Compound, liquid crystal alignment accelerator, liquid crystal composition, cured product, and film

Abstract

The present invention addresses the problem of providing a compound that, when being mixed with a liquid crystal compound to align the liquid crystal compound, suppresses disarray in the alignment of the liquid crystal compound. A compound according to the present invention is represented by formula (11). In formula (11), Rf represents a linear perfluoroalkyl group. p1 represents an integer of 1-3. Each A11 independently represents a hydrocarbon group having a valence of p1+1. q1 represents an integer of 2-4. X12 represents an aromatic ring group having a valence of q1+1. Each X13 independently represents a divalent aromatic ring group optionally having a substituent group. L13 and L14 each independently represent a single bond or a prescribed linkage group. r1 represents an integer of 0-4. X14 represents a monovalent aromatic ring group in which a substituent group is optionally substituted, or represents a group having the following structure. In the following structure, * represents a binding position with respect to L14.

Description

Compound, liquid crystal alignment promoter, liquid crystal composition, cured product, film

[0001] The present invention relates to a compound, a liquid crystal alignment promoter, a liquid crystal composition, a cured product, and a film.

[0002] Cured products formed using liquid crystal compositions containing liquid crystal compounds often have optical anisotropy, and are therefore used, for example, as optical compensation sheets (retardation plates) by utilizing this optical anisotropy. Such optically anisotropic layers are produced, for example, by applying a liquid crystal composition containing a liquid crystal compound onto an alignment film, aligning the liquid crystal compound, and fixing the alignment direction. However, it is generally difficult to align the liquid crystal compound uniformly from the alignment film interface to the air interface (monodomain alignment). In particular, it is difficult to align the liquid crystal compound on the air interface side.

[0003] Therefore, a technique of using a liquid crystal alignment promoter to align a liquid crystal compound also on the air interface side is known. For example, Patent Document 1 discloses a compound having a specific structure, and a liquid crystal composition to which the compound is added as a liquid crystal alignment promoter.

[0004] International Publication No. 2021 / 220794

[0005] The inventors have studied the compound described in Patent Document 1 and have found that when a liquid crystal compound is mixed with the compound to align the liquid crystal compound, the alignment of the liquid crystal compound is likely to be disturbed if the amount of the compound used is large, and that this problem needs to be improved.

[0006] Therefore, an object of the present invention is to provide a compound that suppresses disorder in the alignment of a liquid crystal compound when mixed with the compound to align the liquid crystal compound. Another object of the present invention is to provide a liquid crystal alignment promoter containing the compound, a liquid crystal composition containing the compound and a liquid crystal compound, a cured product formed from the liquid crystal composition, and a film containing the cured product.

[0007] The present inventors have conducted extensive research to solve the above problems and have completed the present invention. That is, they have found that the above problems can be solved by the following configuration.

[0008] [1] A compound represented by formula (11) described below. [2] The compound according to [1], wherein the linear perfluoroalkyl group has 2 to 8 carbon atoms, and when two or more Rfs are contained in formula (11), each Rf represents the same group. [3] The compound according to [1] or [2], wherein the number of Rfs contained in formula (11) is 2 to 9. [4] The compound according to any one of [1] to [3], wherein the number of Rfs contained in formula (11) is 3 to 6. [5] The compound according to any one of [1] to [4], wherein the number of Rfs contained in formula (11) is 3 or 4. [6] The compound according to any one of [1] to [5], wherein the linear perfluoroalkyl group has 4 carbon atoms, and each Rf in formula (11) has the same structure. [7] In formula (11), r1 is 2 or more, or r1 is 1, and X １３ is a divalent aromatic ring group having a plurality of ring structures. [8] A liquid crystal alignment promoter comprising the compound according to any one of [1] to [7]. [9] A liquid crystal composition comprising the compound according to any one of [1] to [8] and a polymerizable liquid crystal compound.

[10] The liquid crystal composition according to [9], wherein the polymerizable liquid crystal compound is selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable discotic liquid crystal compounds.

[11] The liquid crystal composition according to [9] or

[10] , further comprising a chiral dopant.

[12] A cured product obtained by polymerizing the liquid crystal composition according to any one of [9] to

[11] .

[13] A film comprising the cured product according to

[12] .

[14] The film according to

[13] , which exhibits optical anisotropy.

[15] A film obtained by polymerizing the liquid crystal composition according to

[11] , in which a cholesteric liquid crystal phase is fixed.

[16] The film according to

[15] , which reflects infrared light.

[17] The film according to

[15] , which reflects visible light.

[0009] According to the present invention, there is provided a compound that, when mixed with a liquid crystal compound to align the liquid crystal compound, suppresses the disorder of the alignment of the liquid crystal compound. The present invention also provides a liquid crystal alignment promoter containing the compound, a liquid crystal composition containing the compound and the liquid crystal compound, a cured product formed from the liquid crystal composition, and a film containing the cured product.

[0010] The present invention will be described in detail below. The following description of the components may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0011] The following describes the meanings of each description in this specification. In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​before and after "to" as the lower and upper limits. Furthermore, in this specification, each component may use a single substance corresponding to the component, or two or more substances may be used in combination. Here, when two or more substances are used in combination for each component, the content of that component refers to the total content of the substances used in combination, unless otherwise specified. Furthermore, in this specification, "(meth)acrylate" is a notation that represents "acrylate" or "methacrylate," "(meth)acrylic" is a notation that represents "acrylic" or "methacrylic," and "(meth)acryloyl" is a notation that represents "acryloyl" or "methacryloyl."

[0012] In addition, the bonding direction of the divalent group (for example, —O—CO—) described in this specification is not particularly limited. １ -L ２ -L ３ In the bond ２ When is —O—CO—, L １ The position where it is bonded to the side is *1, L ３ If the position bonded to the side is *2, then L ２ may be *1-O-CO-*2 or *1-CO-O-*2.

[0013] <Compound> The compound of the present invention is a compound represented by the following formula (11) (hereinafter also referred to as "the present compound"): Each symbol in formula (11) will be explained later.

[0014]

[0015] In the present invention, when the present compound is mixed with a liquid crystal compound to align the liquid crystal compound, the disorder of the alignment of the liquid crystal compound is suppressed. Furthermore, even when a large amount of the present compound is used, the disorder of the alignment of the liquid crystal compound is easily suppressed. The mechanism by which the disorder of the alignment of the liquid crystal compound is suppressed when the present compound is used is not entirely clear, but the inventors speculate as follows. Liquid crystal alignment promoters used to align liquid crystal compounds generally have an alignment-controlling force on the liquid crystal compound, and it is believed that the formation of aggregates of the liquid crystal alignment promoter causes the alignment of the liquid crystal compound to become disordered. The present compound has a linear perfluoroalkyl group. Because perfluoroalkyl groups have weak intermolecular forces, the present compound is prone to segregation toward the air interface. Furthermore, linear perfluoroalkyl groups are more compatible with liquid crystal compounds than branched perfluoroalkyl groups, and are therefore less likely to form aggregates of the present compound (liquid crystal alignment promoter). The present compound also has multiple aromatic ring groups. A structure having multiple aromatic ring groups is commonly found in liquid crystal compounds and is believed to have a high alignment-controlling force on the liquid crystal compound. Therefore, when the present compound is mixed with a liquid crystal compound to align the liquid crystal compound, it is thought that the compound is less likely to aggregate, and as a result, the disorder in the alignment of the liquid crystal compound is suppressed.

[0016] Each symbol in formula (11) will be explained below.

[0017] In formula (11), Rf represents a linear perfluoroalkyl group. When two or more Rfs are contained in formula (11), each Rf may represent the same group or different groups, but preferably represents the same group. The number of carbon atoms in the linear perfluoroalkyl group is preferably 2 to 8, more preferably 3 to 6, and even more preferably 4. In formula (11), the number of Rfs contained is preferably 2 to 9, more preferably 3 to 6, and even more preferably 3 or 4.

[0018] In formula (11), p1 represents an integer of 1 to 3. Of these, p1 is preferably 1 or 2.

[0019] In formula (11), A １１ each independently represents a p1+1 valent hydrocarbon group. The p1+1 hydrocarbon group may contain one or more atoms selected from the group consisting of oxygen atoms and nitrogen atoms. １１ The carbon number of the p1+1 valent hydrocarbon group represented by A is preferably 2 to 40, and more preferably 3 to 30. １１ The p1+1 valent hydrocarbon group represented by the formula (I) preferably includes an aliphatic hydrocarbon structure, an aromatic hydrocarbon structure, or a structure formed by combining these structures. The aliphatic hydrocarbon structure may be linear or branched, or may include a cyclic structure. The number of carbon atoms in the aliphatic hydrocarbon structure is preferably 2 to 10, more preferably 2 to 6. Examples of the aromatic hydrocarbon structure include a benzene structure and a naphthalene structure. Of these, a benzene structure is preferred. A １１ The p1+1 valent hydrocarbon group represented by the formula (I) may contain two or more atoms of one or more kinds selected from the group consisting of oxygen atoms and nitrogen atoms.

[0020] In formula (11), q1 represents an integer of 2 to 4. １１ may be different or the same, but are preferably the same. It is also preferable that q1 and p1 are set so that the number of Rf falls within the above-mentioned preferred range. For example, when p1 is 1, q1 is preferably 3; when p1 is 2, q1 is preferably 2 or 3; and when p1 is 3, q1 is preferably 2.

[0021] In formula (11), X １２ represents a q1+1 valent aromatic ring group. １２ The q1+1-valent aromatic ring group represented by X may have a monocyclic structure or a polycyclic structure. １２The q1+1-valent aromatic ring group represented by may contain heteroatoms other than carbon atoms (for example, one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms). １２ Examples of the q1+1 valent aromatic ring group represented by the formula (I) include groups obtained by removing q1+1 hydrogen atoms from a compound selected from the group consisting of benzene and naphthalene.

[0022] In formula (11), X １３ each independently represents a divalent aromatic ring group which may have a substituent. １３ The aromatic ring group represented by may have a monocyclic structure or a polycyclic structure. １３ The aromatic ring group represented by may contain heteroatoms other than carbon atoms (for example, one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms). １３ Examples of the aromatic ring group represented by X include groups obtained by removing two hydrogen atoms from a compound selected from the group consisting of benzene, naphthalene, anthracene, phenanthrene, and 1,2,4-oxadiazole. The position at which the hydrogen atoms are removed is not particularly limited, and examples thereof include groups such as X １３ When the aromatic ring group represented by X is a group obtained by removing two hydrogen atoms from benzene, the position of one hydrogen atom relative to the other hydrogen atom may be any position, and the para position is preferred. １３ is a group obtained by removing two hydrogen atoms from naphthalene, the position of one hydrogen atom relative to the other hydrogen atom may be any of the ortho position (1,2 positions), meta position (1,3 positions), para position (1,4 positions), ana position (1,5 positions), epi position (1,6 positions), cata position (1,7 positions), peri position (1,8 positions), pros position (2,3 positions), and amphi position (2,6 positions), and the para position, ana position, or amphi position is preferred.

[0023] X １３ The substituents that the aromatic ring group represented by the formula (I) may have include —CN, —R ３ , -OR ３ , -OH, -(CH ２ ) ｍ-OH, -F, -COOR ３ , and -COR ３ R ３ represents a linear or branched alkyl group having 1 to 20 carbon atoms. m represents an integer of 1 to 3. R ３ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, and more preferably 1 to 4. ３ Examples of the alkyl group represented by X include a methyl group, an ethyl group, a 1-propyl group, a 2-propyl group, a 1-butyl group, and a t-butyl group. １３ The substituent that the aromatic ring group represented by the formula (I) may have is -R ３ , -OR ３ , -COOR ３ , and -COR ３ One or more substituents selected from the group consisting of:

[0024] In formula (11), L １３ and L １４ each independently represents a single bond, —CO—, —COO—, or —CONR １ -, -O-, -(CH ２ ) ｎ -, -(CH ２ ) ｎ -O-, -O-(CH ２ ) ｎ -, -CO-CH=CH-, -COO-(CH ２ ) ｎ - or -C≡C-. １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents an integer of 1 to 3. L １３ represents a single bond, —COO—, or —CONR １ -, -O-, or -COO-(CH ２ ) ｎ - is preferred, and a single bond, -COO- or -CONR １ - is more preferred, a single bond or -COO- is even more preferred, and -COO- is particularly preferred. １４ represents a single bond, —CO—, —COO—, or —CONR １ -, -O-, -(CH ２ ) ｎ-, -O-(CH ２ ) ｎ -, -COO-(CH ２ ) ｎ -, -CO-CH=CH-, or -C≡C- is preferred, and a single bond, -COO-, or -CONR １ - is more preferable, a single bond or -COO- is further preferable, and -COO- is particularly preferable.

[0025] In formula (11), r1 represents an integer of 0 to 4. １４ -COO-CH ２ When r1 is 0, L １３ and X １３ The groups represented by may be different from each other or may be the same. r1 is preferably 1 to 3, and more preferably 1 or 2.

[0026] In addition, in formula (11), r1 is 2 or more, or r1 is 1, and X １３ It is also preferred that is a divalent aromatic ring group having a plurality of ring structures.

[0027] In formula (11), X １４ is -CN, -R ２ , -OR ２ , -OH, -(CH ２ ) ｍ -OH, -F, or -COOR ２ represents an optionally substituted monovalent aromatic ring group, or represents a group having the following structure:

[0028]

[0029] In the above structure, * indicates L １４ represents the bonding position with

[0030] R ２ represents a linear or branched alkyl group having 1 to 20 carbon atoms. m represents an integer of 1 to 3. R ２ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 12, and more preferably 1 to 8. ２ Examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group, a butyl group, a propyl group, a hexyl group, a heptyl group, and an octyl group.２ is preferably a linear alkyl group. The substituent that may be substituted on the aromatic ring group is also preferably selected depending on the liquid crystal compound used in the liquid crystal composition described below. １４ The aromatic ring group represented by may have a monocyclic structure or a polycyclic structure. １４ The aromatic ring group represented by may contain heteroatoms other than carbon atoms (for example, one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms). Examples of monocyclic structures include phenyl groups and pyridyl groups. Examples of polycyclic structures include naphthyl groups, anthracenyl groups, phenanthrenyl groups, fluorenyl groups, benzofuranyl groups, benzimidazolyl groups, and benzothiazolyl groups. X １４ It is also preferable that the aromatic ring group represented by does not have the above-mentioned substituent.

[0031] The present compound is also preferably a compound represented by the following formula (12):

[0032]

[0033] In formula (12), Rf represents a linear perfluoroalkyl group. When two or more Rfs are contained in formula (12), each Rf may represent the same group or different groups, but preferably represents the same group. The number of carbon atoms in the linear perfluoroalkyl group is preferably 2 to 8, more preferably 3 to 6, and even more preferably 4. In formula (12), the number of Rfs is preferably 2 to 9, more preferably 3 to 6, and even more preferably 3 or 4.

[0034] In formula (12), p2 represents an integer of 1 to 3. ２１ represents a single bond, a p2+1 valent aromatic ring group, or a p2+1 valent aliphatic hydrocarbon group having 3 to 10 carbon atoms. ２１ The p2+1-valent aromatic ring group represented by X may have a monocyclic structure or a polycyclic structure. ２１Examples of the p2+1-valent aromatic ring group represented by X include groups obtained by removing p2+1 hydrogen atoms from a compound selected from the group consisting of benzene and naphthalene. Of these, groups obtained by removing p2+1 hydrogen atoms from benzene are preferred. ２１ The aliphatic hydrocarbon group having a valence of p2+1 and having 3 to 10 carbon atoms represented by X may be linear or branched, or may contain a cyclic structure. ２１ Examples of the p2+1 valent aliphatic hydrocarbon group having 3 to 10 carbon atoms represented by include groups obtained by removing p2+1 hydrogen atoms from a compound selected from the group consisting of n-propane, n-butane, n-pentane, n-hexane, isobutane, 3-ethylpentane, neopentane, neohexane, cyclobutane, and cyclohexane. Of these, groups obtained by removing p2+1 hydrogen atoms from n-propane are preferred. ２１ represents a single bond, p2 is 1.

[0035] In formula (12), L ２１ represents a divalent linking group represented by the following formulas (2-1) to (2-4).

