JP2020041026A - Polymerizable composition, retardation film and method for producing the same, transfer laminate, optical member and method for producing the same, and display device - Google Patents

Abstract

To provide a polymerizable composition that can form a phase difference layer having high birefringence, reverse wavelength dispersibility, and improved orientation, and has improved storage stability.SOLUTION: A polymerizable composition contains a polymerizable liquid crystal compound having a biphenyl group and a polymerizable compound having a biphenyl group.SELECTED DRAWING: None

Description

  The present disclosure relates to a polymerizable composition, a retardation film and a method for producing the same, a transfer laminate, an optical member and a method for producing the same, 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 phase difference is designed at each wavelength, and a broadband phase difference film capable of giving a uniform phase difference to light in a wide wavelength range, a so-called reverse phase difference film. There is a need for a retardation film having wavelength dispersibility.

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 having reverse wavelength dispersion, for example, a method of laminating two retardation layers at an angle to the direction of the alignment axis has been proposed (Patent Documents 1 and 2). 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 reverse wavelength dispersion property of reducing or inverting the wavelength dispersion property of the birefringence (△ n) is realized so that the retardation layer having the reverse wavelength dispersion property can be constituted by one layer. Liquid crystal compounds have been developed (for example, Patent Documents 3 and 4). 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 slope of the liquid crystal compound is positive (ascending to the right), the wavelength dispersion of the birefringence is opposite, or the liquid crystal compound of the material constituting the retardation film has the opposite wavelength dispersion. Have been

However, a conventional liquid crystal compound having reverse wavelength dispersion, such as the compounds of Patent Documents 3 and 4, has a small birefringence (Δn), so that a desired retardation (Re (λ) = birefringence Δn ( In order to obtain λ) × film thickness d), it was necessary to increase the film thickness.
Further, for example, if an ideal reverse wavelength dispersion can be obtained in a 波長 wavelength plate, it can be converted into circularly polarized light at all wavelengths in the visible light range, so that complete reflection of external light can be prevented. However, a conventional liquid crystal compound having reverse wavelength dispersion has insufficient reverse wavelength dispersion, and it is desired that the liquid crystal compound approach ideal reverse wavelength dispersion.

  Patent Document 5 discloses a polymerizable compound having a practically low melting point, excellent solubility in general-purpose solvents, and a polymerizable compound capable of obtaining an optical film capable of performing uniform polarization conversion in a wide wavelength range. A structure having two side chains on one tetravalent benzene ring group of the chain is disclosed. It is shown that the polymerizable compound itself of Patent Document 5 has no liquid crystallinity (Table 1 of Patent Document 5). An optical film having reverse wavelength dispersion is shown by mixing a conventional reverse wavelength dispersion liquid crystal compound with the polymerizable compound of Patent Document 5, but the reverse wavelength dispersion is an ideal reverse wavelength dispersion. Are far apart.

Further, a liquid crystal compound having reverse wavelength dispersion generally has poor solubility in a solvent, and therefore, an improvement in solvent solubility and an improvement in stability in a solution are required.
Patent Document 6 discloses that as a polymerizable compound which does not cause precipitation of crystals when added to a polymerizable composition and has high storage stability, one trivalent benzene ring group M in the main chain of the compound is used. Among the two substituents in the main chain direction of the trivalent benzene ring group M having one side chain, one substituent has one ring structure and the other substituent has two ring structures. A polymerizable compound characterized by having a ring structure is disclosed.
Patent Document 7 discloses, as a polymerizable compound which does not precipitate crystals when added to a polymerizable composition and has high storage stability, compounds similar to Patent Document 6 and compounds similar to Patent Document 5 Discloses a structure having two side chains in one tetravalent benzene ring group of the main chain.

JP-A-10-68816 JP 2001-4837 A JP 2010-522893 A Japanese Patent No. 5962760 International Publication No. 2014/061709 WO 2016/136533 International Publication No. 2016/104317

Further, the conventional retardation layer having reverse wavelength dispersion may have a defect when observed by a polarizing microscope, and further improvement of the orientation is required.
In view of the above-described circumstances, embodiments of the present disclosure can form a retardation layer having a large birefringence (Δn), reverse wavelength dispersion, and improved orientation, and storage stability. The polymerizable composition having improved, a retardation film having a retardation layer containing a cured product of the polymerizable composition and a method for producing the same, a transfer laminate capable of transferring the retardation layer, the retardation film It is an object to provide an optical member, a method for manufacturing the same, and a display device.

  One embodiment of the present disclosure provides a polymerizable composition containing a polymerizable liquid crystal compound represented by the following general formula (1) and a polymerizable compound represented by the following general formula (2).

(In the general formulas (1) and (2), 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 -, - OCO-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;
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, A cycloheptane-1,4-diyl group, a cycloheptane-1,3-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-1,4-diyl group, cycloheptane-1,3-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 a single ^{bond, R sp1} represents an alkylene group or a single bond having 1 to 20 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - Are each independently replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C≡C-. Z ¹ may represent a polymerizable functional group.
D ¹ and D ² each independently represent a group selected from the following general formula (D-1), and a plurality of D ¹ and D ² in the general formula (2) are the same, and the general formula (D-1) In the formula (1) and the formula (2), D ¹ and D ² are the same,
The substituents E, E ¹ and E ² 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 Group, 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, and one of- 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- H = CH-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom; Alternatively, substituents E, ^{E 1} and ^{E 2} are each ^{independently,} may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are each said ^{L 5, R sp1,} and represent those same as defined in ^{Z 1,} each of the ^{L 5, R sp1,} and ^{Z 1} and may be the same or different and the compound When a plurality of substituents E, E ¹ and E ² are present, each may be the same or different,
L ¹¹ and L ¹² each independently represent the same as defined in L ^{1 to} L ⁴ , but may be the same or different from L ^{1 to} L ⁴ ,
A ¹¹ represents the same as defined in A ^{1 to} A ² , but may be the same as or different from A ^{1 to} A ² ,
In each of the general formula (1) and the general formula (2), when a plurality of L ³ , L ⁴ , L ¹¹ , L ¹² , A ³ , A ^4, and A ¹¹ are present, each is the same. L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² are the same in the general formulas (1) and (2). Or different.
m1 and m2 each independently represent an integer of 1 to 4; n1 and n2 each independently represent an integer of 0 to 3; n represents an integer of 1 or more; N1 and n2 may be the same or different. In general formulas (1) and (2), m1, m2, n1 and n2 may be the same or different. Is also good. )

(In the general formula (D-1), G ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is unsubstituted or substituted by one or more substituents E. May be
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;
J ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NQ 2 -, - N = CQ 2 -, - CO-NQ 2 -, - OCO-NQ 2 — Or —O—NQ ² —, wherein Q ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic group. the organic group of 2 to 30 carbon atoms having a ring, or ^{- (L} 6 _-A ⁵⁾ represents a q ^{-L 7 -R} sp2 -Z ^2, the alkyl group, cycloalkyl group, cycloalkenyl group, and an aromatic ring May each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group, One —CH ₂ — or adjacent Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, and —SO— _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO- CH = CH -, - CH = CH -, - CF = CF- or may be replaced with -C≡C-, said cycloalkyl group or one -CH during cycloalkenyl group ₂ - or adjacent Two or more —CH ₂ — that are not each may be independently replaced with —O—, —CO—, —COO—, —OCO—, or —O—CO—O—, L ⁶ , A ⁵ , L ⁷ , R ^sp2 , and Z ² are the aforementioned L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^{sp1, respectively.} , And Z ¹ , which are the same or different from L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^sp1 , and Z ¹ , respectively. In addition, q represents an integer of 0 to 4, and when a plurality of L ⁶ and A ⁵ are present, they may be the same or different. Further, Q ¹ and Q ² may combine to form a ring. )

  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,
At least aligning the polymerizable liquid crystal compound represented by the general formula (1) in the formed polymerizable composition;
Providing a method for producing a retardation film, comprising, after the aligning step, at least a step of polymerizing the polymerizable liquid crystal compound represented by the general formula (1), thereby including a step of forming a retardation layer. I do.

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 of 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 the embodiment of the present disclosure, a polymerizable composition having a large birefringence (△ n), having a reverse wavelength dispersion property, being capable of forming a retardation layer having improved orientation, and having improved storage stability is provided. , A retardation film having a retardation layer containing a cured product of the polymerizable composition and a method for producing the same, a transfer laminate capable of transferring the retardation layer, an optical member having the retardation film, and a method for producing the same , 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 the interpretation of the present disclosure is not limited thereto. There is no limitation. 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 composition The polymerizable composition of the present disclosure contains a polymerizable liquid crystal compound represented by the following general formula (1) and a polymerizable compound represented by the following general formula (2).

(In the general formulas (1) and (2), 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 -, - OCO-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;
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, A cycloheptane-1,4-diyl group, a cycloheptane-1,3-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-1,4-diyl group, cycloheptane-1,3-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 a single ^{bond, R sp1} represents an alkylene group or a single bond having 1 to 20 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - Are each independently replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C≡C-. Z ¹ may represent a polymerizable functional group.
D ¹ and D ² each independently represent a group selected from the following general formula (D-1), and a plurality of D ¹ and D ² in the general formula (2) are the same, and the general formula (D-1) In the formula (1) and the formula (2), D ¹ and D ² are the same,
The substituents E, E ¹ and E ² 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 Group, 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, and one of- 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- H = CH-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom; Alternatively, substituents E, ^{E 1} and ^{E 2} are each ^{independently,} may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are each said ^{L 5, R sp1,} and represent those same as defined in ^{Z 1,} each of the ^{L 5, R sp1,} and ^{Z 1} and may be the same or different and the compound When a plurality of substituents E, E ¹ and E ² are present, each may be the same or different,
L ¹¹ and L ¹² each independently represent the same as defined in L ^{1 to} L ⁴ , but may be the same or different from L ^{1 to} L ⁴ ,
A ¹¹ represents the same as defined in A ^{1 to} A ² , but may be the same as or different from A ^{1 to} A ² ,
In each of the general formula (1) and the general formula (2), when a plurality of L ³ , L ⁴ , L ¹¹ , L ¹² , A ³ , A ^4, and A ¹¹ are present, each is the same. L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² are the same in the general formulas (1) and (2). Or different.
m1 and m2 each independently represent an integer of 1 to 4; n1 and n2 each independently represent an integer of 0 to 3; n represents an integer of 1 or more; N1 and n2 may be the same or different. In general formulas (1) and (2), m1, m2, n1 and n2 may be the same or different. Is also good. )

(In the general formula (D-1), G ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is unsubstituted or substituted by one or more substituents E. May be
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;
J ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NQ 2 -, - N = CQ 2 -, - CO-NQ 2 -, - OCO-NQ 2 — Or —O—NQ ² —, wherein Q ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic group. the organic group of 2 to 30 carbon atoms having a ring, or ^{- (L} 6 _-A ⁵⁾ represents a q ^{-L 7 -R} sp2 -Z ^2, the alkyl group, cycloalkyl group, cycloalkenyl group, and an aromatic ring May each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group, One —CH ₂ — or adjacent Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, and —SO— _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO- CH = CH -, - CH = CH -, - CF = CF- or may be replaced with -C≡C-, said cycloalkyl group or one -CH during cycloalkenyl group ₂ - or adjacent Two or more —CH ₂ — that are not each may be independently replaced with —O—, —CO—, —COO—, —OCO—, or —O—CO—O—, L ⁶ , A ⁵ , L ⁷ , R ^sp2 , and Z ² are the aforementioned L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^{sp1, respectively.} , And Z ¹ , which are the same or different from L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^sp1 , and Z ¹ , respectively. In addition, q represents an integer of 0 to 4, and when a plurality of L ⁶ and A ⁵ are present, they may be the same or different. Further, Q ¹ and Q ² may combine to form a ring. )

