JP2016081035A - Optically anisotropic layer and manufacturing method of the same, laminate, polarizing plate, display device, liquid crystal compound and manufacturing method of the same, and carboxylic acid compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a liquid crystal compound having a reverse wavelength dispersion property in which solubility and phase transition temperature are improved and an optically anisotropic layer using the same, a laminate, a polarizing plate, a display device, manufacturing methods of the liquid crystal compound and optically anisotropic layer, and a carboxylic acid compound that is an intermediate body of the liquid crystal compound.SOLUTION: An optically anisotropic layer includes a liquid crystal compound having a specific optical active carbon, or formed by curing a polymerizable composition including the liquid crystal compound, and the major axes of molecules of the liquid crystal compound are aligned.SELECTED DRAWING: None

Description

  The present invention relates to an optically anisotropic layer having reverse wavelength dispersion and a method for producing the same, a laminate including the optically anisotropic layer, a polarizing plate, and a display device, a liquid crystal compound exhibiting reverse wavelength dispersion, and its The present invention relates to a production method and a carboxylic acid compound which is an intermediate of a liquid crystal compound.

Optically anisotropic layers have been widely used for the purpose of improving a wide viewing angle, a high contrast ratio, and a color shift in liquid crystal display devices of various display modes. In general, a material used in an image display device, particularly a polymer, has a forward wavelength dispersion (also referred to as normal dispersion) in which a phase difference, that is, a birefringence increases on the short wavelength side. For this reason, there is a concern about the influence on the display characteristics due to the difference in wavelength of transmitted light.
In the optically anisotropic layer, in order to prevent the difference in the wavelength of transmitted light from affecting the display characteristics, it is required to control the chromatic dispersion of the phase difference. It is required that the phase difference on the long wave side is larger than the phase difference, that is, reverse wavelength dispersion (also referred to as anomalous dispersion).

  As an optically anisotropic layer having reverse wavelength dispersion, optically anisotropic layers using a reverse wavelength dispersion liquid crystal compound are disclosed in Patent Documents 1 and 2 and the like.

JP 2010-031223 A JP 2009-242718 A

  However, although the liquid crystal compounds disclosed in these documents exhibit reverse wavelength dispersibility, they have a high phase transition temperature necessary for obtaining an alignment state and have a problem in lamination operability on a resin film. There is a problem that the solubility in a solvent at the time of forming a liquid is not good.

The present invention has been made in view of the above circumstances, and a liquid crystal compound exhibiting reverse wavelength dispersibility, which has a low phase transition temperature necessary for liquid crystal alignment and high solubility in a solvent, as compared with the prior art. It is an object of the present invention to provide an optically anisotropic layer having a reverse wavelength dispersibility excellent in production suitability and a method for producing the same.
Another object of the present invention is to provide a laminate, a polarizing plate, and a display device in consideration of the influence on the display characteristics due to the difference in wavelength of transmitted light.
The present invention also provides a liquid crystal compound having a low phase transition temperature necessary for liquid crystal alignment, high solubility in a solvent, and exhibiting reverse wavelength dispersion, a method for producing the same, and a carboxylic acid compound as an intermediate of the liquid crystal compound Is intended to provide.

The optically anisotropic layer of the present invention comprises a liquid crystal compound represented by the following general formula 1 or is formed by curing a polymerizable composition comprising a liquid crystal compound represented by the following general formula 1, The major axis of the molecule of the liquid crystal compound represented by Formula 1 is aligned.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, respectively;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the Ar group is 8 or more.

As described above, the optically anisotropic layer of the present invention includes a liquid crystal compound represented by the above general formula 1, that is, a first aspect that is an uncured aspect, and the above general formula 1. A second embodiment formed by curing a polymerizable composition containing a liquid crystal compound. In the second embodiment, the liquid crystal compound represented by the general formula 1 is dispersed in a binder polymer, and the end groups of T ₁ and / T _{2 in} the general formula 1 are polymerizable groups. In the latter case, “the long axis of molecules of the liquid crystal compound represented by the general formula 1 is aligned” is represented by the general formula 1. In the polymer of a liquid crystal compound, it means that the molecular long axis part at the time of monomer is oriented.

In the general formula 1, Ar is preferably any aromatic ring represented by the following general formulas 2-1 to 2-4, and more preferably an aromatic ring represented by the general formula 2-2. .
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded,
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring possessed by may have a substituent, and Ax and Ay may combine to form a ring,
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

In the general formula 1, T1 and T2 can have a structure represented by the following general formula 3. By making the terminal a polymerizable group as in the general formula 3, the polymerizable composition containing the liquid crystal compound represented by the general formula 1 can be formed into an optically anisotropic layer formed by curing.
In the formula, Sp1 and Sp2 each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O—. , —S—, —C (═O) —, —OC (═O) —, —C (═O) O—, —OC (═O) O—, —NR ¹ C (═O) —, — C (═O) NR ² —, —OC (═O) NR ³ —, —NR ⁴ C (═O) O—, —SC (═O) — or —C (═O) S— is substituted. R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ and P ₂ each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.

In the optically anisotropic layer of the present invention, the alignment state is preferably fixed with a nematic phase or a smectic phase, and more preferably fixed with a smectic phase.
In this specification, the smectic phase means a state in which molecules aligned in one direction have a layer structure, and the nematic phase means that the constituent molecules have an orientational order but do not have a three-dimensional positional order. State.

In the optically anisotropic layer of the present invention, the major axis of the molecule of the liquid crystal compound represented by general formula 1 is fixed in a homogeneous orientation, and the phase difference Re (450 nm), Re (550 nm) at wavelengths of 450 nm, 550 nm, and 650 nm, It is preferable that Re (650 nm) satisfies the following formulas A and B.
Re (450 nm) / Re (550 nm) <0.95 Formula A
Re (650 nm) / Re (550 nm)> 1.02 Formula B

  The laminate of the present invention is obtained by laminating the above optically anisotropic layer of the present invention on a resin film directly or via an alignment film.

  The polarizing plate of this invention is equipped with the laminated body of the said invention whose resin film is a polarizer.

  The display device of the present invention includes the polarizing plate of the present invention.

The method for producing an optically anisotropic layer of the present invention develops a composition containing a liquid crystal compound represented by the following general formula 1 or a polymerizable composition containing a liquid crystal compound represented by the following general formula 1, The composition or polymerizable composition is cured after heating to align the long axes of the molecules of the liquid crystal compound represented by the following general formula 1. The preferred structure of general formula 1 is the same as that of the optically anisotropic layer of the present invention.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, respectively;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the Ar group is 8 or more.

  In the method for producing an optically anisotropic layer of the present invention, a composition comprising a liquid crystal compound represented by general formula 1 on a support having a glass transition temperature higher than the alignment temperature of the liquid crystal compound represented by general formula 1 Alternatively, it is preferable to develop a polymerizable composition.

  In the present specification, the “alignment temperature of the liquid crystal compound” means a phase transition temperature necessary for the liquid crystal compound to obtain an alignment state.

The liquid crystal compound of the present invention is represented by the following general formula 1. The preferred structure of general formula 1 is the same as that of the optically anisotropic layer of the present invention.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, respectively;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents any aromatic ring represented by the following general formulas 2-1 to 2-4.
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded,
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring possessed by may have a substituent, and Ax and Ay may combine to form a ring,
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

The method for producing a liquid crystal compound of the present invention is a method for producing a liquid crystal compound represented by the following general formula 1, which comprises reacting a compound represented by the following general formula 4 with a compound represented by the following general formula 5. Is.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, respectively;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar is a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represent.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
T ₁ is a linear or branched alkylene group having 2 to 20 carbon atoms;
However, in the formula, Ar has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represents a divalent group.

The carboxylic acid compound of the present invention is represented by the following general formula 7, and is suitable as the carboxylic acid compound used in the method for producing the liquid crystal compound of the present invention.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
Sp ₁ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O—, —S—, —C (= O) —, —OC (═O) —, —C (═O) O—, —OC (═O) O—, —NR ¹ C (═O) —, —C (═O) NR ² —, ^{-OC (= O) NR 3 -} , - NR 4 C (= O) O -, - SC (= O) - or -C (= O) S- may be substituted ^{by, R 1,} R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ represents a polymerizable group.

  The optically anisotropic layer of the present invention is obtained by using a liquid crystal compound that has a low phase transition temperature necessary for liquid crystal alignment, a high solubility in a solvent, and a reverse wavelength dispersibility as compared with the conventional one. It is. Therefore, according to the present invention, it is possible to provide an optically anisotropic layer having reverse wavelength dispersion that is excellent in production suitability.

It is a cross-sectional schematic diagram which shows the structure of the optically anisotropic layer and polarizing plate of one Embodiment which concerns on this invention. It is a schematic top view of a part of the pixel electrode on the inner surface of the substrate of the IPS type liquid crystal cell. 1 is a schematic cross-sectional configuration diagram of an IPS liquid crystal display device including a polarizing plate according to an embodiment of the present invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In the present specification, a numerical range represented by using “to” means a range including numerical values described before and after “to” as a lower limit value and an upper limit value. Further, “orthogonal” and “parallel” with respect to an angle shall mean a range of a strict angle ± 10 °, and “identical” and “different” with respect to an angle indicate whether or not the difference is less than 5 °. It can be judged on the basis of.

In this specification, the “slow axis” means a direction in which the refractive index becomes maximum in the plane, and the “polarizing plate” means a long polarizing plate and a display device unless otherwise specified. It is used to include both polarizing plates cut to the size to be incorporated. Here, “cutting” includes “punching” and “cutting out”. Further, in the present specification, among the “polarizing plates”, in particular, a form including a laminate of the optical film of the present invention or a general λ / 4 plate and a polarizing film is referred to as a “circular polarizing plate”.
The organic EL display device means an organic electroluminescence display device.

In this specification, “tilt angle” (also referred to as tilt angle) means an angle formed by tilted liquid crystal with the layer plane, and the direction of the maximum refractive index in the refractive index ellipsoid of the liquid crystal compound is the layer plane. It means the maximum angle among the angles. Therefore, in a liquid crystal compound having positive optical anisotropy, the tilt angle means an angle formed between the major axis direction of the liquid crystal compound, that is, the director direction and the layer plane. In the present invention, “average tilt angle” means an average value of tilt angles from the tilt angle at the upper interface to the lower interface of the retardation layer.
In the present specification, the reverse wavelength dispersion means a property that the absolute value of the in-plane retardation becomes larger as the wavelength becomes longer.

  In this specification, Re (λ) and Rth (λ) respectively represent in-plane retardation and retardation in the thickness direction at a wavelength λ. Re (λ) is measured by making light having a wavelength of λ nm incident in the normal direction of the film in KOBRA 21ADH or WR (trade name, manufactured by Oji Scientific Instruments).

When the film to be measured is represented by a uniaxial or biaxial refractive index ellipsoid, Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), with the in-plane slow axis (determined by KOBRA 21ADH or WR) as the tilt axis (rotation axis) (if there is no slow axis, it is arbitrary in the film plane) The light is incident at a wavelength of λ nm from the inclined direction in steps of 10 degrees from the normal direction to 50 degrees on one side with respect to the film normal direction of the rotation axis of It is calculated in KOBRA 21ADH or WR based on the measured retardation value, the assumed value of the average refractive index, and the input film thickness value.

In the above case, in the case of a film having a direction in which the retardation value is zero at a certain tilt angle with the in-plane slow axis from the normal direction as the rotation axis, retardation at a tilt angle larger than the tilt angle. The value is calculated in KOBRA 21ADH or WR after changing its sign to negative.
In addition, the retardation value is measured from the two inclined directions, with the slow axis as the tilt axis (rotation axis) (when there is no slow axis, the arbitrary direction in the film plane is the rotation axis), Based on the value, the assumed value of the average refractive index, and the input film thickness value, Rth can also be calculated by the following formulas (7) and (8).

  In the formula, Re (θ) represents a retardation value in a direction inclined by an angle θ from the normal direction. In particular, when θ is not described, θ indicates 0 °. nx represents the refractive index in the slow axis direction in the plane, ny represents the refractive index in the direction perpendicular to nx in the plane, and nz represents the refractive index in the direction perpendicular to nx and ny. d represents the film thickness of the film.

In the case where the film to be measured cannot be expressed by a uniaxial or biaxial refractive index ellipsoid, that is, a film having no so-called optical axis (OPTIC AXIS), Rth (λ) is calculated by the following method.
Rth (λ) is Re (λ), and the in-plane slow axis (determined by KOBRA 21ADH or WR) is the tilt axis (rotation axis) from −50 degrees to +50 degrees with respect to the film normal direction. The light of wavelength λ nm is incident from each inclined direction in 10 degree steps and measured at 11 points, and KOBRA 21ADH or Calculated by WR.

In the above measurement, as the assumed value of the average refractive index, the values in the polymer handbook (John Wiley & Sons, Inc.) and catalogs of various optical films can be used. Those whose average refractive index is not known can be measured with an Abbe refractometer. The average refractive index values of main optical films are exemplified below: cellulose acylate (1.48), cycloolefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), Polystyrene (1.59). By inputting the assumed value of the average refractive index and the film thickness, nx, ny, and nz are calculated in KOBRA 21ADH or WR. Nz = (nx−nz) / (nx−ny) is further calculated from the calculated nx, ny, and nz.
The retardations Re and Rth can also be measured by using AxoScan (AXOMETRIC), and Nz can also be obtained by Nz = Rth / Re + 0.5.

[Optically anisotropic layer]
The optically anisotropic layer of the present invention contains the liquid crystal compound of the present invention represented by the general formula 1 or is formed by curing of a polymerizable composition containing the liquid crystal compound of the present invention. It is a layer having the long axis of the molecule of the compound oriented, and has a single incident direction and wavelength where retardation is not 0 when measuring retardation, that is, a layer having optical properties that are not isotropic.

  The thickness of the optically anisotropic layer varies depending on the material used and the retardation value to be set, but is preferably 0.1 to 20 μm, more preferably 0.5 to 15 μm, and 1.0 to More preferably, it is 10 μm. Further, the in-plane retardation Re (550) and Rth at a wavelength of 550 nm of the optically anisotropic layer are appropriately selected because preferred ranges differ depending on the application. In addition, in this specification, the thickness of each layer shows the value which measured the film thickness of five places at random, and averaged the film thickness.

  In the optically anisotropic layer of the present invention, the alignment state of the long axis of the molecule of the liquid crystal compound of the present invention, which will be described in detail later, is preferably fixed in a nematic phase or a smectic phase, and is fixed in a smectic phase. Is more preferable. The liquid crystal compound of the present invention exhibits a smectic phase and / or a nematic phase in which the major axes of the molecules are aligned, and a chiral nematic phase can also be formed by using a chiral agent. The optically anisotropic layer used for optical compensation is preferably a smectic phase having a high degree of orientational order.

Smectic liquid crystals can be more preferably used in applications that require a relatively large retardation of 100 nm or more, because the scattering and depolarization of the optically anisotropic layer due to orientation fluctuation is small. The smectic phase is not particularly limited and may be any higher-order phase that can be taken by liquid crystal molecules such as SmA, SmB, and SmC, and is appropriately selected depending on desired optical characteristics.
In order to confirm whether the liquid crystal compound is fixed in the state of the smectic phase, it can be performed by observation with an X-ray diffraction pattern. If the smectic phase is fixed, an X-ray diffraction pattern derived from the layer order is observed, so that the fixed state can be determined. In order to confirm whether the liquid crystal compound is fixed in a nematic phase, it can be performed by observation with an X-ray diffraction pattern. If the nematic phase is fixed, the sharp peak on the low-angle side due to the layer formation is not observed, and only the broad halo peak on the wide-angle side is observed, thereby determining the fixed state. Is possible.

