JP2020019848A - Polymerizable liquid crystal compound, polymerizable composition, polymer, phase difference film and method for producing the same, transfer laminate, optical member, method for producing optical member, and display device - Google Patents

Abstract

To provide a polymerizable liquid crystal compound that can provide a phase difference film that has liquid crystallinity in a low temperature range and allows uniform polarization conversion in a wide wavelength region.SOLUTION: The present invention provides a polymerizable liquid crystal compound having a structure illustrated by the following formula 1.SELECTED DRAWING: None

Description

  The present disclosure relates to a polymerizable liquid crystal compound, a polymerizable composition, a polymer, a retardation film and a method for producing the same, a transfer laminate, an optical member, a method for producing an optical member, and a display device.

2. Description of the Related Art Conventionally, with respect to display devices such as a liquid crystal display device and a light emitting display device, a configuration in which optical members such as a retardation film and a polarizing plate are arranged on a panel surface has been proposed.
For example, in a light-emitting display device such as an organic light-emitting display device, a metal electrode having excellent reflectivity is provided in order to efficiently use light from a light-emitting layer. On the other hand, the use of the metal electrode increases external light reflection. Therefore, in the light emitting display device, for the purpose of suppressing the reflection of external light, it is known that a circularly polarizing plate including a quarter-wave plate that converts linearly polarized light into circularly polarized light and a polarizer is used on the viewing side. Have been.

  Examples of the retardation film include a 波長 wavelength plate, which converts the polarization vibration plane of linearly polarized light by 90 °, in addition to the 波長 wavelength plate. These retardation films can accurately convert a specific monochromatic light into a retardation of １ ／ λ or λλ of the light wavelength. However, the conventional retardation film has a problem that polarized light output through the retardation film is converted into colored polarized light. This is because the material constituting the retardation film has a wavelength dispersion property with respect to the retardation, and a distribution is generated in the polarization state for each wavelength with respect to white light in which light rays in the visible light region are mixed. In order to prevent this problem, it is necessary to control the wavelength dispersion so that the retardation becomes designed at each wavelength, and a broadband retardation film capable of giving a uniform retardation to light in a wide wavelength range is required. ing.

Retardation film, the method of stretching and manufacturing the film, for example, on a support that has been subjected to alignment treatment, a polymerizable composition containing a liquid crystal compound is applied, the solvent is dried, and after the liquid crystal compound is aligned, A method of producing by polymerization by ultraviolet rays or heat may be mentioned.
As a retardation film capable of giving a uniform retardation to light in a wide wavelength range, for example, a method has been proposed in which two retardation layers are laminated at an angle in the direction of the orientation axis. Reference 1). However, in such a laminate, two retardation layers are required, and there are problems such as complicated manufacturing when laminating the two retardation layers and an increase in the thickness of the retardation film. there were.

With the advancement of functions and the spread of portable information terminals, it has been required to reduce the thickness of the display device. As a result, the thickness of the retardation film, which is a constituent member, has also been required.
Therefore, the wavelength dispersion of the birefringence (△ n) is reduced or reversed so that a single layer can form a retardation layer capable of giving a uniform retardation to light in a wide wavelength range. A liquid crystal compound that realizes characteristics has been developed (for example, Patent Document 1). Incidentally, taking the wavelength of the incident light with respect to the phase difference film λ in the horizontal axis, the birefringence index - obtained by plotting the (△ n = refractive index for extraordinary light n _e index of refraction n ₀ for ordinary _light) on the vertical axis graph When the inclination of is close to 1, the wavelength dispersion of the birefringence is small or flat, or the liquid crystal compound of the material constituting the retardation film shows low wavelength dispersion or flat wavelength dispersion. If the slope of the graph is positive (upward to the right), the wavelength dispersion of the birefringence is opposite, or the liquid crystal compound of the material constituting the retardation film exhibits reverse wavelength dispersion, It is generally said.
As such a liquid crystal compound, for example, Patent Document 2 proposes a polymerizable liquid crystal compound containing an aromatic ring group having 12 or more π electrons in the center of the main chain.

A polymerizable liquid crystal compound as disclosed in Patent Document 2 is dissolved in an organic solvent together with a photopolymerization initiator and other additives such as a surfactant, if necessary, to obtain a liquid crystal composition ink. Then, the ink is applied to an alignment-treated substrate, the solvent is dried, the liquid crystal composition is aligned on the substrate, and light irradiation such as ultraviolet light is performed to polymerize the polymerizable liquid crystal compound, and the alignment state of the liquid crystal is changed. By fixing, a retardation layer is formed.
However, conventional polymerizable liquid crystal compounds such as the polymerizable liquid crystal compound of Patent Document 2 have problems that the temperature at which liquid crystallinity is exhibited is high and the solubility in a solvent is insufficient.
When the temperature at which liquid crystallinity is exhibited is high, the load in the process of aligning the liquid crystal increases, and there is a restriction that a substrate that is weak to high temperatures cannot be used. In addition, if the solvent solubility is insufficient, it is difficult to form a uniform coating film, the load on the manufacturing process and manufacturing equipment for drying a large amount of solvent increases, and the liquid crystal compound aggregates at room temperature. This tends to cause poor alignment.

JP 2001-4837 A JP 2010-31223 A

  In view of the above-described circumstances, embodiments of the present disclosure have a liquid crystallinity in a low temperature range and can provide a retardation film capable of performing uniform polarization conversion in a wide wavelength range. A polymerizable composition containing a polymerizable liquid crystal compound, a polymer obtained by polymerizing the polymerizable liquid crystal compound or the polymerizable composition, a retardation film having a retardation layer containing a cured product of the polymerizable composition, and An object of the present invention is to provide a manufacturing method thereof, a transfer laminate capable of transferring the retardation layer, an optical member having the retardation film, a method of manufacturing an optical member using the transfer laminate, and a display device. And

  One embodiment of the present disclosure provides a polymerizable liquid crystal compound represented by the following general formula (I).

(In the general formula (I), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² each independently represent a cyclopentane-1,3-diyl group, a cyclohexane-1,3-diyl group, which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclopentane-1,3-diyl group, a cyclopentane-1,3-diyl group, which may be substituted by one or more substituents E, a cyclohexane-1,4-diyl group, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- Or represents a single bond, R ^sp1 represents an alkylene group having 1 to 20 carbon atoms or a single bond, and the alkylene group has one or more -CH ₂ -or is adjacent when having 2 or more carbon atoms. two or more -CH ₂ no - are each independently -O -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH- or It may be replaced by —C 置 き 換 え C—, and Z ¹ represents a polymerizable functional group.
J ¹ represents -N = or-(CH) =,
Q ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic ring, and the aromatic ring may be unsubstituted or substituted with one or more substituents E;
Q ² represents an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an organic group having 2 to 30 carbon atoms having an aromatic ring. And the alkyl group, the cycloalkyl group, the cycloalkenyl group, and the aromatic ring may each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be the cycloalkyl group or may be substituted by a cycloalkenyl group, the alkyl group, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - SO 2 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH-COO-, -CH = CH- OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, and the cycloalkyl group or cyclo one -CH ₂ in the alkenyl - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or -O-CO It may be replaced by -O-.
The substituents E and E ¹ each independently represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, Represents a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these; in the case of 2 or more carbon atoms, one -CH ₂ - or nonadjacent two or more -CH ₂ - -O are each independently -, - S -, - CO -, - COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- H = CH—OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, or substituents E, and ^{E 1} are each ^{independently,} may represent a group represented by -L ^{E -R} SPE -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the L ⁵ , R ^sp1 , and Z ¹ represent the same as defined above, but may be the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively. and if E ¹ is present in plural may be each independently selected from the same,
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 represents an integer of 0 to 2. )

In one embodiment of the present disclosure, in the aforementioned general formula (I), J ¹ is -N =, and Q ¹ is unsubstituted or carbon which may be substituted by one or more substituents E. Q ³ is an aromatic ring group having 3 to 18 atoms, and Q ² is such that one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, and —COO. Provided is a polymerizable liquid crystal compound, which is an alkyl group having 3 to 12 carbon atoms, which may be replaced by-, -OCO-, or -O-CO-O-.

  An embodiment of the present disclosure provides a polymerizable composition containing the polymerizable liquid crystal compound of the embodiment of the present disclosure.

  One embodiment of the present disclosure provides a polymerizable composition further containing the polymerizable liquid crystal compound of the embodiment of the present disclosure and a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound.

  An embodiment of the present disclosure provides a polymer obtained by polymerizing the polymerizable liquid crystal compound of the embodiment of the present disclosure or the polymerizable composition of the embodiment of the present disclosure.

  One embodiment of the present disclosure provides a retardation film having a retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition according to the one embodiment of the present disclosure. I do.

One embodiment of the present disclosure includes a step of forming a film of the polymerizable composition according to the one embodiment of the present disclosure,
A step of at least orienting the polymerizable compound in the formed polymerizable composition,
A method for producing a retardation film, comprising a step of forming a retardation layer by having at least a step of polymerizing the polymerizable compound after the orientation step.

One embodiment of the present disclosure includes a retardation layer, and a support that releasably supports the retardation layer,
The retardation layer contains a cured product of the polymerizable composition according to the embodiment of the present disclosure,
Provided is a transfer laminate for transferring a retardation layer.

  An embodiment of the present disclosure provides an optical member including a polarizing plate on the retardation film of the embodiment of the present disclosure.

One embodiment of the present disclosure includes a retardation layer and a support that releasably supports the retardation layer, wherein the retardation layer is a cured product of the polymerizable composition according to the one embodiment of the present disclosure. A step of preparing a transfer laminate for transfer of the retardation layer,
A transfer object including at least a polarizing plate and the phase difference layer of the transfer laminate facing each other, and a transfer step of transferring the transfer laminate on the transfer target;
A peeling step of peeling the support from the transfer laminate transferred onto the transfer target,
And a method for manufacturing an optical member.

  Further, an embodiment of the present disclosure provides a retardation film of the embodiment of the present disclosure or a display device including the optical member of the embodiment of the present disclosure.

  According to an embodiment of the present disclosure, a polymerizable liquid crystal compound having liquid crystallinity in a low temperature range and capable of providing a retardation film capable of performing uniform polarization conversion in a wide wavelength range, including the polymerizable liquid crystal compound A polymerizable composition, a polymer obtained by polymerizing the polymerizable liquid crystal compound or the polymerizable composition, a retardation film having a retardation layer containing a cured product of the polymerizable composition, a method for producing the retardation film, A transfer laminate capable of transferring a retardation layer, an optical member having the retardation film, a method of manufacturing an optical member using the transfer laminate, and a display device can be provided.

FIG. 1 is a schematic sectional view showing one embodiment of the retardation film. FIG. 2 is a schematic sectional view showing one embodiment of the retardation film. FIG. 3 is a schematic sectional view showing one embodiment of the retardation film. FIG. 4 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 5 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 6 is a schematic cross-sectional view showing one embodiment of the transfer laminate. FIG. 7 is a schematic sectional view showing one embodiment of the optical member. FIG. 8 is a schematic cross-sectional view showing one embodiment of the display device.

Hereinafter, embodiments and examples of the present disclosure will be described with reference to the drawings and the like. However, the present disclosure can be implemented in many different aspects, and is not to be construed as being limited to the description of the embodiments and examples illustrated below. Further, in order to make the description clearer, the width, thickness, shape, and the like of each part may be schematically illustrated as compared with actual embodiments, but this is merely an example, and It is not limited. In the specification and the drawings, components similar to those described in regard to a drawing thereinabove are marked with like reference numerals, and a detailed description is omitted as appropriate. In addition, for convenience of description, the description may be made using the word “upward” or “downward”, but the vertical direction may be reversed.
“In this specification, when a certain structure such as a certain member or a certain region is“ above (or below) ”another structure such as another member or another region, unless otherwise specified, , This includes not only directly above (or directly below) another configuration, but also above (or below) another configuration, i.e., another (above or below) another configuration in between. This includes cases where components are included.

In the present disclosure, (meth) acryl represents each of acryl and methacryl, and (meth) acrylate represents each of acrylate and methacrylate.
Further, in the present specification, the terms “plate”, “sheet”, and “film” are not distinguished from each other based only on the difference in name, and are referred to as “film surface (plate surface, sheet surface)”. When the target film-shaped member (plate-shaped or sheet-shaped) is viewed as a whole and globally, the surface of the target film-shaped member (plate-shaped or sheet-shaped member) coincides with the plane direction. Refers to

A. Polymerizable liquid crystal compound
The polymerizable liquid crystal compound of the present disclosure is a compound represented by the following general formula (I).

(In the general formula (I), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² each independently represent a cyclopentane-1,3-diyl group, a cyclohexane-1,3-diyl group, which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclopentane-1,3-diyl group, a cyclopentane-1,3-diyl group, which may be substituted by one or more substituents E, a cyclohexane-1,4-diyl group, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- Or represents a single bond, R ^sp1 represents an alkylene group having 1 to 20 carbon atoms or a single bond, and the alkylene group has one or more -CH ₂ -or is adjacent when having 2 or more carbon atoms. two or more -CH ₂ no - are each independently -O -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH- or It may be replaced by —C 置 き 換 え C—, and Z ¹ represents a polymerizable functional group.
J ¹ represents -N = or-(CH) =,
Q ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic ring, and the aromatic ring may be unsubstituted or substituted with one or more substituents E;
Q ² represents an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an organic group having 2 to 30 carbon atoms having an aromatic ring. And the alkyl group, the cycloalkyl group, the cycloalkenyl group, and the aromatic ring may each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be the cycloalkyl group or may be substituted by a cycloalkenyl group, the alkyl group, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - SO 2 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH-COO-, -CH = CH- OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, and the cycloalkyl group or cyclo one -CH ₂ in the alkenyl - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or -O-CO It may be replaced by -O-.
The substituents E and E ¹ each independently represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, Represents a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these; in the case of 2 or more carbon atoms, one -CH ₂ - or nonadjacent two or more -CH ₂ - -O are each independently -, - S -, - CO -, - COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- H = CH—OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, or substituents E, and ^{E 1} are each ^{independently,} may represent a group represented by -L ^{E -R} SPE -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the L ⁵ , R ^sp1 , and Z ¹ represent the same as defined above, but may be the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively. and if E ¹ is present in plural may be each independently selected from the same,
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 represents an integer of 0 to 2. )

Since the compound represented by the general formula (I) of the present disclosure has a specific structure in the main chain structure from the specific R ¹ to R ² , the orientation between molecules is improved, and the liquid crystallinity alone is improved. It is a compound which shows. Further, the compound represented by the general formula (I) of the present disclosure is a polymerizable liquid crystal compound because it has a polymerizable group at a terminal.
The compound represented by the general formula (I) of the present disclosure has a phthalimide ring at the center of the main chain, which has a side chain in which Q ¹ and Q ² are bonded to each other via -N = or-(CH) =. Having a structure having an organic group having 2 to 30 carbon atoms and having at least one aromatic ring, a direct bond to the aromatic ring at the center of the main chain of the prior art (Patent Document 2), -C = Lower than when the aromatic group is bonded via C- or -C≡C-, or when the aromatic group is bonded as a condensed ring of the aromatic ring at the center of the main chain. It can have liquid crystallinity in a temperature range. Therefore, by using the polymerizable liquid crystal compound represented by the general formula (I) of the present disclosure, the load in the step of aligning the liquid crystal can be reduced, or the substrate can be used for a substrate that is vulnerable to high temperatures.
By bonding the organic group having at least one aromatic ring having 2 to 30 carbon atoms to the phthalimide ring at the center of the main chain via -N = or-(CH) =, the molecular structure is rigid. Is reduced. It is presumed that the relaxation of the rigidity increases the degree of freedom of the side chain, lowers the melting point of the compound, and enables the compound to have liquid crystallinity in a low temperature range.
In addition, the organic group having at least one aromatic ring and having 2 to 30 carbon atoms is bonded to the phthalimide ring at the center of the main chain via -N = or-(CH) = to form a side chain. When compared to a liquid crystal compound in which the directionality of the conjugated system of the part shows positive dispersion, it is easier to adjust in the short axis direction, the absorption in the short axis direction of the liquid crystal compound is maintained even in the long wavelength region, and it becomes easier to show flat wavelength dispersion. Presumed.

The polymerizable liquid crystal compound represented by the general formula (I) of the present disclosure can exhibit liquid crystallinity at, for example, 100 ° C. or lower. The polymerizable liquid crystal compound represented by the general formula (I) of the present disclosure has a solid-liquid crystal phase transition temperature of preferably 95 ° C or lower, more preferably 90 ° C or lower, and more preferably 80 ° C or lower. Is even more preferred.
Here, the solid-liquid crystal phase transition temperature means a temperature at which a liquid crystal compound changes from a solid to a liquid crystal. In the present disclosure, the solid-liquid crystal phase transition temperature is confirmed at the time of temperature rise by texture observation using a polarizing microscope equipped with a temperature control stage.

