more —O—, —S—, —O—C (═O) —, —C (═O) —O—, —O—C per one aliphatic group. Even if (═O) —O—, —NR ² —C (═O) —, —C (═O) —NR ² —, —NR ² —, or —C (═O) — are present. Good. However, the case where two or more of -O- or -S- are adjacent to each other is excluded. Here, R ² represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and is preferably a hydrogen atom or a methyl group.
As the group intervening in the aliphatic group, —O—, —O—C (═O) —, —C (═O) —O—, and —C (═O) — are preferable.

Specific examples of the aliphatic group mediated by these groups include, for example, —CH ₂ —CH ₂ —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —S—CH ₂ —CH ₂ —, — _{CH 2 -CH 2 -O-C (} = O) -CH 2 -CH 2 -, - CH 2 -CH 2 -C (= O) -O-CH 2 -CH 2 -, - CH 2 -CH 2 - C (═O) —O—CH ₂ —, —CH ₂ —O—C (═O) —O—CH ₂ —CH ₂ —, —CH ₂ —CH ₂ —NR ² —C (═O) —CH _{2 -CH 2 -, - CH 2} -CH 2 -C (= O) -NR 2 -CH 2 -, - CH 2 -NR 2 -CH 2 -CH 2 -, - CH 2 -C (= O) - CH ₂ — may be mentioned.

Among these, G ¹ and G ² are each independently an alkylene group having 1 to 20 carbon atoms, an alkenylene group having 2 to 20 carbon atoms, or the like, from the viewpoint of better expressing the desired effect of the present invention. A divalent aliphatic group having a chain structure is preferable, and a methylene group, an ethylene group, a trimethylene group, a propylene group, a tetramethylene group, a pentamethylene group, a hexamethylene group, an octamethylene group, a decamethylene group [— (CH ₂ ) ₁₀ - a] and the like, more preferably an alkylene group having 1 to 12 carbon atoms, a tetramethylene group [- _{(CH 2) 4} -], hexamethylene group [- _{(CH 2) 6} -], octamethylene [- ( CH ₂ ) ₈ —] and decamethylene group [— (CH ₂ ) ₁₀ —] are particularly preferred.

In the formula (I), Z ¹ and Z ² each independently represent an alkenyl group having 2 to 10 carbon atoms which may be substituted with a halogen atom.
As carbon number of this alkenyl group, 2-6 are preferable. Examples of the halogen atom that is a substituent of the alkenyl group of Z ¹ and Z ² include a fluorine atom, a chlorine atom, a bromine atom, and the like, and a chlorine atom is preferable.

Specific examples of the alkenyl group having 2 to 10 carbon atoms of Z ¹ and Z ² include CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, CH ₂ ═CH—CH ₂ —, CH ₃ —CH═. _{CH-, CH 2 = CH-CH} 2 -CH 2 -, CH 2 = C (CH 3) -CH 2 -CH 2 -, (CH 3) 2 C = CH-CH 2 -, (CH 3) 2 C _{= CH-CH 2 -CH 2 -} , CH 2 = C (Cl) -, CH 2 = C (CH 3) -CH 2 -, CH 3 -CH = CH-CH 2 - and the like.

Especially, from a viewpoint of expressing the desired effect of the present invention better, Z ¹ and Z ² are each independently CH ₂ = CH-, CH ₂ = C (CH ₃ )-, CH ₂ = _{C (Cl) -, CH 2} = CH-CH 2 -, CH 2 = C (CH 3) -CH 2 -, _{or, CH 2 = C (CH 3} ) -CH 2 -CH 2 - are preferred, CH ₂ ═CH—, CH ₂ ═C (CH ₃ ) —, or CH ₂ ═C (Cl) — is more preferable, and CH ₂ ═CH— is particularly preferable.

In the formula (I), A ^x represents an organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. “Aromatic ring” means a cyclic structure having a broad sense of aromaticity according to the Huckle rule, that is, a cyclic conjugated structure having (4n + 2) π electrons, and sulfur, oxygen, typified by thiophene, furan, benzothiazole, etc. It means a cyclic structure in which a lone electron pair of a hetero atom such as nitrogen is involved in the π-electron system and exhibits aromaticity.

Of A ^x, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic organic group having 2 to 30 carbon atoms may be those having a plurality of aromatic rings And having both an aromatic hydrocarbon ring and an aromatic heterocycle.

  Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, and an anthracene ring. Examples of the aromatic heterocyclic ring include monocyclic aromatic heterocyclic rings such as a pyrrole ring, a furan ring, a thiophene ring, a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a pyrazole ring, an imidazole ring, an oxazole ring, and a thiazole ring; Benzothiazole ring, benzoxazole ring, quinoline ring, phthalazine ring, benzimidazole ring, benzopyrazole ring, benzofuran ring, benzothiophene ring, thiazolopyridine ring, oxazolopyridine ring, thiazolopyrazine ring, oxazolopyrazine ring, thia And a condensed aromatic heterocycle such as a zolopyridazine ring, an oxazolopyridazine ring, a thiazolopyrimidine ring, and an oxazolopyrimidine ring.

The aromatic ring of A ^x may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and carbon number 2 such as vinyl group and allyl group. -6 alkenyl groups; C 1-6 halogenated alkyl groups such as trifluoromethyl groups; substituted amino groups such as dimethylamino groups; C 1-6 alkoxys such as methoxy groups, ethoxy groups, and isopropoxy groups group; a nitro group; a phenyl group, an aryl group such as phenyl or ^{naphthyl; -C (= O) -R 5} ; -C (= O) -OR 5; -SO 2 R 6; and the like. Here, R ⁵ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms, and R ⁶ is the same as R ⁴ described later. An alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group is represented.

Further, the aromatic ring within A ^x may have a plurality of identical or different substituents, bonded two adjacent substituents together may form a ring. The ring formed may be a monocycle, a condensed polycycle, an unsaturated ring, or a saturated ring.
Furthermore, the “carbon number” of the organic group having 2 to 30 carbon atoms of A ^x means the total carbon number of the whole organic group not including the carbon atom of the substituent (the same applies to A ^y described later). .

Of A ^x, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring, examples of the organic group having 2 to 30 carbon atoms, for example, an aromatic hydrocarbon ring group, aromatic A heterocyclic group; a group containing a combination of an aromatic hydrocarbon ring and a heterocyclic ring; an alkyl group having 3 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring An alkenyl group having 4 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring; selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring And an alkynyl group having 4 to 30 carbon atoms having at least one aromatic ring.

Preferred specific examples of A ^x are shown below. However, ^Ax is not limited to the following. In the following formulae, “-” represents a bond extending from any position of the ring (the same applies hereinafter).
(1) Aromatic hydrocarbon ring group

  (2) Aromatic heterocyclic group

In the above formula, E represents NR ^6a , an oxygen atom or a sulfur atom. Here, R ^6a represents a hydrogen atom; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group.

In the above formulas, X and Y each independently represent NR ⁷ , an oxygen atom, a sulfur atom, —SO—, or —SO ₂ — (provided that an oxygen atom, a sulfur atom, —SO—, —SO _2- except when adjacent to each other). R ⁷ represents the same hydrogen atom as R ^6a ; or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group.

  (In the above formula, X represents the same meaning as described above.)

[In each formula, X ¹ represents —CH ₂ —, —NR ^c —, an oxygen atom, a sulfur atom, —SO— or —SO ₂ —, and E ¹ represents —NR ^c —, an oxygen atom or a sulfur atom. Represents. Here, R ^c represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms such as a methyl group, an ethyl group, or a propyl group. (However, in each formula, an oxygen atom, a sulfur atom, —SO—, and —SO ₂ — are not adjacent to each other.)]
(3) A group containing a combination of an aromatic hydrocarbon ring and a heterocyclic ring

(In the above formula, X and Y each independently represent the same meaning as described above. In the above formula, Z represents NR ⁷ , an oxygen atom, a sulfur atom, —SO—, or —SO _2. - a represents (wherein an oxygen atom, a sulfur atom, -SO -, - SO ₂ - is, unless the respective adjacent.)).
(4) an alkyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring

  (5) An alkenyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring

  (6) An alkynyl group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring

Among the A ^x as described above, an aromatic hydrocarbon ring group having 6 to 30 carbon atoms, an aromatic heterocyclic group having 4 to 30 carbon atoms or 4 carbon comprising a combination of an aromatic hydrocarbon ring and heterocyclic 30 groups are preferred, and any of the groups shown below is more preferred.

Further, A ^x is more preferably any of the groups shown below.

Ring within A ^x may have a substituent. Examples of the substituent include halogen atoms such as fluorine atom and chlorine atom; cyano group; alkyl group having 1 to 6 carbon atoms such as methyl group, ethyl group and propyl group; and carbon number 2 such as vinyl group and allyl group. -6 alkenyl groups; C 1-6 halogenated alkyl groups such as trifluoromethyl groups; substituted amino groups such as dimethylamino groups; C 1-6 alkoxys such as methoxy groups, ethoxy groups, and isopropoxy groups Group; nitro group; aryl group such as phenyl group and naphthyl group; -C (= O) -R ⁸ ; -C (= O) -OR ⁸ ; -SO ₂ R ⁶ ; Here, R ⁸ represents an alkyl group having 1 to 6 carbon atoms such as a methyl group or an ethyl group; or an aryl group having 6 to 14 carbon atoms such as a phenyl group. Especially, as a substituent, a halogen atom, a cyano group, a C1-C6 alkyl group, and a C1-C6 alkoxy group are preferable.

The ring of A ^x may have a plurality of the same or different substituents, and two adjacent substituents may be bonded together to form a ring. The ring formed may be a single ring or a condensed polycycle.
The “carbon number” of the organic group having 2 to 30 carbon atoms of A ^x means the total number of carbon atoms of the entire organic group not including the carbon atom of the substituent (the same applies to A ^y described later).

In the formula (I), A ^y is a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having from 3 to 12 carbon atoms which may have a substituent, which may have a substituent group an alkynyl group having a carbon number of ^{2~20, -C (= O) -R} 3, -SO 2 An organic group having 2 to 30 carbon atoms having at least one aromatic ring selected from the group consisting of —R ⁴ , —C (═S) NH—R ⁹ , or an aromatic hydrocarbon ring and an aromatic heterocyclic ring; Represent. Here, R ³ has an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. Or a C3-C12 cycloalkyl group or a C5-C12 aromatic hydrocarbon ring group. R ⁴ represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group. R ⁹ is an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon. The C3-C12 cycloalkyl group or the C5-C20 aromatic group which may have a substituent is represented.

Of A ^y, the alkyl group having 1 to 20 carbon atoms an alkyl group having 1 to 20 carbon atoms that may have a substituent, such as methyl group, ethyl group, n- propyl group, an isopropyl radical, n -Butyl group, isobutyl group, 1-methylpentyl group, 1-ethylpentyl group, sec-butyl group, t-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group, isohexyl group, n -Heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n -Heptadecyl group, n-octadecyl group, n-nonadecyl group, n-icosyl group are mentioned. The carbon number of the alkyl group having 1 to 20 carbon atoms which may have a substituent is preferably 1 to 12, and more preferably 4 to 10.

Examples of the alkenyl group having 2 to 20 carbon atoms that may have a substituent in A ^y include, for example, a vinyl group, a propenyl group, an isopropenyl group, a butenyl group, and an isobutenyl group. Pentenyl group, hexenyl group, heptenyl group, octenyl group, decenyl group, undecenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, pentadecenyl group, hexadecenyl group, heptadecenyl group, octadecenyl group, nonadecenyl group, icocenyl group. It is preferable that carbon number of the C2-C20 alkenyl group which may have a substituent is 2-12.

Of A ^y, a cycloalkyl group having 3 to 12 carbon atoms a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, A cyclooctyl group is mentioned.