The polymerizable liquid crystal compound represented by the general formula (1) contained in the polymerizable composition of the present disclosure has high orientation between molecules due to a biphenylene group contained in a main chain portion, and further has two molecules of the biphenylene group. Since there are two side chains, one for each benzene ring, a liquid crystal compound having a large birefringence (△ n) while having reverse wavelength dispersion. Therefore, a retardation layer having a large birefringence (Δn) and having reverse wavelength dispersion can be formed using the polymerizable composition of the present disclosure.
Further, since the polymerizable composition of the present disclosure has improved storage stability, precipitation of a precipitate is suppressed even when stored as a solution further containing a solvent, even when stored for a long time. In the polymerizable composition of the present disclosure, in the polymerizable liquid crystal compound represented by the general formula (1), the specific alicyclic hydrocarbon group is introduced into A ¹ and A ² adjacent to the biphenylene group. By this, a decrease in solvent solubility is suppressed, and the polymerizable liquid crystal compound represented by the general formula (1) is further combined with a polymerizable compound represented by the general formula (2). By containing, aggregation of the polymerizable liquid crystal compound represented by the general formula (1) is suppressed. In the polymerizable compound represented by the general formula (2), two or more biphenylene groups having side chains are introduced into the main chain portion of the structure represented by the general formula (1) via a specific linking group. A compound having the same structure as that of the general formula (1) except for the above. The polymerizable compound represented by the general formula (2) has a solvent in which the number of side chains of the biphenylene group is at least twice that of the polymerizable liquid crystal compound represented by the general formula (1). Solubility is improved. When the polymerizable compound represented by the general formula (2) is used in combination with the polymerizable liquid crystal compound represented by the general formula (1), the general formula (2) having higher solvent solubility in a solvent is used. The polymerizable compound represented by the formula (1) assists dissolution of the polymerizable liquid crystal compound represented by the general formula (1) having a similar structure, and causes the aggregation of the polymerizable liquid crystal compound represented by the general formula (1). It is presumed that the precipitation is suppressed to suppress the precipitation of the precipitate.
Furthermore, the polymerizable composition of the present disclosure can form a retardation layer with improved orientation. In the polymerizable composition of the present disclosure, as described above, since the aggregation of the polymerizable liquid crystal compound represented by the general formula (1) is suppressed, when the polymerizable composition of the present disclosure is formed into a film, It is presumed that the orientation of the retardation layer is improved because the coating film is likely to be uniform, and if the coating film is uniform, the orientation of the liquid crystalline components in the coating film is also likely to be uniform.

In addition, in the polymerizable composition of the present disclosure, the polymerizable liquid crystal compound represented by the general formula (1) has a large birefringence (△ n) and an inverse wavelength dispersion, and therefore, the compound represented by the general formula (1) Even if the amount of the polymerizable liquid crystal compound represented by 1) is reduced, a retardation layer having a desired reverse wavelength dispersion can be obtained, and a thinner retardation layer can be obtained.
In the polymerizable composition of the present disclosure, the phase difference can be adjusted by using another liquid crystal compound in combination.

  The polymerizable composition of the present disclosure contains at least a polymerizable liquid crystal compound represented by the general formula (1) and a polymerizable compound represented by the general formula (2), and typically further includes a solvent. , 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. Polymerizable liquid crystal compound represented by general formula (1) The polymerizable liquid crystal compound represented by general formula (1) has a specific structure in the main chain structure from the specific R ¹ to R ^2. , A polymerizable liquid crystal compound capable of polymerizing with a compound having another polymerizable group because the alignment between molecules is improved, and can exhibit liquid crystallinity alone, and has a polymerizable group at a terminal. It is.

L ¹ , L ² , L ³ and L ⁴ in the general formula (1) 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 are independently present, 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-, -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— or a single bond; when present may be different from each be the same, each independently _{-O -, - OCH 2 -,} - CH 2 O -, - COO -, - OCO -, - COO-CH = CH- _{, -OCO-CH = CH -,} - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 - , _-CH 2 _CH 2 -COO _-, - it is more preferable that represent _CH 2 CH 2 -OCO- or a single bond, if there are two or more may each have the same or different and each independently - O -, - COO -, - OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, or a single bond Is particularly preferred.

A ¹ and A ² in the general formula (1) are each independently unsubstituted or a cyclopentane-1,3-diyl group which may be substituted by one or more substituents E, cyclohexane- 1,4-diyl group, cycloheptane-1,4-diyl group, cycloheptane-1,3-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane-2,5-diyl group In particular, cyclopentane-1, which may be unsubstituted or substituted with one or more substituents E from the viewpoint of improving the liquid crystallinity and improving the alignment property. More preferably, it is a 3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane-1,4-diyl group, or a cyclododecane-1,5-diyl group, which is unsubstituted or one or more. Replace It may be substituted by E, and particularly preferably is cyclohexane-1,4-diyl group.

A ¹ and A ² in the general formula (1) are cis- and trans-stereoisomers based on the difference in the configuration of carbon atoms bonded to L ¹ and L ³ (or L ² and L ⁴ ). The compound may exist in a cis form, a trans form, or a mixture of cis and trans isomers. It is preferably of the type, and more preferably the trans type.

A ³ and A ⁴ in the general formula (1) 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-1,4-diyl group, cycloheptane-1,3-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 Represents a benzene-1,4-diyl group, a cyclohexane- group or a 1,3-dioxane-2,5-diyl group. , 4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2,6-diyl group, naphthalene-1,4-diyl group, 1,2,3,4- It is preferably a tetrahydronaphthalene-2,6-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group, which is unsubstituted or one or more. It is preferably a benzene-1,4-diyl group, a naphthalene-2,6-diyl group or a cyclohexane-1,4-diyl group which may be substituted by the substituent E, and a benzene-1,4-diyl group Or it is more preferably a cyclohexane-1,4-diyl group, particularly preferably a benzene-1,4-diyl group.
When a plurality of A ³ and A ⁴ are present in the general formula (1), they may be the same or different.

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, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, Chioisoshiano group, or one -CH 2 _- or nonadjacent two or more -CH 2 _- independently are each -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- Replaced Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom, or the substituents E are each independently Te ^may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively defined by ^{L 5, R sp1,} and ^{Z 1} to be described later And the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively. When a plurality of substituents E are present in the compound, each is the same. Or different.

From the viewpoints of liquid crystallinity and ease of synthesis, the substituent E is 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 arbitrary group. the hydrogen atoms may be substituted by a fluorine atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO-, -COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C- which may be substituted with a group selected from 1 to 20 carbon atoms. Represents preferably a linear or branched alkyl group, and a fluorine atom, a chlorine atom, or an arbitrary hydrogen atom may be substituted with a fluorine atom, and one —CH ₂ — or non-adjacent 2 more than five -CH ₂ - are each independently More preferably represents a linear or branched alkyl group having 1 to 12 carbon atoms which may be replaced by a group selected from -O-, -COO- or -OCO-, and a fluorine atom, a chlorine atom, Or, any hydrogen atom more preferably represents a linear or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted by a fluorine atom, and a fluorine atom, a chlorine atom, or a carbon atom It is particularly preferable to represent a straight-chain alkyl group or a straight-chain alkoxy group of Formulas 1 to 8.
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 (1) each independently represent an integer of 1 to 4. Among them, from the viewpoint of liquid crystallinity and orientation, one or both of m1 and m2 is preferably an integer of 1 to 3, and both m and n are more preferably integers of 1 to 3, and m1 and More preferably, both of 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 general formula (R-1), R ^sp1 is such that one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—, —COO—, —OCO—, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or an alkylene group having 1 to 20 carbon atoms which may be replaced by -C≡C- or a single bond.

In the general formula (R-1), more specifically, as R ^sp1 , from the viewpoint of the availability of raw materials and the ease of synthesis, each independently represents one —CH ₂ — or non-adjacent 2 More preferably, -CH _2- or more each independently represents an alkylene group having 1 to 12 carbon atoms or a single bond which may be independently replaced by -O-, -COO-, -OCO-, and each independently And further preferably represents an alkylene group having 1 to 12 carbon atoms or a single bond, even more preferably each independently represents an alkylene group having 2 to 10 carbon atoms, 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 ^{(1), 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 (1), 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 is preferably 2. N in R ^sp1 represents 1 to 20, but is preferably 2 or more, more preferably 4 or more, on the other hand, preferably 12 or less, and more preferably 10 or less. .
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.

On the other hand, in the general formula (D-1), G ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is unsubstituted or substituted by one or more substituents E. The substituent E is preferably F, Cl, CF ₃ , OCF ₃ or a cyano group. G ¹ is more preferably a hydrogen atom or an unsubstituted or an alkyl group having 1 to 6 carbon atoms in which one or more hydrogen atoms are substituted by a fluorine atom, and G ¹ is particularly preferably a hydrogen atom.

Q ¹ represents an organic group having an aromatic ring and having 2 to 30 carbon atoms, and the aromatic ring may be unsubstituted or substituted with one or more substituents E; ¹ may constitute a ring and Q ^2.
When Q ¹ represents an organic group having 2 to 30 carbon atoms having an aromatic ring, the aromatic ring may be any of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. In this case, Q ¹ represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocyclic ring. The aromatic ring is preferably a group selected from the following formulas (Q-1) to (Q-22).
Q ¹ is preferably an organic group having an aromatic heterocyclic ring, in which one or more carbon atoms are substituted with a hetero atom, from the viewpoint of improving wavelength dispersibility. From the viewpoint of exhibiting high birefringence, an organic group having an aromatic heterocyclic ring which is a condensed ring of a 5-membered ring and a 6-membered ring is more preferable. Examples of the aromatic heterocyclic ring which is a condensed ring of a 5-membered ring and a 6-membered ring include, for example, compounds represented by the following formulas (Q-10), (Q-11), (Q-21) and (Q-22). Aromatic heterocycles in which one or more of the carbon atoms of the group selected are replaced by heteroatoms are preferred.

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

The aromatic group contained in Q ¹ may be unsubstituted or substituted by one or more of the substituents E. The above formulas (Q-1-1), (Q-7-1) and (Q-7-1) 7-2), Formula (Q-7-7), Formula (Q-8), Formula (Q-10-2), Formula (Q-10-3), Formula (Q-10-4), Formula (Q-10-4) 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-11-7), Formula (Q-11-7) -11-8), Formula (Q-11-9), Formula (Q-11-10), Formula (Q-11-11), Formula (Q-11-12), Formula (Q-21-1) , A group selected from the formulas (Q-21-2), (Q-22-1) and (Q-22-2). More preferably, formulas (Q-10-2), (Q-10-3), (Q-10-4), and (Q-10-4) which may be unsubstituted or substituted by one or more substituents E -10-5), formula (Q-10-6), formula (Q-10-7), formula (Q-10-8), formula (Q-10-9), formula (Q-21-1) ), Formula (Q-21-2), Formula (Q-22-1), and Formula (Q-22-2).

Further, the substituent E ^Q when the aromatic group included in the Q ¹ is substituted, inter alia a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, isocyano group, amino group, hydroxyl group, a mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, Chioisoshiano group, or 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 Represents a linear or branched alkyl group having 1 to 20 carbon atoms which may be substituted by-, and it is preferable that any hydrogen atom in the alkyl group be substituted with a fluorine atom. , Fluorine atom Chlorine atom, bromine atom, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO -, - A linear chain having 1 to 20 carbon atoms which may be substituted by OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-; Represents a linear or branched alkyl group, and it is more preferable that any hydrogen atom in the alkyl group may be substituted with a fluorine atom.

Furthermore, ^{Q 1} is the following formula (Q-10-2), the formula (Q-10-2a), the formula (Q-10-3), the formula (Q-10-3a), the formula (Q-10-3b ), Formula (Q-10-6), Formula (Q-10-6a), Formula (Q-10-6b), Formula (Q-10-6c), Formula (Q-10-6d), Formula (Q-10-6d) -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-10-9a), Formula (Q-10-9b), Formula (Q-21-1), Formula (Q-21-1) 21-2), particularly preferably a group selected from the formulas (Q-22-1) and (Q-22-2).

J ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NQ 2 -, - N = CQ 2 -, - CO-NQ 2 -, - OCO-NQ 2 — Or —O—NQ ² —, wherein Q ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic group. An organic group having a ring (which may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring) having 2 to 30 carbon atoms, or-(L ⁶ -A ⁵ ) _q -L ⁷ -R ^sp2- Z ² , 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 is Substituted by an alkyl group or a cycloalkenyl group Even if well, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - S -, - CO -, - COO- _{, -OCO -, - CO-S} -, - S-CO -, - SO 2 -, - 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- alkyl group or cycloalkenyl one -CH in group ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or may be substituted with ^{-O-CO-O-, L 6} , a 5, L 7, R sp2, and ^{Z 2,} which Is the ^{L 1 ~L 4, A 1 ~A} 4, L 5, R sp1, and represent those same as defined in ^{Z 1,} wherein each ^{L 1 ~L 4, A 1 ~A} 4 , L ⁵ , R ^sp1 , and Z ¹ may be the same or different, and q represents an integer of 0 to 4. When a plurality of L ⁶ and A ⁵ are present, respectively, they are the same. Or different.

J ^1, from the viewpoint of easy good birefringence synthesis, among others, -O -, - S -, - N = CQ 2 - or -NQ ² - is preferably further wavelength dispersion and a double from the refractive good points, -O -, - S-, or -NQ ² - is preferably.
Here, Q ² is preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an aromatic ring (an aromatic hydrocarbon ring and the organic group of 2 to 30 carbon atoms having a matching or) at either an aromatic heterocycle, or ^{- (L} 6 _-A ⁵⁾ represents a q ^{-L 7 -R} sp2 -Z ^2, the alkyl group, Each of the cycloalkyl group, cycloalkenyl group, and aromatic ring may be unsubstituted or substituted with one or more substituents E, and the alkyl group is substituted with the cycloalkyl group or cycloalkenyl group. may be, one -CH ₂ in the alkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO -, -O- CO-O- or may be replaced by -CH = CH-, the cycloalkyl group and cycloalkenyl one -CH in group ₂ - or nonadjacent two or more -CH ₂ - are each independently And may be replaced by -O-, -CO-, -COO-, -OCO- or -O-CO-O-.
Q ² is, it can be appropriately selected depending on the purpose. For example, it is preferable that Q ² has a structure containing no hetero atom from the viewpoint of birefringence. Further, Q ² has a structure containing more heteroatoms, in particular, one -CH ₂ -or two or more non-adjacent -CH ₂ -are each independently -O-, -CO It is preferable to have a structure substituted by-, -COO-, -OCO-, or -O-CO-O-, since the solvent solubility of the compound is improved and the choice of base materials to be combined increases. Further, ^{Q 2 is} - it ^(L 6 ^-A 5) is a ^{q-L 7 -R} sp2 -Z ² is preferable from the viewpoint of improving the durability by improving the curing of the film.
An unsubstituted alkyl group having 1 to 20 carbon atoms or an alkenyl group in which one —CH ₂ — in the alkyl group is replaced by —CH ＝ CH— or one —CH ₂ in the alkyl group -May be substituted by -C≡C-, an alkynyl group having 3 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, Examples of the good alkyl group and the organic group having 2 to 30 carbon atoms having an aromatic ring include, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group and t-butyl. Group, n-pentyl group, n-hexyl group, 1-methylpentyl group, n-heptyl group, 1-ethylpentyl group, n-octyl group, 2-ethylhexyl group, n- Nonyl group, n-decyl group, 3,7-dimethyloctyl group, n-undecyl group, n-dodecyl group, vinyl group, allyl group, isopropenyl group, butynyl group, cyclopentyl group, cyclohexyl group, cyclopentenyl group, cyclo Examples include a hexenyl group, a cyclooctenyl group, a cyclopentylmethyl group, a cyclohexylmethyl group, and a benzyl group.

Among them The substituent in Q ^2, fluorine atom, chlorine atom, bromine atom, a cyano group, a hydroxyl group, a mercapto group, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, or 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-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = It is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, which may be replaced by CH-, -CH = CH-, -CF = CF- or -C≡C-. Atom, chlorine atom, cyano group, hydroxy Group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - OCO-, or -O-CO It is preferably a linear or branched alkyl group having 1 to 20 carbon atoms which may be replaced by -O-.

Among them, Q ² is preferably an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkyl group having 3 to 12 carbon atoms from the viewpoint of birefringence, solvent solubility, or durability. cycloalkenyl group, or ^{- (L} 6 ^-A 5) represents a ^{q-L 7 -R sp2 -Z 2} , the alkyl groups, each cycloalkyl and cycloalkenyl groups, or is one or more unsubstituted The alkyl group may be substituted by the substituent E, the alkyl group may be substituted by the cycloalkyl group or the cycloalkenyl group, and one —CH ₂ — or non-adjacent 2 more than five -CH ₂ - -O are each independently -, - CO -, - COO -, - OCO -, - OCO-O- , or be replaced by -CH = CH- well, the cyclo Alkyl And one -CH ₂ in the cycloalkenyl group - or nonadjacent two or more -CH ₂ - -O are each independently -, - CO -, - COO -, - OCO-, or -O It may be replaced by -CO-O-. Q ² is more preferably a linear or branched alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or-(L ⁶ -A ⁵ ) q-L ⁷ -R represents ^sp2 -Z ^2, the alkyl group may be substituted by the cycloalkyl group, any hydrogen atom of the alkyl group and the cycloalkyl group may be substituted by a fluorine atom, and the alkyl group one -CH ₂ in the cycloalkyl group - or nonadjacent two or more -CH ₂ - are each independently -O -, - CO -, - COO- or -OCO- be replaced by good. Q ² is, even more preferably, a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or ^{- (L 6 -A 5) q} -L 7 - R ^sp2 —Z ² , wherein the alkyl group may be substituted by the cycloalkyl group, and one —CH ₂ — or two or more non-adjacent — in the alkyl group and the cycloalkyl group CH ₂ — may each be replaced by —O—.
The preferred structure ^of- (L ⁶ -A ⁵ ) q-L ⁷ -R ^sp2 -Z ² is defined by L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , L ⁵ , R ^sp1 , and Z ¹ , respectively. It is desirably the same as the preferred structure. q represents an integer of 0 to 4, more preferably represents an integer of 0 to 2, more preferably represents 0 or 1, and particularly preferably represents 0.

Among them, Q ² may have a hydrogen atom replaced with a fluorine atom from the viewpoint of birefringence and solvent solubility, and one —CH ₂ — or two or more non-adjacent —CH ₂ — A linear or branched alkyl group having 2 to 20 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, which may be independently replaced by -O-, -CO-, -COO-, -OCO-. Alternatively, it is preferably the above-mentioned alkyl group which may be substituted by the cycloalkyl group, and a hydrogen atom may be substituted by a fluorine atom, and one --CH ₂ -or two or more which are not adjacent to each other may be used. -CH _2- may be a linear or branched alkyl group having 2 to 20 carbon atoms which may be independently replaced by -O-, -CO-, -COO-, -OCO-. More preferably, a hydrogen atom is May be substituted by atom, one -CH ₂ - or nonadjacent two or more -CH ₂ - independently are each -O -, - CO -, - COO -, - OCO- to replace Even more preferably, it is a linear alkyl group having 2 to 20 carbon atoms which may be used.
Number of carbon atoms in Q ² is preferably 4 or more, and more preferably 12 or less.

Alternatively, Q ¹ and Q ² may combine to form a ring, in which case, for example, a cyclic group represented by -NQ ¹ Q ² or -N = CQ ¹ Q ² Cyclic groups. The ring formed together with the nitrogen atom or carbon atom to which Q ¹ and Q ² are bonded includes a ring having an aromatic ring and having 2 to 30 carbon atoms. -18, more preferably 2-14. Above all, the cyclic group represented by -NQ ¹ Q ² may be unsubstituted or substituted by one or more substituents E from the following formulas (QQ-1) to (QQ-22) It preferably represents a group selected from The cyclic group represented by -N = CQ ¹ Q ² preferably represents the following formula (QQ-23) or (QQ-24).

Formula (QQ-1) from the equation may be replaced (QQ-22) -CH = in group selected from each independently a -N =, -CH ₂ - are each independently -O-, —S—, —NR ^Qa — (wherein, R ^Qa represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.) It may be replaced by —SO—, or —SO ₂ — or —CO—. (However, the case where oxygen atoms are directly bonded to each other is excluded.) 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.

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

The fact that D ¹ and D ² each represent a group selected from the following formulas (D-1) to (D-47) indicates that the raw materials are easily available, the solubility is good, and the birefringence is high. Is particularly preferred.

E ¹ and E ² which may be substituted on the benzene ring of the biphenylene group may be each independently the same as the substituent E.
A good E ¹ and E ² may be substituted on the benzene ring of biphenylene group, among others, from the birefringence good synthetic easiness, fluorine atom, chlorine atom, hydroxyl group, mercapto group, methylamino group, dimethylamino group, or one -CH ₂ - or nonadjacent two or more -CH ₂ - independently are each -O -, - S -, - CO -, - COO -, - OCO- , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- linear or branched having 1 to 6 carbon atoms. It is preferably an alkyl group.

Further, n1 and n2 each independently represent an integer of 0 to 3, preferably 0 to 2, and more preferably 0 or 1.
Further, when E ¹ and E ² are each independently substituted by a biphenylene group, the substitution position is preferably the 6-position or 6′-position of the biphenylene group from the viewpoint of improving the birefringence. . In such a case, the twist angle of the two benzene rings in the biphenylene group becomes large, and the π-electron conjugate structure is easily cut.

  The structure of the biphenylene group in the main chain preferably represents a group selected from the following formulas (Co-1) to (Co-8).

  The polymerizable liquid crystal compound represented by the general formula (1) is a polymerizable liquid crystal compound having good orientation, a large birefringence (Δn), and reverse wavelength dispersion. For example, a polymerizable composition containing only the polymerizable liquid crystal compound represented by the general formula (1) and a photopolymerization initiator is prepared, a cured film (retardation layer) is formed, and the birefringence of the cured film is obtained. When (Δn) is measured, it is preferably 0.075 or more, and more preferably 0.08 or more.

In addition, the polymerizable liquid crystal compound represented by the general formula (1) has good reverse wavelength dispersion, and in order to approach an ideal reverse wavelength dispersion, the polymerizable liquid crystal compound represented by the general formula (1) is used. When a polymerizable composition containing only a hydrophilic liquid crystal compound and a photopolymerization initiator is prepared, a cured film (retardation layer) is formed, and the retardation value is measured, Re (450) / Re (550) is: It is preferably in the range of 0.50 or more and less than 0.95, more preferably in the range of 0.55 or more and less than 0.93, and even more preferably in the range of 0.60 or more and less than 0.90. It is particularly preferable that it is in the range of 0.60 or more and 0.83 or less, and it may be in the range of 0.60 or more and less than 0.80. Further, Re (650) / Re (550) is preferably more than 1, and more preferably in the range of 1.02 or more and 1.1 or less.
As a method for testing the phase difference value, the following measuring methods are exemplified.
[Test method]
100 parts by mass of the polymerizable liquid crystal compound represented by the general formula (1) and 4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are 900 parts by mass of cyclopentanone. After the rubbing treatment, the polymerizable composition dissolved in the above is coated on the alignment film of the glass with a polyimide alignment film so that the film thickness after curing becomes 1 μm, formed into a film, dried, and then irradiated with ultraviolet rays. Irradiation is performed at an amount of 400 mJ / cm ² to form a retardation layer, and an in-plane retardation Re (450 for a wavelength of 450 nm) is measured by a retardation measuring device (for example, product name: KOBRA-WR, manufactured by Oji Scientific Instruments). ) And the in-plane retardation Re (550) for a wavelength of 550 nm.
Here, as the glass with a polyimide alignment film after the rubbing treatment, a commercially available glass may be used, and for example, a product name “alignment-treated glass substrate” manufactured by EC Corporation can be used. The alignment-treated glass substrate is subjected to rubbing treatment by applying polyimide LX-1400 manufactured by Hitachi Chemical Co., Ltd.
Similar results can be obtained by forming a retardation layer by the method described in Comparative Example 1 described below and measuring the retardation value.