[0036]

[0037] In the formulas (2-1) to (2-4), p represents an integer of 1 to 3. In the formulas (2-1) to (2-4), ** represents X ２１ * represents the bonding position to Rf.

[0038] In formula (12), q2 represents an integer of 2 to 4. ２１ , X ２１ , and L ２２ may be different or the same, but are preferably the same. It is also preferable that q2 and p2 are set so that the number of Rf falls within the above-mentioned preferred range. For example, when p2 is 1, q2 is preferably 3; when p2 is 2, q2 is preferably 2 or 3; and when p2 is 3, q2 is preferably 1 or 2.

[0039] In formula (12), X ２２ represents a q2+1-valent aromatic ring group.２２ The q2+1-valent aromatic ring group represented by X may have a monocyclic structure or a polycyclic structure. ２２ The q2+1-valent aromatic ring group represented by X １２ The preferred embodiments are also the same.

[0040] In formula (12), X ２３ each independently represents a divalent aromatic ring group which may have a substituent. ２３ The aromatic ring group represented by may have a monocyclic structure or a polycyclic structure. ２３ The aromatic ring group represented by X １３ The preferred embodiments are also the same. ２３ The substituents that may be present on X １３ The substituents are the same as those that may be possessed by the group, and preferred embodiments are also the same.

[0041] In formula (12), L ２２ , L ２３ and L ２４ each independently represents a single bond, —CO—, —COO—, or —CONR １ -, -O-, -(CH ２ ) ｎ -, -(CH ２ ) ｎ -O-, -O-(CH ２ ) ｎ -, -CO-CH=CH-, -COO-(CH ２ ) ｎ - or -C≡C-. １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents an integer of 1 to 3. L ２２ represents a single bond, —COO—, or —CONR １ -, -O-, or -COO-(CH ２ ) ｎ - is preferred, and a single bond, -O-, or -COO- is more preferred. ２３ represents a single bond, —COO—, or —CONR １ -, -O-, or -COO-(CH ２ ) ｎ - is preferred, and a single bond, -COO- or -CONR１ - is more preferred, a single bond or -COO- is even more preferred, and -COO- is particularly preferred. ２４ represents a single bond, —CO—, —COO—, or —CONR １ -, -O-, -(CH ２ ) ｎ -, -O-(CH ２ ) ｎ -, -COO-(CH ２ ) ｎ -, -CO-CH=CH-, or -C≡C- is preferred, and a single bond, -COO-, or -CONR １ - is more preferable, a single bond or -COO- is further preferable, and -COO- is particularly preferable.

[0042] In formula (12), r2 represents an integer of 0 to 4. ２４ -CO-O-CH ２ When r2 is -, r2 represents 0. r2 is preferably 1 to 3.

[0043] In formula (12), X ２４ is -CN, -R ２ , -OR ２ , -OH, -(CH ２ ) ｍ -OH, -F, or -OCOOR ２ represents an optionally substituted monovalent aromatic ring group. ２ represents a linear or branched alkyl group having 1 to 20 carbon atoms. m represents an integer of 1 to 3. R ２ Specific examples and preferred embodiments of are R ２ It is the same as that of X. ２４ The aromatic ring group represented by may have a monocyclic structure or a polycyclic structure. ２４ The aromatic ring group represented by may contain heteroatoms other than carbon atoms (for example, one or more atoms selected from the group consisting of nitrogen atoms, oxygen atoms, and sulfur atoms). ２４ Specific examples and preferred embodiments of the aromatic ring group represented by X in formula (11) are １４ It is similar to the one in

[0044] Specific examples of compounds represented by formula (11) (preferably compounds represented by formula (12)) are given below, but the present invention is not limited to these compounds. In the compounds below, the structures represented by the symbols in formula (11) (or formula (12)) can be changed to the structures described above as long as the effects of the present invention are not impaired. In the compound formulas below, "Me" represents a methyl group.

[0045]

[0046]

[0047]

[0048]

[0049]

[0050]

[0051]

[0052]

[0053]

[0054]

[0055]

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062] As described above, the present compound can be mixed with a liquid crystal compound and used as an alignment promoter for the liquid crystal compound (liquid crystal alignment promoter).

[0063] When the present compound is mixed with a liquid crystal compound and used as an alignment promoter for the liquid crystal compound, the alignment direction of the liquid crystal compound may be parallel or perpendicular to the in-plane direction of the film containing the liquid crystal compound. The alignment direction of the liquid crystal compound may also be tilted from a direction parallel to the in-plane direction of the film containing the liquid crystal compound. It is particularly preferred that the alignment direction of the liquid crystal compound be perpendicular to the in-plane direction of the film containing the liquid crystal compound. That is, it is also preferred that the present compound has the function of aligning the liquid crystal compound in a direction perpendicular to the in-plane direction of the film containing the liquid crystal compound. In other words, the present compound preferably functions as a vertical alignment agent for the liquid crystal compound.

[0064] When the compound has a function of aligning the liquid crystal compound in the vertical direction, X １２ The number of q1+1 valent aromatic ring groups represented by the formula １３ and the number of divalent aromatic ring groups represented by X １４ and the number of monovalent aromatic ring groups represented by X １２ The number of q1+1 valent aromatic ring groups represented by X １２ is a phenanthrenylene group, a fluorenylene group, or an anthracenylene group, X １２ The number of q1+1-valent aromatic ring groups represented by the formula: １３ The number of divalent aromatic ring groups represented by X is usually 1. １３ is a phenanthrenylene group, a fluorenylene group, or an anthracenylene group, X １３ The number of divalent aromatic ring groups represented by the formula (I) is 2. For example, when r1 is 1 and X １３ is a phenylene group, r1 X １３ The number of divalent aromatic ring groups represented by the formula (1) is 1. １３ is a phenanthrenylene group, １３ The number of divalent aromatic ring groups represented by X is 4. １４ The number of monovalent aromatic ring groups represented by X is usually 1, but １４ is a phenanthrenyl group, an anthracenyl group, or a fluorenyl group, X １４The number of monovalent aromatic ring groups represented by the formula (11) is 2. When the compound has the function of aligning a liquid crystal compound in the vertical direction, it is also preferable that r1 in the formula (11) is 1 or more. It is also preferable that r2 in the formula (12) is 1 or more.

[0065] When the compound has a function of aligning the liquid crystal compound in the vertical direction, L １３ and L １４ is the preferred embodiment described above. ２３ and L ２４ is preferably the preferred embodiment described above.

[0066] The compound can be synthesized by a known method.

[0067] <Liquid Crystal Composition> The liquid crystal composition of the present invention contains the present compound (liquid crystal alignment promoter) and a polymerizable liquid crystal compound. Components that can be contained in the liquid crystal composition will be described below.

[0068] The content of the liquid crystal alignment promoter is preferably 0.05 to 1.0 mass %, more preferably 0.1 to 0.8 mass %, and even more preferably 0.1 to 0.6 mass %, relative to the content of the polymerizable liquid crystal compound.

[0069] [Polymerizable Liquid Crystal Compound] The polymerizable liquid crystal compound is not particularly limited, and known polymerizable liquid crystal compounds can be used. Generally, liquid crystal compounds can be classified into rod-shaped (rod-shaped liquid crystal compounds) and discotic (discotic liquid crystal compounds) based on their shape. Liquid crystal compounds can also be classified into low-molecular-weight and high-molecular-weight compounds. A high-molecular-weight compound generally refers to a compound with a degree of polymerization of 100 or more (see "Polymer Physics: Phase Transition Dynamics," by Masao Doi, p. 2, Iwanami Shoten, 1992). In the present invention, either a polymerizable rod-shaped liquid crystal compound or a polymerizable discotic liquid crystal compound may be used. Two or more polymerizable rod-shaped liquid crystal compounds, two or more polymerizable discotic liquid crystal compounds, or a mixture of a polymerizable rod-shaped liquid crystal compound and a polymerizable discotic liquid crystal compound may also be used.

[0070] As the polymerizable discotic liquid crystal compound, for example, those described in paragraphs 0161 to 0171 of JP-A No. 2002-129162, paragraphs 0020 to 0067 of JP-A No. 2007-108732, paragraphs 0013 to 0108 of JP-A No. 2010-244038, and the like can be preferably used.

[0071] As the polymerizable rod-shaped liquid crystal compound, azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, alkoxy-substituted phenylpyrimidines, phenyldioxanes, tolanes, or alkenylcyclohexylbenzonitriles are preferably used.

[0072] Specific examples of polymerizable rod-like liquid crystal compounds include those described in, for example, Makromol. Chem., Vol. 190, p. 2255 (1989), Advanced Materials 5, p. 107 (1993), U.S. Patent Nos. 4,683,327, 5,622,648, 5,770,107, WO 95 / 22586, 95 / 024455, 97 / 000600, 98 / 023580, 98 / 052905, JP-A Nos. 1-272551, 6-016616, 7-110469, 11-080081, JP-T-11-513019, JP-A Nos. 2001-328973, 2005-289980, 2014-198815, and JP-A No. 2014-198814. Two or more polymerizable liquid crystal compounds may be used in combination. The use of two or more polymerizable liquid crystal compounds in combination can lower the alignment temperature.

[0073] The content of the polymerizable liquid crystal compound in the liquid crystal composition of the present invention is not particularly limited, but is preferably 50% by mass or more, more preferably 70% by mass or more, based on the total mass of all solids in the liquid crystal composition. The upper limit is not particularly limited, but is often 95% by mass or less. The solid content refers to a component that can form a cured product after removing the solvent, and is considered to be a solid content even if it is in a liquid state.

[0074] [Chiral Dopant] The liquid crystal composition of the present invention may further contain a chiral dopant. When the liquid crystal composition of the present invention contains a chiral dopant, the polymerizable liquid crystal compound can be twisted and aligned along the helical axis. This alignment state is also called cholesteric alignment. The type of chiral dopant is not particularly limited. Any of the known chiral dopants (for example, those described in "Liquid Crystal Device Handbook," edited by the 142nd Committee of the Japan Society for the Promotion of Science, Chapter 3, Section 4-3, "Chiral Dopants for TN and STN," p. 199, 1989) can be used.

[0075] The chiral agent may be a photosensitive chiral agent (hereinafter simply referred to as "chiral agent A") whose helical twisting force changes upon irradiation with light. Chiral agent A may be liquid crystalline or non-liquid crystalline. Chiral agent A generally contains an asymmetric carbon atom. Note that chiral agent A may be an axially asymmetric compound or a planar asymmetric compound that does not contain an asymmetric carbon atom. Chiral agent A may have a polymerizable group.

[0076] The chiral agent A may be a chiral agent whose helical twisting power increases or decreases upon light irradiation. Among these, a chiral agent whose helical twisting power decreases upon light irradiation is preferred. In this specification, "increase and decrease in helical twisting power" refers to an increase or decrease when the initial helical direction of the chiral agent A (before light irradiation) is defined as "positive." Therefore, even when the helical twisting power continues to decrease upon light irradiation and exceeds 0, the helical direction becomes "negative" (i.e., when a helical twist is induced in the opposite helical direction to the initial helical direction (before light irradiation)), this also falls under the category of a "chiral agent whose helical twisting power decreases."

[0077] Examples of the chiral agent A include so-called photoreactive chiral agents. A photoreactive chiral agent is a compound that has a chiral moiety and a photoreactive moiety that undergoes structural changes upon irradiation with light, and that significantly changes the twisting power of a liquid crystal compound depending on the amount of irradiation, for example. Among the chiral agents A, compounds having at least a photoisomerizable moiety are preferred, and it is more preferable that the photoisomerizable moiety has a photoisomerizable double bond. When the chiral agent has a photoisomerizable group, this is preferred 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 the photoisomerizable group include an isomerizable moiety of a compound exhibiting photochromic properties, an azobenzene moiety, a cinnamoyl moiety, an α-cyanocinnamoyl moiety, a stilbene moiety, and a chalcone moiety. Specific compounds that can be used include those described in JP-A-2002-080478, JP-A-2002-080851, JP-A-2002-179668, JP-A-2002-179669, JP-A-2002-179670, JP-A-2002-179681, JP-A-2002-179682, JP-A-2002-338575, JP-A-2002-338668, JP-A-2003-313189, and JP-A-2003-313292.

[0078] The liquid crystal composition of the present invention may contain two or more types of chiral dopants A, or may contain at least one type of chiral dopants A and at least one type of chiral dopants whose helical twisting power does not change upon irradiation with light.

[0079] The content of the chiral dopant A in the liquid crystal composition is not particularly limited, but is preferably 5.0% by mass or less, more preferably 3.0% by mass or less, and even more preferably 2.0% by mass or less, relative to the total mass of the polymerizable liquid crystal compound, in order to facilitate uniform alignment of the polymerizable liquid crystal compound. The lower limit of the content of the chiral dopant A is not particularly limited, but is preferably 0.01% by mass or more, more preferably 0.02% by mass or more, and even more preferably 0.05% by mass or more, relative to the total mass of the polymerizable liquid crystal compound.

[0080] The liquid crystal composition of the present invention may contain another polymerizable compound having one or more polymerizable groups. The polymerizable group of the other polymerizable compound is not particularly limited, and examples thereof include an acryloyl group, a methacryloyl group, a vinyl group, a styryl group, and an allyl group. Among these, an acryloyl group or a methacryloyl group is preferred.

[0081] Other polymerizable compounds include non-liquid crystal polymerizable compounds. Specific examples include esters of polyhydric alcohols and (meth)acrylic acid (e.g., ethylene glycol di(meth)acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, 1,2,3-cyclohexane tetramethacrylate, polyurethane polyacrylate, and polyester polyacrylate), vinylbenzene and derivatives thereof, vinyl sulfone, acrylamide, and methacrylamide.

[0082] When such other polymerizable compounds are contained, the content thereof is preferably less than 50% by mass, more preferably 40% by mass or less, and even more preferably 2 to 30% by mass, based on the mass of the above-mentioned polymerizable liquid crystal compound (total mass of the polymerizable liquid crystal compounds when a plurality of polymerizable liquid crystal compounds are present).

[0083] [Polymerization initiator] The liquid crystal composition of the present invention may contain a polymerization initiator. Polymerization reactions suitable for the present invention are thermal polymerization reactions using a thermal polymerization initiator or photopolymerization reactions using a photopolymerization initiator, with photopolymerization reactions being more preferred. Examples of photopolymerization initiators include α-carbonyl compounds (described in U.S. Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (described in U.S. Patent Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in U.S. Patent No. 3,549,367), acrylic esters (described in U.S. Patent Nos. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (described in U.S. Patent Nos. 2,722,512), polynuclear quinone compounds (described in U.S. Patents Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketones (described in U.S. Patent No. 3,549,367), and the like. Examples of suitable oxime ester compounds include azine and phenazine compounds (described in JP-A-60-105667 and U.S. Pat. No. 4,239,850), oxadiazole compounds (described in U.S. Pat. No. 4,212,970), acylphosphine oxide compounds (described in JP-B-63-040799, JP-B-5-029234, JP-A-10-095788, and JP-A-10-029997), and oxime ester compounds (e.g., OXE-01 and OXE-02 manufactured by Omni Corporation, and NCI-1919 manufactured by Adeka Corporation).

[0084] When the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 20% by mass, more preferably 0.4 to 8% by mass, based on the total mass of the solid content of the liquid crystal composition.

[0085] [Solvent] The liquid crystal composition of the present invention may contain a solvent. As the solvent, an organic solvent is preferably used. Examples of the organic solvent include amides (e.g., N,N-dimethylformamide, etc.), sulfoxides (e.g., dimethyl sulfoxide, etc.), hydrocarbons (e.g., toluene, hexane, etc.), alkyl halides (e.g., chloroform, dichloromethane, etc.), esters (e.g., methyl acetate, butyl acetate, ethyl propionate, etc.), ketones (e.g., acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, cyclopentanone, etc.), and ethers (e.g., tetrahydrofuran, 1,2-dimethoxyethane, etc.). Of these organic solvents, esters and ketones are preferred. One type of solvent may be used alone, or two or more types may be used in combination.