Of A ^y, the alkynyl group having 2 to 20 carbon atoms alkynyl group having carbon atoms of 2 to 20 which may have a substituent, such as ethynyl group, propynyl group, 2-propynyl group (propargyl group), Butynyl, 2-butynyl, 3-butynyl, pentynyl, 2-pentynyl, hexynyl, 5-hexynyl, heptynyl, octynyl, 2-octynyl, nonanyl, decanyl, 7-decanyl Is mentioned.

Examples of the substituent of the alkyl group having 1 to 20 carbon atoms that may have a substituent and the alkenyl group having 2 to 20 carbon atoms that may have a substituent of A ^y include, for example, a fluorine atom Halogen atom such as chlorine atom; cyano group; substituted amino group such as dimethylamino group; alkoxy group having 1 to 20 carbon atoms such as methoxy group, ethoxy group, isopropoxy group, butoxy group; methoxymethoxy group, methoxyethoxy group A C1-C12 alkoxy group substituted with a C1-C12 alkoxy group; a nitro group; an aryl group such as a phenyl group or a naphthyl group; a carbon number such as a cyclopropyl group, a cyclopentyl group, or a cyclohexyl group A cycloalkyl group having 3 to 8 carbon atoms; a cycloalkyloxy group having 3 to 8 carbon atoms such as a cyclopentyloxy group and a cyclohexyloxy group; A cyclic ether group having 2 to 12 carbon atoms such as a ru group, a tetrahydropyranyl group, a dioxolanyl group and a dioxanyl group; an aryloxy group having 6 to 14 carbon atoms such as a phenoxy group and a naphthoxy group; a trifluoromethyl group and pentafluoroethyl A fluoroalkoxy group having 1 to 12 carbon atoms in which at least one is substituted with a fluorine atom, such as a group, —CH ₂ CF ₃ ; benzofuryl group; benzopyranyl group; benzodioxolyl group; benzodioxanyl group; _{^{(= O) -R 7a; -C}} (= O) -OR 7a; alkoxy group ^{-SR 10} carbon atoms substituted with ^{1~12;; -SO 2 R 8a;} -SR 10 hydroxyl; and the like. Here, R ^7a and R ¹⁰ are each independently an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or 6 to 12 carbon atoms. Represents an aromatic hydrocarbon ring group. R ^8a represents an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group, similar to R ⁴ described above.

Examples of the substituent of the cycloalkyl group having 3 to 12 carbon atoms that may have a substituent for A ^y include, for example, a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; a substituted amino group such as a dimethylamino group Groups: alkyl groups having 1 to 6 carbon atoms such as methyl, ethyl, and propyl groups; alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, and isopropoxy groups; nitro groups; phenyl groups, naphthyl groups, and the like A cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group; —C (═O) —R ^7a ; —C (═O) —OR ^7a ; —SO ₂ R ^8a A hydroxyl group. Here, R ^7a and R ^8a represent the same meaning as described above.

Examples of the substituent of the alkynyl group having 2 to 20 carbon atoms that may have a substituent of A ^y include, for example, an alkyl group having 1 to 20 carbon atoms that may have a substituent, and substitution. The same substituent as the substituent of the C2-C20 alkenyl group which may have a group is mentioned.

In the group of A ^y represented by —C (═O) —R ³ , R ³ may have a substituent, an alkyl group having 1 to 20 carbon atoms, or a substituent. It represents a good alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring group having 5 to 12 carbon atoms. Specific examples of these include 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 a substituent of the above ^Ay. a cycloalkyl group having from 3 to 12 carbon atoms which may have a group; and, the same as the number of carbon atoms of the aromatic hydrocarbon ring group described in the a ^x is given as an example of what the 5-12 Things.

Of A ^y, in the group represented by _-SO 2 -R ^{4, R 4} is an alkyl group having 1 to 20 carbon atoms, an alkenyl group having 2 to 20 carbon atoms, a phenyl group, or a 4-methylphenyl group Represent. Specific examples of the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of R ⁴ include the alkyl group having 1 to 20 carbon atoms and the alkenyl group having 2 to 20 carbon atoms of the above ^Ay . The thing similar to what was mentioned as an example is mentioned.

In the group of A ^y represented by —C (═S) NH—R ⁹ , R ⁹ has an optionally substituted alkyl group having 1 to 20 carbon atoms and a substituent. May be an alkenyl group having 2 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, or an aromatic group having 5 to 20 carbon atoms which may have a substituent. Represents. Specific examples of these include 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 a substituent of the above ^Ay. has also been a good 3 to 12 carbon atoms a cycloalkyl group; and the carbon number of the aromatic group and aromatic hydrocarbon ring group and the aromatic heterocyclic group described for a ^x is 5-20 The thing similar to what was mentioned as an example of a thing is mentioned.

Of A ^y, having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and aromatic heterocyclic ring, examples of the organic group having 2 to 30 carbon atoms, the same as those described in the A ^x Is mentioned.

Among these, as ^Ay , a hydrogen atom, 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 a substituent A cycloalkyl group having 3 to 12 carbon atoms which may have an alkynyl group having 2 to 20 carbon atoms which may have a substituent, —C (═O) —R ³ , —SO ₂ —R ⁴ or a group represented by an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Further, ^Ay includes a hydrogen atom, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and a substituent. An optionally substituted cycloalkyl group having 3 to 12 carbon atoms, an optionally substituted alkynyl group having 2 to 20 carbon atoms, and an aromatic carbon atom having 6 to 12 carbon atoms that may have a substituent. 3 to 9 carbon atoms including a combination of a hydrogen ring group, an aromatic heterocyclic group having 3 to 9 carbon atoms which may have a substituent, and an aromatic hydrocarbon ring and heterocyclic ring which may have a substituent. The group represented by the group 9, —C (═O) —R ³ , —SO ₂ —R ⁴ is more preferable. Here, R ³ and R ⁴ represent the same meaning as described above.

^Ay , an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 2 to 20 carbon atoms, and an optionally substituted carbon As a substituent of the alkynyl group having 2 to 20 carbon atoms, a halogen atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, an alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms, phenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, benzodioxanyl group, phenylsulfonyl group, 4-methyl phenylsulfonyl group, a benzoyl group, ^{-SR 10} Is preferred. Here, R ¹⁰ represents the same meaning as described above.

^Ay has a cycloalkyl group having 3 to 12 carbon atoms which may have a substituent, an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent, and a substituent. Examples of the substituent for the group having 3 to 9 carbon atoms, which may have an aromatic heterocyclic group having 3 to 9 carbon atoms, and may include a combination of an aromatic hydrocarbon ring and a heterocyclic ring, include fluorine An atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, and a cyano group are preferable.

A ^x and A ^y may be combined to form a ring. Examples of such a ring include an unsaturated heterocyclic ring having 4 to 30 carbon atoms and an unsaturated carbocyclic ring having 6 to 30 carbon atoms, which may have a substituent.

The unsaturated heterocyclic ring having 4 to 30 carbon atoms and the unsaturated heterocyclic ring having 6 to 30 carbon atoms are not particularly limited and may or may not have aromaticity.
Examples of the ring formed by combining A ^x and A ^y include the rings shown below. In addition, the ring shown below is the one in the formula (I)

  The part represented as is shown.

(In the formula, X, Y and Z have the same meaning as described above.)
Moreover, these rings may have a substituent. Such substituent groups include the same as those described as substituents of the aromatic ring within A ^x.

The total number of π electrons contained in A ^x and A ^y is preferably 4 or more, more preferably 6 or more, preferably 24 or less, more preferably from the viewpoint of better expressing the desired effect of the present invention. 20 or less, particularly preferably 18 or less.

Preferred combinations of A ^x and A ^y include the following combination (α) and combination (β).
(Α) A ^x is a group containing 4 to 30 carbon atoms, an aromatic hydrocarbon ring group, an aromatic heterocyclic group, or a combination of an aromatic hydrocarbon ring and a heterocyclic ring, and A ^y is a hydrogen atom, A cycloalkyl group having 3 to 8 carbon atoms (a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cycloalkyl group having 3 to 8 carbon atoms) as a substituent An aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have (halogen atom, alkyl group having 1 to 6 carbon atoms, alkoxy group having 1 to 6 carbon atoms, cyano group) as a substituent And optionally having an aromatic heterocyclic group having 3 to 9 carbon atoms (a halogen atom, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, or a cyano group) as a substituent. 3-9 carbon atoms often containing a combination of aromatic hydrocarbon rings and heterocyclic rings Group, an optionally substituted alkyl group having 1 to 20 carbon atoms, an optionally substituted alkenyl group having 1 to 20 carbon atoms, or an optionally substituted group. An alkoxy group having 2 to 20 carbon atoms, and the substituent is a halogen atom, a cyano group, an alkoxy group having 1 to 20 carbon atoms, or an alkoxy group having 1 to 12 carbon atoms substituted with an alkoxy group having 1 to 12 carbon atoms group, a phenyl group, a cyclohexyl group, a cyclic ether group having 2 to 12 carbon atoms, an aryloxy group having 6 to 14 carbon atoms, a hydroxyl group, benzodioxanyl group, benzenesulfonyl group, with either a benzoyl group, and -SR ¹⁰ A combination.
(Β) A combination in which A ^x and A ^y together form an unsaturated heterocyclic ring or unsaturated carbocyclic ring.
Here, R ¹⁰ represents the same meaning as described above.

More preferable combinations of A ^x and A ^y include the following combination (γ).
(Γ) A ^x is any of the groups having the following structure, and A ^y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, (a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, carbon An aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms as a substituent, (halogen atom, 1 to carbon atoms) An aromatic heterocyclic group having 3 to 9 carbon atoms which may have 6 alkyl groups, an alkoxy group having 1 to 6 carbon atoms, or a cyano group as a substituent, (halogen atom, alkyl having 1 to 6 carbon atoms) Group, an alkoxy group having 1 to 6 carbon atoms, a cyano group) as a substituent, and a group having 3 to 9 carbon atoms including a combination of an aromatic hydrocarbon ring and a heterocyclic ring, or a substituent. Even if it has a C1-C20 alkyl group and a substituent which may be A good alkenyl group having 1 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms which may have a substituent, and the substituent is a halogen atom, a cyano group or an alkoxy having 1 to 20 carbon atoms. Group, a C1-C12 alkoxy group substituted with a C1-C12 alkoxy group, a phenyl group, a cyclohexyl group, a C2-C12 cyclic ether group, a C6-C14 aryloxy group, a hydroxyl group , benzodioxanyl group, a benzenesulfonyl group, a benzoyl group, a combination is either -SR ^10. Here, R ¹⁰ represents the same meaning as described above.

(In the formula, X and Y have the same meaning as described above.)
A particularly preferred combination of A ^x and A ^y includes the following combination (δ).
(Δ) A ^x is any of the groups having the following structure, and A ^y is a hydrogen atom, a cycloalkyl group having 3 to 8 carbon atoms, (a halogen atom, a cyano group, an alkyl group having 1 to 6 carbon atoms, carbon An aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have an alkoxy group having 1 to 6 carbon atoms or a cycloalkyl group having 3 to 8 carbon atoms as a substituent, (halogen atom, 1 to carbon atoms) An aromatic heterocyclic group having 3 to 9 carbon atoms which may have 6 alkyl groups, an alkoxy group having 1 to 6 carbon atoms, or a cyano group as a substituent, (halogen atom, alkyl having 1 to 6 carbon atoms) Group, an alkoxy group having 1 to 6 carbon atoms, a cyano group) as a substituent, and a group having 3 to 9 carbon atoms including a combination of an aromatic hydrocarbon ring and a heterocyclic ring, or a substituent. Even if it has a C1-C20 alkyl group and a substituent which may be A good alkenyl group having 1 to 20 carbon atoms or an alkynyl group having 2 to 20 carbon atoms which may have a substituent, and the substituent is a halogen atom, a cyano group or an alkoxy having 1 to 20 carbon atoms. Group, a C1-C12 alkoxy group substituted with a C1-C12 alkoxy group, a phenyl group, a cyclohexyl group, a C2-C12 cyclic ether group, a C6-C14 aryloxy group, a hydroxyl group , benzodioxanyl group, a benzenesulfonyl group, a benzoyl group, and the combination is either -SR ^10. In the following formula, X represents the same meaning as described above. Here, R ¹⁰ represents the same meaning as described above.

