Compound, composition, cured product, optically anisotropic body, and light guide element

Abstract

The present invention provides: a compound capable of forming a cured product that has low light absorptivity and high birefringence; a composition; a cured product; an optically anisotropic body; and a light guide element. The compound according to the present invention is represented by formula (1).

Description

Compound, composition, cured product, optically anisotropic body, light guide element

[0001] The present invention relates to a compound, a composition, a cured product, an optically anisotropic body, and a light-guiding element.

[0002] Recently, polarized light has been utilized in many optical devices or systems, and optical elements using polymerizable liquid crystal compounds are in demand for controlling the reflection, collection, and divergence of polarized light. For example, compounds containing a tolan structure (hereinafter also referred to as "tolane compounds") are known as polymerizable liquid crystal compounds. Because tolanane compounds have a relatively high refractive index, optically anisotropic bodies formed using liquid crystal compositions containing tolanane compounds tend to have a high refractive index and exhibit favorable incident-angle-dependent diffraction efficiency, whether the tolanane compounds themselves have liquid crystallinity or are used in combination with other liquid crystal compounds without having liquid crystallinity.

[0003] For example, Patent Document 1 discloses a liquid crystal compound having a tolan structure moiety.

[0004] International Publication No. 2009 / 086911

[0005] The present inventors have studied the liquid crystal compounds described in Patent Document 1 and have found that a cured product formed using the liquid crystal compound does not sufficiently achieve both suppression of light absorption and high birefringence.

[0006] In view of the above circumstances, an object of the present invention is to provide a compound capable of forming a cured product having low light absorption and high birefringence. Another object of the present invention is to provide a composition, a cured product, an optically anisotropic body, and a light guide element.

[0007] As a result of extensive research into solving the above problems, the present inventors have found that the above problems can be solved by the following configuration.

[0008] (1) A compound represented by the formula (1) described below. (2) A １１ and A １２ (3) The compound according to (1), wherein A represents a divalent aromatic ring group which may have a substituent. １１ , A １２ and A １３each independently represents a divalent ring group represented by any one of formulas (1-1) to (1-6) described below. １１ , A １２ and A １３ (5) The compound according to any one of (1) to (3), wherein each independently represents an optionally substituted 1,4-phenylene group or an optionally substituted 2,6-naphthylene group. １１ and A １２ (6) The compound according to any one of (1) to (4), wherein at least one of n represents a divalent fused ring group which may have a substituent. １１ (7) The compound according to any one of (1) to (5), wherein Z is 0. １２ (8) The compound according to (6), wherein P represents —O— or —S—. １１ represents a polymerizable group represented by any one of formulas (P-1) to (P-12) described below. １１ represents a polymerizable group represented by any one of formulas (P-13) to (P-21) described below. １１ represents a polymerizable group represented by formula (P-1) or formula (P-2). (11) The compound according to any one of (1) to (10), which has liquid crystal properties. (12) A compound represented by formula (3) described later. (13) The compound according to (12), which is a compound represented by formula (4) described later. (14) The compound according to (13), in which T is -NCS. (15) A ４１ ~A ４４ each independently represents a divalent aromatic ring group represented by any one of formulas (5-1) to (5-8) described below. ４１ ~A ４４ are each independently a divalent aromatic ring group represented by formula (5-1) or formula (5-2), and W ２ are each independently: =CR ５１-. (17) The compound according to any one of (13) to (16), in which P represents a radical polymerizable group. (18) The compound according to any one of (13) to (17), in which P represents a polymerizable group represented by any one of formulas (P-31) to (P-42) described below. (19) The compound according to (18), in which P represents a polymerizable group represented by formula (P-31). (20) The compound according to (15), in which n represents 1. (21) The compound according to any one of (13) to (20), in which the compound represented by formula (3) has two polymerizable groups represented by P. (22) Z ４１ and Z ４２ is a single bond, -O-, -S-, -OCH ２ -, -COO-, or -CONR ａ -. (23) The compound according to any one of (13) to (22), wherein t represents 1. (24) The compound according to any one of (13) to (23), which has liquid crystallinity. (25) A composition comprising the compound according to any one of (1) to (24). (26) The composition according to (25), which further comprises a polymerizable liquid crystal compound. (27) The composition according to (26), wherein the polymerizable liquid crystal compound is a compound represented by formula (2) described below. (28) n ２１ Z ２１wherein at least one of the groups represents —C≡C—. (29) The composition according to any one of (25) to (28), which has liquid crystal properties. (30) A cured product obtained by curing the composition according to any one of (25) to (29). (31) An optically anisotropic body obtained by curing the composition according to any one of (25) to (30). (32) An optically anisotropic body obtained by curing a composition containing a compound according to any one of (1) to (11), which has an alignment pattern in which the direction of the optical axis derived from the compound represented by formula (1) is continuously rotated along at least one direction in the plane. (33) An optically anisotropic body obtained by curing a composition containing a compound according to any one of (12) to (24), which has an alignment pattern in which the direction of the optical axis derived from the compound represented by formula (3) is continuously rotated along at least one direction in the plane. (34) A light guide element comprising the optical anisotropic body according to (32) and a light guide plate. (35) A light guide element comprising the optical anisotropic body according to (33) and a light guide plate.

[0009] According to the present invention, there is provided a compound capable of forming a cured product having low light absorption and high birefringence. Furthermore, according to the present invention, there are provided a composition, a cured product, an optically anisotropic body, and a light guide element.

[0010] Fig. 2 is a schematic diagram showing an embodiment of an optically anisotropic layer. Fig. 3 is a schematic plan view of the optically anisotropic layer shown in Fig. 1. Fig. 4 is a conceptual diagram showing the function of the optically anisotropic layer shown in Fig. 2. Fig. 5 is a conceptual diagram showing the function of the optically anisotropic layer shown in Fig. 2. Fig. 6 is a schematic diagram showing another example of an optically anisotropic layer. Fig. 7 is a schematic diagram showing another example of an optically anisotropic layer.

[0011] The present invention will be described in detail below. The following description of the components will be based on a representative embodiment of the present invention, but the present invention is not limited to such an embodiment. In each drawing, the scale of the components is appropriately different from the actual scale for ease of viewing.

[0012] In addition, in this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits.

[0013] In this specification, n represents the refractive index, ne represents the refractive index in the slow axis direction, and no represents the refractive index in the fast axis direction. Unless otherwise specified, n, ne, and no represent values ​​at a wavelength of 550 nm. In this specification, n, ne, and no are values ​​measured by ellipsometry.

[0014] In addition, in this specification, the term "(meth)acryloyloxy group" refers to both an acryloyloxy group and a methacryloyloxy group.

[0015] Furthermore, the bonding direction of divalent groups represented in this specification is not limited unless otherwise specified. For example, when Y is -COO- in a compound represented by the formula "X-Y-Z", Y may be -CO-O- or -O-CO-. Furthermore, the compound may be either "X-CO-O-Z" or "X-O-CO-Z".

[0016] Furthermore, in this specification, when simply referring to a "substituent," the substituent is not limited unless otherwise specified. Examples of the substituent include the groups exemplified by the substituent L below. In this specification, when referring to a "substituent L," the substituent L refers to the substituent L below.

[0017] (Substituent L) Examples of the substituent L include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkylthiocarbonyl group having 2 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, a carboxy group, a sulfo group, an amido group, a cyano group, a nitro group, a halogen atom, an NCS group, SO ２ Examples of the substituent L include an NCS group, an OCN group, a trifluoromethyl group, a vinyl group, and a polymerizable substituent. ２ When - (methylene group) is contained, -CH contained in the above group ２The substituent L also includes a group in which at least one of - is replaced with -O- or -CO-. ２ ) ２ When -(ethylene group) is contained, -(CH ２ ) ２ The substituent L also includes a group in which at least one of - is replaced by -CH=CH- or -C≡C-. For example, when the above group has two or more -CH ２ -, one -CH ２ - is replaced with -O-, and one adjacent -CH ２ - may be replaced with -CO- to form an ester group (-O-CO-). When the above group described as the substituent L has a hydrogen atom, the substituent L also includes a group in which at least one of the hydrogen atoms contained in the above group is replaced with at least one selected from the group consisting of a fluorine atom and a polymerizable group. ２ - is replaced by -O- or -CO-, and -(CH ２ ) ２ When at least one of the - is replaced with -CH=CH- or -C≡C-, the number of carbon atoms after the replacement satisfies the above-mentioned predetermined range. Furthermore, examples of the polymerizable substituent include monovalent substituents containing an ethylenically unsaturated group and a ring-polymerizable group. Among them, P １ -L １ - is preferably a monovalent substituent represented by L １ represents a single bond or an alkylene group having 10 or less carbon atoms which may have a branch, and —CH ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. R represents a hydrogen atom or a substituent. P １represents a polymerizable group, and is preferably a substituent selected from the polymerizable groups P described below. Among them, the substituent L is preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 1 to 10 carbon atoms, a halogen atom, or a polymerizable substituent, more preferably an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 2 to 10 carbon atoms, an alkanoyloxy group having 2 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a trifluoromethyl group, or a halogen atom, and even more preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkanoyloxy group having 2 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, a trifluoromethyl group, or a fluorine atom.

[0018] In addition, in this specification, when the term "polymerizable group" is simply used, examples of the polymerizable group include polymerizable groups capable of addition polymerization and ring polymerization (for example, radically polymerizable groups containing an unsaturated double bond), and examples thereof include the following polymerizable group P.

[0019] (Polymerizable Group P) Examples of the polymerizable group P include polymerizable groups represented by any of the following formulas (P-1) to (P-12) or formulas (P-13) to (P-21). In the following formulas, * represents a bonding position, and Me represents a methyl group. Among them, as the polymerizable group P, a polymerizable group represented by formula (P-1), formula (P-2), formula (P-3), formula (P-8), formula (P-9), formulas (P-12) to (P-18), or formula (P-21) is preferred, a polymerizable group represented by formula (P-1), formula (P-2), formula (P-3), formula (P-8), formula (P-9), or formulas (P-13) to (P-18) is more preferred, and a polymerizable group represented by formula (P-1) or formula (P-2) (a (meth)acryloyloxy group) is even more preferred. The polymerizable group represented by formula (P-1) or formula (P-2) (a (meth)acryloyloxy group) is also preferred in that it is subject to oxygen inhibition. Oxygen inhibition allows only a desired thickness from the air interface to be left as an uncured region, and the uncured region can be removed by solvent washing or non-oriented by heating, thereby controlling the thickness of the optically anisotropic layer. This allows, for example, adjustment of the diffraction efficiency when the present compound is used as a diffraction element.

[0020]

[0021]

[0022] Me represents a methyl group. * represents the bonding position. R ４１ represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms. ４２ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group. ４３ represents a halogen atom or an aliphatic hydrocarbon group having 2 to 10 carbon atoms, and preferably an aliphatic hydrocarbon group having 2 to 6 carbon atoms. ４４ represents a halogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. ４１ ~R ４４is an aliphatic hydrocarbon group, a hydrogen atom in the aliphatic hydrocarbon group may be replaced by a halogen atom, and —CH ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The alkyl group represented by R preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

[0023] In this specification, the "solid content" of a composition refers to components that form a cured product (e.g., an optically anisotropic layer) formed using the composition, and when the composition contains a solvent (organic solvent, water, etc.), refers to all components excluding the solvent. Furthermore, liquid components that form a cured product (e.g., an optically anisotropic layer) are also considered to be solid content.

[0024] In this specification, unless otherwise specified, the thickness of a layer is a value obtained by observing a cross section cut by a microtome with a SEM (scanning electron microscope) or a TEM (transmission electron microscope) and measuring the thickness at 10 points, and averaging the thickness.

[0025] [Compound of the Present Invention] The compounds of the present invention (the compound represented by formula (1) described later and the compound represented by formula (3) described later) will hereinafter also be referred to as "specific compounds". Hereinafter, the achievement of at least one of the effects of further suppressing light absorption in a cured product (e.g., an optically anisotropic layer) formed using the specific compounds and higher birefringence of the cured product will also be referred to as "excellent effects of the present invention". Note that, since the main use of liquid crystal compounds is expected to be in displays that use light in the visible range, it is desirable that the cured product has low light absorption (particularly absorption of light in the visible range). Since the amount of light absorption in the visible range is minute and not easy to evaluate, light absorption is evaluated using light with a wavelength of 420 nm, which is the short-wavelength light that is most easily detectable.

[0026] The compound represented by formula (1), which is one of the specific compounds, will be described in detail below.

[0027]

[0028] P １１ represents a radical polymerizable group containing an unsaturated double bond. Examples of the radical polymerizable group containing an unsaturated double bond include an ethylenically unsaturated group. Specifically, the polymerizable group represented by any one of the above formulas (P-1) to (P-12) is preferred, and the polymerizable group represented by either formula (P-1) or formula (P-2) is more preferred.

[0029] L １１ represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. ２ - is -O-, -S-, -NR-, -CO-, -CS-, -SO-, -SO ２ - or -C(=CH ２ )- in the alkylene group may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH-, -C≡C-, or -CH=N-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, more preferably 1 to 3. The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5, in terms of excellent refractive index and liquid crystal properties of the specific compound. L １１ As the alkylene group, a linear or branched alkylene group having 1 to 10 carbon atoms or -a linear or branched alkylene group having 1 to 10 carbon atoms -X- is preferred in terms of the effects of the present invention being more excellent. X is -O-, -S-, -NR-, -CO-, -CS-, -SO-, -SO ２ -, -CO-O-, or -C(=CH ２ )-. X is preferably -O-. The hydrogen atoms in the alkylene group may be replaced by fluorine atoms or chlorine atoms.

[0030] Z １１represents a single bond, —O—, —S—, —NR—, —CO—, —CS—, —SO—, or —SO ２ R represents -, and from the viewpoint of excellent refractive index and liquid crystal properties of the specific compound, a single bond, -O- or -S- is preferred, -O- or -S- is more preferred, and -O- is even more preferred. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms of the alkyl group represented by R is preferably 1 to 6, and more preferably 1 to 3. In addition, in the formula, Z １１ If there are multiple Z １１ They may be the same as or different from each other.

[0031] Z １２ represents a single bond or a divalent linking group not containing a ring structure. Examples of the divalent linking group not containing a ring structure include -O-, -S-, -NR-, -CO-, -CS-, -SO-, and -SO ２ -, -C(=CH ２ )-, a linear or branched alkylene group, or a group combining these. ２ - is -O-, -S-, -NR-, -CO-, -CS-, -SO-, -SO ２ - or -C(=CH ２ )- in the alkylene group may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH-, -C≡C-, or -CH=N-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, more preferably 1 to 3. The number of carbon atoms in the alkylene group is preferably 1 to 15, more preferably 1 to 10, and even more preferably 1 to 5, in terms of excellent refractive index and liquid crystal properties of the specific compound. Z １２ As the group, a single bond, —O—, —S—, —NR—, —CO—, —CS—, —SO—, —SO２ -, -CO-O-, or -X-, a linear or branched alkylene group having 1 to 10 carbon atoms, is preferred. X is -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ -, -CO-O-, or -C(=CH ２ )-. A hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. Of these, -O- or -S- is preferred, and -O- is more preferred.

[0032] A １１ and A １２ each independently represents a divalent aromatic ring group which may have a substituent, or a divalent alicyclic group which may have a substituent. １３ represents a divalent aromatic ring group which may have a substituent. １３ If there are multiple A's, １３ They may be the same as or different from each other.

[0033] Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the divalent aromatic hydrocarbon ring group is preferably 6 to 20, and more preferably 6 to 10. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group is preferably a benzene ring or a naphthalene ring.

[0034] The number of ring members in the aromatic heterocycle constituting the divalent aromatic heterocyclic group is preferably 5 to 10, and more preferably 5 or 6. Examples of heteroatoms contained in the aromatic heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of carbon atoms in the aromatic heterocycle is preferably 3 to 20, and more preferably 3 to 10. Examples of the aromatic heterocycle include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a thienothiophene ring group, a thienothiazole ring, a thiazolothiazole ring, and a benzothiophene ring.

[0035] Examples of the divalent alicyclic group include a divalent aliphatic hydrocarbon ring group and a divalent aliphatic heterocyclic group. The aliphatic hydrocarbon ring constituting the divalent aliphatic hydrocarbon ring group may be either a monocyclic or a polycyclic ring. The number of ring members in the aliphatic hydrocarbon ring is preferably 3 to 20, more preferably 3 to 10, and even more preferably 5 or 6. Specific examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a norbornene ring, and an adamantane ring. Of these, a cyclopentane ring or a cyclohexane ring is preferred.

[0036] The aliphatic heterocycle constituting the divalent aliphatic heterocyclic group may be either a monocycle or a polycycle. Examples of heteroatoms contained in the aliphatic heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of ring members in the aliphatic heterocycle is not particularly limited, but 5 to 10 is preferable. Examples of the aliphatic heterocycle include an oxolane ring, an oxane ring, a piperidine ring, and a piperazine ring. Note that the aliphatic heterocycle is preferably a ring containing -CH ２ The - may be substituted with -CO-, for example, a phthalimide ring.

[0037] A １１ , A １２ and A １３ is preferably a divalent aromatic ring group which may have a substituent, and more preferably a divalent ring group represented by any one of the following formulas (1-1) to (1-6): In formulas (1-1) to (1-6), * represents a bonding position.

[0038]

[0039] In formulas (1-1) to (1-6), W １ are each independently: =CR １ - or =N-. １ are each independently -NR １ represents -, -O-, or -S-. １ represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. １ is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.１ The alkyl group represented by the formula (I) preferably has 1 to 6 carbon atoms, more preferably 1 to 3 carbon atoms.

[0040] A １１ , A １２ , and A １３ is preferably a 1,4-phenylene group which may have a substituent or a 2,6-naphthylene group which may have a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L.

[0041] A １１ and A １２ The number of rings in the fused ring group may be 2 to 4, and the fused ring group is preferably a bicyclic fused ring group, since this makes it easier for the specific compound to exhibit liquid crystallinity and provides excellent solubility.

[0042] The bicyclic fused ring group is preferably a divalent ring group represented by any one of formulas (1-2) to (1-6). The fused ring constituting the bicyclic fused ring group is preferably a naphthalene ring, a thienothiophene ring, a thienothiazole ring, or a thiazolothiazole ring, and more preferably a naphthalene ring.

[0043] The divalent aromatic ring group and the divalent alicyclic group may have a substituent L. The substituent L is as described above.

[0044] n １１ represents an integer of 0 to 4, preferably 0. １２ When is a single bond, n １１ is 0.

[0045] Examples of the specific compound represented by formula (1) are given below, but the invention is not limited thereto.

[0046]

[0047]

[0048]

[0049] The compound represented by formula (3), which is one of the specific compounds, will be described in detail below.

[0050] (R ３１ ) ｍ -MG-NCS In formula (3), MG represents a mesogenic structure that does not contain an aliphatic ring and may have a substituent. MG corresponds to an m+1 valent group. A mesogenic structure is a highly rigid partial structure, and is a structure derived from a functional group that has strong intermolecular forces and orientation. The mesogenic structure contributes to the formation of liquid crystals. The mesogenic structure typically contains an aromatic ring. The aromatic ring may be an aromatic hydrocarbon ring or an aromatic heterocycle. The mesogenic structure does not contain an aliphatic ring. The substituent that the mesogenic structure may have is not particularly limited, and examples thereof include the substituent L described above. Among these, the substituent A described below is preferred.

[0051] m represents an integer of 1 to 4. Among these, an integer of 1 to 3 is preferred, and 1 or 2 is more preferred, in terms of refractive index.

[0052] R ３１ represents a group represented by formula (X). * represents a bonding position.

[0053]

[0054] In formula (X), Sp represents a single bond or a linear or branched (n+1)-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 6, more preferably 1 to 3, from the viewpoints of refractive index and liquid crystal properties. Any —CH ２ - is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ -, and any -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and any hydrogen atom in the aliphatic hydrocarbon group may be replaced by a fluorine atom or a chlorine atom. ａrepresents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the alkyl group is preferably 1 to 6, and more preferably 1 to 3. From the viewpoints of refractive index and liquid crystal properties, Sp is preferably a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, or -linear or branched alkylene group having 1 to 10 carbon atoms-X ａ - is preferred. ａ is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ - represents X ａ is preferably —O—. The hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom.

[0055] P represents a polymerizable group. The type of polymerizable group is not particularly limited, and examples include radically polymerizable groups and cationically polymerizable groups. Among these, polymerizable groups represented by any of formulas (P-31) to (P-42) are preferred, and the polymerizable group represented by formula (P-31) is more preferred in that the refractive index of the cured film increases due to cure shrinkage. The polymerizable group of formula (P-31) is also preferred in that it is subject to oxygen inhibition. Due to oxygen inhibition, only a desired thickness from the air interface is left as an uncured region, and the uncured region can be removed by solvent washing or de-oriented by heating, thereby controlling the thickness of the optically anisotropic layer. This allows, for example, adjustment of the diffraction efficiency when the present compound is used as a diffraction element.