  In the optically anisotropic layer of the present invention, the alignment state of the long axis of the liquid crystal compound represented by the general formula 1 is various alignments such as homogeneous alignment and homeotropic alignment in order to obtain a desired phase difference. The state can be selected, but is preferably fixed in a homogeneous orientation.

  In the present invention, the angle between the maximum direction of the refractive index and the layer plane is 10 ° by fixing the orientation state of homogeneous orientation or substantially horizontal tilt orientation (hereinafter also referred to as (substantially) horizontal orientation). In the following, an optically anisotropic layer having an angle of preferably 3 ° or less and particularly preferably 1 ° or less can be obtained. On the other hand, by fixing the orientation state of homeotropic orientation or substantially vertical tilt orientation (hereinafter also referred to as (substantially) vertical orientation), the angle between the maximum direction of the refractive index and the normal direction of the layer plane Is 10 ° or less, preferably 3 ° or less, and particularly preferably 1 ° or less.

  As one embodiment of the optically anisotropic layer of the present invention, when a homogeneously oriented smectic phase is immobilized, the compound represented by the general formula 1 that expresses the smectic phase is regulated so that it becomes homogeneously oriented. By maintaining the conditions such as the temperature at which the smectic phase is developed in such a state, it can be formed into a homogeneously oriented smectic phase state and fixed by polymerization, photocrosslinking or thermal crosslinking. Details of the method of manufacturing the optically anisotropic layer will be described later.

The optically anisotropic layer of the present invention has reverse wavelength dispersion. Inverse wavelength dispersion means a property in which the phase difference on the long wave side is larger than the phase difference on the short wave side. For example, in an optically anisotropic layer (so-called A plate) in which the major axis orientation state of the molecule is fixed in a substantially horizontal orientation, the phase difference Re at wavelengths of 450 nm, 550 nm, and 650 nm of the optically anisotropic layer. (450 nm), Re (550 nm), and Re (650 nm) satisfy the following formulas (I) and (II). In the present invention, preferable ranges of blue (450 nm) and red (650 nm) when giving positive birefringence to green (550 nm), which is most important for improving the viewing angle characteristics, are represented by Formulas I and II. It becomes a range. In the optically anisotropic layer of the present invention, the higher the steepness of reverse wavelength dispersion, the better. Therefore, the phase differences Re (450 nm), Re (550 nm), and Re (650 nm) satisfy the following formulas A and B. It is preferable that the value of Re (450 nm) / Re (550 nm) satisfy the following formula C. By having steep reverse wavelength dispersion, a high-performance optical instrument can be provided.
Re (450 nm) / Re (550 nm) <1.0 Formula I
Re (650 nm) / Re (550 nm)> 1.0 Formula II
Re (450 nm) / Re (550 nm) <0.95 Formula A
Re (650 nm) / Re (550 nm)> 1.02 Formula B
0.50 ≦ Re (450 nm) / Re (550 nm) <0.90 Expression C

In order to obtain an optically anisotropic layer that satisfies the above formulas I and II, it is necessary to arrange the absorption wavelength and the direction of the transition moment in the direction orthogonal to the alignment direction.
The wavelength dispersion of the refractive index is closely related to the absorption of the substance, as represented by the Lorentz-Lorenz equation. To make the wavelength dispersion in the orthogonal direction more downward, the absorption transition wavelength in the molecular minor axis direction is made longer than the absorption transition wavelength in the molecular major axis direction (orientation direction). Thus, an optically anisotropic layer satisfying Formulas I and II can be obtained.
Hereinafter, the liquid crystal compound of the present invention represented by Formula 1 will be described.

<< Liquid Crystal Compound >>
The liquid crystal compound of the present invention is represented by the following general formula 1.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, and most preferably 2.
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the Ar group is 8 or more.
In addition, L1, L2, F1, F2, T ₁ , T ₂ , and Ar may have a substituent.

  In the present specification, the number of the substituents when they may have a substituent, as well as the type and substitution position thereof are not limited, and when two or more substituents are present, they are the same. Or different. The type of substituent is not particularly limited. Examples of substituents include alkyl groups, alkoxy groups, alkyl-substituted alkoxy groups, cyclic alkyl groups, aryl groups such as phenyl groups, naphthyl groups, cyano groups, amino groups, nitro groups, alkylcarbonyl groups, sulfo groups, hydroxyl groups, etc. Is mentioned.

The spacer portions T ₁ and T ₂ are terminal portions in the compound represented by the general formula 1. The spacer portion is not particularly limited as long as it contains a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms. Specific examples of the alkylene group or alkylene oxide group include — (CH ₂ ) _{x. -, - (CH 2) x} -O -, - (CH 2 -O-) x -, - such as (CH ₂ CH _{2 -O-) x} may be mentioned.

In the general formula 1, by setting T1 and T2 to the structure represented by the following general formula 3, the liquid crystal compound represented by the above general formula 1 can be polymerized and fixed in the optically anisotropic layer.
In the formula, Sp1 and Sp2 each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O—. , —S—, —C (═O) —, —OC (═O) —, —C (═O) O—, —OC (═O) O—, —NR ¹ C (═O) —, — C (═O) NR ² —, —OC (═O) NR ³ —, —NR ⁴ C (═O) O—, —SC (═O) — or —C (═O) S— is substituted. R ¹ , R ² , R ³ , and R ⁴ each independently represent a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ and P ₂ each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.

P ₁ and P ₂ are preferably an ethylenically unsaturated group or a ring-opening polymerizable group. The ethylenically unsaturated group is preferably a (meth) acryloyl group, and the ring-opening polymerizable group is preferably an epoxy group or an oxetanyl group.

In the general formula 1, Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of Π electrons contained in the Ar group is 8 That's it.
A direction intersecting with the direction in which the cyclic group is linked and the direction in which the spacer portion extends (molecular long axis direction) in the compound represented by the general formula 1 when the number of Π electrons contained in the Ar group is 8 or more, That is, it is presumed that the absorption wavelength in the short axis direction of the molecule becomes a long wavelength, and the phase difference generated by the aligned liquid crystal molecules has reverse wavelength dispersion. The number of Π electrons is preferably 8 or more and 40 or less, more preferably 10 or more and 36 or less, and still more preferably 12 or more and 30 or less.

Ar is preferably a divalent aromatic ring group represented by the following formulas 2-1, 2-2, 2-3, or 2-4.
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded,
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring possessed by may have a substituent, and Ax and Ay may combine to form a ring,
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.

Preferred examples of the liquid crystal compound of the present invention represented by the general formula 1 are shown below, but are not particularly limited thereto.

The liquid crystal compound of the present invention can be produced by reacting a compound represented by the following general formula 4 with a compound represented by the following general formula 5. That is, the method for producing a liquid crystal compound of the present invention is a method for producing a liquid crystal compound represented by the following general formula 1, which comprises a compound represented by the following general formula 4 and a compound represented by the following general formula 5. It is what makes it react.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represent an integer of 1 to 4, preferably 1 or 2, and most preferably 2.
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar is a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represent.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
T ₁ is a linear or branched alkylene group having 2 to 20 carbon atoms;
However, in the formula, Ar has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represents a divalent group. For a preferred configuration of Ar, the description relating to Ar shown in the general formula 1 can be referred to.

Among the carboxylic acid compounds represented by the above general formula 4, the carboxylic acid compound of the present invention represented by the following general formula 7 is represented by the general formula 1 in which the spacer portions T ₁ and T ₂ are represented by the above general formula 3. The liquid crystal compound of the present invention can be produced. The carboxylic acid compound represented by the general formula 7 is a novel compound.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
Sp ₁ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O—, —S—, —C (= O) —, —OC (═O) —, —C (═O) O—, —OC (═O) O—, —NR ¹ C (═O) —, —C (═O) NR ² —, ^{-OC (= O) NR 3 -} , - NR 4 C (= O) O -, - SC (= O) - or -C (= O) S- may be substituted ^{by, R 1,} R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ represents a polymerizable group.

  In addition, the compound of the general formula (4) which is the intermediate is esterified with (4-hydroxyphenyl) alcohol and a chain carboxylic acid or isocyanate having a spacer part T1, and then further with 1,4-cyclohexanedicarboxylic acid and an ester. Or a method in which (4-hydroxyphenyl) alkylcarboxylic acid and a chain alcohol having a spacer part T1 are esterified and then further esterified with 1,4-cyclohexanedicarboxylic acid.

<< Method for Producing Optical Anisotropic Layer >>
The method for producing an optically anisotropic layer of the present invention comprises developing a composition containing the liquid crystal compound of the present invention or a polymerizable composition containing the liquid crystal compound of the present invention, and heating the composition. After orienting the long axis of the compound molecule, the composition or polymerizable composition is cured.

  In the method for producing an optically anisotropic layer of the present invention, a composition containing the liquid crystal compound of the present invention on a support having a glass transition temperature higher than the alignment temperature of the liquid crystal compound of the present invention, or the present invention It is preferable to develop a polymerizable composition containing the liquid crystal compound.

For the production of the optically anisotropic layer using the liquid crystal compound of the present invention, a method similar to the method for producing an optically anisotropic layer using a general liquid crystal compound can be applied.
Examples of a method for producing an optically anisotropic layer using a general liquid crystal compound include, for example, a method in which a composition containing a liquid crystal compound is sealed in a gap and the like, and an alignment state and the like are manipulated by heat, electric field, pressure, etc. In addition, after a polymerizable composition containing a liquid crystal compound is applied to a support as a coating liquid and subjected to an alignment treatment, the liquid crystal compound itself or a polymerizable component in the composition is polymerized and cured in order to fix the alignment state. The method of making it known is known.
Hereinafter, as an example, the polymerizable composition containing the liquid crystal compound of the present invention, which is the latter, is developed and heated to align the major axis of the molecules of the liquid crystal compound of the present invention, and then the polymerizable composition A method for producing an optically anisotropic layer by fixing the orientation state by curing is described.

"Polymerizable composition"
The polymerizable composition used in the method for producing an optically anisotropic layer of the present invention is not particularly limited as long as it contains at least one liquid crystal compound of the present invention, but in the general formula 1, the spacer portion T ₁ or T _{When 2} does not have a polymerizable group, it is necessary to contain other polymerizable compounds.
In addition to the liquid crystal compound of the present invention represented by the general formula 1, the polymerizable composition can contain a polymerizable compound, an alignment controller, an arbitrary solvent, an additive, and the like. The polymerizable liquid crystal compound is preferably 50 to 98 mass%, more preferably 70 to 95 mass%, based on the total solid content mass of the polymerizable composition.

(Polymerizable compound)
The polymerizable compound that can be contained in the polymerizable composition may be liquid crystalline or not. By adding a polymerizable compound, various physical properties such as a phase transition temperature and crystallinity of the polymerizable composition can be controlled. As described above, since this polymerizable compound is mixed with the liquid crystal compound of the present invention and handled as a polymerizable composition, it is preferably highly compatible with the liquid crystal compound of the present invention. Hereinafter, suitable polymerizable compounds will be described.

((Non-liquid crystalline polyfunctional polymerizable compound))
By adding the non-liquid crystalline polyfunctional polymerizable compound to the polymerizable composition, the liquid crystal compound of the present invention functions as a binder by polymerization and curing even when the liquid crystal compound of the present invention has no polymerizable group. The state can be fixed. Furthermore, in the case of a smectic phase, the interlayer is connected by a non-liquid crystalline polyfunctional polymerizable compound, so that proximity between the layers can be suppressed.
As such a non-liquid crystalline polyfunctional polymerizable compound,
Esters of polyhydric alcohol and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate, pentaerythritol tri (meth) acrylate, trimethylolpropane Tri (meth) acrylate, trimethylolethane tri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,2,3-cyclohexanetetra Methacrylate, polyurethane polyacrylate, polyester polyacrylate), vinylbenzene and its derivatives (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-a) Leroy Le ethyl ester, 1,4-divinyl cyclohexanone), vinyl sulfones (e.g., divinyl sulfone), acrylamides (e.g., include methylenebisacrylamide) and methacrylamide.

  If the content of the non-liquid crystalline polyfunctional polymerizable compound in the polymerizable composition is too large, the expression of retardation of the optically anisotropic layer is diluted, so that the solid content concentration is 0.1 to 20% by mass. It is preferably 0.1 to 10% by mass, more preferably 0.1 to 5% by mass, or 1 to 20% by mass, preferably 1 to 10% by mass. It is more preferable that it is mass%, and it is especially preferable that it is 1-5 mass%.

(Polymerization initiator)
In order to polymerize and cure the liquid crystal compound of the present invention having a polymerizable group or the polymerizable compound added as a binder, it is preferable to include a polymerization initiator in the polymerizable composition. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator, a photopolymerization reaction using a photopolymerization initiator, and EB curing using an electron beam, and a photopolymerization reaction is preferred. In the polymerization composition, the content of the photopolymerization initiator is 0.01 to in terms of solid concentration with respect to the total polymerizable compound including the liquid crystal compound of the present invention having a polymerizable group and other polymerizable compounds. The content is preferably 20% by mass, and more preferably 0.5 to 5% by mass.

(Orientation control agent)
The polymerizable composition can contain an alignment control agent as necessary. As the orientation control agent, for example, a low molecular orientation control agent or a high molecular orientation control agent can be used. Examples of the low molecular orientation control agent include paragraphs 0009 to 0083 of JP-A No. 2002-20363, paragraphs 011 to 0120 of JP-A No. 2006-10662, and paragraphs 0021 to 0029 of JP-A No. 2012-211306. Description can be taken into account, the contents of which are incorporated herein. Examples of the polymer orientation control agent may include, for example, descriptions in paragraphs 0021 to 0057 of JP-A-2004-198511 and paragraphs 0121 to 0167 of JP-A-2006-106662. Is incorporated herein.
The amount of the alignment control agent used is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the solid content of the liquid crystal composition of the present invention in the polymerizable composition. . By using the alignment control agent, for example, the liquid crystal compound of the present invention can be brought into a homogeneous alignment state in which the liquid crystal compound is aligned in parallel with the surface of the layer.

(Additive)
In addition to the above, examples of additives that can be contained in the polymerizable composition include surfactants for controlling surface properties and surface shapes, and additives for controlling the tilt angle of liquid crystal compounds (alignment aids). Agent), an additive (plasticizer) for lowering the orientation temperature, and other agents for imparting functionality, and the like can be used as appropriate.

(solvent)
In order to improve the production suitability during development of the optically anisotropic layer, a solvent can be added to the polymerizable composition for the purpose of adjusting the viscosity.
The solvent that can be used is not particularly limited as long as the production suitability is not impaired, but is preferably selected from at least one of the group consisting of ketone, ester, ether, alcohol, alkane, toluene, chloroform, and methylene chloride. ,
More preferably, it is selected from at least one selected from the group consisting of ketones, esters, ethers, alcohols, alkanes,
It is particularly preferred to be selected from at least one member selected from the group consisting of ketones, esters, ethers and alcohols.
Although the usage-amount of a solvent is generally 50-90 mass% as a density | concentration in polymeric composition, it is not specifically limited.

[Development of polymerizable composition]
In the method for producing an optically anisotropic layer of the present invention, the polymerizable composition is developed and heated to align the long axes of the molecules of the liquid crystal compound of the present invention, and then the polymerizable composition is cured. Thus, the alignment state is fixed to obtain an optically anisotropic layer.
Although it does not restrict | limit especially as a expansion | deployment method of polymeric composition, It is preferable to implement by apply | coating (including casting) polymeric composition on a support body. In such a method, the support to be used is not particularly limited, but in order to obtain the alignment state of the liquid crystal compound developed on the support, the liquid crystal compound of the present invention is aligned in the aligning step. In order to heat the support so as to be equal to or higher than the phase transition temperature necessary for obtaining the orientation temperature, that is, the alignment temperature, the support has the same glass transition temperature than the alignment temperature of the liquid crystal compound of the present invention. A high support is preferred. If the support has a glass transition temperature higher than the orientation temperature, the support can be prevented from being thermally deformed by heating during orientation.