In the formula (I), A ¹ represents a trivalent aromatic group which may have a substituent. The trivalent aromatic group may be a trivalent carbocyclic aromatic group or a trivalent heterocyclic aromatic group. From the viewpoint of better expressing the desired effect of the present invention, a trivalent carbocyclic aromatic group is preferable, a trivalent benzene ring group or a trivalent naphthalene ring group is more preferable, and a trivalent represented by the following formula: The benzene ring group or trivalent naphthalene ring group is more preferable. In the following formula, the substituents Y ¹ and Y ² are described for convenience in order to clarify the bonding state (Y ¹ and Y ² represent the same meaning as described above, and the same applies hereinafter). .

Among these, the ^{A 1,} and more preferably a group represented by the formula (A11) ~ (A25) shown below, equation (A11), (A13), (A15), in (A19), (A23) Groups represented by formulas (A11) and (A23) are particularly preferred.

Examples of the substituent that the trivalent aromatic group of A ¹ may have include the same groups as those described as the substituent of the aromatic ring of A ^x . A ¹ preferably has no substituent.

In the formula (I), A ² and A ³ each independently represent a C 3-30 divalent alicyclic hydrocarbon group which may have a substituent. Examples of the divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms include a cycloalkanediyl group having 3 to 30 carbon atoms and a divalent alicyclic condensed ring group having 10 to 30 carbon atoms.

  Examples of the cycloalkanediyl group having 3 to 30 carbon atoms include cyclopropanediyl group; cyclobutanediyl group such as cyclobutane-1,2-diyl group and cyclobutane-1,3-diyl group; cyclopentane-1,2- Cyclopentanediyl group such as diyl group, cyclopentane-1,3-diyl group; cyclohexanediyl group such as cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, cyclohexane-1,4-diyl group Groups: cycloheptane-1,2-diyl group, cycloheptane-1,3-diyl group, cycloheptanediyl group such as cycloheptane-1,4-diyl group; cyclooctane-1,2-diyl group, cyclooctane Cyclooctane such as -1,3-diyl group, cyclooctane-1,4-diyl group, cyclooctane-1,5-diyl group, etc. Cyclodecane-1, 2-diyl group, cyclodecane-1,3-diyl group, cyclodecane-1,4-diyl group, cyclodecane-1,5-diyl group and the like; cyclododecane-1, Cyclododecanediyl groups such as 2-diyl group, cyclododecane-1,3-diyl group, cyclododecane-1,4-diyl group, cyclododecane-1,5-diyl group; cyclotetradecane-1,2-diyl group Cyclotetradecane-1,3-diyl group, cyclotetradecane-1,4-diyl group, cyclotetradecane-1,5-diyl group, cyclotetradecane-1,7-diyl group and the like; cycloeicosane And cycloeicosanediyl groups such as -1,2-diyl group and cycloeicosane-1,10-diyl group.

  Examples of the divalent alicyclic fused ring group having 10 to 30 carbon atoms include decalindiyl groups such as decalin-2,5-diyl group and decalin-2,7-diyl group; adamantane-1,2-diyl group An adamantanediyl group such as an adamantane-1,3-diyl group; a bicyclo [2.2.1] heptane-2,3-diyl group, a bicyclo [2.2.1] heptane-2,5-diyl group And bicyclo [2.2.1] heptanediyl group such as bicyclo [2.2.1] heptane-2,6-diyl group.

These divalent alicyclic hydrocarbon groups may have a substituent at any position. Examples of the substituent include the same as those described as substituents of the aromatic ring of the A ^x.

Among these, the ^{A 2} and ^{A 3,} preferably a divalent alicyclic hydrocarbon group having 3 to 12 carbon atoms, more preferably a cycloalkane-diyl group having 3 to 12 carbon atoms, following formula (A31) ~ A group represented by (A34) is more preferred, and a group represented by the following formula (A32) is particularly preferred.

The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms is based on a difference in configuration of carbon atoms bonded to Y ¹ and Y ³ (or Y ² and Y ⁴ ). Stereoisomers can exist. For example, in the case of a cyclohexane-1,4-diyl group, as shown below, a cis-type isomer (A32a) and a trans-type isomer (A32b) may exist.

  The divalent alicyclic hydrocarbon group having 3 to 30 carbon atoms may be cis, trans, or a mixture of cis and trans isomers. Of these, the trans-type or cis-type is preferable because the orientation is good, and the trans-type is more preferable.

In the formula (I), A ⁴ and A ⁵ each independently represent a C 6-30 divalent aromatic group which may have a substituent. The aromatic groups of A ⁴ and A ⁵ may be monocyclic or polycyclic. Preferable specific examples of A ⁴ and A ⁵ include the following.

The divalent aromatic groups of A ⁴ and A ⁵ may have a substituent at any position. Examples of the substituent include a halogen atom, a cyano group, a hydroxyl group, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, a nitro group, and a —C (═O) —OR ^8b group. Can be mentioned. Here, R ^8b is an alkyl group having 1 to 6 carbon atoms. Especially, as a substituent, a halogen atom, a C1-C6 alkyl group, and an alkoxy group are preferable. Moreover, as a halogen atom, a fluorine atom is more preferable, As a C1-C6 alkyl group, a methyl group, an ethyl group, and a propyl group are more preferable, As a alkoxy group, a methoxy group and an ethoxy group are more preferable.

Among these, from the viewpoint of better expressing the desired effect of the present invention, A ⁴ and A ⁵ may each independently have a substituent, and the following formulas (A41) and (A42) Or the group represented by (A43) is more preferable, and the group represented by the formula (A41) which may have a substituent is particularly preferable.

In the formula (I), Q ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. As a C1-C6 alkyl group which may have a substituent, C1-C20 among the C1-C20 alkyl groups which may have a substituent ^demonstrated by said ^Ay. ~ 6. Among these, Q ¹ is preferably an alkyl group having a hydrogen atom and 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group.

  In the formula (I), m and n each independently represents 0 or 1. Among these, m is preferably 1, and n is preferably 1.

  Compound (I) can be produced, for example, by the reaction shown below.

^{(Wherein, Y 1 ~Y 8, G 1} , G 2, Z 1, Z 2, A x, A y, A 1 ~A 5, Q 1, m and n are as defined above.)

  As shown in the above reaction formula, compound (I) can be produced by reacting the hydrazine compound represented by formula (3) with the carbonyl compound represented by formula (4). Hereinafter, the hydrazine compound represented by the formula (3) may be referred to as “hydrazine compound (3)” as appropriate. In addition, the carbonyl compound represented by the formula (4) may be referred to as “carbonyl compound (4)” as appropriate.

  In the above reaction, the molar ratio of “hydrazine compound (3): carbonyl compound (4)” is preferably 1: 2 to 2: 1, more preferably 1: 1.5 to 1.5: 1. By reacting at such a molar ratio, the target compound (I) can be produced with high selectivity and high yield.

  In this case, the reaction system may contain an acid catalyst such as an organic acid such as (±) -10-camphorsulfonic acid and paratoluenesulfonic acid; an inorganic acid such as hydrochloric acid and sulfuric acid; By using an acid catalyst, the reaction time may be shortened and the yield may be improved. The amount of the acid catalyst is usually 0.001 mol to 1 mol with respect to 1 mol of the carbonyl compound (4). Moreover, an acid catalyst may be mix | blended with a reaction system as it is, and may be mix | blended as a solution dissolved in the appropriate solution.

  As a solvent used in this reaction, a solvent inert to the reaction can be used. Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol; diethyl ether, tetrahydrofuran, 1, Ether solvents such as 2-dimethoxyethane, 1,4-dioxane and cyclopentyl methyl ether; ester solvents such as ethyl acetate, propyl acetate and methyl propionate; aromatic hydrocarbon solvents such as benzene, toluene and xylene; n -Aliphatic hydrocarbon solvents such as pentane, n-hexane and n-heptane; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide; dimethyl sulfoxide, sulfolane and the like Sulfur-containing solvents; and mixed solvents of two or more thereof; and the like. Among these, alcohol solvents, ether solvents, and mixed solvents of alcohol solvents and ether solvents are preferable.

  The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-100g normally with respect to 1g of hydrazine compounds (3).

  The reaction can usually proceed smoothly in a temperature range of −10 ° C. or higher and lower than the boiling point of the solvent used. The reaction time for each reaction depends on the reaction scale, but is usually from several minutes to several hours.

  The hydrazine compound (3) can be produced as follows.

(In the formula, A ^x and A ^y represent the same meaning as described above. X ^a represents ^a leaving group such as a halogen atom, a methanesulfonyloxy group, and a p-toluenesulfonyloxy group.)

  As shown in the above reaction formula, the corresponding hydrazine compound (3a) can be obtained by reacting the compound represented by formula (2a) with hydrazine (1) in an appropriate solvent. The molar ratio of “compound (2a): hydrazine (1)” in this reaction is preferably 1: 1 to 1:20, more preferably 1: 2 to 1:10. Furthermore, the hydrazine compound (3) can be obtained by reacting the hydrazine compound (3a) with the compound represented by the formula (2b).

  As the hydrazine (1), a monohydrate can be usually used. As the hydrazine (1), a commercially available product can be used as it is.

  As a solvent used in this reaction, a solvent inert to the reaction can be used. Examples of the solvent include alcohol solvents such as methyl alcohol, ethyl alcohol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, sec-butyl alcohol, t-butyl alcohol; diethyl ether, tetrahydrofuran, 1, Ether solvents such as 2-dimethoxyethane, 1,4-dioxane and cyclopentyl methyl ether; aromatic hydrocarbon solvents such as benzene, toluene and xylene; aliphatic carbonization such as n-pentane, n-hexane and n-heptane Hydrogen solvents; amide solvents such as N, N-dimethylformamide, N-methylpyrrolidone and hexamethylphosphoric triamide; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; and a mixed solvent composed of two or more of these solvents Cited . Among these, alcohol solvents, ether solvents, and mixed solvents of alcohol solvents and ether solvents are preferable.

  The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-100g normally with respect to 1g of hydrazine.

  The reaction can usually proceed smoothly in a temperature range of −10 ° C. or higher and lower than the boiling point of the solvent used. The reaction time for each reaction depends on the reaction scale, but is usually from several minutes to several hours.

  The hydrazine compound (3) can also be produced by reducing the diazonium salt (5) using a known method as follows.

In formula (5), A ^x and A ^y represent the same meaning as described above. X ^b− represents an anion which is a counter ion for diazonium. Examples of ^Xb- include inorganic anions such as hexafluorophosphate ion, borofluoride ion, chloride ion, sulfate ion; polyfluoroalkylcarboxylate ion, polyfluoroalkylsulfonate ion, tetraphenylborate Organic anions such as ions, aromatic carboxylate ions, and aromatic sulfonate ions.

  As a reducing agent used for the said reaction, a metal salt reducing agent is mentioned, for example. The metal salt reducing agent is generally a compound containing a low-valent metal, or a compound comprising a metal ion and a hydride source (“Organic Synthesis Experiment Handbook” 1990, published by Maruzen Co., Ltd., edited by the Society of Synthetic Organic Chemistry, Japan) Page).

