Composition, optically anisotropic film, and compound

Abstract

The present invention addresses the problem of providing a composition capable of forming an optically anisotropic film in which visibility unevenness and alignment unevenness are suppressed. A composition according to the present invention contains: a silicon-containing compound selected from the group consisting of compounds A that satisfy requirements (a1)-(a3) and compounds B that satisfy requirements (b1)-(b4); and a liquid crystal compound.　Requirement (a1): The value obtained by dividing the total number of methyl groups bound to a silicon atom within the molecule by the molecular weight of the compound is 0.0140 or more. Requirement (a2): Being represented by A-(Za1-Ya1-(Xa1)m)n. Requirement (a3): Having a molecular weight of 500-8000.　Requirement (b1): The value obtained by dividing the total number of methyl groups bound to a silicon atom within the molecule by the molecular weight of the compound is 0.0140 or more. Requirement (b2): Having two or more groups represented by -Lb1-Xb1. Requirement (b3): Having a partial structure represented by *-(Zb1-Yb1)s-Wb1. Requirement (b4): Having a molecular weight of 500-8000.

Description

Composition, optically anisotropic film, compound

[0001] The present invention relates to a composition, an optically anisotropic film, and a compound.

[0002] Optically anisotropic films formed by using a composition containing a liquid crystal compound and orienting the liquid crystal compound in a predetermined orientation state are used in various applications such as optical compensation sheets. The composition containing a liquid crystal compound may contain an alignment agent that can regulate the alignment of the liquid crystal compound from the air interface side, where the alignment regulation force from the support side is weaker. As such alignment agents, fluorine-based alignment agents having perfluoroalkyl chains, which have low surface free energy and tend to be unevenly distributed on the surface, have traditionally been widely used. However, in recent years, PFAS-free alternative materials have been required from the perspective of environmental pollution, and silicon-based alignment agents are expected to be such alternatives.

[0003] For example, Patent Document 1 discloses a liquid crystal compound having a silicon-containing moiety, which is a compound having a predetermined silicon-containing structural moiety and a predetermined mesogenic moiety.

[0004] Japanese Patent Application Publication No. 8-113577

[0005] The performance required for such an alignment agent includes suppressing visual unevenness in a film formed from a composition containing such an alignment agent, and suppressing alignment unevenness of a liquid crystal compound. The visual unevenness refers to a phenomenon in which color unevenness is visually recognized due to uneven film thickness, etc. When the present inventors formed an optically anisotropic film using the compound described in the above document, they were unable to achieve both suppression of visual unevenness and suppression of alignment unevenness.

[0006] Therefore, an object of the present invention is to provide a composition capable of forming an optically anisotropic film in which visual unevenness and alignment unevenness are suppressed. Another object of the present invention is to provide an optically anisotropic film formed from the composition, and a compound related to the composition.

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

[0008] [1] A composition comprising a silicon-containing compound selected from the group consisting of compound A satisfying requirements (a1) to (a3) ​​described below and compound B satisfying requirements (b1) to (b4) described below, and a liquid crystal compound. [2] The composition according to [1], wherein compound A is a compound represented by formula (A2) described below or a compound represented by formula (A3) described below. [3] The composition according to [1] or [2], wherein compound B is a compound represented by formula (B1) described below. [4] In formula (A2) described below, when Y ａ３ is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-, and in formula (A3) described below, the site bonding to the aromatic ring constituting the aromatic ring group in substituent T is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-. [5] An optically anisotropic film formed using the composition described in any one of [1] to [4]. [6] A compound satisfying requirements (a1) to (a3) ​​described below. [7] The compound described in [6], which is represented by formula (A2) or formula (A3) described below. [8] In formula (A2) above, in substituent T, Y ａ３

[0023] The compound according to [7], wherein the site bonding to the group represented by formula (A3) below is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-, and the site bonding to the aromatic ring constituting the aromatic ring group in substituent T in formula (A3) below is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-. [9] A compound satisfying requirements (b1) to (b4) below.

[10] The compound according to [9], which is represented by formula (B1) below.

[0009] According to the present invention, there is provided a composition capable of forming an optically anisotropic layer in which visibility unevenness and alignment unevenness are suppressed. Furthermore, according to the present invention, there are also provided an optically anisotropic film and a compound related to the composition.

[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] In this specification, a numerical range expressed using "to" means a range that includes the numerical values ​​written before and after "to" as the lower and upper limits. Furthermore, in this specification, when two or more types of a certain component are present, the "content" of that component means the total content of those two or more components. In this specification, in a numerical range described in stages, the upper or lower limit value described in a certain numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. Furthermore, in a numerical range described in this specification, the upper or lower limit value described in a certain numerical range may be replaced with a value shown in the Examples. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment.

[0012] In this specification, when there are multiple substituents and linking groups, etc. (hereinafter referred to as substituents, etc.) represented by a specific symbol, or when multiple substituents, etc. are simultaneously defined, this means that the respective substituents, etc. may be the same or different from each other. The same applies to the definition of the number of substituents, etc. In this specification, the bonding direction of a divalent group (e.g., -CO-O-) represented is not limited unless otherwise specified. For example, when Y is -CO-O- in a compound represented by the formula "X-Y-Z", the compound may be "X-O-CO-Z" or "X-CO-O-Z".

[0013] In this specification, the solid content of the composition refers to components that form a film (e.g., a cured product, a film, etc.), and does not include solvents. The film-forming component referred to here may be a component whose chemical structure changes as a result of reaction (polymerization) when forming the film. Furthermore, a film-forming component is considered to be a solid content even if it is in a liquid state.

[0014] In this specification, unless otherwise specified, when a molecular weight distribution exists, the molecular weight is the weight average molecular weight (Mw). In this specification, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are values ​​determined by gel permeation chromatography (GPC) in terms of polystyrene.

[0015] In this specification, Re(λ) and Rth(λ) represent the in-plane retardation and the thickness direction retardation, respectively, at a wavelength λ. Unless otherwise specified, the wavelength λ is 550 nm. In this specification, Re(λ) and Rth(λ) are values ​​measured at a wavelength λ using an AxoScan OPMF-1 (manufactured by Optoscience). Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and the film thickness (d (μm)) into the AxoScan OPMF-1, the following slow axis direction (°) is calculated: Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d. Although R0(λ) is displayed as a numerical value calculated by the AxoScan OPMF-1, it means Re(λ).

[0016] [Composition] The composition of the present invention (hereinafter also referred to simply as "composition") contains a silicon-containing compound selected from the group consisting of compound A satisfying requirements (a1) to (a3) ​​and compound B satisfying requirements (b1) to (b4) described below, and a liquid crystal compound.

[0017] While the reason why the composition having the above-described configuration can solve the problem of the present invention is not entirely clear, the inventors speculate as follows. The following speculation does not limit the mechanism by which the effect is obtained. In other words, even if the effect is obtained by a mechanism other than the one described below, it is still within the scope of the present invention. When forming an optically anisotropic film using a composition containing a liquid crystal compound, including a specific silicon-containing compound selected from Compound A and Compound B can suppress visual unevenness and alignment unevenness. Specifically, as shown in requirements (a2) and (b2), the silicon-containing compound has a silicon-containing moiety that tends to be unevenly distributed on the coating film surface. Furthermore, as shown in requirements (a1) and (b1), the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is equal to or greater than a predetermined value. Furthermore, as shown in requirements (a3) ​​and (b4), the specific compound has a predetermined molecular weight. This allows the silicon-containing compound to efficiently unevenly distribute on the coating film surface, thereby efficiently reducing the surface tension of the composition on the surface. As a result, it is speculated that visual unevenness in the formed film is suppressed. Furthermore, the silicon-containing compound can contribute to the alignment of the liquid crystal compound by having a structure including a predetermined linking group and a ring structure as shown in requirement (a2) and requirement (b3). Furthermore, as described above, the silicon-containing compound is efficiently distributed unevenly on the surface, so that it does not become scattered among the liquid crystal compounds within the layer and disrupt the alignment. As a result, it is presumed that alignment unevenness in the formed film can also be suppressed. Hereinafter, the ability to form an optically anisotropic film in which visible unevenness is suppressed is simply referred to as "excellent visibility unevenness suppression performance," the ability to form an optically anisotropic film in which alignment unevenness is suppressed is simply referred to as "excellent alignment unevenness suppression performance," and the ability to form an optically anisotropic film in which at least one of visible unevenness and alignment unevenness is further suppressed is simply referred to as "excellent effects of the present invention."

[0018] Each component contained in the composition will be described in detail below.

[0019] [Silicon-Containing Compound] The composition contains a silicon-containing compound selected from the group consisting of Compound A and Compound B.

[0020] <Compound A> Compound A satisfies requirements (a1) to (a3). (a1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. (a2) It is represented by formula (A1). Formula (A1) A-(Z ａ１ -Y ａ１ -(X ａ１ ) ｍ ) ｎ In formula (A1), A represents an aromatic ring or an aliphatic ring which may have a substituent; １ -L Ａ -A ２ A represents a group represented by the formula: １ and A ２ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. Ａ is -C≡C- or -CH ２ - represents Z ａ１ are each independently a chain alkylene group, —O—, —CO—, or a chain alkylene group, —O—, —CO—, and —NR Ｎ represents a group formed by combining two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ａ１ each independently represents a silicon-containing group having an Si—O—Si structure. n represents an integer of 2 or greater. each independently represents an integer of 1 or greater. (a3) ​​The molecular weight is 500 to 8,000. Each requirement will be described in detail below.

[0021] (Requirement (a1)) (a1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. If the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is less than 0.0140, the silicon-containing compound will be less unevenly distributed on the coating film surface, and alignment unevenness and visibility unevenness will be poor, which is undesirable. The value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound can be calculated specifically by the formula: (total number of methyl groups directly bonded to silicon atoms) / (molecular weight). For example, if the molecular weight of the compound is 2000.00 and the compound has a structure in which silicon atoms and methyl groups are bonded, such as -Si(CH ３ ) ３ In the case where the compound has only four structures, the number of methyl groups bonded to silicon atoms is 12, and therefore the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is 12 / 2000.00 = 0.006.

[0022] In compound A, the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is preferably 0.0140 to 0.0280, more preferably 0.0140 to 0.0245, even more preferably 0.0150 to 0.0245, and particularly preferably 0.0170 to 0.0245, in terms of better effects of the present invention.

[0023] (Requirement (a2)) (a2) is represented by formula (A1). Formula (A1) A-(Z ａ１ -Y ａ１ -(X ａ１ ) ｍ ) ｎ

[0024] In formula (A1), A represents an aromatic ring or an aliphatic ring which may have a substituent; １ -L Ａ -A ２ A is an aromatic ring which may have a substituent or a group represented by the formula: １ -L Ａ -A ２A group represented by the formula (I) is preferred, and an aromatic ring optionally having a substituent is more preferred. The number of ring atoms in the aromatic ring is preferably 5 to 10, more preferably 5 or 6. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocycle, and an aromatic hydrocarbon ring is preferred. The number of heteroatoms in the aromatic heterocycle is preferably 4 or less, more preferably 2 or less. In particular, in terms of superior alignment unevenness suppression performance, it is preferred that the number of nitrogen atoms in the aromatic heterocycle is 2 or less. The aromatic ring may be a monocycle or a condensed ring, or may have a structure in which two aromatic rings are linked by a single bond. The number of condensed rings in the condensed ring is preferably 2 or 3, more preferably 2. A structure in which two aromatic rings are linked by a single bond is more specifically a structure represented by Ar-Ar (Ar is an aromatic ring), and examples thereof include a biaryl structure. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthroline ring, and a biphenyl ring. Examples of the aromatic heterocycle include a pyridine ring, a pyridazine ring, an imidazole ring, a thiophene ring, a quinoline ring, an isoquinolylene ring, an oxazole ring, a thiazole ring, an oxadiazole ring, a benzothiazole ring, a benzothiadiazole ring, a phthalimide ring, a thienothiazole ring, a thiazolothiazole ring, a thienothiophene ring, and a thienoxazole ring. The aromatic ring is preferably a benzene ring, a naphthalene ring, or a biphenyl ring, and more preferably a benzene ring. The number of ring atoms in the aliphatic ring is preferably 5 to 10, more preferably 5 or 6. The aliphatic ring may be either an aliphatic hydrocarbon ring or an aliphatic heterocycle, and is preferably an aliphatic hydrocarbon ring. The aliphatic ring may be a monocycle, a condensed ring, or a structure in which two aliphatic rings are linked by a single bond. The number of condensed rings in the condensed ring is preferably 2 or 3, and more preferably 2. More specifically, the structure in which two aliphatic rings are linked by a single bond is a structure represented by Cy-Cy (Cy is an aliphatic ring), and examples thereof include a bicycloalkane structure.Examples of the aliphatic hydrocarbon ring include a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclononane ring, a cyclododecane ring, a cyclodocosane ring, and a bicyclohexane ring. Examples of the aliphatic heterocycle include a pyrrolidine ring, an oxolane ring, a thiolane ring, a piperidine ring, a tetrahydropyran ring, a thiane ring, a piperazine ring, and a morpholine ring. Examples of the aliphatic ring include a cyclohexane ring or a bicyclohexane ring, and a cyclohexane ring is more preferred. Examples of the substituent that the aromatic ring and the aliphatic ring may have include an alkyl group which may have a halogen atom, a silicon-containing group having a Si—O—Si structure, an alkyl ester group, an acyl group, an alkoxy group, an alkylthio group, an alkyloxycarbonyl group, a carbamoyl group, an acylamino group, a halogen atom, a cyano group, and a nitro group, with an alkyl group, a silicon-containing group having a Si—O—Si structure, an alkyl ester group, an alkoxy group, or an acyl group being preferred, a linear alkyl group having 1 to 4 carbon atoms, a silicon-containing group having a Si—O—Si structure, a methyl ester group, a methoxy group, or an acetyl group being more preferred, and a methyl group, an ethyl group, a methoxy group, or a methyl ester group being even more preferred. The definition and preferred embodiments of the silicon-containing group having a Si—O—Si structure will be described later. ａ１ is the same as the group represented by １ and A ２ Each independently represents an aromatic ring or an aliphatic ring which may have a substituent. The definitions and preferred embodiments of the aromatic ring which may have a substituent and the aliphatic ring which may have a substituent are the same as those of the aromatic ring which may have a substituent and the aliphatic ring which may have a substituent represented by A. １ and A ２ is preferably a monocyclic ring or a fused ring, and more preferably a monocyclic ring. Ａ is -C≡C- or -CH ２ - represents A １ -L Ａ -A ２ When A is a group represented by １ At least one -Z ａ１ -Y ａ１ -(Xａ１ ) ｍ and A ２ At least one -Z ａ１ -Y ａ１ -(X ａ１ ) ｍ It is preferable that the aryl group is bonded to a group represented by the following formula:

