JP2020042088A - Polymerizable composition, polymer, retardation film, method of manufacturing the same, transfer laminate, optical member, method of manufacturing the same, and display device - Google Patents

Abstract

To provide a polymerizable composition which exhibits good solution stability as well as inverse wavelength dispersibility.SOLUTION: A polymerizable composition is provided, containing a polymerizable liquid crystal compound (A) having a biphenyl group, and a polymerizable liquid crystal compound (B) represented by a formula (2-2).SELECTED DRAWING: None

Description

  The present disclosure relates to a polymerizable composition, a polymer, 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, in order to form a retardation layer having reverse wavelength dispersion with one layer, the reverse wavelength dispersion which realizes the characteristic of making the wavelength dispersion of the birefringence (△ n) small or reverse is realized. The following 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 It is generally said that when the slope of the liquid crystal compound is positive (increased to the right), the wavelength dispersion of the birefringence is opposite, or the liquid crystal compound of the material constituting the retardation film exhibits the reverse wavelength dispersion. Has been done.

  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), and thus has a desired retardation (Re (λ) = birefringence Δn (λ). In order to obtain (1) × film thickness d), it was necessary to increase the film thickness. In addition, conventional liquid crystal compounds exhibiting reverse wavelength dispersion have low solubility in organic solvents as a whole, and when forming a coating film by dissolving in an organic solvent and applying ink, it is difficult to form a uniform coating film. In addition, there has been a problem that a load on a manufacturing process or a manufacturing apparatus for drying a large amount of solvent is increased.

  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.

  Patent Document 6 discloses that since the transmittance in the visible region is high and the liquid crystal phase retention time at room temperature is long, it is easy to handle and the wavelength dispersion characteristics can be controlled without a complicated process. As a polymerizable liquid crystal composition capable of producing an optically anisotropic film exhibiting low wavelength dispersion characteristics and reverse wavelength dispersion characteristics; Discloses a polymerizable liquid crystal composition containing a compound represented by the formula (1) having an aromatic ring. In Patent Document 6, by using the polymerizable liquid crystal composition, the birefringence Δn (450) for light having a wavelength of 450 nm and the birefringence Δn (550) for light having a wavelength of 550 nm are Δn (450) / It is described that an optically anisotropic film satisfying the relationship of Δn (550) ≦ 1.05, that is, an optically anisotropic film having low wavelength dispersion characteristics and reverse wavelength dispersion characteristics can be produced. However, Δn (450) / Δn (550) realized by the compound represented by the formula (1) in Patent Document 6 is at least 0.996, and is at most low wavelength dispersion (flat wavelength dispersion). ) Is obtained, and the reverse wavelength dispersion of less than 0.99 is not obtained. Further, in the case of a structure in which an aromatic ring is bonded directly or via a double bond to the 2- or 3-position of 1,4-phenylene disclosed in Patent Document 6, when the solubility in an organic solvent is still insufficient There is. In the examples of Patent Document 6, although the compound represented by the formula (1) of Patent Document 6 is shown to have high solvent solubility, a solvent containing an alkylene group between the ring structures in the long axis direction contains a solvent. A high solvent solubility is realized by adopting a liquid crystal structure with high solubility. Further, in a polymerizable liquid crystal composition containing the compound represented by the formula (1) of Patent Document 6, as shown in a comparative example described later, the compound is easily precipitated during storage, and the stability is insufficient. There was a problem that was. The stability of the composition (ink) is an important performance in producing an optically anisotropic film.

  For example, in a quarter wavelength plate, if ideal reverse wavelength dispersion can be obtained, 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 exhibiting reverse wavelength dispersion is not enough to exhibit ideal reverse wavelength dispersion by itself, and it is desired to approach the ideal reverse wavelength dispersion. Therefore, the solvent dispersibility is good, the ink is hardly deposited, the stability of the ink (solution stability) is good, and the wavelength dispersion characteristics can be adjusted so as to approach ideal wavelength dispersion characteristics. There has been a demand for a polymerizable liquid crystal composition having the following formula:

JP-A-10-68816 JP 2001-4837 A JP 2010-522893 A Japanese Patent No. 5962760 International Publication No. 2014/061709 JP-A-2006-166344

  Embodiments of the present disclosure have been made in view of the above-described circumstances, and have good solution stability, a polymerizable composition exhibiting reverse wavelength dispersion, a polymer obtained by polymerizing the polymerizable composition, and a polymerizable polymer. A retardation film having a retardation layer containing a cured product of the 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 the transfer laminate were used. It is an object to provide a method for manufacturing an optical member and a display device.

  One embodiment of the present disclosure includes a polymerizable liquid crystal compound (A) represented by the following general formula (1) and a polymerizable liquid crystal compound (B) represented by the following general formula (2). A composition is provided.

(In the general formula (1), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- or 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 formula (D _g -1);
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, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, 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-, -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- may be replaced with, or substituents E, ^{E 1} and E ² each independently ^may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the ^{L 5, R sp1} and, It represents the same as defined for Z ¹ , but may be the same as or different from L ⁵ , R ^sp1 and Z ¹ , respectively, and the substituents E, E ¹ and E ² in the compound May be the same or different, respectively.
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 and n2 each independently represent an integer of 0 to 3. )

(In the general formula (D _g -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, each may be the same or different. Alternatively, Q ¹ and Q ² may combine to form a ring. )

(In the general formula (2), A ^core is a monocyclic ring, a condensed ring or a ring-assembled aromatic group which may be unsubstituted or substituted by one or more substituents E ³ , and has 4 carbon atoms. Represents a trivalent or tetravalent group of ~ 16,
M represents -CH = CH-, -N = CH-, -CH = N-, or -N = N-;
D ³ represents a monovalent group containing an indolenine ring structure,
L ¹¹ , L ¹² , L ¹³ and L ¹⁴ 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-CH 2 -, _{-CH 2 -COO -, - CH 2} -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF ＣＦCF—, —C≡C— or a single bond;
A ¹¹ and A ¹² each independently represent a cyclohexane-1,4-diyl group or a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . A cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ¹³ and A ¹⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . , Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- 2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3- Represents a dioxane-2,5-diyl group,
R ¹¹ and R ¹² each independently represent a group selected from the following formula (R-11);
Formula ^{(R-11): -L 15} -R sp11 -Z 11
In the general formula ^(R-11), L 15 _{is, -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-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 SP11} 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 Each independently represents -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C−C- Z ¹¹ represents a polymerizable functional group.
The substituent E ³ is 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, a dimethylamino group , A diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, one —CH ₂ — in the alkyl group 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- be replaced well, or substituents ^{E 3 is} represented by -L ^{E3 -R} spE3 ^{-Z E3} may represent that group, wherein ^{L E3, R SPE3,} and ^{Z E3,} respectively, wherein ^{L 15, R SP11,} and ^{Z 11} represents what is the one and the same defined, each of the ^{L 15} , R ^sp11 and Z ¹¹ may be the same or different, and when there are a plurality of substituents E ³ in the compound, they may be the same or different;
When a plurality of M, D ³ , L ¹³ , L ¹⁴ , A ¹³ , and A ¹⁴ appear, they may be the same or different.
n11 represents an integer of 1 or 2, and m11 and m12 each independently represent an integer of 1 to 4. )

One embodiment of the present disclosure provides a polymerizable composition, wherein in the general formula (2), the D ³ represents a group selected from the following general formula (D _g -2).

(In the general formula (D _g -2), R ^d1 and R ^d2 each independently represent an alkyl group having 1 to 20 carbon atoms, and the alkyl group is unsubstituted or one or more of the above substituted groups. may be substituted by a group E ^3, 1 single -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 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Alternatively, R ^d1 and R ^d2 may combine with each other to form a 3- to 7-membered non-aromatic hydrocarbon ring And the non-aromatic hydrocarbon ring may be unsubstituted or substituted by one or more substituents E ³ , and any carbon atom of the non-aromatic hydrocarbon ring may be May be substituted with a hetero atom,
And ^{R e1,} R e2, R ^e3 and ^{R e4} are each independently a hydrogen atom, or wherein a substituent ^{E 3, R e1, R e2} , R e3 and ^{R e4} are 3-7 membered ring bonded to each other It may form a non-aromatic or aromatic hydrocarbon ring, optionally substituted by the non-aromatic or aromatic hydrocarbon ring or is unsubstituted or one or more of the substituents E ³ Also, any carbon atom of the non-aromatic or aromatic hydrocarbon ring may be substituted with a hetero atom. * (Asterisk) indicates the bonding position with M. )

In one embodiment of the present disclosure, in the general formula (D _g -1) of the general formula (1), J ¹ is -O-, -S-, -N = CQ ² -or -NQ ^2- . Certain polymerizable compositions are provided.

In one embodiment of the present disclosure, in the general formula (D _g -1) of the general formula (1), J ¹ is —NQ ² —, and the Q ² is a hydrogen atom substituted with a fluorine atom. At best, one -CH ₂ - or nonadjacent two or more -CH ₂ - independently are each -O -, - CO -, - COO -, - OCO- may be replaced by A polymerizable composition which is a linear or branched alkyl group having 2 to 20 carbon atoms or a cycloalkyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group which may be substituted by the cycloalkyl group; I will provide a.

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

  One embodiment of the present disclosure provides a polymer obtained by polymerizing the polymerizable composition of the one embodiment of the present disclosure.

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

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

One embodiment of the present disclosure includes a retardation layer, and a support that releasably supports the retardation layer,
The retardation layer contains a cured product of the polymerizable composition 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, the solution stability is good, a polymerizable composition exhibiting reverse wavelength dispersion, a polymer obtained by polymerizing the polymerizable composition, a cured product of the polymerizable composition. A retardation film having a retardation layer including the same and a method for producing the same, a transfer laminate capable of transferring the retardation layer, an optical member having the retardation film, a method for producing an optical member using the transfer laminate, In addition, 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, the alignment regulating force refers to an action of arranging a liquid crystal compound in a retardation layer in a specific direction.
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 includes a polymerizable liquid crystal compound (A) represented by the following general formula (1) and a polymerizable liquid crystal compound (B) represented by the following general formula (2). including.