The polymerizable liquid crystal compound represented by the general formula (I) of the present disclosure is prepared, for example, by a method shown in Example 1 described below to prepare a polymerizable composition containing only the polymerizable liquid crystal compound of the present disclosure and a photopolymerization initiator. Then, when a cured film (retardation layer) is formed and the retardation value is measured as described below, Re (450) / Re (550) is close to 1, specifically 1.00 or more. It is possible to show a flat wavelength dispersion of less than 10 and Re (650) / Re (550) close to 1, specifically, 0.92 or more and less than 1.00.
However, in the method described in Example 1 described below, the drying temperature (orientation temperature) should be in the range of (solid-liquid crystal phase transition temperature) or more and 10 ° C. added to (solid-liquid crystal phase transition temperature). Can be.

Further, conventional compounds having reverse wavelength dispersion or flat wavelength dispersion have a tendency to be inferior in solvent solubility due to rigidity, but the polymerization represented by the general formula (I) of the present disclosure The liquid crystalline compound is characterized in that the organic group having 2 to 30 carbon atoms having at least one aromatic ring is bonded to the phthalimide ring at the center of the main chain via -N = or-(CH) =. The rigidity of the molecular structure is reduced, and the solvent solubility tends to be good. Therefore, when the compound represented by the general formula (I) of the present disclosure is dissolved in an organic solvent to prepare an ink and forms a coating film using the ink, a uniform coating film is easily formed, The load on the manufacturing process and the manufacturing apparatus for drying the solvent is reduced, and the liquid crystal compound is less likely to aggregate at room temperature, thereby suppressing poor alignment.
In addition, the polymerizable liquid crystal compound represented by the general formula (I) of the present disclosure can have liquid crystallinity in a low temperature range and has good solvent solubility, and therefore has a high liquid crystal transition temperature or a high solvent solubility. When mixed with another liquid crystal compound having low liquid crystal properties, the liquid crystal transition temperature is lowered, and a liquid crystal composition having improved solvent solubility is obtained. It is also suitably used as a liquid crystal compound for adjustment.

L ¹ , L ² , L ³ and L ⁴ in the general formula (I) are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH —, —CF ＝ CF—, —C≡C— or a single bond. Represents a divalent linking group or a single bond. When a plurality of L ³ and L ⁴ appear independently of each other, they may be the same or different.

More specifically, L ¹ and L ² each independently represent —COO—, —OCO—, —OCH ₂ —, and —CH ₂ O from the viewpoints of liquid crystallinity, availability of raw materials, and ease of synthesis. _{-, - CF 2 O -,} - OCF 2 -, - CH 2 CH 2 -, - CF 2 CF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH- _{, -OCO-CH = CH -,} - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - CH = CH- , —CF ＝ CF—, —C≡C— or a single bond, preferably —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, —OCF ₂ —. _{, -CH 2 CH 2 -, -} COO-CH 2 CH 2 -, - OCO-CH 2 CH _{2 -, - CH 2 CH 2} -COO -, - CH 2 CH 2 -OCO -, - CH = CH -, - C≡C- or is more preferably a single bond, -COO -, - OCO-, _{-OCH 2 -, - CH 2 O} -, - CF 2 O -, - OCF 2 - or more preferably a single _{bond, -COO -, - OCO -,} - OCH 2 -, - CH 2 O-, or even more preferably a single bond, -COO -, - OCO -, - OCH 2 -, or is particularly preferably represents _-CH 2 O-.

More specifically, L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, − from the viewpoint of availability of raw materials and ease of synthesis. COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO -, - COO- CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH It preferably represents ₂ CH ₂ —OCO— or a single bond, and when _two or more are present, they may be the same or different, and each is independently —O—, —OCH ₂ —, —CH ₂ O— , -COO-, -OCO-, -CH = CH-COO-, -CH = CH-OCO-, -CO _{-CH = CH -, - OCO-} CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO- or More preferably, it represents a single bond, and when two or more are present, they may be the same or different.

A ¹ and A ² in the general formula (I) are each independently a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, cyclohexane- 1,4-diyl group, cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, decahydronaphthalene-2,6-diyl group, or 1,3-dioxane-2,5-diyl group Represents

Among these, A ¹ and A ² are each independently unsubstituted or have one or more substitutions, from the viewpoint of improving liquid crystallinity and improving the orientation of the polymer easily. A cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane-1,3-diyl group, or a cycloheptane-1,4-diyl group, which may be substituted by the group E; And more preferably a cyclohexane-1,4-diyl group which is unsubstituted or optionally substituted by one or more substituents E.

The divalent alicyclic hydrocarbon group includes cis-type and trans-type stereoisomers based on the difference in the configuration of carbon atoms bonded to L ¹ and L ³ (or L ² and L ⁴ ). obtain. The divalent alicyclic hydrocarbon group may be cis-type or trans-type, or may be a mixture of cis-type and trans-type isomers, since the orientation is good. , Trans or cis type, and trans type is more preferable.

A ³ and A ⁴ in the general formula (I) are each independently unsubstituted or a cyclopentane-1,3-diyl group optionally substituted by one or more substituents E, cyclohexane- 1,4-diyl group, cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5 -Diyl group, naphthalene-2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl A 1,3-dioxane-2,5-diyl group. When a plurality of A ³ and A ⁴ appear independently, each may be the same or different.

A ³ and A ⁴ in the general formula (I) each independently represent, among others, benzene-1,4-diyl, since it is easy to improve the liquid crystallinity and the orientation of the polymer. Group, cyclohexane-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene- It is preferably a 2,6-diyl group, a decahydronaphthalene-2,6-diyl group, or a 1,3-dioxane-2,5-diyl group.

A ³ and A ⁴ in the general formula (I) each independently represent a benzene-1,4-diyl group which may be unsubstituted or may be substituted by one or more substituents E, and naphthalene-2. , 6-diyl group or cyclohexane-1,4-diyl group, more preferably benzene-1,4-diyl group or cyclohexane-1,4-diyl group, and benzene-1,4-diyl group. Particularly preferred is a diyl group. With these groups, the liquid crystallinity of the polymerizable liquid crystal compound of the present embodiment can be improved, and the alignment of the polymer can be easily improved.

The substituents E are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, Represents a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these; There in the case of two or more, one -CH ₂ - or nonadjacent two or more -CH ₂ - each independently is -O -, - S -, - CO -, - COO -, - OCO -, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH- OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, or the substituent E is each independently ^may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively, ^L 5, which will be described ^{later, R sp1,} and Z Represents the same as defined in ¹ , but may be the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively, and each of the compounds has a plurality of substituents E and E ¹ When present, they may be the same or different.

From the viewpoints of liquid crystallinity and ease of synthesis, the substituents E are each independently a fluorine atom, a chlorine atom, a pentafluorosulfuranyl group, a nitro group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group. or an alkyl group of any of the hydrogen atoms may having 1 to 20 carbon atoms be substituted by a fluorine atom, the alkyl group in the case of 2 or more carbon atoms, one -CH ₂ - Or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO—, —OCO—, —O—CO—O—, —CH ＝ CH -, -CF = CF- or preferably represents an alkyl group which may be replaced by -C−C-, and may be a fluorine atom, a chlorine atom, or a carbon atom in which any hydrogen atom may be replaced by a fluorine atom. 1 to 20 atoms An alkyl group, when the alkyl group carbon atoms of 2 or more, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - More preferably, it represents an alkyl group having 1 to 12 carbon atoms which may be replaced by COO- or -OCO-, and a fluorine atom, a chlorine atom, or any hydrogen atom may be replaced by a fluorine atom More preferably represents a linear or branched alkyl group or alkoxy group having 1 to 12 carbon atoms, and a fluorine atom, a chlorine atom, or a linear alkyl group or linear alkoxy group having 1 to 8 carbon atoms. It is particularly preferred to represent.
Also, A ³ and A ⁴ in which may be substituted substituents E, among others, as R ¹ and R ² may substituent E may be substituted with A ³ and A ⁴ are bonded, respectively, - the group represented by ^{L E} -R spE -Z ^E also preferred.

M1 and m2 in the general formula (I) each independently represent an integer of 1 to 4.
When emphasizing the liquid crystallinity and orientation of the polymerizable compound of this embodiment, one or both of m1 and m2 are preferably an integer of 1 to 3, and both m1 and m2 are integers of 1 to 3 It is more preferable that both m1 and m2 are 1 or 2.

R ¹ and R ² each independently represent a group selected from the following formula (R-1).
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- Or a single bond.

In the general formula (R-1), more specifically, as L ⁵ , from the viewpoint of availability of raw materials and ease of synthesis, each independently represents —O—, —S—, —COO—, and —OCO. -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO Or preferably represents a single bond, more preferably each independently represents -O-, -COO-, -OCO-, -O-CO-O-, or a single bond. They may be the same or different.

In the general formula (R-1), R ^sp1 represents an alkylene group having 1 to 20 carbon atoms or a single bond, and the alkylene group has one or more —CH ₂ — or nonadjacent two or more -CH ₂ - are each independently -O -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH- or -C≡C- may be substituted.

In the general formula (R-1), more specifically, from the viewpoint of availability of raw materials and easiness of synthesis, each of R ^sp1 independently represents one —CH ₂ — or non-adjacent 2 It is more preferable that at least _two -CH2-s each independently represent an alkylene group having 2 to 12 carbon atoms or a single bond which may be substituted by -O-, -COO-, or -OCO-. And further preferably represents an alkylene group having 2 to 10 carbon atoms or a single bond, more preferably each independently represents an alkylene group having 2 to 8 carbon atoms, more preferably 4 to 8 carbon atoms. More preferably, the alkylene group of the formula (1) is more preferable, and when a plurality of alkylene groups are present, they may be the same or different.

In the general formula (R-1), Z ¹ represents a polymerizable functional group. As the polymerizable functional group, groups used in conventional polymerizable liquid crystal compounds can be applied without limitation.
It is preferable that the polymerizable functional groups each independently represent a group selected from the following formulas (Z-1) to (Z-8). In the following formulas (Z-1) to (Z-8), * (asterisk) indicates a bonding position with R ^sp1 .

(In the formulas (Z-1) to (Z-8), R ^z is each independently a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a methyl group, an ethyl group, or a trifluoromethyl group. is there.)

When the UV polymerization as the polymerization method, ^{Z 1} has the formula (Z-1), the formula (Z-2), the formula (Z-3), formula (Z-5), formula (Z-7) is Preferably, formula (Z-1), formula (Z-3), and formula (Z-7) are more preferable, formula (Z-1) is more preferable, and in formula (Z-1), R ^z is a hydrogen atom, Particularly preferred is a methyl group or a trifluoromethyl group.

In the general formula ^{(I), Lc1: -L 1} -A 1 - (L 3 -A 3) m1 -L 5 -R sp1 -Z 1, ^{and, Lc2: -L 2 -A 2 -} (L 4 -A ⁴⁾ examples of _m2 -L ⁵ -R ^sp1 -Z ¹ include, but are not limited to, groups represented by the following Lc-1~Lc-244. In the polymerizable liquid crystal compound represented by the general formula (I), Lc1 and Lc2 may be the same or different.

In the groups represented by Lc-1 to Lc-244, m in L ³ and L ⁴ represents 1 or 2, and 2 is preferable. N in R ^sp1 represents 1 to 20, and in particular, n in R ^sp1 is preferably 2 or more, more preferably 4 or more, on the other hand, preferably 12 or less, and more preferably 10 or less. It is preferable that
In Z ¹ , R ^z in the formula (Z-1) is preferably each independently, particularly preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

E ¹ which may be substituted on the benzene ring of the phthalimide group contained in the main chain may be each independently the same as the substituent E.
As the E ^1, among others, in terms of simplicity and availability of raw materials for introducing a substituent, a fluorine atom, a chlorine atom, a hydroxyl group, a mercapto group, methylamino group, dimethylamino group, or it may be substituted by these one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted by Preferably, the above-mentioned —CH ₂ — is a linear alkyl group having 1 to 6 carbon atoms which may be substituted.

  Further, n1 represents an integer of 0 to 2, and is more preferably 0 or 1.

On the other hand, was replaced by a nitrogen atom of phthalimide group comprised in the backbone, ^{J 1} is, -N =, or - (CH) = represents a. J ¹ is only to be appropriately selected, but tend to have liquid crystallinity in the lower temperature region, the temperature region having a liquid crystallinity - (CH) terms is a wide area compared to =, with -N = Preferably, there is.

Q ¹ represents an organic group having an aromatic ring and having 2 to 30 carbon atoms. The aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring, and Q ¹ represents at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. Represents an organic group having 2 to 30 carbon atoms. The aromatic ring is preferably a group selected from the following formulas (Q-1) to (Q-22). Note that the number of carbon atoms of the substituent is added to the number of carbon atoms of the organic group.

These groups have a bond at an arbitrary position. Q ^a is -O -, - S -, - NR Qa - (. ^{Wherein, R Qa} represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms) represents a or -CO-, in these groups of -CH = may be replaced each independently -N =, -CH ₂ - are each independently -O -, - S -, - NR Qa - ( ^{wherein, R Qa} is hydrogen or represents an alkyl group having 1 to 8 carbon atoms) -. SO-, or -SO ₂ - or -CO- may be replaced by (unless each other oxygen atom is attached directly).. One or more hydrogen atoms bonded to these rings may be substituted by the substituent E. Examples of the alkyl group constituting the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, and a hexyl group. . The number of carbon atoms of the alkyl group is preferably 1 to 4, more preferably 1 or 2, and still more preferably 1.

  Examples of the group represented by the formula (Q-1) include the following formulas (Q-1-1) to (Q-1-8) which may be unsubstituted or substituted by one or more substituents E. It is preferable to represent a group selected from the following, and these groups have a bond at an arbitrary position.

  Examples of the group represented by the formula (Q-7) include the following formulas (Q-7-1) to (Q-7-7) which may be unsubstituted or substituted with one or more substituents E. It is preferable to represent a group selected from the following, and these groups have a bond at an arbitrary position.

  Examples of the group represented by the formula (Q-10) include the following formulas (Q-10-1) to (Q-10-9) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-11) include the following formulas (Q-11-1) to (Q-11-12) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-13) include the following formulas (Q-13-1) to (Q-13-19) which may be unsubstituted or substituted with one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-14) include the following formulas (Q-14-1) to (Q-14-10) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-15) include the following formulas (Q-15-1) to (Q-15-4) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-16) include the following formulas (Q-16-1) to (Q-16-16) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-17) include the following formulas (Q-17-1) to (Q-17-4) which may be unsubstituted or substituted with one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-18) include the following formulas (Q-18-1) to (Q-18-6) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-19) include the following formulas (Q-19-1) to (Q-19-6) which may be unsubstituted or substituted with one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

  Examples of the group represented by the formula (Q-20) include the following formulas (Q-20-1) to (Q-20-9) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

(In the formula, R ^Q represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. These groups have a bond at an arbitrary position.)

The group represented by the formula (Q-21) includes a group represented by the following formulas (Q-21-1) to (Q-21-3) which may be unsubstituted or substituted with one or more substituents E. It preferably represents a group selected from
The group represented by the formula (Q-22) includes a group represented by the following formulas (Q-22-1) to (Q-22-3) which may be unsubstituted or substituted by one or more substituents E. It preferably represents a group selected from

Among them, Q ¹ is preferably an unsubstituted or an aromatic ring group having 3 to 18 carbon atoms which may be substituted by one or more substituents E from the viewpoint of solubility.

The aromatic ring contained in Q ¹ may be unsubstituted or substituted by one or more of the substituents E in view of wavelength dispersibility and solubility. 7-1), Formula (Q-7-2), Formula (Q-7-7), Formula (Q-8), Formula (Q-10-2), Formula (Q-10-3), Formula (Q-10-3) Q-10-4), Formula (Q-10-5), Formula (Q-10-6), Formula (Q-10-7), Formula (Q-10-8), Formula (Q-10-9) ), Formula (Q-11-2), Formula (Q-11-3), Formula (Q-11-4), Formula (Q-11-5), Formula (Q-11-6), Formula (Q-11-6) -11-7), Formula (Q-11-8), Formula (Q-11-9), Formula (Q-11-10), Formula (Q-11-11), Formula (Q-11-12) , Formula (Q-18-4), Formula (Q-18-5), Formula (Q-21-1), Formula (Q-21-2), More preferably, it represents a group selected from the formulas (Q-22-1) and (Q-22-2), and may be unsubstituted or substituted by one or more substituents E (Q-1 -1), Formula (Q-10-2), Formula (Q-10-3), Formula (Q-10-4), Formula (Q-10-5), Formula (Q-10-6), Formula (Q-10-7), Formula (Q-10-8), Formula (Q-10-9), Formula (Q-18-4), Formula (Q-18-5), Formula (Q-21) -1), a group selected from the formulas (Q-21-2), (Q-22-1), and (Q-22-2).