[0025] In formula (A1), Z ａ１ are each independently a chain alkylene group, —O—, —CO—, or a chain alkylene group, —O—, —CO—, and —NR Ｎ - represents a group formed by combining two or more selected from the group consisting of ａ１ represents a chain alkylene group, —O—, or —CO—, or represents a chain alkylene group, —O—, —CO—, and —NR Ｎ represents a group formed by combining two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ When the group represented by R is the above group, the alignment of the liquid crystal compound is less likely to be disturbed, and the alignment unevenness suppression performance is excellent. Ｎ Examples of the substituent represented by the formula (I) include an alkyl group, an alkenyl group, and an aryl group, with an alkyl group being preferred, a linear alkyl group having 1 to 4 carbon atoms being more preferred, and a methyl group or an ethyl group being even more preferred. The chain alkylene group may be either linear or branched. The number of carbon atoms in the chain alkylene group is preferably 1 to 6, more preferably 1 to 4, and even more preferably 1 to 3. Z ａ１ In terms of the effects of the present invention being more excellent, the group represented by the formula (I) is preferably a chain alkylene group having 1 to 3 carbon atoms, -O-, -CO-O-, -O-CO-O-, -NR Ｎ —CO—, —NR Ｎ -CO-O-, -CO-NR Ｎ - or -NR Ｎ -CO-NR Ｎ- is preferred, a chain alkylene group having 1 to 3 carbon atoms, -O-, -CO-, -CO-NH-, -CO-O-, or -NH-CO-O- is more preferred, -O-, -CO-, -CO-O-, or -NH-CO-O- is still more preferred, and -O- or -CO-O- is particularly preferred.

[0026] In formula (A1), Y ａ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. The definitions and preferred embodiments of the aromatic ring and aliphatic ring which may have a substituent are the same as the definitions and preferred embodiments of the aromatic ring which may have a substituent and the aliphatic ring which may have a substituent represented by A described above. Y ａ１ The aromatic ring represented by Y is preferably a monocyclic ring or a condensed ring, and more preferably a monocyclic ring. ａ１ The aliphatic ring represented by the formula (I) is preferably a monocyclic ring or a condensed ring, and more preferably a monocyclic ring.

[0027] In formula (A1), X ａ１ each independently represents a silicon-containing group having a Si—O—Si structure. ａ１ The number of silicon atoms contained in the group represented by X is 2 or more, preferably 3 or more, more preferably 4 or more, and even more preferably 5 or more. There is no particular upper limit, and in most cases it is 12 or less. ａ１ In particular, it is preferable that the siloxane structure has a monovalent substituent S having a siloxane structure containing three or more silicon atoms. The siloxane structure containing three or more silicon atoms is intended to mean a structure in which three or more silicon atoms are linked together to form an Si—O—Si structure, and may be either linear or branched. Examples of the substituent S include monovalent groups represented by the following formulas (C-1) to (C-3), with a group represented by formula (C-2) or a group represented by formula (C-3) being preferred, and a group represented by formula (C-3) being more preferred.

[0028]

[0029] In formula (C-1), R Ｃ１ ~R Ｃ３ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent.Ｃ４ represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. Ｃ５ and R Ｃ６ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent or a group represented by formula (C-1X). Ｃ７ ~R Ｃ９ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent, or a group represented by formula (C-1X).

[0030]

[0031] In formula (C-1X), R Ｃ１０ ~R Ｃ１２ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent; and 1 represents an integer of 0 to 20.

[0032] In formulas (C-1) to (C-3) and formula (C-1X), R Ｃ１ ~R Ｃ１２ The alkyl group having 1 to 10 carbon atoms represented by the formula (I) may be either linear or cyclic, preferably linear, and more preferably straight-chain. The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms is preferably 1 to 6, more preferably 1 to 3. It is also preferable that the alkyl group having 1 to 10 carbon atoms does not have a substituent.

[0033] R Ｃ１ ~R Ｃ４ and R Ｃ１０ ~R Ｃ１２ Among these, a methyl group is preferred as R Ｃ５ ~R Ｃ９ Among these, a methyl group or a group represented by formula (C-1X) is preferred.

[0034] In formula (C-1), k represents an integer of 2 to 20. In terms of achieving better effects of the present invention, k is preferably an integer of 3 to 10, and more preferably an integer of 3 to 8.

[0035] In formula (C-1X), l represents an integer of 0 to 20. In terms of achieving better effects of the present invention, l is preferably an integer of 0 to 10, and more preferably an integer of 0 to 8.

[0036] Xａ１ The number of substituents S in the group represented by the formula (I) is preferably 1 or more, more preferably 1 to 6, and even more preferably 1 to 3. ａ１ Examples of the group represented by the formula: ｘ -(X ａ２ ) ｘ Examples of the group include a group represented by the following formula: ｘ represents a linking group with a valence of x+1. ａ２ each independently represents a substituent S; x represents an integer of 1 or more; when x is 1, L ｘ represents a divalent linking group. Examples of the divalent linking group include a chain alkylene group, —O—, —CO—, and —NR Ｎ -, or a combination thereof. Ｎ represents a hydrogen atom or a substituent. Examples of the combined group include a chain alkylene group -O-, a chain alkylene group -O-CO-, a chain alkylene group -NR Ｎ -CO- and -chain alkylene group -NR Ｎ Examples of the divalent linking group include —CO—O—. Examples of the divalent linking group also include groups formed by combining the above groups with a divalent aromatic ring group or a divalent aliphatic ring group.

[0037] In formula (A1), n ​​represents an integer of 2 or greater. n is preferably an integer of 2 to 6, more preferably an integer of 2 to 4, and even more preferably 2 or 3.

[0038] In formula (A1), m represents an integer of 1 or more. m is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2. ａ１ is a siloxane structure containing three or more silicon atoms, and is a group represented by formula (C-1) in which k is 2, or R Ｃ５ and R Ｃ６ When the group represented by formula (C-2) is an alkyl group having 1 to 10 carbon atoms, it is preferable that m is an integer of 2 or more.

[0039] (Requirement (a3)) (a3) ​​The molecular weight is 500 to 8000. If the molecular weight is less than 500, the silicon-containing compound will be less unevenly distributed on the surface, resulting in poor alignment and visual unevenness, which is undesirable. Furthermore, if the molecular weight exceeds 8000, the silicon-containing compound is likely to inhibit the alignment of the liquid crystal compound, resulting in poor alignment and visual unevenness, which is undesirable. The molecular weight of compound A is preferably 700 or more, and more preferably 800 or more, in terms of providing better effects of the present invention. Furthermore, the molecular weight of the compound is preferably 6000 or less, and more preferably 4000 or less, in terms of providing better performance in suppressing visual unevenness. In particular, the molecular weight of compound A is preferably 700 to 6000, and more preferably 800 to 4000, in terms of providing better performance in suppressing visual unevenness.

[0040] Compound A is preferably a compound represented by formula (A2) or a compound represented by formula (A3): ａ１ -(Y ａ２ -Z ａ２ ) ｒ -Y ａ３ - (T ａ１ ) ｍ１ ) ｎ Formula (A3) A-(Z ａ１ -Y ａ１ -(Z ａ３ -B ａ１ ) ｍ２ ) ｎ

[0041] In formula (A2) and formula (A3), A, Z ａ１ , Y ａ１ , and n is A, Z in the above formula (A1). ａ１ , Y ａ１ , and n.

[0042] In formula (A2), Z ａ２ are each independently a chain alkylene group, —O—, —CO—, or a chain alkylene group, —O—, —CO—, and —NR Ｎ represents a group formed by combining two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. Ｎ The details of Z are as described above. ａ２The definition and preferred embodiments of the group represented by Z ａ１ The definition and preferred embodiments are the same as those of the group represented by the following formula:

[0043] In formula (A2), Y ａ２ and Y ａ３ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ａ２ and Y ａ３ The definition and preferred embodiments of the group represented by Y ａ１ The definition and preferred embodiments are the same as those of the group represented by the following formula:

[0044] In formula (A2), each r independently represents an integer of 0 or more. r is preferably an integer of 0 to 3, more preferably 0 or 1. When r is 0, Y ａ３ is Y in formula (A1). ａ１ and when r is an integer of 1 or more, Z ａ１ Y bonded to ａ２ is Y in formula (A1). ａ１ is synonymous with.

[0045] In formula (A2), T ａ１ represents a monovalent substituent T having a siloxane structure containing three or more silicon atoms. ａ３ is bonded to a group represented by —O—, —CO—, or —NR Ｎ -, -S-, or a combination thereof. Ｎ represents a hydrogen atom or a substituent. Ｎ The details are as described above. The above-mentioned substituent T preferably has the above-mentioned substituent S as a siloxane structure containing three or more silicon atoms. ａ３ In terms of achieving better effects of the present invention, the site bonding to the group represented by the formula (I) is preferably -O-, -CO-, -NH-, or a combination thereof, more preferably -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-, and still more preferably -CO-O- or -O-CO-O-. ａ３ The site bonding to the group represented by the formula (I) is preferably —CO—O— or —O—, in view of the superior ability to suppress alignment unevenness.ａ３ The site of bonding to the group represented by the formula (I) is the site of bonding to the group represented by the formula (I) in the substituent T. ａ３ From the bonding position with the group represented by Ｎ A moiety between - and a linking group (eg, a hydrocarbon group) different from -S- is intended.

[0046] The substituent T is, for example, -Z Ｔ１ -L Ｔ１ -(X Ｔ１ ) ｍ３ Examples of the group include a group represented by the following formula: Ｔ１ represents the structure in which the substituent T is substituted (specifically, for example, Y ａ３ and B in formula (A3) ａ１ and —O—, —CO—, —NR Ｎ represents -, -S-, or a combination thereof. Ｔ１ is preferably —O—, —CO—, —NH—, or a combination thereof, more preferably —CO—O—, —O—CO—O—, —NH—CO—O—, or —CO—O—NH—, and still more preferably —CO—O— or —O—CO—O—. Ｔ１ As L, —CO—O— or —O— is also preferred. Ｔ１ represents an m3+1 valent aliphatic hydrocarbon group, wherein at least one carbon atom of the m3+1 valent aliphatic hydrocarbon group is —NR Ｎ -, -O-, -S-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted with -. Ｔ１ The carbon atom adjacent to X is not substituted. The aliphatic hydrocarbon group is preferably a chain, more preferably a straight chain. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4, in terms of achieving better effects of the present invention. Ｔ１ represents the above-mentioned substituent S, and is more preferably a group represented by formula (C-2) or a group represented by formula (C-3), and even more preferably a group represented by formula (C-3). m3 represents an integer of 1 or more, preferably an integer of 1 to 3, more preferably an integer of 1 or 2, and even more preferably 1.