Examples of the metal salt reducing agent include NaAlH ₄ , NaAlH _p (Or) _q (p and q each independently represent an integer of 1 to 3, and p + q = 4. R is 1 to 6 carbon atoms. And LiAlH ₄ , iBu ₂ AlH, LiBH ₄ , NaBH ₄ , SnCl ₂ , CrCl ₂ , and TiCl ₃ . Here, “iBu” represents an isobutyl group.

In the reduction reaction, known reaction conditions can be employed. For example, the reaction can be performed under the conditions described in Japanese Patent Application Laid-Open No. 2005-336103, New Experimental Chemistry Course, 1978, published by Maruzen Co., Ltd., Volume 14, Experimental Chemical Course, 1992, published by Maruzen Co., Ltd.
The diazonium salt (5) can be produced from a compound such as aniline by a conventional method.

  The carbonyl compound (4) includes, for example, an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), a carbonate bond (—O—C (= O) -O-) and amide bond (-C (= O) -NH-, -NH-C (= O)-) are arbitrarily combined to appropriately combine a plurality of known compounds having a desired structure. It can be produced by binding to and modifying.

Formation of an ether bond can be performed as follows.
(I) A compound represented by the formula: D1-hal (hal represents a halogen atom; the same shall apply hereinafter) and a formula: D2-OMet (Met represents an alkali metal (mainly sodium). The same) is mixed and condensed (Williamson synthesis). In the formula, D1 and D2 represent arbitrary organic groups (the same applies hereinafter).
(Ii) A compound represented by the formula: D1-hal and a compound represented by the formula: D2-OH are mixed and condensed in the presence of a base such as sodium hydroxide or potassium hydroxide.
(Iii) A compound represented by the formula: D1-J (J represents an epoxy group) and a compound represented by the formula: D2-OH in the presence of a base such as sodium hydroxide or potassium hydroxide, Mix and condense.
(Iv) A compound represented by the formula: D1-OFN (OFN represents a group having an unsaturated bond) and a compound represented by the formula: D2-OMet, such as sodium hydroxide, potassium hydroxide, etc. In the presence of a base, they are mixed and subjected to an addition reaction.
(V) A compound represented by the formula: D1-hal and a compound represented by the formula: D2-OMet are mixed and condensed in the presence of copper or cuprous chloride (Ullman condensation).

Formation of an ester bond and an amide bond can be performed as follows.
(Vi) formula: a compound represented by D1-COOH, wherein: the D2-OH or D2-NH is represented by ₂ compounds, dehydrated in the presence of a dehydrating condensing agent (N, N-dicyclohexylcarbodiimide, etc.) Allow to condense.
(Vii) A compound represented by the formula: D1-CO-hal is obtained by allowing a halogenating agent to act on the compound represented by the formula: D1-COOH, and this is combined with the formula: D2-OH or D2- The compound represented by NH ₂ is reacted in the presence of a base.
(Viii) Formula: by the action of an acid anhydride to a compound represented by D1-COOH, after obtaining a mixed acid anhydride, the ones with the formula: D2-OH or a compound represented by D2-NH ₂ And react.
(Ix) formula: a compound represented by D1-COOH, wherein: the D2-OH or a compound represented by D2-NH _2, dehydration condensation in the presence of an acid catalyst or base catalyst.

  More specifically, the carbonyl compound (4) can be produced by the method shown in the following reaction formula.

(Wherein, Y ^{1 to} Y ⁸ , G ¹ , G ² , Z ¹ , Z ² , A ^{1 to} A ⁵ , Q ¹ , m and n represent the same meaning as described above. L ¹ and L ² are independently, a hydroxyl group, a halogen atom, a methanesulfonyloxy group, p- toluenesulfonyl represents a leaving group such as a group.-Y ^1b is reacted with -L ¹ -Y 1 ^- represents the result can group, -Y ^2b reacts with -L ² -Y ² - represents a and becomes capable group).

  As shown in the above reaction formula, an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), or a carbonate bond (—O—). By using the formation reaction of C (═O) —O—), the compound represented by the formula (6d) is converted into the compound represented by the formula (7a), and then the compound represented by the formula (7b). The carbonyl compound (4) can be produced by reaction.

As a specific example, Y ¹ is a group represented by the formula: Y ¹¹ —C (═O) —O—, and the formula: Z ² —Y ⁸ —G ² —Y ⁶ —A ⁵ — (Y ⁴ -A ³⁾ _m -Y ² - is a group represented by the ^{formula: Z 1 -Y 7 -G 1 -Y} 5 -A 4 - is represented by _{^{- (Y 3 -A 2) n}} -Y 1 The production method of the compound (4 ′) which is the same as the group is shown below.

(Wherein Y ³ , Y ⁵ , Y ⁷ , G ¹ , Z ¹ , A ¹ , A ² , A ⁴ , Q ¹ , n and L ¹ represent the same meaning as described above. Y ¹¹ represents Y ^11. -C (= O) -O- represents a group that becomes Y ^1. Y ¹ represents the same meaning as described above.

  As shown in the above reaction formula, the compound by reacting the dihydroxy compound represented by formula (6) (compound (6)) and the compound represented by formula (7) (compound (7)) is obtained. (4 ′) can be produced. The molar ratio of “compound (6): compound (7)” in this reaction is preferably 1: 2 to 1: 4, more preferably 1: 2 to 1: 3. By reacting at such a molar ratio, the target compound (4 ') can be obtained with high selectivity and high yield.

When compound (7) is a compound (carboxylic acid) in which L ¹ is a hydroxyl group, in the presence of a dehydration condensing agent such as 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride or dicyclohexylcarbodiimide. The target product can be obtained by reacting with. The amount of the dehydrating condensing agent to be used is generally 1 mol-3 mol with respect to 1 mol of compound (7).

When the compound (7) is a compound (carboxylic acid) in which L ¹ is a hydroxyl group, sulfonyl halides such as methanesulfonyl chloride and p-toluenesulfonyl chloride, and triethylamine, diisopropylethylamine, pyridine, 4- ( The target product can also be obtained by reacting in the presence of a base such as (dimethylamino) pyridine. The usage-amount of a sulfonyl halide is 1 mol-3 mol normally with respect to 1 mol of compounds (7). Moreover, the usage-amount of a base is 1 mol-3 mol normally with respect to 1 mol of compounds (7). In this case, in the formula (7), a compound (mixed acid anhydride) in which L ¹ is a sulfonyloxy group may be isolated and the following reaction may be performed.

Furthermore, when the compound (7) is a compound (acid halide) in which L ¹ is a halogen atom, the desired product can be obtained by reacting in the presence of a base. Examples of the base include organic bases such as triethylamine and pyridine; and inorganic bases such as sodium hydroxide, sodium carbonate, and sodium bicarbonate. The amount of the base to be used is generally 1 mol to 3 mol per 1 mol of compound (7).

Examples of the solvent used in the above reaction include chlorine solvents such as chloroform and methylene chloride; amide solvents such as N-methylpyrrolidone, N, N-dimethylformamide, N, N-dimethylacetamide, and hexamethylphosphate triamide; Ether solvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; aromatic hydrocarbon solvents such as benzene, toluene and xylene; Aliphatic hydrocarbon solvents such as n-pentane, n-hexane and n-octane; Alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane; and mixed solvents composed of two or more of these solvents; It is done.
The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-50g normally with respect to 1g of hydroxy compounds (6).

  Most of the compound (6) is a known substance and can be produced by a known method. For example, it can be produced by the method shown in the following reaction formula (see International Publication No. 2009/042544 and The Journal of Organic Chemistry, 2011, 76, 8082-8087, etc.). What is marketed as compound (6) may be purified if desired.

(Wherein A ¹ and Q ¹ represent the same meaning as described above, A ^1b represents a divalent aromatic group that can be converted to A ¹ by formylation or acylation, and R ′ represents methyl. And a hydroxyl-protecting group such as an alkyl group having 1 to 6 carbon atoms such as a group and an ethyl group, and an alkoxyalkyl group having 2 to 6 carbon atoms such as a methoxymethyl group.)

As shown in the above reaction formula, the hydroxy group of the dihydroxy compound (1,4-dihydroxybenzene, 1,4-dihydroxynaphthalene, etc.) represented by the formula (6a) is alkylated to represent the formula (6b). To obtain a compound. Thereafter, the ortho-position of the OR ′ group is formylated or acylated by a known method to obtain a compound represented by the formula (6c). And the target compound (6) can be manufactured by deprotecting (dealkylating) this thing.
In addition, as the compound (6), a commercially available product may be used as it is or after purification as desired.

  Many of the compounds (7) are known compounds such as an ether bond (—O—), an ester bond (—C (═O) —O—, —O—C (═O) —), a carbonate bond (— A plurality of compounds having a desired structure by arbitrarily combining the formation reaction of O—C (═O) —O—) and amide bond (—C (═O) —NH—, —NH—C (═O) —) Can be produced by appropriately binding and modifying the known compounds.

  For example, when the compound (7) is a compound represented by the following formula (7 ′) (compound (7 ′)), a dicarboxylic acid represented by the formula (9 ′) (compound (9 ′)) Can be used as follows.

(Wherein Y ⁵ , Y ⁷ , G ¹ , Z ¹ , A ² , A ⁴ and Y ¹¹ represent the same meaning as described above. Y ¹² represents —O—C (═O) —Y ¹² represents Y. .R representing the ³ become group, an alkyl group such as a methyl group, an ethyl group, represents a); phenyl, p- aryl group which may have a substituent such as a methyl phenyl group.

First, the compound (9 ′) is reacted with a sulfonyl chloride represented by the formula (10) in the presence of a base such as triethylamine or 4- (dimethylamino) pyridine. Next, the reaction is performed by adding the compound (8) and a base such as triethylamine or 4- (dimethylamino) pyridine to the reaction mixture.
The amount of sulfonyl chloride to be used is generally 0.5 equivalent to 0.7 equivalent relative to 1 equivalent of compound (9 ′).
Moreover, the usage-amount of a compound (8) is 0.5 equivalent-0.6 equivalent normally with respect to 1 equivalent of compound (9 ').
The usage-amount of a base is 0.5 equivalent-0.7 equivalent normally with respect to 1 equivalent of compounds (9 ').
The reaction temperature is 20 ° C. to 30 ° C., and the reaction time is several minutes to several hours, depending on the reaction scale and the like.

As a solvent used for the said reaction, what was illustrated as a solvent which can be used when manufacturing the said compound (4 ') is mentioned. Of these, ether solvents are preferred.
The amount of the solvent used is not particularly limited and can be set in consideration of the type of compound used, reaction scale, and the like. The specific usage-amount of a solvent is 1g-50g normally with respect to 1g of compounds (9 ').

In any reaction, after the reaction is completed, normal post-treatment operations in organic synthetic chemistry can be performed. If desired, the desired product can be isolated by performing known separation and purification methods such as column chromatography, recrystallization, and distillation.
The structure of the target compound can be identified by measurement of NMR spectrum, IR spectrum, mass spectrum, etc., elemental analysis or the like.

[4. Fluorosurfactant]
The fluorosurfactant has a predetermined range of 1-octanol / water partition coefficient. In the following description, the 1-octanol / water partition coefficient may be referred to as “logP” as appropriate. The specific log P range of the fluorosurfactant is usually 4.8 or more, usually 6.7 or less, preferably 6.3 or less. When the log P of the fluorosurfactant is at least the lower limit of the above range, the occurrence of alignment defects in the liquid crystal cured layer can be suppressed. Further, when the log P of the fluorosurfactant is not more than the upper limit of the above range, a specific structure of the liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction can be realized.