[0056]

[0057] X １ represents O (oxygen atom) or S (sulfur atom). １ is preferably O. ２ is O, S or NR ４２ represents. ２ is preferably O. ４２ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom in the aliphatic hydrocarbon group may be replaced by a halogen atom; ２- represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be replaced by R ４２ is preferably a hydrogen atom or an aliphatic hydrocarbon group having 1 to 6 carbon atoms, more preferably a hydrogen atom or a methyl group. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the above-mentioned alkyl group represented by R is preferably 1 to 6, more preferably 1 to 3. * represents a bonding position.

[0058] n represents 1 or 2. However, when Sp is a single bond, n represents 1. Among these, n is preferably 1 in terms of refractive index.

[0059] The compound represented by formula (3) has two or more polymerizable groups represented by P. In other words, the product of m and n is 2 or more. The number of polymerizable groups represented by P that the compound represented by formula (3) has may be 2 or more, and is preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.

[0060] As the compound represented by formula (3), the compound represented by formula (4) is preferred in that the effects of the present invention are more excellent.

[0061]

[0062] In formula (4), A ４１ ~A ４４ each independently represents a divalent aromatic ring group which may have a substituent A. Among them, A is particularly preferred in terms of curability. ４１ ~A ４４ At least one of the groups is preferably a divalent aromatic ring group having a substituent A, and A ４１ ~A ４４It is more preferable that one or two of the groups be a divalent aromatic ring group having a substituent A. Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the divalent aromatic hydrocarbon ring group is preferably 6 to 20, more preferably 6 to 10. The aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group is preferably a benzene ring or a naphthalene ring.

[0063] The number of ring members in the aromatic heterocycle constituting the divalent aromatic heterocyclic group is preferably 5 to 10, and more preferably 5 or 6. Examples of heteroatoms contained in the aromatic heterocycle include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of carbon atoms in the aromatic heterocycle is preferably 3 to 20, and more preferably 3 to 10. Examples of the aromatic heterocycle include a pyridine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a thiophene ring, a thiazole ring, an imidazole ring, a thienothiophene ring group, a thienothiazole ring, a thiazolothiazole ring, and a benzothiophene ring.

[0064] The substituent A represents a group represented by formula (X), a group represented by formula (Y), or a substituent not containing an aliphatic ring other than a group represented by formula (X) and a group represented by formula (Y). Among them, the group represented by formula (X) is preferred as the substituent A. * represents a bonding position. The group represented by formula (X) has been described above.

[0065]

[0066] The definitions of P, Sp, and n in formula (Y) are the same as those of P, Sp, and n in formula (X). In formula (Y), Ar represents a divalent aromatic ring group. Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. Preferred embodiments of the divalent aromatic hydrocarbon ring group and the divalent aromatic heterocyclic group include the above-mentioned A ４１ ~A ４４ These are the same as the preferred embodiments of the divalent aromatic hydrocarbon ring group and the divalent aromatic heterocyclic group exemplified as the divalent aromatic ring group represented by the following formula:

[0067] Examples of the substituents not containing an aliphatic ring other than the group represented by formula (X) and the group represented by formula (Y) include at least one or more —CH ２ - is -NH-, -O-, -S-, -CO-, -SO-, or -SO ２ Examples of the alkyl group include an alkyl group having 1 to 10 carbon atoms, which may be substituted with -, a hydroxy group, an amino group, a mercapto group, a carboxy group, a sulfo group, an amido group, a cyano group, a nitro group, and a halogen atom. In terms of having an excellent refractive index, examples of the alkyl group include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an alkanoyl group having 1 to 6 carbon atoms, an alkanoyloxy group having 1 to 6 carbon atoms, an alkanoylamino group having 1 to 6 carbon atoms, an alkanoylthio group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, an alkylaminocarbonyl group having 2 to 6 carbon atoms, an alkylthiocarbonyl group having 2 to 6 carbon atoms, and the like.

[0044] Preferred are an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkylthio group having 1 to 6 carbon atoms, an alkanoyl group having 1 to 6 carbon atoms, an alkanoyloxy group having 1 to 6 carbon atoms, an alkanoylamino group having 1 to 6 carbon atoms, an alkanoylthio group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, an alkylaminocarbonyl group having 2 to 6 carbon atoms, an alkylthiocarbonyl group having 2 to 6 carbon atoms, an amido group, a cyano group, a nitro group, or a halogen atom, more preferred are an alkyl group having 1 to 6 carbon atoms, an alkanoylamino group having 1 to 6 carbon atoms, an alkanoylthio group having 1 to 6 carbon atoms, an alkyloxycarbonyl group having 2 to 6 carbon atoms, an alkylaminocarbonyl group having 2 to 6 carbon atoms, an alkylthiocarbonyl group having 2 to 6 carbon atoms, an amido group, a cyano group, a nitro group, or a halogen atom.

[0068] A ４１ ~A ４４ As the aromatic ring group, a divalent aromatic ring group represented by any one of the following formulas (5-1) to (5-8) is preferred, and a divalent aromatic ring group represented by formula (5-1) or formula (5-2) is more preferred, in terms of superior effects of the present invention. In formulas (5-1) to (5-8), * represents a bonding position.

[0069]

[0070] In formula (4), A ４１ ~A ４４When the total number of monocyclic aromatic rings contained in is 5 or more, the birefringence is more excellent. The monocyclic aromatic ring refers to an uncondensed monocyclic aromatic ring or an individual monocyclic aromatic ring in a condensed ring. That is, the phenylene group is a group having one benzene ring, which is a monocyclic aromatic ring, and the naphthylene group is a group having two benzene rings, which are monocyclic aromatic rings. Therefore, for example, A ４１ is a naphthylene ring, the number of monocyclic aromatic rings is 2. There is no particular upper limit to the total number, but it is preferably 10 or less, more preferably 6 or less.

[0071] W ２ are each independently: =CR ５１ - or =N-. In particular, W ２ As = CR ５１ - is preferred. ２ are each independently -NR ５１ represents -, -O-, or -S-. ５１ represents a hydrogen atom, a group represented by formula (X), a group represented by formula (Y), or a substituent not containing an aliphatic ring other than the group represented by formula (X) and the group represented by formula (Y). The group represented by formula (X) and the group represented by formula (Y) have been described above. Examples of the substituent not containing an aliphatic ring other than the group represented by formula (X) and the group represented by formula (Y) include the groups exemplified in the description of the substituent A above.

[0072] Z ４１ and Z ４２ each independently represents a single bond, —O—, —S—, or —CHR ａ CHR ａ --OCHR ａ -, -CO-, -SO-, -SO ２ -, -COO-, -CO-S-, -O-CO-O-, -CO-NR ａ -, -SCHR ａ --, --SO-CHR ａ -, -SO ２ -CHR ａ -, -CF ２ O-, -CF ２ S-, -OCHR ａ CHR ａ O-, -SCHR ａ CHRａ S-, -SO-CHR ａ CHR ａ -SO-, -SO ２ -CHR ａ CHR ａ -SO ２ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CHR ａ CHR ａ -, -OCO-CHR ａ CHR ａ -, -COO-CHR ａ -, -OCO-CHR ａ -, -CR ａ =CR ａ -, -CR=N-, -N=N-, -CR ａ =N-N=CR ａ Among them, a single bond, —O—, —S—, —OCH ２ -, -COO-, or -CONR ａ As mentioned above, R ａ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.

[0073] L ４１ represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. The number of carbon atoms in the alkylene group is preferably 1 to 10, and more preferably 1 to 5. Any —CH ２ - is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ -, and any -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and any hydrogen atom of the alkylene may be replaced by a fluorine atom or a chlorine atom. ａ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. ４１ In terms of refractive index and liquid crystal property, a linear or branched alkylene group having 1 to 10 carbon atoms or -X ｂ- a linear or branched alkylene group having 1 to 10 carbon atoms -X ｂ - is preferred. ｂ is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ - represents X ｂ is preferably —O—. The hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom.

[0074] T represents -NCS, a group represented by formula (X), or a substituent not containing an aliphatic ring other than NCS and a group represented by formula (X). Of these, -NCS is preferred in terms of refractive index. The group represented by formula (X) is as described above. Examples of substituents other than NCS and the group represented by formula (X) that do not contain an aliphatic ring include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, alkylamino groups having 1 to 10 carbon atoms, alkylthio groups having 1 to 10 carbon atoms, alkanoyl groups having 1 to 10 carbon atoms, alkanoyloxy groups having 1 to 10 carbon atoms, alkanoylamino groups having 1 to 10 carbon atoms, alkanoylthio groups having 1 to 10 carbon atoms, alkyloxycarbonyl groups having 2 to 10 carbon atoms, alkylaminocarbonyl groups having 2 to 10 carbon atoms, alkylthiocarbonyl groups having 2 to 10 carbon atoms, hydroxy groups, amino groups, mercapto groups, carboxy groups, sulfo groups, amido groups, cyano groups, nitro groups, and halogen atoms.

[0075] s1 represents an integer of 1 to 4. In particular, s1 is preferably 1 or 2 in terms of absorbency. s2 represents an integer of 0 to 4. In particular, s2 is preferably 1 or 2 in terms of refractive index and absorbency. t represents an integer of 0 or 1. In particular, t is preferably 1 in terms of refractive index and curability.

[0076] The number of polymerizable groups represented by P contained in the compound represented by formula (4) may be 2 or more, preferably 2 to 10, more preferably 2 to 4, and even more preferably 2.

[0077] An example of the compound represented by formula (3), which is one type of specific compound, will be given below, but the present invention is not limited to this.

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090] The specific compounds (compounds represented by formula (1) and formula (3)) may or may not have liquid crystallinity, but preferably have liquid crystallinity. The phrase "a compound exhibits liquid crystallinity" means that the compound has the property of exhibiting an intermediate phase between a crystalline phase (low temperature side) and an isotropic phase (high temperature side) when the temperature is changed. A specific observation method involves heating or cooling the compound using a Mettler Toledo hot stage system FP90 or the like while observing under a polarizing microscope, thereby confirming the optical anisotropy and fluidity derived from the liquid crystal phase.

[0091] [Composition] [Specific Compound] The composition of the present invention contains a compound represented by Formula (1) or a compound represented by Formula (3) (specific compound). The specific compound is as described above. The composition of the present invention preferably has liquid crystallinity. The content of the specific compound in the composition is not particularly limited, but is, for example, preferably 5 to 100% by mass, more preferably 10 to 95% by mass, and even more preferably 20 to 80% by mass, relative to the total mass of the liquid crystal compounds in the composition. The composition may contain one specific compound alone, or two or more specific compounds. When two or more specific compounds are used, the total content thereof preferably falls within the above range. The content of the specific compound in the composition is not particularly limited, but is preferably 5 to 100% by mass, more preferably 10 to 95% by mass, and even more preferably 20 to 80% by mass, relative to the total mass of the solids in the composition.

[0092] [Polymerizable Liquid Crystal Compound] The composition of the present invention may contain a polymerizable liquid crystal compound other than the specific compound. The polymerizable liquid crystal compound is a compound that has a polymerizable group and exhibits liquid crystallinity.

[0093] The polymerizable liquid crystal compound may be a rod-shaped liquid crystal compound or a discotic liquid crystal compound, and examples thereof include rod-shaped nematic liquid crystal compounds having a polymerizable group. Examples of rod-shaped nematic liquid crystal compounds include azomethines, azoxy compounds, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, and alkenylcyclohexylbenzonitriles. In addition to low-molecular-weight liquid crystal compounds, polymeric liquid crystal compounds can also be used.

[0094] The number of polymerizable groups that the polymerizable liquid crystal compound has may be one or more, and is preferably 1 to 6, more preferably 1 to 3, and even more preferably 2. The polymerizable liquid crystal compound can be obtained by introducing a polymerizable group into a liquid crystal compound.

[0095] Examples of the polymerizable group include known chain-polymerizable groups (chain-polymerizable groups), of which unsaturated bond groups (e.g., ethylenically unsaturated groups) are preferred, and radically polymerizable groups containing an unsaturated double bond are more preferred. Specific examples of the polymerizable group include the groups represented by the above-mentioned formulas (P-1) to (P-12) or formulas (P-13) to (P-21), and among these, an acryloyloxy group (corresponding to the above formula (P-1)) or a methacryloyloxy group (corresponding to the above formula (P-2)) is preferred in terms of achieving better effects of the present invention.

[0096] The polymerizable liquid crystal compound is preferably a compound represented by the following formula (2).

[0097]

[0098] In formula (2), P ２１ and P ２２ each independently represents a polymerizable group, the definition of which is as described above.

[0099] n ２１ represents an integer of 1 to 10. ２１ is preferably an integer of 2 to 8, and more preferably an integer of 2 to 6.

[0100] L ２１ and L ２２ each independently represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. R represents a hydrogen atom or a substituent. The substituent is not particularly limited, and examples thereof include the above-mentioned substituent L. R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, and more preferably 1 to 3. L ２１ and L ２２The number of carbon atoms in the alkylene group represented by the formula (I) is preferably 1 to 12, more preferably 1 to 10, and even more preferably 1 to 6. ２１ and L ２２ Among them, -CH ２ An alkylene group having 1 to 10 carbon atoms in which - may be substituted by -O-, -S-, or -COO- is preferred, and -CH ２ An alkylene group having 1 to 6 carbon atoms, in which - may be substituted with -O-, -S-, or -COO-, is more preferred. ２１ and L ２２ The alkylene group represented by the formula (I) may have a substituent (preferably the above-mentioned substituent L), but preferably has no substituent.

[0101] Z ２１ represents a single bond or a divalent linking group. ２１ Examples of the divalent linking group represented by the formula: ２ represents one or a combination of two or more selected from the group consisting of -, -O-, -NH-, -S-, -C=C-, -CO-, -CS-, -CH=N-, -N=N-, and -C≡C-, provided that any substitutable hydrogen atom in these groups may be substituted with a halogen atom (such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom). Z ２１ Examples of the alkyl group include a single bond, —O—, —S—, and —OCH ２ -, -CH ２ CH ２ -, -CO-, -CS-, -COO-, -CSO-, -CSS-, -CO-S-, -O-CO-O-, -CO-CO-, -CO-NH-, -SCH ２ -, -CF ２ O-, -CF ２ S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH ２ CH ２ --, --OCO-CH ２ CH ２ --, --COO-CH ２ --, --OCO-CH ２ -, -COO-NH-, -OCO-NH-, -CH=CH-, -N=N-, -CH=N-N=CH-, -CH=N-, -CF=CF-, -C≡C-, -C≡C-C≡C-, -OCH２ CH ２ O- or -SCH ２ CH ２ S- is preferred, a single bond, —OCH ２ -, -CH ２ CH ２ -, -COO-, -CSO-, -CSS-, -CO-S-, -CO-CO-, -CO-NH-, -SCH ２ -, -CF ２ O-, -CF ２ S—, —CH═N—, —C≡C—, or —C≡C—C≡C— is more preferred, and a single bond, —OCH ２ -, -C≡C-, or -COO- is more preferred. ２１ Z ２１ It is preferred that at least one of the divalent linking groups represented by the formula (I) is -C≡C-, in that excellent anisotropy is obtained when the compound is used as an optically anisotropic layer.

[0102] A ２１ and A ２２ each independently represents a divalent aromatic ring group which may have a substituent, or a divalent alicyclic group which may have a substituent.

[0103] Examples of the divalent aromatic ring group include a divalent aromatic hydrocarbon ring group and a divalent aromatic heterocyclic group. The aromatic ring constituting the divalent aromatic ring group may be either a monocyclic or polycyclic ring. The number of carbon atoms in the aromatic hydrocarbon ring constituting the divalent aromatic hydrocarbon ring group is preferably 6 to 10. Specific examples of the aromatic hydrocarbon ring include a benzene ring and a naphthalene ring, and a benzene ring is more preferred. The number of ring members in the aromatic heterocyclic ring constituting the divalent aromatic heterocyclic group is preferably 5 to 10, and more preferably 5 or 6. Examples of heteroatoms contained in the aromatic heterocyclic ring include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms contained in the aromatic heterocyclic ring is not particularly limited, and is, for example, preferably 1 to 4, and more preferably 1 or 2. Specific examples of the aromatic heterocyclic ring include A １１ and A １２ Examples of the aromatic heterocycles include those described above.

[0104] Examples of the divalent alicyclic group include a divalent aliphatic hydrocarbon ring group and a divalent aliphatic heterocyclic group. The alicyclic ring constituting the divalent alicyclic group may be either a monocyclic or polycyclic ring. The number of ring members in the aliphatic hydrocarbon ring constituting the divalent aliphatic hydrocarbon ring group is preferably 5 to 12, more preferably 5 to 10, and even more preferably 5 or 6. Specific examples of the aliphatic hydrocarbon ring include A １１ and A １２ Examples of the aliphatic heterocycle include the aliphatic hydrocarbon rings described above. Examples of heteroatoms contained in the aliphatic heterocycle constituting the divalent aliphatic heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of ring members in the aliphatic heterocycle is not particularly limited, but is preferably 5 to 10. Specific examples of the aliphatic heterocycle include the aliphatic heterocycles described above in the aliphatic hydrocarbon ring.

[0105] The hydrogen atoms in the divalent aromatic ring group and the divalent alicyclic group may be substituted with other substituents. Examples of the other substituents include the above-mentioned substituent L and a group represented by formula (PA), and the above-mentioned substituent L is preferred. Formula (PA)*-L Ａ -P Ａ In formula (PA), L Ａ represents a single bond or a divalent linking group. Ａ The divalent linking group represented by is not particularly limited, and for example, is at least one or more —CH ２ - is -NH-, -O-, -S-, -CO-, -SO-, or -SO ２ L represents an alkylene group having 1 to 10 carbon atoms, which may be substituted with -. The alkylene group is preferably linear or branched. Ａ The divalent linking group represented by the formula (I) is at least one -CH ２ A linear or branched alkylene group having 1 to 10 carbon atoms in which - is substituted with -O- is preferred. Ａ represents a polymerizable group. The polymerizable group is as described above.

[0106] In formula (2), A ２１ and A ２２ A is preferably a divalent aromatic hydrocarbon ring group which may have a substituent. ２１ and A ２２An example of the above is a phenylene group bonded at the 1- and 4-positions.

[0107] Also, A ２１ and A ２２ Another aspect of the present invention is ２１ A ２１ and A ２２ and at least one of the groups represented by the formulas (Ar-1) to (Ar-5) below is an aromatic hydrocarbon ring group selected from the group consisting of groups represented by the formulas (Ar-1) to (Ar-5) below. ２１ and A ２２ contains any aromatic hydrocarbon ring group selected from the group consisting of groups represented by formula (Ar-1) to formula (Ar-5), n ２１ represents 2, and P ２１ The second A from the side ２１ represents any one of aromatic hydrocarbon rings selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-5), or n ２１ represents 4, and P ２１ The third A from the side ２１ represents any one of aromatic hydrocarbon rings selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-5), or n ２１ represents 4, and P ２１ The second and fourth A from the side ２１ represents any one of aromatic hydrocarbon rings selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-5), or n ２１ represents 5, and P ２１ The second and fifth A's from the side ２１ represents any one of the aromatic hydrocarbon rings selected from the group consisting of groups represented by formulae (Ar-1) to (Ar-5).

[0108]

[0109] In formula (Ar-1), Q １ represents ═N— or ═CH—. ２ is -S-, -O-, or -N(R ６ )-. ６ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. ６Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0110] Y １ represents an aromatic hydrocarbon ring group having 6 to 12 carbon atoms which may have a substituent, an aromatic heterocyclic group having 3 to 12 carbon atoms which may have a substituent, or an alicyclic hydrocarbon group having 6 to 20 carbon atoms which may have a substituent, and -CH ２ One or more of - may be substituted with -O-, -S-, or -NH-. １ Examples of the aromatic hydrocarbon ring group having 6 to 12 carbon atoms represented by the formula (I) include a phenyl group, a 2,6-diethylphenyl group, and a naphthyl group. １ Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by the formula (I) include a thienyl group, a thiazolyl group, a furyl group, and a pyridyl group. １ Examples of the alicyclic hydrocarbon group having 6 to 20 carbon atoms represented by the formula (I) include a cyclohexylene group, a cyclopentylene group, a norbornylene group, and an adamantylene group. １ Examples of the substituent that may be possessed by include the substituent L described above.

[0111] In addition, in the above formulas (Ar-1) to (Ar-5), Z １ , Z ２ , and Z ３ each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms, a monovalent aromatic heterocyclic group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ７ , -NR ８ R ９ , -SR １０ , -COOR １１ , or -COR １２ Represents R ７ ~R １２ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. １and Z ２ may be bonded to each other to form an aromatic ring.

[0112] Z １ , Z ２ , and Z ３ The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms. １ , Z ２ , and Z ３ Examples of the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, an isopropyl group, a tert-pentyl group (1,1-dimethylpropyl group), a tert-butyl group, and a 1,1-dimethyl-3,3-dimethyl-butyl group.