[0047] In formula (A2), m1 represents an integer of 1 or greater. m1 is preferably an integer of 1 to 6, more preferably an integer of 1 to 3, and even more preferably 1 or 2.

[0048] In formula (A3), Z ａ３ are each independently a chain alkylene group, —O—, —CO—, or a chain alkylene group, —O—, —CO—, and —NR Ｎ represents a group formed by combining two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. Ｎ The details of Z are as described above. ａ３ The definition and preferred embodiments of the group represented by Z ａ１ The definition and preferred embodiments are the same as those of the group represented by the following formula:

[0049] In formula (A3), B ａ１ represents a monovalent aromatic ring group substituted with one or more monovalent substituents T having a siloxane structure containing three or more silicon atoms, provided that the site of bonding to the aromatic ring constituting the aromatic ring group in the substituent T is not -O-, -CO-, -NR Ｎ -, -S-, or a combination thereof. ａ１ The aromatic ring constituting the monovalent aromatic ring group represented by is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, and is preferably an aromatic hydrocarbon ring. Examples of the aromatic hydrocarbon ring and the aromatic heterocyclic ring are as exemplified above for the aromatic ring represented by A, and among these, a benzene ring is preferred. B ａ１ The definition and preferred embodiments of the substituent T in the aromatic ring group represented by the formula (A2) are the same as those of the substituent T in the formula (A2). ａ１The number of substituents T substituting the aromatic ring group represented by the formula (I) is 1 or more, preferably 1 to 6, more preferably 1 to 3, and more preferably 1 or 2. The aromatic ring may have a substituent different from the substituent T. Examples of the substituent different from the substituent T include substituents that do not contain silicon atoms, and more specific examples include alkyl groups, alkyl ester groups, acyl groups, alkoxy groups, alkylthio groups, alkyloxycarbonyl groups, carbamoyl groups, acylamino groups, halogen atoms, cyano groups, and nitro groups, which may have halogen atoms. Examples of the substituent different from the substituent T include alkyl groups, alkyl ester groups, alkoxy groups, and acyl groups, and more preferably linear alkyl groups having 1 to 4 carbon atoms, methyl ester groups, methoxy groups, and acetyl groups, and even more preferably methyl groups, ethyl groups, methoxy groups, and methyl ester groups. When the substituent T is B ａ１ A site that bonds to an aromatic ring that constitutes an aromatic ring group represented by (for example, -Z Ｔ１ -L Ｔ１ -(X Ｔ１ ) ｍ３ In the group represented by Ｔ１ In terms of the effects of the present invention being more excellent, the moiety is preferably -O-, -CO-, -NH-, or a combination thereof, more preferably -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-, and even more preferably -CO-O- or -O-CO-O-. In addition, in terms of the performance of suppressing alignment unevenness being more excellent, the moiety is also preferably -CO-O- or -O-.

[0050] B ａ１ For example, -Y ａ４ - (T ａ１ ) ｍ４ Examples of the group include a group represented by the following formula: ａ４ represents an aromatic ring which may have a substituent. ａ１ represents a substituent T. In the above-mentioned substituent T, Y ａ４ The bonding site is -O-, -CO-, or -NR Ｎ m4 represents an integer of 1 or more, preferably 1 to 6, more preferably 1 to 3, and more preferably 1 or 2.

[0051] In formula (A3), m2 represents an integer of 2 or greater. m2 is preferably an integer of 2 to 6, more preferably 2 or 3, and even more preferably 2.

[0052] Examples of compound A include the following compounds.

[0053]

[0054]

[0055]

[0056] <Compound B> Compound B satisfies requirements (b1) to (b4): (b1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. (b2) -L ｂ１ -X ｂ１ L ｂ１ each independently represents an alkylene group which may have a hetero atom or —O—. ｂ１ represents a monovalent group selected from the group consisting of groups represented by formulae (C-1) to (C-3).

[0057] In formula (C-1), R Ｃ１ ~R Ｃ３ each independently represents an alkyl group having 1 to 10 carbon atoms, and k represents an integer of 2 to 20. In formula (C-2), R Ｃ４ represents an alkyl group having 1 to 10 carbon atoms. Ｃ５ and R Ｃ６ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X). Ｃ７ ~R Ｃ９ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X).

[0058] In formula (C-1X), R Ｃ１０ ~R Ｃ１２ each independently represents an alkyl group having 1 to 10 carbon atoms; and l represents an integer of 0 to 20. (b3) *-(Z ｂ１ -Y ｂ１ )ｓ -W ｂ１ * represents the bonding position. Z ｂ１ each independently represents an alkylene group, —O—, —CO—, or —NR Ｎ -, or a group formed by combining these. Ｎ represents a hydrogen atom or a substituent. ｂ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ｂ１ represents a substituent that does not contain a hydrogen atom or a silicon atom. s represents an integer of 1 or more. (b4) The molecular weight is 500 to 8000. Each requirement will be described in detail below.

[0059] (Requirement (b1)) (b1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. If the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is less than 0.0140, the silicon-containing compound will be less unevenly distributed on the coating film surface, and alignment unevenness and visibility unevenness will be poor, which is undesirable. The method for calculating the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is the same as the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound in requirement (a1) of compound A.

[0060] In compound B, the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound is preferably 0.0140 to 0.0280, more preferably 0.0140 to 0.0250, even more preferably 0.0150 to 0.0250, and particularly preferably 0.0150 to 0.0200, in terms of better effects of the present invention.

[0061] (Requirement (b2)) (b2) -L ｂ１ -X ｂ１ L ｂ１each independently represents an alkylene group which may have a heteroatom or -O-. Examples of heteroatoms which the alkylene group may have include an oxygen atom, a nitrogen atom, and a sulfur atom. The alkylene group may have two or more heteroatoms as long as the same heteroatoms are not adjacent. The alkylene group is preferably a chain alkylene group, more preferably a linear alkylene group. The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4. L ｂ１ is preferably —O— or a chain alkylene group having 1 to 6 carbon atoms. ｂ１ represents a monovalent group selected from the group consisting of groups represented by formulas (C-1) to (C-3), preferably a group represented by formula (C-2) or a group represented by formula (C-3), more preferably a group represented by formula (C-3). Formulas (C-1) to (C-3) are as described above for compound A.

[0062] Compound B has -L ｂ１ -X ｂ１ The number of groups represented by the formula (I) is 2 or more, preferably 2 to 8, more preferably 2 to 6, and even more preferably 2 to 4.

[0063] (Requirement (b3)) (b3) *-(Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１ (hereinafter also referred to as "partial structure B").

[0064] * indicates the bond position.

[0065] Partial structure B, Z ｂ１ each independently represents an alkylene group, —O—, —CO—, or —NR Ｎ -, or a group formed by combining these. Ｎ represents a hydrogen atom or a substituent. Ｎ The details of Z are as described above. ｂ１ The definition and preferred embodiments of the alkylene group in Z ａ１ It is the same as the alkylene group represented by the formula: ｂ１is a chain alkylene group, —O—, —CO—, or a chain alkylene group, —O—, —CO—, and —NR Ｎ It is also preferable that Z is a group formed by combining two or more selected from the group consisting of ｂ１ Among these, the group represented by the formula (I) is preferably a chain alkylene group having 1 to 3 carbon atoms, —O—, —CO—O—, —O—CO—O—, —NR Ｎ —CO—, —NR Ｎ -CO-O-, -CO-NR Ｎ - or -NR Ｎ -CO-NR Ｎ - is preferred, a chain alkylene group having 1 to 3 carbon atoms, -O-, -CO-, -CO-NH-, -CO-O-, or -NH-CO-O- is more preferred, -O-, -CO-, -CO-O-, or -NH-CO-O- is still more preferred, and -O- or -CO-O- is particularly preferred.

[0066] Partial structure B, Y ｂ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ｂ１ The definitions and preferred embodiments of the aromatic ring and the aliphatic ring represented by Y ａ１ The definitions and preferred embodiments of the aromatic ring and the aliphatic ring in the group represented by the formula (I) are the same as those of the aromatic ring and the aliphatic ring. It is also preferable that the substituents on the aromatic ring and the aliphatic ring do not contain a silicon atom. Examples of the substituents include an alkyl group, an alkyl ester group, an acyl group, an alkoxy group, an alkylthio group, an alkyloxycarbonyl group, a carbamoyl group, an acylamino group, a halogen atom, a cyano group, and a nitro group, each of which may contain a halogen atom. An alkyl group, an alkyl ester group, an alkoxy group, or an acyl group is preferred, a linear alkyl group having 1 to 4 carbon atoms, a methyl ester group, a methoxy group, or an acetyl group is more preferred, and a methyl group, an ethyl group, a methoxy group, or a methyl ester group is even more preferred. It is also preferable that the substituents on the aromatic ring and the aliphatic ring do not contain a cyclic group (an aromatic ring group or an aliphatic ring group).

[0067] Partial structure B, W ｂ１represents a substituent that does not contain a hydrogen atom or a silicon atom. Examples of the substituent that does not contain a silicon atom include an aryl group that may have an alkyl group, a heteroaryl group that may have an alkyl group, an alkyl group that may have a halogen atom, an alkyl ester group, an acyl group, an alkoxy group, an alkylthio group, an alkyloxycarbonyl group, a carbamoyl group, an acylamino group, a halogen atom, a cyano group, and a nitro group, of which an aryl group, an alkyl group, an alkyl ester group, an alkoxy group, or an acyl group is preferred, a phenyl group, a naphthyl group, a linear alkyl group having 1 to 4 carbon atoms, a methyl ester group, a methoxy group, or an acetyl group is more preferred, and a phenyl group, a methyl group, an ethyl group, a methoxy group, or a methyl ester group is even more preferred.

[0068] In the partial structure B, s represents an integer of 1 or more. As s, an integer of 1 to 8 is preferable, an integer of 1 to 6 is more preferable, and an integer of 1 to 4 is even more preferable.

[0069] (Requirement (b4)) (b4) The molecular weight is 500 to 8000. If the molecular weight is less than 500, the silicon-containing compound will be less unevenly distributed on the surface, resulting in poor alignment and visibility irregularities, which is undesirable. If the molecular weight is more than 8000, the silicon-containing compound will likely inhibit the alignment of the liquid crystal compound, resulting in poor alignment and visibility irregularities, which is undesirable. The molecular weight of compound B is preferably 800 to 4000, more preferably 800 to 1400, in that the effects of the present invention are more excellent.

[0070] Compound B preferably has two or more ring structures, and more preferably has three or more ring structures in that it has better alignment unevenness suppression performance. The upper limit is not particularly limited, but is often 10 or less, and preferably 6 or less. The ring structure includes an aromatic ring and an aliphatic ring.

[0071] Compound B is preferably a compound represented by formula (B1). ｂ１ -(Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１

[0072] In formula (B1), Z ｂ１ , Yｂ１ , W ｂ１ , and s is Z in the partial structure B described above. ｂ１ , Y ｂ１ , W ｂ１ , and s.

[0073] In formula (B1), B ｂ１ Is, -L ｂ１ -X ｂ１ or -L ｂ１ -X ｂ１ represents an aromatic ring substituted with one or more groups having two or more groups represented by the following formula: ｂ１ The aromatic ring constituting the monovalent aromatic ring group represented by is preferably a monocyclic ring or a condensed ring, more preferably a monocyclic ring. The aromatic ring may be either an aromatic hydrocarbon ring or an aromatic heterocyclic ring, with an aromatic hydrocarbon ring being preferred. Examples of the aromatic hydrocarbon ring and aromatic heterocyclic ring are as exemplified above for the aromatic ring represented by A, with a benzene ring being preferred. -L ｂ１ -X ｂ１ The group represented by the formula (b1) is as described above in the requirement (b2).

[0074] B ｂ１ has -L ｂ１ -X ｂ１ The number of groups represented by the above formula (I) is 2 or more, preferably 2 to 6, and more preferably 2 to 4. ｂ１ -X ｂ１ The number of groups represented by -L directly substituted on the aromatic ring is ｂ１ -X ｂ１ and the number of groups represented by -L ｂ１ -X ｂ１ -L is included in a group having two or more groups represented by ｂ１ -X ｂ１ is the total number of groups represented by

[0075] -L ｂ１ -X ｂ１ Examples of the group having two or more groups represented by the formula: ｂ２ -L ｂ２ - (L ｂ１ -X ｂ１ ) ｍ５ and -Z ｂ２ -L ｂ３ -SiRＳｉ ３－ｗ (L ｂ１ -X ｂ１ ) ｗ Examples of the group include a group represented by the following formula:

[0076] Z ｂ２ represents a single bond, or —O—, —CO—, or —NR Ｎ represents -, -S-, or a combination thereof. Ｎ represents a hydrogen atom or a substituent. Ｎ The details of Z are as described above. ｂ２ is preferably —O—, —CO—, —NH—, or a group formed by combining these, more preferably —O—, —CO—O—, —O—CO—O—, —NH—CO—O—, or —CO—O—NH—, and still more preferably —CO—O— or —O—CO—O—. ｂ２ is also preferably —CO—O— or —O— in that it has better suppression performance of alignment unevenness. ｂ２ represents an m5+1 valent aliphatic hydrocarbon group, wherein at least one carbon atom of the m5+1 valent aliphatic hydrocarbon group is —NR Ｎ -, -O-, -S-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted with -. ｂ２ and L ｂ１ and the carbon atom adjacent thereto is not substituted. The aliphatic hydrocarbon group is preferably chain-like, more preferably linear. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6. m5 represents an integer of 2 or more, preferably 2 to 4, more preferably 2 or 3, and even more preferably 2.