[0086] [Other Components] The liquid crystal composition of the present invention may contain components other than those described above, such as an acid generator, a surfactant, a tilt angle control agent, an alignment film interface aligning agent, a plasticizer, and a crosslinking agent. The liquid crystal composition of the present invention may also contain raw materials used in the synthesis of the liquid crystal alignment promoter (the present compound), intermediates of the present compound, and decomposition products of the present compound (hereinafter also referred to as "impurities of the present compound"). Examples of raw materials used in the synthesis and intermediates of the present compound include the raw materials and intermediates of Synthesis Example (A1-3) described below, as well as compounds similar to these compounds. Examples of decomposition products of the present compound include nonafluorohexanol, (A1-3-b) described below, (A1-3-d) described below, and (A1-3-a) described below, which are hydrolyzates of the present compound, as well as hydroquinone and 4-biphenylcarboxylic acid. The total content of impurities of the present compound is preferably 10% by mass or less, more preferably 5% by mass or less, of the content of the present compound in the liquid crystal composition. Impurities of the present compound may not be contained in the liquid crystal composition. When the impurities of the present compound are contained in the liquid crystal composition, the total content of the impurities of the present compound is, for example, 0.1 ppm by mass or more relative to the content of the present compound contained in the liquid crystal composition.

[0087] <Cured Product> The cured product of the present invention is obtained by polymerizing the liquid crystal composition of the present invention. The cured product of the present invention is preferably a cured product in which the orientation state of the polymerizable liquid crystal compound contained in the liquid crystal composition is fixed. In a cured product in which the orientation direction of the polymerizable liquid crystal compound is fixed, optical properties inherent to the polymerizable liquid crystal compound are exhibited, and these optical properties vary depending on the polymerizable liquid crystal compound and the orientation direction and orientation state of the polymerizable liquid crystal compound. In a cured product in which the orientation direction of the polymerizable liquid crystal compound is fixed, it is sufficient that the orientation direction of the polymerizable liquid crystal compound is fixed; the polymerizable liquid crystal compound may no longer have liquid crystallinity. Examples of the cured product of the present invention include a cured product in which the orientation direction of the polymerizable liquid crystal compound is constant, and a cured product in which the orientation direction of the polymerizable liquid crystal compound is twisted along the helical axis. The form of the cured product of the present invention is not particularly limited, but a film-like form is preferred.

[0088] The method for polymerizing the liquid crystal composition of the present invention may be selected depending on the components contained in the liquid crystal composition and is not particularly limited, but a method of irradiating with actinic rays is preferred, and a method of irradiating with ultraviolet rays is more preferred. A method for obtaining the cured product of the present invention and preferred embodiments of the cured product of the present invention will be described in the section on the film containing the cured product of the present invention.

[0089] <Film> The film of the present invention comprises the cured product of the present invention. The film of the present invention preferably comprises a film-like cured product of the present invention (hereinafter also referred to as a "cured product film"). The film of the present invention only needs to contain the cured product of the present invention, and may consist of only the cured product of the present invention, or may contain other components. The film of the present invention may also contain two or more cured product films. Other components that the film of the present invention may contain include an alignment film and a support. The alignment film and support are appropriately selected so that the film exhibits desired properties.

[0090] [Cured Film] In the film of the present invention, the cured film contains a component derived from the polymerizable liquid crystal compound, and as described above, exhibits optical properties derived from the polymerizable liquid crystal compound. When the alignment direction of the polymerizable liquid crystal compound is a fixed direction, the film of the present invention often exhibits optical anisotropy. The alignment direction of the polymerizable liquid crystal compound may be parallel to the in-plane direction of the cured film or perpendicular to the in-plane direction of the cured film. Furthermore, the alignment direction of the polymerizable liquid crystal compound may be tilted from a direction parallel to the in-plane direction of the cured film or perpendicular to the in-plane direction of the cured film. Examples of optical anisotropy exhibited by the film of the present invention include a positive A plate, a positive C plate, a negative A plate, and a negative C plate.

[0091] Here, a positive A plate (positive A plate) and a positive C plate (positive C plate) are defined as follows. When the refractive index in the in-plane slow axis direction of the film (the direction in which the in-plane refractive index is maximum) is nx, the refractive index in the in-plane direction perpendicular to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, a positive A plate satisfies the relationship of formula (A1), and a positive C plate satisfies the relationship of formula (C1). Note that a positive A plate has a positive Rth, and a positive C plate has a negative Rth. Formula (A1) nx>ny≒nz Formula (C1) nz>nx≒ny Note that the above "≒" includes not only the case where both are completely identical, but also the case where both are substantially identical. "Substantially the same" means that, for a positive A plate, for example, "ny ≒ nz" also includes a case where (ny - nz) x d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, and "nx ≒ nz" also includes a case where (nx - nz) x d is -10 to 10 nm, preferably -5 to 5 nm. Furthermore, for a positive C plate, for example, "nx ≒ ny" also includes a case where (nx - ny) x d (where d is the film thickness) is 0 to 10 nm, preferably 0 to 5 nm. Furthermore, Rth refers to the value expressed by Rth = ((nx + ny) / 2 - nz) x d, and is also referred to as out-of-plane retardation. Furthermore, hereinafter, Re may refer to the value expressed by Re = (nx - ny) x d. Incidentally, Re is also referred to as in-plane retardation.

[0092] The negative A plate (negative A plate) and the negative C plate (negative C plate) correspond to plates that satisfy the relationships of the following formulas (A2) and (C2), respectively: ny>nx≒nz in formula (A2) and nz<nx≒ny in formula (C2).

[0093] The Re and Rth may be appropriately adjusted depending on the application of the film of the present invention, and can be adjusted by the thickness of the cured film and the type of polymerizable liquid crystal compound contained therein.

[0094] When the orientation direction of the polymerizable liquid crystal compound in the cured film of the present invention is twisted along the helical axis (particularly when a cholesteric liquid crystal phase is fixed), the film of the present invention may exhibit optical anisotropy derived from the polymerizable liquid crystal compound and may reflect electromagnetic waves in a specific wavelength range. The helical axis is preferably in the same direction as the direction perpendicular to the surface of the film of the present invention. When the film of the present invention exhibits optical anisotropy derived from the polymerizable liquid crystal compound, the twist angle of the polymerizable liquid crystal compound (the change in angle from one surface to the other surface of the cured film) can be adjusted according to the purpose. When the film of the present invention is to reflect electromagnetic waves in a specific wavelength range, the wavelength range of the reflected electromagnetic waves can be adjusted by adjusting the pitch of the helical structure of the twisted orientation (cholesteric orientation). The wavelength range of the reflected electromagnetic waves may be, for example, the infrared light range (wavelength 750 nm to 1000 μm, preferably 750 nm to 10 μm) or the visible light range (wavelength 400 to 750 nm). The central wavelength of the reflected light can be determined as follows. When the transmission spectrum of the film of the present invention is measured from the normal direction of the film using a spectrophotometer UV3150 (Shimadzu Corporation), a spectrum having a peak where the transmittance decreases in the region near the center wavelength λ is obtained. Of the two wavelengths where the transmittance is half the value of the largest peak, the value of the wavelength on the shorter wavelength side is λ ｌ (nm), and the wavelength on the long wavelength side is λ ｈ (nm), the central wavelength λ of the reflected light is calculated by the following formula: λ = (λ ｌ +λ ｈ ) / 2

[0095] The reflectance of the film of the present invention at the center wavelength λ is preferably 40% or more, more preferably 45% or more, even more preferably 47% or more, and particularly preferably 49% or more. The upper limit of the reflectance is 50% or less.

[0096] The pitch of the helical structure varies depending on the type and concentration of the chiral agent added to the liquid crystal composition, and a desired pitch alignment state can be obtained by adjusting one or more of the above. Regarding the method for measuring the helical direction and pitch, the methods described in "Introduction to Liquid Crystal Chemistry Experiments" (edited by the Japanese Liquid Crystal Society, Sigma Publishing, 2007, p. 46) and "Liquid Crystal Handbook" (Liquid Crystal Handbook Editorial Committee, Maruzen, p. 196) can be used.

[0097] The thickness of the cured film can be adjusted as appropriate, but is preferably 0.1 to 50 μm, more preferably 0.3 to 20 μm, and even more preferably 1 to 10 μm.

[0098] [Support] The support is preferably a transparent support. As the transparent support, a glass plate or a polymer film, preferably a polymer film, is used. A transparent support means that the light transmittance is 80% or more. An optically isotropic polymer film is generally used as the transparent support. Specifically, optical isotropy means that the in-plane retardation (Re) at a wavelength of 550 nm is preferably less than 10 nm, more preferably less than 5 nm. Furthermore, in an optically isotropic transparent support, the retardation in the thickness direction (Rth) at a wavelength of 550 nm is also preferably less than 10 nm, more preferably less than 5 nm. The in-plane retardation (Re) and the retardation in the thickness direction (Rth) of the transparent support are each defined by the following formulas: Re=(nx-ny)d Rth=[{(nx+ny) / 2}-nz]d In the formula, nx and ny are the in-plane refractive indices of the transparent support, nz is the refractive index in the thickness direction of the transparent support, and d is the thickness of the transparent support.

[0099] An optically anisotropic polymer film may be used as the transparent support. In such cases, the transparent support preferably has optical uniaxiality or optical biaxiality. In the case of an optically uniaxial support, it may be optically positive (the refractive index in the optical axis direction is greater than the refractive index in the direction perpendicular to the optical axis) or negative (the refractive index in the optical axis direction is smaller than the refractive index in the direction perpendicular to the optical axis). In the case of an optically biaxial support, the refractive indices nx, ny, and nz in the above formula are all different values ​​(nx ≠ ny ≠ nz). The in-plane retardation (Re) at a wavelength of 550 nm of an optically anisotropic transparent support is preferably 10 to 1,000 nm, more preferably 15 to 300 nm, and even more preferably 20 to 200 nm. The retardation (Rth) in the thickness direction of the optically anisotropic transparent support at a wavelength of 550 nm is preferably from 10 to 1,000 nm, more preferably from 15 to 300 nm, and even more preferably from 20 to 200 nm.

[0100] The material for forming the transparent support is determined depending on whether it is an optically isotropic support or an optically anisotropic support. For an optically isotropic support, glass or cellulose ester is generally used. For an optically anisotropic support, a synthetic polymer (e.g., polycarbonate, polysulfone, polyethersulfone, polyacrylate, polymethacrylate, and norbornene resin) is generally used.

[0101] The thickness of the transparent support is preferably 10 to 500 μm, and more preferably 50 to 200 μm. To improve adhesion between the transparent support and a layer (e.g., an adhesive layer, an alignment film, or a cured film) formed thereon, the transparent support may be subjected to a surface treatment (e.g., glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, or flame treatment). An ultraviolet absorber may also be added to the transparent support. An adhesive layer (undercoat layer) may also be formed on the transparent support. Details of adhesive layers are described in JP-A-7-333433. The thickness of the adhesive layer is preferably 0.1 to 2 μm, and more preferably 0.2 to 1 μm. The transparent support may be peeled off after the film is formed.

[0102] [Film manufacturing method] Examples of methods for obtaining the film of the present invention include a method in which the liquid crystal composition of the present invention is applied to a support to form a coating film, the solvent contained in the coating film is removed as needed, an alignment treatment is performed as needed to align the polymerizable liquid crystal compound contained in the coating film, and a polymerization treatment is performed to fix the alignment direction of the polymerizable liquid crystal compound contained in the coating film, thereby forming a cured film.

[0103] The method for applying the liquid crystal composition is not particularly limited, and can be carried out by a known method (for example, extrusion coating, direct gravure coating, reverse gravure coating, die coating, bar coating, etc.).

[0104] The alignment treatment is not particularly limited, and examples thereof include a method of applying an electric field to the coating film and a method of heating the coating film, with the method of heating the coating film being preferred. The heating temperature may be selected depending on the type of polymerizable liquid crystal compound contained. The alignment treatment may be performed simultaneously with the removal of the solvent. When heating is performed as the alignment treatment, it is also preferable to maintain the temperature lower than that of the alignment treatment in order to stabilize the alignment direction of the polymerizable liquid crystal compound.

[0105] The polymerization treatment is not particularly limited, but a method of irradiating ultraviolet rays is preferred. It is also preferable to carry out ultraviolet irradiation in an environment with a low oxygen concentration. In this specification, "ultraviolet rays" refers to electromagnetic waves mainly containing electromagnetic waves with wavelengths of 200 to 400 nm, and preferably mainly containing electromagnetic waves with wavelengths of 300 to 400 nm. The light source of ultraviolet rays is not particularly limited, and known light sources can be used, and ultraviolet rays containing any wavelength range may be irradiated using a filter or the like. Examples of ultraviolet light sources include high-pressure mercury lamps, metal halide lamps, and light-emitting diodes (LEDs). The irradiation energy is 5 mJ / cm. ２ ~100 J / cm ２ is preferred, and 30 to 600 mJ / cm ２ More preferably, 100 to 400 mJ / cm ２ In order to promote the photopolymerization reaction, the light irradiation may be carried out under heated conditions.

[0106] When the film of the present invention has two or more layers of cured product films, the film of the present invention may be obtained by laminating separately prepared cured product films or laminates containing cured product films, or by preparing another cured product film on the prepared cured product film. A method for preparing another cured product film on the prepared cured product film includes the above-described procedure of applying the liquid crystal composition of the present invention to a support to form a first cured product film, applying the liquid crystal composition of the present invention to the first cured product film to form a coating film, and then preparing a second cured product film by the above-described method. Furthermore, a third cured product film, etc., may be prepared on the prepared second cured product film by a similar method. When the liquid crystal composition of the present invention is applied to the first cured product film to form a coating film and another cured product film (e.g., a second cured product film) is formed, the present compound is often present in large amounts on the surface of the first cured product film facing the other cured product film. Here, when the liquid crystal composition of the present invention is applied to form another cured product film, some of the present compound present on the surface of the first cured product film may migrate to the applied liquid crystal composition. In such a case, the content of the present compound in the liquid crystal composition increases, but even in such a case, it is thought that aggregates of the present compound are unlikely to occur, and as a result, disorder in the orientation of the polymerizable liquid crystal compound is likely to be suppressed. In other words, the present compound is particularly useful when forming a cured product film by sequential coating as described above.

[0107] The cured film of the present invention may be formed on an alignment film. The alignment film can be formed by rubbing an organic compound (preferably a polymer), oblique vapor deposition of an inorganic compound, formation of a layer with microgrooves, or deposition of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearate, etc.) using the Langmuir-Blodgett method (LB film). Furthermore, alignment films that exhibit alignment function upon application of an electric field, a magnetic field, or light irradiation are also known. Among these, photoalignment films that exhibit alignment function upon light irradiation are preferred. Rubbing is performed by rubbing the surface of the polymer layer several times in a specific direction with paper or cloth. The type of polymer used in the alignment film is determined depending on the desired orientation (particularly the average tilt angle) of the polymerizable liquid crystal compound. To align the polymerizable liquid crystal compound horizontally (average tilt angle: 0 to 50°), a polymer that does not reduce the surface energy of the alignment film (a typical alignment film polymer) is used. To align the polymerizable liquid crystal compound vertically (average tilt angle: 50 to 90°), a polymer that reduces the surface energy of the alignment film is used. To reduce the surface energy of the alignment film, it is preferable to introduce a hydrocarbon group having 10 to 100 carbon atoms into the side chain of the polymer.

[0108] Specific types of polymers are described in literature on optical compensation sheets using liquid crystal molecules compatible with various display modes. The thickness of the alignment film is preferably 0.01 to 5 μm, more preferably 0.05 to 1 μm. The alignment film may be used to align the polymerizable liquid crystal compound in the coating film, and then the coating film may be transferred onto a transparent support. The polymerizable liquid crystal compound fixed in an aligned state can maintain the aligned state even without an alignment film.

[0109] [Applications of Film] The film of the present invention can be used for various applications depending on its optical properties. For example, the film of the present invention can be used as a retardation plate. It is also preferable that the Re of the retardation plate at a specific wavelength is about ¼ of the specific wavelength, and such a retardation plate is also called a λ / 4 plate. When used together with a linear polarizer, the λ / 4 plate exhibits the function of a circular polarizing plate, converting unpolarized light into circularly polarized light. The film of the present invention can also be used as a retardation adjustment film. The retardation adjustment film is preferably used in a laminate in which it is laminated with other optical layers, and it is more preferable to adjust the Rth of the entire laminate. By adjusting the Rth of the entire laminate, the retardation of light in a direction inclined from the plane perpendicular to the laminate can be adjusted, thereby improving the display performance of, for example, an image display device.