[0113] Z １ , Z ２ , and Z ３ Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms represented by the formula (I) include monocyclic saturated hydrocarbon groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecyl group, methylcyclohexyl group, and ethylcyclohexyl group; monocyclic unsaturated hydrocarbon groups such as cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, and cyclodecadiene; bicyclo[2.2.1]heptyl group, bicyclo[2.2.2]octyl group, tricyclo[5.2.1.0]heptyl group, bicyclo[5.2.1.0]octyl group, tri ... ２，６ ]decyl group, tricyclo[3.3.1.1 ３，７ ]decyl group, tetracyclo[6.2.1.1 ３，６ .0 ２，７ ] dodecyl group, and polycyclic saturated hydrocarbon groups such as adamantyl group; and the like.

[0114] Z １ , Z ２ , and Z ３ As the monovalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms represented by the formula: Z, an aryl group having 6 to 12 carbon atoms (particularly a phenyl group) is preferred. １, Z ２ , and Z ３ Examples of the monovalent aromatic hydrocarbon ring group having 6 to 20 carbon atoms represented by the formula Z include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group. １ , Z ２ , and Z ３ Examples of the monovalent aromatic heterocyclic group having 6 to 20 carbon atoms represented by the formula (I) include a 4-pyridyl group, a 2-furyl group, a 2-thienyl group, a 2-pyrimidinyl group, and a 2-benzothiazolyl group. １ , Z ２ , and Z ３ Examples of the halogen atom represented by the formula (I) include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0115] R ７ ~R １２ Examples of the alkyl group having 1 to 6 carbon atoms represented by the formula (I) include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group.

[0116] In the above formula (Ar-2) and formula (Ar-3), A ３ and A ４ are each independently —O—, —N(R １３ represents a group selected from the group consisting of —, —S—, and —CO—. １３ represents a hydrogen atom or a substituent. １３ Examples of the substituent represented by the formula (I) include the substituent L described above.

[0117] In formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 which may have a substituent bonded thereto. Examples of the nonmetallic atom of Groups 14 to 16 represented by X include an oxygen atom, a sulfur atom, a hydrogen atom, or a nitrogen atom bonded to a substituent [═N—R Ｎ１ , R Ｎ１ represents a hydrogen atom or a substituent.], a carbon atom to which a hydrogen atom or a substituent is bonded [═C—(R Ｃ１ ) ２ , R Ｃ１represents a hydrogen atom or a substituent. Examples of the substituent include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, an alkylcarbonyl group, a sulfo group, and a hydroxyl group.

[0118] In formula (Ar-3), D ７ and D ８ each independently represents a single bond, or —CO—, —O—, —S—, —C(═S)—, or —CR １ R ２ -, -CR ３ =CR ４ -, -NR ５ -, or a divalent linking group consisting of two or more of these. １ ~R ５ each independently represents a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 12 carbon atoms. ７ and D ８ Examples of the divalent linking group represented by the formula (I) include -CO-, -O-, -CO-O-, -CSO-, and -CR １ R ２ -, -CR １ R ２ -CR １ R ２ -, -O-CR １ R ２ -, -CR １ R ２ -O-CR １ R ２ -, -CO-O-CR １ R ２ -, -O-CO-CR １ R ２ -, -CR １ R ２ -O-CO-CR １ R ２ -, -CR １ R ２ -CO-O-CR １ R ２ -, -NR ５ -CR １ R ２ - and -CO-NR ５- is exemplified, and -CO-, -O-, or -CO-O- is preferred.

[0119] In formula (Ar-3), L ３ and L ４ are each independently a single bond, a chain (linear or branched) alkylene group having 1 to 14 carbon atoms, or a —CH ２ represents a divalent linking group in which one or more -'s are substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-. Q represents a substituent. Examples of the substituent include the substituent L described above.

[0120] In formula (Ar-3), P ３ and P ４ each independently represents a monovalent organic group. ３ and P ４ At least one of them represents a polymerizable group. ３ and P ４ Examples of the monovalent organic group represented by the formula (P-1) include a group corresponding to the organic group exemplified as the substituent L (preferably an alkyl group, an aryl group, or a heteroaryl group), and a polymerizable group (preferably a polymerizable group represented by the above-mentioned formula (P-1) to formula (P-12)).

[0121] In formulas (Ar-4) to (Ar-5), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. Here, the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may be bonded to form a ring. Q ３ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent. Examples of Ax and Ay include those described in paragraphs 0039 to 0095 of WO 2014 / 010325. ３Examples of the alkyl group having 1 to 20 carbon atoms represented by include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, and an n-hexyl group. Examples of the substituent include the substituent L described above.

[0122] In addition, in formula (2), A ２１ If there are multiple A's, ２１ may be the same or different. ２１ If there are multiple Z ２１ They may be the same as or different from each other.

[0123] The polymerizable liquid crystal compound preferably contains a tolan structure moiety in its molecule. The tolan structure moiety refers to a structural moiety represented by *-Ph-C≡C-Ph-* (where Ph represents a benzene ring group which may have a substituent, and * represents a bonding position). When a polymerizable liquid crystal compound contains a tolan structure moiety in its molecule, an optically anisotropic layer formed from the composition has a large diffraction angle and is likely to produce diffracted light with high diffraction efficiency. Furthermore, conventional optically anisotropic layers formed from compositions containing liquid crystal compounds having a tolan structure moiety have sometimes exhibited poor lamination properties. The present inventors' recent studies have shown that by using a specific compound in combination with a polymerizable liquid crystal compound having a tolan structure moiety (in other words, when a composition contains a polymerizable liquid crystal compound having a tolan structure moiety and a specific compound), an optically anisotropic layer having excellent transparency, refractive index, and lamination properties can be formed.

[0124] In addition, the polymerizable liquid crystal compound is preferably a polymerizable liquid crystal compound having reverse wavelength dispersion. In this specification, the phrase "a liquid crystal compound having reverse wavelength dispersion" refers to a property in which, when an optically anisotropic layer prepared using such a liquid crystal compound is measured for in-plane retardation (Re) in the visible light region, the Re value increases as the measured wavelength increases.

[0125] As the polymerizable liquid crystal compound, there are mentioned Makromol. Chem. , Vol. 190, p. 2255 (1989), Advanced Materials Vol. 5, p. 107 (1993), U.S. Pat. No. 4,683,327, U.S. Pat. No. 5,622,648, U.S. Pat. No. 5,770,107, WO 95 / 022586, WO 95 / 024455, WO 97 / 000600, WO 98 / 023580, WO 98 / 052905, JP-A-1-272551, JP-A-6-016616, JP-A-7-110469, JP-A-11-080081, and compounds described in JP-A-2001-328973 can also be preferably used. Furthermore, as the polymerizable liquid crystal compound, for example, those described in JP-A-11-513019 and JP-A-2007-279688 can also be preferably used.

[0126] Two or more types of polymerizable liquid crystal compounds may be used in combination, which can lower the alignment temperature.

[0127] Other polymerizable liquid crystal compounds that can be used include cyclic organopolysiloxane compounds having a cholesteric phase, such as those disclosed in JP-A-57-165480. The polymerizable liquid crystal compound may also be a polymeric liquid crystal compound. Examples of polymeric liquid crystal compounds that can be used include polymers having mesogenic groups that exhibit liquid crystallinity introduced into the main chain, side chain, or both the main chain and side chain; polymeric cholesteric liquid crystals having cholesteryl groups introduced into the side chain; liquid crystalline polymers such as those disclosed in JP-A-9-133810; and liquid crystalline polymers such as those disclosed in JP-A-11-293252.

[0128] As the polymerizable liquid crystal compound, for example, those described in JP-A Nos. 2007-108732 and 2010-244038 can also be preferably used.

[0129] The birefringence Δn of the polymerizable liquid crystal compound is preferably 0.15 or more, more preferably 0.20 or more, and even more preferably 0.25 or more, from the viewpoint that when used as an optically anisotropic layer, the compound has excellent anisotropy, and when used as a diffraction element, the compound can obtain diffracted light with high diffraction efficiency at a large diffraction angle. The upper limit is not particularly limited, but is often 0.80 or less. Specific examples of polymerizable liquid crystal compounds having large refractive index anisotropy include, for example, JP 2009-102245 A, JP 4655348 A, JP 4524827 A, JP 4720200 A, JP 2004-091380 A, JP 3972430 A, JP 4517416 A, JP 2002-128742 A, JP 4810750 A, JP 5888544 A, JP 2014-019654 A, and JP 6241654 A , Japanese Patent No. 6372060, Japanese Patent No. 6323144, Japanese Patent Application Laid-Open No. 2005-015406, Japanese Patent Application Laid-Open No. 2007-230968, Japanese Patent No. 6761484, Japanese Patent No. 6681992, International Publication No. 19 / 182129, CN01134217A, KR101069555B, KR101690767B, CN20120229730A, Japanese Patent No. 4053782, Japanese Patent Application Laid-Open No. 2009-249406, Japanese Patent No. 4121075, Japanese Patent Publication No. 2005 -528416, US6514578, WO06 / 006819, JP2011-184417A, JP2013-095685A, JP2013-103897A, JP2002-088008A, JP2002-226412A, JP2012-167214A, JP2012-167068A, Japanese Patent Application No. 2018-084511A, JP2003-055317A, JP2001-32926A No. 4, JP 2002-030016 A, JP 2003-055664 A, JP 2018-070889 A, CN102557896 A, US2015369982 A, JP 2020-105264 A, JP 2014-224237 A, JP 2012-051862 A, JP 2010-106274 A, JP 2005-179557 A, JP 2005-035985 A, JP 2002-012579 A,Examples of compounds described in JP 2002-003845 A, JP 2001-233837 A, JP 2019-532167 A, JP 2016-509247 A, JP 2010-503733 A, JP 2003-533557 A, WO 19 / 098115, WO 18 / 034216, WO 18 / 221236, WO 18 / 123396, WO 18 / 003482, WO 17 / 086143, WO 14 / 192655, WO 13 / 161669, and WO 09 / 104468 are mentioned.

[0130] The content of the polymerizable liquid crystal compound in the composition is not particularly limited, but is preferably 0 to 95% by mass, more preferably 5 to 90% by mass, and even more preferably 20 to 80% by mass, relative to the total mass of the solids in the composition. The composition may contain one polymerizable liquid crystal compound alone, or two or more polymerizable liquid crystal compounds. When two or more polymerizable liquid crystal compounds are used, the total content thereof is preferably within the above range. Note that, in terms of facilitating a decrease in the alignment temperature, it is also preferable that the composition contain two or more polymerizable liquid crystal compounds.

[0131] Specific examples of the polymerizable liquid crystal compound are shown below, but the invention is not limited thereto.

[0132]

[0133]

[0134]

[0135]

[0136]

[0137]

[0138]

[0139] Furthermore, as the polymerizable liquid crystal compound, compounds represented by the following formulas (1) to (22) (particularly, those exhibiting smectic properties) are preferred. K (side chain structure) in the following formulas (1) to (22) corresponds to any of Tables K1 to K3 described below. In Tables K1 to K3, the "*" shown in the side chain structure of K represents the bonding position with the aromatic ring specified in the following formulas (1) to (22). In addition, in the side chain structures represented by 2-2 in Table K2 and 3-2 in Table 3, the groups adjacent to the acryloyloxy group and the methacryloyl group, respectively, represent a propylene group (a group in which a methyl group is substituted with an ethylene group), and represent a mixture of positional isomers in which the position of the methyl group differs.

[0140]

[0141]

[0142]

[0143]

[0144] [Polymerization initiator] The composition preferably contains a polymerization initiator. Examples of the polymerization initiator include a photopolymerization initiator and a thermal polymerization initiator. Among them, in an embodiment in which the polymerization reaction is caused to proceed by ultraviolet irradiation, the polymerization initiator used is preferably a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation. Examples of photopolymerization initiators include α-carbonyl compounds (described in U.S. Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Pat. No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Pat. No. 2,722,512), polynuclear quinone compounds (described in U.S. Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in U.S. Pat. No. 3,549,367), acridine and phenazine compounds (described in JP-A Nos. 60-105,667 and 4,239,850), oxadiazole compounds (described in U.S. Pat. No. 4,212,970), oxime ester compounds, and phosphine oxide compounds. The content of the polymerization initiator in the composition is preferably 0.1 to 20% by mass, more preferably 1 to 8% by mass, based on the content of the polymerizable compounds including the specific compound. The composition may contain one polymerization initiator alone or two or more polymerization initiators. When two or more polymerization initiators are used, the total content thereof is preferably within the above range.

[0145] [Solvent] The composition may contain a solvent. The solvent is preferably one that can dissolve each component blended in the composition, and examples thereof include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (e.g., dioxane and tetrahydrofuran), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, ... Examples of suitable solvents include chloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, etc.), water, alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), and amides (e.g., dimethylformamide, dimethylacetamide, etc.). When the composition contains a solvent, the content of the solvent in the composition is preferably an amount that results in a solids concentration of 0.5 to 30% by mass, more preferably an amount that results in a solids concentration of 1 to 20% by mass. The composition may contain one solvent alone, or two or more solvents. When two or more solvents are used, the total content is preferably within the above range.

[0146] [Chiral Agent] The composition may contain a chiral agent. A chiral agent (optically active compound) has the function of inducing a helical structure in a cholesteric liquid crystal phase. Chiral agents can be selected according to the purpose, as the twist direction or helical pitch of the helix induced varies depending on the compound. The chiral agent is not particularly limited, and examples include compounds described in "Liquid Crystal Device Handbook, Chapter 3, Section 4-3, Chiral Agents for TN (Twisted Nematic) and STN (Super Twisted Nematic)," p. 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989," isosorbide, and isomannide derivatives. Chiral agents generally contain an asymmetric carbon atom, but axially asymmetric or planar asymmetric compounds without an asymmetric carbon atom can also be used as chiral agents. Examples of axially asymmetric or planar asymmetric compounds include binaphthyl, helicene, paracyclophane, and their derivatives. The chiral agent may also have a polymerizable group. When both the chiral agent and the liquid crystal compound have a polymerizable group, a polymer having a repeating unit derived from the polymerizable liquid crystal compound and a repeating unit derived from the chiral agent can be formed by a polymerization reaction between the polymerizable chiral agent and the polymerizable liquid crystal compound. In this embodiment, the polymerizable group of the polymerizable chiral agent is preferably the same type of group as the polymerizable group of the polymerizable liquid crystal compound. Furthermore, the chiral agent itself may be a liquid crystal compound.

[0147] When the chiral agent has a photoreactive group, it is preferable because a pattern with a desired reflection wavelength corresponding to the emission wavelength can be formed by irradiating a photomask with actinic rays or the like after coating and orientation. Examples of photoreactive moieties contained in the photoreactive group that undergo structural changes upon light irradiation include structures exemplified by photochromic compounds (Kingo Uchida, Masahiro Irie, Chemical Industry, Vol. 64, p. 640, 1999; Kingo Uchida, Masahiro Irie, Fine Chemical, Vol. 28(9), p. 15, 1999). The structural change refers to decomposition, addition reaction, isomerization, racemization, [2+2] photocyclization, dimerization, and the like that occur upon light irradiation of the photoreactive moiety, and the structural change may be irreversible. Examples of chiral moieties in the chiral agent include the asymmetric carbons described in Hiroyuki Nodaira, Chemistry Review, No. 22, Chemistry of Liquid Crystals, p. 73, 1994.

[0148] Examples of the chiral agent include photoreactive chiral agents described in paragraphs 0044 to 0047 of JP-A No. 2001-159709, optically active compounds described in paragraphs 0019 to 0043 of JP-A No. 2002-179669, optically active compounds described in paragraphs 0020 to 0044 of JP-A No. 2002-179633, optically active compounds described in paragraphs 0016 to 0040 of JP-A No. 2002-179670, optically active compounds described in paragraphs 0017 to 0050 of JP-A No. 2002-179668, and optically active compounds described in paragraphs 0018 to 0020 of JP-A No. 2002-180051. 44, optically active compounds described in paragraphs

[0016] to

[0055] of JP-A-2002-338575, optically active isosorbide derivatives described in paragraphs

[0016] to

[0055] of JP-A-2002-338575, photoreactive optically active compounds described in paragraphs

[0023] to

[0032] of JP-A-2002-080478, photoreactive chiral agents described in paragraphs

[0019] to

[0029] of JP-A-2002-080851, optically active compounds described in paragraphs

[0022] to

[0049] of JP-A-2002-179681, optically active compounds described in paragraphs

[0015] to

[0044] of JP-A-2002-302487, optically active compounds described in paragraphs

[0015] to

[0044] of JP-A-2002-338668 optically active polyesters described in paragraphs

[0015] to

[0050] of JP-A-2003-055315, binaphthol derivatives described in paragraphs

[0019] to

[0041] of JP-A-2003-073381, optically active fulgide compounds described in paragraphs

[0008] to

[0043] of JP-A-2003-073381, optically active isosorbide derivatives described in paragraphs

[0015] to

[0057] of JP-A-2003-306490, optically active isosorbide derivatives described in paragraphs

[0015] to

[0041] of JP-A-2003-306491, optically active isosorbide derivatives described in paragraphs

[0015] to

[0049] of JP-A-2003-313187 Examples of the optically active isosorbide derivatives include the optically active isomannide derivatives described in paragraphs 0015 to 0057 of JP-A-2003-313188, the optically active isosorbide derivatives described in paragraphs 0015 to 0049 of JP-A-2003-313189, the optically active polyester / amides described in paragraphs 0015 to 0052 of JP-A-2003-313292, the optically active compounds described in paragraphs 0012 to 0053 of WO 2018 / 194157, and the optically active compounds described in paragraphs 0020 to 0049 of JP-A-2002-179682.The photoreactive group is preferably an isomerization site of a compound exhibiting photochromic properties, an azo group, an azoxy group, or a cinnamoyl group.

[0149] When the composition contains a chiral agent, the content of the chiral agent in the composition is not particularly limited, but is preferably 0.01 to 15% by mass, more preferably 1.0 to 10% by mass, relative to the content of the liquid crystal compound.

[0150] [Surfactant] The composition may contain a surfactant. The surfactant is preferably a compound that can function as an alignment control agent that contributes to stably or quickly achieving a planar aligned cholesteric liquid crystal phase. Examples of the surfactant include silicone-based surfactants and fluorine-based surfactants.

[0151] Specific examples of surfactants include the compounds described in paragraphs 0082 to 0090 of JP-A-2014-119605, the compounds described in paragraphs 0031 to 0034 of JP-A-2012-203237, the compounds exemplified in paragraphs 0092 to 0093 of JP-A-2005-99248, the compounds exemplified in paragraphs 0076 to 0078 and 0082 to 0085 of JP-A-2002-129162, and fluorine (meth)acrylate polymers described in paragraphs 0018 to 0043 of JP-A-2007-272185. The surfactants may be used alone or in combination of two or more. As silicone surfactants, the compounds described in WO 2025 / 013896 are preferred. As the fluorine-based surfactant, the compounds described in paragraphs 0082 to 0090 of JP-A-2014-119605 are preferred.

[0152] The amount of the surfactant added in the composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.02 to 1% by mass, based on the total mass of the liquid crystal compound.

[0153] [Other Additives] The composition may contain other components in addition to the above-mentioned components. Examples of other components include silicon-containing compounds other than the specific compounds, non-polymerizable liquid crystal compounds, antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, antifoaming agents, leveling agents, thickeners, flame retardants, surfactants, dispersants, and coloring materials such as dyes and pigments.

[0154] [Uses of the Composition] A cured product can be obtained from the composition of the present invention. More specifically, a cured product can be obtained by polymerizing a specific compound in the composition of the present invention. The obtained cured product can be used as an optically anisotropic body (optically anisotropic layer).

[0155] [Refractive index of optical anisotropic body] The refractive index n of the optical anisotropic body of the present invention is preferably 1.65 or more, more preferably 1.70 or more, in order to increase the diffraction efficiency of the film obtained.Furthermore, the refractive index ne of the optical anisotropic body in the slow axis direction is preferably 1.90 or more, more preferably 1.94 or more, and even more preferably 1.95 or more.The upper limit is not particularly limited, but is, for example, 3.0 or less.

[0156] [Δn of Optical Anisotropic Body] The refractive index anisotropy Δn of the optical anisotropic body of the present invention is preferably 0.30 or more, more preferably 0.35 or more, in order to increase the diffraction efficiency of the resulting film. The upper limit is not particularly limited, but is, for example, 0.80 or less.

[0157] The optically anisotropic layer and the method for producing the same will be described below.

[0158] [Example of an embodiment of an optically anisotropic layer] An example of an embodiment of an optically anisotropic layer which is a cured product of the above-mentioned composition will be described with reference to the drawings. Figures 1 and 2 show schematic cross-sectional views of an optically anisotropic layer 1. Figure 1 is a side view showing the optically anisotropic layer 1, and Figure 2 is a plan view showing the orientation pattern of the optically anisotropic layer 1 shown in Figure 1. In the drawings, the sheet surface of the sheet-like optically anisotropic layer 1 is defined as the xy plane, and the thickness direction is defined as the z direction.