[0077] L ｂ３ represents a divalent aliphatic hydrocarbon group, at least one carbon atom of which is —NR Ｎ -, -O-, -S-, -CO-, -CS-, -SO-, or -SO ２ - may be substituted with -. ｂ２The carbon atom adjacent to R is not substituted. The aliphatic hydrocarbon group is preferably a chain, more preferably a straight chain. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 10, more preferably 1 to 6, and even more preferably 2 to 4. Ｓｉ each independently represents an alkyl group having 1 to 10 carbon atoms which may have a substituent. The alkyl group having 1 to 10 carbon atoms may be either linear or cyclic, with linear being preferred, and linear being more preferred. The number of carbon atoms in the alkyl group having 1 to 10 carbon atoms is preferably 1 to 6, and more preferably 1 to 3. w represents 2 or 3.

[0078] B is superior in terms of suppressing alignment irregularities. ｂ１ In the group represented by the formula: ｂ１ -X ｂ１ The number of groups represented by -L is 2 or less, and ｂ１ -X ｂ１ -L in a group having two or more groups represented by ｂ１ -X ｂ１ It is also preferred that the number of groups represented by the formula: is two.

[0079] Examples of compound B include the following compounds.

[0080]

[0081] The silicon-containing compound may be used alone or in combination of two or more. When two or more silicon-containing compounds are used in combination, two or more of either Compound A or Compound B may be combined, or Compound A and Compound B may be combined. The content of the silicon-containing compound is preferably 0.01 to 5.0 mass%, more preferably 0.01 to 1.0 mass%, relative to the total solid content of the composition, in terms of better achieving the effects of the present invention.

[0082] [Liquid Crystal Compound] The composition of the present invention contains a liquid crystal compound. The liquid crystal compound is not particularly limited, and any known liquid crystal compound can be used. Generally, liquid crystal compounds can be classified into rod-shaped types (rod-shaped liquid crystal compounds) and discotic types (discotic liquid crystal compounds) based on their shape. Liquid crystal compounds can also be classified into low-molecular-weight types and high-molecular-weight types. A high-molecular-weight compound generally refers to a compound with a degree of polymerization of 100 or more (Polymer Physics: Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).

[0083] The liquid crystal compound may be either a rod-shaped liquid crystal compound or a discotic liquid crystal compound. The composition of the present invention may contain two or more rod-shaped liquid crystal compounds, two or more discotic liquid crystal compounds, or a mixture of a rod-shaped liquid crystal compound and a discotic liquid crystal compound.

[0084] The liquid crystal compound contained in the composition may be either a low molecular weight liquid crystal compound or a polymer liquid crystal compound, or a mixture thereof. From the viewpoint of alignment, the liquid crystal compound is preferably a polymerizable liquid crystal compound. A polymerizable liquid crystal compound is a liquid crystal compound having a polymerizable group, and the alignment state can be fixed by polymerization after alignment. Furthermore, the alignment state of a polymer liquid crystal compound can be fixed by removing the solvent from the composition and drying it after alignment.

[0085] The polymerizable liquid crystal compound is preferably at least one polymerizable liquid crystal compound selected from the group consisting of polymerizable rod-shaped liquid crystal compounds and polymerizable discotic liquid crystal compounds. The polymerizable group of the polymerizable liquid crystal compound is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferred. Examples of the polymerizable group include an acryloyl group, a methacryloyl group, an epoxy group, and a vinyl group.

[0086] As the rod-shaped liquid crystal compound, those described in claim 1 of JP-A-11-513019 or paragraphs

[0026] to

[0098] of JP-A-2005-289980 are preferred, and as the discotic liquid crystal compound, those described in paragraphs

[0020] to

[0067] of JP-A-2007-108732 or paragraphs

[0013] to

[0108] of JP-A-2010-244038 are preferred.

[0087] The liquid crystal compound may be a liquid crystal compound having reverse wavelength dispersion (reverse dispersion compound). In this specification, the term "reverse wavelength dispersion" refers to a liquid crystal compound that, when the in-plane retardation (Re) value of a film produced using the compound is measured at a specific wavelength (visible light range), exhibits a constant or higher Re value as the measured wavelength increases. The liquid crystal compound of reverse wavelength dispersion is not particularly limited as long as it can form a layer of reverse wavelength dispersion, for example, the general formula (I) described in JP-A-2008-297210 compounds (particularly, the compounds described in paragraphs

[0034] to

[0039] ), the general formula (1) described in JP-A-2010-084032 compounds (particularly, the compounds described in paragraphs

[0067] to

[0073] ), the general formula (1) described in JP-A-2016-081035 compounds (particularly, the compounds described in paragraphs

[0043] to

[0055] ), and the general formula (II) described in JP-A-2016-053709 compounds (particularly, the compounds described in paragraphs

[0036] to

[0043] ). Further, paragraphs

[0027] to

[0100] of JP-A No. 2011-006360, paragraphs

[0028] to

[0125] of JP-A No. 2011-006361, paragraphs

[0034] to

[0298] of JP-A No. 2012-207765, paragraphs

[0016] to

[0345] of JP-A No. 2012-077055, / 141245, paragraphs

[0017] to

[0072] , WO12 / 147904, paragraphs

[0021] to

[0088] , WO14 / 147904, paragraphs

[0028] to

[0115] , and WO 2021 / 060427, paragraphs

[0025] to

[0056] .

[0088] The liquid crystal compound may be used alone or in combination of two or more. The content of the liquid crystal compound is preferably 50 to 99.99 mass %, more preferably 70 to 99 mass %, based on the total solid content of the composition.

[0089] The composition may contain other components in addition to the silicon-containing compound and the liquid crystal compound. The other components that the composition may contain are described below.

[0090] [Polymerization Initiator] The composition preferably contains a polymerization initiator. Examples of the polymerization initiator include photopolymerization initiators and thermal polymerization initiators. Photopolymerization initiators are preferred, and photopolymerization initiators capable of initiating a polymerization reaction upon ultraviolet irradiation are preferred. Examples of photopolymerization initiators include alkylphenone compounds, α-carbonyl compounds, acyloin ethers, α-hydrocarbon-substituted aromatic acyloin compounds, polynuclear quinone compounds, combinations of triarylimidazole dimers and p-aminophenyl ketones, acridine and phenazine compounds, oxadiazole compounds, o-acyloxime compounds, and acylphosphine oxide compounds. Commercially available photopolymerization initiators can also be used, such as Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02, all manufactured by BASF.

[0091] The polymerization initiator may be used alone or in combination of two or more. The content of the polymerization initiator is preferably 0.01 to 30% by mass, more preferably 0.1 to 15% by mass, based on the total solid content of the composition.

[0092] [Solvent] From the viewpoint of workability in forming a coating film, the composition preferably contains a solvent. Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chloroform), and the like. toluene), esters (for example, methyl acetate, ethyl acetate, ethyl propionate, butyl acetate, and diethyl carbonate), alcohols (for example, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (for example, methyl cellosolve, ethyl cellosolve, and 1,2-dimethoxyethane), cellosolve acetates, sulfoxides (for example, dimethyl sulfoxide), amides (for example, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, and 1,3-dimethyl-2-imidazolidinone), and heterocyclic compounds (for example, pyridine, etc.), as well as water.

[0093] The solvent may be used alone or in combination of two or more. When the composition contains a solvent, the content of the solvent in the composition is preferably an amount that makes the solid content concentration 0.5 to 30 mass %, more preferably an amount that makes 1 to 20 mass %.

[0094] [Alignment Control Agent] The composition may contain an alignment control agent other than the silicon-containing compound, if necessary. The alignment control agent can form various alignment states such as homogeneous alignment, homeotropic alignment (vertical alignment), tilted alignment, hybrid alignment, and cholesteric alignment, and can also realize specific alignment states more uniformly and more precisely.

[0095] As the alignment control agent for promoting homogeneous alignment, for example, a low molecular weight alignment control agent and a high molecular weight alignment control agent can be used. For low molecular weight alignment control agents, for example, the descriptions in paragraphs

[0009] to

[0083] of JP 2002-020363 A, paragraphs

[0111] to

[0120] of JP 2006-106662 A, and paragraphs

[0021] to

[0029] of JP 2012-211306 A can be referred to, the contents of which are incorporated herein by reference. Regarding polymer orientation control agents, reference can be made to, for example, paragraphs

[0021] to

[0057] of JP-A No. 2004-198511 and paragraphs

[0121] to

[0167] of JP-A No. 2006-106662, the contents of which are incorporated herein by reference.

[0096] Examples of alignment control agents that form or promote homeotropic alignment include boronic acid compounds and onium salt compounds. Specifically, the compounds described in JP-A-2008-225281, paragraphs

[0023] to

[0032] , JP-A-2012-208397, paragraphs

[0052] to

[0058] , JP-A-2008-026730, paragraphs

[0024] to

[0055] , and JP-A-2016-193869, paragraphs

[0043] to

[0055] , etc., can be referred to, the contents of which are incorporated herein by reference.

[0097] The composition may contain a chiral agent. Chiral agents (optically active compounds) have the function of inducing a helical structure in a cholesteric liquid crystal phase. Chiral agents can be selected according to the purpose, as the twist direction or helical pitch of the helix induced varies depending on the compound. The chiral agent is not particularly limited, and examples include compounds described in "Liquid Crystal Device Handbook, Chapter 3, Section 4-3, Chiral Agents for TN (Twisted Nematic) and STN (Super Twisted Nematic)," p. 199, edited by the 142nd Committee of the Japan Society for the Promotion of Science, 1989," isosorbide, and isomannide derivatives. Chiral agents generally contain an asymmetric carbon atom, but axially asymmetric or planarly asymmetric compounds without an asymmetric carbon atom can also be used as chiral agents. Examples of axially asymmetric or planarly asymmetric compounds include binaphthyl, helicene, paracyclophane, and their derivatives. The chiral agent may also have a polymerizable group. The polymerizable group of the polymerizable chiral agent is preferably the same type as the polymerizable group of the polymerizable liquid crystal compound. The chiral agent itself may be a liquid crystal compound.

[0098] The chiral agent may have a photoisomerizable moiety. The photoisomerizable moiety is preferably a cinnamoyl moiety, a chalcone moiety, an azobenzene moiety, or a stilbene moiety, more preferably a cinnamoyl moiety, a chalcone moiety, or a stilbene moiety. As the chiral agent, compounds 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 can be used.

[0099] The chiral agent may be used alone or in combination of two or more. When forming a film having multiple alignment states in one layer, it is preferable to use two or more chiral agents including chiral agent A and chiral agent B that induces a helix in the opposite direction to that of chiral agent A. For example, when the helix induced by chiral agent A is right-handed, the helix induced by chiral agent B will be left-handed. The content of the chiral agent is preferably 0.01 to 15 mass %, more preferably 1.0 to 10 mass %, of the content of the liquid crystal compound.

[0100] [Other Additives] The composition may contain other components in addition to the above-mentioned components, such as antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, tilt angle controllers, thickeners, flame retardants, surfactants, dispersants, and coloring materials such as dyes and pigments.

[0101] [Optically anisotropic film] An optically anisotropic film can be obtained using the composition of the present invention. In other words, the composition of the present invention is suitable for use in forming an optically anisotropic film. The liquid crystal compound in the optically anisotropic film may be in a state exhibiting liquid crystallinity, or may be a film in which the orientation state is fixed (liquid crystal cured film), and a film in which the orientation state is fixed is preferred. In the liquid crystal cured film, the liquid crystal compound may no longer exhibit liquid crystallinity.

[0102] The orientation state of the liquid crystal compound in the optically anisotropic film may be any of horizontal orientation, vertical orientation, tilted orientation, and twisted orientation. Furthermore, as described in WO 2021 / 033640, a liquid crystal cured layer may have multiple orientation states within the film, such as a first region in which the orientation state of the liquid crystal compound is fixed in a twisted orientation along a helical axis extending along the thickness direction, and a second region in which the orientation state of the liquid crystal compound is fixed in a homogeneous orientation, along the thickness direction. In this specification, "horizontal orientation" refers to the main surface of the optically anisotropic film (or, if the optically anisotropic film is formed on a member such as a support and an alignment film, the surface of the member) being parallel to the long axis direction of the liquid crystal compound. Strict parallelism is not required, and in this specification, it refers to an orientation in which the angle between the long axis direction of the liquid crystal compound and the main surface of the specific film is less than 10°.