(In the general formula (1), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- or 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 formula (D _g -1);
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, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, 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-, -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- may be replaced with, or substituents E, ^{E 1} and E ² each independently ^may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the ^{L 5, R sp1} and, It represents the same as defined for Z ¹ , but may be the same as or different from L ⁵ , R ^sp1 and Z ¹ , respectively, and the substituents E, E ¹ and E ² in the compound May be the same or different, respectively.
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 and n2 each independently represent an integer of 0 to 3. )

(In the general formula (D _g -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, each may be the same or different. Alternatively, Q ¹ and Q ² may combine to form a ring. )

(In the general formula (2), A ^core is a monocyclic ring, a condensed ring or a ring-assembled aromatic group which may be unsubstituted or substituted by one or more substituents E ³ , and has 4 carbon atoms. Represents a trivalent or tetravalent group of ~ 16,
M represents -CH = CH-, -N = CH-, -CH = N-, or -N = N-;
D ³ represents a monovalent group containing an indolenine ring structure,
L ¹¹ , L ¹² , L ¹³ and L ¹⁴ 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-CH 2 -, _{-CH 2 -COO -, - CH 2} -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF ＣＦCF—, —C≡C— or a single bond;
A ¹¹ and A ¹² each independently represent a cyclohexane-1,4-diyl group or a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . A cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ¹³ and A ¹⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . , Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- 2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3- Represents a dioxane-2,5-diyl group,
R ¹¹ and R ¹² each independently represent a group selected from the following formula (R-11);
Formula ^{(R-11): -L 15} -R sp11 -Z 11
In the general formula ^(R-11), L 15 _{is, -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-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 SP11} 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 Each independently represents -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C−C- Z ¹¹ represents a polymerizable functional group.
The substituent E ³ is 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, a dimethylamino group , A diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, one —CH ₂ — in the alkyl group 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- be replaced well, or substituents ^{E 3 is} represented by -L ^{E3 -R} spE3 ^{-Z E3} may represent that group, wherein ^{L E3, R SPE3,} and ^{Z E3,} respectively, wherein ^{L 15, R SP11,} and ^{Z 11} represents what is the one and the same defined, each of the ^{L 15} , R ^sp11 and Z ¹¹ may be the same or different, and when there are a plurality of substituents E ³ in the compound, they may be the same or different;
When a plurality of M, D ³ , L ¹³ , L ¹⁴ , A ¹³ , and A ¹⁴ appear, they may be the same or different.
n11 represents an integer of 1 or 2, and m11 and m12 each independently represent an integer of 1 to 4. )

Since the compound represented by the general formula (1) of the present disclosure has a specific structure in the main chain structure from the specific R ¹ to R ² , the orientation between molecules is improved, and the liquid crystallinity alone is improved. It is a compound which shows. Further, the compound represented by the general formula (1) of the present disclosure is a polymerizable liquid crystal compound because it has a polymerizable group at a terminal.
The compound represented by the general formula (1) of the present disclosure has high orientation between molecules due to a biphenylene group contained in a main chain portion, and further has two biphenylene groups, one for each of the two benzene rings. Since it has a side chain, it becomes a liquid crystal compound having a large birefringence (Δn) while having reverse wavelength dispersion.
Since the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure has a large birefringence (Δn) and reverse wavelength dispersion, a desired reverse wavelength dispersion can be obtained with a small amount of use. It is possible to obtain a retardation layer having a thinner retardation layer.
Compounds having reverse wavelength dispersibility generally have poor solubility, but the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure has oils in A ¹ and A ² close to the biphenylene group. By introducing a cyclic hydrocarbon group, the reduced solubility can be improved. However, the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure requires further improvement in solubility.

On the other hand, since the compound represented by the general formula (2) of the present disclosure has a specific structure in the main chain structure from the specific R ¹¹ to R ¹² , the orientation between molecules is good, and Is a compound showing liquid crystallinity. Further, the compound represented by the general formula (2) of the present disclosure is a polymerizable liquid crystal compound because it has a polymerizable group at a terminal.
The compound represented by the general formula (2) of the present disclosure has an indolenine ring structure in a side chain portion via a double bond, so that a compound having an opposite wavelength as compared with a conventional case having an aromatic ring is obtained. Dispersibility is easily exhibited, the solubility in a solvent is improved, and precipitation is difficult, and the stability of the ink is improved.
The indolenine ring structure has an sp3 carbon atom to which R ^d1 and R ^d2 are bonded as in the following general formula (d _g ). When the side chain portion has an indolenine ring structure through a double bond due to the effect of the sp3 carbon atom to which R ^d1 and R ^d2 are bonded, the directionality of the π-conjugated system of the side chain portion is It is presumed that the liquid crystal compound is easily adjusted in the short axis direction, the absorption in the short axis direction of the liquid crystal compound is easily expanded in a long wavelength region, and the liquid crystal compound exhibits reverse wavelength dispersion and flat wavelength dispersion.
The compound having a conventional reverse wavelength dispersion, flat wavelength dispersion property is poor generally soluble, but the compound represented by the general formula of the present disclosure (2) is, A ¹¹ and A adjacent to the core portion ¹² , an alicyclic hydrocarbon group is introduced, and further, by having an sp3 carbon atom to which the R ^d1 and R ^d2 are bonded, solvent solubility is improved, and further, an sp3 carbon atom to which the R ^d1 and R ^d2 are bonded. Precipitation is difficult to deposit due to the three-dimensional structure of the atoms, and the stability of the ink is improved.
Since the polymerizable liquid crystal compound (B) represented by the general formula (2) of the present disclosure has good solvent solubility, it is dissolved in an organic solvent to prepare an ink, and a coating film is formed using the ink. In this case, a uniform coating film is easily formed, and the load on the manufacturing process and the manufacturing apparatus for drying the solvent is reduced.

(In the general formula (d _g ), R ^d1 and R ^d2 each independently represent an alkyl group having 1 to 20 carbon atoms, and the alkyl group is unsubstituted or one or more of the substituents E may be substituted by ^3, 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 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH -COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Alternatively, R ^d1 and R ^d2 may be bonded to each other to form a 3- to 7-membered non-aromatic hydrocarbon ring. Even if good, the non-aromatic hydrocarbon ring may be substituted by one or one or more of the substituents E ³ is an unsubstituted, any carbon atoms of the non-aromatic hydrocarbon ring hetero It may be substituted by an atom.)

As described above, although the solvent solubility is required to be further improved, the polymerizable liquid crystal compound (A) represented by the general formula (1) having a large birefringence (△ n) and exhibiting reverse wavelength dispersion, By containing the polymerizable liquid crystal compound (B) represented by the general formula (2), which has good solvent solubility, hardly precipitates and has improved solution stability, and exhibits flat wavelength dispersion and reverse wavelength dispersion, The polymerizable compositions of the present disclosure complement each other's strengths, and can be a polymerizable composition having good solution stability and exhibiting reverse wavelength dispersion.
The polymerizable composition of the present disclosure has a large birefringence (Δn) and a birefringence (Δn) by a polymerizable liquid crystal compound (A) represented by the general formula (1) that exhibits reverse wavelength dispersion. Can also be increased.
Since the polymerizable composition of the present disclosure includes the polymerizable liquid crystal compound (A) having a large birefringence (△ n) and having reverse wavelength dispersion, the polymerizable liquid crystal compound (B) may further include, if necessary, By mixing other liquid crystal compounds, it is possible to adjust the phase difference so as to exhibit a desired reverse wavelength dispersion.

  In addition, the polymerizable composition of the present disclosure improves the alignment by using a composition of the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B). This is considered to be because the polymerizable composition of the present disclosure has a wide liquid crystal phase transition temperature as a composition, a process margin at the time of alignment is widened, and a liquid crystal state is easily obtained. Furthermore, the polymerizable composition of the present disclosure is a composition of the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B). By improving the compatibility and the orientation, a retardation layer having excellent in-plane uniformity of retardation value can be obtained.

1. Polymerizable liquid crystal compound (A) represented by the general formula (1)
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 appear independently of each other, they may be the same or different.

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

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

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

Among these, A ¹ and A ² are each independently unsubstituted or have at least one substitution, because they improve liquid crystallinity and facilitate the improvement of the orientation of the polymer. A cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group, a cycloheptane-1,3-diyl group or a cycloheptane-1,4-diyl group which may be substituted by the group E; More preferably, it is particularly preferably a cyclohexane-1,4-diyl group which is unsubstituted or optionally substituted by one or more substituents E.

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

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

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

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

The substituents E are each independently a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a pentafluorosulfuranyl group, a nitro group, a cyano group, an isocyano group, an amino group, a hydroxyl group, a mercapto group, a methylamino group, Represents a dimethylamino group, a diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by one of the above. , - - or nonadjacent two or more -CH ₂ - - -O are each independently -CH ₂ a 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- may be replaced with, or substituents E are each independently, -L ^E —R ^spE —Z ^E may be represented by a group represented by L ^E , R ^spE , and Z ^E , which are respectively the same as those defined by L ⁵ , R ^sp1 , and Z ¹ described below. Which may be the same as or different from L ⁵ , R ^sp1 , and Z ¹ , respectively, and when there are a plurality of substituents E in the compound, they may be the same or different. May be. The alkyl group having 1 to 20 carbon atoms may be linear or branched.

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-, 1 to 20 carbon atoms which may be substituted by a group selected from -COO-, -OCO-, -O-CO-O-, -CH = CH-, -CF = CF- or -C≡C-. 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 substituted by a group selected from -O-, -COO- or -OCO-, and a fluorine atom, a chlorine atom Or, more preferably, any hydrogen atom represents a linear or branched alkyl group or an alkoxy group having 1 to 12 carbon atoms which may be substituted with a fluorine atom, and a fluorine atom, a chlorine atom, or a carbon atom Particularly preferably, it represents a straight-chain alkyl group or a straight-chain alkoxy group having 1 to 8 atoms.
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.
When emphasizing the liquid crystallinity and orientation of the polymerizable compound of the present embodiment, one or both of m1 and m2 is preferably an integer of 1 to 3, and both m1 and m2 are integers of 1 to 3 It is more preferable that both m1 and m2 are 1 or 2.

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

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

In 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 represent an alkylene group having 1 to 12 carbon atoms or a single bond which may be substituted 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 more preferably represents 4 to 8 carbon atoms. More preferably, the alkylene group of the formula (1) is more preferable, and when a plurality of alkylene groups are present, they may be the same or different.

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

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

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

In the general formula ^{(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.

Wherein the group represented by Lc-1~Lc-244, it represents ^{L 3} or ^{L 4} in m1 or m2 each 1 or 2, 2 being preferred. N in R ^sp1 represents 1 to 20, and among them, n in R ^sp1 is preferably 2 or more, more preferably 4 or more, while it is preferably 12 or less, and more preferably 10 or less. It is preferable that
In Z ¹ , R ^z in the formula (Z-1) is preferably each independently, particularly preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

On the other hand, in the general formula (D _g -1), G ¹ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and the alkyl group is unsubstituted, It may be substituted, and 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 alkyl group having 1 to 6 carbon atoms in which at least one hydrogen atom is substituted by a fluorine atom, and a hydrogen atom is particularly preferable.

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).
From the viewpoint of improving wavelength dispersibility, it is preferable that at least one of carbon atoms is substituted with a hetero atom, and the organic group is an organic group having an aromatic heterocyclic ring. From the viewpoints shown below, an organic group having an aromatic heterocycle 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).