As the substituent E in the case where the aromatic ring contained in Q ¹ is substituted, from the viewpoint of solubility, fluorine, chlorine, bromine, iodine, nitro, cyano, isocyano, An amino group, a hydroxyl group, a mercapto group, a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a thioisocyano group, or 1 to 20 carbon atoms in which any hydrogen atom may be replaced by a fluorine atom When the alkyl group has 2 or more carbon atoms, one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, Replaced by -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, or -NH-CO-. Have been Preferably represents an alkyl group having 1 to 20 carbon atoms, preferably a fluorine atom, a chlorine atom, a bromine atom, a cyano group, an amino group, or a carbon atom in which any hydrogen atom may be substituted by a fluorine atom an alkyl group having 1 to 20, the alkyl group in the case of 2 or more carbon atoms, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, or -NH- An alkyl group having 1 to 20 carbon atoms that may be replaced by CO— is more preferable, and a fluorine atom, a chlorine atom, a cyano group, an amino group, or a carbon atom in which any hydrogen atom may be replaced by a fluorine atom A linear or branched alkyl group having 1 to 12 atoms, It is further preferred more representative of the alkoxy group or an alkylthio group. Among them, when the aromatic ring contained in Q ¹ is substituted, the substituent E includes a halogen atom such as a fluorine atom and a chlorine atom; a cyano group; an amino group; An alkyl group having 6 carbon atoms; a fluoroalkyl group having 1 to 6 carbon atoms such as a trifluoromethyl group and a pentafluoroethyl group; an alkoxy group having 1 to 6 carbon atoms such as a methoxy group and an ethoxy group; or a methylthio group and an ethylthio group It is preferably an alkylthio group having 1 to 6 carbon atoms from the viewpoint of solubility.

Furthermore, ^{Q 1} is the following formula (Q-1-1), the formula (Q-18-3), the formula (Q-18-4), the formula (Q-10-2), the formula (Q-10-2a ), Formula (Q-10-3), Formula (Q-10-3a), Formula (Q-10-3b), Formula (Q-10-6), Formula (Q-10-6a), Formula (Q-10-6a) -10-6b), Formula (Q-10-6c), Formula (Q-10-6d), Formula (Q-10-7), Formula (Q-10-7a), Formula (Q-10-7b) , Formula (Q-10-7c), Formula (Q-10-7d), Formula (Q-10-7e), Formula (Q-10-7f), Formula (Q-10-9), Formula (Q-10-9) 10-9a), Formula (Q-10-9b), Formula (Q-21-1), Formula (Q-21-2), Formula (Q-22-1), and Formula (Q-22-2) It is particularly preferable to represent a selected group from the viewpoint of wavelength dispersibility.
In these groups, these groups have a bond at an arbitrary position, and among them, it is preferable to have a bond at a conjugated carbon atom adjacent to the hetero atom.

On the other hand, Q ² represents an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an organic group having 2 to 30 carbon atoms having an aromatic ring. The alkyl group, the cycloalkyl group, the cycloalkenyl group, and the aromatic ring may each be unsubstituted or substituted by one or more substituents E, and the alkyl group may be the cycloalkyl may be substituted by a group or cycloalkenyl group, the alkyl group, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S- , -CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - SO 2 -, - OCO-O -, - CO-NH -, - NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C-, and the cycloalkyl group or cycloalkenyl one -CH in group ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or -O It may be replaced by -CO-O-.

In Q ^2, the alkyl groups of said 3 to 20 carbon atoms, among them an alkyl group having 3 to 12 carbon atoms are preferable from the viewpoint having a liquid crystalline solvent solubility in good low temperature region For example, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, 1-methylpentyl group, n-heptyl group, 1- Examples include an ethylpentyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, an n-decyl group, a 3,7-dimethyloctyl group, an n-undecyl group, and an n-dodecyl group.
Examples of the cycloalkyl group having 3 to 12 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group.
Examples of the cycloalkenyl group having 3 to 12 carbon atoms include those having one or more double bonds in the above cycloalkyl group, and more specifically, a cyclopropenyl group, a cyclopentenyl group, and a cyclohexenyl group. , Cyclooctenyl group and the like.

  Further, the alkyl group substituted by the cycloalkyl group or cycloalkenyl group, such as a cyclopentylmethyl group and a cyclohexylmethyl group, is also preferably used. In this case, the number of carbon atoms of the alkyl group includes the number of carbon atoms of the substituted cycloalkyl group or cycloalkenyl group.

Further, among them, the alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group or cycloalkenyl one -CH in group 2 _- or nonadjacent two or more -CH 2 _- are each independently -O In the case where the compound has a structure substituted by-, -CO-, -COO-, -OCO-, or -O-CO-O-, it is preferably used from the viewpoint of improving solvent solubility.

The organic group of 2 to 30 carbon atoms having an aromatic ring in Q ² are may be the same as the organic group of 2 to 30 carbon atoms having an aromatic ring in Q ^1.

The substituent E of Q ^2, the same as the preferred substituents E of the Q ¹ is preferably used. Alkyl group Q ^2, the cycloalkyl group, the substituent E in the cycloalkenyl group, among them, a fluorine atom, a chlorine atom, a nitro group, a cyano group, a hydroxyl group, such as an alkyl group having 1 to 6 carbon atoms are preferably used . The cycloalkyl group or cycloalkenyl group may be substituted with an alkyl group having 1 to 6 carbon atoms.

Q ² may be unsubstituted or substituted with one or more substituents E from the viewpoint of solubility, and may have one —CH ₂ — or two or more non-adjacent groups. CH ₂ — each independently being —O—, —CO—, —COO—, —OCO—, or —O—CO—O—, an alkyl group having 3 to 12 carbon atoms, A cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, an alkyl group having 3 to 12 carbon atoms substituted by the cycloalkyl group or the cycloalkenyl group, or unsubstituted It is preferably an aromatic ring group having 3 to 18 carbon atoms, which may be substituted by one or more substituents E.

Also, among others, from the viewpoint of improving solubility in a solvent, it may be substituted by unsubstituted or substituted with one or more substituents E, 1 single -CH 2 _- or two or more nonadjacent , - - -O are each independently - -CH ₂ of CO -, - COO -, - OCO-, or -O-CO-O- in may be replaced, alkyl of 3 to 12 carbon atoms A cycloalkyl group having 3 to 6 carbon atoms, a cycloalkenyl group having 3 to 6 carbon atoms, or an alkyl group having 3 to 12 carbon atoms substituted by the cycloalkyl group or the cycloalkenyl group. preferably, furthermore, one -CH ₂ - or nonadjacent two or more -CH ₂ - may be replaced by each independently -O-, an alkyl group having 3 to 10 carbon atoms More preferably, there is.
When the solvent solubility is improved and the solvent solubility at room temperature (25 ° C.) is increased, the liquid crystal compound hardly aggregates at room temperature, and poor alignment is suppressed.

Specific examples Q ² 'in the following, but not limited thereto. In the equation (Q2-26) from the following formula (Q2-1), * (asterisk) indicates the bonding position to ^{J 1.}

When Q ² is an organic group having 2 to 30 carbon atoms having an aromatic ring, the above-mentioned formula (Q-1-1), formula (Q-10-2), formula (Q-10-2a), Formula (Q-10-3), Formula (Q-10-3a), Formula (Q-10-3b), Formula (Q-10-6), Formula (Q-10-6a), Formula (Q-10-6) -6b), Formula (Q-10-6c), Formula (Q-10-6d), Formula (Q-10-7), Formula (Q-10-7a), Formula (Q-10-7b), Formula (Q-10-7c), Equation (Q-10-7d), Equation (Q-10-7e), Equation (Q-10-7f), Equation (Q-10-9), Equation (Q-10- 9a), Formula (Q-10-9b), Formula (Q-18-3), Formula (Q-18-4), Formula (Q-21-1), Formula (Q-21-2), Formula (Q-21-2) Q-22-1) and at least one group selected from formulas (Q-22-2) This is preferred from the viewpoint of ease of synthesis due to availability of raw materials.

The total number of π electrons included in Q ¹ and Q ² is preferably from 4 to 24, and more preferably from 4 to 20, from the viewpoints of wavelength dispersion, liquid crystallinity, and ease of synthesis.

In the general formula (I), Q ¹ is unsubstituted or carbon atom which may be substituted by one or more substituents E, particularly in view of improving solvent solubility and improving orientation. Q ³ is an aromatic ring group having 3 to 18 atoms, and Q ² is such that one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, and —COO. -, -OCO-, or -O-CO-O-, which may be substituted with an alkyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 6 carbon atoms, or a cycloalkyl group having 3 to 6 carbon atoms. It is preferably a cycloalkenyl group, or an alkyl group having 3 to 12 carbon atoms which is substituted by the cycloalkyl group or the cycloalkenyl group.
Among them, in the general formula (I), J ¹ is -N =, since it tends to have liquid crystallinity in a lower temperature range, and particularly, the solvent solubility is improved and the orientation is easily improved. Q ¹ is an unsubstituted or an aromatic ring group having 3 to 18 carbon atoms which may be substituted by one or more substituents E, and Q ² has one -CH ₂ -or an adjacent group. two or more -CH ₂ no - are each independently -O -, - CO -, - COO -, - OCO-, or -O-CO-O- in may be replaced, carbon atoms 3 More preferably, it is an alkyl group of from 12 to 12.

It is preferable that J ¹ , Q ¹ and Q ² each represent a group selected from the following formulas (D-1) to (D-56), from which raw materials are easily available, solvent solubility is good, and low temperature. In terms of being able to have liquid crystallinity in the region, it is preferable, and particularly preferred is a group selected from the following formulas (D-1) to (D-48) from the viewpoint of good orientation. It is even more preferable to represent a group selected from the formulas (D-1) to (D-28) and (D-45) to (D-48), and the following formulas (D-1) to (D-48) (D-6), Formulas (D-8) to (D-15), Formulas (D-20) to (D-23), Formulas (D-25) to (D28), and Formulas (D- 45) to even more preferably a group selected from formulas (D-48). In the following formulas (D-1) to (D-56), * (asterisk) indicates the bonding position of the phthalimide group to the nitrogen atom.

Further, examples of the compound represented by the general formula (I) include the following compounds (i) to (lvi). As for the compounds (i) to (lvi), the combination of J ¹ , Q ¹ and Q ^{2 is} a combination represented by the formulas (D-1) to (D-56). Lc1 in the ^table, -L ¹ -A ¹ - and _{^{(L 3 -A 3) m1 -L}} 5 -R sp1 -Z 1, Lc2 ^{is, -L 2 -A 2 - (L} 4 -A 4) m2 represent a -L ⁵ -R ^sp1 -Z ^1.

  The compound represented by the general formula (I) can be produced, for example, by the following production method. Examples of the production method include, for example, a known organic synthesis reaction described in Method der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, and a reaction method such as condensation reaction, urea reaction, and so on. Reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel Craft reaction, Heck reaction, Aldol reaction, Duff Reaction, etc.) can be produced by appropriately combining them according to the structure. Hereinafter, examples of the manufacturing method will be described, but the present disclosure is not limited to these structures and manufacturing methods.

For example, when L ¹ and L ² are each ** OCO— (* indicates a bonding position to a phthalimide ring), for example, the following production can be performed.
First, a phthalic anhydride compound represented by the formula (ip-1) and a 1,1-disubstituted hydrazine compound or an amino compound represented by the formula (ip-2) are prepared and prepared in dimethylacetamide (DMAc). , A phthalic anhydride compound represented by the formula (ip-1), a 1,1-disubstituted hydrazine compound represented by the formula (ip-2), acetic anhydride (Ac ₂ O), and pyridine, A phthalic anhydride compound represented by the formula (ip-1), a 1,1-disubstituted hydrazine compound represented by the formula (ip-2) or an amino compound is reacted with the phthalic anhydride compound represented by the formula (ip-3). To obtain an intermediate.

  Next, the intermediate represented by the formula (ip-3) and potassium carbonate are mixed in methanol, and the mixture is heated and refluxed at, for example, 170 ° C. to 180 ° C., and hydrochloric acid is added. The intermediate represented is obtained.

Next, an intermediate represented by the formula (ip-4) and an intermediate represented by the formula (ip-5): HOOC-A ^1- (L ³ -A ³ ) _m1 -R ¹ (A ¹ , L ³ , A ³ , R ¹ , and m 1 have the same meanings as described above) by a condensation reaction or the like to obtain an intermediate represented by the formula (ip-6). An intermediate represented by the formula (ip-6) and an intermediate (A ² , L ⁴ ) represented by the formula (ip-7): HOOC-A ^2- (L ⁴ -A ⁴ ) _m2 -R ² A ⁴ , R ² , and m ² have the same meanings as described above) to obtain a compound represented by the formula (I-ex1). When the intermediate represented by the formula (ip-5) and the intermediate represented by the formula (ip-7) have the same structure, the intermediate represented by the formula (ip-4) The compound represented by the formula (I-ex1) can be obtained by reacting the represented intermediate.

In addition, the unsubstituted phthalic anhydride compound represented by the formula (ip-1) can be purchased commercially. For example, when the substituent E ¹ is n-hexyl, the substituent E ¹ is introduced by a Friedel-Crafts alkylation reaction using n-halogenated hexane and a metal catalyst (iron chloride III or aluminum chloride). be able to.
The 1,1-disubstituted hydrazine compound or amino compound represented by the formula (ip-2) can be prepared by reacting a monosubstituted hydrazine or amino compound with a halogen compound.

  As each intermediate used in the production, a commercially available product may be used as appropriate, or it may be appropriately synthesized by a conventionally known method.

  In the present disclosure, the structure of the polymerizable liquid crystal compound is nuclear magnetic resonance spectroscopy (NMR), pyrolysis-type gas chromatography / mass spectrometry (Py-GC-MS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI). -TOFMS) and the like can be combined as appropriate.

  The polymerizable liquid crystal compound of the present disclosure can be dissolved in at least one solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone in an amount of 10% by mass or more. Is preferred from the viewpoint of spreading, and it is more preferable that the dissolution is 20% by mass or more.

B. Polymerizable composition The polymerizable composition of the present disclosure is a composition containing at least the polymerizable liquid crystal compound of the present disclosure.

  Since the polymerizable composition of the present disclosure contains the polymerizable liquid crystal compound of the present disclosure, as described above, a polymerizable composition capable of forming a phase difference layer capable of performing uniform polarization conversion in a wide wavelength range, as described above. It can be. Further, the polymerizable composition of the present disclosure, since the polymerizable liquid crystal compound of the present disclosure has a liquid crystallinity in a low temperature range, it can be a polymerizable liquid crystal composition having a liquid crystallinity in a low temperature range, The load in the step of aligning the liquid crystal can be reduced, or the liquid crystal can be used for a substrate that is weak to high temperatures. Further, the polymerizable composition of the present disclosure has a tendency that the polymerizable liquid crystal compound of the present disclosure has high solvent solubility. The content ratio of the disclosed polymerizable liquid crystal compound can be increased, the load on the production process can be easily reduced, and a uniform coating film can be easily produced.

The polymerizable composition of the present disclosure contains at least the polymerizable liquid crystal compound of the present disclosure, but preferably further contains a photopolymerization initiator.
Further, the polymerizable composition of the present disclosure is, in terms of adjusting the phase difference and wavelength dispersibility, the orientation, the solubility, in terms of adjusting the phase transition temperature, further, the polymerizable liquid crystal compound of the present disclosure is. It may contain a different polymerizable liquid crystal compound, and may further contain other components as long as the effect is not impaired. Hereinafter, each component constituting the polymerizable composition of the present disclosure will be described in order.

1. The polymerizable liquid crystal compound of the present disclosure In the polymerizable composition of the present disclosure, the polymerizable liquid crystal compound of the present disclosure may be the same as that described in the above “A. Polymerizable liquid crystal compound”. Description is omitted.
In the polymerizable composition of the present disclosure, the polymerizable liquid crystal compound of the present disclosure may be used alone or in combination of two or more.

  In the present embodiment, when a polymerizable composition having flat wavelength dispersibility is obtained, a reverse wavelength dispersibility, a flat wavelength dispersibility, or a positive wavelength dispersion as a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure. When used in combination with any one or more polymerizable liquid crystal compounds exhibiting wavelength dispersibility, the content ratio of the polymerizable liquid crystal compound of the present disclosure, the polymerizable liquid crystal compound of the present disclosure and the polymerizable liquid crystal compound of the present disclosure, May be 50 parts by mass or more and 99.9 parts by mass or less, preferably 54 parts by mass or more and 99 parts by mass or less, and more preferably 57 parts by mass or more with respect to 100 parts by mass of the total amount of different polymerizable liquid crystal compounds More preferably, it is 98 parts by mass or less.