[0103] Examples of optically anisotropic films include an A plate, a C plate, and an optically anisotropic film having, along the thickness direction, a first region in which the orientation state of liquid crystal compounds twistedly aligned along a helical axis extending along the thickness direction is fixed, and a second region in which the orientation state of liquid crystal compounds homogeneously aligned is fixed (hereinafter, this embodiment will be abbreviated as "optically anisotropic film A").

[0104] There are two types of A plates: positive A plates (positive A plates) and negative A plates (negative A plates). When the refractive index in the in-plane slow axis direction (the direction in which the in-plane refractive index is greatest) of the film is nx, the refractive index in the direction perpendicular to the in-plane slow axis is ny, and the refractive index in the thickness direction is nz, the positive A plates satisfy the relationship of formula (A1), and the negative A plates satisfy the relationship of formula (A2). Note that the positive A plates exhibit a positive Rth, while the negative A plates exhibit a negative Rth. Formula (A1) nx>ny≒nz Formula (A2) ny<nx≒nz There are two types of C plates: positive C plates (positive C plates) and negative C plates (negative C plates). The positive C plates satisfy the relationship of formula (C1), and the negative C plates satisfy the relationship of formula (C2). Note that the positive C plates exhibit a negative Rth, while the negative C plates exhibit a positive Rth. Formula (C1): nz>nx≒ny Formula (C2): nz<nx≒ny Note that the above "≒" encompasses not only the case where the two are completely identical, but also the case where the two are substantially identical. "Substantially the same" means, for example, that "ny≒nz" ​​also includes the case where (ny-nz)×d (where d is the film thickness) is -10 to 10 nm, preferably -5 to 5 nm, and that "nx≒nz" also includes the case where (nx-nz)×d is -10 to 10 nm, preferably -5 to 5 nm.

[0105] The Re and Rth may be adjusted appropriately depending on the application of the film of the present invention, and can be adjusted by the thickness of the optically anisotropic film and the type of liquid crystal compound contained therein.

[0106] When the orientation direction of the liquid crystal compound is twisted along the helical axis (particularly when a cholesteric liquid crystal phase is fixed), the twist angle of the liquid crystal compound (the change in angle from one surface of the cured film to the other surface) can be adjusted according to the purpose. The pitch of the helical structure varies depending on the type and concentration of the chiral agent added to the composition, and the desired pitch orientation state can be obtained by adjusting one or more of the above. The helical twist direction and pitch can be measured using the methods described in "Introduction to Liquid Crystal Chemistry Experiments," edited by the Japanese Liquid Crystal Society, Sigma Publishing, 2007, page 46, and "Liquid Crystal Handbook," Liquid Crystal Handbook Editorial Committee, Maruzen, page 196.

[0107] The thickness of the optically anisotropic film may be adjusted appropriately depending on the application, but is preferably 0.1 to 50 μm, more preferably 0.3 to 20 μm, and even more preferably 1 to 10 μm.

[0108] [Method for producing optically anisotropic film] Examples of methods for forming an optically anisotropic film include a method in which a coating film is formed using the composition of the present invention, the liquid crystal compound contained in the coating film is aligned in a desired alignment state, and then the alignment state is fixed by polymerization.

[0109] The alignment treatment for orienting the liquid crystal compound to a desired alignment state 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 liquid crystal compound contained. The alignment treatment may be carried out simultaneously with the removal of the solvent. When heating is carried out 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 liquid crystal compound.

[0110] 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 the 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). Furthermore, the polymerization reaction may be carried out under heated conditions to promote the polymerization reaction.

[0111] [Optical Film] The optically anisotropic film formed by the composition of the present invention is also preferably used in an optical film. In other words, the optically anisotropic film can be used as an optical film in combination with other layers. An example of the optical film is an optical film having a support, an alignment film, and an optically anisotropic layer in this order. Note that both the support and the alignment film are optional components.

[0112] [Optically Anisotropic Layer] The optically anisotropic layer may be the optically anisotropic film described above, or may be a layer combining the optically anisotropic film described above with another liquid crystal film. That is, the optically anisotropic film described above may be formed on the surface of another liquid crystal layer, or another liquid crystal layer may be formed on the surface of the optically anisotropic film described above. For example, when the polarizing plate described below is used as a circular polarizing plate, or when the optical film is used as an optical compensation film for an IPS (In-Plane-Switching) or FFS (Fringe-Field-Switching) liquid crystal display device, the optically anisotropic layer is preferably a laminate of a positive A plate and a positive C plate. The other liquid crystal layer may be a liquid crystal layer formed using the composition of the present invention, or may be a liquid crystal layer formed by fixing a composition containing a liquid crystal compound and, if necessary, optional components (e.g., a polymerization initiator, a dichroic material, and a leveling agent) in a predetermined alignment state.

[0113] When the optically anisotropic film described above is laminated with another liquid crystal layer, it is also preferable to laminate the layers via an adhesive layer. Examples of the adhesive layer include known adhesive layers and pressure-sensitive adhesive layers. Examples of materials for forming the pressure-sensitive adhesive layer include members formed of substances having a ratio of storage modulus G' to loss modulus G" (tan δ = G" / G') measured with a dynamic viscoelasticity measuring device of 0.001 to 1.5, such as so-called pressure-sensitive adhesives and substances that tend to creep. Examples of pressure-sensitive adhesives include polyvinyl alcohol-based pressure-sensitive adhesives. The adhesive layer is preferably a curable adhesive composition that cures upon irradiation with active energy rays or heating. Examples of curable adhesive compositions include curable adhesive compositions containing a cationically polymerizable compound and curable adhesive compositions containing a radically polymerizable compound. The thickness of the adhesive layer is preferably 0.01 to 20 μm, more preferably 0.01 to 10 μm, and even more preferably 0.05 to 5 μm. When the thickness of the adhesive layer is within this range, lifting or peeling is unlikely to occur between the laminated protective layer or cured liquid crystal layer and the polarizer. Furthermore, from the viewpoint of suppressing the generation of bubbles, the thickness of the adhesive layer is preferably 0.4 μm or more. For details of the adhesive layer, see, for example, paragraphs

[0062] to

[0080] of JP 2016-035579 A, ​​the contents of which are incorporated herein by reference.

[0114] The optically anisotropic film described above may be peeled off from the support and used alone as an optical film.

[0115] [Support] The support is a base material for forming a film. The support is preferably transparent. Specifically, it is preferable that the light transmittance be 80% or more.

[0116] Examples of the support include glass substrates and polymer films. Examples of materials for the polymer film include cellulose-based polymers; acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamide; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers. In addition, the polarizer described below may also serve as such a support.

[0117] The thickness of the support is not particularly limited, but is preferably 5 to 100 μm, more preferably 5 to 50 μm. The support is preferably peelable.

[0118] [Alignment Layer] The optical film preferably has an alignment layer between the support and the optically anisotropic film. The support may also serve as the alignment layer.

[0119] Alignment films generally contain a polymer as a main component. Polymer materials for alignment films are described in numerous publications, and many commercially available products are available. The polymer material used in the present invention is preferably polyvinyl alcohol or polyimide, and derivatives thereof. Modified or unmodified polyvinyl alcohol is particularly preferred. Examples of alignment films that can be used in the present invention include those described in WO 01 / 088574, page 43, line 24 to page 49, line 8; modified polyvinyl alcohols described in paragraphs

[0071] to

[0095] of Japanese Patent No. 3907735; and liquid crystal alignment films formed using liquid crystal aligning agents described in JP 2012-155308 A.

[0120] In the present invention, it is also preferable to use a photo-alignment film as the alignment film, because it is possible to prevent deterioration of the surface condition by not contacting the alignment film surface during formation of the alignment film. The photo-alignment film is not particularly limited, but polymer materials such as polyamide compounds and polyimide compounds described in paragraphs

[0024] to

[0043] of WO 2005 / 096041; liquid crystal alignment films formed by liquid crystal aligning agents having a photo-aligning group with a cinnamic acid structure described in JP 2012-155308 A; product name LPP-JP265CP manufactured by Rolic Technologies, Inc., and the like can be used.

[0121] The thickness of the alignment film is not particularly limited, but from the viewpoint of reducing surface irregularities that may be present on the support and forming an optically anisotropic layer with a uniform thickness, it is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

[0122] In consideration of the influence of external light (especially ultraviolet light), the optical film preferably contains an ultraviolet (UV) absorber. The ultraviolet absorber may be contained in the optically anisotropic film or in a component other than the optically anisotropic film. A suitable example of a component other than the optically anisotropic film is a support. Any conventionally known ultraviolet absorber capable of exhibiting ultraviolet absorption properties can be used as the ultraviolet absorber. Among these ultraviolet absorbers, benzotriazole-based or hydroxyphenyltriazine-based ultraviolet absorbers are preferred from the viewpoint of achieving high ultraviolet absorption and the ultraviolet absorption (UV blocking) capabilities required for image display devices. Furthermore, to broaden the ultraviolet absorption bandwidth, two or more ultraviolet absorbers with different maximum absorption wavelengths can be used in combination. Specific examples of ultraviolet absorbers include the compounds described in paragraphs

[0258] to

[0259] of JP 2012-018395 A and the compounds described in paragraphs

[0055] to

[0105] of JP 2007-072163 A. Commercially available products that can be used include Tinuvin 400, Tinuvin 405, Tinuvin 460, Tinuvin 477, Tinuvin 479, and Tinuvin 1577 (all manufactured by BASF).

[0123] [Polarizing Plate] The optically anisotropic film formed from the composition of the present invention is also preferably used in a polarizing plate. Examples of the polarizing plate include a polarizing plate having the above-mentioned optical film and a polarizer. The polarizing plate can be suitably used as a circular polarizing plate, an optical compensation film for an IPS-type or FFS-type liquid crystal display device, or the like, by adjusting the combination of the type and alignment state of the liquid crystal compound in the optically anisotropic layer, the configuration of the optical film, and the angle between the absorption axis of the polarizer and the in-plane slow axis of the optically anisotropic layer.

[0124] [Polarizer] The polarizer is not particularly limited as long as it is a component capable of converting light into specific linearly polarized light, and conventionally known absorptive polarizers, reflective polarizers, and coated polarizers can be used. Examples of absorptive polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable. Preferred are polarizers prepared by adsorbing iodine or a dichroic dye to polyvinyl alcohol and stretching the resulting material. Examples of coated polarizers include polarizers containing a cured product of a liquid crystal compound and a dichroic dye. Examples of reflective polarizers include polarizers formed by laminating thin films with different birefringence, wire-grid polarizers, and polarizers formed by combining a cholesteric liquid crystal having a selective reflection region with a quarter-wave plate.

[0125] The thickness of the polarizer is not particularly limited, but is preferably from 3 to 60 μm, more preferably from 3 to 30 μm, and even more preferably from 3 to 10 μm.

[0126] In the polarizing plate, an adhesive layer may be disposed between the liquid crystal cured layer in the optical film and the polarizer. Examples of the adhesive layer include an adhesive layer that may be included in the optical film.

[0127] [Image display device] The composition of the present invention is also preferably used in an image display device. Examples of the image display device include image displays having the above-mentioned optical film or polarizing plate. The display element used in the image display device is not particularly limited, and examples thereof include a liquid crystal cell, an organic electroluminescence (hereinafter referred to as "organic EL (Electro Luminescence)") display panel, and a plasma display panel, with a liquid crystal cell or an organic EL display panel being preferred.

[0128] A liquid crystal display device, which is an example of an image display device, is a liquid crystal display device having the above-described polarizing plate and a liquid crystal cell. Of the polarizing plates provided on both sides of the liquid crystal cell, it is preferable to use the above-described polarizing plate as the front-side polarizing plate, and it is more preferable to use the above-described polarizing plate as the front-side and rear-side polarizing plates.

[0129] The liquid crystal cell used in the liquid crystal display device is preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, FFS (Fringe-Field-Switching) mode, or TN (Twisted Nematic) mode, but is not limited to these.

[0130] An example of an organic EL display device, which is an example of an image display device, is a mode having, from the viewing side, a polarizer, a λ / 4 plate made of the above-mentioned cured liquid crystal layer, and an organic EL display panel, in this order. The organic EL display panel is a display panel configured using organic EL elements each having an organic light-emitting layer (organic electroluminescence layer) sandwiched between electrodes (a cathode and an anode). The configuration of the organic EL display panel is not particularly limited, and a known configuration may be adopted.

[0131] [Compound] The present invention also includes the invention of Compound A and Compound B.