[0110] The film of the present invention can also be used as a reflective layer. The reflective layer preferably functions as a circularly polarized light selective reflective layer that selectively reflects either right-handed or left-handed circularly polarized light and transmits the other sense of circularly polarized light.

[0111] In this specification, the term "sense" in reference to circularly polarized light means right-handed or left-handed circularly polarized light. The sense of circularly polarized light is defined as follows: when viewed as if the light is traveling toward you, if the tip of the electric field vector rotates clockwise as time increases, it is right-handed circularly polarized light, and if it rotates counterclockwise, it is left-handed circularly polarized light. In this specification, the term "sense" is also used to refer to the twist direction of the cholesteric oriented helix. Selective reflection by a cholesterically oriented liquid crystal compound reflects right-handed circularly polarized light and transmits left-handed circularly polarized light when the twist direction (sense) of the cholesteric oriented helix is ​​right-handed, and reflects left-handed circularly polarized light and transmits right-handed circularly polarized light when the sense is left-handed.

[0112] The reflective layer is preferably used as a reflective layer in an image display device having a reciprocating optical system that reflects light back and forth between the reflective layer and a half mirror. The image display device may be a head-mounted display, and the head-mounted display may be a virtual reality display device. The reflective layer may also be used as a screen and half mirror for projected image display. When the film of the present invention is used as a reflective layer, it is also preferable that the film of the present invention has two or more cured product films. It is also preferable that the center wavelengths of reflected light in the two or more cured product films are different. By having the center wavelengths of reflected light in the two or more cured product films be different, it is possible to make the film function as a reflective layer, for example, across the entire visible light range. For example, by preparing cured product films each having an apparent center wavelength of selective reflection in the red light wavelength range, the green light wavelength range, and the blue light wavelength range, and laminating them, a projection image display component capable of displaying full-color projected images can be produced.

[0113] Furthermore, for example, by configuring the projection image display member to be transparent to light in the visible light region, it can be used as a half mirror for projecting images in a head-up display. The projection image display half mirror can visibly display an image projected from a projector, and when the projection image display half mirror is viewed from the same side where the image is displayed, information or scenery on the opposite side can be simultaneously viewed.

[0114] Furthermore, by controlling the film of the present invention so that it exhibits selective reflection properties in the infrared wavelength region, it can be used as a heat-shielding film or an infrared-cut filter for sensors. Furthermore, the reflective layer can be used for various applications, such as components of optical elements, such as polarizing elements, reflective films, antireflection films, viewing angle compensation films, holography, and alignment films.

[0115] The present invention will be described in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the examples shown below.

[0116] <Preparation and Evaluation of Film> For the films of each Example and Comparative Example, a liquid crystal composition containing a liquid crystal alignment promoter and a polymerizable liquid crystal compound was prepared, the liquid crystal composition was applied to a support to form a coating film, and the coating film was irradiated with ultraviolet light to obtain a cured film. The procedure for obtaining the film of Example 1 is described below.

[0117] The synthesis methods for some of the compounds used in the examples or similar compounds are shown below. Other compounds can be synthesized by following the synthesis procedures below and appropriately changing the materials used. The names of the compounds shown in the examples below (e.g., compound (A2-1)) correspond to the structures shown in the examples of the present compounds described above.

[0118] [Synthesis of Compound (A1-3)] The reaction scheme for the synthesis is as follows.

[0119]

[0120] (Synthesis of Intermediate (A1-3-a)) Under a nitrogen stream, 6.0 g of 4-phenylbenzoyl chloride, 30.5 g of hydroquinone, and 68 mL of butyl acetate were placed in a 200 mL three-necked flask, and the mixture was heated to 110°C to completely dissolve the solution. 108 μL of methanesulfonic acid was added to the content of the three-necked flask, and the mixture was reacted at 110°C for 2 hours. After the reaction, the liquid temperature was cooled to 50°C or below, and after cooling, 120 mL of methanol was added, and the liquid temperature was cooled to 20°C to precipitate a solid. The precipitated solid was collected by filtration, washed with 100 mL of methanol, and air-dried overnight to obtain 5.7 g of a white solid (Intermediate (A1-3-a)) (yield 62%).

[0121] (Synthesis of Intermediate (A1-3-b) and Intermediate (A1-3-c)) 25.0 g of nonafluorohexanol, 10.0 g of succinic anhydride, 2.9 mL of tetrahydrofuran, 0.16 g of 4-dimethylaminopyridine, and 0.13 mL of triethylamine were placed in a 200 mL three-neck flask, and the mixture was reacted at 110°C for 1 hour. After cooling to room temperature, 2 mL of 1 N hydrochloric acid, 94 mL of water, and 18.8 mL of 2-propanol were placed in the three-neck flask, and the liquid temperature was cooled to 5°C or below to precipitate a solid. The precipitated solid was collected by filtration, washed with cold water, and then dried under reduced pressure at 40°C, yielding 33.2 g of a white solid (Intermediate (A1-3-b)) (yield 96%).

[0122] 33.2 g of intermediate (A1-3-b), 48 mL of toluene, and 1.4 mL of dimethylformamide were placed in a 500 mL three-neck flask, and the temperature was raised to 70° C. Then, 8.6 mL of thionyl chloride was added dropwise to the three-neck flask, and the reaction was carried out at 70° C. for 1 hour. The solvent was distilled off under reduced pressure from the solution after the reaction, yielding intermediate (A1-3-c) as a brown oil.

[0123] (Synthesis of Intermediate (A1-3-d) and Intermediate (A1-3-e)) 1.77 g of gallic acid monohydrate and 5.5 mL of toluene were placed in a 100 mL three-neck flask equipped with a Dean-Stark tube, and the mixture was dehydrated under reflux. After cooling to room temperature, 19 mL of tetrahydrofuran was added. After cooling to 15°C, 6.55 g of Intermediate (A1-3-c) and 2.68 g of pyridine were added dropwise, successively. After the dropwise addition, the mixture was reacted at room temperature for 1 hour, and then 34 mL of tetrahydrofuran, 1.12 g of pyridine, and 16.9 mL of water were added, and the mixture was reacted at 35°C for 1 hour. After the reaction, the mixture was cooled to room temperature, and 25 mL of 1 N hydrochloric acid and 50 mL of ethyl acetate were added. The mixture was stirred and then allowed to stand to separate into an aqueous layer and an organic layer, and the aqueous layer was separated and removed. The organic layer was washed with 25 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the anhydrous magnesium sulfate was filtered off, and the organic layer was concentrated under reduced pressure to obtain an orange oily crude product, which was then purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 7.72 g of intermediate (A1-3-d) as an orange solid (yield: 66%).

[0124] 7.5 g of intermediate (A1-3-d), 96 μL of dimethylformamide, and 18 mL of toluene were placed in a 100 mL three-neck flask, and the temperature was raised to 70° C. Then, 0.68 mL of thionyl chloride was added dropwise, and the mixture was reacted at 70° C. for 2 hours. The solvent was distilled off from the solution after the reaction, yielding intermediate (A1-3-e) as an orange oil.

[0125] (Synthesis of Compound (A1-3)) 2.00 g of intermediate (A1-3-e), 6.6 mL of tetrahydrofuran, 8.7 mL of ethyl acetate, and 0.42 g of intermediate (A1-3-a) were placed in a 100 mL three-neck flask, and 11 μL of N-methylimidazole (NMI) was added. Next, 0.22 g of triethylamine was added dropwise while maintaining the liquid temperature at 30° C. or below. The temperature was raised to 35° C., and the mixture was allowed to react for 1 hour. After the reaction, 3 mL of methanol was added, and the mixture was stirred at 35° C. for 10 minutes. After stirring, 1.3 mL of 1 N hydrochloric acid, 3.8 mL of water, and 10 mL of ethyl acetate were added. After the addition, the aqueous layer was separated and removed to obtain an organic layer. The obtained organic layer was washed with 5 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the anhydrous magnesium sulfate was filtered off, and the organic layer was concentrated under reduced pressure. The organic layer concentrated under reduced pressure was heated and completely dissolved in 30 mL of methanol, and after complete dissolution, the solution was cooled to 5° C. or lower to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain 1.6 g of compound (A1-3) as a pale yellow solid (yield 74%).

[0126] The obtained compound (A1-3) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.30 (d, 2H), 7.99 (s, 2H), 7.93 (d, 2H), 7.80 (d, 2H), 7.55 (t, 2H), 7 .50-7.42 (m, 5H), 4.54-4.46 (m, 6H), 3.12-3.02 (m, 6H), 2.93-2.78 (m, 6H), 2.77-2.61 (m, 6H)

[0127] [Synthesis of Compound (A1-1)] The reaction formula for the synthesis is as follows.

[0128]

[0129] (Synthesis of Intermediate (A1-1-a)) Intermediate (A1-1-a) was synthesized in the same manner as for intermediate (A1-3-a), except that methyl gentisate was used instead of hydroquinone, which was used as a raw material for intermediate (A1-3-a), to obtain a white solid (intermediate (A1-1-a)) in a yield of 61%.

[0130] (Synthesis of Compound (A1-1)) 2.50 g of intermediate (A1-3-e), 9.0 mL of tetrahydrofuran, 10.0 mL of ethyl acetate, and 0.63 g of intermediate (A1-1-a) were placed in a 100 mL three-neck flask, and 14.3 μL of N-methylimidazole was added. Next, 0.28 g of triethylamine was added dropwise while maintaining the liquid temperature at 30° C. or below. The temperature was raised to 35° C., and the mixture was allowed to react for 1 hour. After the reaction, 3 mL of methanol was added, and the mixture was stirred at 35° C. for 10 minutes. Then, 1.6 mL of 1 N hydrochloric acid, 4.7 mL of water, and 12.5 mL of ethyl acetate were added. After the addition, the aqueous layer was separated and removed to obtain an organic layer. The resulting organic layer was washed with 6.0 mL of 10% brine and dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the organic layer was concentrated under reduced pressure. The organic layer concentrated under reduced pressure was completely dissolved in 15 mL of acetone, and the completely dissolved solution was added dropwise to 60 mL of methanol. The solution was then cooled to 5° C. or lower to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, yielding 1.0 g of a pale yellow solid (compound (A1-1)) (yield: 36%).

[0131] The obtained compound (A1-1) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 8.01 (s, 3H), 7.93 (d, 2H), 7.81 (d, 2H), 7.80-7.74 (m, 1H), 7.60-7.53 (m. 3H), 7.49-7.47 (m, 1H), 4.51-4.46 (m, 6H), 3.71 (s, 3H), 3.11-3.03 (m, 6H), 2.85-2.82 (m, 6H), 2.76-2.63 (m, 6H)

[0132] [Synthesis of Compound (A1-9)] The reaction formula for the synthesis is as follows.

[0133]

[0134] (Synthesis of Intermediate (A1-9-a)) Intermediate (A1-9-a) was synthesized in the same manner as for intermediate (A1-3-a), except that 2,6-dihydroxynaphthalene was used instead of hydroquinone, which was used as a raw material for intermediate (A1-3-a), to obtain a white solid (intermediate (A1-9-a)) in a yield of 65%.

[0135] (Synthesis of Compound (A1-9)) 2.50 g of intermediate (A1-3-e), 9.0 mL of tetrahydrofuran, 10.0 mL of ethyl acetate, and 0.62 g of intermediate (A1-9-a) were placed in a 100 mL three-neck flask, and 14.3 μL of N-methylimidazole was added. Next, 0.28 g of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or below, and the mixture was heated to 35°C and allowed to react for 1 hour. After the reaction, 3 mL of methanol was added, and the mixture was stirred at 35°C for 10 minutes. 50 mL of methanol was added, and the mixture was cooled to a liquid temperature of 5°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain crude crystals. The obtained crude crystals were dissolved in 15 mL of acetone, and 15 mL of methanol was added, and the mixture was cooled to a liquid temperature of 15°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain 1.5 g of a pale yellow solid compound (A1-9) (yield: 54%).

[0136] The obtained compound (A1-9) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.34 (d, 2H), 8.09 (d, 2H), 8.03 (s, 2H), 7.94 (d, 4H), 7.81 (d, 2H), 7.61-7 .53 (m, 4H), 7.47 (t, 1H), 4.51-4.46 (m, 6H), 3.11-3.03 (m, 6H), 2.85-2.82 (m, 6H), 2.76-2.63 (m, 6H)

[0137] [Synthesis of Compound (A1-10)] The reaction formula for the synthesis is as follows.

[0138]

[0139] (Synthesis of Intermediate (A1-10-a)) A 100 mL three-neck flask was charged with 2.00 g of 4-(4-bromophenyl)phenol, 1.17 g of 4-biphenylboronic acid, 2.55 g of sodium carbonate, 32.0 mL of methanol, and 8.0 mL of water, and 0.019 g of 5% palladium on carbon (55% water content) was further added. The liquid temperature in the three-neck flask was raised to 80°C, and the mixture was stirred for 7 hours. After stirring, the solvent was distilled off under reduced pressure, and then 81 mL of water was added. 3.9 mL of concentrated hydrochloric acid was added to make the mixture acidic, and the mixture was stirred thoroughly to precipitate a solid. The precipitated solid was collected by filtration, washed with 101 mL of water, and then dried. The dried solid was added to ethyl acetate, and the solution was heated to completely dissolve it. A small amount of activated carbon was added, and the mixture was stirred. The added activated carbon was removed by hot filtration using Celite, and the Celite was washed with ethyl acetate. The obtained filtrate was cooled to -20°C or below, and the precipitated solid was collected by filtration. The filtrate was concentrated under reduced pressure until the volume was 20%, and then cooled to -20°C or below, and the precipitated solid was collected by filtration. All solids obtained by the above procedure were dried under reduced pressure at 50°C, and a white solid intermediate (A1-10-a) was obtained in a yield of 55%.

[0140] (Synthesis of Compound (A1-10)) 2.00 g of intermediate (A1-3-e), 6.6 mL of tetrahydrofuran, 8.7 mL of ethyl acetate, and 0.46 g of intermediate (A1-10-a) were placed in a 100 mL three-neck flask, and 11.3 μL of N-methylimidazole was added. Next, 0.22 g of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or less, and the mixture was allowed to react at room temperature for 2 hours. After the reaction, 1.0 mL of methanol was added, and the mixture was stirred at room temperature for 10 minutes. After that, 50 mL of methanol was added, and the mixture was cooled to a liquid temperature of 5°C or less to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain crude crystals. The obtained crude crystals were dissolved in 15 mL of acetone, and 15 mL of methanol was added, and the liquid temperature was cooled to 15°C or less to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, obtaining 1.3 g of compound (A1-10) as a pale yellow solid (yield 60%).

[0141] The obtained compound (A1-10) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.01 (s, 2H), 7.87-7.74 (m, 12H), 7.52-7.45 (m, 4H), 7.41-7 .37 (t, 1H), 4.51-4.46 (m, 6H), 3.10-3.03 (m, 6H), 2.84-2.78 (m, 6H), 2.76-2.63 (m, 6H)

[0142] [Synthesis of Compound (A1-11)] The reaction scheme for synthesis is as follows.

[0143]

[0144] (Synthesis of Intermediate (A1-11-a)) Intermediate (A1-11-a) was synthesized in the same manner as for intermediate (A1-3-a), except that 4,4'-dihydroxybiphenyl was used instead of hydroquinone, which was used as a raw material for intermediate (A1-3-a), to obtain a white solid (intermediate (A1-11-a)) in a yield of 68%.

[0145] (Synthesis of Compound (A1-11)) 2.53 g of intermediate (A1-3-e), 15.0 mL of dimethylacetamide, and 0.67 g of intermediate (A1-11-a) were placed in a 100 mL three-neck flask, and 14.3 μL of N-methylimidazole was further added. Next, 0.28 g of triethylamine was added dropwise while maintaining the liquid temperature at 30° C. or below, and the mixture was allowed to react at room temperature for 1.5 hours. After the reaction, 30 mL of methanol and 20 mL of water were added, and the mixture was stirred at room temperature for 10 minutes. The precipitated solid was collected by filtration and washed with methanol to obtain crude crystals. The obtained crude crystals were purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), and 1.30 g of compound (A1-11) was obtained as a pale yellow solid (yield: 46%).