In addition, the polymerizable liquid crystal compound represented by the general formula (1) preferably has a solid-liquid crystal phase transition temperature of 25 ° C. or more and 200 ° C. or less from the viewpoint of expanding the choice of usable substrates. The temperature is more preferably not less than 180 ° C. and more preferably not less than 30 ° C. and not more than 150 ° C. If the solid-liquid crystal phase transition temperature is low, the load in the step of aligning the liquid crystal can be reduced, or it can be used for a substrate that is vulnerable to high temperatures.
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. 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 cross Nicol observation (the polarizing plate is in an orthogonal state) with the polarizing microscope is specified as the solid-liquid crystal phase transition temperature. can do.

  In addition, the polymerizable liquid crystal compound represented by the general formula (1) is 10 mass% in at least one solvent selected from the group consisting of N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. % Or more is preferred from the viewpoint of expanding the choice of usable base materials and from the viewpoint of solvent solubility and storage stability, and more preferably 20% by mass or more.

The polymerizable composition of the present disclosure may contain one kind of the polymerizable liquid crystal compound represented by the general formula (1), or may contain two or more kinds in combination.
The content of the polymerizable liquid crystal compound represented by the general formula (1) contained in the polymerizable composition of the present disclosure is such that the polymerizable composition having a large birefringence (△ n) and having reverse wavelength dispersion is used. From the viewpoint of being obtained, it is preferably 50 parts by mass or more and 99.9 parts by mass or less, more preferably 54 parts by mass or more and 99 parts by mass or less with respect to 100 parts by mass of the solid content of the polymerizable composition. It is even more preferable that the amount is from not less than 98 parts by mass to not more than parts by mass.
In the present disclosure, the solid content refers to all components except the solvent. For example, other polymerizable liquid crystal compounds different from the polymerizable liquid crystal compound represented by the general formula (1) described below are liquid. However, it should be included in the solid content.

2. Polymerizable compound represented by the general formula (2) The polymerizable compound represented by the general formula (2) has a polymerizable group at a terminal, and thus can be polymerized with a compound having another polymerizable group. It is a polymerizable compound that can be obtained.

In the general formula (2), L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , D ¹ , D ² , substituents E, E ¹ , E ² , m 1, m ² , n 1 and n 2 are L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , D ¹ , D ² , substituents E, E ¹ , E ² , m 1, m ² , n 1 and n 2 in the general formula (1), respectively. Represents the same as defined.
Note that a plurality of D ¹ and D ² in the general formula (2) are the same. That is, a plurality of D ¹ in the general formula (2) are the same, and a plurality of D ² in the general formula (2) are the same. D ¹ and D ² in the general formula (2) may be the same or different from each other.
Further, in the biphenylene groups present in a plurality of general formulas (2), the substitution positions of D ¹ and D ² may be the same or different, but from the viewpoint of storage stability and orientation, they may be the same. preferable.
In general formulas (1) and (2), D ¹ and D ² are the same. That, ^{D 1} of the the general formula (2) has the general formula (1) is identical to ^{D 1} of the in, ^{D 2} in the general formula (2) has the general formula (1) the same as ^{D 2} in is there.
In the general formula (2), L ³ , L ⁴ , A ³ and A ⁴ may be each independently the same or different when a plurality of L ³ , L ⁴ , A ³ and A ⁴ are present.
A plurality of E ¹ , E ² , n1 and n2 present in the general formula (2) may be each independently the same or different. In a plurality of biphenylene groups present in the general formula (2), the substitution positions of E ¹ and E ² may be the same or different, but are preferably the same from the viewpoint of storage stability and orientation.
Further, in the general formulas (1) and (2), L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² , and m 1, m ² , n 1 and n 2 are: Each may be the same or different. That is, L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² , and m 1, m ² , n 1 and n 2 in the general formula (2) are each independently represented by the general formula ( It may be the same as or different from L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² , and m 1, m ² , n 1 and n 2 in 1).

In the general formula ^{(2), 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 those similar to the specific examples of the Lc1 and Lc2 in the general formula (1). In the polymerizable compound represented by the general formula (2), Lc1 and Lc2 may be the same or different.
In the general formula (2), specific examples of ^{D 1} and ^{D 2} include those similar to the specific example of the ^{D 1} and ^{D 2} in the general formula (1).
Further, in the general formula (2), a preferable structure of the biphenylene group in the main chain portion is the same as the preferable structure of the biphenylene group in the main chain portion in the general formula (1).

L ¹¹ and L ¹² in the general formula (2) each independently represent the same as defined in the above-described L ^{1 to} L ⁴ in the general formula (1). from the standpoint of ease of raw material availability and synthesis, each independently _{-COO -, - OCO -, -} OCH 2 -, - CH 2 O -, - 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 represents _{an, -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 a single bond is more preferable, and —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, —CF ₂ O—, — Even more preferably, it represents OCF ₂ — or a single bond, even more preferably —COO—, —OCO—, —OCH ₂ —, —CH ₂ O—, or a single bond. , -OCH ₂ -, or is particularly preferably represents _-CH 2 O-.
Note that L ¹¹ and L ¹² in the general formula (2) may be independently the same as or different from the L ^{1 to} L ⁴ in the general formula (1).

A ¹¹ in the general formula (2) represents the same one defined as A ^{1 to} A ² in the general formula (1), but among others, improves liquid crystallinity and improves orientation. A cyclopentane-1,3-diyl group, a cyclohexane-1,4-diyl group, a cycloheptane which may be unsubstituted or substituted by one or more substituents E More preferably, they are a -1,4-diyl group or a cyclododecane-1,5-diyl group, and may be unsubstituted or substituted by one or more substituents E. Particularly preferred is a 4-diyl group.

A ¹¹ in the general formula (2) may have a cis or trans stereoisomer based on a difference in steric configuration of a carbon atom bonded to L ¹¹ or L ^12. Or trans-form, or a mixture of cis-form and trans-form isomers. Among them, trans-form or cis-form is preferable because of good orientation, and trans-form is more preferable. preferable.
Incidentally, ^{A 11} in the general formula (2), the ^A 1 to A ² and may be different even with the same general formula (1).

In the general formula ^{(2), Lc3: -L 11} -A 11 -L 12 - Examples of include, but are not limited to, for example, represented by the following Lc3-1～Lc3-10 2 Valence groups. When a plurality of Lc3s exist in the polymerizable compound represented by the general formula (2), they may be the same or different.

In the divalent group represented by ^{Lc3-1～Lc3-10,} m in ^{L 12} represents 1 or 2, 2 being preferred.

  N in the general formula (2) represents an integer of 1 or more, and is preferably 1 or 2, and more preferably 1, from the viewpoint of storage stability and orientation.

  In addition, the polymerizable compound represented by the general formula (2) is 10% by mass in at least one solvent selected from the group consisting of N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. The above-mentioned dissolution is preferable from the viewpoint of expanding the choice of usable base materials and the solvent solubility and storage stability, and more preferably 20% by mass or more.

In the polymerizable composition of the present disclosure, the polymerizable compound represented by the general formula (2) is a compound represented by the general formula (1) wherein D ¹ and D ² in the general formula (2) are included in the polymerizable composition. The polymerizable liquid crystal compound represented by (1) may be appropriately selected and used so as to be the same as D ¹ and D ² of the polymerizable liquid crystal compound represented by the formula (2). These polymerizable compounds may be used alone or in a combination of two or more.
The content of the polymerizable compound represented by the general formula (2) contained in the polymerizable composition of the present disclosure is represented by the general formula (1) from the viewpoint of improving storage stability and orientation. In a total of 100% by mass of the polymerizable liquid crystal compound and the polymerizable compound represented by the general formula (2), the ratio of the polymerizable compound represented by the general formula (2) is 0.1% by mass to 33% by mass. It is preferable that the content is not more than mass%.

Further, examples of the combination of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2) contained in the polymerizable composition of the present disclosure include, for example, In the polymerizable liquid crystal compound represented by the formula (1), the structure of the biphenylene group having a side chain located between L ¹ and L ² is L ¹ in the polymerizable compound represented by the general formula (2). and a combination is identical to the structure of biphenylene group having a side chain that is located between the structure of biphenylene group having a side chain position, and the L ¹² and L ² between the L ^11. Specific combinations include, for example, the following combinations (i) to (xci). Note that Core in the table represents D ¹ , D ² , E ¹ and E in each biphenylene group of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2). ^In the table, D 1, D 2, E 1 and E ² are substituted positions of D ¹ , D ² and D ^{1 of} the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2). ² , E ¹ and E ² , and Lc ¹ in the table represents -L ¹ -A ^{1-of the} polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2). (L ³ -A ³ ) a group represented by _{m 1} -L ⁵ -R ^{sp 1} -Z ¹ , and ^{Lc 2} in the table represents a polymerizable liquid crystal compound represented by the general formula (1) and a compound represented by the general formula (2). ^-L 2 ^-A 2 polymerizable compound represented has _{^{- (L 4 -A 4) m2}} -L 5 -R sp1 -Z The group represented by the, Lc3 in the table, ^-L 11 ^-A 11 ^{-L 12} of polymerizable compound represented by the general formula (2) has - represents a divalent group represented by. In the following combinations (i) to (xci), the polymerizable compound represented by the general formula (2) is a compound in which n in the general formula (2) is 1.

  Further, of the combinations (i) to (xci) shown in Tables 8 and 9, typical ones are represented by the structural formula of the polymerizable liquid crystal compound represented by the general formula (1) and the general formula (2). Examples of the structural formula of the polymerizable compound represented by are shown below, but the invention is not limited thereto.

  The mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2) can be produced, for example, by the following 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, an example of a method for producing a mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2) will be described. The method is not limited.

For example, when L ¹ and L ² are each ** OCO— (* indicates the bonding position to the biphenylene group) and G ¹ is a hydrogen atom, the compound can be produced, for example, as follows. .
First, a compound represented by the formula (ip-1) into which 4,4'-dihydroxybiphenyl or a substituent E is further introduced is prepared, and an aldehyde group is introduced into a desired position by a duff reaction or the like (ip- Intermediate A represented by 2) is produced.

Next, an intermediate A represented by the formula (ip-2) and an intermediate B (A ¹ , L ³ , A ³ ) represented by HOOC-A ^1- (L ³ -A ³ ) _m1 -R ¹ , R ¹ , and m 1 have the same meanings as described above) by a condensation reaction or the like to obtain an intermediate C represented by the formula (ip-3). Further, the obtained intermediate C represented by the formula (ip-3) and intermediate D (A ² , L ⁴ ) represented by 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 an intermediate E represented by the formula (ip-4). In the case where the structures of the intermediate B and the intermediate D are the same, the intermediate E can be obtained by reacting the intermediate A with the intermediate B.