[0132] The present invention will be described in more detail below based on 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 interpreted as being limited by the examples shown below. The abbreviations used in the following explanation are as follows: DMF: N,N-dimethylformamide THF: tetrahydrofuran EDCl: 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride DMAP: 4-dimethylaminopyridine DMAc: N,N-dimethylacetamide

[0133] [Silicon-Containing Compound] In the examples, the following compounds A-1 to A-30, B-1 to B-9, and C-1 to C-7 were used as silicon-containing compounds. Compounds A-1 to A-30 correspond to compound A, B-1 to B-9 correspond to compound B, and compounds C-1 to C-7 are comparative compounds. In the following, Mw represents the molecular weight of the compound, and Si-Me / Mw represents the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound.

[0134]

[0135]

[0136]

[0137]

[0138]

[0139]

[0140]

[0141]

[0142]

[0143]

[0144]

[0145]

[0146]

[0147]

[0148] [Synthesis Example] [Synthesis of Compound A-1] Compound A-1 was synthesized according to the following procedure.

[0149]

[0150] <Synthesis of Compound 1b> Compound 1a (8.6 mmol) was added to a solution of p-hydroxybenzaldehyde (8.2 mmol) and cesium carbonate (12.3 mmol) dissolved in DMF (50 mL), and the mixture was stirred at room temperature for 6 hours. After stirring, ethyl acetate, aqueous hydrochloric acid, and brine were added to the resulting reaction solution, followed by separation. The solvent was evaporated, and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 20 / 1) to obtain Compound 1b (yield 70%).

[0151] <Synthesis of Compound 1c> NaH ２ P.O. ４Solution A was prepared by dissolving Compound 1b (7.8 mmol) in ethyl acetate (6 mL) and THF (5 mL) to prepare Solution B, and Solution A was added dropwise to the resulting mixture. Hydrogen peroxide (1.3 mmol) was then added, followed by NaClO ２ An aqueous solution (2.5 mL) of 1,2-dichlorobenzofuran (9.4 mmol) was added, and the mixture was stirred for 1 hour at 40° C. After stirring, the reaction was quenched with an aqueous sodium sulfite solution, and then ethyl acetate and aqueous hydrochloric acid were added, followed by separation of the layers. The solvent was evaporated to obtain Compound 1c (yield 95%).

[0152] <Synthesis of Compound A-1> Methylhydroquinone (1.0 mmol) and Compound 1c (2.2 mmol) were dissolved in dichloromethane (10 mL), and EDCl (3.0 mmol) and DMAP (0.1 mmol) were added under water cooling. The resulting reaction solution was stirred at room temperature for 4 hours, and then water was added for separation. Purification was performed by silica gel column chromatography (hexane / ethyl acetate = 20 / 1) to obtain Compound A-1 (yield 80%). The results of MALDI-MS measurement of the obtained Compound A-1 are shown below. m / z: 1036.38 (100.0%), 1037.38 (89.7%), 1038.38 (56.4%), 1039.38 (28.2%), 1038.39 (12.6%), 1040.38 (10.6%), 1039.39 (8.2%), 1041.38 (4.1%), 1040.37 (3.1%), 1040.39 (2.8%), 1042.38 (1.3%), 1041.39 (1.2%), 1041.37 (1.0%)

[0153] [Synthesis of Compound A-2] Compound A-2 was synthesized according to the following procedure.

[0154]

[0155] <Synthesis of Compound 2b> Under a nitrogen atmosphere, p-hydroxybenzoic acid (17.9 mmol) and compound 1a (26.8 mmol) were dissolved in cyclopentanone (40 mL) and DMAc (40 mL), and the temperature was raised to 100°C, after which N,N-diisopropylethylamine (35.7 mmol) was added. The resulting reaction solution was heated and stirred at 100°C for 5 hours. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain compound 2b.

[0156] <Synthesis of Compound A-2> Terephthalic acid dichloride (8.0 mmol) and compound 6b (17.9 mmol) were dissolved in cyclopentanone (20 mL), and N,N-diisopropylethylamine (20.1 mmol) and N-methylimidazole (1.6 mmol) were added under water cooling. The resulting reaction solution was stirred at room temperature for 1 hour, and then quenched with methanol and HO. The precipitated solid was collected and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain compound A42 (yield 70%). The results of MALDI-MS measurement of the resulting compound A-2 are shown below. m / z: 1078.35 (100.0%), 1079.36 (51.2%), 1079.35 (40.6%), 1080.36 (36.5%), 1080.35 (34.0%), 1081.35 (23.6%), 1081.36 (13.8%), 1082.35 (9.4%), 1082.36 (7.3%), 1083.35 (3.4%), 1083.36 (2.9%), 1084.35 (1.4%)

[0157] [Synthesis of Compound A-3] Compound A-3 was synthesized according to the following procedure.

[0158]

[0159] <Synthesis of Compound 3b> Under a nitrogen atmosphere, 5-hydroxyisophthalic acid (4.47 mmol) and compound 1a (13.4 mmol) were dissolved in cyclopentanone (20 mL) and DMAc (20 mL), and the temperature was raised to 100°C, after which N,N-diisopropylethylamine (17.9 mmol) was added. The resulting reaction solution was heated and stirred at 100°C for 5 hours. The solvent was distilled off, and the mixture was purified by silica gel column chromatography (hexane / ethyl acetate) to obtain compound 3b.

[0160] <Synthesis of Compound A-3> 4,4'-Biphenyldicarbonyl chloride (2.01 mmol) and Compound 3b (4.47 mmol) were dissolved in cyclopentanone (10 mL), and N,N-diisopropylethylamine (5.0 mmol) and N-methylimidazole (0.4 mmol) were added under water cooling. The resulting reaction solution was stirred at room temperature for 1 hour, then quenched with methanol and HO. The precipitated solid was collected and purified by silica gel column chromatography (hexane / ethyl acetate) to obtain Compound A-3 (yield 70%). The results of MALDI-MS measurement of the obtained Compound A-3 are shown below. m / z: 1915.65 (100.0%), 1916.65 (92.4%), 1917.65 (73.1%), 1914.65 (60.4%), 1918.65 (48.6%), 1917.66 (30.0%), 1919.65 (27.4%), 1916.66 (26.8%), 1918.66 (17.3%), 1920.65 (14.1%), 1919.66 (11.7%), 1918.64 (8.1%), 1921.65 (7.7%), 1920.66 (6.8%), 1919.64 (5.8%), 1920.64 (3.2%), 1921.66 (2.7%), 1922.65 (2.7%), 1915.66 (1.6%), 1921.64 (1.2%), 1922.66 (1.2%), 1922.64 (1.2%), 1923.65 (1.0%)

[0161] [Synthesis of Compound A-4] Compound A-4 was synthesized according to the following procedure.

[0162]

[0163] <Synthesis of Compound 4b> Under a nitrogen atmosphere, p-allyloxybenzaldehyde (18.5 mmol) and Compound 2a (18.5 mmol) were dissolved in THF (3 mL), and Karstedt's catalyst (2% Pt xylene solution, 30 μL) was added under water cooling. The resulting reaction solution was stirred at room temperature for 2 hours, after which the solvent was distilled off and the residue was purified by silica gel column chromatography (hexane / ethyl acetate = 9 / 1) to obtain Compound 4b (yield 70%).

[0164] <Synthesis of Compound 4c> Compound 4c was obtained by the same procedure as in the above <Synthesis of Compound 1c>.

[0165] <Synthesis of Compound A-4> Compound A-4 was obtained by the same procedure as in <Synthesis of Compound A-1> above. The MALDI-MS measurement results of the obtained compound A-4 are shown below. m / z: 888.34 (100.0%), 889.35 (45.5%), 889.34 (30.5%), 890.35 (26.0%), 890.34 (24.0%), 891.34 (14.3%), 891.35 (7.9%), 892.34 (5.0%), 892.35 (3.5%), 893.34 (1.5%), 893.35 (1.2%)

[0166] [Synthesis of Compound A-5] Compound A-5 was synthesized according to the following procedure.

[0167]

[0168] Compound A-5 was synthesized in the same manner as in the above-mentioned [Synthesis of Compound A-2], except that compound 1a was replaced with compound 5a. The results of MALDI-MS measurement of the obtained compound A-5 are shown below. m / z: 1226.39 (100.0%), 1227.40 (55.7%), 1227.39 (50.8%), 1228.40 (46.8%), 1228.39 (45.1%), 1229.39 (41.4%), 1230.39 (18.8%), 1229.40 (14.3%), 1230.40 (10.1%), 1231.39 (7.5%), 1231.40 (5.0%), 1232.39 (2.8%), 1232.40 (1.2%), 1233.39 (1.0%)

[0169] [Synthesis of Compound A-6] Compound A-6 was synthesized according to the following procedure.

[0170]

[0171] Compound A-6 was synthesized by the same procedure as in the above [Synthesis of Compound A-4], except that compound 4a was replaced with compound 6a. The MALDI-MS measurement results of the obtained compound A-6 are shown below. m / z: 888.34 (100.0%), 889.35 (45.5%), 889.34 (30.5%), 890.35 (26.0%), 890.34 (24.0%), 891.34 (14.3%), 891.35 (7.9%), 892.34 (5.0%), 892.35 (3.5%), 893.34 (1.5%), 893.35 (1.2%)

[0172] [Synthesis of Compound A-7] Compound A-7 was synthesized according to the following procedure.

[0173]

[0174] Compound A-7 was synthesized by the same procedure as in the above [Synthesis of Compound A-6], except that the raw material aldehyde was changed to Compound 7a. The MALDI-MS measurement results of the obtained Compound A-7 are shown below. m / z: 948.36 (100.0%), 949.37 (47.8%), 949.36 (30.5%), 950.37 (28.2%), 950.36 (24.0%), 951.36 (14.8%), 951.37 (9.0%), 952.36 (4.6%), 952.37 (4.6%), 953.36 (1.5%), 953.37 (1.4%)

[0175] [Synthesis of Compound A-8] Compound A-8 was synthesized according to the following procedure.

[0176]

[0177] Compound 8a was synthesized under general esterification conditions, and compound 8b was synthesized by the same oxidation reaction as in the above-mentioned <Synthesis of Compound 1c>. Compound A-8 was synthesized by the same procedure as in the above-mentioned [Synthesis of Compound A-1], except that the raw materials were changed as described above. The results of MALDI-MS measurement of the obtained compound A-8 are shown below. m / z: 2156.70 (100.0%), 2155.70 (72.7%), 2157.69 (72.5%), 2157.70 (72.3%), 2154.69 (71.1%), 2156.69 (60.0%), 2155.69 (57.7%), 2158.70 (53.2%), 2158.69 (52.1%), 2159.70 (34.5%), 2159.69 (31.0%), 2160.69 (17.8%), 2160.70 (17.4%), 2161.69 (9.1%), 2161.70 (8.2%), 2159.71 (4.1%), 2162.69 (4.1%), 2158.71 (3.7%), 2162.70 (3.6%), 2160.71 (2.4%), 2163.69 (1.6%), 2160.68 (1.5%), 2163.70 (1.3%), 2161.71 (1.3%), 2161.68 (1.0%)

[0178] [Synthesis of Compound A-9] Compound A-9 was synthesized according to the following procedure.

[0179]

[0180] Compound A-9 was synthesized in the same manner as in [Synthesis of Compound A-3], except that 4,4'-biphenyldicarbonyl chloride was replaced with 1,4-naphthalenedicarbonyl dichloride. The results of MALDI-MS measurement of the obtained compound A-9 are shown below. m / z: 1889.64 (100.0%), 1891.64 (65.4%), 1890.64 (65.0%), 1888.64 (60.2%), 1890.63 (50.9%), 1892.64 (47.2%), 1891.63 (29.0%), 1893.63 (21.7%), 1893.64 (19.5%), 1892.63 (17.6%), 1894.64 (11.5%), 1894.63 (10.2%), 1892.65 (7.0%), 1891.65 (5.9%), 1895.64 (5.7%), 1895.63 (4.5%), 1893.65 (2.7%), 1896.64 (2.5%), 1896.63 (2.0%), 1894.65 (1.9%), 1895.65 (1.1%)

[0181] [Synthesis of Compound A-10] Compound A-10 was synthesized according to the following procedure.

[0182]

[0183] <Synthesis of Compound 10b> 5-(benzyloxy)isophthalic acid (2.90 g), potassium carbonate (4.42 g), and Compound 1a (10.89 g) were added to 250 mL of 1-methyl-2-pyrrolidone and stirred at 55°C for 2 hours. The reaction solution was cooled to room temperature, and ethyl acetate (300 mL) and 1 N aqueous hydrochloric acid (150 mL) were added. After stirring, the organic layer was separated. The organic layer was washed twice with 10% brine (100 mL) and dried over anhydrous sodium sulfate. The desiccant was filtered off, and the organic layer was concentrated to obtain a crude product as a brown oil. The obtained crude product was purified by silica gel chromatography (hexane / ethyl acetate = 95 / 5) to obtain 6.7 g of Compound 10b as a colorless oil.