In the case of forming a temporary support that is peeled off after forming the optically anisotropic layer, a material having a surface property that is easy to peel off may be used for the support. As such a support, glass, a polyester film not subjected to easy adhesion treatment, or the like can be used.
In addition, after forming an optically anisotropic layer on a support and using it as a laminate as described later, the support is an optical film substrate such as cellulose, cyclic olefin, acrylic, polycarbonate, polyester, polyvinyl alcohol, etc. Alternatively, a liquid crystal cell substrate or a polarizer can be preferably used.

[Orientation of liquid crystal compound molecules]
In the method for producing an optically anisotropic layer of the present invention, a polymerizable composition developed on a support or the like is brought into a desired alignment state with the major axis of the molecule of the liquid crystal compound of the present invention in the polymerizable composition. . Here, the alignment state generally includes both types of liquid crystal phases such as a nematic phase and a smectic phase, and alignment of liquid crystal molecules necessary for display such as twist alignment, hybrid alignment, homeotropic alignment, and homogeneous alignment. The former is generally controlled by a phase transition due to a change in temperature or pressure, and the latter is generally controlled by an alignment process.

(Orientation treatment)
As a method of alignment treatment, for example, a method of aligning a liquid crystal compound in a desired direction using an alignment film is common. As the alignment film, a rubbing treatment film made of an organic compound such as a polymer, an oblique deposition film of an inorganic compound, a film having a microgroove, or an organic compound such as ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearylate. Examples include a film in which the LB film is accumulated by the Langmuir-Blodgett method. However, when considering a laminating process in which the polymerizable composition is developed, a film formed by rubbing the surface of the polymer layer or a polymer A photo-alignment film formed by photo-aligning the surface of the layer is preferable. The heat resistance of these alignment films is the same as that described for the support.

The rubbing treatment is performed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. The kind of polymer used for the alignment layer is polyimide, polyvinyl alcohol, polymer having a polymerizable group described in JP-A-9-152509, JP-A-2005-97377, JP-A-2005-99228, and An orthogonal alignment film described in JP-A-2005-128503 can be preferably used. The term “orthogonal alignment film” as used in the present invention means an alignment film that aligns the major axis of the molecules of the polymerizable liquid crystal compound of the present invention so as to be substantially orthogonal to the rubbing direction of the orthogonal alignment film. The thickness of the alignment layer is not required to be thick as long as it can provide an alignment function, and is preferably 0.01 to 5 μm, and more preferably 0.05 to 2 μm.
In addition, a so-called photo-alignment film in which a photo-alignment material is irradiated with polarized light or non-polarized light to form an alignment film can also be used. That is, a photo-alignment film may be produced by applying a light distribution material on a support. Irradiation with polarized light can be performed in a vertical direction or an oblique direction with respect to the photo-alignment film, and irradiation with non-polarized light can be performed in an oblique direction with respect to the photo-alignment film.

  The photo-alignment material used for the photo-alignment film that can be used in the present invention is described in many documents. In the photo-alignment film of the present invention, for example, JP 2006-285197 A, JP 2007-76839 A, JP 2007-138138 A, JP 2007-94071 A, JP 2007-121721 A, The azo compounds described in JP2007-140465A, JP2007-156439A, JP2007-133184A, JP2009-109831A, JP3883848B, and JP4151746A, and JP2002 Aromatic ester compounds described in JP-A-229039, maleimide and / or alkenyl-substituted nadiimide compounds having a photo-alignment unit described in JP-A-2002-265541, JP-A-2002-317013, Patent No. 4205195, Photocrosslinking described in Japanese Patent No. 4205198 Silane derivatives, photocrosslinkable polyimides, polyamides, or esters described in JP-A-2003-520878, JP-A-2004-529220, and JP-A-4162850, JP-A-9-118717, JP-A-10-506420 No. 2003, No. 2003-505561, WO 2010/150748, JP 2013-177561 A, JP 2014-12823 A, photodimerizable compounds, particularly cinnamate compounds, chalcone compounds, and coumarin compounds. Is a preferred example. Particularly preferred are azo compounds, photocrosslinkable polyimides, polyamides, esters, cinnamate compounds, and chalcone compounds.

Specific examples of particularly preferred photo-alignment materials include compounds represented by the following formula (X) described in JP-A-2006-285197.
(In the formula, R ¹ and R ² each independently comprises a hydroxy group or a (meth) acryloyl group, a (meth) acryloyloxy group, a (meth) acrylamide group, a vinyl group, a vinyloxy group, and a maleimide group. Represents a polymerizable group selected from the group;
X ¹ represents a single bond when R ¹ is a hydroxy group, and represents a linking group represented by — (A ¹ -B ¹ ) _m — when R ¹ is a polymerizable group, and X ² represents R ^{When 2} is a hydroxy group, it represents a single bond, and when R ² or R ⁸ is a polymerizable group, it represents a linking group represented by — (A ² —B ² ) _n —. Here, A ¹ is bonded to R ¹ or R ⁷ , A ² is bonded to R ² or R ^8, and B ¹ and B ² are bonded to adjacent phenylene groups. A ¹ and A ² each independently represent a single bond or a divalent hydrocarbon group, and B ¹ and B ² each independently represent a single bond, —O—, —CO—O—, —O—CO. -, -CO-NH-, -NH-CO-, -NH-CO-O-, or -O-CO-NH- is represented. m and n each independently represents an integer of 0 to 4. However, when m or n is 2 or more, a plurality of A ¹ , B ¹ , A ² and B ² may be the same or different. However, A ¹ or A ² sandwiched between two B ¹ or B ² is not a single bond. R ³ and R ⁴ each independently represent a hydrogen atom, a halogen atom, a carboxyl group, a halogenated methyl group, a halogenated methoxy group, a cyano group, a nitro group, or —OR ⁷ (wherein R ⁷ has 1 to 6 represents a lower alkyl group having 6 to 6 carbon atoms, a lower alkyl group having 1 to 6 carbon atoms substituted by a cycloalkyl group having 3 to 6 carbon atoms or a lower alkoxy group having 1 to 6 carbon atoms), and 1 to 4 carbon atoms A hydroxyalkyl group, or —CONR ⁸ R ⁹ (R ⁸ and R ⁹ each independently represents a hydrogen atom or a lower alkyl group having 1 to 6 carbon atoms), or a methoxycarbonyl group. However, the carboxyl group may form a salt with the alkali metal.
R ⁵ and R ⁶ each independently represent a carboxyl group, a sulfo group, a nitro group, an amino group, or a hydroxy group. However, the carboxyl group and the sulfo group may form a salt with the alkali metal. )

  Also, by selecting the material of the alignment film, it can be peeled off from the optically anisotropic layer forming temporary support or only the optically anisotropic layer can be peeled off. By combining, a thin optically anisotropic layer having a thickness of several μm can be provided. Furthermore, a mode in which a rubbing alignment film or a photo-alignment film is applied and laminated directly on a linear polarizer, and an alignment function is given by rubbing or photo-alignment treatment is also preferable. That is, the laminate of the present invention may be a laminate having a linear polarizer and having a photo-alignment film or a rubbing alignment film on the surface of the linear polarizer.

In the optically anisotropic layer obtained by homogeneously aligning the liquid crystal compound of the present invention represented by the general formula 1, it is preferable that the pre-tilt angle is low. By using a photo-alignment film as the alignment film and applying it to the IPS system, it is possible to achieve both high contrast with reduced light leakage on the front and good viewing angle dependence with reduced oblique color change. Therefore, an embodiment in which the photo-alignment film is used as the alignment film is preferable. In the photo-alignment film, a mode in which the alignment regulating force is applied to the photo-alignment film by a step of irradiating polarized light from a vertical direction or an oblique direction or a step of irradiating non-polarized light from an oblique direction is preferable. The oblique direction when irradiating from the oblique direction is preferably an angle of 5 to 45 degrees with respect to the photo-alignment film, and more preferably an angle of 10 to 30 degrees. The irradiation intensity is preferably 200 to 2000 mJ / cm ² .

  In the optically anisotropic layer obtained by homeotropic alignment of the liquid crystal compound of the present invention represented by the general formula 1, a desired alignment state can be obtained using a vertical alignment film or a vertical alignment agent. Paragraphs [0081] to [0082] of JP-A-2002-294240 can be referred to for the vertical alignment film, and paragraphs [0083] to [0084] of JP-A-2006-106662 can be referred to for the vertical alignment agent. .

(Control of phase transition)
As already described, the liquid crystal phase of the liquid crystal compound can generally be changed by a change in temperature or pressure. In the case of a liquid crystal having lyotropic properties, the liquid crystal can also be transferred depending on the amount of solvent. In the present invention, it is preferable that the thermotropic liquid crystal undergo a phase transition by a temperature change in consideration of the subsequent operation of fixing the alignment state.
Hereinafter, a case where the state of the smectic phase having the homogeneous orientation is fixed will be described as an example.

  The temperature range in which the liquid crystal compound develops a nematic phase is generally higher than the temperature range in which the liquid crystal compound develops a highly ordered smectic phase. Therefore, the liquid crystal compound is heated from the nematic phase to the smectic phase by heating the liquid crystal compound to a temperature range where the liquid crystal compound develops a nematic phase, and then lowering the heating temperature to a temperature range where the liquid crystal compound develops a smectic phase. It is preferable to transfer.

Due to its structure, the liquid crystal compound of the present invention represented by the general formula 1 has a high free mobility of a terminal chain aliphatic group, and has an appropriate steric hindrance to express an appropriate intermolecular interaction. The temperature drops. The temperature at which the liquid crystal compound of the present invention transitions from the smectic phase to the nematic phase is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and particularly preferably 140 ° C. or lower. The lower limit of the temperature at which the above smectic phase transitions to the nematic phase is not particularly limited, but is generally 20 ° C. or higher.
The lower the phase transition temperature, the better the choice from the viewpoint of the heat resistance of the material used for the support and the alignment layer.

  Here, the temperature at which the compound transitions from the smectic phase to the nematic phase can be easily measured by observing the composition with a polarizing microscope. For example, in the nematic phase, a schlieren texture peculiar to the nematic phase is observed, but in the smectic A phase, it transitions to a focal conic fan texture. Can be measured.

In a temperature range where the liquid crystal compound develops a nematic phase, it is necessary to heat for a certain time until the liquid crystal compound forms a monodomain. The heating time is preferably 10 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, and most preferably 10 seconds to 5 minutes.
In a temperature range where the liquid crystal compound develops a smectic phase, it is necessary to heat for a certain period of time until the liquid crystal compound develops a smectic phase. The heating time is preferably 10 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, and most preferably 10 seconds to 5 minutes.

  In addition, by using a liquid crystal compound that exhibits a higher order smectic phase simultaneously with the nematic phase as the liquid crystal compound of the present invention, the nematic phase is different from the normal nematic phase, and has a low light scattering component and high contrast. Nematic phase can be realized. This feature is particularly achieved by using the liquid crystal compounds of the present invention represented by the above chemical formulas I-1 to I-14 and II-8 to II-10.

Therefore, in the present invention, it is also a preferred embodiment that the liquid crystal compound is heated in a temperature range in which a nematic phase is developed, and a monodomain is formed in this temperature range and then fixed. It has been discovered that the retardation produced in such a manner can provide a significantly higher contrast than the retardation produced from a liquid crystal compound that exhibits only a normal nematic phase.
In a temperature range where the liquid crystal compound develops a nematic phase, it is necessary to heat for a certain time until the liquid crystal compound forms a monodomain. The heating time is preferably 10 seconds to 20 minutes, more preferably 10 seconds to 10 minutes, and most preferably 10 seconds to 5 minutes.

  In addition, when using a composition that transitions in the order of smectic phase → nematic phase → isotropic phase as the temperature rises, the polymerizable composition is once transformed into a nematic phase-isotropic phase transition temperature. After heating to the above, gradually lower the temperature below the phase transition temperature of the smectic phase-nematic phase or the phase transition temperature of the smectic phase-isotropic phase at a predetermined rate. It can be transferred to the phase. The temperature after the reduction is preferably 10 ° C. or more lower than the phase transition temperature of the smectic phase-nematic phase or the phase transition temperature of the smectic phase-isotropic phase. The cooling rate is preferably within a range of 1 to 100 ° C./min, and preferably within a range of 5 to 50 ° C./min. If the cooling rate is too fast, alignment defects will be produced, and if it is too slow, it will take a long production time.

In the present invention, the tilt angle of the optically anisotropic layer can also be controlled by tilting the liquid crystal compound molecules in a state where the primary structure of the smectic phase is appropriately separated.
Means for controlling the tilt angle of the liquid crystal compound include a method of imparting a pre-tilt angle with an alignment film with controlled rubbing conditions, and a polar angle on the support side or air interface side by adding a tilt angle control agent to the liquid crystal layer. It is preferable to use these in combination.
As an example of the tilt angle control agent, a copolymer of a fluoroaliphatic group-containing monomer can be used, and a copolymer with an aromatic condensed ring functional group, a carboxyl group, a sulfo group, a phosphonoxy group or a salt thereof can be used. It is preferable to use a copolymer with the monomer to be contained. Further, by using a plurality of tilt angle control agents, it becomes possible to control more precisely and stably. As such an inclination angle controlling agent, descriptions in paragraphs 0022 to 0063 of JP-A-2008-257205 and paragraphs 0017 to 0124 of JP-A-2006-91732 can be referred to.

[Fixed orientation]
The alignment state can be fixed by thermal polymerization or polymerization by active energy rays, and can be performed by appropriately selecting a polymerizable group and a polymerization initiator suitable for the polymerization. In consideration of production suitability and the like, a polymerization reaction by ultraviolet irradiation can be preferably used. When the irradiation amount of ultraviolet rays is small, unpolymerized polymerizable liquid crystal and other polymerizable compounds remain, which causes a temperature change of optical characteristics and deterioration with time.
Therefore, it is preferable to determine the irradiation conditions so that the ratio of the remaining polymerizable liquid crystal is 5% or less. The irradiation conditions depend on the prescription of the polymerizable composition and the film thickness of the optically anisotropic layer, but as a guideline. It is preferable to carry out at an irradiation dose of 200 mJ / cm ² or more.

<< Application of optically anisotropic layer >>
Since the optically anisotropic layer of the present invention has reverse wavelength dispersion, color shift or the like is unlikely to occur, and reflection of external light is prevented by an optical compensation film for optically compensating a liquid crystal cell or an organic EL display device. Therefore, it can be applied to organic materials with poor heat resistance because it has a low phase transition temperature and high solubility in a solvent. Therefore, it is possible to expect a shortening of the manufacturing process.
Furthermore, in the case of an optically anisotropic layer with a fixed smectic phase, the high orientation order of the liquid crystal compound derived from the smectic phase results in high retardation and low depolarization, so that it has high contrast. It can be preferably used for various applications.

  Moreover, it does not specifically limit as a form to use. For example, a liquid crystal cell substrate or a polarizer may be rubbed, and an optically anisotropic layer may be directly formed thereon, or may be laminated or pasted with a polymer film or another optical film, combined, and optical It is good also as the form of the laminated body which controlled the mechanical and mechanical characteristic.