[0159] As shown in FIG. 1 , the optically anisotropic layer 1 has an orientation pattern (length of one period Λ) in which the direction of the optical axis derived from the liquid crystal compound 30 is continuously rotated along at least one in-plane direction. While FIG. 1 corresponds to an embodiment in which the liquid crystal compound 30 is the specific compound described above, the present invention is not limited to this embodiment, and the liquid crystal compound 30 may be composed of a specific compound and a polymerizable liquid crystal compound. In FIGS. 1 to 4 , only the liquid crystal molecules present on one main surface of the optically anisotropic layer 1 are shown to simplify the drawings and clearly show the configuration of the optically anisotropic layer 1. However, the optically anisotropic layer 1 has a structure in which aligned liquid crystal compounds 30 are stacked, similar to an optically anisotropic layer formed using a composition containing a typical liquid crystal compound. Typically, when the in-plane retardation value of the optically anisotropic layer 1 is set to λ / 2, the optically anisotropic layer 1 functions as a typical λ / 2 plate, i.e., imparts a phase difference of half the wavelength, i.e., 180°, to two orthogonal linearly polarized components contained in light incident on the optically anisotropic layer.

[0160] 2, the optically anisotropic layer 1 has an orientation pattern in which the direction of the optical axis 30A (hereinafter sometimes abbreviated as "optical axis 30A") derived from the liquid crystal compound 30 changes while continuously rotating in one direction within the plane of the optically anisotropic layer 1. Here, the one direction in which the optical axis 30A changes rotationally coincides with the direction of the x-axis in the xy plane. In the following description, the one direction in which the optical axis 30A changes rotationally is referred to as the x-direction.

[0161] The optical axis 30A derived from the liquid crystal compound 30 is the axis along which the refractive index of the liquid crystal compound 30 is the largest, that is, the slow axis. As shown in Fig. 1, when the liquid crystal compound 30 is a rod-shaped liquid crystal compound, the optical axis 30A is aligned with the long axis direction of the rod shape.

[0162] The phrase "the orientation of the optical axis 30A changes while continuously rotating in the x direction" specifically means that the angle formed between the optical axis 30A of the liquid crystal compound 30 aligned along the x direction and the x direction varies depending on the position in the x direction, and the angle formed between the optical axis 30A and the x direction gradually changes along the x direction from θ to θ+180° or θ−180°. Here, "the angle gradually changes" may mean that the angle changes at regular angle intervals or that the angle changes continuously. However, the difference in angle between the optical axes 30A of the liquid crystal compound 30 adjacent to each other in the x direction is preferably 45° or less, more preferably 15° or less, and even more preferably a smaller angle.

[0163] On the other hand, the liquid crystal compounds 30 forming the optically anisotropic layer 1 are arranged at equal intervals in the y direction perpendicular to the x direction in the plane, i.e., in the y direction perpendicular to the one direction (x direction) in which the optical axis 30A continuously rotates. In other words, among the liquid crystal compounds 30 forming the optically anisotropic layer 1, the liquid crystal compounds 30 aligned in the y direction have the same angle between the direction of the optical axis 30A and the x direction. In the optically anisotropic layer 1, in such an orientation pattern of the liquid crystal compounds 30, the length (distance) over which the optical axis 30A of the liquid crystal compound 30 rotates 180° in the x direction in which the orientation of the optical axis 30A continuously changes in the plane is defined as the length Λ of one period of the orientation pattern. In other words, the length of one period of the orientation pattern is defined as the distance from θ to θ+180°, where θ is the angle between the optical axis 30A of the liquid crystal compound 30 and the x direction. 2, the distance between the centers in the x direction of two liquid crystal compounds 30 whose optical axes 30A coincide with the x direction is defined as the length of one period Λ (hereinafter also referred to as "one period Λ" or "period Λ"). The alignment pattern of the optically anisotropic layer 1 is a pattern in which the liquid crystal alignment of this one period Λ is repeated in the x direction.

[0164] As described above, in the optically anisotropic layer 1, the angle between the optical axis 30A of each liquid crystal compound 30 aligned in the y direction and the x direction, along which the optical axis of the liquid crystal compound 30 rotates, is equal. A region in which the liquid crystal compounds 30, each with the same angle between the optical axis 30A and the x direction, are arranged in the y direction, is referred to as region R. In this case, the in-plane retardation (Re) value in each region R is preferably half the wavelength of the light to be diffracted by the optically anisotropic layer (hereinafter referred to as "target light"), i.e., when the wavelength of the target light is λ, the in-plane retardation Re is λ / 2. These in-plane retardations are calculated by the product of the refractive index anisotropy Δn of region R and the thickness (film thickness) d of the optically anisotropic layer. Here, the refractive index difference associated with the refractive index anisotropy of region R in the optically anisotropic layer is a refractive index difference defined by the difference between the refractive index in the direction of the slow axis in the plane of region R and the refractive index in the direction perpendicular to the direction of the slow axis. That is, the refractive index anisotropy Δn associated with the refractive index anisotropy of region R is equal to the difference between the refractive index of liquid crystal compound 30 in the direction of optical axis 30A and the refractive index of liquid crystal compound 30 in the direction perpendicular to optical axis 30A in the plane of region R. In other words, the refractive index anisotropy Δn depends on the liquid crystal compound, and the in-plane retardation of each region R is approximately equal. However, as described above, the direction of the optical axis 30A differs between each region R.

[0165] In the optically anisotropic layer 1, since the direction of the optical axis 30A is rotated in the plane, it is difficult to measure the in-plane retardation of the entire layer. However, the in-plane retardation of the optically anisotropic layer 1 can be estimated from the period and the diffraction efficiency.

[0166] When circularly polarized light is incident on such an optically anisotropic layer 1, the light is refracted and the direction of the circularly polarized light is changed. This action is conceptually shown in FIG. 3, exemplifying the optically anisotropic layer 1. It is assumed that the in-plane retardation of the optically anisotropic layer 1 is λ / 2. In this case, as shown in FIG. 3, left-handed circularly polarized light P Ｌ The incident light L １ When incident, the incident light L １ is given a phase difference of 180° by passing through the optically anisotropic layer 1, and becomes the transmitted light L ２is right-handed circularly polarized light P Ｒ In addition, the incident light L １ When passing through the optically anisotropic layer 1, the absolute phase of the incident light L changes depending on the direction of the optical axis 30A of each liquid crystal compound 30. At this time, the direction of the optical axis 30A changes while rotating along the x direction. １ Furthermore, since the alignment pattern formed in the optically anisotropic layer 1 is a periodic pattern in the x direction, the amount of change in the absolute phase of the incident light L １ 3, a periodic absolute phase Q1 is given to the transmitted light L in the x direction corresponding to the direction of each optical axis 30A. As a result, an equiphase surface E1 tilted in the opposite direction to the x direction is formed. ２ is refracted so as to be inclined toward a direction perpendicular to the equiphase surface E1, and the incident light L １ In this way, left-handed circularly polarized light P Ｌ Incident light L １ is a right-handed circularly polarized light P that is tilted at a certain angle in the x direction with respect to the incident direction. Ｒ Transmitted light L ２ is converted to

[0167] On the other hand, as conceptually shown in FIG. 4, right-handed circularly polarized light P Ｒ Incident light L ４ When incident, the incident light L ４ is given a phase difference of 180° by passing through the optically anisotropic layer 1, and becomes left-handed circularly polarized light P Ｌ Transmitted light L ５ In addition, the incident light L ４ When passing through the optically anisotropic layer 1, the absolute phase of the incident light L changes depending on the direction of the optical axis 30A of each liquid crystal compound 30. At this time, the direction of the optical axis 30A changes while rotating along the x direction. ４ Furthermore, since the alignment pattern formed in the optically anisotropic layer 1 is a periodic pattern in the x direction, the amount of change in the absolute phase of the incident light L ４As shown in FIG. 4, the incident light L is given a periodic absolute phase Q2 in the x direction corresponding to the direction of each optical axis 30A. ４ is right-handed circularly polarized light P Ｒ Therefore, the periodic absolute phase Q2 in the x direction corresponding to the direction of the optical axis 30A is P Ｌ An incident light L １ As a result, the incident light L ４ Now, the incident light L １ Conversely, an equiphase surface E2 inclined in the x direction is formed. ４ is refracted so as to be inclined toward a direction perpendicular to the equiphase surface E2, and the incident light L ４ In this way, the incident light L ４ is the transmitted light L of left-handed circularly polarized light that is tilted at a certain angle in the direction opposite to the x-direction with respect to the incident direction. ５ is converted to

[0168] As mentioned above, the in-plane retardation value of the optically anisotropic layer 1 is preferably half the wavelength of the target light. This is because the closer the in-plane retardation value is to half the wavelength of the target light, the higher the diffraction efficiency can be obtained in diffracting the target light. The in-plane retardation Re(λ) of the optically anisotropic layer for incident light with a wavelength of λ nm in the x direction is expressed as Re(λ)=Δn λ ×d is preferably within the range defined by the following formula and can be set appropriately: 0.7 × (λ / 2) nm≦Δn λ ×d≦1.3×(λ / 2)nm

[0169] Here, by changing one period Λ of the orientation pattern formed on the optically anisotropic layer 1, the transmitted light L ２ and L ５ Specifically, the shorter the period Λ of the orientation pattern, the stronger the interference between the lights passing through the adjacent liquid crystal compounds 30, and therefore the angle of refraction of the transmitted light L ２ and L ５Furthermore, by reversing the rotation direction of the optical axis 30A of the liquid crystal compound 30, which rotates along the x direction, the direction of refraction of transmitted light can be reversed. The period Λ is preferably 50 μm or less, more preferably 25 μm or less, and even more preferably 5 μm or less.

[0170] The thickness d of the optically anisotropic layer 1 may be appropriately set to obtain the desired in-plane retardation, but is preferably 1 μm or less, more preferably 0.8 μm or less, and even more preferably 0.5 μm or less. In particular, when the optically anisotropic layer 1 is used as a birefringent mask to form a photo-alignment pattern, the smaller the thickness d, the more preferable. The smaller the thickness d, the more accurately the photo-alignment pattern can be formed. Note that the ratio Λ / d of the period Λ to the thickness d of the optically anisotropic layer is preferably 1 or more.

[0171] The period Λ of the alignment pattern in the optically anisotropic layer 1 can be determined from the period of light and dark by observing a light-dark periodic pattern of light and dark areas under crossed Nicols conditions using a polarizing microscope. The period Λ of the alignment pattern corresponds to twice the period of the observed light-dark periodic pattern. The film thickness d of the optically anisotropic layer 1 can be measured, for example, by observing a cross section of the optically anisotropic layer using a scanning electron microscope.

[0172] The optically anisotropic layer 1 preferably has a refractive index anisotropy Δn of 0.21 or more at a wavelength of 550 nm. There is no particular upper limit, but it is preferably 0.8 or less.

[0173] It is also preferable to make the optically anisotropic layer substantially broadband with respect to the wavelength of incident light by adding a twist component to the composition or by laminating different retardation layers. For example, JP 2014-089476 A and the like disclose a method for realizing a broadband patterned λ / 2 plate by laminating two layers of liquid crystals with different twist directions in an optically anisotropic layer, and this method can be suitably used in the optically anisotropic layer of the present invention.

[0174] [Method for Producing Optically Anisotropic Layer 1] A specific example of a method for producing the optically anisotropic layer 1 includes a step X of contacting a substrate provided with an alignment film having a predetermined alignment pattern with a composition to form a composition layer on the alignment film on the substrate, and a step Y of subjecting the composition layer to a heat treatment to align the liquid crystal compound, followed by a curing treatment. After producing the optically anisotropic layer 1, the substrate may or may not be removed from the optically anisotropic layer. Similarly, after producing the optically anisotropic layer 1, the alignment film may or may not be removed from the optically anisotropic layer.

[0175] The specific procedures of Step X and Step Y are described in detail below. (Step X) Substrate The type of substrate used in Step X is not particularly limited, and examples thereof include known substrates (for example, resin substrates, glass substrates, ceramic substrates, semiconductor substrates, and metal substrates).

[0176] Alignment film An alignment film is disposed on the substrate. The presence of the alignment film makes it easy to align the liquid crystal compound 30 in a predetermined alignment pattern when preparing the optically anisotropic layer 1. As described above, the optically anisotropic layer 1 has an alignment pattern in which the direction of the optical axis 30A (see FIG. 2 ) derived from the liquid crystal compound 30 changes while continuously rotating along one in-plane direction (x direction). Therefore, the alignment film is formed so that the optically anisotropic layer can form this alignment pattern.

[0177] Various known alignment films can be used, including, for example, a rubbed film made of an organic compound such as a polymer, an obliquely evaporated film of an inorganic compound, a film having microgrooves, and a film obtained by accumulating LB (Langmuir-Blodgett) films made of organic compounds such as ω-tricosanoic acid, dioctadecylmethylammonium chloride, and methyl stearate by the Langmuir-Blodgett method.

[0178] The alignment film formed by rubbing treatment can be formed by rubbing the surface of the polymer layer several times in a certain direction with paper or cloth. Suitable materials for the alignment film include polyimide, polyvinyl alcohol, polymers having polymerizable groups as described in JP-A-9-152509, and materials used to form alignment films as described in JP-A-2005-097377, JP-A-2005-099228, and JP-A-2005-128503.

[0179] As the alignment film, a so-called photo-alignment film can be suitably used, which is formed by irradiating a photo-alignment material with polarized or non-polarized light. When irradiating with polarized light to form an alignment film, the photo-alignment material can be irradiated from a vertical direction or an oblique direction to form the alignment film, and when irradiating with non-polarized light to form an alignment film, the photo-alignment material can be irradiated from an oblique direction to form the alignment film. Examples of photo-alignment materials used for the photo-alignment film include those described in JP 2006-285197 A, JP 2007-076839 A, JP 2007-138138 A, JP 2007-094071 A, JP 2007-121721 A, JP 2007-140465 A, JP 2007-156439 A, and JP 200 azo compounds described in JP-A-7-133184, JP-A-2009-109831, Japanese Patent No. 3883848 and Japanese Patent No. 4151746, aromatic ester compounds described in JP-A-2002-229039, maleic anhydrides having photo-orienting units described in JP-A-2002-265541 and JP-A-2002-317013 and the like. Examples thereof include imide and / or alkenyl-substituted nadimide compounds, photocrosslinkable silane derivatives described in Japanese Patent Nos. 4205195 and 4205198, photocrosslinkable polyimides, photocrosslinkable polyamides, and photocrosslinkable esters described in JP-T-2003-520878, JP-T-2004-529220, and JP-T-4162850, and photodimerizable compounds described in JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, WO 2010 / 150748, JP-A-2013-177561, and JP-A-2014-012823, in particular cinnamate compounds, chalcone compounds, and coumarin compounds. Among these, azo compounds, photocrosslinkable polyimides, photocrosslinkable polyamides, photocrosslinkable esters, cinnamate compounds, and chalcone compounds can be preferably used.

[0180] There is no limitation on the thickness of the alignment film, and the thickness may be appropriately set to obtain the required alignment function depending on the material from which the alignment film is formed.

[0181] The thickness of the alignment film is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm.

[0182] The method for forming the alignment film is not particularly limited, and various known methods can be used depending on the material for forming the alignment film. A photo-alignment film formed by irradiating a photo-alignment material with polarized or non-polarized light is preferred, as this makes it easier to form an alignment pattern in the optically anisotropic layer 1. The methods described in paragraphs

[0078] to

[0080] of WO 2020 / 022496 and the like can be suitably applied.

[0183] - Procedure of Step X The method of bringing a substrate provided with an alignment film having a predetermined alignment pattern (hereinafter also referred to as "alignment film-attached substrate") into contact with the composition is not particularly limited, and examples thereof include a method of applying the composition onto the alignment film on the substrate, and a method of immersing the above-mentioned alignment film-attached substrate in the composition. Note that after bringing the alignment film-attached substrate into contact with the composition, a drying treatment may be carried out, if necessary, to remove the solvent from the composition layer arranged on the alignment film on the substrate.

[0184] (Step Y) Step Y is a step of subjecting the composition layer to a heat treatment to align the liquid crystal compound, followed by a curing treatment. By subjecting the composition layer to a heat treatment, the liquid crystal compound is oriented to form a liquid crystal phase. For example, when the composition layer contains a chiral agent, a cholesteric liquid crystal phase is formed. The conditions for the heat treatment are not particularly limited, and optimal conditions are selected depending on the type of liquid crystal compound. The curing method is not particularly limited, and examples include photocuring and heat curing. Among these, photoirradiation is preferred, and ultraviolet irradiation is more preferred. For ultraviolet irradiation, a light source such as an ultraviolet lamp is used. The cured product obtained by the above treatment corresponds to a layer formed by fixing a liquid crystal phase. In particular, when the composition contains a chiral agent, a layer formed by fixing a cholesteric liquid crystal phase is formed. Note that these layers no longer need to exhibit liquid crystallinity. More specifically, for example, the state in which the cholesteric liquid crystal phase is "fixed" is the most typical and preferred embodiment in which the orientation of the liquid crystal compound in the cholesteric liquid crystal phase is maintained. More specifically, it is preferable that the layer has no fluidity and can stably maintain the fixed orientation state without causing any change in the orientation state due to an external field or external force, usually in a temperature range of 0 to 50°C, or under more severe conditions in a temperature range of −30 to 70°C.

[0185] [Modification of Optically Anisotropic Layer] The optically anisotropic layer 2 shown in FIG. 5 is an optically anisotropic layer in which liquid crystal compounds 30 are cholesterically aligned in the thickness direction.

[0186] It is known that cholesteric liquid crystal phases exhibit selective reflectivity at specific wavelengths. The central wavelength of selective reflection (selective reflection central wavelength) λ depends on the pitch P (= helical period) of the helical structure in the cholesteric liquid crystal phase, and follows the relationship λ = n × P with the average refractive index n of the cholesteric liquid crystal phase. Therefore, the selective reflection central wavelength can be adjusted by adjusting the pitch of this helical structure.

[0187] Cholesteric liquid crystal phases exhibit selective reflection for either left- or right-handed circularly polarized light at a specific wavelength. Whether the reflected light is right-handed or left-handed circularly polarized depends on the twist direction (sense) of the helix of the cholesteric liquid crystal phase. When the twist direction of the helix of the cholesteric liquid crystal phase is right-handed, right-handed circularly polarized light is reflected, and when the twist direction of the helix is ​​left-handed, left-handed circularly polarized light is reflected.

[0188] Furthermore, the half-width Δλ (nm) of the selective reflection band (circularly polarized light reflection band) exhibiting selective reflection depends on Δn of the cholesteric liquid crystal phase and the helical pitch P, and follows the relationship Δλ = Δn × P. Therefore, the width of the selective reflection band can be controlled by adjusting Δn.

[0189] That is, the optically anisotropic layer 2 has the function of selectively reflecting light of a specific circularly polarized light (right-handed or left-handed circularly polarized light) in a predetermined wavelength range.

[0190] On the other hand, the orientation pattern of the optic axis 30A in the in-plane direction of the optically anisotropic layer 2 is the same as the orientation pattern in the optically anisotropic layer 1 shown in Fig. 1, and therefore exhibits the same effect as the optically anisotropic layer 1. That is, the optically anisotropic layer 2 exhibits the effect of changing the absolute phase of incident light and bending it in a predetermined direction, similar to the above-mentioned optically anisotropic layer 1. Therefore, the optically anisotropic layer 2 has both the effect of bending incident light in a direction different from the incident direction and the effect of the above-mentioned cholesteric orientation, and reflects light at a predetermined angle relative to the reflection direction of specular reflection.

[0191] For example, if the cholesteric liquid crystal phase of the optically anisotropic layer 2 is designed to reflect right-handed circularly polarized light, as shown in FIG. Ｒ Light L ６ When the light is incident, the reflected light L ７ That is, the optically anisotropic layer 2 functions as a reflective diffraction grating.

[0192] 1 to 5, the optical axis 30A of the liquid crystal compound 30 rotates continuously in-plane along only the x-direction. However, in the optically anisotropic layer of the present invention, various configurations can be used as long as the optical axis 30A of the liquid crystal compound 30 rotates continuously along one direction.

[0193] Fig. 6 is a schematic plan view of an optically anisotropic layer 3 of a modified design. In Fig. 6, the orientation pattern is represented by the optical axis 30A of the liquid crystal compound. The optically anisotropic layer 3 has an orientation pattern in which regions in which the orientation of the optical axis 30A is the same are arranged concentrically, and one direction in which the orientation of the optical axis 30A changes while continuously rotating is arranged radially from the center of the optically anisotropic layer 3. In the optically anisotropic layer 3, the orientation of the optical axis 30A is arranged in a number of directions from the center of the optically anisotropic layer 3 outward, for example, in the directions indicated by arrows A １ The direction indicated by arrow A ２ The direction indicated by arrow A ３ The circularly polarized light changes while continuously rotating along the direction indicated by the arrows. The absolute phase of the circularly polarized light incident on the optically anisotropic layer 3 having this orientation pattern changes in each local region where the optical axis of the liquid crystal compound 30 has a different orientation. At this time, the amount of change in each absolute phase differs depending on the orientation of the optical axis of the liquid crystal compound 30 into which the circularly polarized light is incident.