[0184] <Synthesis of Compound 3b> Compound 10b (6.00 g) was dissolved in THF (30 mL) and the mixture was purged with nitrogen. 10% palladium carbon (1.35 g) was added thereto, and the atmosphere was purged with hydrogen and stirred at room temperature for 1 hour. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure to obtain 5.2 g of compound 3b as a colorless oil.

[0185] <Synthesis of Compound A-10> 1,3,5-benzenetricarboxylic acid (50 mg) was mixed with compound 3b (672 mg), 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride (408 mg), N,N-dimethylaminopyridine (9 mg), 1-methylimidazole (60 mg), and dichloromethane (1 mL), and the mixture was stirred at room temperature for 1 hour. The reaction solution was purified by silica gel column chromatography (hexane / ethyl acetate=95 / 5), yielding 440 mg of compound A-10 as a colorless oil. The results of MALDI-MS measurement of the resulting compound A-10 are shown below. m / z: 2721.91 (100.0%), 2720.91 (95.2%), 2722.91 (87.7%), 2719.91 (79.3%), 2723.91 (64.5%), 2724.91 (42.5%), 2718.91 (33.2%), 2721.90 (31.1%), 2722.90 (30.0%), 2723.90 (29.9%), 2720.90 (26.6%), 2725.91 (24.8%), 2724.90 (24.2%), 2725.90 (17.7%), 2722.92 (15.4%), 2726.91 (14.0%), 2723.92 (12.9%), 2726.90 (10.0%), 2721.92 (9.9%), 2724.92 (9.5%), 2727.91 (6.9%), 2725.92 (6.0%), 2727.90 (5.6%), 2726.92 (3.5%), 2728.91 (3.3%), 2728.90 (2.8%), 2727.92 (1.7%), 2729.90 (1.3%), 2729.91 (1.3%).

[0186] [Synthesis of Compound A-11] Compound A-11 was synthesized according to the following procedure.

[0187]

[0188] Compound A-11 was obtained by the same procedure as in the above-mentioned [Synthesis of Compound A-3], except that 4,4'-biphenyldicarbonyl chloride was changed to trans-[1,1'-bi(cyclohexane)]-4,4'-dicarbonyl dichloride. The results of MALDI-MS measurement of the obtained Compound A-11 are shown below. m / z: 1928.75 (100.0%), 1929.75 (99.2%), 1926.75 (88.4%), 1927.75 (77.0%), 1928.74 (74.7%), 1927.74 (71.8%), 1930.74 (56.2%), 1930.75 (48.3%), 1929.74 (42.5%), 1931.74 (32.3%), 1931.75 (30.4%), 1932.75 (17.7%), 1932.74 (15.4%), 1933.75 (9.6%), 1929.76 (9.5%), 1933.74 (6.8%), 1930.76 (4.3%), 1931.76 (4.0%), 1934.74 (3.5%), 1932.76 (3.0%), 1934.75 (2.9%), 1935.74 (1.4%), 1935.75 (1.1%), 1933.76 (1.0%)

[0189] [Synthesis of Compound A-12] Compound A-12 was synthesized according to the following procedure.

[0190]

[0191] Compound A-12 was obtained by the same procedure as in the above-mentioned [Synthesis of Compound A-1], except that compound 1a was changed to compound 12a and methylhydroquinone was changed to hydroquinone. The results of MALDI-MS measurement of the obtained compound A-12 are shown below. m / z: 3804.17 (100.0%), 3803.17 (94.7%), 3805.17 (90.1%), 3802.17 (82.9%), 3806.16 (74.3%), 3805.16 (62.9%), 3801.17 (57.8%), 3806.17 (57.3%), 3804.16 (57.3%), 3807.16 (54.4%), 3803.16 (48.2%), 3807.17 (38.1%), 3808.16 (37.5%), 3800.17 (32.0%), 3802.16 (28.8%), 3808.17 (21.4%), 3809.16 (21.3%), 3801.16 (13.2%), 3810.16 (11.6%), 3804.18 (10.5%), 3799.17 (9.0%), 3803.18 (8.8%), 3809.17 (8.4%), 3805.18 (7.8%), 3802.18 (3.5%), 3811.16 (2.3%), 3808.15 (2.1%), 3809.15 (1.4%)

[0192] [Synthesis of Compound A-13] Compound A-13 was synthesized according to the following procedure.

[0193]

[0194] <Synthesis of Compound 13b> 1.8 g of colorless oily compound 13b was obtained in the same manner as in <Synthesis of Compound 10b>, except that the raw materials were changed to compound 3b and 5-(benzyloxy)isophthalic acid.

[0195] <Synthesis of Compound 13c> 1.7 g of colorless oily compound 13c was obtained in the same manner as in <Synthesis of Compound 3b> in [Synthesis of Compound A-10], except that the raw material was changed to compound 13b.

[0196] <Synthesis of Compound A-13> 300 mg of colorless oily Compound A-13 was obtained in the same manner as Compound A-10, except that the raw materials were changed to Compound 13c and 1,3,5-benzenetricarboxylic acid. The results of MALDI-MS measurement of the obtained Compound A-13 are shown below. m / z: 5727.83 (100.0%), 5725.83 (99.7%), 5726.83 (94.5%), 5724.83 (92.7%), 5723.83 (66.5%), 5728.83 (62.7%), 5726.84 (61.6%), 5725.84 (57.2%), 5722.83 (44.7%), 5723.84 (43.3%), 5729.83 (42.1%), 5724.84 (39.7%), 5727.84 (34.7%), 5728.84 (27.7%), 5721.83 (26.8%), 5722.84 (26.0%), 5730.83 (24.8%), 5729.84 (17.4%), 5728.82 (17.0%), 5724.82 (15.3%), 5720.83 (12.2%), 5726.82 (11.9%), 5725.82 (11.6%), 5727.82 (11.5%), 5731.83 (9.8%), 5729.82 (9.5%), 5730.84 (9.3%), 5721.84 (7.7%), 5730.82 (5.7%), 5731.82 (4.9%), 5726.85 (3.7%), 5725.85 (3.5%), 5719.83 (2.6%), 5723.82 (2.4%), 5724.85 (1.7%), 5732.83 (1.3%), 5727.85 (1.1%).

[0197] [Synthesis of Compound A-14] Compound A-14 was synthesized according to the following procedure.

[0198]

[0199] Compound 14b was synthesized under general amidation conditions. Then, compound A-14 was synthesized using compound 14b and terephthalic acid chloride in the same procedure as in [Synthesis of compound A-2]. The results of MALDI-MS measurement of the obtained compound A-14 are shown below. m / z: 1076.39 (100.0%), 1077.39 (91.8%), 1078.39 (43.2%), 1078.38 (27.1%), 1079.39 (25.6%), 1080.39 (11.0%), 1079.38 (9.8%), 1080.38 (4.8%), 1081.39 (3.4%), 1081.38 (2.7%), 1079.40 (2.3%), 1080.40 (1.5%), 1082.39 (1.1%)

[0200] [Synthesis of Compound A-15] Compound A-15 was synthesized according to the following procedure.

[0201]

[0202] Compound 15b was synthesized under general urethanization conditions. Then, compound A-15 was synthesized using compound 15b and terephthalic acid chloride in the same procedure as in [Synthesis of compound A-2]. The results of MALDI-MS measurement of the obtained compound A-15 are shown below. m / z: 1108.38 (100.0%), 1109.38 (91.8%), 1110.38 (43.6%), 1110.37 (27.1%), 1111.38 (26.0%), 1112.38 (11.3%), 1111.37 (9.8%), 1112.37 (4.8%), 1113.38 (3.5%), 1113.37 (2.7%), 1111.39 (2.3%), 1112.39 (1.5%), 1114.38 (1.2%)

[0203] [Synthesis of Compound A-16] Compound A-16 was synthesized using 1,4-phenylenediamine and Compound 1c under general amidation conditions. The results of MALDI-MS measurement of the obtained Compound A-16 are shown below. m / z: 1020.40 (100.0%), 1021.40 (89.5%), 1022.40 (40.7%), 1022.39 (27.1%), 1023.40 (24.0%), 1024.40 (10.1%), 1023.39 (9.8%), 1024.39 (4.8%), 1025.40 (3.0%), 1025.39 (2.7%), 1023.41 (2.0%), 1024.41 (1.2%), 1026.40 (1.0%)

[0204] [Synthesis of Compound A-17] Compound A-17 was obtained in the same manner as in [Synthesis of A-3], except that 4,4'-biphenyldicarbonyl chloride was replaced with 4,4'-oxydibenzoyl chloride. The results of MALDI-MS measurement of the obtained compound A-17 are shown below. m / z: 1931.65 (100.0%), 1932.65 (84.8%), 1933.65 (66.1%), 1930.65 (59.4%), 1934.65 (48.4%), 1932.64 (31.8%), 1933.64 (28.6%), 1935.65 (25.9%), 1934.64 (17.3%), 1935.64 (14.5%), 1936.65 (13.5%), 1936.64 (8.7%), 1934.66 (7.6%), 1933.66 (7.0%), 1937.65 (6.0%), 1935.66 (4.7%), 1937.64 (4.5%), 1938.65 (2.5%), 1936.66 (2.2%), 1938.64 (2.0%), 1937.66 (1.3%)

[0205] [Synthesis of Compound A-18] Compound A-18 was synthesized in the same manner as in [Synthesis of Compound A-8], except that 4,4'-biphenyldicarbonyl chloride was changed to isophthaloyl chloride. The results of MALDI-MS measurement of the obtained compound A-18 are shown below. m / z: 2080.67 (100.0%), 2081.66 (98.7%), 2078.66 (77.5%), 2079.67 (74.3%), 2080.66 (65.5%), 2079.66 (63.0%), 2082.66 (60.6%), 2081.67 (48.3%), 2082.67 (45.7%), 2083.66 (33.5%), 2083.67 (31.9%), 2084.66 (23.1%), 2084.67 (12.0%), 2085.66 (9.7%), 2085.67 (6.7%), 2086.66 (4.2%), 2083.68 (3.2%), 2086.67 (3.2%), 2082.68 (2.6%), 2084.65 (1.6%), 2087.66 (1.6%), 2085.65 (1.6%), 2084.68 (1.3%), 2087.67 (1.2%)

[0206] [Synthesis of Compound A-19] Compound A-19 was synthesized according to the following procedure.

[0207]

[0208] Compound 19a was synthesized from 4-hydroxybenzoic acid and hydroquinone under general esterification conditions. Compound 19b was then synthesized from compound 19a and 6-bromo-1-hexene under the conditions described in JP 2013-209631 A, with reference to the conditions described in JP 2013-209631 A. Compound A-19 was then synthesized from compound 19b and the above silane compound by a hydrosilylation reaction using a Karstedt's catalyst. The results of MALDI-MS analysis of the resulting compound A-19 are shown below. m / z: 1106.46 (100.0%), 1107.46 (96.2%), 1108.46 (59.0%), 1109.46 (36.0%), 1108.47 (15.1%), 1110.46 (11.5%), 1111.46 (4.7%), 1110.45 (4.6%), 1109.47 (4.4%), 1110.47 (2.6%), 1112.46 (1.6%), 1111.47 (1.4%), 1111.45 (1.1%)

[0209] [Synthesis of Compound A-20] Compound A-20 was synthesized according to the following procedure.

[0210]

[0211] Compound 20a was synthesized using 4-(2-propenyloxy)phenol and 1,3-dichlorobenzene under the conditions described in RSC Advances (2016), 6, pp. 33249-33258. Compound 20a was then synthesized from the above silane compound by hydrosilylation using Karstedt's catalyst. The MALDI-MS measurement results for the resulting compound A-20 are shown below. m / z: 670.30 (100.0%), 671.30 (57.3%), 672.30 (23.7%), 673.30 (8.0%), 672.31 (7.0%), 673.31 (2.7%), 674.30 (2.0%).

[0212] [Synthesis of Compound A-21] Compound A-21 was synthesized according to the following procedure.