When the aromatic group contained in Q ¹ is substituted, the substituent E includes, among others, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a nitro group, a cyano group, an isocyano group, an amino group, and a hydroxyl group. , 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- Is a linear or branched alkyl group having 1 to 20 carbon atoms, which may be substituted by any one of the above, and any hydrogen atom in the alkyl group may be substituted with a fluorine atom. Fluorine atom, Atom, a 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-; It is more preferable that any hydrogen atom in the alkyl group is 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. 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 And two or more -CH _2- which are not independently represent -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 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—, and L ⁶ , A ⁵ , L ⁷ , R ^sp2 , and Z ² are the aforementioned L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , L ⁵ , R ^{sp1, respectively.} , And Z ¹ , which are the same as or different from L ^{1 to} L ⁴ , A ^{1 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, respectively, they may be 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 may be substituted by one or more substituents E, and one —CH ₂ — or two or more non-adjacent —CH ₂ — are each independently —O—. , -CO-, -COO-, -OCO-, or -O-CO-O-, an alkyl group or alkenyl group having 1 to 20 carbon atoms, cycloalkyl having 3 to 12 carbon atoms. Or a cycloalkenyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group or alkenyl group which may be substituted by the cycloalkyl group, cycloalkenyl group, or aryl group, or-(L ⁶ -A ⁵⁾ preferably represents a ^{q-L 7 -R sp2 -Z 2} .
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.
Unsubstituted alkyl or alkenyl group having 1 to 20 carbon atoms, cycloalkyl group having 3 to 12 carbon atoms, cycloalkenyl group having 3 to 12 carbon atoms, the cycloalkyl group, cycloalkenyl group, or aryl group Examples of the alkyl group or alkenyl group which may be substituted with, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl Group, n-hexyl group, 1-methylpentyl group, n-heptyl group, 1-ethylpentyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, n-decyl group, 3,7-dimethyl Octyl, n-undecyl, n-dodecyl, vinyl, allyl, isopropenyl, butynyl, cyclopentyl, cyclo Cyclohexyl group, cyclopentenyl group, cyclohexenyl group, cyclooctenyl group, cyclopentylmethyl group, cyclohexylmethyl group, 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 may be substituted with one or more substituents E in view of birefringence, solvent solubility, or durability, and may have one —CH ₂ — or two or more that are not adjacent to each other. of -CH ₂ - each independently is -O -, - CO -, - COO -, - OCO-, or -O-CO-O- in may be replaced, an alkyl group having 1 to 20 carbon atoms Or an alkenyl group, a cycloalkyl group having 3 to 12 carbon atoms, or a cycloalkenyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group or alkenyl group which may be substituted by the cycloalkyl group or cycloalkenyl group Or-(L ⁶ -A ⁵ ) q-L ⁷ -R ^sp2- Z ^2, and an arbitrary hydrogen atom may be replaced by a fluorine atom, and one -CH ₂ -or Not adjacent There two or more -CH ₂ - are each independently -O -, - CO -, - COO -, - may be replaced by OCO- linear or branched alkyl group having 1 to 20 carbon atoms Or a cycloalkyl group having 3 to 12 carbon atoms, or the above-mentioned alkyl group optionally substituted by the cycloalkyl group, or-(L ⁶ -A ⁵ ) q-L ⁷ -R ^sp2- Z ² It is preferable that one —CH ₂ — or two or more non-adjacent —CH ₂ — are each substituted by —O— in a linear or C 1-12 linear or A branched alkyl group or a cycloalkyl group having 3 to 12 carbon atoms, or the aforementioned alkyl group which may be substituted by the cycloalkyl group, or-(L ⁶ -A ⁵ ) q-L ⁷ -R It may represent a ^sp2 -Z ² Masui.
The preferred structure ^of- (L ⁶ -A ⁵ ) q-L ⁷ -R ^sp2 -Z ² is L ^{1 to} L ⁴ , A ^{1 to} A ⁴ , L ⁵ , R ^sp1 , and Z ¹ . Desirably, it is similar to the preferred structure defined. 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-24) -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).

Further, examples of the compound represented by the general formula (1) include the following compounds (i) to (xci). Core in the table, the structure of biphenylene, Lc1 ^is -L ¹ -A ¹ - and _{^{(L 3 -A 3) m1 -L}} 5 -R sp1 -Z 1, Lc2 is ^-L 2 -A ² - it represents the _{^{(L 4 -A 4) m2 -L}} 5 -R sp1 -Z 1.

  Further, typical structural formulas of compounds (i) to (xci) in Tables 7 and 8 are shown below, but are not limited thereto.

  The compound represented by the general formula (1) can be produced, for example, by the following production method. Examples of the production method include, for example, a known organic synthesis reaction described in Method der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, and a reaction method such as condensation reaction, urea reaction, and so on. Reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel Craft reaction, Heck reaction, Aldol reaction, Duff Reaction, etc.) can be produced by appropriately combining them according to the structure. Hereinafter, examples of the manufacturing method will be described, but the present disclosure is not limited to these structures and manufacturing methods.

For example, when L ¹ and L ² are each ** OCO— (* indicates 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). and intermediate C represented by ^{(ip-3), HOOC-} A 2 - (L 4 -A 4) m2 intermediate ^D represented by ^{-R 2 (A 2, L 4} , A 4, R 2, And m2 represent the same meaning as described above) to obtain an intermediate E represented by the formula (ip-4). When the structure of the intermediate B is the same as that of the intermediate D, the intermediate E can be obtained by reacting the intermediate A with the intermediate B.

Then, the compound represented by the formula (1-ex1) is reacted with the intermediate F represented by the formula (ip-4), for example, by an intermediate F represented by Q ¹ -J ¹ -NH ₂ . 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 G 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 G. 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.

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

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

The polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure is a polymerizable liquid crystal compound having good orientation, a large birefringence (Δn), and reverse wavelength dispersion. . For example, a polymerizable composition containing only a polymerizable liquid crystal compound (A) represented by the general formula (1) as a polymerizable liquid crystal compound and a photopolymerization initiator is prepared by the method described in Example 1 described below, and cured. When a film (retardation layer) is formed and the birefringence (Δn) of the cured film is measured, it is preferably 0.075 or more, and more preferably 0.08 or more.
Further, in order to approximate the ideal reverse wavelength dispersion, the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure is prepared by, for example, a method described in Example 1 described later. When only the polymerizable liquid crystal compound (A) represented by the general formula (1) and the photopolymerization initiator are prepared, a cured film (retardation layer) is formed, and the retardation value is measured as described below. Preferably, Re (450) / Re (550) is 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. It is preferably in the range of 0.60 or more and less than 0.90, particularly preferably in the range of 0.60 or more and 0.83 or less, and even in the range of 0.60 or more and less than 0.80. good. 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.

Further, the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure 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 base materials. The temperature is more preferably from 30 ° C to 180 ° C, even more preferably from 30 ° C to 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.

  Further, the polymerizable liquid crystal compound (A) represented by the general formula (1) of the present disclosure is added in an amount of 10% by mass to at least one solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone. % Or more is preferred from the viewpoint of expanding the choice of usable substrates, and more preferably 20% by mass or more.

In the polymerizable composition according to the present disclosure, as the polymerizable liquid crystal compound (A) represented by the general formula (1), one type may be used alone, or two or more types may be used in combination.
In the present embodiment, the polymerizable liquid crystal compound (A) represented by the general formula (1) is contained from the viewpoint that a polymerizable composition having a large birefringence (Δn) and reverse wavelength dispersion can be obtained. The ratio is preferably at least 10 parts by mass, more preferably at least 30 parts by mass, even more preferably at least 50 parts by mass, based on 100 parts by mass of the polymerizable liquid crystal compound in total. On the other hand, from the viewpoint that a polymerizable composition having high solution stability is obtained, the content ratio of the polymerizable liquid crystal compound (A) represented by the general formula (1) is set to 100 parts by mass in total of the polymerizable liquid crystal compound. It is preferably 99 parts by mass or less, more preferably 95 parts by mass or less, and even more preferably 90 parts by mass or less.

In the polymerizable composition according to the present disclosure, the total content of the polymerizable liquid crystal compound including the polymerizable liquid crystal compound (A) represented by the general formula (1) is 100% by mass of the solid content of the polymerizable composition. 70 parts by mass or more and 99.9 parts by mass or less, more preferably 80 parts by mass or more and 99.9 parts by mass or less, more preferably 90 parts by mass or more and 99.9 parts by mass or less. Is even more preferred.
In the present disclosure, the solid content refers to all components except for the solvent. For example, even if the polymerizable liquid crystal compound is liquid, it is included in the solid content.

2. Polymerizable liquid crystal compound (B) represented by the general formula (2)
In the general formula (2), D ³ represents a monovalent group containing an indolenine ring structure. The monovalent group having an indolenine ring structure may include the structure of the general formula (d _g ), may further have a substituent, and includes a benzene ring of the general formula (d _g ). A condensed ring may be formed, and examples thereof include a structure in which any hydrogen atom in the general formula (d _g ) is substituted with M.

In the general formula (2), D ³ is, for example, a group selected from the following general formula (D _g -2), a group selected from the following general formula (D _g -3), or the following general formula (D _g -4) )).

(In the general formulas ( _Dg- 2) to ( _Dg- 4), R ^d1 and R ^d2 each independently represent an alkyl group having 1 to 20 carbon atoms, and the alkyl group is unsubstituted. or may be substituted by one or more of the substituents E ^3, 1 single -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 -, - OCO-O -, - CO-NH-, -NH-CO-, -CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or It may be replaced by -C≡C-, ^or non-aromatic carbon bond to 3-7 membered ring ^{R d1} and ^{R d2} each other May form a hydrocarbon ring, said non-aromatic hydrocarbon ring may be substituted by one or one or more of the substituents E ³ is an unsubstituted, any of the non-aromatic hydrocarbon ring The carbon atom of may be substituted with a hetero atom,
R ^e1 , R ^e2 , R ^e3 and R ^e4 , and R ^d3 each independently represent a hydrogen atom or the substituent E ³ , and R ^e1 , R ^e2 , R ^e3 and R ^e4 are bonded to each other. May form a 3- to 7-membered non-aromatic or aromatic hydrocarbon ring, wherein the non-aromatic or aromatic hydrocarbon ring is unsubstituted or one or more of the substituents E ³ And any carbon atom of the non-aromatic or aromatic hydrocarbon ring may be substituted with a hetero atom. * (Asterisk) indicates the bonding position with M. )

In the general formula (d _g ), the general formula (D _g -2), the general formula (D _g -3), and the general formula (D _g -4), R ^d1 and R ^{d2 each} represent an improvement in solvent solubility and stability. From the viewpoint of improving the dispersibility and adjusting the reverse wavelength dispersion, each is independently an unsubstituted alkyl group having 1 to 10 carbon atoms, or R ^d1 and R ^d2 are bonded to each other to form a 5- to 7-membered ring. It preferably forms a non-aromatic hydrocarbon ring. From the viewpoint of improving solvent solubility, improving stability and adjusting reverse wavelength dispersion, and further manufacturing, R ^d1 and R ^d2 are each independently an unsubstituted alkyl group having 1 to 4 carbon atoms. , R ^d1 and R ^d2 are more preferably bonded to each other to form a 5- to 7-membered non-aromatic hydrocarbon ring, and are an unsubstituted alkyl group having 1 to 2 carbon atoms; It is even more preferred that ^d1 and ^Rd2 combine with each other to form a 6-membered non-aromatic hydrocarbon ring.