[0194] The optically anisotropic layer 3 having such a concentric alignment pattern, i.e., an alignment pattern in which the optical axis changes by continuously rotating radially, can transmit incident light as divergent or convergent light depending on the direction of rotation of the optical axis of the liquid crystal compound 30 and the direction of the incident circularly polarized light. That is, by making the alignment pattern of the optically anisotropic layer concentric, the optically anisotropic layer can function as, for example, a convex lens or a concave lens.

[0195] Here, when the orientation pattern of the optically anisotropic layer is concentric and the optically anisotropic layer is made to function as a convex lens, it is preferable to gradually shorten one period Λ, in which the optical axis rotates 180°, from the center of the optically anisotropic layer 3 toward the outside in one direction in which the optical axis continuously rotates. The angle of refraction of light with respect to the incident direction increases as one period Λ in the orientation pattern becomes shorter. Therefore, by gradually shortening one period Λ in the orientation pattern from the center of the optically anisotropic layer 3 toward the outside in one direction in which the optical axis continuously rotates, the light focusing power of the optically anisotropic layer 3 can be further improved, and the performance as a convex lens can be improved.

[0196] Furthermore, depending on the application of the laminate, for example, when forming a concave lens, it is preferable to rotate one period Λ, in which the optical axis rotates 180°, from the center of the optically anisotropic layer 3 in the opposite direction to the direction in which the optical axis continuously rotates, and gradually shorten the period Λ from the center of the optically anisotropic layer 3 toward the outside in one direction. The angle of refraction of light with respect to the incident direction increases as one period Λ in the orientation pattern becomes shorter. Therefore, by gradually shortening one period Λ in the orientation pattern from the center of the optically anisotropic layer 3 toward the outside in one direction in which the optical axis continuously rotates, the light divergence power of the optically anisotropic layer 3 can be further improved, and the performance as a concave lens can be improved.

[0197] For example, when the optically anisotropic layer is used as a concave lens, it is also preferable to reverse the rotation direction of the incident circularly polarized light.

[0198] Conversely, one period Λ in the concentric circular alignment pattern may be gradually lengthened from the center of the optically anisotropic layer 3 outward in one direction in which the optical axis continuously rotates. Furthermore, depending on the application of the optically anisotropic layer, for example, when it is desired to provide a light intensity distribution in transmitted light, it is also possible to use a configuration in which the period Λ is not gradually changed in one direction in which the optical axis continuously rotates, but has regions in which the period Λ is partially different in one direction in which the optical axis continuously rotates. In addition, the light-emitting element may have an optically anisotropic layer in which the period Λ is uniform throughout and an optically anisotropic layer having regions in which the period Λ is different.

[0199] In this way, the configuration in which the period Λ of the optical axis, which rotates 180°, is changed in one direction in which the optical axis continuously rotates, can also be used in the configurations shown in Figures 1 to 4 in which the optical axis 30A of the liquid crystal compound 30 continuously rotates and changes only in one direction, the x direction. For example, by gradually shortening the period Λ of the alignment pattern in the x direction, an optically anisotropic layer that transmits light in a condensing manner can be obtained. Furthermore, by reversing the direction in which the optical axis rotates 180° in the alignment pattern, an optically anisotropic layer that transmits light in a diffusive manner only in the x direction can be obtained. Note that an optically anisotropic layer that transmits light in a diffusive manner only in the X direction indicated by the arrow can also be obtained by reversing the rotation direction of incident circularly polarized light. Furthermore, depending on the application of the optically anisotropic layer, for example, when it is desired to provide a light intensity distribution in the transmitted light, a configuration in which the period Λ is partially different in the x direction rather than gradually changing the period Λ in the x direction can also be used.

[0200] [Optical Element and Light Guide Element] The optical element of the present invention has the above-mentioned optical anisotropic body (e.g., an optically anisotropic layer). The use of the optical element is not particularly limited, and it can be used for various applications that transmit light in a direction different from the incident direction, such as a light path changing element in an optical device, a light concentrating element, a light diffusing element in a predetermined direction, and a diffraction element. A preferred application among these is a light guide element. The light guide element typically includes a light guide plate and a diffraction element disposed on the light guide plate (preferably disposed at a distance from the light guide plate). The optically anisotropic layer of the present invention is suitably used as a diffraction element. That is, the light guide element of the present invention includes a light guide plate and an optically anisotropic body disposed on the light guide plate.

[0201] The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment details, and treatment procedures shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted as being limited by the examples shown below. The abbreviations used in the following explanation are as follows: DMAc: dimethylacetamide THF: tetrahydrofuran MeOH: methanol DMF: N,N-dimethylformamide

[0202] [Synthesis of Specific Compounds] <Synthesis Example 1: Synthesis of Compound A-1> Compound A-1 was synthesized according to the following scheme.

[0203]

[0204] (1) Synthesis of Compound 2 To a solution of 6-bromo-2-naphthol (compound 1: 10.0 g, 44.8 mmol), 2-bromoethanol (6.7 g, 56.0 mmol), and DMF (40 mL) was added dropwise a solution of potassium hydroxide (3.14 g, 56.0 mmol), potassium iodide (223 mg, 1.34 mmol), and water (6.6 mL) at room temperature. The resulting solution was then heated to 85°C and stirred for 4 hours. The resulting solution was then cooled to room temperature, and diethyl ether was added to the solution. The resulting solution was then filtered. The resulting organic phase was washed successively with water, a 2% aqueous potassium hydroxide solution, and brine, and the solvent was then evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of MeOH and water to obtain compound 2 (7.5 g, yield 63%).

[0205] (2) Synthesis of Compound 4 To a solution of compound 2 (5.0 g, 16.8 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (compound 3, 4.1 g, 18.5 mmol), potassium carbonate (5.12 g, 37.1 mmol), DMF (37.5 mL), and water (12.5 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (2.0 g, 1.68 mmol) was added. The resulting solution was then heated to 110°C and stirred for 2 hours. The resulting solution was then allowed to cool to room temperature, and water was added to the solution. The resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed successively with water and brine, and further dried over magnesium sulfate. The organic phase was then filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 4 (2.45 g, yield 52%).

[0206] (3) Synthesis of Compound 5 To a solution of compound 4 (4.0 g, 14.3 mmol) and THF (40 mL) was added 1,1'-thiocarbonyldi-2(1H)-pyridone (3.5 g, 15.0 mmol). The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 5 (3.45 g, yield 75%).

[0207] (4) Synthesis of Compound A-1 To a solution of Compound 5 (1.0 g, 3.1 mmol) and DMAc (5 mL), acryloyl chloride (0.56 g, 6.2 mmol) was added. After stirring at room temperature for 1 hour, MeOH was added. The resulting solution was filtered to obtain Compound A-1 (1.0 g, yield 95%). １ H-NMR (CDCl ３ ): δ = 4.36 (t, 2H), 4.60 (t, 2H), 5.87 (d, 1H), 6.19 (dd, 1H), 6.48 (d, 1H), 7.17 (d, 1 H), 7.22 (dd, 1H), 7.33 (d, 2H), 7.65-7.97 (m, 2H), 7.80-7.81 (m, 2H), 7.95 (d, 1H)

[0208] Synthesis Example 2: Synthesis of Compound A-2 Compound A-2 was synthesized according to the following scheme.

[0209]

[0210] (1) Synthesis of Compound 7 To a solution of methyl 6-bromo-2-naphthoate (compound 6, 5.0 g, 18.9 mmol) and THF (75 mL) was added sodium borohydride (2.9 g, 75.4 mmol) at room temperature. The resulting solution was then heated to 70°C, and MeOH (15.1 mL) was added dropwise and stirred for 2 hours. The resulting solution was then cooled to 0°C, and the reaction was quenched with aqueous hydrochloric acid. The organic phase was extracted from the resulting solution with ethyl acetate, and the organic phase was washed sequentially with aqueous sodium bicarbonate and brine. The resulting organic phase was evaporated under reduced pressure, and the residue was purified by crystallization using a mixed solvent of THF and hexane to obtain compound 7 (4.1 g, yield 91%).

[0211] (2) Synthesis of Compound A-2 Compound A-2 was synthesized in the same manner as in (2) to (4) of Compound A-1, except that Compound 7 was used. １ H-NMR (CDCl ３ ): δ = 5.38 (s, 2H), 5.90 (d, 1H), 6.20 (dd, 1H), 6.47 (d, 1H), 7.35 (d, 2H), 7.53 (d, 1H), 7.69-7.73 (m, 3H), 7.87-7.94 (m, 3H), 8.01 (s, 1H)

[0212] Synthesis Example 3: Synthesis of Compound A-3 Compound A-3 was synthesized according to the following scheme.

[0213]

[0214] (1) Synthesis of Compound 10 A solution of 6-bromo-2-naphthol (Compound 1: 10.0 g, 44.8 mmol) and DMF (150 mL) was added dropwise to a solution of sodium hydride (8.1 g, 202 mmol) and DMF (120 mL) cooled to 0°C. The resulting solution was warmed to room temperature and stirred for 30 minutes. Dimethylthiocarbamoyl chloride (24.93 g, 202 mmol) was then added to the solution, and the solution was stirred at 80°C for 3 hours. The resulting solution was cooled to room temperature, and aqueous sodium hydroxide solution was added to the solution. The organic phase was extracted from the resulting solution with tert-butyl methyl ether, washed sequentially with aqueous hydrochloric acid and brine, and then dried over magnesium sulfate and filtered. The resulting organic phase was evaporated under reduced pressure, and the residue was purified by silica gel chromatography to obtain Compound 10 (20.0 g, yield 96%).

[0215] (2) Synthesis of Compound 11 A solution of compound 10 (19.0 g, 61.2 mmol) and diphenyl ether (76 mL) was stirred under a nitrogen atmosphere at 220° C. for 2 hours. The resulting solution was cooled to room temperature and then purified by silica gel chromatography to obtain compound 11 (12.5 g, yield 66%).

[0216] (3) Synthesis of Compound 12 To a solution of compound 11 (11 g, 35.5 mmol) and MeOH (330 mL), potassium hydroxide (7.2 g, 128 mmol) was added, and the resulting solution was stirred for 3 hours under a nitrogen atmosphere. After the resulting solution was cooled to 0°C, aqueous hydrochloric acid was added to the solution and stirred. The organic phase was extracted from the resulting solution with dichloromethane, and then the organic phase was dried over magnesium sulfate. The resulting organic phase was filtered. The resulting organic phase was evaporated under reduced pressure to give compound 12 (8.1 g, yield 96%).

[0217] (4) Synthesis of Compound 13 A solution of acetonitrile (15.0 mL), sodium sulfite (4.0 g, 31.2 mmol), and potassium carbonate (4.3 g, 31.2 mmol) was cooled to 0°C. To the solution, a solution of compound 12 (5.0 g, 20.9 mmol), 3-bromo-1-propanol (3.4 g, 22.3 mmol), acetonitrile (10.0 mL), and toluene (5.0 mL) was added dropwise under a nitrogen atmosphere. The resulting solution was cooled to room temperature and stirred for 2 hours, and then further stirred at 80°C for 5 hours. Aqueous hydrochloric acid was added dropwise to the resulting solution, followed by separation, and the resulting organic phase was washed with brine. The resulting organic phase was evaporated under reduced pressure to give compound 13 (5.9 g, yield 95%).

[0218] (5) Synthesis of Compound A-3 Compound A-3 was synthesized in the same manner as in (2) to (4) of Compound A-1, except that Compound 13 was used. １ H-NMR (CDCl ３ ): δ = 2.07 (tt, 2H), 3.13 (t, 2H), 4.31 (t, 2H), 5.84 (dd, 1H), 6.12 (dd, 1H), 6.42 (dd, 1H) ), 7.32-7.35 (m, 2H), 7.46 (dd, 1H), 7.67-7.70 (m, 3H), 7.76 (d, 1H), 7.79-7.83 (m, 2H)

[0219] Synthesis Example 4: Synthesis of Compound A-4 Compound A-4 was synthesized according to the following scheme.

[0220]

[0221] (11) Synthesis of Compound 16 A solution of compound 2 (2.5 g, 9.4 mmol), DMF (37.5 mL), potassium acetate (1.4 g, 14.0 mmol), and bis(pinacolato)diboron (3.6 g, 14.0 mmol) was degassed under reduced pressure, and then [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium-dichloromethane complex (0.8 g, 0.9 mmol) was added to the resulting solution, followed by stirring at 90°C for 2 hours. The resulting solution was filtered through Celite, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel chromatography to obtain compound 16 (2.35 g, yield 80%).

[0222] (12) Synthesis of Compound 18 A solution of 4-bromo-2-iodoaniline (Compound 17, 5.0 g, 16.8 mmol), THF (65 mL), potassium vinyltrifluoroborate (2.7 g, 20.1 mmol), and cesium carbonate (10.9 g, 33.6 mmol) was degassed under reduced pressure, and [1,1'-bis(diphenylphosphino)ferrocene]dichloropalladium-dichloromethane complex (1.4 g, 1.8 mmol) was added, followed by stirring at 90°C for 18 hours. The resulting solution was filtered through Celite, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by silica gel chromatography to obtain Compound 18 (1.4 g, yield 41%).

[0223] (13) Synthesis of Compound A-4 Compound A-4 was synthesized in the same manner as in (2) to (4) of Compound A-1, except that Compound 16 and Compound 18 were used. １ H-NMR (CDCl ３ ): δ = 4.35-4.37 (m, 2H), 4.59-4.61 (m, 2H), 5.51 (dd, 1H), 5.87 (dd, 1H), 5.93 (dd, 1H), 6.19 (dd, 1H), 6.46 (dd, 1H), 7.04 (dd, 1H), 7.17 (d, 1H), 7.22 (dd, 1H), 7.34 (d, 1H), 7.57 (d, 1H)

[0224] Synthesis Example 5 Synthesis of Compound A-5 (14) Synthesis of Compound A-5 Compound A-5 was synthesized according to the following scheme, following the same procedures as those of (1) to (4) of Compound A-1, except that 3-bromo-1-propanol was used instead of 2-bromoethanol.

[0225]

[0226] Compound A-5 １ H-NMR (CDCl ３ ): δ = 2.25 (qq, 2H), 4.21 (t, 2H), 4.42 (t, 2H), 5.85 (d, 1H), 6.15 (dd, 1H), 6.43 (d, 1H) ), 7.15-7.19 (m, 2H), 7.31-7.34 (m, 2H), 7.65-7.70 (m, 3H), 7.80 (d, 2H), 7.94 (d, 1H)

[0227] Synthesis Example 6: Synthesis of compound A-6 Compound A-6 was synthesized according to the following scheme.

[0228]

[0229] (1) Synthesis of Compound 2 6-Bromo-2-naphthol (Compound 1: 20.0 g, 0.090 mol), ethylene carbonate (8.29 g, 0.094 mol), and sodium carbonate (0.95 g, 0.009 mol) were dissolved in DMF (400 mL) and stirred at 150°C for 4 hours. The resulting solution was cooled to room temperature, and water (850 mL) was added. The resulting solution was extracted with methyl tert-butyl ether (850 mL). The resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and further dried over magnesium sulfate. The organic phase was then filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of methanol and water to obtain Compound 2 (23.0 g, yield 96%).

[0230] (2) Synthesis of Compound 3 Compound 2 (20.0 g, 0.075 mol) was dissolved in DMF (80 mL) and then cooled to 0°C. tert-Butyldimethylsilyl chloride (14.7 g, 0.097 mol) and imidazole (7.65 g, 0.11 mol) were added to the resulting solution, followed by stirring at room temperature for 2 hours. The resulting solution was then cooled to 0°C, and water (300 mL) was added. The resulting solution was extracted with methyl tert-butyl ether (300 mL), washed with brine, and the organic phase was dried over magnesium sulfate. The resulting organic phase was then filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain Compound 3 (28.2 g, yield 99%).

[0231] (3) Synthesis of Compound 4 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (4.3 g, 0.005 mol) was added to a solution of compound 3 (20.0 g, 0.052 mol), bis(pinacolato)diboron (20.0 g, 0.079 mol), potassium acetate (7.7 g, 0.079 mol), and anhydrous DMF (300 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 2 hours. The solvent was removed by distillation under reduced pressure, and the resulting residue was purified by flash column chromatography to obtain compound 4 (20.4 g, yield 91%).

[0232] (4) Synthesis of Compound 6 To a solution of 5-bromo-2-nitrophenol (Compound 5: 3.5 g, 0.016 mol), 2-bromoethanol (2.5 g, 0.019 mol), and DMF (14 mL) was added a solution of potassium hydroxide (1.1 g, 0.020 mol), potassium iodide (87 mg, 0.52 mmol), and water (2.3 mL). The resulting solution was then heated to 85°C and stirred for 5 hours. The resulting solution was cooled to room temperature, and water (46 mL) was added. The resulting solution was extracted with methyl tert-butyl ether (94 mL). The resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The residue was purified by crystallization from a mixed solvent of methanol and water to obtain Compound 6 (3.3 g, yield 77%).

[0233] (5) Synthesis of Compound 7 To a solution of compound 6 (1.4 g, 5.4 mmol), L-ascorbic acid (3.9 g, 0.022 mol), sodium carbonate (3.5 g, 0.033 mol), ethanol (18.6 mL), and water (34.9 mL), a solution of iron(II) sulfate heptahydrate (0.30 g, 1.1 mmol) and water (6.5 mL) was added dropwise. The resulting solution was then heated to 80°C and stirred for 3 hours. The solvent was then removed from the resulting solution by distillation under reduced pressure, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with brine and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was removed by distillation under reduced pressure to obtain compound 7 (1.1 g, yield 95%).

[0234] (6) Synthesis of Compound 8 To a solution of compound 4 (5.3 g, 9.8 mmol), compound 7 (2.0 g, 8.5 mmol), potassium carbonate (4.1 g, 29.9 mmol), water (5.0 mL), and DMF (14.9 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (0.99 g, 0.85 mmol) was added. The resulting solution was heated to 60°C and stirred for 3 hours, then cooled to room temperature, and water was added. The resulting solution was extracted with methyl tert-butyl ether, and the resulting organic phase was washed successively with water and brine, and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 8 (3.3 g, yield 84%).

[0235] (7) Synthesis of Compound 9 To a solution of compound 8 (3.3 g, 7.2 mmol) and THF (33 mL) was added 1,1'-thiocarbonyldi-2(1H)-pyridone (1.7 g, 7.4 mmol). The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 9 (3.12 g, yield 88%).

[0236] (8) Synthesis of Compound 10 A solution of compound 9 (3.0 g, 6.1 mmol), MeOH (12 mL), THF (24 mL), and 1N aqueous hydrochloric acid (6 mL) was stirred at room temperature for 1 hour. Water was added to the resulting solution, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was dried over magnesium sulfate, and the organic layer was filtered. The solvent was then evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 10 (1.7 g, yield 75%).

[0237] (9) Synthesis of Compound A-6 To a solution of compound 10 (0.85 g, 2.2 mmol) and DMAc (5 mL), acryloyl chloride (0.81 g, 8.9 mmol) was added. The resulting solution was stirred at room temperature for 1 hour, and then MeOH was added. The resulting solution was filtered to obtain compound A-6 (1.1 g, yield 97%). １ H-NMR (CDCl３ ): δ = 4.21 (dd, 2H), 4.35 (dd, 2H), 4.44 (dd, 2H), 4.60 (dd, 2H), 5.83 (dd, 1H), 5.88 (dd, 1H), 6.05-6.24 (m, 2H), 6.37 (dd, 1H) , 6.48 (dd, 1H), 6.86 (d, 1H), 6.96-7.00 (m, 2H), 7.14-7.20 (m, 2H), 7.41 (d, 1H), 7.62 (d, 1H), 7.68-7.76 (m, 2H), 7.88 (d, 1H)

[0238] Synthesis Example 7: Synthesis of compound A-7 Compound A-7 was synthesized according to the following scheme.

[0239]

[0240] (1) Synthesis of Compound 11 A solution of 2-bromo-5-nitrophenol (compound 10: 3.5 g, 0.016 mol), potassium carbonate (6.7 g, 0.048 mol), chloromethyl ethyl ether (2.3 g, 0.024 mol), and DMF (35 mL) was stirred at room temperature for 2 hours. Water was added to the resulting solution, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was dried over magnesium sulfate, and the organic layer was filtered, after which the solvent was evaporated under reduced pressure. The residue was purified by crystallization using a mixed solvent of DMF and water to obtain compound 11 (4.2 g, yield 95%).

[0241] (2) Synthesis of Compound 12 To a solution of compound 11 (4.1 g, 0.015 mol), L-ascorbic acid (10.8 g, 0.061 mol), sodium carbonate (9.6 g, 0.090 mol), ethanol (54 mL), and water (101 mL), a solution of iron(II) sulfate heptahydrate (0.83 g, 3.0 mmol) and water (18 mL) was added dropwise. The resulting solution was then heated to 80°C and stirred for 3 hours. The solvent was removed from the resulting solution by distillation under reduced pressure, and the resulting mixed solvent was extracted with methyl tert-butyl ether. The resulting organic phase was washed with brine and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was removed by distillation under reduced pressure to obtain compound 12 (2.6 g, yield 70%).