The log P of the fluorosurfactant can be measured by the following measuring method.
A sample solution containing 1% by weight of a fluorosurfactant was prepared, and HPLC / ELSD was a method generally compliant with JIS 7260-117: 2006 {measurement of partition coefficient (1-octanol / water)-high performance liquid chromatography}. Analysis (high performance liquid chromatography / evaporative light scattering detection analysis) is performed to determine the elution time (rt). On the other hand, a labeled compound having a known log P value described in JIS 7260-117: 2006 was subjected to HPLC / ELSD analysis in the same manner as the above-mentioned fluorosurfactant, and the elution time (rt) was determined. taking measurement. Based on the measurement result of the labeled compound, a calibration curve showing the relationship between the elution time and logP is prepared. Thereafter, the logP of the fluorosurfactant is determined by applying the elution time measured for the fluorosurfactant to the calibration curve.
As specific conditions for this measurement method, conditions detailed in the description of the examples may be employed.

The fluorosurfactant can contain a fluoroalkyl group. The fluoroalkyl group is preferably a perfluoroalkyl group, particularly preferably a —C ₆ F ₁₃ group, from the viewpoint of remarkably obtaining the desired effect of the present invention.

  The fluorinated surfactant is preferably a nonionic surfactant. When the fluorosurfactant having a log P in the above range is a nonionic surfactant containing no ionic group, the surface state and orientation of the liquid crystal cured layer can be made particularly good.

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

  Examples of the fluorine-based surfactant include Surflon series (S420, etc.) manufactured by AGC Seimi Chemical Co., and Footgent series (251, FTX209, etc.) manufactured by Neos. Moreover, a fluorine-type surfactant may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  The amount of the fluorosurfactant is preferably 0.11 parts by weight or more, more preferably 0.12 parts by weight or more, with respect to 100 parts by weight of the total of the first liquid crystal compound and the second liquid crystal compound. Preferably it is 0.29 weight part or less, More preferably, it is 0.25 weight part or less, More preferably, it is 0.20 weight part or less. By keeping the amount of the fluorosurfactant in the above range, a liquid crystal cured layer in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction and the alignment defects are few can be easily obtained. .

[5. Arbitrary ingredients]
The liquid crystal composition may further contain an optional component in combination with the first liquid crystal compound, the second liquid crystal compound, and the fluorosurfactant. These arbitrary components may be used individually by 1 type, and may be used combining two or more types by arbitrary ratios.

  For example, the liquid crystal composition can include a solvent. As a solvent, what can melt | dissolve a 1st liquid crystalline compound, a 2nd liquid crystalline compound, and a fluorine-type surfactant is preferable. As such a solvent, an organic solvent is usually used. Examples of organic solvents include ketone solvents such as cyclopentanone, cyclohexanone, methyl ethyl ketone, acetone and methyl isobutyl ketone; acetate solvents such as butyl acetate and amyl acetate; halogenated hydrocarbon solvents such as chloroform, dichloromethane and dichloroethane; 1 , 4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, 1,3-dioxolane, 1,2-dimethoxyethane, and other ether solvents; and toluene, xylene, mesitylene, and other aromatic hydrocarbon solvents.

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

  The amount of the solvent is preferably 200 parts by weight or more, more preferably 250 parts by weight or more, particularly preferably 300 parts by weight or more with respect to 100 parts by weight of the total of the first liquid crystal compound and the second liquid crystal compound. The amount is preferably 650 parts by weight or less, more preferably 550 parts by weight or less, and particularly preferably 450 parts by weight or less. By setting the amount of the solvent to be equal to or higher than the lower limit value of the range, the generation of foreign matters can be suppressed, and by setting the amount of the solvent to be equal to or lower than the upper limit value of the range, the drying load can be reduced.

  Further, for example, the liquid crystal composition can include a polymerization initiator. The kind of polymerization initiator can be selected according to the kind of the polymerizable compound contained in the liquid crystal composition. For example, if the polymerizable compound is radically polymerizable, a radical polymerization initiator can be used. Further, if the polymerizable compound is anionic polymerizable, an anionic polymerization initiator can be used. Furthermore, if the polymerizable compound is cationically polymerizable, a cationic polymerization initiator can 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, preferably 100 parts by weight in total of the first liquid crystal compound and the second liquid crystal compound. 30 parts by weight or less, more preferably 10 parts by weight or less. When the amount of the polymerization initiator falls within the above range, the polymerization can proceed efficiently.

  Furthermore, examples of optional components include metals, metal complexes, metal oxides such as titanium oxide, colorants such as dyes and pigments, luminescent materials such as fluorescent materials and phosphorescent materials, leveling agents, thixotropic agents, and gelling agents. Polysaccharides, ultraviolet absorbers, infrared absorbers, antioxidants, ion exchange resins, and the like. The amount of these components may be 0.1 to 20 parts by weight with respect to 100 parts by weight in total of the first liquid crystal compound and the second liquid crystal compound.

[6. State of liquid crystal composition]
The liquid crystal composition may be fluid or solid. The state of the liquid crystal composition can be adjusted according to the use mode of the liquid crystal composition. For example, when the liquid crystal composition is applied to the support surface to form a liquid crystal composition layer, the liquid crystal composition is preferably fluid. For example, when aligning the liquid crystalline compound contained in the layer of the liquid crystal composition, the liquid crystal composition is preferably fluid.

[7. LCD cured film]
FIG. 1 is a cross-sectional view schematically showing a cross section of a cured liquid crystal film 10 according to an embodiment of the present invention, taken along a plane parallel to the thickness direction.
As shown in FIG. 1, the liquid crystal cured film 10 is a film including a liquid crystal cured layer 100. Although FIG. 1 shows the liquid crystal cured film 10 including only the liquid crystal cured layer 100, the liquid crystal cured film 10 may include any layer (not shown) in combination with the liquid crystal cured layer 100.

  The liquid crystal cured layer 100 is a layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound, and includes a first layer 110, a second layer 120, and a third layer 130 in this order in the thickness direction. Since it is formed of a cured product of the liquid crystal composition, the liquid crystal cured layer 100 and the first layer 110, the second layer 120, and the third layer 130 included in the liquid crystal cured layer 100 include a liquid crystal compound.

  Some or all of the liquid crystalline compounds contained in the liquid crystal cured layer 100 may have their alignment state fixed. Usually, by polymerization, the liquid crystalline compound can become a polymer while maintaining the alignment state of the liquid crystalline compound. Accordingly, examples of the liquid crystalline compound in which the alignment state is fixed include polymerized liquid crystalline compounds. Therefore, the term “liquid crystalline compound in which the alignment state is fixed” includes polymers of liquid crystalline compounds. When the liquid crystal cured layer 100 is manufactured using the liquid crystal composition including the first liquid crystal compound and the second liquid crystal compound described above, the liquid crystal cured layer 100 and the first layer 110 included in the liquid crystal cured layer 100 are used. The second layer 120 and the third layer 130 include a first liquid crystal compound and a second liquid crystal compound that may have their alignment states fixed.

  The first layer 110 and the second layer 120 are usually in direct contact with each other without any layer interposed therebetween. The second layer 120 and the third layer 130 are usually in direct contact with each other without any layer interposed therebetween. Therefore, as shown in FIG. 1, the liquid crystal cured layer 100 is a layer having a three-layer structure that normally includes only the first layer 110, the second layer 120, and the third layer 130.

The first tilt angle formed by the molecules of the liquid crystal compound contained in the first layer 110 with respect to the layer plane is usually constant in the first layer 110.
The second tilt angle formed by the molecules of the liquid crystal compound contained in the second layer 120 with respect to the layer plane is usually constant in the second layer 120. Furthermore, the second tilt angle is discontinuously different from the first tilt angle.
Further, the third tilt angle formed by the molecules of the liquid crystal compound contained in the third layer 130 with respect to the layer plane is usually constant in the third layer 130. Furthermore, the third tilt angle is discontinuously different from the first tilt angle and the second tilt angle.
Since the first layer 110, the second layer 120, and the third layer 130 including molecules of the liquid crystal compound having discontinuously different tilt angles are included, the liquid crystal cured layer 100 includes the tilt angle of the molecules of the liquid crystal compound. Can have a specific structure in which they differ discontinuously in the thickness direction.
Here, the fact that a certain tilt angle and another tilt angle are discontinuously different means that a difference between these tilt angles is 10 ° or more.

The tilt angles (first tilt angle, second tilt angle, and third tilt angle) of the molecules of the liquid crystal compound in each layer included in the liquid crystal cured layer 100, such as the first layer 110, the second layer 120, and the third layer 130. ) Can be measured by the following measurement method.
The liquid crystal cured layer 100 is embedded with an epoxy resin to prepare a sample piece. This sample piece is sliced parallel to the thickness direction of the liquid crystal cured layer 100 using a microtome to obtain an observation sample. The slicing is performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer 100 are parallel to each other. Thereafter, the observation sample is placed on the stage of a polarizing microscope, and the cross section appearing by the slice is observed while rotating the stage. From the rotation angle of the stage when the first layer 110, the second layer 120, and the third layer 130 of the liquid crystal cured layer 100 that appear in the cross section are in the extinction position, the first layer 110, the second layer 120, and the third layer. The tilt angle of the molecules of the liquid crystal compound contained in the layer 130 can be measured.

Further, whether or not the tilt angle of the liquid crystal compound molecules in each of the first layer 110, the second layer 120, and the third layer 130 is constant can be determined by the following determination direction.
The liquid crystal cured layer 100 is embedded with an epoxy resin to prepare a sample piece. This sample piece is sliced parallel to the thickness direction of the liquid crystal cured layer 100 using a microtome to obtain an observation sample. The slicing is performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer 100 are parallel to each other. Then, the cross section which appeared by the slice is observed using a polarization microscope. This observation is performed by inserting a wave plate between the observation sample and the objective lens of the polarizing microscope so that an image having a color corresponding to the retardation of the observation sample can be seen. In the image seen in this observation, each portion of the liquid crystal cured layer 100 is colored in a color corresponding to the tilt angle of the molecules of the liquid crystal compound in that portion. When the observed color of the first layer 110 is the same at any position in the first layer 110, the tilt angle (first tilt angle) of the molecules of the liquid crystal compound contained in the first layer 110 is constant. Can be judged. When the observed color of the second layer 120 is the same at any position in the second layer 120, the tilt angle (second tilt angle) of the molecules of the liquid crystal compound contained in the second layer 120 is constant. It can be determined that there is. Further, when the observed color of the third layer 130 is the same at any position in the third layer 130, the tilt angle (third tilt angle) of the molecules of the liquid crystal compound contained in the third layer 130 is constant. It can be determined that there is.
As a specific example, in the experiment conducted by the present inventors, the first layer 110 was observed in a uniform yellow color, the second layer 120 in a uniform reddish purple color, and the third layer 130 in a uniform blue color. In some cases, it has been confirmed that the tilt angles of the molecules of the liquid crystal compound in each of the first layer 110, the second layer 120, and the third layer 130 are constant.

  The magnitudes of the first tilt angle, the second tilt angle, and the third tilt angle can be appropriately set in accordance with the optical characteristics of the liquid crystal cured layer 100 that are required depending on the application of the liquid crystal cured film 10. The preferred range can be specifically shown as follows.

  The first tilt angle is preferably 0 ° or more, preferably 20 ° or less, more preferably 10 ° or less. The first layer 110 having the first tilt angle in such a range can be usually obtained as a layer on the support surface side in the method for producing the liquid crystal cured film 10 described later.

  The second tilt angle is preferably 20 ° or more, preferably 70 ° or less, more preferably 60 ° or less.

  Further, the difference between the first tilt angle and the second tilt angle is preferably 10 ° or more, more preferably 15 ° or more, particularly preferably 20 ° or more, preferably 70 ° or less, more preferably 60 ° or less. It is.

  The third tilt angle is preferably 70 ° or more, more preferably 80 ° or more, and preferably 90 ° or less. The third layer 130 having the third tilt angle in such a range can be usually obtained as a layer on the interface side opposite to the support surface in the method for producing the liquid crystal cured film 10 described later.