[0146] The obtained compound (A1-11) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 7.99 (s, 2H), 7.93 (d, 2H), 7.81-7.79 (m, 6H), 7.57-7.53 (m, 2H), 7.47-7.45 (m, 5H), 4.51-4.46 (m, 6H), 3.09-3.03 (m, 6H), 2.84-2.78 (m, 6H), 2.74-2.65 (m, 6H)

[0147] [Synthesis of Compound (A1-12)] The reaction formula for the synthesis is as follows.

[0148]

[0149] (Synthesis of Intermediate (A1-12-a)) 3.00 g of nicotinic acid, 0.36 mL of dimethylformamide, and 50 mL of toluene were placed in a 300 mL three-neck flask, and the liquid temperature was raised to 70°C. Next, 2.65 mL of thionyl chloride was added dropwise, and the mixture was stirred at a liquid temperature of 70°C for 4 hours. After stirring, the solvent was distilled off under reduced pressure, and the mixture was cooled to a liquid temperature of 15°C or below. After cooling, 150 mL of tetrahydrofuran and 13.61 g of 4,4'-dihydroxybiphenyl were added. Next, 8.2 mL of triethylamine was added dropwise, and the mixture was stirred for 2.5 hours. After stirring, 30 mL of water and 20 mL of methanol were added to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain crude crystals. The obtained crude crystals were dispersed in 50 mL of tetrahydrofuran, and the mixture was stirred at a liquid temperature of 40°C for 30 minutes. After stirring, the mixture was cooled to room temperature, and the solid was collected by filtration and washed with tetrahydrofuran to obtain intermediate (A1-12-a) as a yellow solid in a yield of 70%.

[0150] (Synthesis of Compound (A1-12)) 2.50 g of intermediate (A1-3-e), 20 mL of tetrahydrofuran, 10 mL of ethyl acetate, and 0.53 g of intermediate (A1-12-a) were placed in a 100 mL three-neck flask, and 14.3 μL of N-methylimidazole was further added. Next, 0.4 mL of triethylamine was added dropwise while maintaining the liquid temperature at 30° C. or less, and the mixture was allowed to react at room temperature for 2 hours. After the reaction, 20 mL of water and 50 mL of methanol were added, and the mixture was stirred at room temperature for 10 minutes to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain crude crystals. The obtained crude crystals were purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), and 0.74 g of compound (A1-12) was obtained as a white solid (yield 28%).

[0151] The obtained compound (A1-12) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.90 (d, 2H), 8.07 (d, 2H), 7.99 (s, 2H), 7.83 (d, 4H), 7.47 (d, 4H), 4.51-4.46 (m, 6H), 3.10-3.03 (m, 6H), 2.85-2.80 (m, 6H), 2.75-2.63 (m, 6H)

[0152] [Synthesis of Compound (A1-15)] The reaction scheme for synthesis is as follows.

[0153]

[0154] (Synthesis of Intermediate (A1-15-a) and Intermediate (A1-15-b)) Intermediate (A1-15-a) was synthesized in the same manner as for compound (A1-3-d), except that 3,4-dihydroxybenzoic acid was used instead of 3,4,5-trihydroxybenzoic acid, which was used as the raw material for intermediate (A1-3-d), to obtain intermediate (A1-15-a) as a pale yellow solid in a yield of 68%.

[0155] Intermediate (A1-15-b) was obtained as a brown oil in the same manner as in the synthesis of compound (A1-3-e), except that intermediate (A1-15-a) was used instead of intermediate (A1-3-d) used in the synthesis of intermediate (A1-3-e).

[0156] (Synthesis of Compound (A1-15)) A pale yellow solid compound (A1-15) was obtained in a yield of 71% in the same manner as in the synthesis of compound (A1-1), except that intermediate (A1-15-b) was used instead of intermediate (A1-3-e) used in the synthesis of compound (A1-1).

[0157] The obtained compound (A1-15) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.30 (d, 2H), 8.01-7.97 (m, 4H), 7.95 (d, 2H), 7.83 (d, 2H), 7.80-7.74 (m, 1H), 7.60-7.53 (m.3H), 7.49-7.47 (m, 1H), 4.51-4.45 (m, 4H), 3.71 (s, 3H), 3.12-3.04 (m, 4H), 2.85-2.81 (m, 4H), 2.77-2.65 (m, 4H)

[0158] [Synthesis of Compound (A1-17)] The reaction scheme for synthesis is as follows.

[0159]

[0160] (Synthesis of Compound (A1-17-a)) 7.17 g of 2,6-dihydroxynaphthalene, 30 mL of dimethylacetamide, and 3.30 g of 2-naphthoyl chloride were placed in a 100 mL three-neck flask, and 2.5 mL of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or below. Next, after stirring at room temperature for 3 hours, 1.6 mL of methanol was added and the mixture was stirred for an additional 1 hour to allow the reaction to proceed. 250 mL of 1 N hydrochloric acid was added to the resulting reaction liquid to precipitate a solid, which was collected by filtration and washed with methanol to obtain crude crystals. The resulting crude crystals were dispersed in 200 mL of methanol and stirred at 50°C for 1 hour. After stirring, the mixture was cooled to room temperature, and the solid was collected by filtration and washed with methanol to obtain intermediate (A1-17-a) as a white solid in a yield of 65%.

[0161] (Synthesis of Compound (A1-17)) 2.50 g of intermediate (A1-3-e), 20 mL of tetrahydrofuran, and 0.56 g of intermediate (A1-17-a) were placed in a 100 mL three-neck flask, and 14.1 μL of N-methylimidazole was added. Next, 0.4 mL of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or below, and the mixture was allowed to react at room temperature for 4 hours. After the reaction, 1.25 mL of methanol was added, and the mixture was stirred at room temperature for 1 hour. After stirring, the mixture was allowed to stand overnight. After standing overnight, 1.6 mL of 1 N hydrochloric acid, 4.7 mL of water, and 12.5 mL of ethyl acetate were added, and after the addition, the aqueous layer was separated and removed to obtain an organic layer. The organic layer was washed with 6.3 mL of 10% brine and dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the organic layer was concentrated under reduced pressure to obtain a crude brown oil. 50 mL of methanol was added to the crude product to precipitate a solid, which was then filtered and washed with methanol to obtain 0.39 g of compound (A1-17) as a light brown solid (yield 14%).

[0162] The obtained compound (A1-17) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.92 (s, 1H), 8.29-8.19 (m, 2H), 8.17-8.07 (m, 4H), 8.04 (s, 2H), 7.99-7.95 (d, 2H), 7 .75-7.67 (m, 2H), 7.64-7.58 (d, 2H), 4.54-4.46 (m, 6H), 3.12-3.05 (m, 6H), 2.90-2.83 (m, 6H), 2.76-2.62 (m, 6H)

[0163] [Synthesis of Compound (A2-1)] The reaction scheme for the synthesis is as follows.

[0164]

[0165] (Synthesis of Intermediate (A2-1-a) and Intermediate (A2-1-b)) A 2 L three-neck flask was charged with 100.0 g of 3,3,4,4,5,5,6,6,6-nonafluorohexanol, 25.7 g of tetrabutylammonium hydrogen sulfate, 11.0 mL of water, and 90 mL of toluene, and 88.3 g of t-butyl bromoacetate was further added. After the liquid temperature was raised to 30°C, an aqueous sodium hydroxide solution (60.6 g of sodium hydroxide, 60.6 mL of water) was added dropwise while maintaining the liquid temperature at 40°C or less. After the dropwise addition, the liquid was stirred at a liquid temperature of 35°C for 2 hours and cooled to 20°C or less. Next, while maintaining the liquid temperature at 30°C or less, a mixed liquid of 72.8 mL of 12 N hydrochloric acid and 72.8 mL of water was added dropwise, and the liquid was separated and the aqueous layer was removed. To the organic layer, brine (25.6 g of salt, 230 mL of water) and 90 mL of toluene were added, and after stirring, the aqueous layer was removed. The resulting organic layer was washed with 180 mL of 25% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the organic layer was concentrated under reduced pressure to obtain intermediate (A2-1-a) as a colorless oil.

[0166] Under a nitrogen stream, 122.3 g of sodium bis(2-methoxyethoxy)aluminum hydride (70% toluene solution) and 196 mL of toluene were placed in a 2 L three-neck flask. After cooling the liquid temperature to below 10°C, the entire amount of intermediate (A2-1-a) synthesized above was added dropwise while maintaining the liquid temperature at 30°C or below. The dropping funnel was washed with 49 mL of toluene. After the dropwise addition, the liquid temperature was raised to 40°C, and 30 minutes after the temperature increase, 10.9 g of sodium bis(2-methoxyethoxy)aluminum hydride (70% toluene solution) was added, followed by stirring for an additional 30 minutes. After stirring, the liquid temperature was cooled to below 15°C, and a mixed solution of 132.6 g of Rochelle salt tetrahydrate and 152.6 mL of water was added dropwise. After stirring for 30 minutes at 30 to 40°C, the liquids were separated and the aqueous layer was removed. A mixed solution of 66.3 g of Rochelle salt tetrahydrate and 76.3 mL of water was added dropwise to the obtained organic layer, and after stirring for 5 minutes, the aqueous layer was removed. The obtained organic layer was washed with 265 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was removed by filtration through Celite, and the filtrate was concentrated under reduced pressure to obtain 110 g (yield 94%) of intermediate (A2-1-b) as a colorless oil.

[0167] (Synthesis of Intermediate (A2-1-c) and Intermediate (A2-1-d)) 106.7 g of Intermediate (A2-1-b), 126 mL of ethyl acetate, and 46.9 g of methanesulfonyl chloride were placed in a 1 L three-neck flask and cooled to a liquid temperature of 10°C or less. Furthermore, 37.5 g of triethylamine was added dropwise while maintaining the liquid temperature at 20°C or less, and after raising the temperature to room temperature, the mixture was stirred for 2 hours to allow the reaction to proceed. 126 mL of hexane and a mixture of 126 mL of 10% brine and 3.2 g of sodium bicarbonate were added to the resulting reaction liquid and stirred at room temperature for 5 minutes. The liquids were separated and the aqueous layer was removed. The resulting organic layer was washed with 126 mL of 10% brine and dried over anhydrous sodium sulfate. After drying, the drying agent was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product as a pale yellow oil. The crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 98.8 g of a colorless oily intermediate (A2-1-c) (yield: 75%).

[0168] Under a nitrogen stream, 9.0 g of 3,4,5-trihydroxybenzoic acid, 190 mL of dimethylacetamide, and 30.4 g of potassium carbonate were placed in a 1 L three-neck flask and the liquid temperature was raised to 90°C. Next, 61.3 g of intermediate (A2-1-c) was added dropwise, and the dropping funnel was washed with 10 mL of dimethylacetamide. The solution was reacted at 90°C for 3 hours, cooled to room temperature, and then 190 mL of ethyl acetate and hydrochloric acid (a mixture of 30 mL of concentrated hydrochloric acid and 332 mL of water) were added dropwise while maintaining the liquid temperature at 40°C or below. After separation and removal of the aqueous layer, the organic layer was washed with 152 mL of 10% brine. After separation and removal of the transition layer, the organic layer was concentrated under reduced pressure to obtain 38.1 g of colorless oily intermediate (A2-1-d) (yield 74%).

[0169] (Synthesis of Intermediate (A2-1-e) and Intermediate (A2-1-f)) 54.9 g of (A2-1-d), 186 mL of ethanol, and an aqueous potassium hydroxide solution (6.86 g of potassium hydroxide, 68 mL of water) were placed in a 1 L three-neck flask, and the liquid temperature was raised to 70°C. After stirring at 70°C for 1 hour, the temperature was lowered to room temperature, and 310 mL of ethyl acetate and hydrochloric acid (14 mL of concentrated hydrochloric acid, 310 mL of water) were added dropwise and stirred. After removing the aqueous layer, the organic layer was washed with 125 mL of 10% brine and dried over anhydrous magnesium sulfate. The desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain (A2-1-e) as a pale brown oil.

[0170] 30.2 g of intermediate (A2-1-e), 0.22 mL of dimethylformamide, and 88 mL of toluene were placed in a 200 mL three-neck flask, and the liquid temperature was raised to 70° C. Furthermore, 4.2 mL of thionyl chloride was added dropwise, and the mixture was stirred at 70 to 80° C. for 1 hour. After stirring, the solvent was concentrated under reduced pressure to obtain intermediate (A2-1-f) as a brown oil.

[0171] (Synthesis of Compound (A2-1)) 8.50 g of intermediate (A2-1-f), 33.0 mL of tetrahydrofuran, 32.5 mL of ethyl acetate, and 2.22 g of intermediate (A1-1-a) were placed in a 100 mL three-neck flask, and 50.3 μL of N-methylimidazole was added. 1.25 g of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or below, and the mixture was allowed to react at room temperature for 2 hours. After the reaction, 150 mL of methanol and 20 mL of water were added to the reaction liquid, and the mixture was cooled to 10°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain a crude product. The obtained crude product was dissolved in 20 mL of acetone, and 50 mL of methanol was added, and the mixture was cooled to 10°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, obtaining 4.72 g of compound (A2-1) as a pale yellow solid (yield 54%).

[0172] The obtained compound (A2-1) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.33 (d, 2H), 7.99 (s, 1H), 7.94 (d, 2H), 7.80 (d, 2H), 7.72 (d, 1H), 7.57-7. 53 (m, 4H), 7.50-7.45 (m, 2H), 4.36-4.33 (m, 6H), 3.96-3.85 (m, 12H), 3.77 (s, 3H), 2.64-2.49 (m, 6H)

[0173] [Synthesis of Compound (A2-3)] The reaction scheme for the synthesis is as follows.

[0174]

[0175] Compound (A2-3) was obtained as a pale yellow solid in a yield of 58% by synthesizing it in the same manner as in the synthesis of compound (A2-1), except that intermediate (A1-1-a) used in the synthesis of compound (A2-1) was changed to intermediate (A1-3-a).

[0176] The obtained compound (A2-3) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.33 (d, 2H), 7.99 (d, 2H), 7.95 (d, 2H), 7.31 (d, 2H), 7.71 (d, 1H), 7 .56-7.54 (m, 4H), 7.51-7.45 (m, 2H), 4.36-4.33 (m, 6H), 3.96-3.85 (m, 12H), 2.64-2.49 (m, 6H)

[0177] [Synthesis of Compound (A2-43)] The reaction scheme for synthesis is as follows.

[0178]

[0179] 2.50 g of intermediate (A2-1-f), 9.0 mL of tetrahydrofuran, 10.8 mL of ethyl acetate, and 0.73 g of intermediate (A1-9-a) were placed in a 100 mL three-neck flask, and 16.9 μL of N-methylimidazole was added. While maintaining the liquid temperature at 30°C or below, 0.33 g of triethylamine was added dropwise, and the mixture was allowed to react at room temperature for 2 hours. After the reaction, 50 mL of methanol and 10 mL of water were added to the reaction liquid, and the mixture was cooled to 10°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain a crude product. The obtained crude product was dissolved in 10 mL of acetone, and 50 mL of methanol was added to the solution, and the mixture was cooled to 10°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, yielding 1.37 g of compound (A2-43) as a pale yellow solid (yield 47%).

[0180] The obtained compound (A2-43) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.35 (d, 2H), 8.09 (d, 2H), 7.96-7.92 (m, 3H), 7.87-7.86 (m, 1H), 7. 84-7.80 (m, 2H), 7.58-7.47 (m, 7H), 4.35-4.32 (m, 6H), 3.97-3.85 (m, 12H), 2.64-2.45 (m, 6H)

[0181] [Synthesis of Compound (A2-45)] The reaction scheme for synthesis is as follows.

[0182]

[0183] (Synthesis of Compound (A2-45-a)) Intermediate (A1-10-a) was synthesized in the same manner as for (A1-10-a), except that 4-biphenylboronic acid used in the synthesis of intermediate (A1-10-a) was changed to phenylboronic acid, thereby obtaining intermediate (A2-45-a) as a white solid in a 50% yield.