In the general formula (D _g -2), the general formula (D _g -3), and the general formula (D _g -4), R ^e1 , R ^e2 , R ^e3 and R ^e4 , and R ^d3 are each independently. And may be a hydrogen atom, but is substituted with at least one of R ^e1 , R ^e2 , R ^e3 and R ^e4 , and R ^d3 from the viewpoint of adjustment of reverse wavelength dispersion and adjustment of solvent solubility. it may be introduced to the group E ^3. When a substituent E ³ is introduced into at least one of R ^e1 , R ^e2 , R ^e3, R ^e4 , and R ^d3 , it tends to exhibit reverse wavelength dispersion.
Incidentally, the substituents E ³ in the general formula (2) is omitted here because may be the same as the substituent E in the general formula (1).
From the viewpoint of adjusting the reverse wavelength dispersion, when a substituent E ³ is introduced into at least one of R ^e1 , R ^e2 , R ^e3 and R ^e4 , and R ^d3 , among the substituents E ³ , indolenine It is preferable to introduce a substituent capable of expanding the π-conjugated system of the ring (a group that expands the π-conjugated system of the indolenine ring). Examples of the substituent capable of expanding the π-conjugated system of the indolenine ring include, for example, a π-bonded electron pair, a lone electron pair, or a group having an empty orbit capable of accepting a lone electron pair, or a group exhibiting an inducing effect. is, specifically, a halogen atom, a nitro group, a cyano group, or a linear or branched alkyl group having a hydroxyl number of carbon atoms which may be substituted with a group 20, 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 = CH- , -CH = CH-, -CF = CF- or -C≡C- A linear or branched alkyl group having 1 to 20 carbon atoms, a halogen atom, a nitro group, a cyano group, an amino group, or a hydroxyl group which may be preferred, and among them, a linear chain having 1 to 10 carbon atoms is preferable. Or a branched alkyl group, an alkoxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a hydroxyalkyl group having 1 to 10 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, An amino group or a hydroxyl group is more preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms, a halogen atom, a nitro group, an alkoxy group having 1 to 10 carbon atoms, and the like are still more preferable.
Further, R ^e1 , R ^e2 , R ^e3, and R ^e4 are bonded to each other to form a 5- to 7-membered aromatic hydrocarbon ring, and benzene to which R ^e1 , R ^e2 , R ^e3, and R ^e4 are bonded. The formation of a condensed ring containing a ring is also preferable in that the conjugated system of the indolenine ring structure can be expanded.

In the general formula (2), D ³ preferably represents a group selected from the general formula (D _g -2) from the viewpoint of adjusting the reverse wavelength dispersion.

Specifically, D ³ represents a group selected from the following formulas (d-1) to (d-17), so that the raw material is easily available, the solubility is good, and the reverse wavelength dispersion property is high. It is particularly preferable because it is easily adjusted.

In the general formula (2), M represents -CH = CH-, -N = CH-, -CH = N-, or -N = N-. Among them, in view of ease of synthesis and stability. From -CH = CH-, -N = CH-, or -CH = N-, more preferably CH = CH-, or -CH = N-, and even more preferably -CH = CH-. . Further, M is a trans type, and it is preferable that D and A ^core are bonded from the viewpoint of reverse wavelength dispersion.

In the general formula (2), as the ^{-M-D 3,} preferably a group selected from the following general formulas (MD-1).

(In the general formula (MD-1), R ^d1 and R ^d2 , R ^e1 , R ^e2 , R ^e3 and R ^e4 are the same as those in the general formula (D _g -2), respectively, and X ¹ and X ² are Each is independently CH or N. * (asterisk) indicates the binding position to A ^core .)

In the general formula (MD-1), X ¹ and X ² are preferably at least ^one of CH, more preferably at least X ¹ , from the viewpoint of ease of synthesis and stability. ^Even more preferably, both ¹ and X ² are CH.

In the general formula (2), n11 represents an integer of 1 or 2, ^{-M-D 3} is one or two bonds to A ^core to be described later. It is -M-D ^3, when attached one to A ^core to be described later, A ^core is a trivalent radical, where the two binding to A ^core to be described later, A ^core is tetravalent radical.
In the general formula (2), n11 may be appropriately selected from 1 or 2 in order to adjust the wavelength dispersion characteristics.
Above all, when n11 is set to 1, reverse wavelength dispersion is easily exhibited.
In particular, when n11 is 2, at least one of R ^e1 , R ^e2 , R ^e3 and R ^e4 , and R ^d3 is ^added to the above-mentioned India from the viewpoint of enhancing the effect of adjusting the reverse wavelength dispersion. It is preferable to introduce a substituent capable of expanding the conjugate system of the renin ring structure.

In the general formula (2), A ^core is a monocyclic, condensed ring, or ring-assembled aromatic group which may be unsubstituted or substituted with one or more substituents E ³ and has 4 to 4 carbon atoms. Represents 16 trivalent or tetravalent groups.
Examples of the monocyclic aromatic hydrocarbon ring constituting the monocyclic aromatic group include a benzene ring, and examples of the monocyclic aromatic heterocycle constituting the monocyclic aromatic group include a furan ring, a pyridine ring and a pyrimidine. And a pyrazine ring. Examples of the condensed ring aromatic hydrocarbon ring constituting the condensed ring aromatic group include a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like.As the condensed ring aromatic heterocyclic ring constituting the condensed ring aromatic group, Examples include a quinoline ring, an acridine ring, a phenanthridine ring and the like. The ring assembly refers to a structure in which two rings have no shared atom and are connected via a bond. The structure constituting the ring-assembled aromatic group includes the monocyclic and condensed aromatic hydrocarbon rings. And a structure in which at least two types of rings selected from the group consisting of the aforementioned monocyclic ring and fused aromatic heterocyclic ring are directly connected. Examples of the structure constituting the ring-assembled aromatic group having 4 to 16 carbon atoms include biphenyl, 2-phenylnaphthalene, 1-phenylnaphthalene and the like.

Monocyclic, trivalent or tetravalent group having a carbon number of 4 to 16 is a fused ring or ring assembly aromatic group may be unsubstituted, but substituted by one or more later-described substituent E ³ It may be.
The substituent in A ^core, among others, from the synthesis easiness, fluorine atom, chlorine atom, hydroxyl group, mercapto group, methylamino group, dimethylamino group, or one -CH 2 _- or-adjacent no more than one -CH ₂ - independently are each -O -, - S -, - CO -, - COO -, - OCO -, - CO-S -, - S-CO -, - OCO It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms which may be substituted by -O-, -CO-NH-, -NH-CO-.

Examples of the trivalent or tetravalent group having 4 to 16 carbon atoms, which is an unsubstituted monocyclic, condensed ring, or ring-assembled aromatic group in A ^core , include the following formula (Co-11) to formula (Co-11). -28), preferably, but not limited to, the following.
In the formula (Co-28) from the following equation (Co-11), one or more hydrogen atoms of the aromatic group may be substituted by one or more substituents E ^3.

In (Formula (Co-11) from the formula (Co-28), -M- D 3 is the is the same as in the general formula (2), M, ^{if D 3} appears more, even each identical it may be different. * (asterisk) shows a bonding site to the ^{L 11} or ^{L 12.)}

The ring structure of the single ring, condensed ring or ring-assembled aromatic group in A ^core is preferably benzene, naphthalene, or biphenyl from the viewpoint of ease of material procurement, and benzene from the viewpoint of wavelength dispersibility. Is preferable, and biphenyl is preferable from the viewpoint of improving the orientation between molecules and the birefringence. When the polymerizable liquid crystal compound of the present disclosure has a large birefringence (Δn), it is possible to realize a phase difference with a thin film as compared with the related art.
In A ^core , a trivalent or tetravalent group having 4 to 16 carbon atoms, which is an unsubstituted monocyclic, condensed ring, or ring-assembled aromatic group, is represented by the formula (Co-11) to the formula (Co-18) And at least one of the groups selected from the formulas (Co-26) to (Co-28).

Here, L ¹¹ , L ¹² , L ¹³ and L ¹⁴ in the general formula (2) may be independently the same as L ¹ , L ² , L ³ and L ⁴ in the general formula (1). Is omitted.
A ¹¹ and A ¹² in the general formula (2) may be independently the same as A ¹ and A ² in the general formula (1), and thus description thereof will be omitted.
A ¹³ and A ¹⁴ in the general formula (2) may be independently the same as A ³ and A ⁴ in the general formula (1), and thus description thereof will be omitted.

M11 and m12 in the general formula (2) each independently represent an integer of 1 to 4.
When emphasizing the liquid crystallinity and orientation of the polymerizable compound of the present embodiment, one or both of m11 and m12 is preferably an integer of 1 to 3, and both m11 and m12 are integers of 1 to 3 It is more preferable that both m11 and m12 are 1 or 2.

Further, R ¹¹ and R ¹² in the general formula (2) each independently represent a group selected from the general formula (R-11), and are represented by the general formula (R-11): -L ¹⁵ -R ^{sp11 L 15, R SP11} in -Z ^11, and ^{Z 11} each, ^{L 5, R sp1} in the general formula (1), and since ^{Z 1} and may be the same, description thereof will be omitted here.

In the general formula ^{(2), Lc11: -L 11} -A 11 - (L 13 -A 13) m11 -L 15 -R sp11 -Z 11 ^{and,, Lc12: -L 12 -A 12} - (L 14 -A ¹⁴⁾ specific examples of _m12 -L ¹⁵ -R _sp11 -Z ¹¹ include groups represented by Lc-1~Lc-244 listed in tables 1 to 6 described in the general formula (1) . In the polymerizable liquid crystal compound represented by the general formula (2), Lc11 and Lc12 may be the same or different.

Further, examples of the compound represented by the general formula (2) include the following compounds (b1) to (b85). Lc11 in the ^table, -L ¹¹ -A ¹¹ - a _{^{(L 13 -A 13) m11 -L}} 15 -R sp11 -Z 11, Lc12 ^{is, -L 12 -A 12 - (L} 14 -A 14) m12 represents an -L ¹⁵ -R sp11 -Z ^11.

Furthermore, typical structural formulas of the compounds (b1) to (b85) in Tables 9 and 10 are illustrated below, but are not limited thereto. In the ^{following, R 11} and ^{R 12} each independently represent a group selected from the general formula (R-11), among them ^L 15 is, -O -, - COO -, - OCO-, or -O It is more preferable to represent -CO-O-, and each of R ¹¹ and R ¹² may be the same or different. More preferably, R ^sp11 independently represents an alkylene group having 1 to 20 carbon atoms, and R ¹¹ and R ¹² may be the same or different. Further, Z ¹¹ is more preferably the above formula (Z-1), and particularly preferably, in the formula (Z-1), R ^z is a hydrogen atom, a methyl group or a trifluoromethyl group.