  As described above, the optically anisotropic layer of the present invention is a liquid crystal compound that has a low phase transition temperature necessary for liquid crystal alignment, high solubility in a solvent, and exhibits reverse wavelength dispersibility as compared with the prior art. It is obtained by using. Therefore, according to the present invention, it is possible to provide an optically anisotropic layer having reverse wavelength dispersion that is excellent in production suitability.

[Laminated body, polarizing plate, display device]
The optically anisotropic layer of the present invention can be laminated on other various optical members directly or using transfer or the like and used as a laminate. For example, it may be laminated on a glass substrate and used for a wavelength plate, a polarizing beam splitter, or the like, or preferably laminated on a resin film directly or via an alignment film. As will be described later, a laminate in which an optically anisotropic layer is laminated on a polarizer directly or via an alignment film is suitable as a polarizing plate.
Hereinafter, a laminate, a polarizing plate, and a display device according to an embodiment of the present invention will be described with reference to the drawings. FIG. 1 is a schematic diagram showing a configuration of a polarizing plate (laminated body) 10 according to an embodiment of the present invention. FIG. 2 is a schematic top view of a part of the pixel electrode on the inner surface of the substrate of the IPS liquid crystal cell, and FIG. 3 is a schematic cross-sectional configuration diagram of the IPS liquid crystal display device 1 including the polarizing plate 10 of the present embodiment. is there. In the drawings of the present specification, the scale of each part is appropriately changed and shown for easy visual recognition.

  As shown in FIG. 1, the polarizing plate (laminate) 10 includes a polarizing plate protective film 110 on the surface on the viewing side of the polarizer 100 and a polarizing plate protective film 120 on the surface on the liquid crystal cell side. The polarizing plate protective film 120 is provided with the optically anisotropic layer 130 of the present invention.

  The polarizer 100 is not particularly limited, and any of an iodine polarizer, a dye polarizer using a dichroic dye, and a polyene polarizer may be used. The iodine-based polarizer and the dye-based polarizer can be generally produced by immersing and stretching a polyvinyl alcohol-based film in an iodine solution.

  The polarizing plate protective films 110 and 120 are protective films for suppressing the deterioration of the polarizer 100, and are preferably films having low moisture permeability. There is no restriction | limiting in particular as polarizing plate protective film 110,120, It is preferable to select from the example of the polymer film which can be utilized as an above-described support body. A preferred example of the polarizing plate protective film is a cellulose acylate film such as a triacetyl cellulose film.

  When the optically anisotropic layer 130 of the present invention that is homogeneously oriented is used as the optically anisotropic layer 130 and laminated with a linear polarizer, the angle formed by the slow axis and the absorption axis of the linear polarizer is 45 ° ± 10. It is preferable that it is (degree)-90 degrees +/- 10 degree, and it is more preferable that it is 45 degrees-90 degrees.

As described above, the optically anisotropic layer 130 is an optically anisotropic layer having reverse wavelength dispersion, and is excellent in manufacturing suitability. Therefore, it can be preferably used for a display device using a phase difference. For example, the aspect etc. which are used as an antireflection layer using the optical compensation film of a liquid crystal display device, and the circularly-polarizing plate of an organic EL display device are mentioned.
The driving mode of the liquid crystal cell of the liquid crystal display device is preferably a TN mode, a VA mode, an OCB mode, an IPS mode or an ECB mode, and more preferably an IPS mode. The IPS mode using photo-alignment is particularly preferable.

  As shown in FIG. 2, the IPS mode liquid crystal cell is a mode in which the liquid crystal molecules 14a and 14b are always rotated within the substrate surface, and the pixel electrode 15 is disposed only on the substrate in one direction and is applied with a lateral electric field. It is supposed to be. In the IPS type, a relatively wide viewing angle is obtained because the liquid crystal molecules do not rise obliquely, but when viewing from a direction deviated from the normal direction of the substrate, the phenomenon that the viewing angle becomes narrow due to light leakage is avoided. I can't. The optically anisotropic layer 130 of this embodiment is suitable as an optically anisotropic layer that compensates for this phenomenon.

  When the optically anisotropic layer 130 is used in the liquid crystal display device, it is preferably disposed between the liquid crystal cell and the viewing side polarizing plate or the backlight side polarizing plate. Further, it may function as a protective film for the viewing-side polarizing plate or the backlight-side polarizing plate, and may be incorporated in a liquid crystal display device as a member of the polarizing plate and disposed between the liquid crystal cell and the polarizer.

  When used for optical compensation of an IPS mode liquid crystal cell (especially for reducing color shift in an oblique direction during black display), it may be used in combination with a positive A plate.

  The liquid crystal display device 1 of FIG. 3 shows an example in which the optically anisotropic layer 130 of this embodiment is provided in a transmissive IPS liquid crystal display device. A mode provided on the surface of the plate on the liquid crystal cell side is shown. The liquid crystal display device 1 includes a pair of polarizing plates (an upper polarizing plate 10 and a lower polarizing plate 18) and a liquid crystal cell 2 sandwiched between them. The liquid crystal cell 2 includes a liquid crystal layer 14 and upper and lower sides thereof. The liquid crystal cell upper substrate 13 and the liquid crystal cell lower substrate 16 are disposed on the lower substrate 16, and the lower substrate 16 includes transparent pixel electrodes 15a and 15b. Although not shown, the backlight unit and the color filter are provided between the liquid crystal layer 14 and the viewing side polarizing plate 10 below the polarizing plate 18.

  The state of the liquid crystal molecules 14a on the left side of FIG. 3 is a state when the voltage is OFF, and the state of the liquid crystal molecules 14b on the right side indicates a state when the voltage is ON. When the voltage is turned on, a voltage is applied between the pixel electrodes 15a and 15b to generate an electric field, and the liquid crystal molecules 14a rotate in a substantially horizontal direction almost simultaneously with the substrate surface, resulting in the state shown in the right figure of FIG. In FIG. 3, the absorption axes 17 and 12 of the backlight-side polarizing plate 18 and the viewing-side polarizing plate 10 are substantially orthogonal to each other. When the voltage is OFF, the optical axis direction 12 of the liquid crystal molecules is approximately 17. It is parallel.

  In the present embodiment, it is preferable that no retardation layer other than the optically anisotropic layer 130 exists between the display surface side polarizing plate and the backlight side polarizing plate and the liquid crystal cell. Therefore, it is preferable to use an isotropic polymer film in which both the in-plane retardation Re and the film thickness direction retardation Rth are almost zero for the polarizing plate protective films 100 and 120. As such a polymer film, The cellulose acylate film described in JP-A-2006-030937 is preferably used.

  Since the optically anisotropic layer 130 is the optically anisotropic layer of the present invention, the phase transition temperature required for liquid crystal alignment is low and the solubility in a solvent is high, as compared with the conventional case. It is obtained using a liquid crystal compound that expresses. Therefore, the polarizing plate 10 and the liquid crystal display device 1 are provided with an optically anisotropic layer having reverse wavelength dispersion, and the display characteristics due to the difference in wavelength of transmitted light are less affected.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

Example 1
Compound (I-1) was synthesized according to the following scheme.

<Synthesis of Compound (I-1B)>
182 g (839 mmol) of mono (2-acryloyloxyethyl) succinate (I-1A), ethyl acetate 600 mL, N, N-dimethylacetamide 150 mL, 2,6-di-t-butyl-4-methylphenol 680 mg were mixed. The internal temperature was cooled to 5 ° C. To the mixture, 642 mL (879 mmol) of thionyl chloride was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C for 1 hour, a solution of 111 g (800 mmol) of 2- (4-hydroxyphenyl) ethanol in 220 mL of N, N-dimethylacetamide was added. Then, after stirring at room temperature for 12 hours, 400 mL of water was added and liquid separation was performed. The collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was removed by a rotary evaporator to obtain 255 g (758 mmol) of compound (I-1B) as a transparent oil (yield 95%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 2.63 (t, 4H), 2.85 (t, 2H), 4.25 (t, 2H), 4.28-4.40 ( m, 4H), 5.75 (brs, 1H), 5.86 (dd, 1H), 6.14 (dd, 1H), 6.45 (dd, 1H), 6.78-6.80 ( m, 2H), 7.02-7.10 (m, 2H)

<Synthesis of Compound (I-1C)>
1,4-trans-cyclohexanedicarboxylic acid 305 g (1.77 mol), methanesulfonic acid chloride (MsCl) 74.2 g (648 mmol), tetrahydrofuran 576 mL, N, N-dimethylacetamide 576 mL were mixed at room temperature. To the resulting mixture, 72 g (708 mmol) of triethylamine was added dropwise so that the internal temperature did not rise above 30 ° C., and then the mixture was stirred at room temperature for 2 hours. To this reaction solution, a solution of compound (I-1B) (198 g, 589 mmol) and 2,6-di-tert-butyl-4-methylphenol (12 mg) in tetrahydrofuran (50 mL) was added. Thereafter, 1.4 g (11 mmol) of N, N-dimethylaminopyridine was added, and 72 g (708 mmol) of triethylamine was added dropwise so that the internal temperature did not rise above 30 ° C. Then, after stirring for 12 hours at room temperature, 57 mL of water was added to stop the reaction. The obtained reaction solution was dropped into 5.7 L of 1.8 wt% sodium bicarbonate water, and the precipitated solid was collected by filtration. After the obtained solid content was mixed with 1.6 L of methanol, 1.9 L of water was added, and the precipitated solid content was collected by filtration. The obtained solid was dried and then dissolved in 1.6 L of ethyl acetate. 1.9 L of hexane was slowly added to the obtained solution to perform recrystallization, and the precipitated crystals were collected by filtration to obtain 202 g of a white solid (I-1C) (yield 70%). At this time, although the diester of cyclohexanedicarboxylic acid remains as an impurity, it can be removed in the next step, so that it was used in the next step in a mixture state.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.40-1.73 (m, 4H), 2.08-2.31 (m, 4H), 2.31-2.45 (m , 1H), 2.45-2.70 (m, 1H), 2.63 (m, 4H), 2.93 (t, 2H), 4.29 (t, 2H), 4.29-4. 40 (m, 4H), 5.86 (dd, 1H), 6.15 (dd, 1H), 6.44 (dd, 1H), 6.95-7.05 (m, 2H), 7.17 -7.25 (m, 2H)

<Synthesis of Compound (I-1D)>
The synthesis of compound (ID) is described in “Journal of Chemical Crystal Algography” (1997); 27 (9); p. 515-526. It carried out by the method of description.

<Synthesis of Compound (I-1)>
Compound (I-1C) 92.0 g (188 mmol), ethyl acetate 560 mL, N, N-dimethylacetamide 140 mL, 2,6-di-t-butyl-4-methylphenol 910 mg were mixed at room temperature, and the internal temperature was adjusted. Cooled to 5 ° C. To the mixture, thionyl chloride (18 mL, 248 mmol) was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, 30.3 mL (174 mmol) of N, N-diisopropylethylamine was added. Thereafter, a solution of 19.6 g (79 mmol) of Compound (ID) in 190 mL of tetrahydrofuran and 1.4 g (11 mmol) of N, N-dimethylaminopyridine were added, and then 67 mL (385 mmol) of N, N-diisopropylethylamine was added at the internal temperature. Was added dropwise so as not to rise above 10 ° C. Then, after stirring at room temperature for 3 hours, water 650mL and ethyl acetate 800mL were added, reaction was stopped, and liquid separation was performed. The collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off and the solvent was removed with a rotary evaporator. Then, recrystallization was performed using 110 mL of ethyl acetate and 200 mL of methanol to obtain 85.0 g of Compound (I-1) (yield 90%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.50-1.80 (m, 8H), 2.20-2.45 (m, 8H), 2.50-2.75 (m , 4H), 2.65 (s, 8H), 2.93 (t, 4H), 4.30 (t, 4H), 4.25-4.40 (m, 8H), 5.84 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.95-7.05 (m, 4H), 7.17-7.26 (m, 4H), 7.32 (S, 2H)

(Example 2)
Compound (I-2) was synthesized according to the following scheme.

<Synthesis of Compound (I-2A)>
2-hydroxyethyl methacrylate (I-2a) 40 g (307 mmol), dichloromethane 300 mL, N, N-dimethylaminopyridine 3.8 g (30.7 mmol), succinic anhydride 33.8 g (338 mmol), 2,6-di -200 mg of t-butyl-4-methylphenol was mixed, and the internal temperature was heated to 40 ° C. After stirring for 12 hours, the mixture was cooled to room temperature, 300 mL of water was added, and the mixture was stirred for 1 hour, followed by liquid separation. The collected organic layer was washed with 1N aqueous hydrochloric acid and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was removed by a rotary evaporator to obtain 64 g (278 mmol) of compound (I-2A) as a transparent oil (yield 91%).

<Synthesis of Compound (I-2B)>
Compound (I-2A) 30 g (130 mmol), ethyl acetate 50 mL, N, N-dimethylacetamide 15 mL, 2,6-di-t-butyl-4-methylphenol 100 mg were mixed, and the internal temperature was cooled to 5 ° C. . To the mixture, 10.0 mL (137 mmol) of thionyl chloride was added dropwise so that the internal temperature did not rise above 10 ° C. After stirring at 5 ° C. for 1 hour, a solution of 18.0 g (130 mmol) of 2- (4-hydroxyphenyl) ethanol in 100 mL of N, N-dimethylacetamide was added. Then, after stirring at room temperature for 12 hours, 100 mL of water was added and liquid separation was performed. The collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, and the solvent was removed by a rotary evaporator to obtain 44.1 g (126 mmol) of compound (I-2B) as a transparent oil (yield 97%).

<Synthesis of Compound (I-2C)>
1,4-trans-cyclohexanedicarboxylic acid 14.7 g (85.6 mol), methanesulfonic acid chloride 3.60 g (31.4 mmol), tetrahydrofuran 28 mL, N, N-dimethylacetamide 28 mL were mixed at room temperature. To the resulting mixture, 3.2 g (31.6 mmol) of triethylamine was added dropwise so that the internal temperature did not rise above 30 ° C., and then the mixture was stirred at room temperature for 2 hours. To this reaction solution, 10 g (28.5 mmol) of the compound (I-1B) and 50 mL of 2,6-di-tert-butyl-4-methylphenol were added in 10 mL of tetrahydrofuran. Thereafter, 171 mg (1.4 mmol) of N, N-dimethylaminopyridine was added, and 3.2 g (31.6 mmol) of triethylamine was added dropwise so that the internal temperature did not rise to 30 ° C. or higher. Then, after stirring for 12 hours at room temperature, 7 mL of water was added to stop the reaction. The obtained reaction solution was dropped into 275 mL of 1.8 wt% sodium bicarbonate water, and the precipitated solid was collected by filtration. The obtained solid content was mixed with 80 mL of methanol, 92 mL of water was added, and the precipitated solid content was collected by filtration. The obtained solid was dried and then dissolved in 80 mL of ethyl acetate. To the resulting solution, 92 mL of hexane was slowly added to perform recrystallization, and the precipitated crystals were collected by filtration to obtain 9.8 g (19.4 mmol) of a white solid (I-2C) (yield 68%). ). At this time, although the diester of cyclohexanedicarboxylic acid remains as an impurity, it can be removed in the next step, so that it was used in the next step in a mixture state.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.40-1.73 (m, 4H), 1.95 (s, 3H), 2.08-2.31 (m, 4H), 2.31-2.45 (m, 1H), 2.45-2.70 (m, 1H), 2.63 (m, 4H), 2.93 (t, 2H), 4.29 (t, 2H), 4.31 (s, 4H), 5.59 (s, 1H), 6.12 (s, 1H), 6.95-7.05 (m, 2H), 7.18-7.25. (M, 2H)

<Synthesis of Compound (I-2)>
Compound (I--) was prepared in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-2C). 2C) was synthesized. (Yield 80%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.60-1.80 (m, 8H), 1.95 (s, 6H), 2.20-2.45 (m, 8H), 2.50-2.75 (m, 4H), 2.65 (t, 8H), 2.93 (t, 4H), 4.29 (t, 4H), 4.32 (s, 8H), 5 .60 (s, 2H), 6.12 (s, 2H), 6.95-7.05 (m, 4H), 7.17-7.26 (m, 4H), 7.32 (s, 2H) )

(Example 3)
Compound (I-3) was synthesized according to the following scheme.