On the other hand, when synthesizing the intermediate C represented by the formula (ip-3), the intermediate A represented by the formula (ip-2) is added by further adding 1,4-cyclohexanedicarboxylic acid. HOOC-A ^1- (L ³ -A ³ ) _{m 1} -R ¹ , an intermediate B (A ¹ , L ³ , A ³ , R ¹ and m 1 have the same meanings as described above); The reaction with 1,4-cyclohexanedicarboxylic acid gives an intermediate F represented by the formula (ip-5), and furthermore, the obtained intermediate F represented by the formula (ip-5) and HOOC _{^{-A 2 - (L 4 -A 4}} ) intermediate represented by ^{m2 -R 2 D (a 2,} L 4, a 4, R 2, and m2 represents the same meaning as above) by reaction with And the intermediate G represented by the formula (ip-6) is obtained. When the structure of the intermediate B is the same as that of the intermediate D, the intermediate A is reacted with 1,4-cyclohexanedicarboxylic acid and the intermediate B to form an intermediate represented by the formula (ip-6). G can be obtained.

Next, an intermediate H represented by, for example, Q ¹ -J ¹ -NH ₂ is reacted with the intermediate E represented by the formula (ip-4) and the intermediate G represented by the formula (ip-6). Thereby, the compound represented by the formula (1-ex1) and the compound represented by the formula (1-ex2) can be obtained.

The intermediate A represented by the formula (ip-2) may be, for example, 3,4-methylenedioxyphenol (3,4-methylenedioxyphenol) depending on the types and substitution positions of E ¹ and E ² and the substitution positions of D ¹ and D ^2. The compound may be obtained by performing a Duff reaction to introduce an aldehyde group into Tokyo Chemical Industry Co., Ltd.) or a derivative thereof, and performing a Suzuki-Miyaura coupling reaction.

Further, for example, after obtaining an intermediate I in which D ¹ and D ^{2 serving} as side chains are previously introduced into the intermediate A represented by the formula (ip-2), HOOC-A is added to the intermediate I. ¹ - ^{(L ₃} -A _³⁾ intermediate ^B represented by ^{m1 -R 1 (a 1, L} 3, a 3, R 1, and m1 represents the same meaning as above) and, ^{HOOC-a 2} - ^{(L ₄} -A _⁴⁾ intermediate represented by ^{m2 -R 2 D (a 2,} L 4, a 4, R 2, and m2 represents the same meaning as above) by reacting the formula The compound represented by (1-ex1) may be obtained. Similarly, in the intermediate I, the intermediate B (A ¹ , L ³ , A ³ , R ¹ , and m ¹ represented by HOOC-A ^1- (L ³ -A ³ ) _m1 -R ¹ represents the same meaning), 1,4-cyclohexanedicarboxylic acid, and ^{HOOC-a 2 - (L 4} -A 4) intermediate ^D represented by ^{m2 -R 2 (a 2, L} 4, a 4, R ² and m2 represent the same meaning as described above) to obtain a compound represented by the formula (1-ex2).

  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 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-MS). TOFMS) and the like can be combined as appropriate.

In a mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2), the polymerizable liquid crystal compound represented by the general formula (1) content ratio of the polymerizable compound represented by the general formula (2) is, ^-L 11 ^-A 11 ^{-L 12} in the general formula (2) - compounds that induce a divalent group represented, That is, in the above-described example, it can be controlled by the amount of 1,4-cyclohexanedicarboxylic acid added.

3. Solvent The polymerizable composition of the present disclosure typically further contains a solvent 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.

  In the polymerizable composition of the present disclosure, the content of the solvent is not particularly limited, but from the viewpoint of coatability and storage stability, the solid content concentration of the polymerizable composition is 7% by mass or more. The content is preferably 9% by mass or less, more preferably 10% by mass or more and 45% by mass or less.

4. Photopolymerization initiator The polymerizable composition of the present disclosure preferably further contains a photopolymerization initiator.
In the present 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, borate compounds, 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 this embodiment, the content 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 accelerating the curing of the polymerizable compound. Preferably, it is 1 part by mass or more and 8 parts by mass or less.

5. Other Polymerizable Liquid Crystal Compounds The polymerizable composition of the present disclosure further has the general formula (1) in terms of adjusting retardation and reverse wavelength dispersion, adjusting alignment, solubility, and phase transition temperature. ) May contain other polymerizable liquid crystal compounds different from the polymerizable liquid crystal compounds represented by
The other polymerizable liquid crystal compound can be appropriately selected from conventionally known compounds and 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 reverse wavelength dispersion, or a polymerizable liquid crystal compound having substantially no wavelength dispersion (flat dispersion or low wavelength dispersion). May be. As the other polymerizable liquid crystal compound, for example, as examples of compounds exhibiting reverse wavelength dispersion, polymerizable liquid crystal compounds described in Patent Nos. 5,463,666, 4,186,981, 5,962,760, and 5,826,759 are exemplified. No. 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 on 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 represented by the following general formula (II-1) having the same structure as the main chain portion of the polymerizable compound, and a polymerizable liquid crystal compound represented by 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, for example, 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, and a (meth) acryloyl group. 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—, Ar ⁴ represents a benzene-1,4-diyl group, a cyclohexane-1,4-diyl group, a linking group represented by —OC (＝ O) — or —C (＝ O) —O—, 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 And 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 represent 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.
Further, the alkyl group having 1 to 6 carbon atoms in R ²⁴ and R ²⁵ in the general formula (III) may be any of linear, branched or cyclic, and includes, for example, a methyl group, an ethyl group, 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 particularly 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, in terms of orientation among _{others, -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.

As described above, since the polymerizable liquid crystal compound represented by the general formula (1) has a very good reverse wavelength dispersion, even if a compound having a wide wavelength dispersion is added, the cured product of the composition can be used. The phase difference value tends to show reverse wavelength dispersion. The polymerizable liquid crystal compound represented by the general formula (1) tends to have a relatively small Re (450) / Re (550) when the retardation value is measured as described above.
Therefore, as the other polymerizable liquid crystal compound, a ratio value (Re (550)) between an in-plane retardation (Re (450)) at a wavelength of 450 nm and an in-plane retardation (Re (550)) at a wavelength of 550 nm in the following test method. (450) / Re (550)) may further contain a polymerizable liquid crystal compound larger than Re (450) / Re (550) of the polymerizable liquid crystal compound represented by the general formula (1). It is preferable from the viewpoint of adjusting to ideal wavelength dispersion. As the other polymerizable liquid crystal compound, Re (450) / Re (550) can be selected from those having a ratio of 0.6 to less than 1.2, but a ratio of 0.8 to less than 1.2. It is preferable to select from those that are not less than 0.9 and less than 1.2.
[Test method]
A polymerizable composition in which 100 parts by mass of a polymerizable liquid crystal compound and 4 parts by mass of 2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one are dissolved in 900 parts by mass of cyclopentanone, After the rubbing treatment, a film having a cured film thickness of 1 μm is applied and formed on the alignment film of the glass with a polyimide alignment film, dried, and then irradiated with ultraviolet rays at a dose of 400 mJ / cm ^2. A retardation layer is formed, and an in-plane retardation Re (450) for a wavelength of 450 nm and an in-plane retardation Re for a wavelength of 550 nm are measured by a retardation measuring device (for example, product name: KOBRA-WR, manufactured by Oji Scientific Instruments). (550) is measured.
In addition, as the glass with a polyimide alignment film after the rubbing treatment, the same glass as that used in the test method performed on the polymerizable liquid crystal compound represented by the general formula (1) can be used.

  In the exemplary embodiment, the other polymerizable liquid crystal compound is contained in an amount of 20% by mass or more in at least one solvent selected from the group consisting of N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Dissolution is preferred in that the solvent solubility and storage stability of the polymerizable composition are improved. When the solvent solubility of the polymerizable composition is improved, when forming a coating film using the polymerizable composition, a uniform coating film is easily formed, and the load on the manufacturing process and the manufacturing apparatus for drying the solvent is increased. Is preferred because the liquid crystal phase transition temperature as a composition is widened, the process margin at the time of alignment is widened, and the alignment is more uniformly improved. .

In the present embodiment, the other polymerizable liquid crystal compounds can be used alone or in combination of two or more.
In the present embodiment, the content ratio of the other polymerizable liquid crystal compound may be appropriately adjusted in order to adjust a desired retardation or the like, and is not limited. 7 parts by mass or more and 49.9 parts by mass or less, more preferably 10 parts by mass or more and 45 parts by mass or less, more preferably 10 parts by mass or more and 42 parts by mass or less. More preferred.
The content ratio of the other polymerizable liquid crystal compound may be appropriately adjusted in order to adjust a desired retardation or the like. However, the content ratio of the polymerizable liquid crystal compound represented by the general formula (1) may be adjusted. The amount is preferably 50 parts by mass or less, more preferably 45 parts by mass or less, with respect to 100 parts by mass of the total amount of the polymerizable liquid crystal compound.

6. 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. Further, it does not exhibit liquid crystallinity by itself, but can be used in combination with the polymerizable liquid crystal compound represented by the general formula (1) to adjust retardation, reverse wavelength dispersion, phase transition temperature, hardness, and durability, Another polymerizable compound different from the polymerizable compound represented by the general formula (2) may be contained. These may be appropriately selected from conventionally known materials.

As the other polymerizable compound, a so-called polyfunctional monomer can also be used. For example, trimethylolpropane tri (meth) acrylate, tripropylene glycol di (meth) acrylate, diethylene glycol di (meth) acrylate, dipropylene glycol (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, ditrimethylolpropanetetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, tripentae Thritol 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, dicyclopentanedi (meth) acrylate, tricyclodecane di (meth) acrylate, ditrimethylolpropane tetra (meth) acrylate Acrylates and those obtained by modifying them with PO, EO, etc., are mentioned. 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.
In the case where the other polymerizable compound is used in the present embodiment, its content is preferably 40 parts by mass or less, and more preferably 30 parts by mass or less based on 100 parts by mass of the solid content of the polymerizable composition. More preferably, it is even more preferably 20 parts by mass or less.
In this embodiment, the other polymerizable compound is dissolved in at least 20% by mass of at least one solvent selected from the group consisting of N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. That, the solvent solubility and storage stability of the polymerizable composition is improved, and when forming a coating film using the polymerizable composition, a uniform coating film is easily formed and the solvent is dried. It is preferable because the load on the manufacturing process and the manufacturing apparatus is reduced, and the choice of usable base materials is expanded.

  In the polymerizable composition of the present disclosure, all the polymerizable liquid crystal compounds and polymerizable compounds contained therein are selected from the group consisting of N-methylpyrrolidone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. Dissolving at least 20% by mass in at least one solvent improves the solvent solubility and storage stability of the polymerizable composition, and enables uniform coating when forming a coating film using the polymerizable composition. This is preferable because the film can be easily formed, the load on the manufacturing process and the manufacturing apparatus for drying the solvent is reduced, and the choice of usable base materials is widened.

  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, TSF series manufactured by Momentive Performance Materials Japan, and Neos manufactured by Neos 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.

7. Method for Producing Polymerizable Composition The method for producing the polymerizable composition of the present disclosure is not particularly limited as long as the method is capable of obtaining the above-described polymerizable composition of the present disclosure. For example, a mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2), which is produced by the above-described production method, is further contained as necessary. By mixing with other components by a known method, the polymerizable composition of the present disclosure can be obtained.
When dissolving a mixture of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2) in a solvent, the temperature of the solution is set to 20 ° C. or higher and 60 ° C. The heating may be performed within the following range. If the temperature of the solution exceeds 80 ° C., the polymerizable liquid crystal compound may be polymerized or decomposed.

8. Applications The polymerizable composition of the present disclosure 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.

B. Retardation Film The retardation film of the present disclosure is a retardation film having a retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition of the present disclosure.
Since the retardation film of the present embodiment has a retardation layer containing a cured product of the polymerizable composition of the present disclosure, it has good orientation and a birefringence (Δn) as described above. It is large and has reverse wavelength dispersion.

  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. Means for expressing an alignment controlling force may be provided on the surface of the 2 ′ retardation layer 1 side.In the present disclosure, the alignment controlling force is an action of arranging the orientation components in the retardation layer in a specific direction. Say.