[0242] (3) Synthesis of Compound 13 To a solution of compound 4 (4.5 g, 10.6 mmol), compound 12 (2.0 g, 8.1 mmol), potassium carbonate (3.9 g, 28.4 mmol), water (5.0 mL), and DMF (15 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (0.94 g, 0.81 mmol) was added. The resulting solution was heated to 60°C and stirred for 6 hours, then cooled to room temperature, and water was added. The resulting solution was extracted with methyl tert-butyl ether, and the resulting organic phase was washed successively with water and brine, and further dried over magnesium sulfate. The resulting organic layer was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 13 (3.0 g, yield 80%).

[0243] (4) Synthesis of Compound 14 To a solution of compound 13 (3.0 g, 6.4 mmol) and THF (30 mL) was added 1,1'-thiocarbonyldi-2(1H)-pyridone (1.5 g, 6.6 mmol). The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 14 (2.6 g, yield 80%).

[0244] (5) Synthesis of Compound 15 A mixed solution of compound 14 (0.5 g, 1.0 mmol), MeOH (2 mL), THF (2 mL), and concentrated hydrochloric acid (1 mL) was stirred at room temperature for 1 hour. Water was added to the resulting solution, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was dried over magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 15 (0.3 g, yield 90%).

[0245] (6) Synthesis of Compound A-7 To a solution of compound 15 (0.5 g, 1.5 mmol) and DMAc (2.5 mL), acryloyl chloride (0.54 g, 5.9 mmol) was added. The resulting solution was stirred at room temperature for 3 hours, and then MeOH was added. The resulting solution was filtered to obtain compound A-7 (0.6 g, yield 85%). １ H-NMR (CDCl３ ): δ = 4.36 (dd, 2H), 4.60 (dd, 2H), 5.88 (dd, 1H), 5.91 (dd, 1H), 6.10-6.24 (m, 2H), 6.47 (dd, 1H), 6.48 (dd, 1H) ), 6.86-6.92 (dd, 2H), 7.17-7.24 (m, 2H), 7.30 (d, 1H), 7.55 (dd, 1H), 7.79 (d, 1H), 7.81 (d, 1H), 7.87 (d, 1H)

[0246] Synthesis Example 8: Synthesis of compound A-8 Compound A-8 was synthesized according to the following scheme.

[0247]

[0248] (1) Synthesis of Compound 17 To a solution of solketal (compound 16: 5.0 g, 0.040 mol), pyridine (13.8 mL), and dichloromethane (60 mL) cooled to 0°C, p-toluenesulfonyl chloride (24.5 g, 0.17 mol) was added, and the mixture was stirred at room temperature for 3 hours. The resulting solution was cooled to 0°C again, and then a 6N aqueous hydrochloric acid solution was added. The resulting solution was extracted with dichloromethane, and the resulting organic phase was washed with brine and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 17 (9.5 g, yield 94%).

[0249] (2) Synthesis of Compound 18 Under a nitrogen atmosphere at 0°C, sodium hydride (60% dispersion in liquid paraffin: 0.57 g, 4.3 mmol) was added to a solution of compound 2 (1.1 g, 4.1 mmol) and anhydrous DMF (11 mL). The resulting solution was stirred at the same temperature for 30 minutes, and then a solution of compound 17 (1.3 g, 4.5 mmol) and anhydrous DMF (2.2 mL) was added dropwise. The resulting solution was stirred at 80°C for 5 hours, and then water was added, and the resulting solution was extracted with ethyl acetate. The resulting organic phase was dried over magnesium sulfate, filtered, and the solvent was evaporated under reduced pressure. MeOH was added to the resulting residue, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered, and the solvent was evaporated under reduced pressure to obtain compound 18 (0.93 g, yield 59%).

[0250] (3) Synthesis of Compound 19 To a solution of compound 18 (0.93 g, 2.4 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline (0.64 g, 2.9 mmol), potassium carbonate (0.74 g, 5.4 mmol), DMF (7 mL), and water (2.3 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (0.14 g, 0.12 mmol) was added. The resulting solution was then heated to 60°C and stirred for 5 hours. The solvent was removed from the resulting solution by distillation under reduced pressure, and the resulting residue was purified by flash column chromatography to give compound 19 (0.86 g, yield 90%).

[0251] (4) Synthesis of Compound 20 A solution of compound 19 (0.84 g, 2.1 mmol), 1N aqueous hydrochloric acid (3.2 mL), and THF (6.3 mL) was stirred at 40°C for 4 hours. 1N aqueous hydrochloric acid was added, and the resulting solution was extracted with a mixed solvent of ethyl acetate and THF. The resulting organic phase was washed sequentially with aqueous sodium bicarbonate and brine, and then dried over magnesium sulfate. The organic phase was filtered, and the solvent was evaporated under reduced pressure to obtain compound 20 (0.68 g, yield 90%).

[0252] (5) Synthesis of Compound 21 To a solution of compound 20 (0.95 g, 2.7 mmol) and THF (9.5 mL), 1,1'-thiocarbonyldi-2(1H)-pyridone (0.66 g, 2.8 mmol) was added. The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 21 (0.5 g, yield 47%).

[0253] (6) Synthesis of Compound A-8 To a solution of compound 21 (0.5 g, 1.3 mmol) and DMAc (2.5 mL), acryloyl chloride (0.25 g, 2.8 mmol) was added. The resulting solution was stirred at room temperature for 3 hours, and then MeOH was added. The resulting solution was filtered to obtain compound A-8 (0.32 g, yield 50%). １H-NMR (CDCl3): δ = 3.81 (qd, 2H), 3.88-3.99 (m, 2H), 4.25 (t, 2H), 4.38 (dd, 1H), 4.49 (dd, 1H), 5.35-5.41 (m, 1H), 5.83 (dd, 1H), 5.85 (dd, 1H) , 6.08-6.17 (m, 2H), 6.40 (dd, 1H), 6.44 (dd, 1H), 7.15 (d, 1H), 7.20 (d d, 1H), 7.30-7.34 (m, 2H), 7.64-7.70 (m, 3H), 7.78 (d, 1H), 7.80 (d, 1H)

[0254] Synthesis Example 9: Synthesis of Compound A-9 Compound A-9 was synthesized according to the following scheme.

[0255]

[0256] (1) Synthesis of Compound 22 To a solution of compound 2 (15.0 g, 0.056 mol) and pyridine (75 mL) cooled to 0°C, p-toluenesulfonyl chloride (32.1 g, 0.17 mol) was added and stirred at the same temperature for 3 hours. Water was added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting mixture was filtered to obtain compound 22 (19.0 g, yield 99%).

[0257] (2) Synthesis of Compound 23 A solution of compound 22 (18.0 g, 0.048 mol), cesium carbonate (17.1 g, 0.053 mol), 6-bromo-2-naphthol (compound 1: 11.2 g, 0.050 mol), and DMF (540 mL) was stirred at 90°C for 4 hours. The resulting solution was cooled to room temperature, and water was added thereto, followed by stirring at room temperature for 1 hour. The resulting mixture was filtered to obtain compound 23 (16.2 g, yield 72%).

[0258] (3) Synthesis of Compound 24 Compound 6 (8.5 g, 0.032 mol) was dissolved in DMF (34 mL) and then cooled to 0°C. To the resulting solution, tert-butyldimethylsilyl chloride (6.4 g, 0.042 mol) and imidazole (3.3 g, 0.49 mol) were added and the mixture was stirred at room temperature for 2 hours. The resulting solution was then cooled to 0°C, and water was added. The resulting solution was extracted with methyl tert-butyl ether, and the resulting organic phase was washed with brine and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 24 (23.3 g, yield 98%).

[0259] (4) Synthesis of Compound 25 To a solution of compound 24 (20.0 g, 0.053 mol), L-ascorbic acid (38.6 g, 0.22 mol), sodium carbonate (34.3 g, 0.34 mol), ethanol (262 mL), and water (492 mL), a solution of iron(II) sulfate heptahydrate (2.2 g, 7.9 mmol) and water (63 mL) was added dropwise. The resulting solution was then heated to 95°C and stirred for 7 hours. The solvent was removed from the resulting solution by distillation under reduced pressure, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with brine and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was removed by distillation under reduced pressure to obtain compound 25 (15.9 g, yield 87%).

[0260] (5) Synthesis of Compound 26 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (3.1 g, 0.004 mol) was added to a solution of compound 25 (13.0 g, 0.038 mol), bis(pinacolato)diboron (14.3 g, 0.056 mol), potassium acetate (5.5 g, 0.056 mol), and anhydrous DMF (195 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 14 hours. The solvent was removed from the resulting solution by distillation under reduced pressure, and the resulting residue was purified by flash column chromatography to give compound 26 (11.8 g, 80% yield).

[0261] (6) Synthesis of Compound 27 To a solution of compound 23 (1.0 g, 2.1 mmol), compound 26 (2.4 g, 4.9 mmol), potassium carbonate (1.0 g, 7.4 mmol), water (2.5 mL), and DMF (7.5 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (0.25 g, 0.21 mmol) was added. The resulting solution was heated to 60°C and stirred for 7 hours. The resulting solution was then cooled to room temperature, water was added, and the mixture was stirred at room temperature for 30 minutes. The resulting solution was filtered. The resulting residue was purified by flash column chromatography to give compound 27 (0.44 g, yield 25%).

[0262] (7) Synthesis of Compound 28 To a solution of compound 27 (0.44 g, 0.52 mmol) and THF (4.4 mL), 1,1'-thiocarbonyldi-2(1H)-pyridone (0.25 g, 1.1 mmol) was added. The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 28 (0.25 g, yield 52%).

[0263] (8) Synthesis of Compound 29 A solution of compound 28 (0.25 g, 2.7 mmol), MeOH (1 mL), THF (5 mL), and concentrated hydrochloric acid (0.5 mL) was stirred at room temperature for 1 hour. MeOH was added to the resulting solution, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was dried over magnesium sulfate and filtered, and then the solvent was evaporated under reduced pressure from the resulting organic phase. The resulting residue was purified by flash column chromatography to obtain compound 29 (0.16 g, yield 84%).

[0264] (9) Synthesis of Compound A-9 To a solution of compound 29 (0.16 g, 0.23 mmol) and DMAc (1.6 mL), acryloyl chloride (83 mg, 0.92 mmol) was added. The resulting solution was stirred at room temperature for 2 hours, and then MeOH was added. The resulting solution was filtered to obtain compound A-9 (0.17 g, yield 97%). １ H-NMR (CDCl ３): δ = 4.42 (dd, 4H), 4.56 (s, 4H), 4.63 (dd, 4H), 5.88 (d, 2H), 6.20 (dd, 2H) ), 6.50 (d, 2H), 7.16-7.30 (m, 6H), 7.66 (d, 2H), 7.82 (d, 4H), 7.94 (s, 2H)

[0265] Synthesis Example 10: Synthesis of compound A-10 Compound A-10 was synthesized according to the following scheme: Compound A-10 was synthesized in the same manner as in the synthesis of compound A-9, except that compound 30 was used.

[0266]

[0267] (1) Synthesis of Compound 30 A solution of 6-bromo-2-naphthol (compound 1: 7.0 g, 0.031 mol), potassium carbonate (17.4 g, 0.13 mol), and DMF (70 mL) was stirred at room temperature for 30 minutes, and then 1,4-dibromobutane (3.3 g, 0.015 mol) was added. The resulting solution was stirred at 50°C for 3 hours, and then water was added. The resulting solution was filtered, and the resulting residue was purified by flash column chromatography to obtain compound 30 (9.1 g, yield 98%).

[0268] (2) Compound A-10 １ H-NMR (CDCl ３ ) δ = 2.10-2.16 (m, 4H), 4.18-4.24 (m, 4H), 4.42 (dd, 4H), 4.62 (dd, 4H), 5.88 (dd, 2H), 6.2 0 (dd, 2H), 6.48 (dd, 2H), 7.16-7.26 (m, 10H), 7.64 (dd, 2H), 7.79 (dd, 4H), 7.92 (dd, 2H)

[0269] Synthesis Example 11: Synthesis of compound A-11 Compound A-11 was synthesized according to the following scheme.

[0270]

[0271] (1) Synthesis of Compound 32 To a reduced-pressure degassed solution of 5-bromo-2-iodotoluene (Compound 31: 6.7 g, 23 mmol), 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenol (5.0 g, 23 mmol), potassium carbonate (11 g, 80 mmol), DMF (100 mL), and water (5 mL) was added tetrakis(triphenylphosphine)palladium (1.3 g, 0.11 mmol). The resulting solution was then heated to 60°C and stirred for 10 hours. The solvent was removed from the resulting solution by distillation under reduced pressure, and the resulting residue was purified by flash column chromatography to give Compound 32 (5.6 g, yield 94%).

[0272] (2) Synthesis of Compound 33 Compound 32 (2.0 g, 5.9 mmol), compound 22 (2.4 g, 5.8 mmol), potassium iodide (0.10 g, 0.6 mmol), and potassium carbonate (0.92 g, 6.7 mmol) were dissolved in DMAc (8 mL), and the resulting solution was stirred at 80°C for 1 hour. After the resulting solution was cooled to room temperature, a mixed solution of acetic acid (0.42 g) and MeOH (2 mL) was added and stirred for 30 minutes. Then, water and MeOH were added to the resulting solution, and the mixture was stirred at 20°C for 1 hour. The resulting solution was filtered to obtain compound 33 (1.4 g, yield 48%).

[0273] (3) Synthesis of Compound 34 A solution of compound 6 (10.0 g, 0.038 mol), N,N-diisopropylethylamine (24.7 g, 0.19 mol), chloromethyl ethyl ether (14.4 g, 0.15 mol), and DMF (100 mL) was stirred at 60°C for 2 hours. After the resulting solution was cooled to 0°C, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 34 (10.8 g, yield 88%).

[0274] (4) Synthesis of Compound 35 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (1.0 g, 1.2 mmol) was added to a solution of compound 34 (4.0 g, 0.013 mol), bis(pinacolato)diboron (4.8 g, 0.019 mol), potassium acetate (2.1 g, 0.022 mol), and anhydrous DMF (60 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 3 hours. After cooling to room temperature, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 35 (3.6 g, yield 78%).

[0275] (5) Synthesis of Compound 36 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.17 g, 0.21 mmol) was added to a solution of compound 33 (1.0 g, 2.1 mmol), compound 35 (1.9 g, 4.8 mmol), potassium carbonate (1.0 g, 7.3 mmol), water (2 mL), and N-methylpyrrolidone (20 mL) that had been degassed under reduced pressure. The resulting solution was heated to 60°C and stirred for 4 hours. After cooling to room temperature, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 36 (0.47 g, yield 29%).

[0276] (6) Compound 37: Under a hydrogen atmosphere, a mixed solution of compound 36 (0.47 g, 0.56 mmol), 10% palladium-activated carbon (0.14 g), and THF (14 mL) was stirred at room temperature for 8 hours. The resulting solution was filtered, and 1,1'-thiocarbonyldi-2(1H)-pyridone (0.27 g, 1.2 mmol) was added. The resulting solution was stirred at room temperature for 1 hour, and then the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 37 (0.19 g, yield 39%).

[0277] (7) Compound 38: A solution of compound 37 (0.19 g, 2.2 mmol), MeOH (0.57 mL), THF (3.8 mL), and concentrated hydrochloric acid (0.57 mL) was stirred at room temperature for 1 hour. MeOH was added to the resulting solution, and the mixture was stirred at 0° C. for 1 hour. The resulting solution was filtered to give compound 38 (0.15 g, yield 90%).

[0278] (8) Synthesis of Compound A-11 Acryloyl chloride (49 mg, 0.54 mmol) was added to a solution of compound 38 (0.15 g, 0.13 mmol) and DMAc (1 mL). The resulting solution was stirred at room temperature for 2 hours, and then MeOH was added. The resulting solution was filtered to obtain compound A-11 (0.10 g, yield 85%). １ H-NMR (CDCl ３ ): δ = 3.26 (s, 3H), 4.36-4.44 (m, 2H), 4.44-4.54 (m, 4H), 4.58-4.64 (m, 4H), 5.86-5.90 (m, 2H), 6.12 -6.24 (m, 2H), 6.44-6.52 (m, 2H), 7.04-7.50 (m, 15H), 7.65 (dd, 1H), 7.78-7.85 (m, 2H), 7.94 (d, 1H)

[0279] Synthesis Example 12 Synthesis of Compound A-12 Compound A-12 was synthesized according to the following scheme: Compound A-12 was synthesized in the same manner as in the synthesis of Compound A-11, except that Compounds 40 and 41 were used.

[0280]

[0281] (1) Synthesis of Compound 39 To a solution of 2-bromo-5-nitrophenol (compound 10: 5.0 g, 0.023 mol), 2-bromoethanol (3.6 g, 0.028 mol), and DMF (20 mL) was added a solution of potassium hydroxide (1.6 g, 0.029 mol), potassium iodide (0.12 g, 0.75 mmol), and water (3.3 mL). The resulting solution was then heated to 85°C and stirred for 5 hours. The resulting solution was cooled to room temperature, water was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and further dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The residue was purified by crystallization using a mixed solvent of MeOH and water to obtain compound 39 (3.5 g, yield 58%).

[0282] (2) Synthesis of Compound 40 A solution of compound 39 (3.4 g, 0.013 mol), N,N-diisopropylethylamine (8.4 g, 0.065 mol), chloromethyl ethyl ether (4.9 g, 0.052 mol), and DMF (34 mL) was stirred at 60°C for 1 hour. After the resulting solution was cooled to 0°C, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 40 (1.4 g, yield 74%).

[0283] (3) Synthesis of Compound 41 To a solution of compound 23 (1.0 g, 2.1 mmol), bis(pinacolato)diboron (1.6 g, 6.4 mmol), potassium acetate (0.73 g, 7.4 mmol), and anhydrous DMF (15 mL) that had been degassed under reduced pressure, dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.17 g, 0.21 mmol) was added. The resulting solution was then heated to 90°C and stirred for 6 hours. After cooling to room temperature, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 41 (0.96 g, yield 80%).

[0284] (4) Compound A-12 １ H-NMR (CDCl ３ ) δ = 4.22 (dd, 4H), 4.44 (dd, 4H), 4.54 (s, 4H), 5.82 (dd, 2H), 6.10 (dd, 2H), 6.38 (dd, 2H), 6.86 (d, 2H), 6.98 (dd, 2H), 7.21-7.26 (m, 4H), 7.42 (d, 2H), 7.63 (dd, 2H), 7.70-7.78 (m, 4H), 7.89 (d, 2H)

[0285] Synthesis Example 13 Synthesis of Compound A-13 Compound A-13 was synthesized according to the following scheme: Compound A-13 was synthesized in the same manner as in the synthesis of compound A-11, except that compounds 43 and 44 were used.

[0286]

[0287] (1) Synthesis of Compound 42 A solution of compound 2 (10.0 g, 0.037 mol), N,N-diisopropylethylamine (24.2 g, 0.19 mol), chloromethyl ethyl ether (14.2 g, 0.15 mmol), and DMF (1000 mL) was stirred at 60°C for 1 hour. After the resulting solution was cooled to 0°C, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 42 (11.8 g, yield 97%).

[0288] (2) Synthesis of Compound 43 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (2.4 g, 2.9 mmol) was added to a solution of compound 42 (10.0 g, 0.029 mol), bis(pinacolato)diboron (11.0 g, 0.044 mol), potassium acetate (5.0 g, 0.051 mol), and anhydrous DMF (150 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 3 hours. After cooling to room temperature, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with methyl tert-butyl ether. The resulting organic phase was washed with water and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 43 (8.6 g, yield 80%).

[0289] (3) Synthesis of Compound 44 A solution of 5-bromo-2-nitrophenol (Compound 5: 10.0 g, 0.046 mol), 1,2-dibromoethane (4.2 g, 0.022 mol), potassium carbonate (12.2 g, 0.097 mol), and DMF (100 mL) was heated to 80°C and stirred for 5 hours. The resulting solution was cooled to room temperature, and water was added thereto, followed by stirring at room temperature for 1 hour. The resulting solution was filtered, and toluene was added to the resulting residue. After stirring at room temperature for 1 hour, the mixture was filtered to obtain Compound 44 (6.5 g, yield 59%).

[0290] (4) Compound A-13１ H-NMR (CDCl ３ ) δ = 4.36 (dd, 4H), 4.60 (dd, 4H), 4.64 (s, 4H), 5.88 (dd, 2H), 6.20 (dd, 2H), 6.48 (d d, 2H), 7.16-7.28 (m, 8H), 7.33 (d, 2H), 7.67 (dd, 2H), 7.81 (dd, 4H), 7.97 (m, 2H)

[0291] Synthesis Example 14 Synthesis of Compound A-14 Compound A-14 was synthesized according to the following scheme: Compound A-14 was synthesized in the same manner as in the synthesis of compound A-11, except that compounds 48 and 50 were used.