Further, in the present embodiment, the total content ratio of the polymerizable liquid crystal compound including the polymerizable liquid crystal compound of the present disclosure (total of the polymerizable liquid crystal compound of the present disclosure and the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure) From the viewpoint of curability of the polymerizable composition, the content is preferably 90 parts by mass or more and 99.9 parts by mass or less with respect to 100 parts by mass of the solid content of the polymerizable composition, and 92 parts by mass or more. It is more preferable that the amount be 99 parts by mass or less.
In the present disclosure, the solid content refers to all components except the solvent, for example, those which are included in the solid content even if a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure described below is liquid. And

2. Photopolymerization initiator In this embodiment, the photopolymerization initiator can be appropriately selected from conventionally known ones and used. Specific examples of such a photopolymerization initiator include, for example, aromatic ketones including thioxanthone and the like, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, aromatic onium Salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, borates, azinium compounds, metallocene compounds, active ester compounds, compounds having a carbon-halogen bond, and alkylamine compounds are preferably mentioned. Among them, among them, to cure the interior of the coating and improve the durability, acylphosphine oxide-based polymerization initiator, α-aminoalkylphenone-based polymerization initiator, α-hydroxyketone-based polymerization initiator, and oxime ester-based Selected from the group consisting of polymerization initiators At least one that is preferable.

  Examples of the acylphosphine oxide-based polymerization initiator include bis (2,4,6-trimethylbenzoyl) -phenyl-phosphine oxide (for example, trade name: Irgacure 819, manufactured by BASF), bis (2,6-dimethoxy). (Benzoyl) -2,4,4-trimethyl-pentylphenylphosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide (trade name: Lucirin TPO: manufactured by BASF, etc.) and the like.

  Examples of the α-aminoalkylphenone-based polymerization initiator include 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one (for example, Irgacure 907, manufactured by BASF), Benzyl-2- (dimethylamino) -1- (4-morpholinophenyl) -1-butanone (for example, Irgacure 369, manufactured by BASF), 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone (Irgacure 379EG, manufactured by BASF) and the like.

  Examples of the α-hydroxyketone polymerization initiator include, for example, 2-hydroxy-1- {4- [4- (4-hydroxy-2-methyl-propionyl) -benzyl] -phenyl} -2-methyl-propane -1-one (for example, trade name: Irgacure 127, manufactured by BASF), 2-hydroxy-4′-hydroxyethoxy-2-methylpropiophenone (for example, trade name: Irgacure 2959, manufactured by BASF), 1-hydroxy-cyclohexyl-phenyl-ketone (for example, trade name: Irgacure 184, manufactured by BASF, etc.), oligo {2-hydroxy-2-methyl-1- [4- (1-methylvinyl) phenyl] propanone} ( For example, trade name: ESACURE ONE, manufactured by Lamberti, etc.).

  Examples of the oxime ester-based polymerization initiator include 1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), methanone, ethanone , 1- [9-ethyl-6- (1,3-dioxolane, 4- (2-methoxyphenoxy) -9H-carbazol-3-yl]-, 1- (o-acetyloxime) (trade name ADEKA OPT- N-1919, manufactured by ADEKA).

In the present embodiment, the photopolymerization initiator can be used alone or in combination of two or more.
In the present embodiment, the content ratio of the photopolymerization initiator is from 0.1 part by mass to 10 parts by mass with respect to 100 parts by mass of the solid content of the polymerizable composition from the viewpoint of promoting the curing of the polymerizable compound. Preferably, it is 1 part by mass or more and 8 parts by mass or less.

3. Polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure In the polymerizable composition of the present disclosure, the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure is appropriately selected from conventionally known ones. Can be used. The wavelength of the incident light with respect to the retardation film is plotted on the horizontal axis, and the birefringence is plotted on the vertical axis. It may be a polymerizable liquid crystal compound, a polymerizable liquid crystal compound having flat wavelength dispersion, or a polymerizable liquid crystal compound having reverse wavelength dispersion. As a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure, for example, examples of compounds exhibiting reverse wavelength dispersion include, for example, Patent Nos. 5,463,666, 4,186,981, 5,962,760, and No. 5,826,759. Examples of compounds exhibiting flat dispersibility include the compounds described in Recueil des Travaux Chimiques des Pays-Bas (1996), 115 (6), 321-328.

In the present embodiment, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having a polymerizable functional group at at least one end of the rod-shaped mesogen because it is easily aligned in combination with the polymerizable liquid crystal compound. More preferably, it is a polymerizable liquid crystal compound having a polymerizable functional group. A polymerizable liquid crystal compound having two or more polymerizable functional groups in one molecule can improve the hardness and durability of a coating film.
Examples of the polymerizable liquid crystal compound used in the present disclosure include, for example, a polymerizable liquid crystal compound having the same structure as the main chain portion of the polymerizable compound and represented by the following general formula (II-1), and the following general formula: And a polymerizable liquid crystal compound represented by (II-2).

^{(Wherein, Z 10,} and ^{Z 20} are each independently represents a polymerizable functional ^{group, R SP10,} and ^{R sp20} represents an each independently a single bond or an alkylene group having a carbon atom number of 1 to 20, one -CH ₂ - or nonadjacent two or more _-CH 2 - is -O -, - COO -, - OCO -, - OCOO- may be replaced ^by, L ^{10, L 20} and L ³⁰ are each independently _{-O -, - S -, -} OCH 2 -, - CH 2 O -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - O-CO-O -, - CO-NH -, - NH-CO -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = C _{-, - COO-CH 2 CH} 2 -, - OCO-CH 2 CH 2 -, - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 —, —CH ₂ —COO—, —CH ₂ —OCO—, —CH ＝ CH—, —CF ＝ CF—, —C≡C— or a single bond, and A ¹⁰ and A ²⁰ are each independently Benzene-1,4-diyl group, cyclohexane-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1, Represents a 4-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein A ¹⁰ and A ²⁰ are each independently unsubstituted or an alkyl group; , Halogenated alkyl group, alkoxy Group, a halogenated alkoxy group, a halogen atom, a cyano group or a nitro group, and R may be a hydrogen atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a cyano group, A nitro group, an isocyano group, a thioisocyano group, or one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —S—, —CO—, —COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH —OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, which has 1 to 20 carbon atoms. Represents a linear or branched alkyl group, wherein s1 and s2 are 0 Represents a 1, 2, 3 or 4, if s1 and s2 are independently represents a 2, 3 or 4, different two, even each identical ^{A 20, L 10} present three or four May be. )

The polymerizable functional group polymerizable liquid crystal compound has, the same as Z ¹ or the like of the polymerizable compound. Examples of the polymerizable functional group of the polymerizable liquid crystal compound include an oxirane ring, a cyclic ether-containing group such as an oxetane ring, and an ethylenic double bond-containing group. From the standpoint of being excellent, an ethylenic double bond-containing group is preferred. Examples of the cyclic ether group include a glycidyl group. Examples of the ethylenic double bond-containing group include a vinyl group, an allyl group, a (meth) acryloyl group and the like, and among them, a (meth) acryloyl group is preferable.

  In the present embodiment, the polymerizable liquid crystal compound is at least one selected from compounds represented by the following general formula (III) and compounds represented by the following general formula (IV) from the viewpoint of orientation. Are preferred.

(In the general formula (III), R ²¹ represents a hydrogen atom or a methyl group, and R ²² represents a group represented by — (CH ₂ ) _p — or — (C ₂ H ₄ O) _{p ′} —. L ²³ represents a direct bond or a linking group represented by —O—, —OC (＝ O) —, or —C (＝ O) —O—, and Ar ³ represents benzene-1, 4-diyl group, cyclohexane-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, Represents a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, wherein Ar ³ is unsubstituted or an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group , Substituted with a halogen atom, a cyano group or a nitro group It is good, a plurality of ^{L 23} and Ar ³ each may be different even identical ^.R 23 _{is, -F, -Cl, -CN, -OCF} 3, -OCF 2 H, -NCO, -NCS _{^{, -NO 2, -NHC (= O}} ) -R 24, -C (= O) -OR 24, -OH, -SH, -CHO, -SO 3 H, -NR 24 2, -R 25, or - For OR ²⁵ , R ²⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, R ²⁵ represents an alkyl group having 1 to 6 carbon atoms, b is an integer of 2 to 5, p and p 'are each independently an integer of 2 or more and 10 or less.)

(In the general formula (IV), R ³¹ and R ³² each independently represent a hydrogen atom or a methyl group, and R ³³ represents — (CH ₂ ) _q — or — (C ₂ H ₄ O) _{q ′} — R ³⁴ represents a group represented by — (CH ₂ ) _r — or — (OC ₂ H ₄ ) _{r ′} —, and L ³⁴ represents a direct bond or —O—, -O-C (= O) - , or -C (= O) a linking group represented by -O-, Ar ⁴ is 1,4-diyl group, cyclohexane-1,4-diyl group, Pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group or 1,3- It represents a dioxane-2,5-diyl group, or an alkyl radical Ar ⁴ is unsubstituted, halogenated Al Group, alkoxy group, halogenated alkoxy group, a halogen atom, may be substituted with a cyano group or a nitro group, a plurality of L ³⁴ and Ar ⁴ may .c be different even in the same respective 2 The integers of 5 or more and q, q ', r and r' are each independently an integer of 2 or more and 10 or less.)

P, p ′ in the general formula (III), and q, q ′, r and r ′ in the general formula (IV) are preferably 2 or more and 8 or less, and more preferably 2 or more and 6 or less from the viewpoint of orientation. Is more preferable, and it is further more preferable that it is 2 or more and 5 or less.
Ar ³ and Ar ⁴ are a benzene-1,4-diyl group, a cyclohexane-1,4-diyl group, a pyridine-2,5-diyl group, a pyrimidine-2,5-diyl group, a naphthalene-2, Represents a 6-diyl group, a naphthalene-1,4-diyl group, a tetrahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, among which a benzene-1,4-diyl group; A naphthalene-2,6-diyl group or a cyclohexane-1,4-diyl group is more preferred. Examples of the substituent which Ar ³ and Ar ⁴ may have include an alkyl group, a halogenated alkyl group, an alkoxy group, a halogenated alkoxy group, a halogen atom, a cyano group and a nitro group, and more preferably a carbon atom. Examples thereof include an alkyl group having a number of 1 to 5 and a halogen atom.
The alkyl group having 1 or more and 6 or less carbon atoms in R ²⁴ and R ²⁵ in the general formula (III) may be any of linear, branched or cyclic, such as methyl, ethyl, n -Propyl group, n-butyl group, linear alkyl group such as n-pentyl group and n-hexyl group, i-propyl group, i-butyl group, t-butyl group, branched alkyl group such as 2-methylbutyl group, And cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group and cyclohexyl group. R ²⁴ is particularly preferably a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. R ²⁵ is preferably an alkyl group having 1 to 5 carbon atoms, and more preferably an alkyl group having 1 to 3 carbon atoms.
R ²³ is preferably -Cl, -CN, -OCF ₃ , -OCF ₂ H, -NCO, -NCS, -NO ₂ , -NHC (= O) -R ²⁵ , -C (= _{^{O) -OR 24, -OH, -SH}} , -CHO, -SO 3 H, -NR 24 2, preferably ^{-R 25,} or ^{-OR 25, -Cl, -CN, -OCF} 3 or - More preferably, it is C (＝ O) —OR ²⁴ , —R ²⁵ , or —OR ²⁵ .

  As the mesogen structure contained in the polymerizable liquid crystal compound, partial structures represented by the following chemical formulas (V-1) to (V-6) are preferably used, and among them, the following chemical formula (V) containing three or more ring structures is preferable. -1), (V-2), (V-4), (V-5), and a partial structure represented by at least one selected from the group consisting of (V-6) are preferably used. The hydrogen atom in the phenylene group or naphthylene group in the partial structures represented by the following chemical formulas (V-1) to (V-6) may be substituted by an alkyl group having 1 to 3 carbon atoms or a halogen atom. .

  Preferred specific examples of the compound represented by the general formula (III) and the compound represented by the general formula (IV) include those represented by the following chemical formulas (1) to (22). It is not limited.

(G is an integer of 2 to 5.)

In the present embodiment, a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure can be used alone or in combination of two or more.
In the present embodiment, the content ratio of the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure in the polymerizable composition may be appropriately adjusted in order to adjust a desired retardation or the like, and is limited. Not something.
For example, in the present embodiment, in the case of obtaining a polymerizable composition having flat wavelength dispersion, reverse wavelength dispersion, flat wavelength dispersion as a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure, Or when used in combination with any one or more polymerizable liquid crystal compounds exhibiting positive wavelength dispersion, the content ratio of the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure, the polymerizable liquid crystal compound of the present disclosure And the polymerizable liquid crystal compound of the present disclosure is different from the polymerizable liquid crystal compound in a total amount of 100 parts by mass, and may be 0.1 to 50 parts by mass, and 1 to 46 parts by mass. Preferably, it is 2 parts by mass or more and 43 parts by mass or less.

4. Other Components The polymerizable composition of the present embodiment may further contain other components as long as the effect is not impaired. Specifically, it may contain a leveling agent, an antioxidant, a light stabilizer, and a solvent from the viewpoint of coatability as other components. In addition, it may not contain a polymerizable compound which does not exhibit liquid crystallinity alone but can adjust retardation or reverse wavelength dispersion, phase transition temperature, hardness, and durability by being used together with the polymerizable liquid crystal compound of the present disclosure. . These may be appropriately selected from conventionally known materials.

In order to improve the hardness and durability of the coating film, it is preferable to further contain a polymerizable compound having two or more polymerizable functional groups in one molecule. As the polymerizable compound having two or more polymerizable functional groups in one molecule, a polymerizable compound having no liquid crystal property can be used in addition to the polymerizable liquid crystal compound described above.
As the polymerizable compound having two or more polymerizable functional groups in one molecule, a so-called polyfunctional monomer can be used. For example, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol Di (meth) acrylate, dipropylene glycol di (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, dipentaerythritol hexa (meth) acrylate, 1,6-hexanediol di (meth) Acrylate, neopentyl glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate, dipentaerythritol penta (meth) Acrylate, tripentaerythritol octa (meth) acrylate, tetrapentaerythritol deca (meth) acrylate, isocyanuric acid tri (meth) acrylate, isocyanuric acid di (meth) acrylate, polyester tri (meth) acrylate, polyester di (meth) acrylate, Bisphenol di (meth) acrylate, diglycerin tetra (meth) acrylate, adamantyl di (meth) acrylate, isobornyl di (meth) acrylate, dicyclopentane di (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra Examples thereof include (meth) acrylates and those obtained by modifying them with PO, EO, or the like. Since the crosslinking reaction proceeds and the durability of the coating film is improved, pentaerythritol triacrylate (PETA), dipentaerythritol hexaacrylate (DPHA), pentaerythritol tetraacrylate (PETTA), dipentaerythritol pentaacrylate (DPPA), A polymerizable compound having three or more polymerizable functional groups in one molecule such as trimethylolpropane triacrylate (TMPTA) is preferable.
When a polymerizable compound having no liquid crystallinity is used in the present embodiment, the content is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less with respect to 100 parts by mass of the solid content of the polymerizable composition. It is more preferable that the content be 20 parts by mass or less.

  It is preferable to use a fluorine-based or silicone-based leveling agent as the leveling agent. Specific examples of the leveling agent include, for example, Megafac series manufactured by DIC Corporation, TSF series manufactured by Momentive Performance Materials Japan, and Neos Corporation described in JP-A-2010-122325. Futhergent series and the like. When a leveling agent is used in the present embodiment, its content is preferably 0.001 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the solid content of the polymerizable composition.

  The polymerizable composition of the present embodiment may contain a solvent, if necessary, from the viewpoint of coatability. The solvent may be appropriately selected from conventionally known solvents that can dissolve or disperse each component contained in the polymerizable composition. Specifically, for example, hydrocarbon solvents such as hexane, cyclohexane and toluene, ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, tetrahydrofuran, 1,3-dioxolan, propylene glycol monoethyl ether ( Ether solvents such as PGME), alkyl halide solvents such as chloroform and dichloromethane, ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate, amide solvents such as N, N-dimethylformamide and N-methylpyrrolidone; And sulphoxide solvents such as dimethylsulfoxide, and alcohol solvents such as methanol, ethanol and propanol. In the present embodiment, the solvent can be used alone or in combination of two or more as a mixed solvent.

  The polymerizable composition of the present embodiment is suitably used for various applications because of its good orientation. The polymerizable composition of the present embodiment is suitably used as a liquid crystal composition, for example, for a later-described retardation film or various optical member applications.