[0184] (Synthesis of Compound (A2-45)) 2.09 g of intermediate (A2-1-f), 15.0 mL of tetrahydrofuran, and 0.42 g of intermediate (A2-45-a) were placed in a 100 mL three-neck flask, and 13.6 μL of N-methylimidazole was added. While maintaining the liquid temperature at 30°C or below, 0.26 g of triethylamine was added dropwise, and the mixture was allowed to react at room temperature for 3 hours. After the reaction, 1.0 mL of methanol was added to the reaction liquid, and the mixture was stirred at 35°C for 10 minutes. Then, 1.3 mL of 1 N hydrochloric acid and 3.8 mL of water were added and stirred. 65 mL of methanol was added to the stirred solution, and the temperature was lowered to 0°C to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), and 1.60 g of compound (A2-45) was obtained as a white solid (yield: 73%).

[0185] The obtained compound (A2-45) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 7.85-7.73 (m, 8H), 7.54-7.48 (m, 4H), 7.41-7.37 (m, 3H), 4.34-4.31 (m, 6H), 3.96-3.84 (m, 12H), 2.64-2.44 (m, 6H)

[0186] [Synthesis of Compound (A2-46)] The reaction scheme for synthesis is as follows.

[0187]

[0188] A 100 mL three-neck flask was charged with 2.00 g of intermediate (A2-1-f), 10.0 mL of tetrahydrofuran, and 0.33 g of intermediate (A1-10-a), and 8.2 μL of N-methylimidazole was added. Next, 0.26 g of triethylamine was added dropwise while maintaining the liquid temperature at 30°C or below, and the mixture was allowed to react at room temperature for 3 hours. After the reaction, 10.0 mL of methanol was added to the reaction mixture, and the mixture was stirred at room temperature for 30 minutes. An additional 50 mL of methanol was then added, and the mixture was stirred at room temperature for 30 minutes to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, yielding 1.0 g of compound (A2-46) as a white solid (yield 49%).

[0189] The obtained compound (A2-46) １ The H-NMR is shown below. １ H-NMR (solvent: deuterated acetone) δ (ppm): 7.89-7.74 (m, 12H), 7.55-7.49 (m, 4H), 7.42-7.38 (m, 3H), 4.34-4.31 (m, 6H), 3.96-3.84 (m, 12H), 2.65-2.46 (m, 6H)

[0190] [Synthesis of Compound (A2-47)] The reaction scheme for synthesis is as follows.

[0191]

[0192] 2.50 g of intermediate (A2-1-f), 15.0 mL of tetrahydrofuran, and 0.79 g of intermediate (A1-11-a) were placed in a 100 mL three-neck flask, and 16.9 μL of N-methylimidazole was added. While maintaining the liquid temperature at 30°C or below, 0.33 g of triethylamine was added dropwise, and the mixture was allowed to react at room temperature for 3 hours. After the reaction, 10.0 mL of methanol was added to the reaction liquid, and the mixture was stirred at room temperature for 30 minutes. An additional 50 mL of methanol was then added, and the mixture was stirred at 5°C or below for 30 minutes to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, yielding 1.90 g of compound (A2-47) as a white solid (yield 64%).

[0193] The obtained compound (A2-47) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 7.93 (d, 2H), 7.85-7.80 (m, 6H), 7.58-7.53 (m, 4H), 7. 48-7.42 (m, 3H), 7.40-7.37 (m, 2H), 4.34-4.31 (m, 6H), 3.96-3.84 (m, 12H), 2.64-2.44 (m, 6H)

[0194] [Synthesis of Compound (A5-1)] The reaction scheme for the synthesis is as follows.

[0195]

[0196] (Synthesis of Intermediate (A5-1-a) and Intermediate (A5-1-b)) A 200 mL three-neck flask was charged with 15.0 g of 2,2-dimethyl-1,3-dioxolane-4-methanol, 78 mL of ethyl acetate, and 13.8 g of triethylamine. 14.3 g of methanesulfonyl chloride was added dropwise while maintaining the liquid temperature at 20°C or below. The mixture was allowed to react at room temperature for 1 hour, and 50 mL of water was added. The mixture was then separated and the aqueous layer was removed. 20 mL of 0.5 N hydrochloric acid was added to the organic layer, and the mixture was stirred and allowed to stand. The aqueous layer was then removed by separation. The organic layer was washed twice with 20 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain Intermediate (A5-1-a) as a colorless oil.

[0197] Under a nitrogen stream, 2.0 g of 3,4-dihydroxybenzaldehyde, 40 mL of dimethylacetamide, and 18.9 g of cesium carbonate were placed in a 200 mL three-neck flask, and the liquid temperature was raised to 90°C. Next, 6.8 g of intermediate (A5-1-a) was added dropwise, and the dropping funnel was washed with 10 mL of dimethylacetamide. The mixture was reacted at 90°C for 3 hours, and after cooling to room temperature, 70 mL of ethyl acetate and hydrochloric acid (8.0 mL of concentrated hydrochloric acid, 100 mL of water) were added, and the mixture was separated and the aqueous layer was removed. The organic layer was washed with 32 mL of 10% brine, and the solvent was distilled off under reduced pressure to obtain a crude product. The obtained crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), and 3.2 g of colorless oily intermediate (A5-1-b) was obtained (yield 60%).

[0198] (Synthesis of Intermediate (A5-1-c) and Intermediate (A5-1-d)) 13.5 g of Intermediate (A5-1-b) and 100 mL of acetone were placed in a 300 mL three-neck flask, and 1.0 mL of concentrated hydrochloric acid was added dropwise. The mixture was allowed to react at a liquid temperature of 50°C for 40 minutes, and sodium bicarbonate was added to neutralize the mixture. The solvent was concentrated under reduced pressure, and the mixture was purified by silica gel column chromatography (developing solvent: chloroform / methanol), yielding 5.9 g of Intermediate (A5-1-c) as a colorless oil (yield 60%).

[0199] A 200 mL three-neck flask was charged with 2.37 g of intermediate (A5-1-c), 69.0 mL of tetrahydrofuran, and 1.0 mL of dimethylacetamide. 15.0 g of intermediate (A1-3-c) was added dropwise, and the dropping funnel was washed with 3.0 mL of tetrahydrofuran. Next, 3.93 g of pyridine was added dropwise, and the mixture was stirred at room temperature for 2 hours to allow the reaction to proceed. 3.8 mL of methanol was added to the reaction solution, and after stirring at room temperature for 10 minutes, 9.4 mL of 1 N hydrochloric acid, 28.0 mL of water, and 75.0 mL of ethyl acetate were added. After the addition, the mixture was separated and the aqueous layer was removed. The organic layer was washed with 38.0 mL of 10% brine and then dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), yielding 5.47 g of colorless oily intermediate (A5-1-d) (yield: 40%).

[0200] (Synthesis of Intermediate (A5-1-e) and Intermediate (A5-1-f)) 5.58 g of Intermediate (A5-1-d) and 15.2 mL of ethyl acetate were placed in a 100 mL three-neck flask, and a previously prepared aqueous solution (6.0 mL of water, 0.11 g of sodium dihydrogen phosphate, 0.01 g of tetrabutylammonium hydrogen sulfate, and 0.44 g of 30% aqueous hydrogen peroxide) was added. After the addition, the temperature was raised to 30°C, and an aqueous sodium bisulfite solution (0.44 g of sodium bisulfite, 0.96 mL of water) was added dropwise. After the addition, the mixture was reacted at 40°C for 1 hour, and the aqueous layer was removed by liquid separation. 37.3 mL of methanol was added to the resulting organic layer, and the mixture was cooled to a liquid temperature of 5°C or below, and then 0.08 g of phosphoric acid was added dropwise. 30 mL of water was then added, and the mixture was stirred at 5°C or below for 30 minutes to precipitate a solid. The precipitated solid was collected by filtration, and 3.01 g of intermediate (A5-1-e) was obtained as a white solid (yield: 54%).

[0201] 2.20 g of intermediate (A5-1-e), 16.5 μL of dimethylformamide, and 3.2 mL of toluene were added to a 100 mL three-neck flask, and the liquid temperature was raised to 70° C. Next, 123 μL of thionyl chloride was added dropwise, and the mixture was stirred at 70° C. for 1 hour. After stirring, the solvent was distilled off under reduced pressure, yielding intermediate (A5-1-f) as a brown oil.

[0202] (Synthesis of Compound (A5-1)) A 100 mL three-neck flask was charged with 1.92 g of intermediate (A5-1-f), 0.35 g of intermediate (A1-1-a), 8.3 mL of tetrahydrofuran, and 8.3 mL of ethyl acetate, and then 8.9 μL of N-methylimidazole and 234 μL of triethylamine were added dropwise. The mixture was stirred at room temperature for 2 hours, 2.2 mL of methanol was added, and after stirring for 10 minutes, 2.2 mL of 1 N hydrochloric acid was added. The aqueous layer was removed by separation, and the resulting organic layer was washed with 11.0 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 0.96 g of compound (A5-1) as a pale yellow solid (yield: 47%).

[0203] The obtained compound (A5-1) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 7.98 (s, 1H), 7.97-7.90 (m, 3H), 7.81-7.79 (m, 3H), 7.71 (d, 1H), 7.58-7. 54 (m, 2H), 7.50-7.45 (m, 2H), 7.25 (d, 1H) 5.55-5.46 (m, 2H), 4.56-4.38 (m, 16H), 3.76 (s, 3H), 2.75-2.60 (m, 24H)

[0204] [Synthesis of Compound (A5-3)] The reaction scheme for the synthesis is as follows.

[0205]

[0206] A 100 mL three-neck flask was charged with 1.92 g of intermediate (A5-1-f), 0.37 g of intermediate (A1-11-a), 8.3 mL of tetrahydrofuran, and 8.3 mL of ethyl acetate, and then 8.9 μL of N-methylimidazole and 234 μL of triethylamine were added dropwise. The mixture was stirred at room temperature for 2 hours, 2.2 mL of methanol was added, and after stirring for 10 minutes, 2.2 mL of 1 N hydrochloric acid was added. After separation and removal of the aqueous layer, the resulting organic layer was washed with 11.0 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 1.03 g of compound (A5-3) as a pale yellow solid (yield: 50%).

[0207] The obtained compound (A5-3) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.32 (d, 2H), 7.95-7.90 (m, 3H), 7.85-7.80 (m, 7H), 7.59-7.55 (m, 2 H), 7.50-7.40 (m, 5H), 7.26 (d, 1H), 5.55-5.46 (m, 2H), 4.55-4.34 (m, 16H), 2.71-2.59 (m, 24H)

[0208] [Synthesis of Compound (A5-4)] The reaction scheme for synthesis is as follows.

[0209]

[0210] A 100 mL three-neck flask was charged with 0.90 g of intermediate (A5-1-f), 0.15 g of intermediate (A1-10-a), 3.9 mL of tetrahydrofuran, and 3.9 mL of ethyl acetate, and then 4.2 μL of N-methylimidazole and 110 μL of triethylamine were added dropwise. The mixture was stirred at room temperature for 2 hours, 1.0 mL of methanol was added, and after 10 minutes of stirring, 1.0 mL of 1 N hydrochloric acid was added. After separation and removal of the aqueous layer, the organic layer was washed with 5.0 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), yielding 0.42 g of compound (A5-4) as a white solid (yield: 44%).

[0211] The obtained compound (A5-4) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 7.92-7.75 (m, 14H), 7.52-7.48 (m, 2H), 7.41-7.38 ( m, 3H), 7.26 (d, 1H), 5.58-5.49 (m, 2H), 4.57-4.38 (m, 16H), 2.78-2.60 (m, 24H)

[0212] [Synthesis of Compound (A6-1)] The reaction scheme for the synthesis is as follows.

[0213]

[0214] (Synthesis of Intermediate (A6-1-a) and Intermediate (A6-1-b)) Under a nitrogen stream, 5.0 g of methyl 3,4,5-trihydroxybenzoate, 70 mL of dimethylacetamide, and 44.2 g of cesium carbonate were placed in a 200 mL three-neck flask, and the liquid temperature was raised to 90°C. 20.4 g of Intermediate (A5-1-a) was then added dropwise, and the dropping funnel was washed with 10 mL of dimethylacetamide. The mixture was reacted at 90°C for 3 hours, and after cooling to room temperature, 100 mL of ethyl acetate and hydrochloric acid (18.6 mL of concentrated hydrochloric acid, 205 mL of water) were added, followed by separation and removal of the aqueous layer. The resulting organic layer was washed three times with 60 mL of 10% brine, and the solvent was distilled off under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane), to obtain 9.0 g of Compound (A6-1a) as a white solid (yield: 63%).

[0215] A 300 mL three-neck flask was charged with 8.00 g of intermediate (A6-1-a), 57.8 mL of ethanol, and an aqueous potassium hydroxide solution (2.56 g of potassium hydroxide, 21.1 mL of water), and the mixture was stirred at 40°C for 1 hour. After stirring, the mixture was cooled to room temperature, and 96.4 mL of ethyl acetate, 96.4 mL of water, and 3.88 mL of concentrated hydrochloric acid were added and stirred. After stirring, the mixture was separated and the aqueous layer was removed. The resulting organic layer was washed three times with 50 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain 7.49 g of intermediate (A6-1-b) as a white solid (yield 96%).

[0216] (Synthesis of Intermediate (A6-1-c)) 2.00 g of Intermediate (A6-1-b), 1.13 g of Intermediate (A1-1-a), 40 mg of N,N-dimethylaminopyridine, 8.0 mL of chloroform, and 0.87 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride were placed in a 100 mL three-neck flask and stirred at room temperature for 6 hours. The reaction solution was added dropwise to a hydrochloric acid solution (5.0 mL of 1 N hydrochloric acid, 40 mL of water, 90 mL of methanol), and the precipitated solid was collected by filtration and washed with water. The washed solid was reslurried and washed with water and methanol, yielding 2.36 g of Intermediate (A6-1-c) as a white solid (yield 86%).

[0217] (Synthesis of Intermediate (A6-1-d)) 1.75 g of Intermediate (A6-1-c) and 50.0 mL of acetone were placed in a 300 mL three-neck flask, and 22.0 mL of 1 N hydrochloric acid was added dropwise. The mixture was stirred at 50°C for 3 hours to allow the reaction to proceed, and 100 mL of ethyl acetate and 10 mL of methanol were added to the reaction solution, which was then cooled to 5°C or below to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol to obtain a crude product. The obtained crude product was recrystallized with ethyl acetate to obtain 1.26 g of Intermediate (A6-1-d) as a white solid (yield 98%).

[0218] (Synthesis of Compound (A6-1)) 0.92 g of intermediate (A6-1-d), 16.2 mL of dimethylacetamide, and 5.00 g of intermediate (A1-3-c) were placed in a 100 mL three-neck flask, and 1.51 g of pyridine was added dropwise. The mixture was stirred at room temperature for 4 hours to allow the reaction to proceed, and 1.0 mL of methanol was added and stirred for 10 minutes. After stirring, 10.0 mL of 1 N hydrochloric acid, 20.0 mL of water, and 50.0 mL of ethyl acetate were added to the reaction mixture and stirred. After stirring, the mixture was separated and the aqueous layer was removed. The resulting organic layer was washed twice with 20.0 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 1.25 g of compound (A6-1) as a pale yellow oil (yield: 35%).

[0219] The obtained compound (A6-1) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 7.99 (s, 1H), 7.93 (d, 2H), 7.81 (d, 2H), 7.74 (d, 1H), 7. 60-7.49 (m, 6H), 5.53 (m, 2H), 5.40 (m, 1H), 4.62-4.38 (m, 24H), 3.78 (s, 3H), 2.71-2.61 (m, 36H)

[0220] [Synthesis of Compound (A6-3)] The reaction scheme for the synthesis is as follows.

[0221]

[0222] (Synthesis of Intermediate (A6-3-a) and Intermediate (A6-3-b)) Intermediate (A6-1-c) was synthesized in the same manner as for intermediate (A6-1-c), except that intermediate (A1-1-a) used in the synthesis of intermediate (A6-1-c) was changed to intermediate (A1-11-a), and 2.39 g of intermediate (A6-3-a) was obtained as a white solid (yield 88%).