[0292]

[0293] (1) Synthesis of Compound 46 4-Bromo-o-cresol (Compound 45: 25.0 g, 0.13 mol), ethylene carbonate (12.4 g, 0.14 mol), and sodium carbonate (1.42 g, 0.013 mol) were dissolved in DMF (400 mL) and stirred at 150°C for 3 hours. The resulting solution was cooled to room temperature, and water (850 mL) was added. The resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and normal hexane to obtain Compound 46 (27.4 g, yield 89%).

[0294] (2) Synthesis of Compound 47 Methanesulfonyl chloride (9.61 mL, 0.12 mol) was added dropwise to a mixed solution of compound 46 (27.0 g, 0.12 mol), triethylamine (19.7 mL, 0.14 mol), and THF (135 mL) cooled to 0°C, and the mixture was stirred at the same temperature for 1 hour. After adding water, the resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed sequentially with a 1N aqueous solution of hydrochloric acid, an aqueous solution of sodium bicarbonate, and brine. The resulting organic phase was dried over magnesium sulfate and filtered, after which the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and normal hexane to obtain compound 47 (34.7 g, yield 96%).

[0295] (3) Synthesis of Compound 48 Compound 47 (9.9 g, 0.032 mol), 4-bromo-4'-hydroxybiphenyl (8.0 g, 0.032 mol), and potassium carbonate (6.7 g, 0.048 mol) were dissolved in DMAc (80 mL) and stirred at 80°C for 6 hours. The resulting solution was cooled to room temperature, and then water and ethyl acetate were added sequentially and stirred for 30 minutes. Normal hexane was then added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered to obtain Compound 48 (12.5 g, yield 84%).

[0296] (4) Synthesis of Compound 50 A mixed solution of compound 47 (2.2 g, 2.78 mmol) and THF (14.4 mL) was added dropwise to a mixed solution of ammonium chloride (0.30 g, 5.57 mmol), reduced iron (3.1 g, 55.7 mmol), water (6.5 mL), and 2-propanol (39 mL) heated to 80°C, and the mixture was stirred for 2 hours. After the resulting solution was cooled to room temperature, aqueous sodium bicarbonate solution and ethyl acetate were added, and the mixture was filtered through Celite. The resulting organic phase was washed with brine and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure to obtain compound 50 (2.0 g, yield 99%).

[0297] (5) Compound A-14 １ H-NMR (CDCl ３ ) δ = 2.28 (s, 3H), 4.38-4.41 (m, 8H), 4.61 (q, 4H), 5.88 (dd, 2H), 6.20 (dd, 2H), 6.4 8 (dd, 2H), 6.95 (d, 1H), 7.05-7.20 (m, 8H), 7.33-7.36 (m, 2H), 7.56-7.67 (m, 6H)

[0298] Synthesis Example 15 Synthesis of Compound A-15 Compound A-15 was synthesized according to the following scheme: Compound A-15 was synthesized in the same manner as in the synthesis of Compound A-14, except that Compound 1 (6-bromo-2-naphthol) was used instead of 4-bromo-4'-hydroxybiphenyl.

[0299]

[0300] (1) Compound A-15１ H-NMR (CDCl ３ ) δ = 2.30 (s, 3H), 4.38 (t, 2H), 4.42 (t, 2H), 4.44-4.48 (m, 2H), 4.49-4.54 (m, 2H), 4.57-4.64 (m, 4H), 5.88 (dd, 2H), 6.19 (dd, 2H), 6.48 (d d, 2H), 6.97 (d, 1H), 7.06-7.14 (m, 3H), 7.18 (d, 1H), 7.21-7.26 (m, 4H), 7.33-7.38 (m, 2H), 7.65 (dd, 1H), 7.78-7.84 (m, 2H), 7.93 (d, 1H)

[0301] Synthesis Example 16: Synthesis of compound A-16 Compound A-16 was synthesized according to the following scheme. Compound 57 was synthesized in the same manner as in the synthesis of compound 41, except that compound 56 (4-iodophenol) was used. Compound A-16 was synthesized in the same manner as in the synthesis of compound A-14, except that compounds 55 and 57 were used.

[0302]

[0303] (1) Synthesis of Compound 52 A mixed solution of 3-bromophenol (compound 51: 25.0 g, 0.14 mol), potassium iodide (16.6 g, 0.10 mol), potassium iodate (9.59 g, 0.049 mol), sulfuric acid (14 mL), acetonitrile (75 mL), and water (500 mL) was stirred at room temperature for 5 hours. The resulting solution was cooled to 0°C, and then an aqueous solution of sodium thiosulfate was added. The resulting solution was extracted with ethyl acetate, washed with brine, and the organic phase was dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 52 (16.9 g, yield 39%).

[0304] (2) Synthesis of Compound 53 Compound 52 (14.0 g, 0.048 mol), ethylene carbonate (4.4 g, 0.050 mol), and sodium carbonate (0.50 g, 0.005 mol) were dissolved in DMAc (210 mL) and stirred at 150°C for 3 hours. The resulting solution was cooled to room temperature, and water (850 mL) was added. The resulting solution was extracted with tert-butyl methyl ether, and the resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization from a mixed solvent of methanol and water to obtain Compound 53 (15.5 g, yield 95%).

[0305] (3) Synthesis of Compound 54 To a solution of compound 53 (15.5 g, 0.039 mmol), 4,4,5,5-tetramethyl-2-(4-nitrophenyl)-1,3,2-dioxaborolane (13.1 g, 0.053 mmol), potassium carbonate (16.1 g, 0.12 mmol), DMF (310 mL), and water (16 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (2.2 g, 0.002 mol) was added. The resulting solution was then heated to 80°C and stirred for 4 hours. The resulting solution was cooled to 0°C, and a 1N aqueous solution of hydrochloric acid was added. The resulting solution was extracted with ethyl acetate, washed with brine, and the organic phase was dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 54 (7.9 g, yield 60%).

[0306] (4) Synthesis of Compound 55 A solution of compound 54 (7.9 g, 0.023 mol), N,N-diisopropylethylamine (9.1 g, 0.070 mol), chloromethyl ethyl ether (4.4 g, 0.047 mmol), and DMF (79 mL) was stirred at 60°C for 2 hours. The resulting solution was cooled to 0°C, and then a 1N aqueous solution of hydrochloric acid was added. The resulting solution was extracted with ethyl acetate. The resulting organic phase was washed sequentially with an aqueous solution of sodium bicarbonate and brine, and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 55 (8.7 g, yield 94%).

[0307] (5) Compound A-16 １ H-NMR (DMSO-d ６ ) δ = 4.30 (t, 4H), 4.42 (s, 4H), 4.48 (t, 4H), 5.88 (d, 2H), 6.13 (dd, 2H), 6.42 (d , 2H), 7.01 (d, 4H), 7.16 (s, 2H), 7.22-7.29 (m, 6H), 7.37 (d, 2H), 7.58 (dd, 8H)

[0308] Synthesis Example 17 Synthesis of Compound A-17 Compound A-17 was synthesized according to the following scheme: Compound A-17 was synthesized in the same manner as in the synthesis of compound A-14, except that compounds 55 and 59 were used.

[0309]

[0310] (1) Synthesis of Compound 59 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (0.94 g, 1.2 mmol) was added to a reduced-pressure degassed solution of 4,4'-diiodo-2,2'-dimethylbiphenyl (Compound 58: 5.0 g, 0.029 mol), bis(pinacolato)diboron (8.8 g, 0.035 mol), potassium acetate (4.3 g, 0.044 mol), and anhydrous DMF (75 mL). The resulting solution was then heated to 90°C and stirred for 3 hours. After cooling to 0°C, a 1N aqueous hydrochloric acid solution was added, and the resulting solution was extracted with ethyl acetate. The resulting organic phase was washed with brine and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was removed by distillation under reduced pressure. The resulting residue was purified by flash column chromatography to give Compound 43 (2.9 g, yield 58%).

[0311] (2) Compound A-17 １ H-NMR (CDCl ３ ) δ = 2.20 (s, 6H), 4.34 (t, 4H), 4.51 (t, 4H), 5.88 (d, 2H), 6.14 (d, 2H), 6.43 (d, 2H), 7.2 2-7.29 (m, 8H), 7.36 (dd, 2H), 7.42 (d, 2H), 7.51 (dd, 2H), 7.54 (brs, 2H), 7.61 (d, 4H)

[0312] Synthesis Example 18 Synthesis of Compound A-18 Compound A-18 was synthesized according to the following scheme: Compound A-18 was synthesized in the same manner as in the synthesis of compound A-14, except that compounds 62 and 64 were used.

[0313]

[0314] (1) Synthesis of Compound 61 Methanesulfonyl chloride (2.4 g, 0.021 mol) was added dropwise to a mixed solution of 6-iodo-2-naphthalenemethanol (compound 60: 5.0 g, 0.018 mol), triethylamine (2.7 g, 0.026 mol), and THF (25 mL) cooled to 0°C, and the mixture was stirred at the same temperature for 1 hour. After adding water, the resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed successively with a 1N aqueous solution of hydrochloric acid, an aqueous solution of sodium bicarbonate, and brine. The resulting organic phase was dried over magnesium sulfate and filtered, after which the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and normal hexane to obtain compound 61 (5.1 g, yield 82%).

[0315] (2) Synthesis of Compound 62 Compound 61 (4.4 g, 0.015 mol), compound 32 (4.0 g, 0.015 mol), potassium carbonate (2.4 g, 0.018 mol), and potassium iodide (0.25 g, 1.5 mmol) were dissolved in DMAc (20 mL), and the resulting solution was stirred at 80° C. for 6 hours. After the resulting solution was cooled to room temperature, water and ethyl acetate were added sequentially and the mixture was stirred for 30 minutes. Then, normal hexane was added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered to obtain compound 62 (6.5 g, yield 81%).

[0316] (3) Synthesis of Compound 63 A mixed solution of 5-bromo-2-nitrophenol (compound 5: 75.0 g, 0.34 mol), N,N-diisopropylethylamine (65.9 mL, 0.38 mol), sodium iodide (5.2 g, 0.034 mmol), propylene carbonate (87.1 g, 1.03 mmol), and DMAc (300 mL) was stirred at 165°C for 4 hours. After adding 1N aqueous hydrochloric acid to the resulting solution, the resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed sequentially with aqueous sodium bicarbonate and brine. The resulting organic phase was dried over magnesium sulfate and filtered, and the solvent was distilled off under reduced pressure. The resulting residue was purified by flash column chromatography and then crystallized and purified using a mixed solvent of ethyl acetate and normal hexane to obtain compound 63 (30.8 g, yield 32%).

[0317] (4) Synthesis of Compound 64 A solution of compound 63 (30.0 g, 0.11 mol), N,N-diisopropylethylamine (75.7 mL, 0.43 mol), chloromethyl ethyl ether (29.1 mL, 0.33 mmol), and DMF (254 mL) was stirred at 60°C for 4 hours. The resulting solution was cooled to 0°C, and then a 1N aqueous solution of hydrochloric acid was added. The resulting solution was extracted with ethyl acetate. The resulting organic phase was washed sequentially with an aqueous solution of sodium bicarbonate and brine, and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give compound 64 (36.2 g, yield 95%).

[0318] (5) Synthesis of Compound 65 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (7.0 g, 8.6 mmol) was added to a solution of compound 64 (20.0 g, 0.057 mol), bis(pinacolato)diboron (22.5 g, 0.086 mol), potassium acetate (10.1 g, 0.10 mol), and anhydrous DMF (300 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 6 hours. After cooling to 0°C, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with ethyl acetate. The resulting organic phase was washed with brine and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 65 (10.3 g, yield 47%).

[0319] (6) Compound A-18 １ H-NMR (CDCl ３ ) δ = 1.52 (d, 3H), 1.53 (d, 3H), 2.37 (s, 3H), 4.16-4.30 (m, 4H), 5.31 (s, 2H), 5.35-5.47 (m, 2H), 5.85 (dd, 2H), 6.16 (dd, 2H), 4.27-4 .50 (m, 2H), 7.07-7.21 (m, 6H), 7.23-7.32 (m, 5H), 7.38-7.45 (m, 2H), 7.63 (dd, 1H), 7.71 (dd, 1H), 7.92-7.97 (m, 3H), 8.01 (d, 1H)

[0320] Synthesis Example 19 Synthesis of Compound A-19 Compound A-19 was synthesized according to the following scheme: Compound A-19 was synthesized in the same manner as in the synthesis of Compound A-18, except that Compound 66 (4-bromophenol) was used.

[0321]

[0322] (1) Compound A-19 １ H-NMR (CDCl ３ ) δ = 1.50 (d, 3H), 1.53 (d, 3H), 4.17-4.30 (m, 4H), 5.30 (s, 2H), 5.34-5.45 (m, 2H), 5.85 (dd, 2H), 6.14-6.21 (m, 2H), 6.45 (dd, 2H), 7 .04-7.13 (m, 5H), 7.19 (d, 1H), 7.22-7.27 (m, 2H), 7.46-7.51 (m, 2H), 7.60 (dd, 1H), 7.70 (dd, 1H), 7.91-7.96 (m, 3H), 8.00 (d, 1H)

[0323] Synthesis Example 20: Synthesis of compound A-20 Compound A-20 was synthesized according to the following scheme: Compound A-20 was synthesized in the same manner as in the synthesis of compound A-18, except that compound 67 (4-iodobenzyl bromide) was used.

[0324]

[0325] (1) Compound A-20 １ H-NMR (CDCl ３ ) δ = 1.51 (s, 3H), 1.52 (s, 3H), 4.14-4.24 (m, 4H), 5.16 (s, 2H), 5.36-5.44 (m, 2H), 5.83 -5.87 (m, 2H), 6.15 (dd, 2H), 6.41-6.48 (m, 2H), 7.03-7.17 (m, 8H), 7.46-7.60 (m, 6H)

[0326] Synthesis Example 21: Synthesis of compound A-21 Compound A-21 was synthesized according to the following scheme: Note that A-21 was synthesized in the same manner as in the synthesis of compound A-18, except that compound 69 was used.

[0327]

[0328] (1) Synthesis of Compound 68 Compound 67 (15.0 g, 0.051 mol), compound 66 (8.8 g, 0.051 mol), and potassium carbonate (8.0 g, 0.058 mol) were dissolved in DMAc (60 mL) and stirred at 80° C. for 2 hours. The resulting solution was cooled to room temperature, and acetic acid was added and stirred for 30 minutes. MeOH and water were then added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered to obtain compound 68 (19.0 g, yield 97%).

[0329] (2) Synthesis of Compound 69 To a solution of compound 68 (6.5 g, 0.017 mmol), 4-bromophenyl pinacol borate (5.0 g, 0.018 mmol), potassium carbonate (9.3 g, 0.067 mmol), DMF (111 mL), and water (15 mL) that had been degassed under reduced pressure, tetrakis(trifluorophosphine)palladium (1.9 g, 1.7 mmol) was added. The resulting solution was then heated to 60°C and stirred for 3 hours. The resulting solution was cooled to room temperature, and acetic acid was added and stirred for 30 minutes. MeOH and water were then added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered to obtain compound 69 (7.0 g, yield 99%).

[0330] (3) Compound A-21 １ H-NMR (CDCl ３ ) δ = 1.51 (d, 3H), 1,53 (d, 3H), 4.14-4.28 (m, 4H), 5.17 (s, 2H), 5.33-5.45 (m, 2H), 5.82-5.88 (m, 2H), 6.14 (dd, 1H), 6.17 (dd, 1H), 6.41-6.50 (m, 2H), 7.05-7.20 (m, 8H), 7.53 (dd, 4H), 7.61-7.71 (m, 6H)

[0331] Synthesis Example 22: Synthesis of compound A-22 Compound A-22 was synthesized according to the following scheme: Compound A-21 was synthesized in the same manner as in the synthesis of compound A-18, except that compound 74 was used.

[0332]

[0333] (1) Synthesis of Compound 70 4-iodophenol (compound 56: 20.0 g, 0.091 mol), ethylene carbonate (8.41 g, 0.095 mol), and sodium carbonate (0.96 g, 0.009 mol) were dissolved in DMF (400 mL) and stirred at 150°C for 4 hours. The resulting solution was cooled to room temperature, and water was added. The resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed successively with a 2% aqueous potassium hydroxide solution and brine, and further dried over magnesium sulfate. The organic phase was then filtered, and the solvent was evaporated under reduced pressure to obtain compound 70 (22.8 g, yield 95%).

[0334] (2) Synthesis of Compound 71 Methanesulfonyl chloride (10.4 g, 0.091 mol) was added dropwise to a mixed solution of compound 70 (20.0 g, 0.076 mol), triethylamine (11.5 g, 0.114 mol), and THF (300 mL) cooled to 0°C, and the mixture was stirred at the same temperature for 2 hours. Water was added to the resulting solution, and the resulting solution was extracted with ethyl acetate. The resulting organic phase was washed sequentially with a 1N aqueous hydrochloric acid solution, an aqueous sodium bicarbonate solution, and brine. The organic phase was dried over magnesium sulfate and filtered, after which the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and normal hexane to obtain compound 71 (21.3 g, yield 82%).

[0335] (3) Synthesis of Compound 72 Compound 71 (10.0 g, 0.029 mol), compound 45 (5.5 g, 0.030 mol), potassium carbonate (4.7 g, 0.034 mol), and potassium iodide (0.49 g, 2.9 mmol) were dissolved in DMAc (80 mL), and the resulting solution was stirred at 80° C. for 6 hours. After the resulting solution was cooled to room temperature, acetic acid and methanol were added and the mixture was stirred for 30 minutes. Then, a mixed solvent of methanol and water was added to the resulting solution, and the mixture was stirred at room temperature for 1 hour. The resulting solution was filtered to obtain compound 72 (10.8 g, yield 85%).

[0336] (4) Synthesis of Compound 73 Dichloro[1,1'-bis(diphenylphosphino)ferrocene]palladium(II) dichloromethane adduct (1.5 g, 1.8 mmol) was added to a solution of compound 72 (8.0 g, 0.019 mol), bis(pinacolato)diboron (14.1 g, 0.055 mol), potassium acetate (6.3 g, 0.065 mol), and anhydrous DMF (120 mL) that had been degassed under reduced pressure. The resulting solution was then heated to 90°C and stirred for 3 hours. After cooling to 0°C, a 1N aqueous solution of hydrochloric acid was added, and the resulting solution was extracted with ethyl acetate. The resulting organic phase was washed with brine and then dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to obtain compound 73 (4.8 g, yield 55%).

[0337] (5) Synthesis of Compound 74 To a solution of compound 73 (4.6 g, 8.9 mmol), 5-bromo-2-iodotoluene (compound 31: 6.6 g, 0.022 mol), potassium carbonate (4.9 g, 0.035 mol), DMF (112 mL), and water (14 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (1.0 g, 9.0 mmol) was added. The resulting solution was then heated to 80°C and stirred for 9 hours. The resulting solution was cooled to 0°C, and a 1N aqueous hydrochloric acid solution was added. The resulting solution was extracted with ethyl acetate, washed with brine, and the organic phase was dried over magnesium sulfate. The resulting organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was dispersed and washed with methyl tert-butyl ether to give compound 74 (3.3 g, yield 65%).

[0338] (6) Compound A-22 １ H-NMR (CDCl ３) δ=1.53 (d, 6H), 2.29 (s, 3H), 2.37 (s, 6H), 4.23 (qd, 4H), 4.41-4.48 (m, 4H), 5.36-5.46 (m, 2H), 5.86 (dd, 2H), 6. 16 (dd, 2H), 6.46 (dd, 2H), 6.96 (d, 1H), 7.04-7.09 (m, 2H), 7.11-7.19 (7H), 7.28-7.33 (m, 4H), 7.38-7.47 (m, 5H)

[0339] Synthesis Example 23: Synthesis of compound A-23 Compound A-23 was synthesized according to the following scheme: Compound A-23 was synthesized in the same manner as in the synthesis of compound A-22, except that compound 35 was used.

[0340]

[0341] (1) Compound A-23 １ H-NMR (CDCl ３ ) δ = 2.30 (s, 3H), 2.36 (s, 6H), 4.39 (t, 4H), 4.41-4.47 (m, 4H), 4.62 (t, 4H), 5.88 (d, 2H), 6.19 (dd, 2H), 6 .48 (d, 2H), 6.93-6.97 (1H), 7.04-7.08 (m, 2H), 7.13-7.20 (m, 8H), 7.28-7.33 (m, 4H), 7.40-7.45 (m, 4H)

[0342] Synthesis Example 24: Synthesis of compound A-24 Compound A-24 was synthesized according to the following scheme: Compound A-24 was synthesized in the same manner as in the synthesis of compound A-14, except that compound 78 was used.

[0343]

[0344] (1) Synthesis of Compound 76 To a solution of 4-hydroxyphenyl pinacol borate (Compound 75: 9.5 g, 0.040 mol), 5-bromo-2-iodotoluene (Compound 31: 40.0 g, 0.13 mol), potassium carbonate (32.6 g, 0.24 mol), DMF (320 mL), and water (16 mL) that had been degassed under reduced pressure, tetrakis(triphenylphosphine)palladium (15.6 g, 0.013 mmol) was added. The resulting solution was then heated to 70°C and stirred for 4 hours. After cooling to room temperature, a 1N aqueous solution of hydrochloric acid was added. The resulting solution was extracted with ethyl acetate and washed sequentially with an aqueous solution of sodium bicarbonate and brine, and the organic phase was dried over magnesium sulfate. The organic phase was filtered, and the solvent was evaporated under reduced pressure. The resulting residue was purified by flash column chromatography to give Compound 76 (9.9 g, yield 87%).