C. Polymer The polymer of the present disclosure is obtained by polymerizing the polymerizable liquid crystal compound of the present disclosure or the polymerizable composition of the present disclosure. The polymerization method can be appropriately selected according to the polymerizable functional group contained in the polymerizable liquid crystal compound of the present disclosure.
The polymerizable liquid crystal compound of the present disclosure, or a polymer obtained by polymerizing the polymerizable composition of the present disclosure without aligning the same, for example, can be used as a light scattering plate, a depolarizing plate, and a moiré fringe preventing plate. It is.
Further, the polymerizable liquid crystal compound of the present disclosure, or a polymer obtained by polymerizing the polymerizable composition of the present disclosure after orientation, has an optical anisotropy, and a retardation film and various types described below. It is suitably used for optical member applications.

D. Retardation Film The retardation film of the present disclosure is a retardation film having a retardation layer, wherein the retardation layer is made of a cured product of the polymerizable composition of the present disclosure.
The retardation film of the present embodiment, since the retardation layer is made of a cured product of the polymerizable composition, as described above, shows flat wavelength dispersion or reverse wavelength dispersion, in a wide wavelength range. Uniform polarization conversion is possible.

  The layer structure of the retardation film will be described with reference to the drawings. 1 to 3 each show an embodiment of the retardation film of the present disclosure. One embodiment of the retardation film 10 shown in the example of FIG. 1 is a retardation film in which an alignment film 3 and a retardation layer 1 are laminated on a base material 2 in this order. One embodiment of the retardation film 10 shown in the example of FIG. 2 is a retardation film including only the retardation layer 1. In the embodiment of the retardation film 10 shown in the example of FIG. 3, the retardation layer 1 is formed directly on the base material 2 '. The retardation film shown in the example of FIG. 3 may be provided with means for expressing an alignment regulating force on the surface of the substrate 2 ′ on the side of the retardation layer 1. Here, in the present disclosure, the orientation regulating force refers to an action of arranging the orientation components in the retardation layer in a specific direction.

1. Retardation Layer The retardation layer 1 of the embodiment of the present disclosure is made of a cured product of the polymerizable composition of the present disclosure containing the polymerizable liquid crystal compound of the present disclosure.
Here, the polymerizable liquid crystal compound of the present disclosure and the polymerizable composition of the present disclosure are the same as those described in the polymerizable liquid crystal compound and the polymerizable composition of the embodiment of the present disclosure, respectively. Since it may be possible, the description here is omitted.

  The retardation layer, in the state where the main chain portion having the orientation of the polymerizable liquid crystal compound of the present disclosure, and the polymerizable liquid crystal compound that may be further included are substantially horizontally aligned with respect to the film surface, It is preferably a cured one. The cured product of the polymerizable composition according to the embodiment of the present disclosure includes a structure in which at least a part of the polymerizable functional group of the polymerizable compound is polymerized. Since the structure in which at least a part of the polymerizable functional group of the polymerizable compound is polymerized is included, the phase difference layer of the present embodiment is a phase difference layer having improved durability.

  The phase difference can be measured by an automatic birefringence measurement device (for example, product name: KOBRA-WR, manufactured by Oji Scientific Instruments). The measurement light is incident on the surface of the phase difference layer perpendicularly or obliquely, and from the chart of the optical phase difference and the angle of incidence of the measurement light, the anisotropy to increase or decrease the phase difference of the phase difference layer or the vertical (thickness) of the liquid crystal S) The degree of orientation in the direction can be confirmed.

  Further, the retardation layer has a structure in which at least a part of the polymerizable functional groups of the polymerizable liquid crystal compound of the present disclosure contained in the polymerizable composition of the present disclosure and the polymerizable liquid crystal compound that may be further contained are polymerized. Can be confirmed by collecting and analyzing the material from the retardation layer. As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a method combining these can be applied.

  The retardation layer may include other components such as a photopolymerization initiator, a leveling agent, an antioxidant, and a light stabilizer. Components such as a photopolymerization initiator, which may decompose all when irradiated with light to react the polymerizable functional group of the polymerizable liquid crystal compound, are not included in the retardation layer. There is also.

The thickness of the retardation layer may be appropriately set according to the application.
When the retardation film of the present disclosure is, for example, a broadband quarter-wave plate, the Re (550) of the obtained retardation film is 113 nm or more and 163 nm or less, preferably 135 nm or more and 140 nm or less, and particularly preferably about 137. The film thickness may be adjusted to about 0.5 nm. In the case of a half-wave plate, the resulting optical film has a Re (550) of 250 nm to 300 nm, preferably 273 nm to 277 nm, and particularly preferably about 275 nm. The film thickness may be adjusted so as to be about the same.

By appropriately adjusting the amount of the polymerizable composition applied and the concentration of the polymerizable liquid crystal compound, the film thickness can be adjusted so as to give a desired retardation. The retardation value (retardation value, Re (λ)) of the obtained retardation layer is determined as in the following equation. Therefore, in order to obtain a desired Re (λ), it is necessary to adjust the film thickness d. Good.
Re (λ) = d × Δn (λ)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)
Above all, the thickness of the retardation layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less.

The wavelength dispersibility of the retardation film of the present disclosure can be arbitrarily determined by the content of the polymerizable liquid crystal compound of the present disclosure and other polymerizable liquid crystal compounds that may be contained in the retardation layer. Increasing the content of the polymerizable liquid crystal compound of the present disclosure in the retardation layer tends to increase reverse wavelength dispersion and flat wavelength dispersion.
In the retardation layer of the present disclosure, Re (450) / Re (550) may be close to 1, specifically 1.00 or more and less than 1.10. It is preferably at least 0.000 and less than 1.08, and Re (650) / Re (550) may be close to 1, specifically 0.92 or more and less than 1.00, and more preferably 0.94 or less. It is preferably at least 1.00 and less than 1.00.

2. Alignment film In this specification, the alignment film refers to a layer for arranging liquid crystal components contained in the retardation layer in a certain direction.
As the alignment film used in the embodiment of the present disclosure, it is preferable to use a horizontal alignment film because the polymerizable composition of the embodiment of the present disclosure is easily horizontally aligned.
The horizontal alignment film is a film that, by being provided as a coating film, aligns the major axis of the mesogen of the liquid crystalline component contained in the retardation layer substantially horizontally with respect to the horizontal alignment film surface (film surface). Good.
As the horizontal alignment film, a conventionally known one can be appropriately selected and used, and examples thereof include a rubbing method, a photo alignment method, and an alignment film to which an alignment regulating force is applied by a shaping method and the like. A horizontal alignment film provided with an alignment control force by a rubbing method, a photo alignment method or a shaping method is preferable.

  When imparting an alignment regulating force by a rubbing method, a polymer that exhibits an alignment regulating force by rubbing is used for the horizontal alignment film. Examples of the polymer include polyvinyl alcohol, polyimide, polyamide, and derivatives thereof, and among them, polyvinyl alcohol is preferable.

  The method of forming the horizontal alignment film by the rubbing method may be appropriately selected from conventionally known methods. For example, a horizontal alignment film can be obtained by forming a coating film containing the above-mentioned polymer on the transparent base material and rubbing it using a known rubbing roller or the like.

  When the horizontal alignment film is formed by a photo-alignment method, a photo-alignment composition containing a photo-alignment material that develops an alignment regulating force by irradiating polarized light is used as the composition for the alignment film. The photo-alignment material may be a photodimerization type material or a photoisomerization type material. Specifically, for example, cinnamate, coumarin, benzylidenephthalimidine, benzylidene acetophenone, diphenylacetylene, stilbazole, uracil, quinolinone, maleimide, or a polymer having a cinnamylideneacetic acid derivative. Polymers having at least one of them and derivatives thereof are preferably used. Specific examples of such a light dimerization type material include, for example, JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, WO2010 / 150748, and JP-A-2015-2015. The compounds described in JP-A-151548 can be exemplified.

  The method for forming the photo-alignment film by the photo-alignment method may be appropriately selected from conventionally known methods. For example, a photo-alignment film can be obtained by uniformly applying the photo-alignment composition on the transparent base material, irradiating polarized light, and then irradiating the entire coating film with light.

  When the horizontal alignment film is formed by a shaping method, the composition for an alignment film may be appropriately selected from those capable of shaping a desired fine concavo-convex shape, and may be, for example, an ultraviolet curable resin or a thermosetting resin. A shaping composition containing a curable resin, an electron beam curable resin, or the like can be used. Above all, it is preferable to use an ultraviolet curable resin in that the formation of the alignment film is easy. Specific examples of the ultraviolet curable resin include, for example, urethane acrylate, epoxy acrylate, polyester acrylate, polyether acrylate, melamine acrylate, and the like, in addition to the above polymerizable monomers and polymerizable oligomers. More than one species can be used in combination.

  The method of forming the horizontal alignment film by the shaping method may be appropriately selected from conventionally known methods. For example, on the transparent substrate, the composition for shaping is uniformly applied, and on a mold on which a desired fine unevenness is formed, after contacting the coating film, pressure is applied, and ultraviolet rays are irradiated. Thereby, it is possible to obtain an alignment film having a desired fine unevenness.

  Further, the horizontal alignment film may be a film that has been subjected to a patterning process and has portions having alignment performance arranged in a pattern. As the horizontal alignment film that has been subjected to the patterning treatment, a known material can be used, and is not particularly limited. For example, a rubbing alignment film that has been subjected to patterning treatment by mask rubbing, a photo alignment that has been subjected to patterning treatment by mask exposure And an alignment film obtained by patterning a film or an alignment film by printing or the like.

  The thickness of the horizontal alignment film is not particularly limited as long as the polymerizable rod-like liquid crystal compound can be aligned in the horizontal direction, and is not particularly limited, but is usually 1 nm or more, preferably 60 nm or more, From the viewpoint of thinning, the thickness is 15 μm or less, preferably 10 μm or less, more preferably 1 μm or less, and even more preferably 0.3 μm or less.

3. Substrate In the present embodiment, the substrate includes a glass substrate, a metal foil, a resin substrate and the like. Among them, the substrate preferably has transparency, and can be appropriately selected from conventionally known transparent substrates. As the transparent substrate, other than a glass substrate, acetylcellulose-based resins such as triacetylcellulose, polyethylene-based resins such as polyethylene terephthalate, polyethylene naphthalate, polybutylene terephthalate, and polylactic acid, polypropylene, polyethylene, and polymethylpentene Formed using resins such as olefin resin, acrylic resin, polyurethane resin, polyether sulfone, polycarbonate, polysulfone, polyether, polyether ketone, acronitrile, methacrylonitrile, cycloolefin polymer, cycloolefin copolymer, etc. Transparent resin substrates.

  The transparent substrate preferably has a transmittance in the visible light region of 80% or more, and more preferably 90% or more. Here, the transmittance of the transparent substrate can be measured according to JIS K7361-1 (test method for total light transmittance of plastic-transparent material).

When the retardation layer is formed by a roll-to-roll method, the transparent substrate is preferably a flexible material having flexibility that can be wound into a roll.
Examples of such flexible materials include cellulose derivatives, norbornene-based polymers, cycloolefin-based polymers, polymethyl methacrylate, polyvinyl alcohol, polyimide, polyarylate, polyethylene terephthalate, polysulfone, polyethersulfone, amorphous polyolefin, modified acrylic polymers, and polystyrene. , Epoxy resins, polycarbonates, polyesters and the like. Especially, in this embodiment, it is preferable to use a cellulose derivative or polyethylene terephthalate. This is because the cellulose derivative is particularly excellent in optical isotropy and can be excellent in optical characteristics. Further, polyethylene terephthalate is preferred because it has high transparency and excellent mechanical properties.

The thickness of the substrate used in the present embodiment is not particularly limited as long as necessary self-supporting properties can be imparted depending on the use of the retardation film or the like, but is usually in a range of about 10 μm or more and about 1000 μm or less. It is.
Among them, the thickness of the substrate is preferably in the range of 25 μm or more and 125 μm or less, and more preferably in the range of 30 μm or more and 100 μm or less. If the thickness is greater than the above range, for example, after forming a long retardation film, and then cut to form a single-wafer retardation film, processing waste increases, or the cutting blade is worn. This is because there is a case where it becomes faster.

The configuration of the base material used in the present embodiment is not limited to a configuration including a single layer, and may have a configuration in which a plurality of layers are stacked. In the case of having a structure in which a plurality of layers are stacked, layers having the same composition may be stacked or a plurality of layers having different compositions may be stacked.
For example, when the alignment film used in the present embodiment contains an ultraviolet curable resin, a transparent substrate and a primer layer for improving the adhesiveness of the ultraviolet curable resin are formed on the substrate. You may. The primer layer may have any adhesiveness to both the base material and the ultraviolet curable resin, be visible and optically transparent, and allow ultraviolet rays to pass therethrough. For example, a vinyl chloride / vinyl acetate copolymer system And urethane-based materials can be appropriately selected and used.

Further, an anchor coat layer may be laminated on the substrate. The strength of the substrate can be improved by the anchor coat layer. As the anchor coat material, a metal alkoxide, particularly a metal silicon alkoxide sol can be used. The metal alkoxide is usually used as an alcohol-based solution. Since a uniform and flexible film is required for the anchor coat layer, the thickness of the anchor coat layer is preferably about 0.04 μm or more and 2 μm or less, more preferably about 0.05 μm or more and 0.2 μm or less.
When the base material has an anchor coat layer, a binder layer may be further laminated between the base material and the anchor coat layer, or the anchor coat layer may contain a material that enhances the adhesion to the substrate, thereby providing a base material. The adhesion between the material and the anchor coat layer may be improved. As the binder material used for forming the binder layer, those capable of improving the adhesion between the base material and the anchor coat layer can be used without particular limitation. Examples of the binder material include a silane coupling agent, a titanium coupling agent, a zirconium coupling agent, and the like.

4. Production method of retardation film The production method of the retardation film of the embodiment of the present disclosure,
A step of forming a film of the polymerizable composition of the embodiment of the present disclosure (film formation step);
A step of orienting at least the polymerizable compound in the formed polymerizable composition (orientation step);
After the orientation step, a step (polymerization step) of polymerizing the polymerizable compound at least is included, so that a phase difference layer is formed.
As the polymerizable composition, the same one as in the above “B. Polymerizable composition” can be used, and the description is omitted here.

(1) Film-forming step of polymerizable composition A film is formed by uniformly applying the polymerizable composition on a support.
As described above, by appropriately adjusting the coating amount of the polymerizable composition and the concentration of the polymerizable liquid crystal compound, the film thickness is adjusted so as to give a desired retardation. It may be on a material or on an alignment film of a base material provided with the alignment film.

  The application method may be any method as long as it can form a film with a desired thickness with high accuracy, and may be appropriately selected. For example, gravure coating, reverse coating, knife coating, dip coating, spray coating, air knife coating, spin coating, roll coating, printing, dipping and pulling, curtain coating, die coating, casting Method, bar coating method, extrusion coating method, E-type coating method and the like.

(2) Alignment Step Next, at least the polymerizable liquid crystal compound in the formed polymerizable composition is aligned. The temperature is adjusted to a temperature at which the polymerizable liquid crystal compound in the formed polymerizable composition can be aligned and heated. By the heat treatment, the polymerizable liquid crystal compound of the present disclosure has a main chain portion having an orientation, and the polymerizable liquid crystal compound different from the polymerizable compound of the present disclosure, which is further included as needed, is dried. It can be fixed while maintaining the alignment state.
Since the temperature at which the alignment can be performed differs depending on each substance in the polymerizable composition, it is necessary to appropriately adjust the temperature. For example, the heat treatment is preferably performed in the range of 60 ° C to 200 ° C, and more preferably in the range of 60 ° C to 100 ° C. Since the polymerizable liquid crystal compound of the present disclosure can have liquid crystallinity in a relatively low temperature range such as 100 ° C. or lower, the load on the alignment step is reduced.
Known heating and drying means can be appropriately selected and used as the heating means.
The heating time may be appropriately selected, and is selected, for example, within a range from 10 seconds to 2 hours, preferably from 20 seconds to 30 minutes.

(3) Polymerization Step After the alignment step, at least the polymerizable liquid crystal compound is polymerized. In the alignment step, the polymerizable liquid crystal compound can be polymerized by irradiating, for example, light to the coating film fixed while maintaining the alignment state of the polymerizable liquid crystal compound, and curing of the polymerizable composition. A retardation layer made of a product can be obtained.
As light irradiation, ultraviolet irradiation is preferably used. The ultraviolet irradiation can use ultraviolet rays emitted from light rays such as an ultra-high pressure mercury lamp, a high pressure mercury lamp, a low pressure mercury lamp, a carbon arc, a xenon arc, and a metal halide lamp. Irradiation of energy beam source may if appropriately selected, accumulative exposure at an ultraviolet wavelength of 365 nm, it is preferably in the range of, for example, 10 mJ / cm ² or more 10000 mJ / cm ² or less.

5. Applications The retardation film of the present disclosure is suitably used, for example, as a quarter-wave plate for antireflection, and is suitably used for optical members for various display devices as described below.