  The polymerizable liquid crystal compound (B) represented by the general formula (2) can be produced, for example, by the following production method. Examples of the production method include, for example, a known organic synthesis reaction described in Method der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, New Experimental Chemistry Lecture, and a reaction method such as condensation reaction, urea reaction, and so on. Reaction, Wittig reaction, Schiff base formation reaction, benzylation reaction, Sonogashira reaction, Suzuki-Miyaura reaction, Negishi reaction, Kumada reaction, Hiyama reaction, Buchwald-Hartwig reaction, Friedel Craft reaction, Heck reaction, Aldol reaction, Duff Reaction, etc.) can be produced by appropriately combining them according to the structure. Hereinafter, examples of the manufacturing method will be described, but the present disclosure is not limited to these structures and manufacturing methods.

For example, L ¹¹ and L ¹² are each ** OCO— (* indicates a bonding position to A ^core ), D ³ represents a group selected from the general formula (D _g −2), and M represents − In the case of a compound where CH = CH-, for example, it can be produced as follows.
First, an indolenine compound represented by the formula (ip-11) is prepared and subjected to bromination to obtain an intermediate H represented by the formula (ip-12).

On the other hand, an intermediate I in which an aldehyde group is introduced at the position where M is introduced in A ^core is prepared. When A ^core is a benzene ring, for example, 2,5-dihydroxybenzaldehyde is prepared. For example, when A ^core is biphenyl, 4,4′-dihydroxybiphenyl or a substituent E ³ (in the formulas (ip-13) and (ip-14), E ¹¹ and E ¹² are the substituents E ^{11 3} , n12 or n13 is 0 or 1), and a compound represented by the formula (ip-13) into which an aldehyde group is introduced at a desired position by a duff reaction or the like is prepared. Intermediate I ′ represented by -14) is produced.

Next, an aldehyde group is introduced at a position where M is introduced into A ^core , such as the intermediate H represented by the formula (ip-12) and 2,5-dihydroxybenzaldehyde represented by the formula (ip-15). To give intermediate J of formula (ip-16).

Next, the intermediate J of formula ^{(ip-16), HOOC-} A 11 - (L 13 -A 13) m1 Intermediate ^{K1 (A} 11 represented by ^{-R 11, L 13, A 13} , R 11 , And m11 represent the same meaning as described above) by a condensation reaction or the like to obtain an intermediate L represented by the formula (ip-17), and further, the obtained formula (ip- and intermediate L represented by ^{17), HOOC-A 12 -} (L 14 -A 14) m12 intermediate ^{K2 (A} 12 represented by ^{-R 12, L 14, A 14} , R 12, and m12 is With the same meaning as described above) to obtain a compound represented by the formula (2-ex1). When the structures of the intermediate K1 and the intermediate K2 are the same, the compound represented by the formula (2-ex1) can be obtained by reacting the intermediate K1 with the intermediate J of the formula (ip-16). it can.

Further, in A ^core, when using a ring assembly aromatic groups biphenyl, types and substitution positions of substituents E ^3, by substitution position of M, such as 3,4-methylenedioxy phenol (Tokyo Chemical Industry (Co. )) Or a derivative thereof may be obtained by performing a Duff reaction to introduce an aldehyde group and performing a Suzuki-Miyaura coupling reaction.

Further, for example, HOOC-A serving as a main chain portion is added to an intermediate I such as 2,5-dihydroxybenzaldehyde represented by the formula (ip-15) in which an aldehyde group is introduced at a position where M is introduced in A ^core . _{^{11 - (L 13 -A 13)}} m1 intermediate ^K1 represented by ^{-R 11 (a 11, L 13} , a 13, R 11, and m11 represents the same meaning as above) and, ^{HOOC-a 12} -(L ¹⁴ -A ¹⁴ ) _{m12 -Reacting} an intermediate K2 represented by R ¹² (A ¹² , L ¹⁴ , A ¹⁴ , R ¹² and m ¹² represent the same meaning as described above), and then reacting with an aldehyde The compound represented by the formula (2-ex1) may be obtained by reacting the group with an intermediate H represented by the formula (ip-12).

In addition, when M is -CH = N-, the compound can be produced, for example, as follows.
The corresponding amine form of indolenine is prepared as an intermediate H ′ represented by the formula (ip-12 ′), and the intermediate H ′ represented by the formula (ip-12 ′) is prepared by adding the intermediate H ′ represented by the formula (ip-15) With an intermediate I having an aldehyde group introduced at the position where M is introduced in A ^core , such as 2,5-dihydroxybenzaldehyde represented by the following formula (ip-16 ′): Except for obtaining J ′, it can be produced in the same manner as described above.

  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.

  The polymerizable liquid crystal compound (B) represented by the general formula (2) of the present disclosure can be used as a polymerizable liquid crystal compound represented by the general formula (2) as a polymerizable liquid crystal compound by, for example, a method described in Example 1 described below. When a polymerizable composition containing only the compound (B) and the photopolymerization initiator is prepared, a cured film (retardation layer) is formed, and the retardation value is measured as described below, the Re (450) / Re (550) can exhibit a flat wavelength dispersion of 0.99 or more and less than 1.01 or an inverse wavelength dispersion of Re (450) / Re (550) of less than 0.99, and Re (450) / Preferably, Re (550) exhibits a reverse wavelength dispersion of less than 0.99, more preferably less than 0.95. In the polymerizable liquid crystal compound (B) represented by the general formula (2) of the present disclosure, Re (650) / Re (550) is preferably 1 or more, more preferably 1 or more, Even more preferably, it is in the range of 1.02 or more and 1.1 or less.

In the polymerizable composition according to the present disclosure, as the polymerizable liquid crystal compound (B) represented by the general formula (2), one type may be used alone, or two or more types may be used in combination.
In the present embodiment, the content ratio of the polymerizable liquid crystal compound (B) represented by the general formula (2) is determined from the viewpoint that a polymerizable composition having high solution stability and excellent in-plane uniformity is obtained. It is preferably at least 1 part by mass, more preferably at least 5 parts by mass, even more preferably at least 10 parts by mass with respect to 100 parts by mass in total of the hydrophilic liquid crystal compound. On the other hand, the content ratio of the polymerizable liquid crystal compound (B) represented by the general formula (2) is high in that a polymerizable composition having a large birefringence (Δn) and having reverse wavelength dispersion can be obtained. The amount is preferably 90 parts by mass or less, more preferably 70 parts by mass or less, and even more preferably 50 parts by mass or less, based on 100 parts by mass of the polymerizable liquid crystal compound in total.

3. Other Components The polymerizable composition of the present disclosure comprises at least a polymerizable liquid crystal compound (A) represented by the general formula (1) and a polymerizable liquid crystal compound (B) represented by the general formula (2). It is preferable that the composition further contains a photopolymerization initiator.
Further, the polymerizable composition of the present disclosure is further represented by the general formula (1) from the viewpoint of adjusting retardation and reverse wavelength dispersibility, and adjusting the orientation, solubility, and phase transition temperature. And a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) represented by the general formula (2). It may contain other components. Hereinafter, each component constituting the polymerizable composition of the present disclosure will be described in order.

3-1. Photopolymerization initiator In this embodiment, the photopolymerization initiator can be appropriately selected from conventionally known ones and used. Specific examples of such a photopolymerization initiator include, for example, aromatic ketones including thioxanthone and the like, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, aromatic onium Salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketoxime ester compounds, 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.

3-2. A polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) In the polymerizable composition of the present disclosure, the polymerizable liquid crystal compound (A) represented by the general formula (1) The polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (B) represented by the general formula (2) can be appropriately selected from conventionally known compounds. 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 polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B), for example, as a compound exhibiting reverse wavelength dispersion, Patent Nos. 5,463,666 and 4,186,981; No. 5,962,760 and Japanese Patent No. 5,826,759. Examples of compounds exhibiting flat dispersibility include the compounds described in Recueil des Travaux Chimiques des Pays-Bas (1996), 115 (6), 321-328.

In the present embodiment, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having a polymerizable functional group 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 (I) and having the same structure as the main chain portion of the polymerizable compound; )).

^{(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.

(G is an integer of 2 to 5.)

In the embodiment, the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (B) can be used alone or in combination of two or more.
The content ratio of the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) may be appropriately adjusted in order to adjust a desired retardation or the like. The amount is preferably 30 parts by mass or less, more preferably 10 parts by mass or less with respect to the total 100 parts by mass of the liquid crystal compound.

3-3. Other Components The polymerizable composition of the present embodiment may further contain other components as long as the effect is not impaired. Specifically, it may contain a leveling agent, an antioxidant, a light stabilizer, and a solvent from the viewpoint of coatability as other components. In addition, even if it contains a polymerizable compound that does not exhibit liquid crystallinity alone but can adjust the phase difference and reverse wavelength dispersion, the phase transition temperature, the hardness, and the durability by using the polymerizable liquid crystal compound of the present disclosure together with the compound. Good. These may be appropriately selected from conventionally known materials.

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

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

  The polymerizable composition of the present embodiment is suitably used for various applications because of its good orientation. The polymerizable composition of the present embodiment is suitably used as a liquid crystal composition having good solution stability and reverse wavelength dispersion, for example, for a later-described retardation film or various optical members.

B. Polymer The polymer of the present disclosure is obtained by polymerizing the polymerizable composition of the present disclosure. The polymerization method is appropriately adjusted according to the polymerizable functional groups contained in the polymerizable liquid crystal compound (A) represented by the general formula (1) and the polymerizable liquid crystal compound (B) represented by the general formula (2). You can choose.
A polymer obtained by polymerizing the polymerizable composition of the present disclosure without orientation can be used, for example, as a light scattering plate, a depolarizing plate, and a moiré fringe preventing plate.
Further, a polymer obtained by polymerizing after orienting the polymerizable composition of the present disclosure has optical anisotropy, and is suitably used for later-described retardation films and various optical member applications.

C. 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, as described above, the retardation film exhibits reverse wavelength dispersion, has good orientation, and has a good alignment property. The in-plane uniformity of the phase difference value is excellent.

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

1. Retardation Layer The retardation layer 1 of the embodiment of the present disclosure contains 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.

  The retardation layer may further include a main chain portion having orientation of the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) included in the polymerizable composition of the present disclosure, and may further be included. It is preferable that the polymerizable liquid crystal compound is cured while being substantially horizontally aligned with the film surface. The cured product of the polymerizable composition according to the embodiment of the present disclosure includes a structure in which at least a part of the polymerizable functional group of the polymerizable compound is polymerized. Since the structure in which at least a part of the polymerizable functional group of the polymerizable compound is polymerized is included, the phase difference layer of the present embodiment is a phase difference layer having improved durability.