<Synthesis of Compound (I-3A)>
The compound (I-a) was synthesized in the same manner as in Example 2 except that compound (I-2a) was changed to compound (I-3a) in the synthesis method of compound (I-2A) described in Example 2. 3A) was synthesized. (Yield 92%).

<Synthesis of Compound (I-3B)>
Compound (I--) was prepared in the same manner as in Example 1 except that compound (I-1A) was changed to compound (I-3A) in the synthesis method of compound (I-1B) described in Example 1. 3B) was synthesized. (Yield 94%)

<Synthesis of Compound (I-3C)>
Compound (I--) was prepared in the same manner as in Example 1, except that Compound (I-1B) was changed to Compound (I-3B) in the synthesis method of Compound (I-1C) described in Example 1. 3C) was synthesized. (Yield 70%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): 1.45-1.72 (m, 4H), 1.72-1.80 (m, 4H), 2.10-2.30 (m, 4H), 2.33-2.45 (m, 1H), 2.47-2.65 (m, 1H), 2.62 (s, 4H), 2.93 (t, 2H), 4.10 -4.22 (m, 4H), 4.30 (t, 2H), 5.83 (dd, 1H), 6.12 (dd, 1H), 6.41 (dd, 1H), 6.95- 7.05 (m, 2H), 7.20-7.26 (m, 2H)

<Synthesis of Compound (I-3)>
Compound (I) was prepared in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-3C). -3) was synthesized. (Yield 88%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): 1.60-1.81 (m, 16H), 2.21-2.30 (m, 8H), 2.55-2.75 (m, 4H), 2.62 (s, 8H), 2.94 (t, 4H), 4.09-4.22 (m, 8H), 4.30 (t, 4H), 5.83 (dd, 2H) ), 6.12 (dd, 2H), 6.41 (dd, 2H), 6.95-7.05 (m, 4H), 7.20-7.26 (m, 4H), 7.32 ( s, 2H)

Example 4
Compound (I-4) was synthesized according to the following scheme.

<Synthesis of Compound (I-4A)>
Compound (I— 4A) was synthesized. (Yield 99%).

<Synthesis of Compound (I-4B)>
Compound (I-A) was synthesized in the same manner as in Example 1 except that compound (I-1A) was changed to compound (I-4A) in the synthesis method of compound (I-1B) described in Example 1. 4B) was synthesized. (Yield 91%)

<Synthesis of Compound (I-4C)>
Compound (I--) was prepared in the same manner as in Example 1 except that compound (I-1B) was changed to compound (I-4B) in the synthesis method of compound (I-1C) described in Example 1. 4C) was synthesized. (Yield 67%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): [Major Isomer] 1.27 (d, 3H), 1.45-1.73 (m, 4H), 2.10-2.32 (m, 4H), 2.32-2.45 (m, 1H), 2.48-2.70 (m, 1H), 2.62 (s, 4H), 2.93 (t, 2H), 4.15. (Dd, 1H), 4.25 (dd, 1H), 4.29 (t, 2H), 5.20 (m, 1H), 5.85 (dd, 1H), 6.13 (dd, 1H) 6.42 (dd, 1H), 6.95-7.06 (m, 2H), 7.16-7.25 (m, 2H) [Minor Isomer] 1.29 (d, 3H), 1. 45-1.73 (m, 4H), 2.10-2.32 (m, 4H), 2.32-2.45 (m, 1H), 2.48-2.70 (m, 1H), 2.62 (s, 4 ), 2.93 (t, 2H), 4.13 (dd, 1H), 4.22 (dd, 1H), 4.29 (t, 2H), 5.20 (m, 1H), 5.84 (Dd, 1H), 6.11 (dd, 1H), 6.41 (dd, 1H), 6.95-7.06 (m, 2H), 7.16-7.25 (m, 2H)

The purity of compound (I-4) is 92%, and it contains a total of 6% of the following compound (I-4E) derived from impurities (I-4b) contained in the raw material (I-4a).

<Synthesis of Compound (I-4)>
Compound (I) was synthesized in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-4C). -3) was synthesized. (Yield 80%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): [Major Isomer] 1.27 (d, 6H), 1.56-1.79 (m, 8H), 2.22-2.40 (m, 8H), 2.55-2.75 (m, 4H), 2.62 (s, 8H), 2.94 (t, 4H), 4.15 (dd, 2H), 4.25 (dd, 2H) ), 4.28 (t, 4H), 5.20 (m, 2H), 5.86 (dd, 2H), 6.13 (dd, 2H), 6.43 (dd, 2H), 6.99 -7.06 (m, 4H), 7.20-7.25 (m, 4H), 7.32 (s, 2H) [Minor Isomer] 1.29 (d, 6H), 1.56-1. 79 (m, 8H), 2.22-2.40 (m, 8H), 2.55-2.75 (m, 4H), 2.62 (s, 8H), 2.94 (t, 4H) , 4.12 (dd, 2 H), 4.22 (dd, 2H), 4.28 (t, 4H), 5.20 (m, 2H), 5.84 (dd, 2H), 6.11 (dd, 2H), 6. 41 (dd, 2H), 6.99-7.06 (m, 4H), 7.20-7.25 (m, 4H), 7.32 (s, 2H)

(Example 5)
Compound (I-5) was synthesized according to the following scheme.

<Synthesis of Compound (I-5A)>
Compound (I— 5A) was synthesized.

<Synthesis of Compound (I-5B)>
Compound (I-A) was synthesized in the same manner as in Example 1 except that compound (I-1A) was changed to compound (I-5A) in the synthesis method of compound (I-1B) described in Example 1. 5B) was synthesized.

<Synthesis of Compound (I-5C)>
The compound (I-C) was prepared in the same manner as in Example 1 except that the compound (I-1B) in the synthesis method of the compound (I-1C) described in Example 1 was changed to the compound (I-5B). 5C) was synthesized. (3 process yield 45%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): 1.45-1.72 (m, 4H), 2.10-2.32 (m, 4H), 2.32-2.45 (m, 1H), 2.48-2.70 (m, 1H), 2.63 (m, 4H), 2.93 (t, 2H), 3.72 (m, 4H), 4.22-4.35 (M, 4H), 4.32 (t, 2H), 5.84 (dd, 1H), 6.16 (dd, 1H), 6.44 (dd, 1H), 6.95-7.05 ( m, 2H), 7.16-7.25 (m, 2H)

<Synthesis of Compound (I-5)>
Compound (I-1) was synthesized in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-5C). -5) was synthesized. (Yield 88%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): 1.61-1.79 (m, 8H), 2.25-2.40 (m, 8H), 2.55-2.73 (m, 4H), 2.61 (t, 4H), 2.62 (t, 4H), 2.94 (t, 4H), 3.72 (m, 8H), 4.22 to 4.33 (m, 8H) ), 4.33 (t, 4H), 5.84 (dd, 2H), 6.16 (dd, 2H), 6.44 (dd, 2H), 6.99-7.06 (m, 4H) 7.18-7.26 (m, 4H), 7.32 (s, 2H)

(Example 6)
Compound (I-6) was synthesized according to the following scheme.

<Synthesis of Compound (I-6A)>
2-hydroxyethyl acrylate (I-6a) 10 g (86.1 mmol), N, N-dimethylacetamide 50 mL, pyridine 15 mL, diglycolic anhydride 11.0 g (94.8 mmol), N, N-dimethylaminopyridine 1.1 g (8.6 mmol) and 50 mg of 2,6-di-tert-butyl-4-methylphenol were mixed, and the internal temperature was heated to 50 ° C. After stirring for 12 hours, the mixture was cooled to room temperature, and 1N aqueous hydrochloric acid was added for liquid separation. The collected organic layer was washed with saturated brine, dried over anhydrous sodium sulfate, and the solvent was removed with a rotary evaporator to obtain 14.3 g (278 mmol) of compound (I-6A) as a transparent oil. (Yield 72%).

<Synthesis of Compound (I-6B)>
Compound (I-A) was synthesized in the same manner as in Example 1 except that compound (I-1A) was changed to compound (I-6A) in the synthesis method of compound (I-1B) described in Example 1. 6B) was synthesized.

<Synthesis of Compound (I-6C)>
The compound (I-C) was prepared in the same manner as in Example 1 except that the compound (I-1B) in the synthesis method of the compound (I-1C) described in Example 1 was changed to the compound (I-6B). 6C) was synthesized. (2 process yield 58%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.42-1.75 (m, 4H), 2.10-2.30 (m, 4H), 2.30-2.48 (m , 1H), 2.48-2.70 (m, 1H), 2.97 (t, 2H), 4.22 (s, 2H), 4.24 (s, 2H), 4.33-4. 45 (m, 6H), 5.86 (dd, 1H), 6.13 (dd, 1H), 6.44 (dd, 1H), 6.98-7.05 (m, 2H), 7.19 -7.25 (m, 2H)

<Synthesis of Compound (I-6)>
Synthesis was carried out in the same manner as in Example 1 except that Compound (I-1C) in Compound (I-1) synthesis method described in Example 1 was changed to Compound (I-6C). Then, the compound (I-6) was obtained by performing purification by silica gel column chromatography using chloroform-methanol as a solvent. (Yield 40%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.62-1.78 (m, 8H), 2.23-2.49 (m, 8H), 2.49-2.67 (m , 4H), 2.97 (t, 4H), 4.22 (s, 4H), 4.24 (s, 4H), 4.35-4.44 (m, 12H), 5.87 (dd, 2H), 6.13 (dd, 2H), 6.44 (dd, 2H), 7.00-7.05 (m, 4H), 7.20-7.25 (m, 4H), 7.32 (S, 2H)

(Example 7)
Compound (I-7) was synthesized according to the following scheme.

<Synthesis of Compound (I-7B)>
Karenz MOI-EG (I-7A, Showa Denko) 3.9 g (19.5 mmol), 2- (4-hydroxyphenyl) ethanol 1.5 g (10.9 mmol), N, N-dimethylacetamide 2 mL, chloroform 10 mL was mixed and the internal temperature was heated to 60 ° C. After stirring for 12 hours, the mixture was cooled to room temperature and further stirred for 12 hours. Next, saturated aqueous sodium hydrogen carbonate was added and stirred for 1 hour, followed by liquid separation. The collected organic layer was washed with 1N aqueous hydrochloric acid and saturated brine, dried over anhydrous sodium sulfate, the solvent was removed with a rotary evaporator, and the mixture was purified by silica gel chromatography to obtain a compound (I -7B) was obtained (g) (9.19 mmol) (yield 85%).

<Synthesis of Compound (I-7C)>
Compound (I--) was prepared in the same manner as in Example 1 except that compound (I-1B) in the synthesis method of compound (I-1C) described in Example 1 was changed to compound (I-7B). 7C) was synthesized. (2 step yield 45%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.42-1.75 (m, 4H), 1.95 (s, 3H), 2.10-2.30 (m, 4H), 2.30-2.48 (m, 1H), 2.48-2.70 (m, 1H), 2.92 (m, 2H), 3.37 (m, 2H), 3.56 (br t , 2H), 3.70 (brt, 2H), 4.20-4.45 (m, 4H), 5.05 (brs, 1H), 5.58 (s, 1H), 6.13 ( s, 1H), 6.98-7.06 (m, 2H), 7.18-7.25 (m, 2H)

<Synthesis of Compound (I-7)>
Compound (I-) was prepared in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-7C). 7) was obtained. (Yield 69%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.52-1.78 (m, 8H), 1.95 (s, 6H), 2.25-2.49 (m, 8H), 2.55-2.72 (m, 4H), 2.93 (br t, 4H), 3.37 (m, 4H), 3.56 (br t, 4H), 3.70 (br t, 4H) ), 4.22-4.35 (m, 8H), 5.04 (br s, 2H), 5.58 (s, 2H), 6.13 (s, 2H), 7.01 (br d, 4H), 7.23 (brd, 4H), 7.32 (s, 2H)

(Example 8)
Compound (I-9) was synthesized according to the following scheme.

<Synthesis of Compound (I-9B)>
Except for changing Karenz MOI-EG (I-7A, Showa Denko) to Karenz MOI (I-9A, Showa Denko) in the synthesis method of compound (I-7B) described in Example 7 Compound (I-9B) was synthesized in the same manner as in Example 1.

<Synthesis of Compound (I-9C)>
The compound (I-C) was prepared in the same manner as in Example 1 except that the compound (I-1B) in the synthesis method of the compound (I-1C) described in Example 1 was changed to the compound (I-9B). 7C) was synthesized. (2 step yield 40%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.42-1.75 (m, 4H), 1.95 (s, 3H), 2.10-2.30 (m, 4H), 2.30-2.48 (m, 1H), 2.48-2.70 (m, 1H), 2.92 (m, 2H), 3.49 (m, 2H), 4.10-4. 35 (m, 4H), 4.90 (br s, 1H), 5.58 (s, 1H), 6.13 (s, 1H), 6.98-7.06 (m, 2H), 7. 18-7.25 (m, 2H)

<Synthesis of Compound (I-9)>
Compound (I--) was prepared in the same manner as in Example 1 except that compound (I-1C) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (I-9C). 9) was obtained. (Yield 66%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.52-1.78 (m, 8H), 1.95 (s, 6H), 2.25-2.49 (m, 8H), 2.55-2.72 (m, 4H), 2.92 (br t, 4H), 3.49 (m, 4H), 4.10-4.35 (m, 8H), 4.91 (br s, 2H), 5.60 (s, 2H), 6.13 (s, 2H), 6.95-7.05 (m, 4H), 7.17-7.26 (m, 4H), 7.32 (s, 2H)

Example 9
Compound (I-14) was synthesized according to the following scheme.

<Synthesis of Compound (I-14B)>
The compound was obtained in the same manner as in Example 1 except that the compound (I-1) in the synthesis method of the compound (I-1B) described in Example 1 was changed to 10-undecenoic acid (I-14A). (I-14B) was synthesized.

<Synthesis of Compound (I-14C)>
Compound (I— 14C) was synthesized. (2 step yield 60%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.20-1.45 (m, 10H), 1.45-1.80 (m, 6H), 2.00-2.10 (m , 2H), 2.10-2.25 (m, 4H), 2.25-2.45 (m, 3H), 2.45-2.70 (m, 1H), 2.94 (t, 2H) ), 4.25 (t, 2H), 4.88-5.07 (m, 2H), 5.71-5.90 (m, 1H), 6.96-7.05 (m, 2H), 7.18-7.26 (m, 2H)

<Synthesis of Compound (I-14)>
Compound (I-14) was prepared in the same manner as in Example 1 except that Compound (I-1C) in the synthesis method of Compound (I-1) described in Example 1 was changed to Compound (I-14C). ) (Yield 91%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.20-1.45 (m, 20H), 1.50-1.60 (m, 4H) 1.60-1.80 (m, 8H), 2.00-2.10 (m, 4H), 2.20-2.45 (m, 12H), 2.65-2.80 (m, 4H), 2.93 (t, 4H) 4.25 (t, 4H), 4.88-5.05 (m, 4H), 5.70-5.90 (m, 2H), 6.95-7.05 (m, 4H), 7 .17-7.26 (m, 4H), 7.32 (s, 2H)

(Example 10)
The following compound (I-15) was synthesized.