  The difference between the second tilt angle and the third tilt angle is preferably 10 ° or more, more preferably 15 ° or more, particularly preferably 20 ° or more, preferably 70 ° or less, more preferably 60 ° or less. It is.

  The thickness of each of the first layer 110, the second layer 120, and the third layer 130 can be appropriately set according to the optical characteristics of the liquid crystal cured layer 100 that are required according to the use of the liquid crystal cured film 10. The preferred range can be specifically shown as follows.

  The ratio of the thickness of the first layer 110 to the total thickness 100% of the first layer 110, the second layer 120, and the third layer 130 is preferably 14% or more, more preferably 18% or more, and preferably 66%. It is as follows.

  The ratio of the thickness of the second layer 120 to the total thickness 100% of the first layer 110, the second layer 120 and the third layer 130 is preferably 1% or more, preferably 80% or less, more preferably 64%. It is as follows.

  The ratio of the thickness of the third layer 130 to the total thickness 100% of the first layer 110, the second layer 120, and the third layer 130 is preferably 6% or more, more preferably 18% or more, and preferably 33%. It is as follows.

The thickness of each layer included in the liquid crystal cured layer 100 such as the first layer 110, the second layer 120, and the third layer 130 can be measured by the following measuring method.
The liquid crystal cured layer 100 is embedded with an epoxy resin to prepare a sample piece. This sample piece is sliced parallel to the thickness direction of the liquid crystal cured layer 100 using a microtome to obtain an observation sample. The slicing is performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer 100 are parallel to each other. Then, the cross section which appeared by slicing is observed using a polarization microscope, and the thickness of each of the first layer 110, the second layer 120 and the third layer 130 can be measured.

In the liquid crystal cured layer 100, the occurrence of alignment defects is usually suppressed. Therefore, the number of alignment defects in the liquid crystal cured layer 100 is small. Specifically, the number of orientation defects per mm ² can be preferably less than 10, more preferably less than 1. Since the liquid crystal cured film 10 including such a liquid crystal cured layer 100 is excellent in the uniformity of optical characteristics in the surface, it can be used as a high-quality optical film.
The number of alignment defects in the liquid crystal cured layer 100 can be measured by observing the liquid crystal cured layer 100 through transmission under a crossed Nicol using a polarizing microscope.

  Since the first tilt angle, the second tilt angle, and the third tilt angle are different, when viewed three-dimensionally, the orientation direction of the molecules of the liquid crystal compound contained in the first layer 110 and the liquid crystal contained in the second layer 120 The orientation direction of the molecules of the crystalline compound and the orientation direction of the molecules of the liquid crystalline compound contained in the third layer 130 are nonparallel. However, in the in-plane direction of the liquid crystal cured layer 100, the orientation direction of the molecules of the liquid crystal compound contained in the first layer 110, the orientation direction of the molecules of the liquid crystal compound contained in the second layer 120, and the third layer The alignment direction of the molecules of the liquid crystal compound contained in 130 is usually parallel. Therefore, the liquid crystal cured layer 100 can be an optically anisotropic layer having an in-plane slow axis parallel to the alignment direction of the molecules of the liquid crystalline compound as viewed from the thickness direction of the liquid crystal cured layer 100.

The liquid crystal cured layer 100 may be an optically anisotropic layer having a reverse wavelength dispersion retardation. Here, the retardation of the inverse wavelength dispersion means a retardation in which the retardation Re (450) at a wavelength of 450 nm and the retardation Re (550) at a wavelength of 550 nm generally satisfy the following formula (N3). By having an inverse wavelength dispersion retardation, the pre-liquid crystal cured layer 100 can uniformly exhibit a function in a wide wavelength band in an optical application such as a quarter wavelength plate or a half wavelength plate.
Re (450) <Re (550) (N3)

  The specific retardation range of the liquid crystal cured layer 100 can be arbitrarily set according to the use of the liquid crystal cured layer. For example, when the liquid crystal cured layer 100 is desired to function as a quarter wavelength plate, the retardation Re (550) of the liquid crystal cured layer 100 is preferably 80 nm or more, more preferably 100 nm or more, and particularly preferably 120 nm or more. Yes, preferably 180 nm or less, more preferably 160 nm or less, particularly preferably 150 nm or less. For example, when the liquid crystal cured layer 100 is desired to function as a half-wave plate, the retardation Re (550) of the liquid crystal cured layer 100 is preferably 245 nm or more, more preferably 265 nm or more, and particularly preferably 270 nm. It is above, Preferably it is 305 nm or less, More preferably, it is 285 nm or less, Most preferably, it is 280 nm or less.

  The thickness of the liquid crystal cured layer 100 can be appropriately set so that characteristics such as retardation can be in a desired range. Specifically, the thickness of the liquid crystal cured layer 100 is preferably 0.5 μm or more, more preferably 1.0 μm or more, preferably 10 μm or less, more preferably 7 μm or less.

  As an arbitrary layer that the liquid crystal cured film 10 can be provided in combination with the liquid crystal cured layer 100, a substrate used for manufacturing the liquid crystal cured layer 100; a retardation film; a polarizing film as a linear polarizer; For example, an adhesive layer for coating; a mat layer for improving the slipperiness of the film; a hard coat layer such as an impact-resistant polymethacrylate resin layer; an antireflection layer; an antifouling layer;

  The liquid crystal cured layer 100 included in the liquid crystal cured film 10 described above has a specific structure in which the tilt angles of the molecules of the liquid crystal compound are discontinuously different in the thickness direction, and therefore has optical characteristics corresponding to the specific structure. Can have. Therefore, if the liquid crystal cured film 10 is used, various optical designs are possible, and thus the degree of freedom in optical design can be increased. Furthermore, unlike the optical film obtained by bonding a plurality of separately prepared liquid crystal cured layers, the liquid crystal cured film 10 does not need to be provided with an adhesive layer, and thus can be made thinner than before. .

[8. Manufacturing method of liquid crystal cured film]
The liquid crystal cured film mentioned above can be manufactured using the said liquid-crystal composition containing the surfactant containing a 1st liquid crystalline compound, a 2nd liquid crystalline compound, and a fluorine atom. For example, liquid crystal cured film
(I) forming a liquid crystal composition layer on the support surface;
(Ii) aligning the first liquid crystalline compound and the second liquid crystalline compound contained in the layer of the liquid crystal composition;
(Iii) curing the liquid crystal composition layer;
It can manufacture by the manufacturing method containing.

  As the support surface, any surface that can support the layer of the liquid crystal composition can be used. As this support surface, from the viewpoint of improving the surface state of the liquid crystal cured layer, a flat surface having no concave portions and convex portions is usually used. From the viewpoint of enhancing the productivity of the liquid crystal cured layer, it is preferable to use a long substrate surface as the support surface. Here, the “long” means a shape having a length of 5 times or more with respect to the width, preferably 10 times or more, and specifically wound in a roll shape. The shape of a film having a length that can be stored or transported.

  As the substrate, a resin film is usually used. As the resin, a thermoplastic resin is usually used. Among them, a resin having a positive intrinsic birefringence value is preferable as the resin from the viewpoints of high orientation regulating force, high mechanical strength, and low cost. Furthermore, it is preferable to use a resin containing an alicyclic structure-containing polymer such as a norbornene-based resin because it is excellent in transparency, low hygroscopicity, dimensional stability, and lightness. If a suitable example of resin contained in a base material is given by a trade name, “ZEONOR 1420” and “ZEONOR 1420R” manufactured by Nippon Zeon Co., Ltd. may be mentioned as norbornene resins.

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

  After preparing a base material as needed, the process of forming the layer of a liquid-crystal composition on support surfaces, such as the surface of a base material, is performed. Usually, a liquid crystal composition is applied to a support surface to form a layer of the liquid crystal composition. Examples of the method for applying the liquid crystal composition include curtain coating method, extrusion coating method, roll coating method, spin coating method, dip coating method, bar coating method, spray coating method, slide coating method, print coating method, and gravure. Examples include a coating method, a die coating method, a gap coating method, and a dipping method.

  After forming the liquid crystal composition layer, a step of aligning the first liquid crystal compound and the second liquid crystal compound contained in the liquid crystal composition layer is performed. In this step, the first liquid crystalline compound and the second liquid crystalline compound are usually aligned in a direction corresponding to the alignment regulating force of the support surface by performing an alignment treatment on the liquid crystal composition layer.

  The alignment treatment is usually performed by adjusting the temperature of the liquid crystal composition layer to a predetermined alignment temperature. The alignment temperature can be a temperature equal to or higher than the liquid crystallizing temperature of the liquid crystal composition. At this time, the orientation temperature is preferably a temperature lower than the glass transition temperature of the resin contained in the substrate. Thereby, generation | occurrence | production of the distortion of the base material by an orientation process can be suppressed.

  If the specific example of the conditions of orientation processing is given, it can be set as the conditions which process for 30 seconds-5 minutes in the temperature conditions of 50 to 160 degreeC.

  However, the alignment of the first liquid crystalline compound and the second liquid crystalline compound may be achieved immediately by application of the liquid crystal composition. Therefore, the alignment treatment for aligning the first liquid crystal compound and the second liquid crystal compound is not necessarily performed on the layer of the liquid crystal composition.

  When the liquid crystal composition of the present invention containing the first liquid crystal compound, the second liquid crystal compound, and the surfactant containing a fluorine atom is used, the molecules of the first liquid crystal compound and the second liquid crystal are obtained by the alignment described above. The orientation state of the molecules of the functional compound is uniform in the in-plane direction but discontinuously differs in the thickness direction. Specifically, in the portion of the liquid crystal composition layer close to the support surface, the molecules of the first liquid crystal compound and the molecules of the second liquid crystal compound are usually parallel or close to parallel to the support surface. Orient uniformly in the direction. Further, in the portion of the liquid crystal composition layer, the portion close to the interface opposite to the support surface (usually the air interface of the liquid crystal composition layer), the molecules of the first liquid crystal compound and the second liquid crystal properties. The molecules of the compound are usually oriented uniformly in the direction perpendicular or nearly perpendicular to the support surface. Further, in the intermediate part between the two parts of the liquid crystal composition layer part, the molecules of the first liquid crystal compound and the molecules of the second liquid crystal compound are usually parallel to the support surface. It is oriented uniformly in a direction that is neither vertical nor vertical. And since the alignment state of each part changes discontinuously in this way, the layer of the liquid crystal composition from which the tilt angle of the molecule | numerator of a liquid crystalline compound differs discontinuously in the thickness direction is obtained.

  After aligning the first liquid crystal compound and the second liquid crystal compound, the liquid crystal composition layer is cured to obtain a liquid crystal cured layer. In this step, usually, one or both of the first liquid crystalline compound and the second liquid crystalline compound are polymerized to cure the liquid crystal composition layer. During the polymerization, the liquid crystalline compound is usually polymerized while maintaining the molecular orientation. Therefore, the above-mentioned polymerization can fix the alignment state of the liquid crystal compound contained in the liquid crystal composition before polymerization, so that a desired liquid crystal cured layer can be obtained.

  As a polymerization method of the liquid crystal compound, a method suitable for the properties of the components contained in the liquid crystal composition can be selected. Examples of the polymerization method include a method of irradiating active energy rays and a thermal polymerization method. Among them, the method of irradiating with active energy rays is preferable because heating is unnecessary and the polymerization reaction can proceed at room temperature. Here, the irradiated active energy rays can include light such as visible light, ultraviolet light, and infrared light, and arbitrary energy rays such as electron beams.

Among these, a method of irradiating light such as ultraviolet rays is preferable because the operation is simple. The temperature during ultraviolet irradiation is preferably not higher than the glass transition temperature of the substrate, preferably not higher than 150 ° C., more preferably not higher than 100 ° C., particularly preferably not higher than 80 ° C. The lower limit of the temperature during ultraviolet irradiation can be 15 ° C. or higher. The irradiation intensity of ultraviolet rays is preferably 0.1 mW / cm ² or more, more preferably 0.5 mW / cm ² or more, preferably 1000 mW / cm ² or less, more preferably 600 mW / cm ² or less.