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

  Further, the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) included in the polymerizable composition of the present disclosure and the polymerizable liquid crystal compound that may be further included in the polymerizable composition of the present disclosure. The fact that at least a part of the functional group contains a polymerized structure can be confirmed by collecting and analyzing the material from the retardation layer. As an analysis method, NMR, IR, GC-MS, XPS, TOF-SIMS, and a method combining these can be applied.

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

The thickness of the retardation layer may be appropriately set 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 × Δn (λ)
(In the formula, Re (λ) represents a retardation value at a wavelength λnm, d represents a film thickness, and Δn (λ) represents a birefringence at a wavelength λnm.)
Above all, the thickness of the retardation layer is preferably 0.1 μm or more and 5 μm or less, more preferably 0.5 μm or more and 3 μm or less.
Since the polymerizable liquid crystal compound (A) represented by the general formula (1) has a large birefringence (Δn), it is possible to realize a phase difference with a thin film as compared with the related art.

The wavelength dispersion characteristic of the retardation film of the present disclosure depends on the content of the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B) in the retardation layer and the content of the polymerizable liquid crystal compound which may be contained. It can be determined arbitrarily. Increasing the content of the polymerizable liquid crystal compound (A) in the retardation layer tends to increase reverse wavelength dispersion characteristics.
In the retardation layer of the present disclosure, Re (450) / Re (550) is preferably in the range of 0.75 or more and less than 0.95, and more preferably 0, in order to approach ideal reverse wavelength dispersion. It is preferably in the range of 0.78 or more and less than 0.93, and more preferably in the range of 0.80 or more and less than 0.90. 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.

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 orienting at least the polymerizable compound in the formed polymerizable composition (orientation step);
After the orientation step, a step (polymerization step) of polymerizing the polymerizable compound at least is included, so that a phase difference layer is formed.
As the polymerizable composition, the same one as in the above-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 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, a main chain portion having orientation of the polymerizable liquid crystal compound (A) represented by the general formula (1) and the polymerizable liquid crystal compound (B) represented by the general formula (2); If necessary, the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (B), which are further included, can be aligned and dried, and fixed while maintaining the alignment state. Can be
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 orientation step, at least the polymerizable compound is polymerized. In the alignment step, the polymerizable compound is polymerized by, for example, irradiating the coating film fixed in a state where the alignment state of the polymerizable compound and the polymerizable liquid crystal compound that may be further included is maintained. And a retardation layer comprising 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.

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

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

The layer configuration of the transfer laminate will be described with reference to the drawings. 4 and 5 each show one embodiment of the transfer laminate of the present disclosure.
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 on the transfer object 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.

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

  Further, one embodiment of the transfer laminate 40 shown in the example of FIG. 6 includes a 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, but the retardation layer can be the same as the retardation layer described in the above “C. Retardation Film”, and thus description thereof will be omitted.
The alignment film and the substrate may be the same as the alignment film and the substrate described in the above “C. Retardation film”, but 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. For example, a method in which the solvent contained in the composition for forming an alignment film can 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 substrate 22 and the alignment film 23 is smaller than the peel strength between the alignment film 23 and the retardation layer 21. In order to achieve this, 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.

E. FIG. 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.

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

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

According to the method for manufacturing an optical member of one embodiment of the present disclosure using the transfer laminate, a polarizing plate and an optical member including only the retardation layer among the retardation films of the present disclosure are obtained. Can be.
The transfer laminate used in the method for manufacturing an optical member according to an embodiment of the present disclosure can be the same as that described in the above “E. 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.

G. 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.
In addition, the phase transition temperature of each of the manufactured 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 compound A-1 represented by formula (1-1)]
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 cyclohexanedicarboxylic acid, 53 g (200 mmol, manufactured by DKSH) of 6- (4-hydroxyphenyl) hexyl acrylate, 0.98 g (8.0 mmol) of N, N-dimethylaminopyridine (DMAP) in dichloromethane (1 L) ) A solution of 43 g (210 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (50 mL) was added dropwise to the suspension. After completion of the dropwise addition, the mixture was stirred for 12 hours, and the precipitate was filtered, washed with an aqueous sodium hydrogen carbonate solution and 1N hydrochloric acid, and the solvent was distilled off. The 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) To a suspension of 0.14 g (1.2 mmol) of N, N-dimethylaminopyridine (DMAP) in dichloromethane (70 mL) was added dropwise a solution of 19 g (90 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (14 mL). did. 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 g (22 mmol, yield: 75%) of an intermediate 2 represented by the formula (1-1-4).

  5.0 g (30 mmol) of 2-hydrazinobenzothiazole and 2.5 g (45 mmol) of potassium hydroxide were added to N, N-dimethylformamide (90 mL), and the mixture was heated at 80 degrees. After reaching a predetermined temperature, 9.2 g (36 mmol) of hexyl p-toluenesulfonate was added dropwise. After completion of the dropwise addition, the mixture was stirred for 4 hours. After completion of the reaction, 10 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 3.0 g (12 mmol, yield: 40%) of an intermediate 3 represented by the formula (1-1-5).

  2.0 g (1.9 mmol) of the intermediate 2 represented by the formula (1-1-4) obtained above and 15 mg of 12 N hydrochloric acid were dissolved in 10 mL of tetrahydrofuran, and the solution was represented by the formula (1-1-5). A solution of 1.2 g (5.0 mmol) of the obtained intermediate 3 in tetrahydrofuran (3 mL) was added dropwise. After completion of the dropwise addition, the mixture was stirred for 12 hours and then added dropwise to 50 ml of methanol. After the generated precipitate was filtered, the solvent was distilled off. Methanol (20 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 crystals were dried to obtain 1.4 g (0.94 mmol, yield 49%) of a compound A-1 represented by the formula (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).

[Production Example 2: Production of compound A-2 represented by formula (1-2)]
4.7 g (24 mmol) of 2-amino-6-ethoxybenzothiazole was added to 20 ml of ethylene glycol. In an ice bath, 3.6 g (71 mmol) of hydrazine monohydrate and 1.9 g (55 mmol) of 12N hydrochloric acid were dropped, and the mixture was stirred at 130 ° C for 5 hours. After completion of the reaction, the mixture was cooled to room temperature, 300 ml of water was added, the precipitate was filtered, and the obtained crystals were dried to obtain 3.1 g (16 mmol, yield 68%) of Intermediate 4.

  In the production of Production Example 1, in the step of obtaining Intermediate 3, Intermediate 5 represented by the formula (1-2-1) was obtained by using Intermediate 4 in place of 2-hydrazinobenzothiazole. In the same manner as in Production Example 1 except for the above, 1.3 g (0.83 mmol, 43% yield) of compound A-2 represented by the formula (1-2) was obtained.

Phase transition temperature (when heated): C 147 N 241 I
1H NMR (CDCl3; δ ppm): 8.39 (s, 2H), 7.80 (s
, 2H), 7.52 (d, 2H), 7.21 (d, 2H), 7.05-6.75 (m, 1
2H), 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), 3.6.
5 (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).

[Production Example 3: Production of compound A-3 represented by formula (1-3)]
In the production of Production Example 1, an intermediate represented by the formula (1-3-1) was obtained by using an equimolar amount of 1-bromo-2-butoxyethane instead of iodohexane in the step of obtaining intermediate 3. Except for obtaining 6, 1.2 g (0.77 mmol, yield 40%) of compound A-3 represented by the formula (1-3) was obtained in the same manner as in Production Example 1.

Phase transition temperature (at elevated temperature): C 120 N 184 I
1H NMR (CDCl ₃ ; δ ppm): 8.39 (s, 2H), 8.13 (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), 4.53. (T, 4H), 4.18 (t, 4H), 3.95 (t, 4H), 3.61 (t, 4H), 3.50 (t, 4H), 2.70-2.55 ( m, 4H), 2.45-2.35 (m, 8H), 1.95-1.30 (m, 28H).

[Production Example 4: Production of compound B-1 represented by formula (2-1)]
5 ml of hydrogen bromide (30% acetic acid solution) is dissolved in 100 ml of ethanol, and 3.2 g (20 mmol) of 2,3,3-trimethylindolenine and 3.4 g (24 mmol) of 2,5-dihydroxybenzaldehyde are added thereto. For 3 hours. After completion of the reaction, the reaction mixture was cooled to room temperature, and after removing the solvent, the obtained crude product was dissolved in 300 mL of dichloromethane, and the organic layer was washed and concentrated. The residue was purified by silica gel chromatography, and the solvent was distilled off, thereby obtaining 1.4 g (3.8 mmol, 19% yield) of an intermediate 7 represented by the formula (2-1-2). The structure of the target product was identified by ¹ H NMR.

Next, 1.0 g (2.8 mmol) of the intermediate 7 represented by the formula (2-1-2) obtained above and the carboxylic acid derivative 13 represented by the formula (1-1-3). To a suspension of 5 g (8.3 mmol) of N, N-dimethylaminopyridine (DMAP) 10 mg (83 μmol) in dichloromethane (10 mL), 2.0 g (9.7 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (1 mL) solution was added dropwise. After completion of the dropwise addition, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Chloroform (10 mL) was added to the obtained crude product, and the mixture was stirred for 1 hour and suspended and purified. The precipitate was filtered, chloroform (10 mL) was added to the obtained crude product, 280 mg (2.8 mmol) of triethylamine was added, and the mixture was stirred for 1 hour and purified by suspension. The precipitate was filtered and the obtained crystals were dried to obtain 1.4 g (1.2 mmol, 45% yield) of a compound B-1 represented by the formula (2-1). The structure of the target product was identified by ¹ H NMR.

Phase transition temperature (at elevated temperature): C 87 N 160 I
¹ H NMR (CDCl ₃ ; δ ppm): 7.87 (s, 1 H), 7.65 (d, 1 H), 7.54 (d, 1 H), 7.49 (d, 1 H), 7.39 − 7.22 (m, 5H), 7.04-7.01 (m, 4H), 6.96-6.93 (m, 4H), 6.32 (d, 2H), 6.17 (d, 2H), 5.93 (d, 2H), 4.12 (t, 4H), 3.96 (t, 4H), 2.86-2.81 (m, 1H), 2.67-2.64. (M, 3H), 2.33-2.17 (m, 8H), 1.75-1.59 (m, 16H), 1.49-1.35 (m, 14H)

[Production Example 5: Production of compound B-2 represented by formula (2-2)]
In the production of Production Example 4, in the step of obtaining Intermediate 7, an equimolar amount of 5-chloro-2,3,3-trimethylindolenine was used instead of 2,3,3-trimethylindolenine, 8 was obtained. Further, in the same manner as in Production Example 1, a carboxylic acid derivative 1 represented by the formula (1-1-3) was obtained.
Next, 1.0 g (2.5 mmol) of the intermediate 8 obtained above, 3.2 g (7.6 mmol) of the carboxylic acid derivative 1 represented by the formula (1-1-3), N, N-dimethyl To a suspension of 9.2 mg (76 μmol) of aminopyridine (DMAP) in dichloromethane (10 mL) was added dropwise a solution of 1.8 g (8.8 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (1 mL). After completion of the dropwise addition, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Chloroform (10 mL) was added to the obtained crude product, and the mixture was stirred for 1 hour and suspended and purified. The precipitate was filtered, chloroform (10 mL) was added to the obtained crude product, 260 mg (2.5 mmol) of triethylamine was added, and the mixture was stirred for 1 hour and purified by suspension. The precipitate was filtered and the obtained crystals were dried to obtain 1.5 g (1.30 mmol, yield 52%) of a compound B-2 represented by the formula (2-2). The structure of the target product was identified by ¹ H NMR.