120 mg (0.106 mmol) of compound (I-14), 56.4 mg of 3-chloroperbenzoic acid (containing 30 wt% water), and 1 mL of dichloromethane were mixed and stirred at room temperature for 4 hours. Then, water was added and liquid separation was performed. The collected organic layer was washed with a saturated aqueous sodium thiosulfate solution, saturated aqueous sodium hydrogen carbonate, and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and recrystallization was performed using ethyl acetate and methanol to obtain 80 mg of Compound (I-15) (yield 65%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.20-1.80 (m, 36H), 2.20-2.45 (m, 12H), 2.45 (m, 2H) 2 .55-2.75 (m, 4H), 2.75 (m, 2H) 2.85-3.00 (m, 2H), 2.93 (t, 4H), 4.27 (t, 4H) 6.95-7.05 (m, 4H), 7.17-7.26 (m, 4H), 7.32 (s, 2H)

(Example 11)
Compound (II-8) was synthesized according to the following scheme.

<Synthesis of Compound (II-8B)>
20 g (131 mmol) of compound (II-8A) and 80 mL of N, N-dimethylacetamide were mixed and cooled to 0 ° C. To the mixture, 19.2 mL (263 mmol) of thionyl chloride was added dropwise so that the internal temperature did not rise above 5 ° C. After stirring at 5 ° C. for 1 hour, 18.2 mL (131 mmol) of 4-hydroxybutyl acrylate was added dropwise. Then, after stirring at room temperature for 12 hours, water 200mL was added and liquid separation was performed. The collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and purification was performed by silica gel chromatography to obtain 23.9 g (96 mmol) of compound (II-8B) as a transparent oil (yield 73%).

<Synthesis of Compound (II-8C)>
The compound (II-C) was prepared in the same manner as in Example 1 except that compound (I-1B) was changed to compound (II-8B) in the synthesis method of compound (I-1C) described in Example 1. 8C) was synthesized. (Yield 57%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.40-1.90 (m, 8H), 2.10-2.30 (m, 4H), 2.30-2.45 (m , 1H), 2.45-2.60 (m, 1H), 3.62 (s, 2H), 4.08-4.22 (m, 4H), 5.83 (dd, 1H), 6. 13 (dd, 1H), 6.41 (dd, 1H), 6.97-7.07 (m, 2H), 7.27-7.34 (m, 2H)

<Synthesis of Compound (II-8)>
536 mg (1.24 mmol) of the compound (II-8C), 150 mg (0.60 mmol) of the compound (ID) and 5 mL of tetrahydrofuran were mixed and stirred at room temperature. To the mixture, 7.5 mg (0.06 mmol) of N, N-dimethylaminopyridine and 350 mg (1.83 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added and stirred at room temperature for 5 hours. . Thereafter, 20 mL of ethyl acetate and 20 mL of water were added for liquid separation, and the collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed by a rotary evaporator, and purification was performed by silica gel chromatography to obtain 257 mg (0.24 mmol) of Compound (II-8) (yield 40%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.62-1.80 (m, 16H), 2.25-2.40 (m, 8H), 2.55-2.75 (m , 4H), 3.62 (s, 4H), 4.10-4.20 (m, 8H), 5.83 (dd, 2H), 6.12 (dd, 2H), 6.41 (dd, 2H), 7.02-7.08 (m, 4H), 7.28-7.33 (m, 4H), 7.32 (s, 2H)

(Example 12)
Compound (II-9) was synthesized according to the following scheme.

<Synthesis of Compound (II-9B)>
The compound (II-B) was synthesized in the same manner as in Example 11 except that 4-hydroxybutyl acrylate in the synthesis method of compound (II-8B) described in Example 11 was changed to 2-hydroxyethyl acrylate. 9B) was synthesized. (Yield 69%)

<Synthesis of Compound (II-9C)>
The compound (II-B) was synthesized in the same manner as in Example 1 except that the compound (I-1B) in the synthesis method of the compound (I-1C) described in Example 1 was changed to the compound (II-9B). 9C) was synthesized. (Yield 59%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.40-1.74 (m, 4H), 2.10-2.30 (m, 4H), 2.30-2.45 (m , 1H), 2.45-2.60 (m, 1H), 3.64 (s, 2H), 4.36 (m, 4H), 5.86 (dd, 1H), 6.13 (dd, 1H), 6.41 (dd, 1H), 6.95-7.05 (m, 2H), 7.27-7.34 (m, 2H)

<Synthesis of Compound (II-9)>
Compound (II-9C) 500 mg (1.24 mmol), compound (ID) 150 mg (0.60 mmol) and tetrahydrofuran 5 mL were mixed and stirred at room temperature. To the mixture, 7.5 mg (0.06 mmol) of N, N-dimethylaminopyridine and 350 mg (1.83 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added and stirred at room temperature for 5 hours. . Thereafter, 20 mL of ethyl acetate and 20 mL of water were added for liquid separation, and the collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium hydrogen carbonate, and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and purification was performed by silica gel chromatography to obtain 270 mg (0.26 mmol) of Compound (II-9) (44% yield).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.62-1.77 (m, 8H), 2.25-2.40 (m, 8H), 2.56-2.73 (m , 4H), 3.65 (s, 4H), 4.32-4.40 (m, 8H), 5.86 (dd, 2H), 6.12 (dd, 2H), 6.41 (dd, 2H), 7.02-7.08 (m, 4H), 7.28-7.33 (m, 4H), 7.32 (s, 2H)

(Example 13)
Compound (III-3) was synthesized according to the following scheme.

<Synthesis of Compound (III-3Db)>
The synthesis of compound (III-3Db) is described in “Journal of Organic Chemistry” (2004); 69 (6); p. 2164-2177. It carried out by the method of description.

<Synthesis of Compound (III-3D)>
Compound (III-3Db) 5.0 g (15.3 mmol), methyl cyanoacetate 1.66 g (16.80 mmol) and isopropyl alcohol 25 mL were mixed, and the mixture was stirred for 3 hours under heating to reflux. Thereafter, the mixture was cooled to room temperature, 50 mL of water was added to the mixture, and the precipitated crystals were filtered. The obtained crystals were washed with a mixed solution of water-isopropyl alcohol (10 to 1) and a 0.5N aqueous hydrochloric acid solution, and then dissolved in N, N-dimethylacetamide and filtered. Water was added to the obtained filtrate, and the precipitated crystals were filtered to obtain 2.2 g (7.82 mmol) of compound (III-3D) (yield 51%).

<Synthesis of Compound (III-3)>
Compound (III-3) was prepared in the same manner as in Example 1 except that compound (I-4D) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (III-3D). ) (Yield 80%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.60-1.85 (m, 8H), 2.20-2.45 (m, 8H), 2.55-2.75 (m , 4H), 2.65 (t, 8H), 2.93 (t, 4H), 3.91 (s, 3H), 4.30 (t, 4H), 4.25-4.40 (m, 8H), 5.84 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.98-7.05 (m, 4H), 7.17-7.26. (M, 4H), 7.27 (s, 2H) 22

(Example 14)
Compound (III-7) was synthesized according to the following scheme.

<Synthesis of Compound (III-7D)>
Compound (III-7D) was synthesized by the method described in JP-A-2008-107767.

<Synthesis of Compound (III-7)>
Compound (III-7) was prepared in the same manner as in Example 1 except that Compound (I-4D) in the synthesis method of Compound (I-1) described in Example 1 was changed to Compound (III-7D). ) (Yield 78%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.31 (s, 6H), 1.65 to 1.80 (m, 8H), 1.96 (t, 2H) 2.25-2 .50 (m, 8H), 2.55-2.75 (m, 4H), 2.65 (t, 8H), 2.93 (t, 4H), 4.30 (t, 4H), 4. 25-4.40 (m, 8H), 4.48 (t, 2H), 5.84 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.98 -7.05 (m, 4H), 7.20-7.26 (m, 4H), 7.27 (s, 2H)

(Example 15)
Compound (IV-1) was synthesized according to the following scheme.

<Synthesis of Compound (IV-1Db)>
8.2 g (50.0 mmol) of ammonium 1-pyrrolidinecarbodithioate and 50 mL of N, N-dimethylformamide were mixed and cooled to 5 ° C. To the mixture, a solution of 6.7 g (55.0 mmol) of toluquinone (IV-1Da) in 40 mL of acetic acid was added dropwise and stirred at room temperature for 2 hours. Thereafter, the internal temperature was cooled to 5 ° C., and a solution of 5.9 g (55.0 mmol) of 1,4-benzoquinone in 40 mL of dimethyl sulfoxide was slowly added dropwise so that the internal temperature did not exceed 15 ° C. After stirring at room temperature for 1 hour, 1 L of water was added. Thereto, 28 wt% sodium hydroxide aqueous solution was added until crystals were precipitated, and the precipitated crystals were filtered and washed with water and methanol to obtain 5.4 g (20.1 mmol) of compound (IV-1Db). (Yield 40%).

<Synthesis of Compound (IV-1D)>
1.5 g (5.6 mmol) of compound (IV-1Db), 410 mg (6.2 mmol) of malononitrile, 16 mL of isopropyl alcohol, 0.3 mL of acetic acid and 0.2 mL of acetic anhydride were mixed, and the mixture was stirred for 3 hours with heating under reflux. Thereafter, the mixture was cooled to room temperature, water was added to the mixture, and the precipitated crystals were filtered to obtain 1.1 g (4.2 mmol) of compound (IV-1D) (yield 75%).
¹ H-NMR (solvent: DMSO-d6) δ (ppm): 2.19 (s, 3H), 6.71 (s, 1H), 9.60 (br s, 1H), 10.55 (br s , 1H)

<Synthesis of Compound (IV-1)>
Compound (IV-1) was prepared in the same manner as in Example 1 except that compound (I-4D) in the synthesis method of compound (I-1) described in Example 1 was changed to compound (IV-1D). ) (Yield 68%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.50-1.80 (m, 8H), 2.20-2.45 (m, 8H), 2.22 (s, 3H), 2.50-2.75 (m, 4H), 2.65 (t, 8H), 2.93 (t, 4H), 4.30 (t, 4H), 4.25-4.40 (m, 8H), 5.86 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.95-7.05 (m, 4H), 7.17-7.26. (M, 4H), 7.23 (s, 1H)

(Example 16)
Compound (IV-2) was synthesized according to the following scheme.

<Synthesis of Compound (IV-2Da)>
The synthesis of compound (IV-2Da) is described in “Tetrahedron Letters” (1985); 26 (7); 819-822. It carried out by the method of description.

<Synthesis of Compound (IV-2D)>
5 mL of water, 1.38 g (21.0 mmol) of potassium hydroxide and 4 mL of isopropyl alcohol were mixed and cooled to 5 ° C. To the mixture, a solution of malononitrile (690 mg, 10.5 mmol) in isopropyl alcohol was added dropwise so that the internal temperature did not exceed 8 ° C., and then carbon disulfide (0.63 mL, 10.5 mmol) in isopropyl alcohol was added at an internal temperature of 8 ° C. It was dripped so that it might not exceed. After stirring for 40 minutes, 0.18 mL of acetic acid was added. Next, a solution of compound (IV-2Da) (3.12 g, 20.8 mmol) and acetic acid (1.19 mL) in acetone (9 mL) was added dropwise so that the internal temperature did not exceed 3 ° C. After stirring for 1 hour, 50 mL of water was added, and the precipitated crystals were filtered to obtain 2.45 g (8.4 mmol) of compound (IV-2D) (yield 80%).
¹ H-NMR (solvent: DMSO-d6) δ (ppm): 1.12 (t, 3H), 2.60 (q, 2H), 6.73 (s, 1H), 9.57 (br s, 1H), 10.55 (br s, 1H)

<Synthesis of Compound (IV-2)>
2.09 g (4.26 mmol) of compound (I-1C), 0.50 g (1.72 mmol) of compound (IV-2D) and 10 mL of tetrahydrofuran were mixed and stirred at room temperature. To the mixture, 84.2 mg (0.69 mmol) of N, N-dimethylaminopyridine and 1.00 g (5.22 mmol) of 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride were added, and 3 hours at room temperature. Stir. Thereafter, ethyl acetate and water were added for liquid separation, and the collected organic layer was washed with 1N aqueous hydrochloric acid, saturated aqueous sodium bicarbonate, and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and purification was performed by silica gel chromatography to obtain 1.00 g (0.81 mmol) of Compound (IV-2) (yield 47%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.25 (t, 3H), 1.50-1.80 (m, 8H), 2.20-2.45 (m, 8H), 2.50-2.75 (m, 4H), 2.57 (q, 2H), 2.65 (t, 8H), 2.93 (t, 4H), 4.30 (t, 4H), 4 .25-4.40 (m, 8H), 5.86 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.95-7.05 (m, 4H) ), 7.17-7.26 (m, 4H), 7.23 (s, 1H)

(Example 17)
Compound (IV-6) was synthesized according to the following scheme.

<Synthesis of Compound (IV-6Db)>
Piperidinium pentamethylenedithiocarbamate 12.5 g (51.0 mmol) and N-methylpyrrolidone 40 mL were mixed and cooled to 5 ° C. To the mixture, a solution of 10.0 g (61.0 mmol) of 2-tert-butyl-1,4-benzoquinone (IV-6Da) and 12.5 mL of acetic acid in 20 mL of N-methylpyrrolidone was added dropwise and stirred at 10 ° C. for 2 hours. did. Next, the internal temperature is cooled to 5 ° C., and 6.6 g (61.0 mmol) of 1,4-benzoquinone and a solution of 12.5 mL of acetic acid in 20 mL of N-methylpyrrolidone are slowly added so that the internal temperature does not exceed 15 ° C. And dripped. After stirring at room temperature for 1 hour, the internal temperature was raised to 50 ° C. and stirred for 1 hour. Thereafter, the mixture was cooled to room temperature, acetone was added until crystals were precipitated, the precipitated crystals were filtered, and washed with acetone to obtain 6.0 g (15.6 mmol) of compound (IV-6Db) (yield 31 %).

<Synthesis of Compound (IV-6D)>
Compound (IV-6Db) (1.5 g, 3.9 mmol), malononitrile (290 mg, 4.4 mmol), isopropyl alcohol (16 mL), acetic acid (0.3 mL), and acetic anhydride (0.2 mL) were mixed, and the mixture was stirred with heating under reflux for 3 hours. Thereafter, the mixture was cooled to room temperature, water was added to the mixture, and the precipitated crystals were filtered to obtain 0.9 g (2.9 mmol) of Compound (IV-1D) (yield 76%).
¹ H-NMR (solvent: DMSO-d6) δ (ppm): 1.35 (s, 9H), 6.89 (s, 1H), 9.32 (brs, 1H), 10.60 (brs , 1H)

<Synthesis of Compound (IV-6)>
Compound (IV-6) was prepared in the same manner as in Example 16 except that compound (IV-2D) in the synthesis method of compound (IV-2) described in Example 16 was changed to compound (IV-6D). Got.
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.65 to 1.80 (m, 8H), 2.25 to 2.40 (m, 8H), 2.50 to 2.75 (m , 4H), 2.65 (t, 8H), 2.94 (t, 4H), 4.30 (t, 4H), 4.25-4.40 (m, 8H), 5.87 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.97-7.05 (m, 4H), 7.20-7.26 (m, 4H), 7.31 (S, 1H)

(Example 18)
Compound (IV-10) was synthesized according to the following scheme.

<Synthesis of Compound (IV-10Da)>
The synthesis of compound (IV-10 Da) is described in “Journal of Agricultural and Food Chemistry” (2003); 51 (18); p. 5329-5336. It carried out by the method of description.