[0223] Intermediate (A6-1-d) was synthesized in the same manner as for intermediate (A6-1-d), except that intermediate (A6-1-c) used in the synthesis of intermediate (A6-1-d) was changed to intermediate (A6-3-a), thereby obtaining 1.52 g of intermediate (A6-3-b) as a white solid (yield 80%).

[0224] (Synthesis of Compound (A6-3)) Compound (A6-3) was synthesized in the same manner as in the synthesis of compound (A6-1), except that intermediate (A6-1-d) used in the synthesis of compound (A6-1) was changed to intermediate (A6-3-b), to obtain 1.25 g of compound (A6-3) as a white solid (yield 77%).

[0225] The obtained compound (A6-3) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.31 (d, 2H), 7.92 (d, 2H), 7.84-7.79 (m, 6H), 7.63- 7.39 (m, 7H), 5.55 (m, 2H), 5.42 (m, 1H), 4.51-4.42 (m, 24H), 2.77-2.62 (m, 36H)

[0226] [Synthesis of Compound (A9-1)] The reaction scheme for the synthesis is as follows.

[0227]

[0228] (Synthesis of Intermediate (A9-1-a)) A 500 mL three-neck flask was charged with 37.31 g of Intermediate (A1-3-e), 73.0 mL of tetrahydrofuran, 73.0 mL of ethyl acetate, and 2.00 g of 3,4-dihydroxybenzaldehyde. 229 μL of N-methylimidazole and 4.40 g of triethylamine were then added dropwise, and the mixture was stirred at room temperature for 2 hours to allow the reaction to proceed. 6.0 mL of methanol and 12.0 mL of 1 N hydrochloric acid were added to the reaction mixture and stirred. After stirring, the mixture was separated and the aqueous layer was removed. The resulting organic layer was washed with 48.0 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 20.2 g of Intermediate (A9-1-a) as a pale yellow oil (yield: 55%).

[0229] (Synthesis of Intermediate (A9-1-b)) 28.0 g of Intermediate (A9-1-a), 77.7 mL of ethyl acetate, 30.8 mL of water, 0.37 g of sodium dihydrogen phosphate, 0.04 g of tetrabutylammonium hydrogen sulfate, and 1.50 g of 30% aqueous hydrogen peroxide were placed in a 500 mL three-neck flask, and the liquid temperature was raised to 30 ° C. Next, an aqueous sodium chlorite solution (1.50 g of sodium chlorite, 3.3 mL of water) was added dropwise, and the mixture was stirred at 40 ° C. for 1 hour to allow the reaction to proceed. The reaction liquid was cooled to 5 ° C., and 0.27 g of phosphoric acid was added, followed by stirring for an additional 20 minutes to precipitate a solid. The precipitated solid was collected by filtration and washed with methanol, yielding 25.3 g of Intermediate (A9-1-b) as a white solid (yield 90%).

[0230] (Synthesis of Intermediate (A9-1-c)) 15.8 g of Intermediate (A9-1-b), 0.05 mL of dimethylformamide, and 19.0 mL of toluene were placed in a 100 mL three-neck flask, and the liquid temperature was raised to 70°C. Next, 0.91 mL of thionyl chloride was added dropwise, and the mixture was reacted at 70°C for 1 hour. After the reaction, the solvent was concentrated under reduced pressure to obtain Intermediate (A9-1-c) as a brown oil.

[0231] (Synthesis of Compound (A9-1)) 2.50 g of intermediate (A9-1-c), 9.0 mL of tetrahydrofuran, 10.8 mL of ethyl acetate, and 0.29 g of intermediate (A1-1-a) were placed in a 100 mL three-neck flask, and 6.7 μL of N-methylimidazole and 0.13 g of triethylamine were added dropwise. The mixture was stirred at room temperature for 2 hours to allow the reaction to proceed, and 1.2 mL of methanol was added and stirred at room temperature for 10 minutes. 1.6 mL of 1 N hydrochloric acid, 4.7 mL of water, and 12.5 mL of ethyl acetate were added to the reaction solution. After stirring, the mixture was separated and the aqueous layer was removed. The resulting organic layer was washed with 10 mL of 10% brine and dried over anhydrous magnesium sulfate. After drying, the desiccant was filtered off, and the filtrate was concentrated under reduced pressure to obtain a crude product. The resulting crude product was purified by silica gel column chromatography (developing solvent: ethyl acetate / hexane) to obtain 1.03 g of compound (A9-1) as a pale yellow solid (yield: 43%).

[0232] The obtained compound (A9-1) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.45 (s, 1H), 8.35-8.29 (m, 3H), 8.04-7.75 (m, 11H), 7.61- 7.48 (m, 4H), 4.49-4.45 (m, 12H), 3.79 (s, 3H), 3.10-2.98 (m, 12H), 2.70-2.53 (m, 24H)

[0233] [Synthesis of Compound (A9-2)] The reaction scheme for synthesis is as follows.

[0234]

[0235] Compound (A9-1) was synthesized in the same manner as in the synthesis of compound (A9-1), except that intermediate (A1-1-a) used in the synthesis of compound (A9-1) was changed to intermediate (A1-3-a), thereby obtaining 1.68 g (yield 69%) of compound (A9-2) as a white solid.

[0236] The obtained compound (A9-2) １ The H-NMR is shown below. １H-NMR (solvent: heavy acetone) δ (ppm): 8.44 (s, 1H), 8.34-8.29 (m, 3H), 7.95-7.80 (m, 9H), 7.58-7.46 (m, 7H), 4.49-4.45 (m, 12H), 3.07-2.98 (m, 12H), 2.80-2.65 (m, 24H)

[0237] [Synthesis of Compound (A9-4)] The reaction formula for the synthesis is as follows.

[0238]

[0239] Compound (A9-4) was synthesized in the same manner as in the synthesis of compound (A9-1), except that intermediate (A1-1-a) used in the synthesis of compound (A9-1) was changed to 4-hydroxybiphenyl, to obtain 1.38 g (yield 61%) of compound (A9-4) as a pale yellow solid.

[0240] The obtained compound (A9-4) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.46 (s, 1H), 8.30 (d, 1H), 7.90-7.89 (m, 5H), 7.81-7.78 (m, 2H), 7.74-7.71 (m , 2H), 7.52-7.48 (m, 4H), 7.40-7.35 (m, 1H), 4.48-4.45 (m, 12H), 3.07-2.98 (m, 12H), 2.80-2.65 (m, 24H)

[0241] [Synthesis of Compound (A15-4)] The reaction formula for the synthesis is as follows.

[0242]

[0243] (Synthesis of Intermediate (A15-4-d)) Intermediate (A1-3-e) was synthesized in the same manner as for intermediate (A1-3-e), except that the raw material nonafluorohexanol was changed to tridecafluorooctanol, to obtain brown oily intermediate (A15-4-d) in a yield of 32%.

[0244] (Synthesis of Compound (A15-4)) Compound (A15-4) was synthesized in the same manner as in the synthesis of compound (A1-3), except that intermediate (A1-3-e) used in the synthesis of compound (A1-3) was changed to intermediate (A15-4-d) and intermediate (A1-3-a) used in the synthesis of compound (A1-3) was changed to 4-methoxyphenol, to obtain compound (A15-4) as a pale yellow solid in a yield of 58%.

[0245] The obtained compound (A15-4) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 7.94 (s, 2H), 7.26 (d, 2H), 7.02 (d, 2H), 4.51-4.47 (m, 6H), 3.83 (s, 3H), 3.10-3.03 (m, 6H), 2.88-2.82 (m, 6H), 2.76-2.64 (m, 6H)

[0246] [Synthesis of Compound (A15-6)] The reaction formula for the synthesis is as follows.

[0247]

[0248] Compound (A15-6) was synthesized as a pale yellow solid in a yield of 65% in the same manner as in the synthesis of compound (A15-4), except that 4-methoxyphenol used as a raw material in the synthesis of compound (A15-4) was changed to ethyl 4-hydroxybenzoate.

[0249] The obtained compound (A15-6) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.14 (s, 2H), 7.97 (s, 2H), 7.50 (d, 2H), 4.53-4.48 (m, 6H) , 4.38 (q, 2H), 3.11-3.04 (m, 6H), 2.88-2.80 (m, 6H), 2.77-2.65 (m, 6H), 1.38 (t.3H)

[0250] [Synthesis of Compound (A15-5)] The reaction formula for the synthesis is as follows.

[0251]

[0252] Compound (A15-5) was synthesized as a pale yellow solid in a yield of 68% in the same manner as in the synthesis of compound (A15-4), except that 4-methoxyphenol used as a raw material in the synthesis of compound (A15-4) was changed to phenyl 4-hydroxybenzoate.

[0253] The obtained compound (A15-5) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.32 (d, 2H), 8.00 (s, 2H), 7.61 (d, 2H), 7.54-7.48 (m, 2H), 7.36 -7.30 (m, 2H), 4.54-4.37 (m, 6H), 3.14-3.08 (m, 6H), 2.90-2.84 (m, 6H), 2.80-2.65 (m, 6H)

[0254] [Synthesis of Compound (A15-7)] The reaction formula for the synthesis is as follows.

[0255]

[0256] Compound (A15-7) was synthesized as a pale yellow solid in a yield of 67% in the same manner as in the synthesis of compound (A15-4), except that 4-methoxyphenyl 4-hydroxybenzoate was used instead of 4-methoxyphenol.

[0257] The obtained compound (A15-7) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.29 (d, 2H), 7.99 (s, 2H), 7.60 (d, 2H), 7.23 (d, 2H), 7.02 (d, 2H) ), 4.52-4.47 (m, 6H), 3.84 (s, 3H), 3.10-3.02 (m, 6H), 2.90-2.82 (m, 6H), 2.79-2.62 (m, 6H)

[0258] [Synthesis of Compound (A15-1)] The reaction formula for the synthesis is as follows.

[0259]

[0260] Compound (A15-1) was obtained as a pale yellow solid in a yield of 63% by synthesis in the same manner as in the synthesis of compound (A15-4), except that 4-methoxyphenol used as a raw material in the synthesis of compound (A15-4) was changed to intermediate (A1-1-a).

[0261] The obtained compound (A15-1) １ The H-NMR is shown below. １ H-NMR (solvent: heavy acetone) δ (ppm): 8.32 (d, 2H), 8.01 (s, 3H), 7.94 (d, 2H), 7.81 (d, 2H), 7.81-7.74 (m, 1H), 7.61-7.53 (m. 3H), 7.49-7.46 (m, 1H), 4.51-4.46 (m, 6H), 3.71 (s, 3H), 3.11-3.03 (m, 6H), 2.85-2.82 (m, 6H), 2.76-2.63 (m, 6H)

[0262] [Preparation of Cured Film] Liquid crystal compositions were prepared using the compound A2-1 synthesized by the above procedure as a liquid crystal alignment promoter, and cured films were formed using the liquid crystal compositions. Specifically, liquid crystal compositions having the following compositions were first prepared. The contents of compound A2-1 were 0.10 parts by mass, 0.20 parts by mass, 0.30 parts by mass, 0.40 parts by mass, and 0.50 parts by mass, based on 100 parts by mass of the total amount of the polymerizable discotic liquid crystal compounds, respectively. ------------------------------------------------ (Liquid crystal composition used in Example 1) -------------------------------------------------- Polymerizable discotic liquid crystal compound M4 described below: 80 parts by mass Polymerizable discotic liquid crystal compound M5 described below: 20 parts by mass Alignment film interface aligning agent 1 described below: 0.55 parts by mass IRGACURE 819 (manufactured by BASF) 3 parts by mass Compound A2-1: The above amount Methyl ethyl ketone (MEK): Amount such that the solids concentration becomes 33% by mass

[0263] Polymerizable discotic liquid crystal compound M4

[0264] Polymerizable discotic liquid crystal compound M5

[0265] Alignment film interface alignment agent 1

[0266] 50 μL of the prepared liquid crystal composition was measured using a micropipette, dropped onto a glass substrate with an alignment film (PVA-103), and spin-coated to form a coating film. The formed coating film was heated at 110°C for 2 minutes, allowed to cool for 1 minute, and then irradiated with ultraviolet light (ultraviolet intensity: 500 mJ / cm) in a nitrogen atmosphere. ２ ) to form a cured film. The film thickness of the cured film was approximately 1.1 μm. The film used in Example 1 was obtained by the above procedure. For other examples, films were obtained in the same manner as in Example 1, except that compound A2-1 was changed to the compound shown in the following paragraph. In Comparative Example 1, a film was obtained in the same manner as in Example 1, except that compound A2-1 was changed to compound C1-1 shown below. Note that compound C1-1 is a compound having a branched perfluoroalkyl group, and does not fall under the category of the present compound described above.

[0267] Compound C1-1

[0268] [Evaluation] The alignment of the cured film of each film obtained from the liquid crystal composition prepared by changing the amount of each compound added was evaluated by haze. Haze was measured using a haze meter NDH2000 manufactured by Nippon Denshoku Co., Ltd. The alignment of the cured film was evaluated based on the haze value of the cured film according to the following criteria. A large haze value corresponds to disordered alignment of the liquid crystal compound. A: Less than 0.15% B: 0.15% or more and less than 0.35% C: 0.35% or more and less than 0.90% D: 0.90% or more

[0269] <Results> The evaluation results are shown in Table 1. The compound numbers shown in Table 1 correspond to the compounds shown as examples of the present compound. In Table 1, the percentages shown in the "Haze evaluation" column indicate the mass percentage of the content of each compound relative to the total mass of the polymerizable discotic liquid crystal compounds.

[0270]

[0271] The results in Table 1 show that when a compound having a branched-chain perfluoroalkyl group is used as a liquid crystal alignment promoter, the alignment of the liquid crystal compound is disturbed, but when this compound is used as a liquid crystal alignment promoter, the disturbance of the alignment of the liquid crystal compound is suppressed. A comparison of Examples 1, 7, and 11 with Examples 10 and 18 confirmed that when the number of Rfs contained in formula (11) is 3 or 4, the disturbance of the alignment of the liquid crystal compound is further suppressed. A comparison of Example 7 with Example 23 confirmed that when the number of carbon atoms in the linear perfluoroalkyl group is 4 and each Rf in formula (11) has the same structure, the disturbance of the alignment of the liquid crystal compound is further suppressed (particularly when the amount of this compound added is large). A comparison of Example 23 with Examples 19 to 22 confirmed that when r1 is 2 or more or r1 is 1 and X １３ It has been confirmed that when is a divalent aromatic ring group having a plurality of ring structures, the disorder of the alignment of the liquid crystal compound is further suppressed.

[0272] <Film Having a Cured Film with a Fixed Cholesteric Liquid Crystal Phase> Using the present compound, a film having a cured film with a fixed cholesteric liquid crystal phase was produced. Specifically, a liquid crystal composition containing a polymerizable liquid crystal compound was first applied to a support, and a predetermined treatment was performed to form a cholesteric liquid crystal layer (a cured film with a fixed cholesteric liquid crystal phase). A liquid crystal composition containing a polymerizable liquid crystal compound and a liquid crystal alignment promoter was applied to the formed cholesteric liquid crystal layer, and a predetermined treatment was performed to form a cholesteric liquid crystal layer. The same treatment was repeated to obtain a film. Each liquid crystal composition and the method for forming the cholesteric liquid crystal layer are described below.

[0273] [Liquid Crystal Composition] The liquid crystal compositions shown below are all liquid crystal compositions for forming a cholesteric liquid crystal layer. Note that liquid crystal compositions with symbols containing "R" refer to liquid crystal compositions containing a polymerizable rod-shaped liquid crystal compound, and liquid crystal compositions with symbols containing "D" refer to liquid crystal compositions containing a polymerizable discotic liquid crystal compound.

[0274] (Liquid Crystal Composition R-1) The components shown below were dissolved by stirring in a container kept at 70° C. to prepare a liquid crystal composition R-1.

[0275] Liquid crystal composition R-1 --------------------------------------------------- Methyl ethyl ketone 176.9 parts by mass Cyclohexanone 44.2 parts by mass Polymerizable rod-shaped liquid crystal compound A1 (mixture) 50.0 parts by mass Polymerizable rod-shaped liquid crystal compound A2 50.0 parts by mass Photopolymerization initiator B 1.00 part by mass Chiral agent A1 3.00 parts by mass Liquid crystal alignment promoter F1 0.06 parts by mass

[0276] Polymerizable rod-shaped liquid crystal compound A1 (mixing ratio is by mass)

[0277] Polymerizable rod-shaped liquid crystal compound A2

[0278] Photopolymerization initiator B

[0279] Chiral agent A1

[0280] The chiral agent A1 is a chiral agent (chiral agent A) whose helical twisting power (HTP) is reduced by light.