Phase transition temperature (at elevated temperature): C 78 N 105 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.46 (s, 1 H), 8.27 (d, 1 H), 7.93 (s, 1 H), 7.85 (d, 1 H), 7.74 ( d, 1H), 7.47 (d, 1H), 7.31-7.25 (m, 2H), 7.04-7.01 (m, 4H), 6.96-6.93 (m, 4H), 6.87 (d, 1H), 6.32 (d, 2H), 6.17 (d, 2H), 5.93 (d, 2H), 4.12 (t, 4H), 3. 96 (t, 4H), 3.79 (s, 3H), 2.86-2.81 (m, 1H), 2.67-2.64 (m, 3H), 2.33-2.17 ( m, 8H), 1.75-1.59 (m, 16H), 1.49-1.35 (m, 14H).

[Comparative Production Example 1: Production of comparative compound C-1 represented by formula (C1-1)]
The comparative compound C-1 represented by the following formula (C1-1) was synthesized with reference to the synthesis of the compound 4 of Example 4 in Japanese Patent No. 5962760.

[Comparative Production Example 2: Production of comparative compound C-2 represented by formula (C1-2)]
The comparative compound C-2 represented by the following formula (C1-2) was synthesized with reference to the synthesis of the compound represented by the formula (1-3) in Example 3 of International Publication WO 2016/136533.

[Comparative Production Example 3: Production of Comparative Compound C-3 represented by Formula (C1-3)]
The comparative intermediate 1 represented by the formula (C1-3-2) was synthesized with reference to the synthesis of the compound (ex-2) of Example 1 in JP-A-2006-166344. Further, in the same manner as in Production Example 1, a carboxylic acid derivative 1 represented by the formula (1-1-3) was obtained.

Next, 1.0 g (3.7 mmol) of the comparative intermediate obtained above, 4.63 g (11 mmol) of the carboxylic acid derivative represented by the formula (1-1-3), N, N-dimethylamino To a suspension of pyridine (DMAP) 14 mg (110 μmol) in dichloromethane (10 mL) was added dropwise a solution of 2.7 g (13 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (1 mL). After completion of the dropwise addition, the mixture was stirred for 12 hours, the precipitate was filtered, and the solvent was distilled off. Chloroform (10 mL) was added to the obtained crude product, and the mixture was stirred for 1 hour and suspended and purified. The precipitate was filtered, and the obtained crystals were dried to obtain 2.3 g (2.4 mmol, yield 65%) of a comparative compound C-3 represented by the following formula (C1-3). The structure of the target product was identified by ¹ H NMR.

Phase transition temperature (at elevated temperature): C 98 N 117 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.14 (d, 1 H), 8.01 (s, 1 H), 7.86 (d, 1 H), 7.73 (d, 1 H), 7.55- 7.47 (m, 3H), 7.30-7.25 (m, 2H), 7.04-7.01 (m, 4H), 6.96-6.93 (m, 4H), 6. 32 (d, 2H), 6.17 (d, 2H), 5.93 (d, 2H), 4.12 (t, 4H), 3.96 (t, 4H), 2.86-2.81 (M, 1H), 2.71-2.61 (m, 3H), 2.33-2.17 (m, 8H), 1.75-1.59 (m, 16H), 1.49-1. .35 (m, 8H)

[Comparative Production Example 4: Production of comparative compound C-4 represented by formula (C1-4)]
6-Bromohexanol (8.5 g, 47 mmol) was added to a suspension of methyl 3- (4-hydroxyphenyl) propionate (7.9 g, 44 mmol) and potassium carbonate (6.5 g, 47 mmol) in DMF (250 ml). And stirred at 80 ° C. for 8 hours. After completion of the reaction, the reaction solution was diluted with water, extracted with ethyl acetate, and the solvent was distilled off. An aqueous solution of potassium hydroxide (2.6 g, 47 mmol) was added to the obtained crude product, and the mixture was reacted at 100 ° C. for 4 hours to hydrolyze. After completion of the reaction, an aqueous hydrochloric acid solution was added, followed by addition of ethyl acetate for extraction, and the solvent was distilled off. The residue was purified by silica gel chromatography, and the solvent was distilled off to obtain 4- (6-hydroxyhexyloxy) phenylpropionic acid in a yield of 68% (7.9 g, 30 mmol).
Next, 4- (6-hydroxyhexyloxy) phenylpropionic acid (7.9 g, 30 mmol), acryloyl chloride (3.0 g, 33 mmol), dimethylaniline (DMA) (3.6 g, 33 mmol), and tetrahydrofuran (150 mL) ) The suspension was stirred for 12 hours. After the completion of the reaction, water and ethyl acetate were added to carry out liquid separation. The solvent was distilled off, the residue was purified by silica gel chromatography, and the solvent was distilled off to give 4- [6- (acryloyloxy) hexyloxy] phenylpropionic acid in a yield of 70% (6.7 g, 21 mmol). ).
trans-4-Hydroxycyclohexanecarboxylic acid (5.0 g, 35 mmol) and triethylamine (5.3 g, 52 mmol) were dissolved in tetrahydrofuran (25 ml), and the mixture was stirred while cooling at 10 ° C or lower under a nitrogen atmosphere. Chloromethyl methyl ether (3.0 g, 37 mmol) was slowly added dropwise thereto, and the mixture was stirred at room temperature for 8 hours. Ethyl acetate and water were added to extract the organic layer, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, and dried over anhydrous magnesium sulfate to give 4.8 g (28 mmol, methoxymethyl trans-4-hydroxycyclohexanecarboxylate). (Yield 80%).
6.7 g (21 mmol) of 4- [6- (acryloyloxy) hexyloxy] phenylpropionic acid, 4.8 g (28 mmol) of methoxymethyl trans-4-hydroxycyclohexanecarboxylate, N, N-dimethylaminopyridine (DMAP) 0 To a suspension of 0.12 g (1.0 mmol) in dichloromethane (150 ml) was added dropwise a solution of 5.6 g (27 mmol) of N, N-dicyclohexylcarbodiimide (DCC) in dichloromethane (5 mL). After the completion of the dropwise addition, the mixture was stirred for 12 hours, and the precipitate was filtered. To a solution of the obtained crude product in tetrahydrofuran (20 ml) was added 0.36 g (2.1 mmol) of p-toluenesulfonic acid (pTSA), and the mixture was heated with stirring at 40 ° C. for 8 hours. The organic layer was extracted by adding ethyl acetate and water, and the organic layer was washed with saturated aqueous sodium hydrogen carbonate and water, dried over anhydrous magnesium sulfate, the solvent was distilled off under reduced pressure, and the residue was recrystallized from methanol. As a result, 3.8 g (8.6 mmol, yield 41%) of a carboxylic acid derivative 2 represented by the formula (1-4-3) was obtained.

In Comparative Production Example 3, except that the carboxylic acid derivative 2 represented by the formula (1-4-3) was used in an equimolar amount instead of the carboxylic acid derivative 1 represented by the formula (1-1-3). In the same manner as in Comparative Production Example 3, 2.3 g (2.2 mmol, yield 61%) of a comparative compound C-4 represented by the following formula (C1-4) was obtained. The structure of the target product was identified by ¹ H NMR.

Phase transition temperature (at elevated temperature): C 67 N 82 I
¹ H NMR (CDCl ₃ ; δ ppm): 8.00 (d, 1 H), 7.89 (d, 1 H), 7.54-7.34 (m, 5 H), 7.15-7.06 (m , 6H), 6.91-6.82 (m, 4H), 6.32 (d, 2H), 6.17 (d, 2H), 5.93 (d, 2H), 4.85-4. 74 (m, 2H), 4.19 (t, 4H), 3.94 (t, 4H), 2.94-2.88 (m, 4H), 2.73-2.53 (m, 6H) , 2.32-2.04 (m, 8H), 1.86-1.67 (m, 12H), 1.56-1.41 (m, 12H).

[Example 1]
(1) Production of Polymerizable Composition A polymerizable liquid crystal compound (90 parts by mass of the compound A-1 represented by the formula (1-1) and 10 parts by mass of the compound B-1 represented by the formula (2-1) 100 parts by mass) and 4 parts by mass of a photopolymerization initiator (Irgacure 907, manufactured by Ciba Specialty Chemicals) were dissolved in 900 parts by mass of cyclopentanone to produce polymerizable composition 1.

(2) Production of retardation film or transfer laminate (2-1) Preparation of composition for photo-alignment film A copolymer obtained by copolymerizing a photo-alignment monomer and hydroxyethyl methacrylate according to the description of Production Example 1 of Japanese Patent No. 5,626,493. Combined 1 was obtained.
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 having a 313 nm emission line in a vertical direction from the substrate normal using an Hg-Xe lamp and a Glan-Taylor prism at an exposure 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 shown in Table 11 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. A retardation film or a laminate for transfer was obtained.

[Examples 2 to 10, Comparative Examples 1 to 6]
(1) Production of polymerizable composition In Example 1, except that the composition of the polymerizable liquid crystal compound was changed according to Table 11 below, the polymerizable compositions 2 to 10 and the comparative polymerizable compound were prepared in the same manner as in Example 1. Compositions 1 to 6 were obtained.
(2) Production of retardation film or transfer laminate The procedure was the same as in Example 1 except that polymerizable compositions 2 to 10 and comparative polymerizable compositions 1 to 6 were used instead of polymerizable composition 1. In the same manner as in Example 1, retardation films or transfer laminates 2 to 10 and comparative retardation films or transfer laminates 1 to 6 were obtained.

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

<Solution stability>
The stability of the polymerizable composition obtained in each example and each comparative example was evaluated. The composition was stored at 25 ° C. for a specified time, and the composition after storage was visually checked, and the stability of the composition (ink) was evaluated based on the presence or absence of precipitate.
(Evaluation criteria for solution stability)
A: No precipitation after storage for 30 days B: Deposition in 7 days or more and less than 30 days C: Deposition in 1 day or more, less than 7 days D: Deposition in less than 1 day

<Orientation> The orientation of the retardation layer was evaluated in four stages by observing with a polarizing microscope.
(Evaluation criteria for orientation)
A: Uniform orientation is obtained visually, and 95% or more is oriented by observation with a polarizing microscope. B: Uniform orientation is obtained visually, and the orientation area is 90% or more and less than 95% with observation by a polarizing microscope. : The orientations of A and B were not obtained by visual observation, and the orientation area observed by a polarizing microscope was 50% or more and less than 90%. D: No orientation was observed visually, and the orientation area was observed by a polarizing microscope under 50%.