<Synthesis of Compound (IV-10Db)>
2.6 g (16.7 mmol) of compound (IV-10Da), water 67 mL, hydrochloric acid 2 mL, and ethyl acetate 67 mL were mixed. To this mixture was added dropwise a solution of 5.4 g (33.4 mmol) of iron (III) chloride in 42 mL of water, and the mixture was stirred for 30 minutes. Thereafter, water and ethyl acetate were added for liquid separation, the solvent was removed using a rotary evaporator, and purification by silica gel chromatography was performed to obtain 0.72 g (4.73 mmol) of compound (IV-10 Da) (yield). Rate 28%).

<Synthesis of Compound (IV-10D)>
Compound (IV-10D) was prepared in the same manner as in Example 16 except that compound (IV-2Db) in the synthesis method of compound (IV-2D) described in Example 16 was changed to compound (IV-10Db). )
¹ H-NMR (solvent: DMSO-d6) δ (ppm): 1.35 (t, 3H), 4.04 (q, 2H), 6.63 (s, 1H), 9.75 (br s, 1H)

<Synthesis of Compound (IV-10)>
Compound (IV-10) was prepared in the same manner as in Example 16 except that compound (IV-2D) in the synthesis method of compound (IV-2) described in Example 16 was changed to compound (IV-10D). )
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.25 (t, 3H), 1.60-1.78 (m, 8H), 2.25-2.40 (m, 8H), 2.55-2.70 (m, 4H), 2.63 (m, 8H), 2.94 (t, 4H), 4.08 (q, 2H) 4.30 (t, 4H), 4. 30-4.40 (m, 8H), 5.86 (dd, 2H), 6.16 (dd, 2H), 6.44 (dd, 2H), 6.90 (s, 1H), 7.00 -7.08 (m, 4H), 7.20-7.25 (m, 4H)

(Example 19)
Compound (VI-1) was synthesized according to the following scheme.

<Synthesis of Compound (VI-1E)>
Compound (VI-1E) was prepared in the same manner as in Example 16 except that Compound (IV-2D) in the synthesis method of Compound (IV-2) described in Example 16 was changed to 2,5-dihydroxybenzaldehyde. )

<Synthesis of Compound (VI-1)>
Compound (VI-1E) 0.5 g (0.46 mmol), 2-hydrazinobenzothiazole 99 mg (0.60 mmol), 10-camphorsulfonic acid 5.4 mg (0.01 mmol) and tetrahydrofuran 10 mL were mixed, and at room temperature. Stir for 12 hours. Ethyl acetate and water were added to the mixture for liquid separation, and the collected organic layer was washed with 1N aqueous hydrochloric acid and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and purification was performed by silica gel chromatography to obtain 0.4 g (0.33 mmol) of Compound (Ia-1) (yield 70%).
¹ H-NMR (solvent: DMSO-d6) δ (ppm): 1.40-1.75 (m, 8H), 2.10-2.30 (m, 8H), 2.55 (s, 8H) 2.60-2.80 (m, 4H), 2.89 (t, 4H), 4.23 (t, 4H), 4.23-4.35 (m, 8H), 5.96 (dd , 2H), 6.18 (dd, 2H), 6.35 (dd, 2H), 7.05 (d, 4H), 7.13 (m, 1H), 7.20-7.35 (m, 3H), 7.30 (d, 4H), 7.47 (brs, 1H), 7.60 (d, 1H), 7.80 (brd, 1H), 8.09 (s, 1H), 12.5 (br s, 1H)

(Example 20)
Compound (VI-7) was synthesized according to the following scheme.

<Synthesis of Compound (VI-7D)>
The synthesis of compound (VI-7D) is described in “Journal of Organic Chemistry” (2004); 69 (6); p. 2164-2177. It carried out by the method of description.

<Synthesis of Compound (VI-7)>
Compound (VI-7) was prepared in the same manner as in Example 16 except that compound (IV-2D) in the synthesis method of compound (IV-2) described in Example 16 was changed to compound (VI-7D). ) (Yield 50%)
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.58-1.78 (m, 8H), 2.20-2.40 (m, 8H), 2.55-2.70 (m , 4H), 2.63 (m, 8H), 2.94 (t, 4H), 4.30 (t, 4H), 4.30-4.40 (m, 8H), 5.86 (dd, 2H), 6.14 (dd, 2H), 6.44 (dd, 2H), 6.98-7.05 (m, 4H), 7.20-7.24 (m, 4H), 7.25 (S, 2H)

(Example 21)
Compound (IV-4) was synthesized according to the following scheme.

<Synthesis of Compound (IV-4)>
Compound (IV) was prepared in the same manner as in Example 1 except that compound (I-1D) in the synthesis method of compound (I-4) described in Example 4 was changed to compound (IV-1D). -4) was synthesized. (Yield 81%)
¹ H-NMR (solvent: CDCl 3) δ (ppm): [Major Isomer] 1.27 (d, 6H), 1.56-1.79 (m, 8H), 2.22 (s, 3H), 2 2.22-2.40 (m, 8H), 2.55-2.75 (m, 4H), 2.62 (s, 8H), 2.94 (t, 4H), 4.15 (dd, 2H) ), 4.25 (dd, 2H), 4.28 (t, 4H), 5.20 (m, 2H), 5.86 (dd, 2H), 6.13 (dd, 2H), 6.43 (Dd, 2H), 6.99-7.06 (m, 4H), 7.20-7.25 (m, 4H), 7.25 (s, 1H) [Minor Isomer] 1.29 (d, 6H), 1.56-1.79 (m, 8H), 2.22 (s, 3H), 2.22-2.40 (m, 8H), 2.55-2.75 (m, 4H) , 2.62 (s, H), 2.94 (t, 4H), 4.12 (dd, 2H), 4.22 (dd, 2H), 4.28 (t, 4H), 5.20 (m, 2H), 5. 84 (dd, 2H), 6.11 (dd, 2H), 6.41 (dd, 2H), 6.99-7.06 (m, 4H), 7.20-7.25 (m, 4H) , 7.25 (s, 1H)
The purity of the compound (IV-4) is 92%, and a total of 6% of the following compound (IV-4E) derived from the impurity (I-4a ′) contained in the raw material (I-4a) is contained.

(Example 22)
Compound (VII-4) was synthesized according to the following scheme.

<Synthesis of Compound (VII-1B)>
4-amino-2,3-dimethylphenol (VII-1A) 25.8 g (0.188 mol) and ethyl acetate 723 ml were mixed, and water 258 ml and concentrated hydrochloric acid 22.6 ml were further added. A solution prepared by dissolving 61.1 g (0.377 mol) of iron (III) chloride in 465 ml of water was added dropwise to the mixture at an internal temperature of 20 to 30 ° C. over 30 minutes. After stirring at room temperature for 1 hour, the solid precipitated in the reaction system was separated by filtration and separated. The organic layer was washed with 400 ml of saturated brine. Then, after performing the same washing | cleaning 3 times, the organic layer was dried with anhydrous magnesium sulfate. Magnesium sulfate was filtered off, the solvent was distilled off under reduced pressure, and the residue was purified by column chromatography (developing solvent: ethyl acetate / n-hexane = 1/6). The solvent was distilled off under reduced pressure to obtain 23.7 g (yield 92.6%) of yellow solidified compound (I-1B). ¹ H-NMR (solvent: CDCl ₃ ) σ (ppm): 2.04 (s, 6H), 6.73 (s, 2H)

<Synthesis of Compound (VII-1D)>
7.55 g (0.114 mol) of potassium hydroxide (85%) was added and dissolved in a mixed solution of 18 ml of isopropanol and 23 ml of water, and the internal temperature was cooled to 0 to 5 ° C. To this mixture, 3.78 g (0.057 mol) of malononitrile (I-1C) and 3 ml of isopropanol were mixed and added dropwise at an internal temperature of 0 to 10 ° C. After stirring at an internal temperature of 0 to 10 ° C. for 10 minutes, 4.36 g (0.057 mol) of carbon disulfide was added dropwise at an internal temperature of 0 to 8 ° C. After stirring for 40 minutes at an internal temperature of 0 to 10 ° C., 1.03 g (0.017 mol) of acetic acid was added dropwise at an internal temperature of 0 to 8 ° C. 60 ml of isopropanol was added, and the mixture was stirred for 10 minutes under a nitrogen stream while cooling the internal temperature to −10 ° C. Under a nitrogen stream, a solution of 15.41 g (0.113 mol) of compound (I-1B), 52 ml of acetone and 6.80 g of acetic acid was added dropwise at an internal temperature of −10 to 0 ° C. After stirring for 50 minutes at an internal temperature of −10 to 0 ° C., the internal temperature was raised to 5 ° C., and 200 ml of water was added dropwise at an internal temperature of 10 ° C. or lower. After stirring for 40 minutes at an internal temperature of 5 to 10 ° C., the precipitated crystals were collected by filtration to obtain 13.2 g (yield 83.6%) of a light brown solid (VII-1D). ¹ H-NMR (solvent: DMSO) σ (ppm): 2.15 (s, 6H), 9.57 (s, 2H)

<Synthesis of Compound (VII-4)>
Compound (VII-4E) (76.17%) 16.98 g (0.026 mol), ethyl acetate 73 ml, N, N-dimethylacetamide 18 ml, 2,6-di-tert-butyl-4-methylphenol 38.8 mg mixed The internal temperature was cooled to 0 ° C. To the mixture, 3.18 g (0.027 mol) of thionyl chloride was added dropwise at an internal temperature of 0 to 5 ° C. After stirring at 5 ° C. for 50 minutes, a solution of 3.0 g (0.011 mol) of compound (I-1E), 22 ml of tetrahydrofuran and 17 ml of N, N-dimethylacetamide was added dropwise at an internal temperature of 0-8 ° C. Thereafter, 6.9 g (0.053 mol) of N, N-diisopropylethylamine was added dropwise at an internal temperature of 0 to 10 ° C. After stirring at an internal temperature of 15 to 20 ° C. for 2 hours, 100 ml of ethyl acetate, 100 ml of water, and 5.3 ml of concentrated hydrochloric acid were added for washing. The organic layer was washed and separated with 100 ml of saturated brine, and then washed and separated with 75 ml of saturated brine and 25 ml of 7.5 wt% sodium bicarbonate. After further washing with 100 ml of saturated saline, the organic layer was dried over anhydrous magnesium sulfate. After magnesium sulfate was filtered off and the solvent was distilled off under reduced pressure, recrystallization was performed using 70 ml of ethyl acetate and 180 ml of methanol to obtain 10.8 g (yield 79.7%) of compound (VII-4). ¹ H-NMR (solvent: CDCl ₃ ) σ (ppm): 1.26 to 1.30 (m, 6H), 1.64 to 1.81 (m, 8H), 2.13 (s, 6H), 2.33-2.35 (m, 8H), 2.62-2.72 (m, 12H), 2.94 (t, 4H), 4.10-4.26 (m, 4H), 4. 27-4.32 (t, 4H), 5.15-5.26 (m, 2H), 5.82-5.88 (m, 2H), 6.07-6.18 (m, 2H), 6.38-6.40 (m, 2H), 7.01-7.04 (m, 4H), 7.22-7.25 (m, 4H)
The purity of compound (VII-4) is 92%, and it contains 6% in total of the following compound (VII-4E) caused by impurities (I-4a ′) contained in the raw material (I-4a).

(Comparative Compound-1)
In Comparative Examples 1 to 7 shown below, compounds having a side chain moiety of the following formula (Ia) mainly used in the prior literature (Japanese Patent Application Laid-Open No. 2011-207765, International Publication No. 2014/010325 pamphlet) ( A synthesis example of a comparative compound) will be described.

The structural formula of the comparative compound used in the comparative example is as follows.

(Comparative Example 1)
Compound (Ia-1) was synthesized according to the following scheme.

<Synthesis of Compound (Ia-1C)>
Compound (Ia-1C) was synthesized by the method described in JP 2010-31223 (5 steps, 28%).

<Synthesis of Compound (Ia-1)>
1.25 g (2.99 mmol) of compound (Ia-1C), 337 mg (1.36 mmol) of compound (I-1D) and 10 mL of dichloromethane were mixed and stirred at room temperature. N, N-dimethylaminopyridine (27 mg, 0.22 mmol) and 1- (3-dimethylaminopropyl) -3-ethylcarbodiimide hydrochloride (840 mg, 4.35 mmol) were added to the mixture, and the mixture was stirred at room temperature for 12 hours. Thereafter, ethyl acetate and water were added for liquid separation, and the collected organic layer was washed with 1N aqueous hydrochloric acid and saturated brine, and then dried over anhydrous sodium sulfate. Sodium sulfate was filtered off, the solvent was removed with a rotary evaporator, and purification was performed by silica gel chromatography to obtain 0.6 g (0.57 mmol) of Compound (Ia-1) (yield 42%).
¹ H-NMR (solvent: CDCl ₃ ) δ (ppm): 1.40-1.55 (m, 8H), 1.65-1.85 (m, 16H), 2.23-2.40 (m , 8H), 2.55-2.73 (m, 4H), 3.94 (t, 4H), 4.17 (t, 4H), 5.84 (dd, 2H), 6.12 (dd, 2H), 6.40 (dd, 2H), 6.84-6.92 (m, 4H), 6.94-7.02 (m, 4H), 7.32 (s, 2H)

(Comparative Example 2)
Comparative compound (IIIa-) was prepared in the same manner as in comparative example 1 except that compound (I-1D) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (III-3D). 3) was obtained.

(Comparative Example 3)
Comparative compound (IIIa-) was prepared in the same manner as in comparative example 1 except that compound (I-1D) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (III-7D). 7) was obtained.

(Comparative Example 4)
Comparative compound (IVa-) was prepared in the same manner as in comparative example 1 except that compound (I-1D) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (IV-1D). 1) was obtained.

(Comparative Example 5)
Comparative compound (IVa-) was prepared in the same manner as in Comparative example 1 except that compound (I-1D) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (IV-6D). 6) was obtained.

(Comparative Example 6)
The synthesis of the comparative compound (VIa-1) was performed by the method described in WO2014-010325.

(Comparative Example 7)
Comparative compound (VIa-) was prepared in the same manner as in comparative example 1 except that compound (I-1D) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (VI-7D). 7) was obtained.

(Comparative Compound-2)
In Comparative Examples 8 to 10 and Comparative Example 15 shown below, synthesis examples of comparative compounds having the following structural formulas are shown.

(Comparative Example 8)
Comparative compound (Ib-) was prepared in the same manner as in Comparative example 1 except that compound (Ia-1C) in the synthesis method of compound (Ia-1) described in comparative example 1 was changed to compound (Ib-1C). 1) was obtained. Compound (Ib-1C) was synthesized by the method described in JP-A-2009-179563.

(Comparative Example 9)
In the same manner as in Comparative Example 1 except that Compound (Ia-1C) in the synthesis method of Compound (Ia-1) described in Comparative Example 1 was changed to Compound (Ic-1C), Comparative Compound (Ic- 1) was obtained. Compound (Ic-1C) was synthesized by the method described in WO2013 / 035733.

(Comparative Example 10)
Compound (Id-1) was prepared in the same manner as in Comparative Example 1 except that Compound (Ia-1C) in the synthesis method of Compound (Ia-1) described in Comparative Example 1 was changed to Compound (Id-1C). ) Compound (Id-1C) was synthesized in the same manner except that 10-undecenoic acid in the synthesis of compound (I-14C) of Example 9 was changed to acrylic acid chloride.