1. Retardation Layer The retardation layer 1 of the embodiment of the present disclosure contains a cured product of the polymerizable composition of the present disclosure, and has a point of birefringence (Δn), orientation, and reverse wavelength dispersion. From the viewpoint of properties, the retardation layer 1 of the embodiment of the present disclosure is preferably made of a cured product of the polymerizable composition of the present disclosure.
Here, the polymerizable composition of the present disclosure may be the same as that described in the polymerizable composition of the embodiment of the present disclosure, and a description thereof will not be repeated.

  In the retardation layer, the polymerizable liquid crystal compound represented by the general formula (1) has a main chain portion having orientation and a polymerizable liquid crystal compound which may be further contained, substantially with respect to the film surface. It is preferable that the resin be cured while being horizontally oriented. 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 liquid crystal compound represented by the general formula (1) is polymerized. Since the structure in which at least a part of the polymerizable functional groups of the polymerizable compound is polymerized is included, the durability of the retardation layer of the present embodiment is improved.

  The phase difference of the retardation layer can be measured by an automatic birefringence measuring 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 may have a structure in which at least a part of the polymerizable functional groups of the polymerizable liquid crystal compound represented by the general formula (1) contained in the polymerizable composition of the present disclosure is polymerized. Can be confirmed by collecting and analyzing a 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 contain 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 when exposed to light to react the polymerizable functional group of the polymerizable compound, may not be included in the retardation layer. .

The thickness of the retardation layer may be appropriately set depending on the application.
When the retardation film of the present disclosure is, for example, a wide-band quarter-wave plate, the obtained retardation film has Re (550) of 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. When a half-wave plate is used, the obtained optical film has a Re (550) of 250 nm or more and 300 nm or less, preferably 273 nm or more and 277 nm or less, and particularly preferably about 275 nm. The film thickness may be adjusted so as to be about the same.

The film thickness can be adjusted so as to give a desired retardation by appropriately adjusting the amount of the polymerizable composition applied and the concentration of the polymerizable liquid crystal compound. Since the retardation value (retardation value, Re (λ)) of the obtained retardation layer is determined as in the following equation, in order to obtain a desired Re (λ), it is necessary to adjust the film thickness d. Good.
Re (λ) = d × △ n (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 index 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.
Since the birefringence (Δn) of the polymerizable liquid crystal compound represented by the general formula (1) is large, it is possible to realize a phase difference with a thin film as compared with the related art.

  The wavelength dispersion characteristics of the retardation film of the present disclosure can be arbitrarily determined by the type and content of the polymerizable liquid crystal compound to be contained in the polymerizable composition of the present disclosure used for forming the retardation layer. When the content of the polymerizable liquid crystal compound represented by the general formula (1) is increased, the reverse wavelength dispersion characteristics tend to increase.

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, a horizontal alignment film is preferably used because the polymerizable composition of the embodiment of the present disclosure is likely to be 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 regulating 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, in addition to 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 preferable because it has high transparency and excellent mechanical properties.

The thickness of the base material used in the present embodiment is not particularly limited as long as the necessary self-supporting property can be imparted, depending on the use of the retardation film or the like, but is usually in the range of about 10 μm or more and about 1000 μm or less. It is.
In particular, 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 larger than the above range, for example, after forming a long retardation film, and then cut to form a single-leaf retardation film, processing waste increases, or the cutting blade is worn. This is because it may be 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 substrate and the ultraviolet curable resin, be visible and optically transparent, and allow ultraviolet light to pass therethrough. For example, a vinyl chloride / vinyl acetate copolymer system And urethane-based ones 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 the anchor coat layer requires a uniform and flexible film, 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 forming step);
A step of aligning at least the polymerizable liquid crystal compound represented by the general formula (1) in the formed polymerizable composition (alignment step);
After the aligning step, at least a step of polymerizing the polymerizable liquid crystal compound represented by the general formula (1) (polymerization step) is included, so that a phase difference layer is formed.
As the polymerizable composition, the same one as in the above-mentioned “A. Polymerizable composition” can be used, and the description is omitted here.

(1) Film-forming step of polymerizable composition A polymerizable composition is uniformly applied on a support to form a film.
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 substrate 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 represented by the general formula (1) 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 represented by the general formula (1) is oriented with the main chain portion having orientation and the other polymerizable liquid crystal compound further included as necessary, and 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.
As the heating means, known heating and drying means can be appropriately selected and used.
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 represented by the general formula (1) is polymerized. In the alignment step, for example, light irradiation is performed on the coating film fixed while maintaining the alignment state of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable liquid crystal compound that may be further included. By doing so, the polymerizable liquid crystal compound and the polymerizable compound in the coating film can be polymerized, and a retardation layer composed of a cured product of the polymerizable composition 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.

C. The transfer laminate 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 of the present disclosure,
This is a transfer laminate for transferring a retardation layer.

Since the retardation layer of the transfer laminate of the present embodiment contains the cured product of the polymerizable composition, the transfer laminate has good orientation and a birefringence (Δn) as described above. Is used for transferring a retardation layer having a reverse wavelength dispersion property. 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 ′ including only the retardation layer 1 illustrated in the example of FIG. 2 and the base material as illustrated in the example of FIG. 5 are not included. It is possible to provide a retardation film including the laminate 26 in which the alignment 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.
In one embodiment of the transfer laminate 20 shown in the example of FIG. 4, an alignment film 13 is provided on a second base material 12 as a retardation layer 11 and a support 15 that supports the retardation layer in a releasable manner. It has a stacked body. In the transfer laminate 20 shown in the example of FIG. 4, the peel strength at the interface between the second base material 12 and the alignment film 13 is larger than the peel strength at the interface between the alignment film 13 and the retardation layer 11. As a result, it is easy to peel off at the interface 17 between the alignment film 13 and the retardation layer 11. Therefore, the laminate in which the alignment film 13 is laminated on the second base material 12 can be peeled from the transfer laminate 20 transferred onto the transfer target as the peelable support 15. Only the phase difference layer 11 can be transferred as the transfer layer 16 including the phase difference layer.
One embodiment of the transfer laminate 30 shown in the example of FIG. 5 includes a retardation layer 21 and a second base material 22 as a support 25 that removably supports the retardation layer. An alignment film 23 is further provided between 21 and the second base material 22. In the transfer laminate 30 shown in the example of FIG. 5, the peel strength at the interface between the second substrate 22 and the alignment film 23 is smaller than the peel strength at the interface between the alignment film 23 and the retardation layer 21. As a result, it is easy to peel off at the interface 27 between the second base material 22 and the alignment film 23. Therefore, the second substrate 22 can be peeled from the transfer laminate 30 transferred onto the transfer target as a peelable support 25, and the laminate of the retardation layer 21 and the alignment film 23 can be peeled off. Can be transferred as a transfer layer 26 including a retardation layer.

  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 is determined by peeling the retardation layer and at which interface. can do. 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 retardation layer 31 and a second base material 32 as a support 35 that removably supports the retardation layer. . The second base material 32 can be peeled from the transfer laminate 40 transferred onto the transfer target as a peelable support 35, and only the retardation layer 31 is transferred including the retardation layer. It can be transferred as layer 36.

Hereinafter, the present embodiment will be described. However, the retardation layer can be the same as the retardation layer described in the above “B. Retardation film”, and the description is omitted here.
The alignment film and the substrate may be the same as the alignment film and the substrate described in the above “B. 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.

D. 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.

  The method for producing the 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 may be the same as that described in the above “C. 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.

E. FIG. 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.
The phase transition temperature of each of the manufactured liquid crystalline compounds was confirmed at the time of temperature increase by texture observation using a polarizing microscope (manufactured by Olympus, BX51) equipped with a temperature control stage. C represents a crystal, N represents a nematic phase, and I represents an isotropic liquid. For example, “C 130 N 180 I” indicates that a transition from a crystal to a nematic phase at 130 ° C. and a transition from a nematic phase to an isotropic liquid at 180 ° C.

[Production Example 1: Production of mixture 1 of compound 1-1 represented by formula (1-1) and compound 2-1 represented by formula (2-1)]
First, in a 500 mL eggplant flask, 27 g (150 mmol) of 4,4′-dihydroxybiphenyl represented by the formula (1-1-1) and 46 g (330 mmol) of hexamethylenetetramine are dissolved in 320 ml of trifluoroacetic acid. The reaction was performed for 3 hours. After the reaction was completed, 3 L of 4N hydrochloric acid was added in an ice bath, and the mixture was stirred overnight. After completion of the stirring, the precipitate was filtered. Water (1 L) was added to the obtained crude product, and the mixture was stirred for 1 hour and subjected to suspension purification. The precipitate was filtered and the obtained crystal was dried, whereby 7.5 g (21 mmol, 21% yield) of an intermediate 1 represented by the formula (1-1-2) was obtained.

  172 g (1.0 mol) of 1,4-cyclohexanedicarboxylic acid, 53 g of 6- (4-hydroxyphenyl) hexyl acrylate (200 mmol, manufactured by DKSH), 0.98 g (8.0 mmol) of N, N-dimethylaminopyridine (DMAP) Was added dropwise to a suspension of N, N-dicyclohexylcarbodiimide (DCC) 43 g (210 mmol) in dichloromethane (50 mL). 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 carboxylate derivative 1 represented by the formula (1-1-3) was synthesized by purifying the obtained crude product by open column chromatography.

  Next, 7.0 g (29 mmol) of the intermediate 1 represented by the formula (1-1-2) obtained above and 132 g (76 mmol) of the carboxylic acid derivative represented by the formula (1-1-3) N, N-dicyclohexyl was added to a suspension of 3.4 mg (0.02 mmol) of 1,4-cyclohexanedicarboxylic acid and 0.14 g (1.2 mmol) of N, N-dimethylaminopyridine (DMAP) in dichloromethane (70 mL). A solution of 19 g (90 mmol) of carbodiimide (DCC) in dichloromethane (14 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 12 hours, the precipitate was filtered, and then the solvent was distilled off. Chloroform (70 mL) was added to the obtained crude product, and the mixture was stirred for 1 hour and purified by suspension. The precipitate was filtered, and the obtained crystal was dried to obtain 23.0 g (22.0 mmol) of the intermediate 2A represented by the formula (1-1-4) and the intermediate 2A represented by the formula (2-1-1). A mixture with 0.02 g (0.014 mmol) of the represented intermediate 2B was obtained.

  25.0 g (150 mmol) of 2-hydrazinobenzothiazole and 7.5 g (225 mmol) of potassium hydroxide were added to N, N-dimethylformamide (450 mL), and heated at 80 degrees. After reaching a predetermined temperature, 46 g (180 mmol) of hexyl p-toluenesulfonate was added dropwise. After completion of the dropwise addition, the mixture was stirred for 4 hours. After the completion of the reaction, 50 ml of water was added for extraction, and the solvent was distilled off. The residue was purified by silica gel chromatography, and the solvent was distilled off, thereby obtaining 15.0 g (60 mmol, 40% yield) of an intermediate 3 represented by the formula (1-1-5).

  23.0 g (22.0 mmol) of the intermediate 2A represented by the formula (1-1-4) obtained above and the intermediate 2B represented by the formula (2-1-1) obtained above A mixture with 0.02 g (0.014 mmol) and 174 mg of 12N hydrochloric acid were dissolved in 115 mL of tetrahydrofuran, and 13.9 g (57.9 mmol) of intermediate 3 represented by the formula (1-1-5) was dissolved in 35 mL of tetrahydrofuran (35 mL). ) The solution was added dropwise. After completion of the dropwise addition, the mixture was stirred for 12 hours and then added dropwise to 580 ml of methanol. After the generated precipitate was filtered, the solvent was distilled off. Methanol (230 mL) was added to the obtained crude product, and the mixture was stirred for 1 hour and purified by suspension. The precipitate is filtered, and the obtained crystal is dried, whereby 30.1 g (20.0 mmol) of a compound 1-1 represented by the formula (1-1) and a compound represented by the formula (2-1) are represented. A mixture 1 with 0.03 g (0.013 mmol) of compound 2-1 was obtained.