E. FIG. The transfer laminate of the present disclosure includes a retardation layer, and a support that releasably supports the retardation layer,
The retardation layer comprises a cured product of the polymerizable composition of the present disclosure,
This is a transfer laminate for transferring a retardation layer.

Since the transfer laminate of the present embodiment has a retardation layer made of a cured product of the polymerizable composition, it can transfer a retardation layer capable of uniform polarization conversion in a wide wavelength range. It is. In addition, the transfer laminate of the present embodiment, since the retardation layer is formed of a cured product of the polymerizable composition, good orientation, the precipitation of the polymerizable compound is suppressed, the optical characteristics Are better. According to the transfer laminate of the present embodiment, for example, the retardation layer of the present disclosure, which is a thin film containing no base material, can be transferred to another arbitrary optical member or the like.
According to the transfer laminate of the present embodiment, for example, the retardation film 10 composed of only the retardation layer 1 shown in the example of FIG. 2 or the base material as shown in the example of FIG. It is possible to provide a retardation film including the laminate 26 in which the film 23 and the retardation layer 21 are laminated. That is, as long as at least the phase difference layer can be peeled off, an alignment film or the like may be laminated on the phase difference layer used for the transfer of the transfer laminate.
Hereinafter, the configuration of such a transfer laminate will be described. However, since the polymerizable composition of the embodiment of the present disclosure is as described above, description thereof will be omitted.

The layer configuration of the transfer laminate will be described with reference to the drawings. 4 and 5 each show one embodiment of the transfer laminate of the present disclosure.
One embodiment of the transfer laminate 20 illustrated in the example of FIG. 4 includes a retardation layer 16 to be transferred and a support 15 that removably supports the retardation layer on the second substrate 12. This is a transfer laminate in which the alignment film 13 and the retardation layer 11 are laminated in this order. In the transfer laminate shown in the example of FIG. 4, the peel strength between the second substrate 12 and the alignment film 13 is larger than the peel strength between the alignment film 13 and the retardation layer 11. This is an example of a transfer laminate that can be transferred at the interface 17 between the alignment film and the retardation layer and transfer the retardation layer 11 (16).
One embodiment of the transfer laminate 30 shown in the example of FIG. 5 includes a phase difference layer 26 to be transferred and a support 25 that removably supports the phase difference layer on the second substrate 22. This is a transfer laminate in which the alignment film 23 and the retardation layer 21 are laminated in this order. In the transfer laminate shown in the example of FIG. 5, the peel strength between the second base material 22 and the alignment film 23 is smaller than the peel strength between the alignment film 23 and the retardation layer 21. The phase difference layer 26 peeled off at the interface 27 between the second base material 22 and the alignment film 23 and used for transfer is an example of a transfer laminate that can transfer the phase difference layer 21 and the alignment film 23. is there.

  For example, whether the peel strength between the second base material and the alignment film is larger or smaller than the peel strength between the alignment film and the retardation layer, by performing peeling of the retardation layer and at which interface You can check with. Which interface is separated can be analyzed by, for example, IR.

  Further, one embodiment of the transfer laminate 40 shown in the example of FIG. 6 includes a second base material 32 as a retardation layer 36 to be transferred and a support 35 that detachably supports the retardation layer. This is a transfer laminate on which a retardation layer 31 is laminated in this order.

Hereinafter, the present embodiment will be described, but the retardation layer can be the same as the retardation layer described in the above “D. Retardation film”, and thus description thereof will be omitted.
The alignment film and the substrate may be the same as the alignment film and the substrate described in the above “D. Retardation film”. Examples of the method for adjusting the peel strength include the following method. be able to.

In order to obtain the transfer laminate 20 shown in the example of FIG. 4, the peel strength between the second base material 12 and the alignment film 13 must be larger than the peel strength between the alignment film 13 and the retardation layer 11. For example, a method in which a solvent contained in the composition for forming an alignment film can be used to dissolve the second base material can be used. It is preferable to use a resin substrate as the second substrate, and a surface treatment for improving the adhesiveness may be performed on the surface of the substrate. In such a case, the adhesion between the resin substrate and the alignment film can be improved.
In order to reduce the peel strength between the alignment film and the retardation layer so that the peel strength between the base material and the alignment film is larger than the peel strength between the alignment film and the retardation layer, the solvent resistance of the alignment film is reduced. It is also preferable to make relatively high. When the solvent resistance of the alignment film is relatively high, when the polymerizable composition is applied on the alignment film to form the retardation layer, the alignment film is less likely to be dissolved in the solvent in the polymerizable composition. Therefore, the adhesion between the alignment film and the retardation layer can be reduced.

On the other hand, in order to obtain the transfer laminate 30 shown in the example of FIG. 5, the peel strength between the second base material 22 and the alignment film 23 is smaller than the peel strength between the alignment film 23 and the retardation layer 21. To do so, for example, a release treatment may be performed on the surface of the base material, or a release layer may be formed. Thereby, the peelability of the base material can be enhanced, and the peel strength of the base material and the alignment layer can be made smaller than the peel strength of the alignment layer and the retardation layer.
Examples of the release treatment include a surface treatment such as a fluorine treatment and a silicone treatment.
Examples of the material of the release layer include a fluorine-based release agent, a silicone-based release agent, and a wax-based release agent. Examples of the method for forming the release layer include a method in which a release agent is applied by an application method such as dip coating, spray coating, or roll coating.
In addition, in order to obtain the transfer laminate 40 shown in the example of FIG. 6, a release treatment may be performed on the surface of the base material as necessary, or a release layer may be formed. Is also good.

The substrate used for the transfer laminate may or may not have flexibility, but preferably has flexibility because the substrate can be easily peeled off.
The thickness of the substrate used for the transfer laminate is generally sufficient for the self-support strength and the flexibility that can be adapted to the production and transfer process of the transfer laminate of the present embodiment. In the case of a sheet of material, the thickness is preferably in the range of 20 μm or more and 200 μm or less.

  The retardation layer that can be provided from the transfer laminate of the present disclosure is suitably used for the same applications as the retardation film, and is suitably used, for example, as an antireflection quarter-wave plate, and is used for various display devices. It can be transferred to a member, and is suitably used for providing a thin-film optical member.

F. Optical Member The optical member of the present disclosure includes a polarizing plate on the retardation film of the present disclosure.

The optical member of the present embodiment will be described with reference to the drawings. FIG. 7 is a schematic sectional view showing one embodiment of the optical member.
In the example of the optical member 60 of FIG. 7, the polarizing plate 50 is disposed on the retardation film 10 of the present disclosure. An adhesive layer (adhesive layer) may be provided between the retardation film 10 and the polarizing plate 50 as necessary (not shown).

In this embodiment, the polarizing plate is a plate-like member that allows only light vibrating in a specific direction to pass therethrough, and can be appropriately selected from conventionally known polarizing plates. For example, a polyvinyl alcohol film, a polyvinyl formal film, a polyvinyl acetal film, an ethylene-vinyl acetate copolymer saponified film, etc., which are dyed and stretched with iodine or a dye, can be used.
In the present embodiment, the pressure-sensitive adhesive or adhesive for the pressure-sensitive adhesive layer (adhesive layer) may be appropriately selected from conventionally known ones, and may be a pressure-sensitive adhesive (pressure-sensitive adhesive), a two-component curable adhesive, Any adhesive form such as an ultraviolet-curable adhesive, a thermosetting adhesive, and a hot-melt adhesive can be suitably used.

  The optical member of the present embodiment may further include another layer included in a known optical member in addition to the polarizing plate. As the other layer, for example, other retardation layers different from the retardation layer of the present embodiment, an antireflection layer, a diffusion layer, an antiglare layer, an antistatic layer, a protective film, and the like. However, the present invention is not limited to these.

  The optical member of the present embodiment can be suitably used, for example, as an optical member that suppresses reflection of external light or a wide viewing angle polarizing plate for various display devices.

G. FIG. Method for Producing Optical Member The method for producing an optical member of the present disclosure is not particularly limited, and a method of laminating a polarizing plate on the retardation film of the present disclosure can be appropriately selected and used. For example, a production method of laminating a polarizing plate on the retardation film of the present disclosure via an adhesive layer or an adhesive layer may be used.

Further, as a method for manufacturing an optical member according to an embodiment of the present disclosure,
A transfer laminate preparing step of preparing the transfer laminate of the present disclosure,
A transfer object including at least a polarizing plate and the phase difference layer of the transfer laminate facing each other, and a transfer step of transferring the transfer laminate on the transfer target;
A method of manufacturing an optical member, comprising a step of separating the support from the transfer laminate transferred onto the transfer target.

According to the method for manufacturing an optical member of one embodiment of the present disclosure using the transfer laminate, a polarizing plate and an optical member including only the retardation layer among the retardation films of the present disclosure are obtained. Can be.
The transfer laminate used in the method for manufacturing an optical member according to an embodiment of the present disclosure can be the same as that described in the above “E. Transfer laminate”, and thus description thereof will be omitted. I do.
In addition, the transfer target used in the method for manufacturing an optical member according to an embodiment of the present disclosure typically includes a transfer target having an adhesive layer and a polarizing plate, but is not limited thereto. The optical member according to the embodiment of the present disclosure described above may further include a layer similar to another layer that may be included.

H. Display Device A display device according to the present disclosure includes the retardation film of the present embodiment or the optical member of the present embodiment.
Examples of the display device include, but are not limited to, a light emitting display device and a liquid crystal display device.

  Among them, in order to include the retardation film of the present embodiment or the optical member of the present embodiment, particularly, in a light-emitting display device such as an organic light-emitting display device having a transparent electrode layer, a light-emitting layer, and an electrode layer in this order. This has the effect of improving the viewing angle while suppressing external light reflection.

An example of a light emitting display device according to one embodiment will be described with reference to the drawings. FIG. 8 is a schematic sectional view showing one embodiment of the optical member.
In the example of the organic light emitting display device 100 of FIG. 8, a polarizing plate 50 is disposed on the light emitting surface side of the retardation film 10, and the transparent electrode layer 71, the light emitting layer 72, and the electrode layer 73 in this order.
As the light emitting layer 72, for example, a configuration in which a hole injection layer, a hole transport layer, a light emitting layer, and an electron injection layer are sequentially stacked from the transparent electrode layer 71 side, or the like is given. In the present embodiment, known structures can be appropriately used for the transparent electrode layer, the hole injection layer, the hole transport layer, the light emitting layer, the electron injection layer, the electrode layer, and other structures. The light emitting display device manufactured in this way is applicable to, for example, a passive drive type organic EL display and an active drive type organic EL display.
Note that the display device of the present embodiment is not limited to the above-described configuration, and may have a known configuration that is appropriately selected.

The chemical structure of each produced compound was confirmed by ¹ H NMR measurement using JEOL JNM-LA400WB manufactured by JEOL Ltd.

[Production Example 1: Production of compound 1]
Compound 1 was prepared by the following synthetic route.

(Synthesis example of compound b)
In a flask, 10.0 g (60.5 mmol) of 2-hydrazinobenzothiazole (manufactured by Tokyo Chemical Industry), 8.9 g (72.6 mmol) of bromopropane, 12.8 g (78.7 mmol) of a 25% aqueous sodium hydroxide solution, A mixture of 3.2 g (6.1 mmol) of butylammonium bromide and 45 mL of toluene was stirred at 60 ° C. for 5 hours. Five hours later, 50 mL of water was added, and the mixture was stirred at room temperature for 30 minutes, and then the aqueous phase was removed. Thereafter, heptane was added at 5 ° C. to precipitate crystals. After filtering the crystals, the crystals were washed with heptane to obtain 9.1 g of compound b (yield: 73%).

(Synthesis example of compound c)
In a flask, 3.6 g (13.6 mmol) of compound a (manufactured by Wako Pure Chemical), 2.8 g (13.6 mmol) of compound b, 7.0 g (68.1 mmol) of acetic anhydride, and 4.9 g (68.1 mmol) of pyridine ) And 25 mL of dimethylacetamide (DMAc) were mixed and stirred at room temperature for 7 hours. After 7 hours, the mixed solution was dropped into methanol prepared in another flask to precipitate crystals. After filtering the crystals, the crystals were washed with water and methanol to obtain 5.6 g of Compound c (yield: 91%).

(Synthesis example of compound d)
In a flask, 5.0 g (11.0 mmol) of Compound c, 7.6 g (55.1 mmol) of potassium carbonate, and 50 mL of methanol were mixed, and the mixture was heated under reflux for 6 hours. Six hours later, 30 mL of hydrochloric acid was added, followed by stirring at 0 ° C. for 30 minutes and filtration to obtain 3.6 g of compound d (88% yield).

(Synthesis example of compound e)
86 g (0.5 mol) of cyclohexanedicarboxylic acid, 27 g (100 mmol, manufactured by DKSH) of 6- (4-hydroxyphenyl) hexyl acrylate, 0.50 g (4.0 mmol) of N, N-dimethylaminopyridine (DMAP) in dichloromethane (500 mL) ) A solution of 22 g (105 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (25 mL) was added dropwise to the suspension. After completion of the dropwise addition, the mixture was stirred for 12 hours, and the precipitate was filtered, washed with an aqueous sodium hydrogen carbonate solution and 1N hydrochloric acid, and the solvent was distilled off. The obtained crude product was purified by open column chromatography to synthesize 18 g (42 mmol) of a compound e.

In a flask, 1.0 g (2.7 mmol) of compound d, 2.9 g (7.0 mmol) of compound e, 0.01 g (0.1 mmol) of 4-dimethylaminopyridine (DMAP), and 15 mL of chloroform were mixed. Subsequently, a solution in which 1.7 g (8.4 mmol) of N, N'-dicyclohexylcarbodiimide (DCC) was dissolved in 5 mL of chloroform was added, and the resulting solution was stirred at room temperature for 23 hours. After 23 hours, the precipitated solid was separated by filtration, and the filtrate was dried under reduced pressure to obtain crystals. The crystals obtained again were dissolved in chloroform, and methanol was added to precipitate crystals. The obtained crystals were washed with methanol to obtain 2.5 g of Compound 1. The yield was 78% based on compound d. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 1 (DMSO-d6): δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.21 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.65 (d, 1H)

[Production Example 2: Production of compound 2]
In the production of Compound 1, Compound b2 was synthesized in the same manner as in Production Example 1 except that Bromobutane was used instead of Bromopropane in the Synthesis Example of Compound b.
In the production of Compound 1, 3.5 g of Compound 2 was obtained in the same manner as in Production Example 1 except that Compound b2 was used in place of Compound b in an equimolar amount. The yield was 83% based on the compound d2. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 2 (DMSO-d6): δ (ppm) 0.93 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.60 (m, 4H), 1.99 (m, 4H) , 2.08 (m, 4H), 2.23 (m, 2H), 2.47 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.95 (t, 4H), 4.14 (t, 4H), 5.93 (d, 2H), 6.17 (dd, 2H), 6.29 (d, 2H), 7.01 (m, 9H), 7.18 (t, 1H), 7.37 (d, 1H), 7.62 (s, 2H), 7.65 (d, 1H)

[Production Example 3: Production of compound 3]
In the production of Compound 1, Compound b3 was synthesized in the same manner as in Production Example 1 except that Bromopentane was used instead of Bromopropane in the Synthesis Example of Compound b.
In the production of compound 1, 4.1 g of compound 3 was obtained in the same manner as in Production Example 1 except that compound b3 was used in place of compound b in an equimolar amount. The yield was 85% based on compound d3. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 3: δ (ppm) 0.92 (t, 3H), 1.41 (m, 16H), 1.51 (m, 8H), 1.62 (m, 6H), 2.00 (m, 4H) , 2.07 (m, 4H), 2.22 (m, 2H), 2.47 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.91 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.17 (dd, 2H), 6.29 (d, 2H), 7.01 (m, 9H), 7.22 (t, 1H), 7.37 (d, 1H), 7.60 (s, 2H), 7.64 (d, 1H)

[Production Example 4: Production of compound 4]
In the production of compound 1, compound b4 was synthesized in the same manner as in the synthesis example of compound b in Production Example 1, except that bromohexane was used instead of bromopropane in the synthesis example of compound b.
In the production of compound 1, 3.8 g of compound 4 was obtained in the same manner as in Production Example 1, except that compound b4 was used in place of compound b in an equimolar amount. The yield was 79% based on compound d4. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of Compound 4 (DMSO-d6): δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.66 (d, 1H)