(Evaluation of phase transition temperature)
The phase transition temperatures of the liquid crystal compounds of Examples and Comparative Examples synthesized using a polarizing microscope were measured, and the degree of temperature decrease was evaluated. Specifically, the compound of the comparative example in which the structure of the side chain moiety is different from that of the compound of the example, that is, the structure of the compound of the example and Ar (of the general formula 1) Ar (central aromatic ring) is common. And, based on the phase transition temperature of the compound of the comparative example having a side chain moiety of the following formula (Ia) as a reference, the evaluation was divided into the following AC according to the degree of temperature decrease from the reference phase transition temperature.
For example, the compounds (I-1) and (I-2) were compared with the comparative compound (Ia-1), and the compound (III-3) was compared with the comparative compound (IIIa-3). Evaluation was performed according to the following criteria.
A: Decrease in melting point or S _m —N (smectic-nematic) transition temperature is 20 ° C. or more B: Decrease in melting point or S _m —N (smectic-nematic) transition temperature is less than 5 to 20 ° C. C: Melting point and S _m -N (smectic-nematic) transition temperature drop below 5 ° C

(Measurement of solubility)
The solubility of the synthesized liquid crystal compound was measured by the method shown below. 50 mg of the compound was weighed into a 1.5 mL sample bottle, and the solvent was added until the solid content became 40 wt% (75 mg). After thoroughly shaking by hand at room temperature, it was terminated by visual observation and judged to be 40 wt% solubility. If there was any undissolved residue, the solvent was added so that the solid content was 35 wt% (+18 mg). After thoroughly shaking by hand at room temperature, it was terminated by visual observation and judged to be 35 wt%. If there was any undissolved residue, the solvent was added so that it might be 30 wt%. The same operation was repeated in increments of 5 wt% until it was 5 wt%. If there was any undissolved residue, it was determined that the solubility was less than 5 wt% (<5 wt%), and the process was completed. MEK (methyl ethyl ketone) and CPN (cyclopentanone) were used as solvents for solubility measurement.

(Evaluation of solubility)
The measured solubility was evaluated. The evaluation is similar to the evaluation of the phase transition temperature, and the solubility of the compound of the comparative example having the same structure as that of the compound of the example and Ar (of the general formula 1) and having the side chain moiety of the formula (Ia). Based on the above, the following AC were evaluated according to the degree of improvement in solubility from the reference.
For example, the compounds (I-1) and (I-2) were compared with the comparative compound (Ia-1), and the compound (III-3) was compared with the comparative compound (IIIa-3). Evaluation was performed according to the following criteria.
A: The solubility is improved twice or more in plural or single solvents. B: The solubility is improved by one or two times in plural or single solvents. C: The solubility is not improved in plural or single solvents.

(Evaluation of suitability for side chain partial synthesis)
The portion of the compound of the present invention excluding the aromatic ring Ar located at the center (a portion that greatly contributes to reverse dispersibility) is defined as a side chain portion. For example, the side chain part of compound (I-1) is represented by the following formula (I), and the side chain part of compound (Ia-1) is represented by the following formula (Ia).
The suitability for synthesis of this side chain moiety was evaluated according to the following criteria.
A: 3 steps or less from commercial raw material and yield 50% or more B: 3 steps or less from commercial raw material and yield 35% or more, or 5 steps or less and yield 50% or more C: Other

  The solubility, phase transition temperature, and synthesis suitability of the compounds synthesized in Examples 1-22 and Comparative Examples 1-10 are shown in Table 1 below. Regarding the phase transition temperature, the numerical value in parentheses represents the value when the temperature is lowered, and the other values represent the values when the temperature is raised.

  As is clear from Table 1, compared with the compounds of Comparative Examples 1 to 7 having side chain moieties mainly used in the prior literature (Japanese Patent Laid-Open No. 2011-207765, International Publication No. 2014/010325 pamphlet), Inventive compounds (Examples 1, 13, 14, 15, 17, 19, and 20) can greatly reduce the smectic-nematic phase transition temperature and melting point, can be synthesized at low cost, and greatly improve solubility. To do.

(Example 23)
A polymerizable composition (coating solution 23 for optically anisotropic layer) having the following composition was prepared, and spin coated on a glass substrate with a rubbed polyimide alignment film (SE-150 manufactured by Nissan Chemical Industries, Ltd.). Was applied. The coating film was subjected to orientation treatment at the temperature shown in Table 2 below to form a liquid crystal layer. Thereafter, the film was cooled to the exposure temperature described in Table 2 and subjected to orientation fixation by irradiation with 1000 mJ / cm ² of ultraviolet rays to form an optically anisotropic layer to obtain an optical film for wavelength dispersion measurement.

(Examples 24-29)
In the same manner as in Example 23 except that the liquid crystal compound in the polymerizable composition was changed to the compounds shown in Table 2 to prepare a polymerizable composition (a coating solution for an optically anisotropic layer). An optically anisotropic layer of the present invention was obtained.
(Example 30)
Instead of the glass substrate with a polyimide alignment film subjected to rubbing treatment, in the same manner as in Example 23 except that a glass substrate with an alignment film containing the following polyvinyl alcohol A prepared by the method described in JP-A-9-152509 was used. An optically anisotropic layer of the present invention was obtained.

(Comparative Examples 11-15)
A liquid crystal compound in the polymerizable composition was changed to the compounds shown in Table 2 to prepare a polymerizable composition (a coating liquid for an optically anisotropic layer), and the drying temperature, the alignment treatment temperature, and the exposure temperature were set in Table 2. The optically anisotropic layer of each comparative example was obtained in the same manner as in Example 23 except that the conditions were changed to the above.
In Comparative Example 15, Comparative Compound 1e-1 obtained by the following method was used as the liquid crystal compound.

<Synthesis of Comparative Compound of Comparative Example 15>
Compound (Ie-1) was prepared in the same manner as in Comparative Example 1 except that Compound (Ia-1C) in the synthesis method of Compound (Ia-1) described in Comparative Example 1 was changed to Compound (Ie-1C). ) Compound (Ie-1C) was synthesized by the method described in JP2010-31223A.

(Comparative Example 16)
Example 23 except that the liquid crystal compound in the polymerizable composition was changed to Ic-1, and 35 parts by mass of chloroform was changed to 70 parts by mass to prepare a polymerizable composition (coating liquid for optically anisotropic layer). The coating was performed on the substrate in the same manner as described above, but crystals were formed on the coated surface immediately after spin coating, and a uniform film could not be obtained even after heat treatment.

(Comparative Example 17)
Example 23 except that the liquid crystal compound in the polymerizable composition was changed to Id-1, and 35 parts by mass of chloroform was changed to 70 parts by mass to prepare a polymerizable composition (a coating liquid for an optically anisotropic layer). The coating was performed on the substrate in the same manner as described above, but crystals were formed on the coated surface immediately after spin coating, and a uniform film could not be obtained even after heat treatment.

(Comparative Example 18)
In Example 30, the liquid crystal compound in the polymerizable composition was changed to Ia-1, and the alignment treatment temperature of the coating film was set to 200 ° C. to form a liquid crystal layer. After that, it was cooled to 160 ° C., and alignment fixation was attempted by irradiation with ultraviolet rays of 1000 mJ / cm ^2. However, since the glass transition temperature (Tg) of the support was low and the function of the alignment film was lowered, a uniformly aligned liquid crystal film was obtained. I couldn't.

(Measurement of retardation and evaluation of chromatic dispersion)
About the optically anisotropic layers obtained in Examples 23 to 30 and Comparative Examples 11 to 15, wavelengths were 450 nm and 550 nm using an automatic birefringence meter (KOBRA-21ADH, manufactured by Oji Scientific Instruments). The retardation value (Re value) at 650 nm was measured. As a result, Table 2 shows the Re value, α (Re (450) / Re (550)), and β (Re (650) / Re (550)) values at a wavelength of 550 nm.

From Table 2, it was confirmed that all of the optically anisotropic layers of the present invention have high reverse wavelength dispersion. Moreover, since the phase transition temperature was low compared with Comparative Examples 11-17, orientation processing temperature was able to be made low. Under the conditions of Comparative Examples 11 to 17, even when the alignment treatment was performed at 150 ° C., the film was not uniformly aligned and it was difficult to produce a film. Since the melting point of the compound is high, a high temperature is considered necessary to exhibit liquid crystallinity. When the temperature was lowered under the conditions of Comparative Example 11, generation of crystals was confirmed at 130 ° C. because the melting point of the compound was high. Comparative Example 15 using a compound having an aromatic ring with strong UV absorbance showed a low value of reverse dispersion.
As described above, the effectiveness of the present invention was confirmed.

1 Liquid crystal display device (display device)
2 Liquid crystal cell 10 Polarizing plate 18 Polarizing plate 100 Polarizer 110 Polarizing plate protective film (viewing side)
120 Polarizing plate protective film 130 Optical anisotropic layer

Claims (19)

An optically anisotropic layer containing a liquid crystal compound represented by the following general formula 1 or formed by curing a polymerizable composition containing the liquid crystal compound, wherein the major axis of the liquid crystal compound is oriented An optically anisotropic layer.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represents an integer of 1 to 4;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the Ar group is 8 or more. The optically anisotropic layer according to claim 1, wherein Ar in the general formula 1 is any aromatic ring represented by the following general formulas 2-1 to 2-4.
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded,
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring possessed by may have a substituent, and Ax and Ay may combine to form a ring,
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.   The optically anisotropic layer according to claim 2, wherein Ar in the general formula 1 is an aromatic ring represented by the general formula 2-2. The optically anisotropic layer according to claim 1, wherein T ₁ and T ₂ of the general formula 1 are represented by the following general formula 3.
In the formula, Sp1 and Sp2 each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O. -, - S -, - C (= O) -, - OC (= O) -, - C (= O) O -, - OC (= O) O -, - NR 1 C (= O) -, Substituted with —C (═O) NR ² —, —OC (═O) NR ³ —, —NR ⁴ C (═O) O—, —SC (═O) — or —C (═O) S— R ¹ , R ² , R ³ , R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ and P ₂ each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group.   The optically anisotropic layer according to any one of claims 1 to 4, wherein the alignment state is fixed in a nematic phase or a smectic phase.   The optically anisotropic layer according to claim 5, wherein the orientation state is fixed in a smectic phase. The major axis of the molecule is fixed in a homogeneous orientation, and the phase differences Re (450 nm), Re (550 nm), and Re (650 nm) at wavelengths of 450 nm, 550 nm, and 650 nm satisfy the following formulas A and B: 2. An optically anisotropic layer according to item 1.
Re (450 nm) / Re (550 nm) <0.95 Formula A
Re (650 nm) / Re (550 nm)> 1.02 Formula B   The laminated body by which the optically anisotropic layer of any one of Claims 1-7 was laminated | stacked directly or through the orientation film on the resin film.   The polarizing plate provided with the laminate according to claim 8, wherein the resin film is a polarizer.   A display device comprising the polarizing plate according to claim 9. Expand a composition containing a liquid crystal compound represented by the following general formula 1, or a polymerizable composition containing the liquid crystal compound,
A method for producing an optically anisotropic layer, wherein the polymerizable composition is cured after heating to align the major axes of the molecules of the liquid crystal compound.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represents an integer of 1 to 4;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the Ar group is 8 or more. The method for producing an optically anisotropic layer according to claim 11, wherein Ar in the general formula 1 is any aromatic ring represented by the following general formulas 2-1 to 2-4.
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. Each of R ¹² and R ¹³ independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded;
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring may have a substituent, Ax and Ay may be bonded to form a ring;
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.   The method for producing an optically anisotropic layer according to claim 12, wherein Ar in the general formula 1 is an aromatic ring represented by the general formula 2-2.   The method for producing an optically anisotropic layer according to claim 11, wherein the composition or the polymerizable composition is developed on a support having a glass transition temperature higher than an alignment temperature of the liquid crystal compound. A liquid crystal compound represented by the following general formula 1.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represents an integer of 1 to 4;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar represents any aromatic ring represented by the following general formulas 2-1 to 2-4.
However, In formula (I), _{Q 1} is -S -, - O-, or ^{NR 11} - ^{represents, R 11} represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms;
Y ₁ represents an alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon group having 6 to 12 carbon atoms, or an aromatic heterocyclic group having 3 to 12 carbon atoms;
Z1, Z2, and Z3 are each independently a hydrogen atom, an aliphatic hydrocarbon group having 1 to 20 carbon atoms or an alkoxy group, an alicyclic hydrocarbon group having 3 to 20 carbon atoms, and a monovalent carbon number of 6 Represents an aromatic hydrocarbon group of ˜20, a halogen atom, a cyano group, a nitro group, —NR ¹² R ¹³ or SR ¹² , and Z ₁ and Z ₂ are bonded to each other to form an aromatic ring or an aromatic heterocyclic ring. R ¹² and R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms,
A ₁ and A ₂ each independently represent a group selected from the group consisting of —O—, —NR ²¹ — (R ²¹ represents a hydrogen atom or a substituent), —S—, and CO—, and X represents Represents a hydrogen atom or a non-metallic atom of group 16 to 16 to which a substituent may be bonded,
Ax 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, and Ay may have a hydrogen atom or a substituent. A good alkyl group having 1 to 6 carbon atoms, or 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, and Ax and Ay The aromatic ring possessed by may have a substituent, and Ax and Ay may combine to form a ring,
Q ₂ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.   The liquid crystal compound according to claim 15, wherein Ar in the general formula 1 is an aromatic ring represented by the general formula 2-2. The liquid crystal compound according to claim 15 or 16, wherein T ₁ and T ₂ of the general formula 1 are represented by the following general formula 3.
In the formula, Sp1 and Sp2 each independently represent a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O. -, - S -, - C (= O) -, - OC (= O) -, - C (= O) O -, - OC (= O) O -, - NR 1 C (= O) -, Substituted with —C (═O) NR ² —, —OC (═O) NR ³ —, —NR ⁴ C (═O) O—, —SC (═O) — or —C (═O) S— R ¹ , R ² , R ³ , R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ and P ₂ each independently represent a polymerizable group or a hydrogen atom, and at least one represents a polymerizable group. A method for producing a liquid crystal compound represented by the following general formula 1, wherein a compound represented by the following general formula 4 is reacted with a compound represented by the following general formula 5.
However, in formula, L1, L2 represents the connection group which has a carbonyl group each independently,
F1 and F2 each independently represent an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n and m each independently represents an integer of 0 to 4;
a and b each independently represents an integer of 1 to 4;
T ₁ and T ₂ each independently represent a spacer part containing a linear or branched alkylene group or alkylene oxide group having 2 to 20 carbon atoms;
Ar is a divalent group having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represent.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
T ₁ is a linear or branched alkylene group having 2 to 20 carbon atoms;
However, in the formula, Ar has at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and the number of negative electrons contained in the aromatic ring in the group is 8 or more. Represents a divalent group. Carboxylic acid compound represented by the following general formula 7.
Where L ₁ represents a connecting group having a carbonyl group;
F ₁ represents an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, or a halogen atom;
n represents an integer of 0 to 4;
a represents an integer of 1 to 4;
Sp ₁ represents a linear or branched alkylene group having 2 to 20 carbon atoms, and one or two or more —CH ₂ — that are not adjacent to each other in the alkylene group are —O—, —S—, —C ( ═O) —, —OC (═O) —, —C (═O) O—, —OC (═O) O—, —NR ¹ C (═O) —, —C (═O) NR ² —. , —OC (═O) NR ³ —, —NR ⁴ C (═O) O—, —SC (═O) — or —C (═O) S— may be substituted, R ¹ , R ² , R ³ and R ⁴ each independently represents a hydrogen atom, a halogen atom, or an alkyl group having 1 to 4 carbon atoms;
P ₁ represents a polymerizable group.