[0281] Liquid crystal alignment promoter F1 (ratio of repeating units is by mass)

[0282] (Liquid Crystal Composition R-2) Liquid crystal composition R-2 was prepared in the same manner as liquid crystal composition R-1, except that the amount of chiral agent A added was changed to 3.63 parts by mass and the amount of liquid crystal alignment promoter F1 added was changed to 0.15 parts by mass.

[0283] (Liquid Crystal Composition D-1) The components shown below were dissolved by stirring in a container kept at 50°C to prepare a liquid crystal composition D-1.

[0284] Liquid crystal composition D-1 ------------------------------------------------ Polymerizable discotic liquid crystal compound (A) 80 parts by mass Polymerizable discotic liquid crystal compound (B) 20 parts by mass Polymerizable monomer E1 4 parts by mass The above compound (A5-1) 0.06 parts by mass Photopolymerization initiator (Irgacure 907, manufactured by BASF) 3 parts by mass Pyridinium salt A 0.1 parts by mass Boronic acid monomer A 3 parts by mass The above chiral agent A1 4.00 parts by mass Methyl ethyl ketone 151 parts by mass Cyclohexanone 37 parts by mass

[0285] Discotic Liquid Crystal Compound (A)

[0286] Discotic Liquid Crystal Compound (B)

[0287] Polymerizable Monomer E1

[0288]

[0289] Pyridinium salt A

[0290] Boronic Acid Monomer A

[0291] (Liquid Crystal Composition D-2) Liquid crystal composition D-2 was prepared in the same manner as liquid crystal composition D-1, except that the amount of chiral dopant A added was changed to 5.28 parts by mass.

[0292] [Film Preparation Procedure] A film was obtained by the following procedure.

[0293] A 50 μm thick PET (polyethylene terephthalate) film (A4100, manufactured by Toyobo Co., Ltd.) was prepared as a temporary support. This PET film had an easy-adhesion layer on one side. The side of the PET film without the easy-adhesion layer was subjected to a rubbing treatment, and the liquid crystal composition R-1 was applied with a wire bar coater to form a coating film. The coating film was then dried at 110° C. for 120 seconds. Thereafter, the coating film was kept at 80° C. and exposed to ultraviolet light (illuminance 100 mW / cm ) from a metal halide lamp in a nitrogen atmosphere (oxygen concentration 100 ppm or less). ２ , irradiation amount 250mJ / cm ２ ) to fix the alignment direction of the liquid crystal compound, thereby forming a cholesteric liquid crystal layer 1 on the PET film. The ultraviolet light irradiation was performed from the coated film side. The amount of liquid crystal composition R-1 applied was adjusted so that the thickness of the formed cholesteric liquid crystal layer 1 would be 4.5 μm. The cholesteric liquid crystal layer 1 was a cholesteric liquid crystal layer that reflected red light (center wavelength of reflected light: 650 nm).

[0294] Next, a discharge amount of 150 W·min / m was applied to the surface of the cholesteric liquid crystal layer 1 opposite to the PET film side. ２ After corona treatment, liquid crystal composition D-1 was applied to the corona-treated surface using a wire bar coater to form a coating film. The coating film was then dried at 70°C for 2 minutes, and then heat-aged at 103°C for 3 minutes to obtain a uniform alignment state. Thereafter, the coating film was kept at 45°C and aged under ultraviolet light (illuminance 100 mW / cm) from a metal halide lamp in a nitrogen atmosphere (oxygen concentration 100 ppm or less). ２ , irradiation amount 250mJ / cm ２ ) to fix the alignment direction of the liquid crystal compound, thereby forming a cholesteric liquid crystal layer 2 on the cholesteric liquid crystal layer 1. The ultraviolet light irradiation was performed from the coated film side. The amount of liquid crystal composition D-1 applied was adjusted so that the thickness of the formed cholesteric liquid crystal layer 2 would be 3.3 μm. The cholesteric liquid crystal layer 2 was a cholesteric liquid crystal layer that reflected yellow light (center wavelength of reflected light: 600 nm).

[0295] Next, the liquid crystal composition R-2 was applied to the surface of the cholesteric liquid crystal layer 2 opposite to the PET film side using a wire bar coater to form a coating film, and the coating film was then dried at 110°C for 120 seconds. Thereafter, the coating film was kept at 80°C and irradiated with ultraviolet light (illuminance 100 mW / cm) from a metal halide lamp in a nitrogen atmosphere (oxygen concentration 100 ppm or less). ２ , irradiation amount 250mJ / cm ２ ) to fix the alignment direction of the liquid crystal compound, thereby forming a cholesteric liquid crystal layer 3 on the cholesteric liquid crystal layer 2. The ultraviolet light irradiation was carried out from the coated film side. The amount of liquid crystal composition R-2 applied was adjusted so that the thickness of the formed cholesteric liquid crystal layer 3 would be 2.7 μm. The cholesteric liquid crystal layer 3 was a cholesteric liquid crystal layer that reflected green light (center wavelength of reflected light: 550 nm).

[0296] Next, a discharge amount of 150 W·min / m was applied to the surface of the cholesteric liquid crystal layer 3 opposite to the PET film side. ２ After corona treatment, liquid crystal composition D-2 was applied to the corona-treated surface using a wire bar coater to form a coating film. The coating film was then dried at 70°C for 2 minutes, and then heat-aged at 100°C for 3 minutes to obtain a uniform alignment state. Thereafter, the coating film was kept at 45°C and irradiated with ultraviolet light (illuminance 100 mW / cm) from a metal halide lamp in a nitrogen atmosphere (oxygen concentration 100 ppm or less). ２ , irradiation amount 250mJ / cm ２ ) to fix the alignment direction of the liquid crystal compound, thereby forming a cholesteric liquid crystal layer 4 on the cholesteric liquid crystal layer 3. The ultraviolet light irradiation was carried out from the coated film side. The amount of liquid crystal composition D-2 applied was adjusted so that the thickness of the formed cholesteric liquid crystal layer 4 would be 2.5 μm. The cholesteric liquid crystal layer 4 was a cholesteric liquid crystal layer that reflects blue light (central wavelength of reflected light: 460 nm). Using the above procedure, a film having a cured film in which a cholesteric liquid crystal phase was fixed was obtained.

[0297] <Evaluation> [Reflectance] The reflectance of the film was measured using a spectrophotometer (V-550, manufactured by JASCO Corporation). The reflectance was measured at the center wavelength of the reflected light from each of the cholesteric liquid crystal layers 1 to 4. The reflectance was 49% at the center wavelength of the reflected light from each of the cholesteric liquid crystal layers 1 to 4.

[0298] <Evaluation of Image Sharpness> The lenses of a virtual reality display device "Huawei VR Glass" manufactured by Huawei, which is a virtual reality display device employing a reciprocating optical system, were disassembled, and the lens closest to the viewing side was removed. This lens was a plano-convex lens with a convex surface on the viewing side, and a reflective circular polarizer was attached to the flat surface side. The reflective circular polarizer was peeled off from this lens, and optical laminate sheet 1, the production method of which will be described later, was attached to the flat surface side so that the absorptive polarizer side was the viewing side. The lens with optical laminate sheet 1 attached was reassembled into the main body, and a virtual reality display device was produced.

[0299] In the virtual reality display device produced, a black and white checkered pattern was displayed on the image display device, and the degree of image sharpness was visually evaluated according to the following criteria. If the image sharpness is poor, part or all of the checkered pattern appears distorted. A: The distortion of the checkered pattern is barely noticeable. B: The distortion of the checkered pattern is slightly noticeable, but not bothersome. C: The distortion of the checkered pattern is clearly noticeable. When the virtual reality display device obtained by the above procedure was evaluated, it was rated A.

[0300] (Preparation of Optical Laminated Sheet) Optical laminated sheet 1 was prepared using the above film.

[0301] First, an ultraviolet-curing adhesive "Aronix UVX-6282" manufactured by Toagosei Co., Ltd. was applied to an anti-reflection film "AR200-T0810-JD" manufactured by Dexerials Corporation. Next, the film and the anti-reflection film were bonded together so that the cholesteric liquid crystal layer 4 of the film faced the applied adhesive layer, and in this bonded state, ultraviolet light (300 mJ / cm) was irradiated. ２) to cure the adhesive. After the adhesive was cured, the PET film of the film was peeled off and removed to obtain a laminate sheet. The laminate sheet had an anti-reflection film, an adhesive layer, cholesteric liquid crystal layer 4, cholesteric liquid crystal layer 3, cholesteric liquid crystal layer 2, and cholesteric liquid crystal layer 1, in this order. The thickness of the adhesive layer after curing was 35 μm. The refractive index of the adhesive layer after curing was 1.48.

[0302] A λ / 4 retarder was attached to the surface of the laminate sheet facing the cholesteric liquid crystal layer 1 with the adhesive, and an absorptive polarizer was attached to the surface of the λ / 4 retarder opposite the cholesteric liquid crystal layer 1 with the adhesive. When attaching the absorptive polarizer, the orientation was adjusted so that the slow axis of the λ / 4 retarder formed a 45° angle with the absorption axis of the absorptive polarizer. The thickness of the adhesive layer after curing was 35 μm. Next, a pressure-sensitive adhesive sheet "NCF-D692(15)" manufactured by Lintec Corporation was attached to the absorptive polarizer to obtain an optical laminate sheet 1. The optical laminate sheet 1 had, in this order, an antireflection film, an adhesive layer, a cholesteric liquid crystal layer 4, a cholesteric liquid crystal layer 3, a cholesteric liquid crystal layer 2, a cholesteric liquid crystal layer 1, an adhesive layer, a λ / 4 retarder, an adhesive layer, an absorptive polarizer, and an adhesive sheet. The optical laminated sheet 1 thus obtained had a thickness of 1 m or less and a thickness of 1 m or less. ２ The winning bid was 90.

[0303] The obtained optical laminate sheet 1 was cut into a circle with a diameter of 35 mm using a picosecond laser processing machine. Furthermore, a part of the edge was cut off to create a notch so as to represent the absorption axis orientation of the absorptive polarizer. During processing, the processing conditions were adjusted so that the angle of the cut edge surface was 5° or less with respect to the vertical direction of the optical laminate sheet 1.

[0304] <Evaluation of ghosting> A black and white checkered pattern was displayed on the virtual reality display device produced for the evaluation of image sharpness, and the degree of ghosting was visually evaluated according to the following criteria. When ghosting occurs, a double image is visible and the contrast of the part where the double image is visible decreases. A: The double image is barely visible B: The double image is slightly visible but not bothersome C: The double image is clearly visible When the virtual reality display device obtained by the above procedure was evaluated, it was rated A.

Claims

1. A compound represented by the following formula (11): 【Chemistry 1】 In formula (11), Rf represents a linear perfluoroalkyl group. In formula (11), p1 represents an integer of 1 to 3. In formula (11), A １１ each independently represents a hydrocarbon group having a valence of p1+1. The hydrocarbon group may contain one or more atoms selected from the group consisting of oxygen atoms and nitrogen atoms. In formula (11), q1 represents an integer of 2 to 4. In formula (11), X １２ represents a q1+1 valent aromatic ring group. In formula (11), X １３ each independently represents a divalent aromatic ring group which may have a substituent. In formula (11), L １３ and L １４ each independently represents a single bond, —CO—, —COO—, or —CONR １ -, -O-, -(CH ２ ) ｎ -, -(CH ２ ) ｎ -O-, -O-(CH ２ ) ｎ -, -CO-CH=CH-, -COO-(CH ２ ) ｎ - or -C≡C-. １ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and n represents an integer of 1 to 3. In formula (11), r1 represents an integer of 0 to 4. １４ -COO-CH ２ If -, then r1 represents 0. In formula (11), X １４ is -CN, -R ２ , -OR ２ , -OH, -(CH ２ ) ｍ -OH, -F, or -COOR ２ represents an optionally substituted monovalent aromatic ring group or a group having the following structure: １４ represents the bonding position with 【Chemistry 2】 R ２ represents a linear or branched alkyl group having 1 to 20 carbon atoms; and m represents an integer of 1 to 3.

2. The compound described in claim 1, wherein the linear perfluoroalkyl group has 2 or more carbon atoms.

3. the linear perfluoroalkyl group has 2 to 8 carbon atoms, The compound according to claim 1, wherein when two or more Rfs are contained in the formula (11), each Rf represents the same group.

4. The compound according to claim 1, wherein, in the formula (11), the number of Rf contained is 2 to 9.

5. The compound according to claim 1, wherein, in the formula (11), the number of Rfs contained is 3 to 6.

6. The compound according to claim 1 , wherein the number of Rfs contained in the formula (11) is 3 or 4.

7. the linear perfluoroalkyl group has 4 carbon atoms, The compound according to claim 5 , wherein, in said formula (11), each Rf has the same structure.

8. The compound according to claim 1, wherein in the formula (11), r1 is 1 to 4.

9. In the formula (11), r1 is 2 or more, r1 is 1 and X １３ The compound according to claim 1 , wherein is a divalent aromatic ring group having a multiple ring structure.

10. The compound according to claim 1, wherein R 2 represents a linear or branched alkyl group having 1 to 8 carbon atoms.

11. The compound described in claim 1, wherein the hydrocarbon group is a linear or branched aliphatic hydrocarbon structure, an aromatic hydrocarbon structure, or a structure formed by combining these structures.

12. The compound according to claim 1, which is a compound represented by the following formula (12): 【Chemistry 3】 In formula (12), Rf represents a linear perfluoroalkyl group. In formula (12), p2 represents an integer of 1 to 3. In formula (12), X 21 represents a single bond, a p2+1 valent aromatic ring group, or a p2+1 valent aliphatic hydrocarbon group having 3 to 10 carbon atoms. In formula (12), L 21 represents a divalent linking group represented by the following formulae (2-1) to (2-4). 【Chemistry 4】 In formulas (2-1) to (2-4), p represents an integer of 1 to 3. In formulae (2-1) to (2-4), ** represents the bonding position to X 21 , and * represents the bonding position to Rf. In formula (12), q2 represents an integer of 2 to 4. In formula (12), X 22 represents a q2+1-valent aromatic ring group. In formula (12), X 23 each independently represents a divalent aromatic ring group which may have a substituent. In formula (12), L 22 , L 23 and L 24 each independently represent a single bond, -CO-, -COO-, -CONR 1 -, -O-, -(CH 2 ) n -, -(CH 2 ) n -O-, -O-(CH 2 ) n -, -CO-CH═CH-, -COO-(CH 2 ) n - or -C≡C-. R 1 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms. n represents an integer of 1 to 3. In formula (12), r2 represents an integer of 0 to 4, provided that when L 24 is —CO—O—CH 2 —, r2 represents 0. In formula (12), X 24 represents a monovalent aromatic ring group which may be substituted with -CN, -R 2 , -OR 2 , -OH, -(CH 2 ) m -OH, -F, or -OCOOR 2 . R 2 represents a linear or branched alkyl group having 1 to 20 carbon atoms. m represents an integer of 1 to 3.

13. A liquid crystal alignment promoter comprising the compound according to claim 1.

14. A liquid crystal composition comprising the compound according to any one of claims 1 to 12 and a polymerizable liquid crystal compound.

15. The liquid crystal composition according to claim 14, wherein the polymerizable liquid crystal compound is selected from the group consisting of polymerizable rod-like liquid crystal compounds and polymerizable discotic liquid crystal compounds.

16. The liquid crystal composition according to claim 14 , further comprising a chiral agent.

17. A cured product obtained by polymerizing the liquid crystal composition according to claim 14.

18. A film comprising the cured product according to claim 17.

19. 20. The film of claim 18, which exhibits optical anisotropy.

20. A film obtained by polymerizing the liquid crystal composition according to claim 14, in which a cholesteric liquid crystal phase is fixed.

21. 21. The film of claim 20 which reflects infrared light.

22. 21. The film of claim 20 which reflects visible light.

Images