[Production Example 5: Production of compound 5]
In the production of compound 1, compound b5 was synthesized in the same manner as in the synthesis example of compound b in Production Example 1, except that bromooctane was used instead of bromopropane in the synthesis example of compound b.
In the production of Compound 1, 4.6 g of Compound 5 was obtained in the same manner as in Production Example 1, except that Compound b5 was used in place of Compound b in an equimolar amount. The yield was 84% based on compound d5. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 5: δ (ppm) 0.87 (t, 3H), 1.24 (m, 4H), 1.40 (m, 18H), 1.54 (m, 12H), 1.98 (m, 4H) , 2.05 (m, 4H), 2.21 (m, 2H), 2.46 (t, 8H), 2.52 (m, 2H), 3.30 (t, 2H), 3.93 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.17 (dd, 2H), 6.28 (d, 2H), 6.99 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.65 (d, 1H)

[Production Example 6: Production of compound 6]
In the production of compound 1, compound b6 was prepared in the same manner as in the synthesis example of compound b in production example 1 except that 1- (2-bromoethoxy) propane was used instead of bromopropane in the synthesis example of compound b. Was synthesized.
In the production of compound 1, 3.5 g of compound 6 was obtained in the same manner as in Production Example 1, except that compound b6 was used in place of compound b in an equimolar amount. The yield was 79% based on compound d6. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 6 (DMSO-d6): δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 10H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.25 (t, 2H), 3.31 (t, 2H), 3.49 (t, 2H), ) 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.66 (d, 1H)

[Production Example 7: Production of compound 7]
In the production of compound 1, compound b7 was prepared in the same manner as in the synthesis example of compound b in production example 1 except that 1- (2-bromoethoxy) heptane was used instead of bromopropane in the synthesis example of compound b. Was synthesized.
In the production of Compound 1, 6.5 g of Compound 7 was obtained in the same manner as in Production Example 1, except that Compound b7 was used in place of Compound b in an equimolar amount. The yield was 82% based on compound d7. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 7 (DMSO-d6): δ (ppm) 0.89 (t, 3H), 1.40 (m, 24H), 1.52 (m, 10H), 1.98 (m, 4H), 2.06 (m, 4H) , 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 2.85 (t, 2H), 3.30 (t, 2H), 3.52 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.66 (d, 1H)

[Production Example 8: Production of compound 8]
In the production of compound 1, in the same manner as in the synthesis example of compound b of production example 1, except that 1- (2-bromoethoxy) 2-methoxyethane was used instead of bromopropane in the synthesis example of compound b. Compound b8 was synthesized.
In the production of compound 1, 5.3 g of compound 8 was obtained in the same manner as in Production Example 1 except that compound b8 was used in place of compound b in an equimolar amount. The yield was 69% based on compound d8. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 8: δ (ppm) 1.42 (m, 16H), 1.52 (m, 8H), 1.98 (m, 4H), 2.06 (m, 4H), 2.22 (m, 2H) , 2.49 (t, 8H), 2.54 (m, 2H), 3.30 (s, 3H), 3.41 (t, 4H), 3.63 (t, 4H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.66 (d, 1H)

[Production Example 9: Production of compound 9]
In the production of compound 1, in the synthesis example of compound b, except that 2-hydrazino 6-fluorobenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b9 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of compound 1, 4.1 g of compound 9 was obtained in the same manner as in Production Example 1 except that compound b9 was used in place of compound b in an equimolar amount. The yield was 76% based on compound d9. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 9: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.25 (t, 1H), 7.40 (d, 1H), 7.62 (s, 2H), 7.68 (d, 1H)

[Production Example 10: Production of compound 10]
In the production of compound 1, except that in the synthesis example of compound b, 2-hydrazino 6-methylbenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b10 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of compound 1, 3.3 g of compound 10 was obtained in the same manner as in Production Example 1, except that compound b10 was used in place of compound b in an equimolar amount. The yield was 82% based on compound d10. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 10: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.35 (s, 3H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.19 (t, 1H), 7.36 (d, 1H), 7.64 (m, 3H)

[Production Example 11: Production of compound 11]
In the production of compound 1, in the synthesis example of compound b, except that 2-hydrazino 6-cyanobenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b11 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of Compound 1, 3.4 g of Compound 11 was obtained in the same manner as in Production Example 1 except that Compound b11 was used in an equimolar amount instead of Compound b. The yield was 77% based on the compound d11. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 11: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.24 (t, 1H), 7.40 (d, 1H), 7.62 (s, 2H), 7.67 (d, 1H)

[Production Example 12: Production of compound 12]
In the production of compound 1, except that in the synthesis example of compound b, 2-hydrazino 6-methoxybenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b12 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of Compound 1, 3.0 g of Compound 12 was obtained in the same manner as in Production Example 1, except that Compound b12 was used in place of Compound b in an equimolar amount. The yield was 81% based on compound d12. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 12: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.78 (s, 3H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.18 (t, 1H), 7.35 (d, 1H), 7.63 (m, 3H)

[Production Example 13: Production of compound 13]
In the production of compound 1, the production example was the same as in the synthesis example of compound b except that 2-hydrazino 6-ethoxybenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b13 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of Compound 1, 3.3 g of Compound 13 was obtained in the same manner as in Production Example 1, except that Compound b13 was used in an equimolar amount instead of Compound b. The yield was 82% based on compound d13. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 13: δ (ppm) 0.93 (t, 3H), 1.21 (t, 3H), 1.42 (m, 16H), 1.51 (m, 8H), 1.60 (m, 2H) , 1.98 (m, 4H), 2.05 (m, 4H), 2.21 (m, 2H), 2.48 (t, 8H), 2.55 (m, 2H), 3.31 (t, 2H), 3.93 (t, 4H), 4.02 (m, 2H), 4.10 (t, 4H), 5.92 (d, 2H), 6.15 (dd, 2H), 6.29 (d, 2H), 7.02 (dd, 8H), 7.15 (t, 1H), 7.34 (d, 1H), 7.62 (m, 3H)

[Production Example 14: Production of compound 14]
In the production of compound 1, except that in the synthesis example of compound b, 2-hydrazino 6-benzothiazoleamine was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b14 was synthesized in the same manner as in Synthesis Example 1 of Compound b.
In the production of compound 1, 2.3 g of compound 14 was obtained in the same manner as in Production Example 1 except that compound b14 was used in an equimolar amount instead of compound b. The yield was 71% based on compound d14. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 14: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.48 (s, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.19 (t, 1H), 7.35 (d, 1H), 7.64 (m, 3H)

[Production Example 15: Production of compound 15]
In the production of compound 1, in the synthesis example of compound b, except that 2-hydrazino 6-trifluoromethylbenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane, Compound b15 was synthesized in the same manner as in the synthesis example of compound b in Production Example 1.
In the production of compound 1, 2.6 g of compound 15 was obtained in the same manner as in Production Example 1 except that compound b15 was used in place of compound b in an equimolar amount. The yield was 72% based on compound d15. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 15: δ (ppm) 0.94 (t, 3H), 1.42 (m, 16H), 1.52 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.32 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (dd, 8H), 7.35 (t, 1H), 7.58 (d, 1H), 7.62 (s, 2H), 7.88 (d, 1H)

[Production Example 16: Production of compound 16]
In the production of compound 1, in the synthesis example of compound b, except that 2-hydrazino 6-trifluoromethoxybenzothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane, Compound b16 was synthesized in the same manner as in the synthesis example of compound b in Production Example 1.
In the production of compound 1, 2.8 g of compound 16 was obtained in the same manner as in Production Example 1 except that compound b16 was used in place of compound b in an equimolar amount. The yield was 73% based on compound d16. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 16: δ (ppm) 0.96 (t, 3H), 1.45 (m, 16H), 1.53 (m, 8H), 1.61 (m, 2H), 1.98 (m, 4H) , 2.08 (m, 4H), 2.23 (m, 2H), 2.52 (t, 8H), 2.90 (m, 2H), 3.41 (t, 2H), 4.01 (t, 4H), 4.15 (t, 4H), 5.98 (d, 2H), 6.22 (dd, 2H), 6.37 (d, 2H), 7.10 (dd, 8H), 7.39 (t, 1H), 7.63 (d, 1H), 7.74 (s, 2H), 7.99 (d, 1H)

[Production Example 17: Production of compound 17]
In the production of compound 1, in the synthesis example of compound b, 2-hydrazinobenzoxazole was used instead of 2-hydrazinobenzothiazole, and bromohexane was used instead of bromopropane. Compound b17 was synthesized in the same manner as in the synthesis example of compound b.
In the production of compound 1, 3.8 g of compound 17 was obtained in the same manner as in Production Example 1, except that compound b17 was used in place of compound b in an equimolar amount. The yield was 80% based on the compound d17. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 17: δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 6.89 (t, 1H), 7.00 (dd, 8H), 7.12 (t, 1H), 7.28 (d, 1H), 7.42 (d, 1H), 7.62 (s, 2H)

[Production Example 18: Production of compound 18]
In the production of Compound 1, the compound of Production Example 1 was the same as that in Synthesis Example of Compound b except that 2-hydrazinothiazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b18 was synthesized in the same manner as in the synthesis example of b.
In the production of compound 1, 1.8 g of compound 18 was obtained in the same manner as in Production Example 1 except that compound b18 was used in an equimolar amount instead of compound b. The yield was 83% based on compound d18. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 18: δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 6.56 (d, 1H), 7.00 (m, 9H), 7.62 (s, 2H)

[Production Example 19: Production of compound 19]
In the production of Compound 1, the compound of Production Example 1 was the same as the synthesis example of Compound b except that 2-hydrazinooxazole was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b19 was synthesized in the same manner as in the synthesis example of b.
In the production of compound 1, 1.5 g of compound 19 was obtained in the same manner as in Production Example 1, except that compound b19 was used in an equimolar amount instead of compound b. The yield was 80% based on compound d19. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 19 (DMSO-d6): δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 6.45 (d, 1H), 6.82 (d, 1H), 7.00 (dd, 8H), 7.62 (s, 2H)

[Production Example 20: Production of compound 20]
In the production of compound 1, in the synthesis example of compound b, phenylhydrazine was used instead of 2-hydrazinobenzothiazole, and bromohexane was used instead of bromopropane. Compound b20 was synthesized in the same manner as in the example.
In the production of compound 1, 2.2 g of compound 20 was obtained in the same manner as in Production Example 1 except that compound b20 was used in place of compound b in an equimolar amount. The yield was 78% based on compound d20. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 20: δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 6.81 (m, 3H), 7.00 (dd, 8H), 7.19 (m, 2H), 7.62 (s, 2H)

[Production Example 21: Production of compound 21]
In the production of compound 1, in the synthesis example of compound b, 2-benzothiazolemethylamine was used instead of 2-hydrazinobenzothiazole, and bromohexane was used instead of bromopropane. Compound b21 was synthesized in the same manner as in the synthesis example of compound b.
In the production of Compound 1, 2.3 g of Compound 21 was obtained in the same manner as in Production Example 1, except that Compound b21 was used in an equimolar amount instead of Compound b. The yield was 74% based on compound d21. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 21 (DMSO-d6): δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.22 (m, 2H), 2.37 (m, 1H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 9H), 7.20 (t, 1H), 7.38 (d, 1H), 7.62 (s, 2H), 7.66 (d, 1H)

[Production Example 22: Production of compound 22]
In the production of compound 1, in the synthesis example of compound b, 2-benzothiazolemethylamine was used instead of 2-hydrazinobenzothiazole, and bromohexane was used instead of bromopropane. Compound b22 was synthesized in the same manner as in the synthesis example of compound b.
In the production of Compound 1, 2.1 g of Compound 22 was obtained in the same manner as in Production Example 1, except that Compound b22 was used in an equimolar amount instead of Compound b. The yield was 73% based on compound d22. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 22 (DMSO-d6): δ (ppm) 0.89 (t, 3H), 1.26 (m, 4H), 1.43 (m, 16H), 1.55 (m, 12H), 2.00 (m, 4H) , 2.09 (m, 4H), 2.24 (m, 2H), 2.38 (m, 1H), 2.53 (t, 8H), 2.57 (m, 2H), 3.35 (t, 2H), 3.98 (t, 4H), 4.17 (t, 4H), 5.98 (d, 2H), 6.18 (dd, 2H), 6.31 (d, 2H), 7.03 (m, 9H), 7.25 (t, 1H), 7.41 (d, 1H), 7.65 (s, 2H), 7.69 (d, 1H)

[Production Example 23: Production of compound 23]
In the production of compound 1, the compound of production example 1 except that in the synthesis example of compound b, 2-thiazolemethylamine was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane Compound b23 was synthesized in the same manner as in the synthesis example of b.
In the production of compound 1, 1.6 g of compound 23 was obtained in the same manner as in Production Example 1 except that compound b23 was used in place of compound b in an equimolar amount. The yield was 72% based on compound d23. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 23: δ (ppm) 0.86 (t, 3H), 1.23 (m, 4H), 1.38 (m, 16H), 1.54 (m, 12H), 1.98 (m, 4H) , 2.03 (m, 4H), 2.14 (m, 1H), 2.21 (m, 2H), 2.45 (t, 8H), 2.51 (m, 2H), 3.26 (t, 2H), 3.88 (t, 4H), 4.06 (t, 4H), 5.90 (d, 2H), 6.17 (dd, 2H), 6.25 (d, 2H), 6.38 (d, 1H), 6.77 (d, 1H), 6.92 (dd, 8H), 7.55 (s, 2H)

[Production Example 24: Production of compound 24]
In the production of Compound 1, the compound of Production Example 1 was used except that, in the synthesis example of Compound b, 2-oxazolemethylamine was used instead of 2-hydrazinobenzothiazole and bromohexane was used instead of bromopropane. Compound b24 was synthesized in the same manner as in the synthesis example of b.
In the production of Compound 1, 1.4 g of Compound 24 was obtained in the same manner as in Production Example 1, except that Compound b24 was used in an equimolar amount instead of Compound b. The yield was 70% based on compound d24. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 24: δ (ppm) 0.88 (t, 3H), 1.25 (m, 4H), 1.42 (m, 16H), 1.55 (m, 12H), 1.98 (m, 4H) , 2.06 (m, 4H), 2.15 (m, 1H), 2.22 (m, 2H), 2.49 (t, 8H), 2.54 (m, 2H), 3.31 (t, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 6.45 (d, 1H), 6.82 (d, 1H), 7.00 (dd, 8H), 7.62 (s, 2H)

[Production Example 25: Production of compound 25]
In the production of compound 1, in the synthesis example of compound b, benzenemethylamine was used instead of 2-hydrazinobenzothiazole, and bromohexane was used instead of bromopropane. Compound b25 was synthesized in the same manner as in the Synthesis Example.
In the production of compound 1, 2.0 g of compound 25 was obtained in the same manner as in Production Example 1, except that compound b25 was used in place of compound b in an equimolar amount. The yield was 74% based on compound d25. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 25 (DMSO-d6): δ (ppm) 0.86 (t, 3H), 1.24 (m, 4H), 1.38 (m, 16H), 1.47 (m, 12H), 1.87 (m, 4H) , 1.97 (m, 4H), 2.06 (m, 1H), 2.20 (m, 2H), 2.38 (t, 8H), 2.47 (m, 2H), 3.28 (t, 2H), 3.88 (t, 4H), 4.01 (t, 4H), 5.90 (d, 2H), 6.07 (dd, 2H), 6.22 (d, 2H), 6.74 (m, 7H), 6.92 (m, 6H), 7.53 (s, 2H)

[Production Example 26: Production of compound 26]
In the production of Compound 1, Compound b26 was synthesized in the same manner as in Synthesis Example of Compound b in Production Example 1, except that 2-bromobenzothiazole was used instead of bromopropane in the synthesis example of compound b. .
In the production of compound 1, 3.3 g of compound 26 was obtained in the same manner as in Production Example 1, except that compound b26 was used in place of compound b in an equimolar amount. The yield was 82% based on compound d26. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 26: δ (ppm) 1.42 (m, 16H), 1.55 (m, 8H), 1.98 (m, 4H), 2.06 (m, 4H), 2.22 (m, 2H) , 2.49 (t, 8H), 2.54 (m, 2H), 3.94 (t, 4H), 4.11 (t, 4H), 5.94 (d, 2H), 6.18 (dd, 2H), 6.30 (d, 2H), 7.00 (m, 10H), 7.20 (t, 2H), 7.38 (d, 2H), 7.62 (s, 2H), 7.66 (d, 2H)

[Production Example 27: Production of compound 27]
In the production of compound 1, except that in the synthesis example of compound b, 2-hydrazinobenzoxazole was used instead of 2-hydrazinobenzothiazole and 2-bromobenzoxazole was used instead of bromopropane. Compound b27 was synthesized in the same manner as in the synthesis example of compound b in Example 1.
In the production of compound 1, 3.0 g of compound 27 was obtained in the same manner as in Production Example 1, except that compound b27 was used in an equimolar amount instead of compound b. The yield was 80% based on compound d27. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 27 (DMSO-d6): δ (ppm) 1.45 (m, 16H), 1.58 (m, 8H), 2.05 (m, 4H), 2.13 (m, 4H), 2.28 (m, 2H) , 2.55 (t, 8H), 2.68 (m, 2H), 3.99 (t, 4H), 4.15 (t, 4H), 6.00 (d, 2H), 6.22 (dd, 2H), 6.39 (d, 2H), 7.12 (m, 10H), 7.28 (t, 2H), 7.45 (d, 2H), 7.77 (s, 2H), 7.83 (d, 2H)

[Production Example 28: Production of compound 28]
Production Example 1 was repeated except that, in the preparation of compound 1, in the synthesis example of compound b, 2-hydrazinothiazole was used instead of 2-hydrazinobenzothiazole and 2-bromothiazole was used instead of bromopropane. Compound b28 was synthesized in the same manner as in Synthesis Example of Compound b.
In the production of compound 1, 1.9 g of compound 28 was obtained in the same manner as in Production Example 1 except that compound b28 was used in place of compound b in an equimolar amount. The yield was 77% based on compound d28. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 28: δ (ppm) 1.41 (m, 16H), 1.53 (m, 8H), 1.95 (m, 4H), 2.01 (m, 4H), 2.20 (m, 2H) , 2.44 (t, 8H), 2.50 (m, 2H), 3.92 (t, 4H), 4.07 (t, 4H), 5.91 (d, 2H), 6.13 (dd, 2H), 6.24 (d, 2H), 6.40 (d, 2H), 6.68 (d, 2H), 6.97 (m, 8H), 7.56 (s, 2H)

[Production Example 29: Production of compound 29]
Production Example 1 was repeated except that, in the preparation of compound 1, in the synthesis example of compound b, 2-hydrazinooxazole was used instead of 2-hydrazinobenzothiazole and 2-bromooxazole was used instead of bromopropane. Compound b29 was synthesized in the same manner as in Synthesis Example of Compound b.
In the production of compound 1, 1.6 g of compound 29 was obtained in the same manner as in Production Example 1 except that compound b29 was used in place of compound b in an equimolar amount. The yield was 75% based on compound d29. The structure of the target product was identified by ¹ H NMR.