<Compound 1-1>
Phase transition temperature (at elevated temperature): C 130 N 180 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.39 (s, 2H), 7.80 (s, 2H), 7.70 to 7.60 (m, 4H), 7.35 to 7.20 (m , 6H), 7.05-6.85 (m, 10H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4. 34 (t, 4H), 4.17 (t, 4H), 3.97 (t, 4H), 2.70-2.55 (m, 4H), 2.45-2.35 (m, 8H) , 1.95-1.65 (m, 20H), 1.55-1.30 (m, 20H), 0.88 (t, 6H).

<Compound 2-1>
_{^{1 H NMR (CDCl 3; δppm}} ): 8.39 (s, 4H), 7.80 (s, 4H), 7.70-7.60 (m, 8H), 7.35-7.20 (m , 12H), 7.05-6.85 (m, 12H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4. 34 (t, 8H), 4.17 (t, 4H), 3.97 (t, 4H), 2.70-2.55 (m, 6H), 2.45-2.35 (m, 12H) , 1.95-1.65 (m, 28H), 1.55-1.30 (m, 32H), 0.88 (t, 12H).

[Production Example 2: Production of mixture 2 of compound 1-1 represented by formula (1-1) and compound 2-1 represented by formula (2-1)]
In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 0.14 g (0.8 mmol), and Intermediate 2A 22 In a step of obtaining a mixture of 0.04 g (21.1 mmol) and 0.84 g (0.59 mmol) of intermediate 2B, and obtaining a mixture of compound 1-1 and compound 2-1, the obtained intermediate Compound represented by the formula (1-1) in the same manner as in Production Example 1 except that a mixture of 22.0 g (21.1 mmol) of 2A and 0.84 g (0.59 mmol) of intermediate 2B was used. A mixture 2 of 28.6 g (19.0 mmol) of 1-1 and 1.25 g (0.53 mmol) of the compound 2-1 represented by the formula (2-1) was obtained.

[Production Example 3: Production of mixture 3 of compound 1-1 represented by formula (1-1) and compound 2-1 represented by formula (2-1)]
In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 0.74 g (4.3 mmol), and Intermediate 2A 18 In a step of obtaining a mixture of 0.3 g (17.5 mmol) and 4.30 g (3.02 mmol) of the intermediate 2B, and obtaining a mixture of the compound 1-1 and the compound 2-1, the obtained intermediate A compound represented by the formula (1-1) in the same manner as in Production Example 1 except that a mixture of 18.3 g (17.5 mmol) of 2A and 4.30 g (3.02 mmol) of intermediate 2B was used. A mixture 3 of 23.7 g (15.8 mmol) of 1-1 and 6.38 g (2.72 mmol) of the compound 2-1 represented by the formula (2-1) was obtained.

[Production Example 4: Production of mixture 4 of compound 1-1 represented by formula (1-1) and compound 2-1 represented by formula (2-1)]
In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 1.15 g (6.7 mmol), and Intermediate 2A 15 In a step of obtaining a mixture of 2.6 g (15.0 mmol) and 6.64 g (4.67 mmol) of intermediate 2B, the intermediate obtained in the step of obtaining a mixture of compound 1-1 and compound 2-1 A compound represented by the formula (1-1) in the same manner as in Production Example 1 except that a mixture of 15.6 g (15.0 mmol) of 2A and 6.64 g (4.67 mmol) of intermediate 2B was used. A mixture 4 of 1-10.3 g (13.5 mmol) and 9.86 g (4.20 mmol) of the compound 2-1 represented by the formula (2-1) was obtained.

[Production Example 5: Production of mixture 5 of compound 1-2 represented by formula (1-2) and compound 2-2 represented by formula (2-2)]
In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 0.14 g (0.8 mmol), and Intermediate 2A 22 0.0g (21.1 mmol) and 0.84 g (0.59 mmol) of Intermediate 2B in a step of obtaining Intermediate 3 in the step of obtaining Hexyl p-toluenesulfonate instead of 1- (2- Using an equimolar amount of (bromoethoxy) butane, an intermediate 4 represented by the formula (1-2-5) is obtained and obtained in a step of obtaining a mixture of the compound 1-1 and the compound 2-1. Production Example 1 except that a mixture of 22.0 g (21.1 mmol) of the intermediate 2A and 0.84 g (0.59 mmol) of the intermediate 2B was used, and the intermediate 4 was used instead of the intermediate 3. In the same manner as described above, the conversion represented by the formula (1-2) A mixture 5 of 29.5 g (19.2 mmol) of the compound 1-2 and 1.55 g (0.64 mmol) of the compound 2-2 represented by the formula (2-2) was obtained.

<Compound 1-2>
Phase transition temperature (at elevated temperature): C 122 N 167 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.39 (s, 2H), 7.80 (s, 2H), 7.70 to 7.60 (m, 4H), 7.35 to 7.20 (m , 6H), 7.05-6.85 (m, 10H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4. 34 (t, 4H), 4.17 (t, 4H), 3.97 (t, 4H), 3.65-3.50 (m, 8H) 2.70-2.55 (m, 4H), 2.45-2.35 (m, 8H), 1.95-1.65 (m, 20H), 1.55-1.30 (m, 12H), 0.88 (t, 6H).

<Compound 2-2>
_{^{1 H NMR (CDCl 3; δppm}} ): 8.39 (s, 4H), 7.80 (s, 4H), 7.70-7.60 (m, 8H), 7.35-7.20 (m , 12H), 7.05-6.85 (m, 12H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4. 34 (t, 8H), 4.17 (t, 4H), 3.97 (t, 4H), 3.65-3.50 (m, 16H) 2.70-2.55 (m, 6H), 2.45-2.35 (m, 12H), 1.95-1.65 (m, 28H), 1.55-1.30 (m, 16H), 0.88 (t, 12H).

[Production Example 6: Production of mixture 6 of compound 1-3 represented by formula (1-3) and compound 2-3 represented by formula (2-3)]
To 180 ml of ethylene glycol, 42.7 g (220 mmol) of 2-amino-6-ethoxybenzothiazole was added. In an ice bath, 33.0 g (650 mmol) of hydrazine monohydrate and 17.4 g (500 mmol) of 12N hydrochloric acid were appropriately added, and the mixture was stirred at 130 ° C for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, 2750 ml of water was added, the precipitate was filtered, and the obtained crystal was dried to obtain 28.3 g (146.3 mmol, yield 65%) of Intermediate 5. Was.

  In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, the amount of 1,4-cyclohexanedicarboxylic acid added was changed to 0.14 g (0.8 mmol), and Intermediate 2A 22 In a step of obtaining a mixture of 0.04 g (21.1 mmol) and 0.84 g (0.59 mmol) of intermediate 2B and obtaining intermediate 3, the intermediate 5 was used in place of 2-hydrazinobenzothiazole. In the step of obtaining an intermediate 6 represented by the formula (1-3-5) and obtaining a mixture of the compound 1-1 and the compound 2-1, 22.0 g of the obtained intermediate 2A ( 21.1 mmol) and 0.84 g (0.59 mmol) of Intermediate 2B, and the same procedure as in Production Example 1 except for using Intermediate 6 in place of Intermediate 3 to obtain the compound of the formula (1 29.8 g of compound 1-3 represented by formula (3) A mixture 6 of 8.7 mmol) and 1.44 g (0.57 mmol) of the compound 2-3 represented by the formula (2-3) was obtained.

<Compound 1-3>
Phase transition temperature (when heated): C 147 N 241 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.39 (s, 2H), 7.80 (s, 2H), 7.52 (d, 2H), 7.21 (d, 2H), 7.05- 6.75 (m, 12H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4.34 (t, 4H), 4 .17 (t, 4H), 3.97 (t, 4H), 3.65 (t, 4H), 2.70-2.55 (m, 4H), 2.45-2.35 (m, 8H) ), 1.95-1.65 (m, 20H), 1.55-1.30 (m, 26H), 0.88 (t, 6H).

<Compound 2-3>
¹ H NMR (CDCl ₃ ; δ ppm): 8.39 (s, 4H), 7.80 (s, 4H), 7.52 (d, 8H), 7.21 (d, 4H), 7.05- 6.75 (m, 16H), 6.41 (dd, 2H), 6.25-6.10 (m, 2H), 5.83 (dd, 2H), 4.34 (t, 8H), 4 .17 (t, 4H), 3.97 (t, 4H), 3.65 (t, 8H), 2.70-2.55 (m, 6H), 2.45-2.35 (m, 12H) ), 1.95-1.65 (m, 28H), 1.55-1.30 (m, 44H), 0.88 (t, 12H).

[Production Example 7: Production of compound 1-1 alone represented by formula (1-1)]
In the production of Production Example 1, in the step of obtaining a mixture of the intermediate 2A and the intermediate 2B, the addition of 1,4-cyclohexanedicarboxylic acid was omitted to obtain a simple substance of the intermediate 2A, and the compound 1-1 was obtained. In the step of obtaining a mixture of the compound (2-1) and the compound (2-1), a compound of the formula (1) was prepared in the same manner as in Production Example 1 except that a simple substance of the intermediate 2A was used instead of the mixture of the intermediate 2A and the intermediate 2B. A simple substance of the compound 1-1 represented by -1) was obtained.

[Production Example 8: Production of mixture 7 of compound 1-1 represented by formula (1-1) and compound 1-2 represented by formula (1-2)]
In the production of Production Example 5, in the step of obtaining a mixture of the intermediate 2A and the intermediate 2B, the addition of 1,4-cyclohexanedicarboxylic acid was omitted to obtain the simple substance of the intermediate 2A, and the compound 1-2 In the step of obtaining a mixture of the compound (2-2) and the compound (2-2), a compound of the formula (1) was prepared in the same manner as in Production Example 5 except that a simple substance of the intermediate 2A was used instead of the mixture of the intermediates 2A and 2B. A simple substance of the compound 1-2 represented by -2) was obtained.
19.0 g (12.6 mmol) of the compound 1-1 represented by the formula (1-1) obtained in Production Example 7 and the compound 1 represented by the formula (1-2) obtained above -2 was mixed with 1.00 g (0.65 mmol) of a simple substance to obtain a mixture 7.

[Production Example 9: Production of compound 1-4 alone represented by formula (1-4)]
The compound 1-4 represented by the following formula (1-4) was obtained with reference to the synthesis of the compound 4 of Example 4 of Japanese Patent No. 5962760.

[Production Example 10: Production of mixture of compound 1-4 represented by formula (1-4) and compound 2-4 represented by formula (2-4)]
In the production of Production Example 1, in the step of obtaining a mixture of Intermediate 2A and Intermediate 2B, 2,5-dihydroxybenzaldehyde was used instead of Intermediate 1, and the amount of 1,4-cyclohexanedicarboxylic acid added Was changed to 0.14 g (0.8 mmol) to obtain a mixture of the intermediate 7A represented by the formula (1-4-1) and the intermediate 7B represented by the formula (2-4-1) In the step of obtaining a mixture of the compound 1-1 and the compound 2-1 in place of the mixture of the intermediate 2A and the intermediate 2B, 19.8 g (21.1 mmol) of the obtained intermediate 7A, 22.2 g (19.0 mmol) of the compound 1-4 represented by the formula (1-4) in the same manner as in Production Example 1 except that a mixture with 0.83 g (0.68 mmol) of the intermediate 7B was used. And 1.07 g of compound 2-4 represented by the formula (2-4) (0 .64 mmol).