<Phase difference (wavelength dispersion)>
The in-plane phase difference Re with respect to wavelengths of 450 nm, 550 nm, and 650 nm was measured by a phase difference measuring device (manufactured by Oji Scientific Instruments, KOBRA-WR). X calculated as follows using the measured phase difference: The wavelength dispersion was evaluated from the y value.
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: 0.60 ≦ x <0.95, 1 ≦ y ... reverse wavelength dispersion B: 0.95 ≦ x <0.99, 1 ≦ y reverse wavelength dispersion C: 0.99 ≦ x <1, 1 ≦ y: flat wavelength dispersion D: 1 ≦ x, 1> y: normal dispersion

<In-plane uniformity evaluation>
The retardation value Re of light having a wavelength of 550 nm of the obtained optical film was measured. A range of 10 cm square was set on the optical film surface, and measurement was performed at 10 points within the range, and in-plane uniformity was evaluated based on the difference (ΔRe) between the maximum value and the minimum value of the obtained retardation values. .
(Evaluation criteria for in-plane uniformity)
A: ΔRe was 2 nm or less.
B: ΔRe was more than 2 nm and 3 nm or less.
C: ΔRe exceeded 3 nm.
If the in-plane uniformity evaluation is A or B, the in-plane uniformity of the retardation value is excellent.

<Birefringence>
Since there is a relationship of retardation Re (λ) = birefringence Δn (λ) × film thickness d, birefringence Δn at 550 nm was evaluated from in-plane retardation Re at 550 nm and film thickness d.
(Evaluation criteria for birefringence)
A: 0.08 or more B: 0.075 ≦ x <0.08
C: less than 0.075

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

Claims (12)

A polymerizable composition comprising a polymerizable liquid crystal compound (A) represented by the following general formula (1) and a polymerizable liquid crystal compound (B) represented by the following general formula (2).
(In the general formula (1), L ¹ , L ² , L ³ and L ⁴ are each independently —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ — , -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH- , -NH-COO -, - NH -CO-NH -, - NH-O -, - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - _{CF 2 S -, - SCF 2} -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 - _{, -OCO-CH 2 CH 2 -} , - CH 2 CH 2 -COO -, - CH 2 CH 2 -OCO -, - COO-CH 2 -, - OCO- _{H 2 -, - CH 2 -COO} -, - CH 2 -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, -CF = CF-, -C≡C- or a single bond;
A ¹ and A ² are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Represents a cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ³ and A ⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or optionally substituted by one or more substituents E, Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene-2 , 6-Diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3-dioxane Represents a -2,5-diyl group,
R ¹ and R ² each independently represent a group selected from the following formula (R-1);
Formula ^{(R-1): -L 5} -R sp1 -Z 1
In the general formula (R-1), L ⁵ represents —O—, —S—, —OCH ₂ —, —CH ₂ O—, —CH ₂ CH ₂ —, —CO—, —COO—, or —OCO—. , -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO- _{NH -, - NH-O -} , - O-NH -, - SCH 2 -, - CH 2 S -, - CF 2 O -, - OCF 2 -, - CF 2 S -, - SCF 2 -, - CH = CH-COO -, - CH = CH-OCO -, - COO-CH = CH -, - OCO-CH = CH -, - COO-CH 2 CH 2 -, - OCO-CH 2 CH 2 -, - CH _{2 CH 2 -COO -, - CH} 2 CH 2 -OCO -, - COO-CH 2 -, - OCO-CH 2 -, - CH 2 -COO -, - CH _2- OCO-, -CH = CH-, -N = N-, -CH = N-, -N = CH-, -CH = NN-CH-, -CF = CF-, -C≡C- or 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 formula (D _g -1);
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, methylamino group, dimethylamino group, diethylamino group, diisopropylamino group, trimethylsilyl group, dimethylsilyl group, thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, 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-, -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- may be replaced with, or substituents E, ^{E 1} and E ² each independently ^may represent a group represented by -L ^{E -R spE} -Z ^E, where ^{L E, R SPE,} and ^{Z E} are respectively the ^{L 5, R sp1} and, It represents the same as defined for Z ¹ , but may be the same as or different from L ⁵ , R ^sp1 and Z ¹ , respectively, and the substituents E, E ¹ and E ² in the compound May be the same or different, respectively.
When a plurality of L ³ , L ⁴ , A ³ , and A ⁴ are present, respectively, they may be the same or different.
m1 and m2 each independently represent an integer of 1 to 4, and n1 and n2 each independently represent an integer of 0 to 3. )
(In the general formula (D _g -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, each may be the same or different. Alternatively, Q ¹ and Q ² may combine to form a ring. )
(In the general formula (2), A ^core is a monocyclic ring, a condensed ring or a ring-assembled aromatic group which may be unsubstituted or substituted by one or more substituents E ³ , and has 4 carbon atoms. Represents a trivalent or tetravalent group of ~ 16,
M represents -CH = CH-, -N = CH-, -CH = N-, or -N = N-;
D ³ represents a monovalent group containing an indolenine ring structure,
L ¹¹ , L ¹² , L ¹³ and L ¹⁴ 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-CH 2 -, _{-CH 2 -COO -, - CH 2} -OCO -, - CH = CH -, - N = N -, - CH = N -, - N = CH -, - CH = N-N = CH -, - CF ＣＦCF—, —C≡C— or a single bond;
A ¹¹ and A ¹² each independently represent a cyclohexane-1,4-diyl group or a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . A cycloheptane-1,3-diyl group, a cycloheptane-1,4-diyl group, a decahydronaphthalene-2,6-diyl group or a 1,3-dioxane-2,5-diyl group;
A ¹³ and A ¹⁴ are each independently a cyclohexane-1,4-diyl group, a cyclopentane-1,3-diyl group which may be unsubstituted or substituted by one or more substituents E ³ . , Cycloheptane-1,3-diyl group, cycloheptane-1,4-diyl group, benzene-1,4-diyl group, pyridine-2,5-diyl group, pyrimidine-2,5-diyl group, naphthalene- 2,6-diyl group, naphthalene-2,7-diyl group, naphthalene-1,4-diyl group, tetrahydronaphthalene-2,6-diyl group, decahydronaphthalene-2,6-diyl group or 1,3- Represents a dioxane-2,5-diyl group,
R ¹¹ and R ¹² each independently represent a group selected from the following formula (R-11);
Formula ^{(R-11): -L 15} -R sp11 -Z 11
In the general formula ^(R-11), L 15 _{is, -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-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 SP11} 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 Each independently represents -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, -CH = CH- or -C−C- Z ¹¹ represents a polymerizable functional group.
The substituent E ³ is 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, a dimethylamino group , A diethylamino group, a diisopropylamino group, a trimethylsilyl group, a dimethylsilyl group, a thioisocyano group, or an alkyl group having 1 to 20 carbon atoms which may be substituted by these, one —CH ₂ — in the alkyl group 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- be replaced well, or substituents ^{E 3 is} represented by -L ^{E3 -R} spE3 ^{-Z E3} may represent that group, wherein ^{L E3, R SPE3,} and ^{Z E3,} respectively, wherein ^{L 15, R SP11,} and ^{Z 11} represents what is the one and the same defined, each of the ^{L 15} , R ^sp11 and Z ¹¹ may be the same or different, and when there are a plurality of substituents E ³ in the compound, they may be the same or different;
When a plurality of M, D ³ , L ¹³ , L ¹⁴ , A ¹³ , and A ¹⁴ appear, they may be the same or different.
n11 represents an integer of 1 or 2, and m11 and m12 each independently represent an integer of 1 to 4. ) In the general formula (2), wherein D ³ is a group selected from the following formulas (D g _-2), the polymerizable composition according to claim 1.
(In the general formula (D _g -2), R ^d1 and R ^d2 each independently represent an alkyl group having 1 to 20 carbon atoms, and the alkyl group is unsubstituted or one or more of the above substituted groups. may be substituted by a group E ^3, 1 single -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 -, - OCO-O -, - CO-NH -, - NH-CO -, - CH = CH-COO-, -CH = CH-OCO-, -COO-CH = CH-, -OCO-CH = CH-, -CH = CH-, -CF = CF- or -C≡C- Alternatively, R ^d1 and R ^d2 may combine with each other to form a 3- to 7-membered non-aromatic hydrocarbon ring And the non-aromatic hydrocarbon ring may be unsubstituted or substituted by one or more substituents E ³ , and any carbon atom of the non-aromatic hydrocarbon ring may be May be substituted with a hetero atom,
And ^{R e1,} R e2, R ^e3 and ^{R e4} are each independently a hydrogen atom, or wherein a substituent ^{E 3, R e1, R e2} , R e3 and ^{R e4} are 3-7 membered ring bonded to each other It may form a non-aromatic or aromatic hydrocarbon ring, optionally substituted by the non-aromatic or aromatic hydrocarbon ring or is unsubstituted or one or more of the substituents E ³ Also, any carbon atom of the non-aromatic or aromatic hydrocarbon ring may be substituted with a hetero atom. * (Asterisk) indicates the bonding position with M. ) During the general formula of the general formula _{(1) (D g -1)} , J 1 is, -O -, - S -, - N = CQ 2 - or -NQ ² - is, in claim 1 or 2 The polymerizable liquid crystal compound according to the above. In the general formula (D _g -1) of the general formula (1), J ¹ is —NQ ² —, and the Q ² may have a hydrogen atom replaced with a fluorine atom, CH ₂ — or two or more non-adjacent —CH ₂ —, each having 2 to 20 carbon atoms which may be independently replaced by —O—, —CO—, —COO—, —OCO—. The chain according to any one of claims 1 to 3, which is a chain or branched alkyl group or a cycloalkyl group having 3 to 12 carbon atoms, or the alkyl group which may be substituted by the cycloalkyl group. The polymerizable liquid crystal compound according to the above.   The polymerizable composition according to any one of claims 1 to 4, further comprising a polymerizable liquid crystal compound different from the polymerizable liquid crystal compound (A) and the polymerizable liquid crystal compound (B).   A polymer obtained by polymerizing the polymerizable composition according to claim 1.   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 5. A step of forming a film of the polymerizable composition according to any one of claims 1 to 5,
A step of at least orienting the polymerizable compound in the formed polymerizable composition,
A method for producing a retardation film, comprising a step of forming a retardation layer by at least a step of polymerizing the polymerizable compound after the orientation step. A retardation layer, comprising a support that releasably supports the retardation layer,
The retardation layer contains a cured product of the polymerizable composition according to any one of claims 1 to 5,
Transfer laminate for transfer of retardation layer.   An optical member, comprising: a polarizing plate on the retardation film according to claim 7. 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 5. 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 7 or the optical member according to claim 10.