[0345] (2) Synthesis of Compound 77 Methanesulfonyl chloride (2.4 g, 0.021 mol) was added dropwise to a mixed solution of compound 76 (4.9 g, 0.018 mol), triethylamine (12.7 g, 0.027 mol), and THF (74 mL) cooled to 0°C. The resulting solution was warmed to room temperature and stirred for 2 hours, then cooled to 0°C, and water was added. The resulting solution was extracted with ethyl acetate, and the resulting organic phase was washed sequentially with a 1N aqueous hydrochloric acid solution, an aqueous sodium bicarbonate solution, and brine. The resulting organic phase was dried over magnesium sulfate and filtered, after which the solvent was evaporated under reduced pressure. The resulting residue was purified by crystallization using a mixed solvent of ethyl acetate and normal hexane to obtain compound 77 (5.4 g, yield 85%).

[0346] (3) Synthesis of Compound 78 Compound 77 (5.4 g, 0.015 mol), 4-bromo-o-cresol (Compound 45: 2.9 g, 0.015 mol), potassium carbonate (2.4 g, 0.017 mol), and potassium iodide (0.25 g, 1.5 mmol) were dissolved in DMAc (70 mL), and the resulting solution was stirred at 80°C for 4 hours. After the resulting solution was cooled to room temperature, acetic acid and methanol were added and the mixture was stirred for 30 minutes. Thereafter, a mixed solvent of methanol and water was added to the resulting solution and the mixture was stirred for 1 hour. The resulting solution was filtered to obtain Compound 78 (5.8 g, yield 86%).

[0347] (4) Compound A-24 １ H-NMR (CDCl ３ ) δ = 2.37 (s, 3H), 2.39 (s, 3H), 4.36-4.42 (m, 4H), 4.58-4.64 (m, 4H), 5.20 (s, 2H), 5.85-5.91 (m, 2H), 6.1 5-6.24 (m, 2H), 6.45-6.52 (m, 2H), 6.97-7.00 (m, 1H), 7.07-7.20 (m, 6H), 7.31-7.47 (m, 7H), 7.53 (d, 2H)

[0348] [Synthesis of Comparative Compounds (Compounds B-1 to B-3)] Compound B-1 was synthesized as a comparative compound according to WO 2022 / 0177782. Compound B-2 was synthesized as a comparative compound according to WO 2019 / 182129. Compound B-3 was synthesized as a comparative compound according to WO 2009 / 086911.

[0349] [Specific Compounds and Comparative Compounds] The specific compounds (compounds A-1 to A-24) and comparative compounds (compounds B-1 to B-3) synthesized in the upper part are shown below.

[0350]

[0351]

[0352]

[0353]

[0354]

[0355] [Examples 1 to 24 and Comparative Examples 1 to 3] The evaluations described below were carried out using compounds A-1 to A-24 synthesized in the upper part of Examples 1 to 24. Furthermore, the evaluations described below were carried out using compounds B-1 to B-3 synthesized in the upper part of Comparative Examples 1 to 3.

[0356] 〔evaluation〕

[0357] <Refractive Index, Birefringence, and Absorbency> The refractive index and birefringence of optically anisotropic layers prepared using compositions containing each of the compounds of the Examples and Comparative Examples (compounds A-1 to A-24, compounds B-1 to B-3) were evaluated.

[0358] (Preparation of optically anisotropic layer for measuring refractive index and birefringence) First, coating composition E was prepared having the composition shown below. ----------------Composition of coating composition E-------------------------------- 50 parts by mass of each compound of the Examples and Comparative Examples shown in Table 1 below Compound C-1 50 parts by mass Polymerization initiator (OMNIRAD (registered trademark) 819, manufactured by BASF) 3 parts by mass Leveling agent T-1 shown below 0.1 parts by mass Cyclopentanone 412 parts by mass

[0359] Compound C-1 is a compound having the following structure:

[0360]

[0361] The leveling agent T-1 is a compound having the following structure:

[0362]

[0363] Coating composition E was dropped onto the rubbed glass with an alignment film, and the glass was rotated at 1500 rpm for 10 seconds using a spin coater to coat coating composition E. The obtained glass with coating composition E was heated on a hot plate until it reached a temperature at which coating composition E exhibited a nematic phase, and then further heated on the hot plate with 300 mJ / cm 2 of light through a filter that cuts off light with a wavelength of 350 nm or less. ２ The film was irradiated with ultraviolet light for 100 seconds to prepare an optically anisotropic layer.

[0364] (Evaluation of Refractive Index, Birefringence, and Absorbency) The refractive index of the prepared optically anisotropic layer was measured using an ellipsometer (manufactured by J.A. WOOLLAM). Specifically, measurements were performed at incident angles of 50°, 60°, and 70°, and Cauchy fitting was performed using the measured values ​​from 450 to 1700 nm to calculate the refractive index. The refractive index n e for extraordinary light at a wavelength of 550 nm and the birefringence Δn (i.e., the difference between n e and n o ) were calculated. Furthermore, using a spectrophotometer (JASCO V-650, manufactured by JASCO), the transmittance T and reflectance R of the optically anisotropic layer at a wavelength of 420 nm were measured under conditions of an incident angle of 5° and a detection angle of 0°, and the absorbance was calculated using the formula (100% - T - R). The measurements were performed for both s-polarized light and p-polarized light, and the optically anisotropic layer was positioned so that the p-polarized light and the liquid crystal alignment direction in the optically anisotropic layer were parallel. The average value of the absorptance when s-polarized light is incident and the absorptance when p-polarized light is incident was taken as absorptance A. Based on absorptance A, evaluation was performed using the following index. The smaller the absorptance A value, the more excellent the transparency. All evaluations were classified based on the following evaluation criteria. A rating of "B" or higher is preferable, with "A" being the most preferable. The results are shown in Table 1 below. <Refractive Index: Evaluation Criteria> "A": 1.94≦ne. "B": 1.90≦ne<1.94. "C": ne<1.90. <Birefringence: Evaluation Criteria> "A": 0.35≦Δn. "B": 0.30≦Δn<0.35. "C": Δn<0.30. <Absorbency: Evaluation Criteria> "A": Absorptance A is less than 1.0%. "B": Absorptance A is 1.0% or more and less than 3.0%. "C": Absorptance A is 3.0% or more.

[0365] (Curing property evaluation) The optically anisotropic layer was immersed in tetrahydrofuran, and the absorbance was measured before and after immersion using a UV-3600iPlus spectrometer manufactured by Shimadzu Corporation. The gel fraction was calculated from the change in absorbance, and the curing property of the optically anisotropic layer was evaluated based on the following evaluation criteria. In practical terms, "B" or higher is preferable, and "A" is most preferable. The results are shown in Table 1 below. Gel fraction (%) = (absorbance after immersion / absorbance before immersion) x 100 Evaluation criteria "A": Gel fraction is 80% or more. "B": Gel fraction is 50% or more but less than 80%. "C": Gel fraction is less than 50%.

[0366] <Evaluation of Pattern Orientation> (Formation of Orientation Film) The following coating liquid for forming an alignment film was dropped onto a glass substrate, and the substrate was rotated at 500 rpm for 5 seconds using a spin coater, followed by rotation at 2500 rpm for 20 seconds to coat the coating liquid for forming an alignment film. The substrate on which the coating film of the coating liquid for forming an alignment film had been formed was dried on a hot plate at 60°C for 60 seconds to form an alignment film.

[0367] ------------------------------------------------------------------ Coating liquid for forming alignment film ------------------------------------------------------------------ Photo alignment material D 4.00 parts by mass Water 16.00 parts by mass Butoxyethanol 42.00 parts by mass Propylene glycol monomethyl ether 42.00 parts by mass ------------------------------------------------------------------

[0368] Photoalignment material D is a compound having the following structure.

[0369]

[0370] (Exposure of Alignment Film) The alignment film was exposed using the exposure device shown in FIG. 5 of WO 2020 / 022496 to form an alignment film P-1 having an alignment pattern. The exposure device used was one that emitted laser light with a wavelength of 325 nm. The exposure dose by the interference light was 2000 mJ / cm. ２One period of the alignment pattern formed by the interference of the two laser beams (the length of a 180° rotation of the optical axis derived from the liquid crystal compound) was controlled by changing the crossing angle (crossing angle β) of the two beams.

[0371] (Evaluation of Pattern Orientation) <<Preparation of Composition for Measurement>> The following Coating Composition F was prepared as a composition for measuring the film thickness capable of pattern orientation. Note that Compound C-1 added together with each compound in the Examples and Comparative Examples was the same as Compound C-1 used in Coating Composition E.

[0372] Coating composition F -------------------------------------------------- 50 parts by mass of each compound of the Examples and Comparative Examples shown in Table 1 below Compound C-1 50 parts by mass Chiral agent (manufactured by BASF, Paliocolor (registered trademark) LC756) 6 parts by mass Polymerization initiator (manufactured by BASF, omnirad (registered trademark) 819) 3 parts by mass Leveling agent T-1 described above 0.1 part by mass Cyclopentanone 436 parts by mass

[0373] The measurement of the film thickness capable of being oriented in patterned alignment was carried out by the following procedure. First, Coating Composition F was dropped onto the alignment film P-1, and the film was spun at 1500 rpm for 10 seconds using a spin coater to coat Coating Composition F. Next, the resulting coating film was subjected to a heat treatment, cooled, and further subjected to a curing treatment by ultraviolet irradiation to produce a cured layer (liquid crystal fixation layer). The resulting cured layer was observed under a polarizing microscope to check for the presence or absence of alignment defects, and was evaluated according to the following evaluation criteria. The results are shown in Table 1. Evaluation Criteria "A": No alignment defects. "B": Alignment defects are observed.

[0374] Table 1 is shown below.

[0375]

[0376] From the results in Table 1, the optically anisotropic layer formed using the specific compound had high birefringence (Δ) and low absorptance (excellent transparency). It is also clear that the thick optically anisotropic layer having an alignment pattern formed using a composition obtained by mixing the specific compound with a liquid crystal compound can suppress the occurrence of alignment defects in the optically anisotropic layer. The optically anisotropic layer formed using the specific compound also had excellent curability. Furthermore, a comparison of Examples 1 to 5 reveals that n １１ is 0, and Z １２ When represents -O- or -S- (Examples 1, 3 to 5), the number of evaluations was A, and it was confirmed that the effect was more excellent. When the pattern-oriented optically anisotropic layer produced in Example 1 was optically adhered to a light guide plate, it was confirmed that light could be extracted from the light guide plate. Furthermore, a comparison between Examples 6 to 8 and Examples 9 to 12 confirmed that when T is -NCS, the refractive index and birefringence were more excellent. Furthermore, a comparison between Examples 6 to 7 and Example 8 confirmed that when n is 1, the curability was more excellent. A comparison between Example 13 and Examples 9 to 12 confirmed that A ４１ ~A ４４ It has been confirmed that when at least one of the groups is a divalent aromatic ring group having a group represented by formula (X), the refractive index and birefringence are more excellent.

[0377] 1, 2, 3 Optically anisotropic layer xy plane sheet surface z direction thickness direction 30 liquid crystal compound Λ length of one period 30A optical axis derived from liquid crystal compound 30 θ angle R region d thickness (film thickness) of optically anisotropic layer P Ｌ Left circularly polarized light P Ｒ Right circularly polarized light L １ , L ４ , L ６ Incident light L ２ , L ５ , L ７ Transmitted light Q1, Q2 Absolute phase E1, E2 Equiphase surface A １ , A ２ , A ３ direction

Claims

1. A compound represented by formula (1). In formula (1), P １１ represents a radical polymerizable group containing an unsaturated double bond. １１ represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. ２ - is -O-, -S-, -NR-, -CO-, -CS-, -SO-, -SO ２ - or -C(=CH ２ )- in the alkylene group may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH-, -C≡C-, or -CH=N-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. １１ represents a single bond, —O—, —S—, —NR—, —CO—, —CS—, —SO—, or —SO ２ R represents a hydrogen atom or a substituent. Z １２ represents a single bond or a divalent linking group that does not contain a ring structure. １１ and A １２ A each independently represents a divalent aromatic ring group which may have a substituent, or a divalent alicyclic group which may have a substituent. １３ represents a divalent aromatic ring group which may have a substituent. １１ represents an integer of 0 to 4. １２ When represents a single bond, n １１ represents 0.

2. A １１ and A １２ The compound according to claim 1 , wherein represents an optionally substituted divalent aromatic ring group.

3. A １１ , A １２ and A １３ each independently represents a divalent ring group represented by any one of formulas (1-1) to (1-6): In formulas (1-1) to (1-6), W １ are each independently: =CR １ - or =N-. １ are each independently -NR １ represents -, -O-, or -S-. １ represents a hydrogen atom or a substituent. * represents a bonding position.

4. A １１ , A １２ and A １３ and each independently represent an optionally substituted 1,4-phenylene group or an optionally substituted 2,6-naphthylene group.

5. A １１ and A １２ The compound according to claim 1 , wherein at least one of the following represents a divalent fused ring group which may have a substituent.

6. n １１ The compound of claim 1 , wherein is 0.

7. Z １２ The compound according to claim 6, wherein represents —O— or —S—.

8. P １１ represents a polymerizable group represented by any one of formulas (P-1) to (P-12): Me represents a methyl group. * represents the bonding position.

9. P １１ represents a polymerizable group represented by any one of formulas (P-13) to (P-21): R ４１ represents an aliphatic hydrocarbon group having 2 to 10 carbon atoms. ４２ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. ４３ represents a halogen atom or an aliphatic hydrocarbon group having 2 to 10 carbon atoms. ４４ represents a halogen atom or an aliphatic hydrocarbon group having 1 to 10 carbon atoms. ４１ ~R ４４ is the aliphatic hydrocarbon group, a hydrogen atom in the aliphatic hydrocarbon group may be replaced by a halogen atom, and —CH ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted. R represents a hydrogen atom or a substituent. * represents the bonding position.

10. P １１ represents a polymerizable group represented by formula (P-1) or formula (P-2).

11. The compound according to claim 1, which has liquid crystal properties.

12. A compound represented by formula (3). (R ３１ ) ｍ -MG-NCS Formula (3) In Formula (3), MG represents a mesogenic structure that does not contain an aliphatic ring and may have a substituent. ３１ represents a group represented by formula (X), and m represents an integer of 1 to 4. In formula (X), Sp represents a single bond or a linear or branched (n+1)-valent aliphatic hydrocarbon group having 1 to 10 carbon atoms. ２ - is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ -, and any -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and any hydrogen atom in the aliphatic hydrocarbon group may be replaced by a fluorine atom or a chlorine atom. ａ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. P represents a polymerizable group. n represents 1 or 2. However, when Sp is a single bond, n represents 1. * represents a bonding position. However, the compound represented by (3) has two or more polymerizable groups represented by P.

13. The compound according to claim 12, which is a compound represented by formula (4). In formula (4), A ４１ ~A ４４ each independently represents a divalent aromatic ring group which may have a substituent A. The substituent A represents a group represented by formula (X), a group represented by formula (Y), or a substituent which does not contain an aliphatic ring other than the group represented by formula (X) and the group represented by formula (Y). Z ４１ and Z ４２ each independently represents a single bond, —O—, —S—, or —CHR ａ CHR ａ --OCHR ａ -, -CO-, -SO-, -SO ２ -, -COO-, -CO-S-, -O-CO-O-, -CO-NR ａ --, --SCHR ａ --, --SO-CHR ａ -, -SO ２ -CHR ａ -, -CF ２ O-, -CF ２ S-, -OCHR ａ CHR ａ O-, -SCHR ａ CHR ａ S-, -SO-CHR ａ CHR ａ -SO-, -SO ２ -CHR ａ CHR ａ -SO ２ -, -CH=CH-COO-, -CH=CH-OCO-, -COO-CHR ａ CHR ａ -, -OCO-CHR ａ CHR ａ -, -COO-CHR ａ -, -OCO-CHR ａ -, -CR ａ =CR ａ -, -CR=N-, -N=N-, -CR ａ =N-N=CR ａ represents -, -CF=CF-, or -C≡C-. ４１ represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. ２ - is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ -, and any -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and any hydrogen atom of the alkylene may be replaced by a fluorine atom or a chlorine atom. ａ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. T represents -NCS, a group represented by formula (X), or a substituent not containing an aliphatic ring other than -NCS and a group represented by formula (X). s1 represents an integer of 1 to 4. s2 represents an integer of 0 to 4. t represents an integer of 0 or 1. However, the compound represented by formula (4) has two or more polymerizable groups represented by P. In formula (X) and formula (Y), Sp represents a single bond or a linear or branched (n+1) valent aliphatic hydrocarbon group having 1 to 10 carbon atoms. ２ - is -O-, -S-, -NR ａ -, -CO-, -CS-, -SO-, or -SO ２ -, and any -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and any hydrogen atom in the aliphatic hydrocarbon group may be replaced by a fluorine atom or a chlorine atom. ａ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. P represents a polymerizable group. Ar represents a divalent aromatic ring group. n represents 1 or 2. However, when Sp is a single bond, n represents 1. * represents a bonding position.

14. The compound of claim 13, wherein T is -NCS.

15. A ４１ ~A ４４ Each of the groups independently represents a divalent aromatic ring group represented by any one of formulas (5-1) to (5-8): In formulas (5-1) to (5-8), W ２ are each independently: =CR ５１ - or =N-. ２ are each independently -NR ５１ represents -, -O-, or -S-. ５１ represents a hydrogen atom, a group represented by formula (X), a group represented by formula (Y), or a substituent not containing an aliphatic ring other than the group represented by formula (X) and the group represented by formula (Y). * represents a bonding position.

16. A ４１ ~A ４４ are each independently a divalent aromatic ring group represented by formula (5-1) or formula (5-2), and W ２ are each independently: =CR ５１ The compound of claim 15, wherein 17. The compound of claim 13, wherein P represents a radically polymerizable group.

18. The compound according to claim 13, wherein P represents a polymerizable group represented by any one of formulas (P-31) to (P-42). X １ represents O or S. X ２ is O, S or NR ４２ Represents R ４２ represents a hydrogen atom, a halogen atom, or an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and a hydrogen atom in the aliphatic hydrocarbon group may be replaced by a halogen atom; ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted. R represents a hydrogen atom or a substituent. * represents the bonding position.

19. The compound according to claim 18, wherein P represents a polymerizable group represented by formula (P-31).

20. The compound of claim 15, wherein n represents 1.

21. The compound according to claim 13, wherein the compound represented by formula (3) has two polymerizable groups represented by P.

22. Z ４１ and Z ４２ is a single bond, -O-, -S-, -OCH ２ -, -COO-, or -CONR ａ The compound of claim 13, wherein 23. The compound of claim 13, wherein t represents 1.

24. The compound according to claim 13, which has liquid crystal properties.

25. A composition comprising a compound according to any one of claims 1 to 24.

26. The composition of claim 25, further comprising a polymerizable liquid crystal compound.

27. The composition according to claim 26, wherein the polymerizable liquid crystal compound is a compound represented by formula (2). In formula (2), P ２１ and P ２２ Each independently represents a polymerizable group. ２１ and L ２２ each independently represents a single bond or a linear or branched alkylene group having 20 or less carbon atoms. ２ - represents -O-, -S-, -NR-, -CO-, -CS-, -SO-, or -SO ２ - may be replaced by -(CH ２ ) ２ - may be replaced by -CH=CH- or -C≡C-, and a hydrogen atom in the alkylene group may be replaced by a fluorine atom or a chlorine atom. R represents a hydrogen atom or a substituent. Z ２１ represents a single bond or a divalent linking group. ２１ and A ２２ each independently represents a divalent aromatic ring group which may have a substituent, or a divalent alicyclic group which may have a substituent. ２１ represents an integer of 1 to 10.

28. n ２１ Z ２１ The composition according to claim 27, wherein at least one of the following is -C≡C-.

29. The composition of claim 25, which has liquid crystal properties.

30. A cured product obtained by curing the composition described in claim 25.

31. An optically anisotropic medium obtained by curing the composition according to claim 25.

32. An optically anisotropic body obtained by curing a composition containing the compound according to any one of claims 1 to 11, wherein the optical anisotropic body has an orientation pattern in which the direction of the optical axis derived from the compound represented by formula (1) is continuously rotated along at least one direction in the plane.

33. An optically anisotropic body obtained by curing a composition containing the compound according to any one of claims 12 to 24, wherein the optical axis of the compound represented by formula (3) has an orientation pattern in which the direction of the optical axis is continuously rotated along at least one direction in the plane.

34. A light guide element comprising the optically anisotropic body according to claim 32 and a light guide plate.

35. A light guide element comprising the optical anisotropic body according to claim 33 and a light guide plate.

Images