[Example 1]
(1) Production of Polymerizable Composition 20 parts by mass of the mixture 1 obtained in Production Example 1 (19.98 parts by mass of a polymerizable liquid crystal compound (compound 1-1 represented by the formula (1-1)) was polymerized. A compound (a mixture of 0.02 parts by mass of the compound 1-2 represented by the formula (1-2)) and a photopolymerization initiator (2-methyl-1- (4-methylthiophenyl) -2-morpholinopro Pan-1-one: A mixture of 4 parts by mass of Irgacure 907) manufactured by Ciba Specialty Chemicals and 80 parts by mass of N-methylpyrrolidone was dissolved by heating at 45 ° C. for 30 minutes, and then to 25 ° C. By cooling, polymerizable composition 1 was produced.

(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-Hexamethoxymethyl melamine (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) Production 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 to form the polymerizable composition. Filmed. Then, after drying in an oven at a drying temperature of 140 ° C. for 120 seconds, ultraviolet rays (UV) were irradiated at a dose of 400 mJ / cm ² using an H bulb manufactured by Fusion to form a retardation layer. A retardation film or a laminate for transfer was obtained.

[Examples 2 to 6, Comparative Examples 1 to 4]
(1) Production of polymerizable composition Same as Example 1 except that in Example 1, mixture 2 to 8 or compound alone obtained in Production Examples 2 to 10 according to Table 10 below was used instead of mixture 1. Thus, polymerizable compositions 2 to 6 and comparative polymerizable compositions 1 to 4 were obtained.
(2) Production of retardation film or transfer laminate In Example 1, instead of polymerizable composition 1, polymerizable compositions 2 to 6 or comparative polymerizable compositions 1 to 4 were used. Except that the temperature was changed to 10, the same procedures as in Example 1 were performed to obtain retardation films or transfer laminates 2 to 6 and comparative retardation films or transfer laminates 1 to 4.

[Evaluation]
<Storage stability>
The polymerizable compositions obtained in each of the examples and comparative examples were stored at 25 ° C. for 50 days, and storage stability was evaluated by visually confirming precipitation of a precipitate after the start of storage.
(Evaluation criteria for storage stability)
AA: No precipitate was deposited even after storage for 50 days.
A: A precipitate was deposited in 30 days or more and less than 50 days.
B: A precipitate was deposited in 7 days or more and less than 30 days.
C: A precipitate was deposited in one day or more and less than seven days.
D: A precipitate was deposited in less than one day.

<Orientation>
The polymerizable composition obtained in each example and each comparative example was stored at 25 ° C. for 50 days, and the phase difference performed in each of the above examples and each comparative example, except that the polymerizable composition after storage was used. In the same manner as in the production of the film or the transfer laminate, a retardation film for evaluating orientation was prepared. The PET substrate of the obtained retardation film for orientation evaluation was peeled off, and a sample in which the retardation layer and the horizontal alignment film were transferred to an adhesive glass was prepared. Was evaluated.
(Evaluation criteria for orientation)
A: Uniform orientation is obtained visually, and no defects are observed by observation with a polarizing microscope.
B: Uniform orientation was obtained by visual observation, and the orientation area was 90% or more by observation with a polarizing microscope, but slight defects were observed.
C: The orientation as large as B was not obtained by visual observation, and the orientation area by observation with a polarizing microscope was 50% or more and less than 90%.
D: No orientation by visual observation, and orientation area by polarization microscope observation is less than 50%.

<Wavelength dispersion (phase difference)>
The PET substrate of the retardation film obtained in each example and each comparative example was peeled off, and a sample in which the retardation layer and the horizontal alignment film were transferred to an adhesive glass was produced. Using the produced sample, the in-plane retardation Re of the retardation layer at 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)
(Evaluation criteria for wavelength dispersion)
A: 0.6 ≦ x <0.90, 1 <y ... reverse wavelength dispersion B: 0.90 ≦ x <0.95, 1 <y ... reverse wavelength dispersion C: 0.95 ≦ x <1, 1 <y
D: 1 ≦ x, 1 ≧ y: Normal dispersibility

<Birefringence index>
The in-plane retardation Re at 550 nm of the retardation layer was measured using a sample similar to the sample used in the evaluation of the wavelength dispersion. Since there is a relationship of retardation Re (λ) = birefringence Δn (λ) × film thickness d, the birefringence index 、 ５n at 550 nm of the retardation layer at 550 nm from the in-plane retardation Re at 550 nm and the film thickness d. Was evaluated.
(Evaluation criteria for birefringence)
A: Δn is 0.08 or more B: Δn is 0.075 ≦ x <0.08
C: Δn is less than 0.075

In addition, glass with a polyimide alignment film after rubbing treatment [Product name: alignment-treated glass substrate, manufactured by EC Corporation, and the alignment-treated glass substrate is coated with polyimide LX-1400 manufactured by Hitachi Chemical Co., Ltd. and rubbed. . And the comparative polymerizable composition 1 obtained in Comparative Example 1 and the comparative polymerizable composition 3 obtained in Comparative Example 3 were applied such that the film thickness after curing became 1 μm. A film was formed. Then, after drying in an oven at a drying temperature shown in Table 10 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 transfer laminate was obtained.
When the in-plane retardation Re of the formed retardation layer was measured in the same manner as in the evaluation of the wavelength dispersibility, the comparative polymerizable composition 1 containing the compound 1-1 and the comparative polymerizable composition containing the compound 1-4 were obtained. In each of No. 3, the wavelength dispersibility was “A” based on the above evaluation criteria.

As shown in Table 10, the polymerizable compositions 1 to 6 of Examples 1 to 6 each containing a combination of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2). It has been found that has improved storage stability, has a large birefringence (Δn), has reverse wavelength dispersion, and can form a retardation layer with improved orientation.
In Comparative Examples 1 and 2, since the polymerizable compound represented by the general formula (2) was not used, the storage stability of the polymerizable composition was poor, and the orientation of the retardation layer was also poor.
Comparative Examples 3 and 4 did not use any of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2), and used a conventional polymerizable liquid crystal compound as the polymerizable liquid crystal compound. Since the compound 1-4 represented by the formula (1-4), which is a crystalline liquid crystal compound, is used, the birefringence of the retardation layer is small, the storage stability of the polymerizable composition is poor, and the orientation of the retardation layer is low. Was also inferior.

DESCRIPTION OF SYMBOLS 1 Retardation layer 2, 2 'base material 3 Orientation film 10, 10', 10 "Retardation film 11, 21, 31 Retardation layer 12, 22, 32 Second base material 13, 23, 33 Orientation film 15, 25, 35 Peelable supports 16, 26, 36 Transfer layer 17 including retardation layer 17 Interface between alignment film and retardation layer 27 Interface between second base material and alignment film 20, 30, 40 Transfer lamination Body 50 polarizing plate 60 optical member 71 transparent electrode layer 72 light emitting layer 73 electrode layer 100 light emitting display

Claims (9)

A polymerizable composition containing a polymerizable liquid crystal compound represented by the following general formula (1) and a polymerizable compound represented by the following general formula (2).

(In the general formulas (1) and (2), 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 -, - OCO-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;
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, A cycloheptane-1,4-diyl group, a cycloheptane-1,3-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-1,4-diyl group, cycloheptane-1,3-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 a single ^{bond, R sp1} represents an alkylene group or a single bond having 1 to 20 carbon atoms, one -CH ₂ in the alkylene group - or nonadjacent two or more -CH ₂ - Are each independently replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C≡C-. Z ¹ may represent a polymerizable functional group.
D ¹ and D ² each independently represent a group selected from the following general formula (D-1), and a plurality of D ¹ and D ² in the general formula (2) are the same, and the general formula (D-1) In the formula (1) and the formula (2), D ¹ and D ² are the same,
The substituents E, E ¹ and E ² 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 Group, 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, and one of- 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- H = CH-, -CH = CH-, -CF = CF- or -C≡C-, and any hydrogen atom in the alkyl group may be replaced by a fluorine atom; Alternatively, substituents E, ^{E 1} and ^{E 2} are each ^{independently,} may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are each said ^{L 5, R sp1,} and represent those same as defined in ^{Z 1,} each of the ^{L 5, R sp1,} and ^{Z 1} and may be the same or different and the compound When a plurality of substituents E, E ¹ and E ² are present, each may be the same or different,
L ¹¹ and L ¹² each independently represent the same as defined in L ^{1 to} L ⁴ , but may be the same or different from L ^{1 to} L ⁴ ,
A ¹¹ represents the same as defined in A ^{1 to} A ² , but may be the same as or different from A ^{1 to} A ² ,
In each of the general formula (1) and the general formula (2), when a plurality of L ³ , L ⁴ , L ¹¹ , L ¹² , A ³ , A ^4, and A ¹¹ are present, each is the same. L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , R ¹ , R ² , E ¹ and E ² are the same in the general formulas (1) and (2). Or different.
m1 and m2 each independently represent an integer of 1 to 4; n1 and n2 each independently represent an integer of 0 to 3; n represents an integer of 1 or more; N1 and n2 may be the same or different. In general formulas (1) and (2), m1, m2, n1 and n2 may be the same or different. Is also good. )
(In the general formula (D-1), G ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is unsubstituted or substituted by one or more substituents E. May be
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;
J ¹ is, -O -, - S -, - COO -, - OCO -, - OCO-O -, - NQ 2 -, - N = CQ 2 -, - CO-NQ 2 -, - OCO-NQ 2 — Or —O—NQ ² —, wherein Q ² is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, or an aromatic group. the organic group of 2 to 30 carbon atoms having a ring, or ^{- (L} 6 _-A ⁵⁾ represents a q ^{-L 7 -R} sp2 -Z ^2, the alkyl group, cycloalkyl group, cycloalkenyl group, and an aromatic ring May each be unsubstituted or substituted with one or more substituents E, and the alkyl group may be substituted with the cycloalkyl group or cycloalkenyl group, One —CH ₂ — or adjacent Two or more —CH ₂ — that are not independently represent —O—, —S—, —CO—, —COO—, —OCO—, —CO—S—, —S—CO—, and —SO— _2- , -O-CO-O-, -CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO- CH = CH -, - CH = CH -, - CF = CF- or may be replaced with -C≡C-, said cycloalkyl group or one -CH during cycloalkenyl group ₂ - or adjacent Two or more —CH ₂ — that are not each may be independently replaced with —O—, —CO—, —COO—, —OCO—, or —O—CO—O—, L ⁶ , A ⁵ , L ⁷ , R ^sp2 , and Z ² are the aforementioned L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^{sp1, respectively.} , And Z ¹ , which are the same or different from L ^{1 to} L ⁴ , A ^{3 to} A ⁴ , L ⁵ , R ^sp1 , and Z ¹ , respectively. In addition, q represents an integer of 0 to 4, and when a plurality of L ⁶ and A ⁵ are present, they may be the same or different. Further, Q ¹ and Q ² may combine to form a ring. )   The polymerizable composition according to claim 1, wherein in the polymerizable compound represented by the general formula (2), n in the general formula (2) is 1.   In a total of 100% by mass of the polymerizable liquid crystal compound represented by the general formula (1) and the polymerizable compound represented by the general formula (2), the polymerizable compound represented by the general formula (2) The polymerizable composition according to claim 1, wherein a ratio of the polymerizable composition is 0.1% by mass or more and 33% by mass or less.   A retardation film having a retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition according to any one of claims 1 to 3. A step of forming a film of the polymerizable composition according to any one of claims 1 to 3,
At least aligning the polymerizable liquid crystal compound represented by the general formula (1) in the formed polymerizable composition;
A method for producing a retardation film, comprising: after the step of aligning, at least a step of polymerizing the polymerizable liquid crystal compound represented by the general formula (1), thereby including a step of forming a retardation layer. 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 any one of claims 1 to 3,
Transfer laminate for transfer of retardation layer.   An optical member comprising a polarizing plate on the retardation film according to claim 4. A retardation layer, comprising a support that releasably supports the retardation layer, wherein the retardation layer contains a cured product of the polymerizable composition according to any one of claims 1 to 3. 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,
A method for producing an optical member, comprising:   A display device comprising the retardation film according to claim 4 or the optical member according to claim 7.