  The liquid crystal cured layer formed on the support surface is obtained by the manufacturing method described above. This liquid crystal cured layer usually includes a first layer, a second layer, and a third layer in this order from the support surface side. The liquid crystal cured layer thus obtained may be peeled off from the support surface and used as a liquid crystal cured film. Such a liquid crystal cured film can be manufactured with the manufacturing method including the process of peeling a liquid crystal cured layer from a support surface.

  For example, when the liquid crystal cured layer formed on the base material is obtained, a multilayer film including the base material and the liquid crystal cured layer may be used as the liquid crystal cured film.

  Furthermore, for example, the liquid crystal cured layer formed on the substrate may be transferred to an arbitrary film layer to obtain a liquid crystal cured film. In such a case, the liquid crystal cured layer and the optional film layer are usually peeled off as necessary after the liquid crystal cured layer formed on the substrate and the arbitrary film layer are bonded together. A liquid crystal cured film containing can be obtained. At this time, an appropriate pressure-sensitive adhesive or adhesive may be used for bonding.

  Moreover, the manufacturing method of the liquid crystal cured film may further include an optional step in combination with the above steps. For example, the method for producing a liquid crystal cured film may include a step of drying the liquid crystal composition layer before the step of curing the liquid crystal composition layer. Such drying can be achieved by a drying method such as natural drying, heat drying, reduced pressure drying, and reduced pressure heat drying. By such drying, the solvent can be removed from the liquid crystal composition layer.

[9. Application]
The liquid crystal cured film can be suitably used as an optical film such as a retardation film, an optical compensation film, a linearly polarizing plate, and a circularly polarizing plate.

  Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to the following examples, and can be implemented with any modifications without departing from the scope of the claims of the present invention and the equivalents thereof. In the following description, “%” and “parts” representing amounts are based on weight unless otherwise specified. Further, the operations described below were performed in a normal temperature and pressure atmosphere unless otherwise specified.

[Description of liquid crystalline compounds]
The structures of the liquid crystal compounds used in Examples and Comparative Examples described later are as follows.

[Evaluation method]
(1. Method for measuring log P of fluorosurfactant)
(1-1. Preparation Method of Sample Solution Containing Fluorosurfactant)
A sample solution containing 1% by weight of a fluorosurfactant was prepared. Tetrahydrofuran or acetonitrile was used as a solvent for this sample solution. When the fluorosurfactant before mixing with tetrahydrofuran or acetonitrile is a solution containing the fluorosurfactant and a diluent solvent, the content of the fluorosurfactant in the obtained sample solution is 1 The amount of tetrahydrofuran or acetonitrile was adjusted to be wt%.

(1-2. HPLC / ELSD analysis)
In accordance with JIS 7260-117: 2006 {Measurement of partition coefficient (1-octanol / water) -high performance liquid chromatography}, HPLC / ELSD analysis of the sample solution containing a fluorosurfactant was performed as follows. The elution time (rt) was measured under the HPLC / ELSD analysis conditions.

-HPLC / ELSD analysis conditions LC system: LC-20A (manufactured by Shimadzu Corporation)
Column: Inertsil ODS-3 3.0 × 150 mm, 5 μm (GL Science)
Mobile phase: A water
B acetonitrile / tetrahydrofuran = 8/2 (vol / vol)
Acetonitrile: for high performance liquid chromatography (made by Kokusan Chemical)
Tetrahydrofuran: inhibitor-free, for HPLC (manufactured by SIGMA-ALDRICH)
Time program: 0min to 15min B 30% to 100%
15min to 25min B 100%
Column temperature: 45 ° C
Flow rate: 0.8mL / min
Injection volume: 10 μL (If sample detection sensitivity is low, adjust to 50 μL or 100 μL)
Detection: ELSD-LTII (Shimadzu Corporation) Gain 6, 350 kPa, 65 ° C.

(1-3. Derivation of calibration curve)
The labeling compounds shown in Table 1 below were prepared. The labeling compounds shown in Table 1 are compounds with known log P described in JIS 7260-117: 2006. Each labeled compound is contained in the same manner as described in (1-1. Method for preparing sample solution containing fluorosurfactant) except that this labeled compound is used instead of the fluorosurfactant. A sample solution was prepared. Thereafter, HPLC / ELSD analysis of the obtained sample solution was performed under the analysis conditions described in (1-2. HPLC / ELSD analysis), and the elution time was measured. However, the temperature of the ELSD detector was set to 25 ° C.

  The analysis result of the labeled compound was plotted on a coordinate system with the elution time on the horizontal axis and logP on the vertical axis, and an approximate straight line was created by the least square method. This approximate straight line was adopted as a calibration curve.

(1-4. Calculation of log P of fluorosurfactant)
By applying the elution time measured for each fluorosurfactant to the calibration curve, the log P of the fluorosurfactant was determined. When multiple peaks indicating the elution time are detected per one fluorosurfactant in HPLC / ELSD analysis, the peak top of the peak with the largest area is adopted as the elution time of the fluorosurfactant. LogP was determined.

(2. Measuring method of tilt angle of molecules of liquid crystal compound in each layer included in liquid crystal cured layer)
A liquid crystal cured film including a liquid crystal cured layer and a substrate film was embedded with an epoxy resin to prepare a sample piece. This sample piece was sliced parallel to the thickness direction of the liquid crystal cured layer using a microtome to obtain an observation sample. The slicing was performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer were parallel to each other. Thereafter, the observation sample was placed on the stage of a polarizing microscope, and the cross section that appeared by slicing was observed while rotating the stage. The liquid crystal contained in the first layer, the second layer, and the third layer from the rotation angle of the stage when the first layer, the second layer, and the third layer of the liquid crystal cured layer that appear in the cross section are in the extinction position. The tilt angle of the molecule of the active compound was measured.

(3. Method for measuring thickness of each layer included in liquid crystal cured layer)
A liquid crystal cured film including a liquid crystal cured layer and a substrate film was embedded with an epoxy resin to prepare a sample piece. This sample piece was sliced parallel to the thickness direction of the liquid crystal cured layer using a microtome to obtain an observation sample. The slicing was performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer were parallel to each other. Then, the cross section which appeared by the slice was observed using the polarization microscope, and the thickness of each of the first layer, the second layer and the third layer was measured.

(4. Method for confirming that the tilt angle of liquid crystal compound molecules in each layer included in the liquid crystal cured layer is constant)
A liquid crystal cured film including a liquid crystal cured layer and a substrate film was embedded with an epoxy resin to prepare a sample piece. This sample piece was sliced parallel to the thickness direction of the liquid crystal cured layer using a microtome to obtain an observation sample. The slicing was performed so that the in-plane slow axis direction and the cross section of the liquid crystal cured layer were parallel to each other. Then, the cross section which appeared by the slice was observed using the polarization microscope. This observation was performed by inserting a wave plate between the observation sample and the objective lens of the polarizing microscope so that an image having a color corresponding to the retardation of the observation sample could be seen. When the observed color of the first layer was the same at any position in the first layer, it was determined that the tilt angle of the molecules of the liquid crystal compound contained in the first layer was constant. Further, when the observed color of the second layer was the same at any position in the second layer, it was determined that the tilt angle of the molecules of the liquid crystal compound contained in the second layer was constant. Furthermore, when the observed color of the third layer was the same at any position in the third layer, it was determined that the tilt angle of the molecules of the liquid crystal compound contained in the third layer was constant.

(5. Evaluation method of reverse wavelength dispersion)
Retardation Re (450) and Re (550) of the front surface (incidence angle 0 °) at a wavelength of 450 nm and 550 nm of the liquid crystal cured layer of the multilayered body for evaluation using a phase difference meter (“AxoScan” manufactured by Axometrics). ) Was measured. From the measured retardation values Re (450) and Re (550), the reverse wavelength dispersion of the liquid crystal cured layer was evaluated according to the following criteria.
○: Re (450) / Re (550) <0.9
Δ: 0.9 ≦ Re (450) / Re (550) ≦ 1.0
X: Re (450) / Re (550)> 1.0

(6. Evaluation method of alignment defect of liquid crystal cured layer)
The multilayer liquid crystal cured layer for evaluation was observed under transmission using a polarizing microscope under crossed Nicols. During this observation, the objective lens was set to 20 times. From the observation results, alignment defects of the liquid crystal cured layer were evaluated according to the following criteria.
○: The number of orientation defects is less than 1 / mm ² .
Δ: The number of alignment defects is 1 or more and less than 10 / mm ² .
X: The number of orientation defects is 10 or more / mm ² or more.

(7. Evaluation method of tilt orientation of liquid crystal cured layer)
The retardation of the liquid crystal cured layer of the multilayer for evaluation was measured in a range of incident angles from −50 ° to 50 ° using a phase difference meter (“AxsoScan” manufactured by Axometrics). From the measured retardation, the analysis software attached to the phase difference meter (analysis software “Malti-Layer Analysis” manufactured by AxsoMetrics); analysis conditions were an analysis wavelength of 590 nm, and a layer division number of 20 layers (approximately every 0.1 μm) The average tilt angle of the liquid crystal compound molecules contained in the liquid crystal cured layer was analyzed. Based on the measured average tilt angle, the tilt orientation of the liquid crystal cured layer was evaluated according to the following criteria.
○: The average tilt angle is 20 ° or more.
Δ: The average tilt angle is 5 ° or more and less than 20 °.
X: The average tilt angle is less than 5 °.

(8. Evaluation method and evaluation result of tilt orientation of first liquid crystalline compound)
Except for using 100 parts by weight of the first liquid crystal compound (forward dispersion liquid crystal compound K35; molecular weight 847; Δn = 0.22) alone as the liquid crystal compound without using the second liquid crystal compound, it will be described later. In the same manner as in Example 1, an evaluation multilayer including the first test layer as the liquid crystal cured layer was obtained. The average tilt angle of the molecules of the liquid crystal compound contained in the first test layer of the multilayer obtained in this manner was measured in the same manner as described above (7. Evaluation method of tilt orientation of liquid crystal cured layer). As a result of the measurement, the average tilt angle of the first test layer was 45 °. Thereby, it was confirmed that the first liquid crystal compound (forward dispersion liquid crystal compound K35) used in Examples described later has tilt alignment.

(9. Evaluation method and evaluation result of tilt orientation of second liquid crystalline compound)
The second liquid crystal compound used in each example as the liquid crystal compound without using the first liquid crystal compound (that is, reverse dispersion liquid crystal compound 1, reverse dispersion liquid crystal compound 2, reverse dispersion liquid crystal compound 3 and reverse liquid crystal compound) A multilayer for evaluation including a second test layer as a liquid crystal cured layer was obtained in the same manner as in Example 1 described later except that 100 parts by weight of each of the dispersed liquid crystalline compounds 4) was used alone. The average tilt angle of the molecules of the liquid crystal compound contained in the second test layer of the multilayer obtained in this manner was measured in the same manner as described above (7. Evaluation method of tilt orientation of liquid crystal cured layer). As a result of the measurement, the average tilt angle of the second test layer was less than 5 °. Thereby, it confirmed that the 2nd liquid crystalline compound used in the Example mentioned later does not have inclination orientation.