^{1 H} NMR of compound 29 (DMSO-d6): δ (ppm) 1.47 (m, 16H), 1.55 (m, 8H), 2.05 (m, 4H), 2.12 (m, 4H), 2.27 (m, 2H) , 2.52 (t, 8H), 2.66 (m, 2H), 4.15 (t, 4H), 4.23 (t, 4H), 6.12 (d, 2H), 6.22 (dd, 2H), 6.33 (d, 2H), 6.50 (d, 2H), 6.79 (d, 2H), 7.11 (m, 8H), 7.60 (s, 2H)

[Production Example 30: Production of compound 30]
In the production of Compound 1, the synthesis of Compound b in Production Example 1 was repeated except that, in the synthesis example of compound b, phenylhydrazine was used instead of 2-hydrazinobenzothiazole and bromobenzene was used instead of bromopropane. Compound b30 was synthesized in the same manner as in the example.
In the production of Compound 1, 2.0 g of Compound 30 was obtained in the same manner as in Production Example 1, except that Compound b30 was used in an equimolar amount instead of Compound b. The yield was 79% based on compound d30. The structure of the target product was identified by ¹ H NMR.

¹ H NMR (DMSO-d6) of compound 30: δ (ppm) 1.47 (m, 16H), 1.55 (m, 8H), 2.05 (m, 4H), 2.12 (m, 4H), 2.27 (m, 2H) , 2.52 (t, 8H), 2.66 (m, 2H), 4.15 (t, 4H), 4.23 (t, 4H), 6.12 (d, 2H), 6.22 (dd, 2H), 6.33 (d, 2H), 6.89 (m, 6H), 7.11 (m, 10H), 7.60 (s, 2H)

[Comparative Production Example 1: Production of Comparative Compound 1]
In the production of Compound 1, 3.5 g of Comparative Compound 1 was obtained in the same manner as in Production Example 1, except that 2-aminobenzoxazole (manufactured by Tokyo Chemical Industry) was used in an equimolar amount instead of Compound b. . The yield was 87% based on the comparative compound d1. The structure of the target product was identified by ¹ H NMR.

[Comparative Production Example 2: Production of Comparative Compound 2]
In the production of compound 1, 3.8 g of comparative compound 2 was obtained in the same manner as in the compound of production example 1, except that 2-aminobenzothiazole (manufactured by Tokyo Chemical Industry) was used in an equimolar amount instead of compound b. . The yield was 88% based on the comparative compound d2. The structure of the target product was identified by ¹ H NMR.

[Evaluation]
<Liquid crystal phase transition temperature>
The phase transition temperature was confirmed at the time of temperature rise by texture observation using a polarizing microscope (manufactured by Olympus, BX51) equipped with a temperature control stage. That is, in the observation with a polarizing microscope, the point at which the solid melts and becomes liquid when the temperature rises, and the point where the bright field is observed in the crossed Nicol observation (the polarizing plate is in the orthogonal state) with the polarizing microscope is specified as the solid-liquid crystal phase transition temperature. did. Cr represents a crystal, N represents a nematic phase, and Iso represents an isotropic liquid. For example, “Cr → N 79 ° C., N → Iso 85 ° C.” indicates that a transition from a crystal to a nematic phase occurs at 79 ° C. and a transition from a nematic phase to an isotropic liquid occurs at 85 ° C.
Table 8 shows the phase transition temperature of each polymerizable liquid crystal compound.

[Example 1]
(1) Production of Polymerizable Composition 100 parts by mass of a polymerizable liquid crystal compound (Compound 1 of Production Example 1), a photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropane-1) -On: 4 parts by mass of Irgacure 907 (manufactured by Ciba Specialty Chemicals) was dissolved in 400 parts by mass of a mixed solvent of cyclopentanone and 1,3-dioxolane (volume ratio 1: 1) to produce polymerizable composition 1.

(2) Production of retardation film or transfer laminate (2-1) Preparation of composition for photo-alignment film 1.30 g of hydroxyethyl methacrylate according to the description of Production Example 1 of Japanese Patent No. 5,626,493, and light represented by the following chemical formula. 3.95 g of an orienting monomer and 50 mg of α, α′-azobisisobutyronitrile (AIBN) as a polymerization catalyst were dissolved in 25 ml of dioxane and reacted at 90 ° C. for 6 hours. After completion of the reaction, the resultant was purified by a reprecipitation method to obtain a copolymer 1 in which a photo-alignable monomer represented by the following chemical formula and hydroxyethyl methacrylate were copolymerized.
A composition for a photo-alignment film having the following composition was prepared.
-Copolymer 1: 0.1 part by mass-Hexamethoxymethylmelamine (HMM): 0.01 part by mass-p-toluenesulfonic acid monohydrate (PTSA): 0.0015 part by mass-Propylene glycol monomethyl ether ( PGME): 2.1 parts by mass

(2-2) Formation of Horizontal Alignment Film On one surface of a PET substrate (manufactured by Toyobo Co., Ltd., E5100, thickness 38 μm), the thickness of the composition for photoalignment film after curing is 0.2 μm. It was then applied by a bar coater, heated in an oven at 120 ° C. for 1 minute, and dried and thermally cured to form a cured coating film. Thereafter, the surface of the cured coating film is irradiated with polarized ultraviolet light including a 313 nm bright line in a vertical direction from the substrate normal using an Hg-Xe lamp and a Glan-Taylor prism at an exposure amount of 100 mJ / cm ² , thereby forming a horizontal alignment film. Formed.

(2-3) Preparation of retardation film or transfer laminate The polymerizable composition 1 is applied on the formed alignment film so that the film thickness after curing becomes 1 μm, and the polymerizable composition is formed. Filmed. Thereafter, after drying in an oven at a drying temperature (orientation temperature) shown in Table 8 for 120 seconds, ultraviolet rays (UV) were irradiated at an irradiation amount of 400 mJ / cm ² using an H bulb manufactured by Fusion to form a retardation layer. Thus, a retardation film or a laminate for transfer was obtained.

[Examples 2 to 30, Comparative Examples 1 and 2]
(1) Production of Polymerizable Composition In Example 1, except that Compound 1 of Production Example 1 was changed according to Table 8 below, the same procedure as in Example 1 was repeated, and the polymerizable compositions 2 to 30 and comparative polymerization were performed. The compositions 1 and 2 were obtained.
(2) Production of Retardation Film or Transfer Laminate The procedure of Example 1 was repeated, except that the polymerizable composition 2 to 30 and the comparative polymerizable composition 1 to 2 were used instead of the polymerizable composition 1. In the same manner as in Example 1, retardation films or transfer laminates 2 to 30 and comparative retardation films or transfer laminates 1 to 2 were obtained.

[Evaluation]
<Sample creation>
A sample in which the PET substrate of the retardation film obtained in each example and each comparative example was peeled off, and the retardation layer and the horizontal alignment film were transferred to an adhesive glass was used.

<Orientation>
The orientation of the retardation layer was evaluated in four stages by observing with a polarizing microscope.
(Evaluation criteria for orientation)
A: Uniform orientation is obtained visually, and the luminescent spot (poor alignment) is less than 10% of the area. B: Alignment similar to A is not obtained visually, and the luminescent point (poor alignment) is 10% of the area. % To less than 30%,
C: The orientations of A and B were not obtained visually, and the luminescent spot (poor orientation) was 30% or more and less than 50% of the area,
D: The orientations of A, B, and C were not obtained by visual observation, and the bright spots (poor orientation) were 50% or more and 100% or less of the area.

<Phase difference (wavelength dispersion)>
The in-plane phase difference Re with respect to wavelengths of 450 nm, 550 nm, and 650 nm was measured by a phase difference measuring device (KOBRA-WR, manufactured by Oji Scientific Instruments).
The chromatic dispersion was evaluated from the x and y values calculated as follows using the measured phase difference.
x = (in-plane retardation Re at 450 nm) / (in-plane retardation Re at 550 nm)
y = (in-plane retardation Re at 650 nm) / (in-plane retardation Re at 550 nm)
Note that x is a value rounded to the second decimal place according to JIS Z8401: 1999 rule B, and y is a value rounded to an integer according to JIS Z8401: 1999 rule B.

[Examples 31 to 39]
(1) Production of Polymerizable Composition In Example 1, instead of using the polymerizable liquid crystal compound 1 of the present disclosure at a content of 100% by mass in the polymerizable liquid crystal compound, the polymerizable liquid crystal compound of the present disclosure was used. Polymerizable compositions 31 to 39 were obtained in the same manner as in Example 1 except that a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure was used by mixing according to Table 9 below.
In addition, as a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound of the present disclosure, a compound represented by a polymerizable liquid crystal compound B-1 represented by the following chemical formula and a comparative compound 1 produced in Comparative Production Example 1 were prepared. did. The phase transition temperature of the following polymerizable liquid crystal compound B-1 is 115 ° C. for Cr → N and 201 ° C. for N → Iso. In addition, the following polymerizable liquid crystal compound B-1 in Example 1 was replaced with the polymerizable liquid crystal compound B-1 instead of the compound 1 which is the polymerizable liquid crystal compound of the present disclosure. %, When the retardation film was prepared in the same manner as in Example 1, the drying temperature was 120 ° C., and the orientation was evaluated as A.
(2) Production of Retardation Film or Transfer Laminate In the same manner as in Example 1, except that polymerizable compositions 31 to 39 were used in place of polymerizable composition 1 in Example 1, Films or transfer laminates 31 to 39 were obtained.

[Evaluation]
<Sample creation>
Evaluation was performed in the same manner as in Example 1 using a sample in which the PET substrate of the retardation film obtained in each of the examples was peeled off, and the retardation layer and the horizontal alignment film were transferred to an adhesive glass.
Table 9 shows the evaluation results.

Table 9 shows the following.
By forming a polymerizable composition in which a polymerizable liquid crystal compound of the present disclosure is mixed with a liquid crystal compound having a high phase transition temperature (Comparative Compound 1, Polymerizable Liquid Crystal Compound B-1), the phase transition temperature can be reduced, The load in the step of aligning the liquid crystal while using a liquid crystal compound having a high phase transition temperature is reduced.
The orientation can be improved by forming a polymerizable composition in which the polymerizable liquid crystal compound of the present disclosure is mixed with a liquid crystal compound having poor orientation (Comparative Compound 1).
By mixing another polymerizable liquid crystal compound having higher orientation with the polymerizable liquid crystal compound of the present disclosure, the orientation of the polymerizable composition can be improved.

DESCRIPTION OF SYMBOLS 1 Retardation layer 2, 2 'Substrate 3 Orientation film 10 Retardation film 11, 21, 31 Retardation layer 12, 22, 32 Second substrate 13, 23, 33 Orientation film 15, 25, 35 Peelable Supports 16, 26, 36 Phase layer 17 used for transfer Interface 27 between alignment film and retardation layer Interface 20, 30, 40 between second base material and alignment film Transfer laminate 50 Polarizing plate 60 Optical member 71 Transparent electrode layer 72 Light emitting layer 73 Electrode layer 100 Light emitting display

Claims (11)

A polymerizable liquid crystal compound represented by the following general formula (I).
(In the general formula (I), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² each independently represent a cyclopentane-1,3-diyl group, a cyclohexane-1,3-diyl group, which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclopentane-1,3-diyl group, a cyclopentane-1,3-diyl group, which may be substituted by one or more substituents E, a cyclohexane-1,4-diyl group, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- Or represents a single bond, R ^sp1 represents an alkylene group having 1 to 20 carbon atoms or a single bond, and the alkylene group has one or more -CH ₂ -or is adjacent when having 2 or more carbon atoms. two or more -CH ₂ no - are each independently -O -, - COO -, - OCO -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH- or It may be replaced by —C 置 き 換 え C—, and Z ¹ represents a polymerizable functional group.
J ¹ represents -N = or-(CH) =,
Q ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic ring, and the aromatic ring may be unsubstituted or substituted with one or more substituents E;
Q ² represents an alkyl group having 3 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an organic group having 2 to 30 carbon atoms having an aromatic ring. And the alkyl group, the cycloalkyl group, the cycloalkenyl group, and the aromatic ring may each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be the cycloalkyl group or may be substituted by a cycloalkenyl group, the alkyl group, one -CH 2 _- or nonadjacent two or more -CH 2 _- are each independently -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - SO 2 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH-COO-, -CH = CH- OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, and the cycloalkyl group or cyclo one -CH ₂ in the alkenyl - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or -O-CO It may be replaced by -O-.
The substituents E and E ¹ each independently represent a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, Represents a methylamino group, a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these; in the case of 2 or more carbon atoms, one -CH ₂ - or nonadjacent two or more -CH ₂ - -O are each independently -, - S -, - CO -, - COO -, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-,- H = CH—OCO—, —COO—CH ＝ CH—, —OCO—CH ＝ CH—, —CH ＝ CH—, —CF ＝ CF— or —C≡C—, or substituents E, and ^{E 1} are each ^{independently,} may represent a group represented by -L ^{E -R} SPE -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the L ⁵ , R ^sp1 , and Z ¹ represent the same as defined above, but may be the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively. and if E ¹ is present in plural may be each independently selected from the same,
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 represents an integer of 0 to 2. ) In the general formula (I), J ¹ is -N =, and Q ¹ is unsubstituted or an aromatic ring group having 3 to 18 carbon atoms which may be substituted by one or more substituents E. And Q ² is such that one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —CO—, —COO—, —OCO—, or —O The polymerizable liquid crystal compound according to claim 1, which is an alkyl group having 3 to 12 carbon atoms, which may be replaced by -CO-O-.   A polymerizable composition comprising the polymerizable liquid crystal compound according to claim 1.   The polymerizable composition according to claim 3, further comprising a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound according to claim 1 or 2.   A polymer obtained by polymerizing the polymerizable liquid crystal compound according to claim 1 or 2, or the polymerizable composition according to claim 3 or 4.   A retardation film having a retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition according to claim 3. Forming a film of the polymerizable composition according to claim 3 or 4,
A step of at least orienting the polymerizable compound in the formed polymerizable composition,
A method for producing a retardation film, comprising a step of forming a retardation layer by at least a step of polymerizing the polymerizable compound after the orientation step. A retardation layer, comprising a support that releasably supports the retardation layer,
The retardation layer contains a cured product of the polymerizable composition according to claim 3 or 4,
Transfer laminate for transfer of retardation layer.   An optical member comprising a polarizing plate on the retardation film according to claim 6. A retardation layer comprising: a retardation layer; and a support that releasably supports the retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition according to claim 3 or 4. Preparing a transfer laminate for transfer of
A transfer object including at least a polarizing plate and the phase difference layer of the transfer laminate facing each other, and a transfer step of transferring the transfer laminate on the transfer target;
A peeling step of peeling the support from the transfer laminate transferred onto the transfer target,
A method for producing an optical member, comprising:   A display device comprising the retardation film according to claim 6, or the optical member according to claim 9.