(10. Evaluation method and evaluation result of tilt alignment of liquid crystal compounds used in Comparative Examples 22 to 24)
Without using the first liquid crystal compound and the second liquid crystal compound, as the liquid crystal compound, the forward dispersion liquid crystal compound LC242, the forward dispersion liquid crystal compound LC1057, and the forward dispersion liquid crystal compound MLC3011 used in Comparative Examples 22 to 24, respectively. Was used in the same manner as in Example 1 described later except that 100 parts by weight of was used alone to obtain a multilayer for evaluation including a test layer as a liquid crystal cured layer. The average tilt angle of the molecules of the liquid crystal compound contained in the test layer of the multilayer obtained in this manner was measured in the same manner as described above (7. Evaluation method of tilt orientation of liquid crystal cured layer). As a result of the measurement, the average tilt angle of the test layer was less than 5 °. Thus, it was confirmed that the forward-dispersed liquid crystalline compound LC242, the forward-dispersed liquid crystalline compound LC1057, and the forward-dispersed liquid crystalline compound MLC3011 used in the examples described later have no tilt alignment.

[Example 1]
(1-1. Preparation of liquid crystal composition)
Polymerizable first liquid crystal compound (forward-dispersed liquid crystal compound K35; molecular weight 847; Δn = 0.22) 10 parts by weight, polymerizable reverse wavelength-dispersible second liquid crystal compound (reverse dispersed liquid crystal compound) 1; molecular weight 1170; Δn = 0.07) 90 parts by weight, fluorosurfactant (“S420” manufactured by AGC Seimi Chemical Co., Ltd .; log P value = 5.3) 0.15 parts by weight, photopolymerization initiator (BASF) "Irgacure OXE04") 4.3 parts by weight, cyclopentanone 162.3 parts by weight as a solvent, and 243.5 parts by weight of 1,3-dioxolane as a solvent were mixed to obtain a liquid crystal composition.

(1-2. Preparation of base film)
As a base film, a resin film made of thermoplastic norbornene resin (“Zeonor film ZF14” manufactured by Nippon Zeon Co., Ltd .; thickness 100 μm) having a masking film bonded on one side was prepared. The masking film was peeled from this base film, and the masking peeled surface was subjected to corona treatment. Subsequently, the corona treatment surface of the base film was rubbed.

(1-3. Formation of liquid crystal composition layer)
A liquid crystal composition was applied to the rubbing-treated surface of the base film using a # 5 wire bar to form a liquid crystal composition layer.

(1-4. Orientation treatment)
Thereafter, the layer of the liquid crystal composition was heated at 110 ° C. for 4 minutes to perform drying treatment and alignment treatment. Thereby, the liquid crystalline compound contained in the layer of the liquid crystal composition was aligned.

(1-5. Curing treatment)
The liquid crystal composition layer subjected to the alignment treatment was irradiated with ultraviolet rays of 500 mJ / cm ² in a nitrogen atmosphere to cure the liquid crystal composition layer to form a liquid crystal cured layer having a thickness of about 2 μm. Thereby, the liquid crystal cured film which has a layer structure of a liquid crystal cured layer / base film was obtained.
Using the obtained liquid crystal cured film, the tilt angle and thickness of the molecules of the liquid crystalline compound contained in the first layer, the second layer, and the third layer contained in the liquid crystal cured layer were evaluated.

(1-6. Transfer of liquid crystal cured layer to slide glass)
The surface on the liquid crystal cured layer side of the liquid crystal cured film was bonded to the slide glass provided with an adhesive. Thereafter, the base film was peeled off. As a result, a multilayer body for evaluation having a layer structure of liquid crystal cured layer / adhesive layer / slide glass was obtained.
Using the obtained multilayer body, the reverse wavelength dispersibility, the alignment defect and the tilt alignment property of the liquid crystal cured layer were evaluated.

[Examples 2 to 7]
The combination of the amount of the first liquid crystal compound; the type and amount of the second liquid crystal compound; and the type of the fluorosurfactant was changed as shown in Table 2 below. Except for the above items, the same operation as in Example 1 was performed to manufacture a liquid crystal cured film and a multilayer for evaluation, and to evaluate the reverse wavelength dispersion, alignment defects, and tilted alignment of the liquid crystal cured layer. It was.

[Comparative Examples 1 to 21]
The combination of the amount of the first liquid crystal compound; the type and amount of the second liquid crystal compound; and the type of the fluorosurfactant was changed as shown in Table 2 below. Except for the above items, the same operation as in Example 1 was performed to manufacture a liquid crystal cured film and a multilayer for evaluation, and to evaluate the reverse wavelength dispersion, alignment defects, and tilted alignment of the liquid crystal cured layer. It was. Moreover, in the comparative example 2, the tilt angle and thickness of the molecule | numerator of the liquid crystalline compound contained in a liquid crystal cured layer were evaluated using the liquid crystal cured film.

[Comparative Examples 22-24]
Instead of the second liquid crystal compound, a forward dispersion liquid crystal compound shown in Table 2 below was used. The amount of the forward-dispersed liquid crystalline compound used was also as shown in Table 2 below. Except for the above items, the same operation as in Example 1 was performed to manufacture a liquid crystal cured film and a multilayer for evaluation, and to evaluate the reverse wavelength dispersion, alignment defects, and tilted alignment of the liquid crystal cured layer. It was.

[result]
Table 2 shows combinations of the first liquid crystalline compound, the second liquid crystalline compound, and the fluorosurfactant of Examples and Comparative Examples, and the evaluation results of the reverse wavelength dispersibility, alignment defects, and tilt alignment of the liquid crystal cured layer are shown. Table 3 shows. Further, Table 4 shows the results of the tilt angles and thicknesses of the molecules of the liquid crystal compounds contained in the first layer, the second layer, and the third layer measured in Example 1 and Comparative Example 2. Here, in any of the embodiments, the tilt angles in the first layer, the second layer, and the third layer included in the liquid crystal cured layer are constant, and the first tilt angle, the second tilt angle, and the third layer are constant. The tilt angle was discontinuously different.
Moreover, the photograph of the cross section of the liquid-crystal hardened layer especially observed with the polarizing microscope in Example 1 is shown in FIG. Further, FIG. 3 shows an explanatory diagram for explaining each part of FIG. In FIG. 3, reference numeral “210” is a base film, reference numeral “220” is a liquid crystal cured layer, reference numeral “221” is a first layer, reference numeral “222” is a second layer, reference numeral “223” is a third layer, reference numeral 230 shows an epoxy resin, respectively. Moreover, it is thought that the white part shown with the code | symbol 240 shows the bright spot by the orientation at the time of shaping | molding of an epoxy resin.

In the following table, the meanings of the abbreviations are as follows.
log P: 1-octanol / water partition coefficient.
K35: Forward-dispersed liquid crystalline compound “K35”.
Reverse wavelength 1: Reverse dispersion liquid crystalline compound 1.
Reverse wavelength 2: Reverse dispersion liquid crystal compound 2.
Inverse wavelength 3: Inversely dispersed liquid crystal compound 3.
Inverse wavelength 4: Inversely dispersed liquid crystal compound 4.
LC242: Forward-dispersed liquid crystalline compound “LC242” manufactured by BASF.
LC1057: Forward-dispersed liquid crystalline compound “LC1057” manufactured by BASF.
MLC3011: Forward-dispersed liquid crystalline compound “MLC3011” manufactured by ADEKA.
S420: A fluorine-based surfactant “S420” manufactured by AGC Seimi Chemical Co., Ltd.
251: Neosurf's fluorosurfactant “Factent 251”.
FTX209: Fluorosurfactant “Fuategent FTX-209” manufactured by Neos.
S242: A fluorosurfactant “Surflon S242” manufactured by AGC Seimi Chemical Co., Ltd.
F444: Fluorosurfactant “Megafac F-444” manufactured by DIC.
250: Fluorosurfactant “Ftergent FTX-250” manufactured by Neos.
215M: Neos fluorine-based surfactant “Factent FTX-215M”.
212M: Neos fluorine-based surfactant “Factent FTX-212M”.
208G: Fluorosurfactant “Ftergent FTX-208G” manufactured by Neos.
RS75: Fluorosurfactant “Megafac RS-75” manufactured by DIC.
RS76E: Fluorosurfactant “Megafac RS-76-E” manufactured by DIC.
NS9013: Fluorine-based surfactant “NS-9013” manufactured by Daikin.
FTX218: Neos fluorine-based surfactant “Factent FTX-218”.
S386: A fluorosurfactant “Surflon S386” manufactured by AGC Seimi Chemical Co., Ltd.
S651: A fluorosurfactant “Surflon S651” manufactured by AGC Seimi Chemical Co., Ltd.
F251: Fluorine-based surfactant “Megafac F-251” manufactured by DIC.
F554: Fluorine-based surfactant “Megafac F-554” manufactured by DIC.
F556: Fluorosurfactant “Megafac F-556” manufactured by DIC.
F562: Fluorosurfactant “Megafac F-562” manufactured by DIC.
F558: Fluorosurfactant “Megafac F-558” manufactured by DIC.
730LM: Fluorosurfactant “Fuategent 730LM” manufactured by Neos.
S611: A fluorosurfactant “Surflon S611” manufactured by AGC Seimi Chemical Co., Ltd.

DESCRIPTION OF SYMBOLS 10 Liquid crystal cured film 100 Liquid crystal cured layer 110 1st layer 120 2nd layer 130 3rd layer 210 Base film 220 Liquid crystal cured layer 221 1st layer 222 2nd layer 223 3rd layer 230 Epoxy resin

Claims (9)

A liquid crystal composition comprising a first liquid crystal compound capable of developing birefringence having a tilted orientation and a forward wavelength dispersion, a second liquid crystal compound capable of exhibiting a birefringence having a reverse wavelength dispersion, and a surfactant Because
The liquid crystal composition, wherein the surfactant contains a fluorine atom and has a 1-octanol / water partition coefficient of 4.8 or more and 6.7 or less.   The liquid crystal composition according to claim 1, wherein the first liquid crystalline compound has a refractive index anisotropy Δn at a measurement wavelength of 550 nm of 0.11 or more.   3. The liquid crystal composition according to claim 1, wherein an amount of the first liquid crystal compound with respect to a total of 100 parts by weight of the first liquid crystal compound and the second liquid crystal compound is 1 part by weight or more and 25 parts by weight or less. .   The amount of the surfactant with respect to a total of 100 parts by weight of the first liquid crystal compound and the second liquid crystal compound is 0.11 part by weight or more and 0.29 part by weight or less. The liquid crystal composition according to one item. A liquid crystal cured film comprising a liquid crystal cured layer formed of a cured product of a liquid crystal composition containing a liquid crystal compound,
The liquid crystal cured layer includes a first layer, a second layer, and a third layer in this order, including the liquid crystalline compound in which the alignment state may be fixed,
A first tilt angle formed by molecules of the liquid crystalline compound contained in the first layer with respect to a layer plane is constant in the first layer;
The second tilt angle formed by the molecules of the liquid crystalline compound contained in the second layer with respect to the layer plane is constant in the second layer, and discontinuously differs from the first tilt angle,
The third tilt angle formed by the molecules of the liquid crystalline compound contained in the third layer with respect to the layer plane is constant in the third layer, and the first tilt angle and the second tilt angle are not. Continuously different liquid crystal cured film.   The liquid crystal cured film according to claim 5, wherein the liquid crystal composition is the liquid crystal composition according to claim 1. The ratio of the thickness of the first layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 14% or more and 66% or less,
The ratio of the thickness of the second layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 1% or more and 80% or less,
The liquid crystal cured film according to claim 5 or 6, wherein a ratio of the thickness of the third layer to the total thickness of 100% of the first layer, the second layer, and the third layer is 6% or more and 33% or less. . The first tilt angle is not less than 0 ° and not more than 20 °;
The second tilt angle is not less than 20 ° and not more than 70 °;
The liquid crystal cured film according to any one of claims 5 to 7, wherein the third tilt angle is 70 ° or more and 90 ° or less. Forming a layer of the liquid crystal composition according to any one of claims 1 to 4 on a support surface;
Aligning the first liquid crystalline compound and the second liquid crystalline compound contained in the layer of the liquid crystal composition;
And a step of curing the liquid crystal composition layer.