[0213]

[0214] Compound A-21 was synthesized in the same manner as Compound A-13, except that the raw material was changed to 4,4'-biphenyldicarboxylic acid. The results of MALDI-MS measurement of the obtained Compound A-21 are shown below. m / z: 3919.27 (100.0%), 3918.27 (93.4%), 3920.27 (93.0%), 3921.27 (77.0%), 3917.27 (71.6%), 3922.27 (54.6%), 3916.27 (42.2%), 3923.27 (34.8%), 3920.26 (30.8%), 3921.26 (30.3%), 3922.26 (27.2%), 3919.26 (26.3%), 3920.28 (25.6%), 3919.28 (23.0%), 3921.28 (22.7%), 3918.26 (21.4%), 3924.27 (17.9%), 3923.26 (16.7%), 3922.28 (14.9%), 3917.26 (13.6%), 3915.27 (12.7%), 3918.28 (10.3%), 3924.26 (9.6%), 3923.28 (6.6%), 3925.27 (6.5%), 3925.26 (4.3%), 3924.28 (1.7%)

[0215] [Synthesis of Compound A-22] Compound A-22 was synthesized according to the following procedure.

[0216]

[0217] Compound 22a was synthesized from compound 3b and 5-nitroisophthaloyl dichloride according to the method described in Chemistry - A European Journal (2008), 14(12), 3544. Compound 22a was then reacted with 4,4'-biphenyldicarbonyl chloride under standard amidation conditions to obtain compound A-22. The results of MALDI-MS analysis of the obtained compound A-22 are shown below. m / z: 3917.30 (100.0%), 3919.30 (94.5%), 3918.30 (92.0%), 3916.30 (91.8%), 3915.30 (67.2%), 3920.30 (54.1%), 3914.30 (42.7%), 3918.31 (38.4%), 3921.30 (35.0%), 3917.31 (26.8%), 3919.31 (24.0%), 3917.29 (23.6%), 3920.29 (23.2%), 3916.29 (21.6%), 3920.31 (19.5%), 3922.30 (19.5%), 3915.31 (19.0%), 3918.29 (18.7%), 3921.29 (13.0%), 3916.31 (12.9%), 3913.30 (12.8%), 3919.29 (12.0%), 3921.31 (10.4%), 3923.30 (6.5%), 3922.31 (5.0%), 3922.29 (5.0%), 3923.29 (4.4%), 3918.32 (1.4%)

[0218] [Synthesis of Compound A-23] Compound A-23 was synthesized according to the following procedure.

[0219]

[0220] Compound 23a was synthesized in the same manner as compound 3b, except that the raw material was changed to 5-aminoisophthalic acid. Compound 23a was then reacted with trimesoyl chloride using a conventional amidation method to obtain compound A-23. The results of MALDI-MS measurement of the obtained compound A-23 are shown below. m / z: 2717.96 (100.0%), 2718.95 (98.7%), 2718.96 (96.5%), 2719.95 (92.1%), 2719.96 (86.9%), 2720.96 (72.0%), 2720.95 (70.9%), 2717.95 (70.8%), 2716.95 (56.5%), 2716.96 (53.8%), 2721.95 (51.9%), 2715.95 (45.9%), 2721.96 (45.0%), 2722.95 (32.2%), 2722.96 (27.0%), 2723.95 (18.1%), 2723.96 (15.1%), 2724.95 (10.6%), 2724.96 (7.2%), 2720.97 (6.5%), 2719.97 (6.4%), 2721.97 (5.6%), 2725.95 (4.6%), 2722.97 (4.3%), 2722.94 (3.8%), 2721.94 (3.7%), 2725.96 (3.2%), 2723.97 (2.9%), 2723.94 (2.6%), 2726.95 (1.9%), 2726.96 (1.4%), 2724.94 (1.3%), 2725.94 (1.2%), 2724.97 (1.2%), 2718.97 (1.1%)

[0221] [Synthesis of Compound A-24] Compound A-24 was synthesized according to the following procedure.

[0222]

[0223] Compound A-24 was synthesized in the same manner as Compound A-13, except that the raw material was changed to 2,6-naphthalenedicarboxylic acid. The results of MALDI-MS measurement of the obtained Compound A-24 are shown below. m / z: 3893.25 (100.0%), 3894.25 (92.1%), 3892.25 (89.9%), 3895.25 (78.5%), 3891.25 (71.0%), 3896.25 (57.1%), 3894.26 (54.4%), 3893.26 (53.6%), 3895.26 (47.9%), 3890.25 (46.2%), 3892.26 (45.8%), 3897.25 (36.8%), 3896.26 (34.1%), 3891.26 (21.7%), 3898.25 (20.2%), 3897.26 (17.6%), 3889.25 (13.9%), 3894.24 (11.8%), 3895.24 (11.0%), 3896.24 (10.5%), 3899.25 (8.1%), 3893.24 (7.8%), 3897.24 (7.6%), 3898.26 (6.6%), 3898.24 (4.2%), 3894.27 (2.5%), 3895.27 (2.5%), 3899.24 (1.6%), 3899.26 (1.6%), 3896.27 (1.6%), 3900.25 (1.2%)

[0224] [Synthesis of Compound A-25] Compound A-25 was synthesized according to the following procedure.

[0225]

[0226] Compound A-25 was synthesized in the same manner as Compound A-13, except that the raw material was changed to 1,4-naphthalenedicarboxylic acid. The results of MALDI-MS measurement of the obtained Compound A-25 are shown below. m / z: 3893.25 (100.0%), 3894.25 (92.1%), 3892.25 (89.9%), 3895.25 (78.5%), 3891.25 (71.0%), 3896.25 (57.1%), 3894.26 (54.4%), 3893.26 (53.6%), 3895.26 (47.9%), 3890.25 (46.2%), 3892.26 (45.8%), 3897.25 (36.8%), 3896.26 (34.1%), 3891.26 (21.7%), 3898.25 (20.2%), 3897.26 (17.6%), 3889.25 (13.9%), 3894.24 (11.8%), 3895.24 (11.0%), 3896.24 (10.5%), 3899.25 (8.1%), 3893.24 (7.8%), 3897.24 (7.6%), 3898.26 (6.6%), 3898.24 (4.2%), 3894.27 (2.5%), 3895.27 (2.5%), 3899.24 (1.6%), 3899.26 (1.6%), 3896.27 (1.6%), 3900.25 (1.2%)

[0227] [Synthesis of Compound A-26] Compound A-26 was synthesized according to the following procedure.

[0228]

[0229] Compound A-26 was synthesized in the same manner as Compound A-13, except that the raw material was changed to anthracene-9,10-dicarboxylic acid. The results of MALDI-MS measurement of the obtained Compound A-26 are shown below. m / z: 3943.27 (100.0%), 3944.27 (93.3%), 3942.27 (93.2%), 3945.27 (77.6%), 3941.27 (71.3%), 3946.27 (55.2%), 3940.27 (41.8%), 3947.27 (35.3%), 3944.26 (30.4%), 3945.26 (30.0%), 3946.26 (27.0%), 3944.28 (26.3%), 3943.26 (25.8%), 3943.28 (23.5%), 3945.28 (23.4%), 3942.26 (21.0%), 3948.27 (18.3%), 3947.26 (16.7%), 3946.28 (15.7%), 3941.26 (13.4%), 3939.27 (12.5%), 3942.28 (10.5%), 3948.26 (9.7%), 3947.28 (7.2%), 3949.27 (6.8%), 3949.26 (4.2%), 3948.28 (1.8%)

[0230] [Synthesis of Compound A-27] Compound A-27 was synthesized according to the following procedure.

[0231]

[0232] Compound A-27 was synthesized in the same manner as Compound A-13, except that the raw material was changed to 4,4'-(ethyne-1,2-diyl)dibenzoic acid. The results of MALDI-MS measurement of the obtained Compound A-27 are shown below. m / z: 3943.27 (100.0%), 3944.27 (93.3%), 3942.27 (93.2%), 3945.27 (77.6%), 3941.27 (71.3%), 3946.27 (55.2%), 3940.27 (41.8%), 3947.27 (35.3%), 3944.26 (30.4%), 3945.26 (30.0%), 3946.26 (27.0%), 3944.28 (26.3%), 3943.26 (25.8%), 3943.28 (23.5%), 3945.28 (23.4%), 3942.26 (21.0%), 3948.27 (18.3%), 3947.26 (16.7%), 3946.28 (15.7%), 3941.26 (13.4%), 3939.27 (12.5%), 3942.28 (10.5%), 3948.26 (9.7%), 3947.28 (7.2%), 3949.27 (6.8%), 3949.26 (4.2%), 3948.28 (1.8%)

[0233] [Synthesis of Compound A-28] Compound A-28 was synthesized according to the following procedure.

[0234]

[0235] Compound 13c was reacted with 4,4'-diisocyanato-2,2'-dimethylbiphenyl under the conditions of a general urethane-forming method to obtain Compound A-28. The results of MALDI-MS measurement of the obtained Compound A-28 are shown below. m / z: 3978.32 (100.0%), 3977.32 (92.5%), 3976.32 (82.7%), 3979.32 (76.0%), 3975.32 (66.6%), 3980.32 (54.7%), 3977.33 (51.6%), 3976.33 (43.7%), 3979.33 (42.3%), 3974.32 (42.3%), 3978.33 (39.5%), 3981.32 (35.3%), 3980.33 (32.6%), 3982.32 (19.8%), 3975.33 (19.2%), 3981.33 (17.6%), 3973.32 (12.6%), 3979.31 (11.8%), 3978.31 (10.6%), 3980.31 (9.5%), 3983.32 (7.9%), 3977.31 (7.0%), 3981.31 (6.9%), 3982.33 (5.3%), 3982.31 (4.9%), 3979.34 (2.6%), 3980.34 (1.9%), 3983.33 (1.8%), 3978.34 (1.4%), 3983.31 (1.3%), 3984.32 (1.2%)

[0236] [Synthesis of Compound A-29] Compound A-29 was synthesized according to the following procedure.

[0237]

[0238] Compound 13c was reacted with 4,4'-methylenediphenyl diisocyanate under general urethane-forming conditions to obtain Compound A-29. The results of MALDI-MS measurement of the obtained Compound A-29 are shown below. m / z: 3963.31 (100.0%), 3964.31 (98.0%), 3962.31 (88.0%), 3965.31 (81.8%), 3963.30 (75.8%), 3964.30 (71.8%), 3961.31 (67.1%), 3962.30 (63.7%), 3965.30 (62.6%), 3966.31 (57.5%), 3966.30 (48.9%), 3961.30 (36.0%), 3967.31 (34.1%), 3967.30 (34.0%), 3960.31 (26.2%), 3960.30 (24.8%), 3968.30 (19.7%), 3968.31 (15.8%), 3959.30 (15.2%), 3964.32 (11.6%), 3965.32 (11.4%), 3966.32 (8.4%), 3969.30 (7.6%), 3963.32 (5.3%), 3969.31 (4.9%), 3966.29 (2.9%), 3965.29 (2.8%), 3970.30 (1.7%), 3967.32 (1.6%), 3967.29 (1.3%)

[0239] [Synthesis of Compound A-30] Compound A-30 was synthesized according to the following procedure.

[0240]

[0241] Compound 13c was reacted with 1,5-diisocyanatonaphthalene under general urethane-forming conditions to synthesize compound A-30. The results of MALDI-MS measurement of the obtained compound A-30 are shown below. m / z: 3923.27 (100.0%), 3924.28 (94.7%), 3922.28 (91.8%), 3923.28 (84.5%), 3924.27 (83.1%), 3925.28 (82.6%), 3921.28 (70.5%), 3922.27 (68.1%), 3925.27 (67.6%), 3926.27 (66.8%), 3926.28 (47.5%), 3927.27 (39.6%), 3921.27 (38.8%), 3927.28 (30.4%), 3920.28 (27.7%), 3920.27 (26.7%), 3928.27 (20.7%), 3919.27 (16.4%), 3928.28 (15.4%), 3924.29 (11.5%), 3925.29 (11.2%), 3929.27 (8.0%), 3923.29 (5.2%), 3929.28 (4.6%), 3926.29 (4.0%), 3926.26 (3.2%), 3925.26 (3.0%), 3927.26 (1.8%), 3930.27 (1.7%)

[0242] [Synthesis of Compound B-1] Compound B-1 was synthesized according to the following procedure.

[0243]

[0244] <Synthesis of Compound (S-1-a)> 50.0 g of Compound (S-1) and 201.0 g of sodium iodide were added to 600 mL of acetone, and the mixture was heated and stirred at 60°C for 12 hours. After stirring, 1000 mL of hexane and 600 mL of water were added to the resulting reaction liquid, followed by separation and removal of the aqueous layer. The organic layer was then dried over anhydrous magnesium sulfate. After drying, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to obtain 54.8 g of Compound (S-1-a) as a colorless oil.

[0245] <Synthesis of Compound (S-1-b)> 4.2 g of 3,5-dihydroxybenzaldehyde, 29.6 g of compound (S-1-a), and 29.7 g of cesium carbonate were added to 270 mL of DMF and stirred at room temperature for 3 hours. After stirring, 500 mL of ethyl acetate was added to the resulting reaction solution, and insoluble matter was filtered off. The filtrate was then washed with 1 N aqueous hydrochloric acid and 10% saline, and then dried over anhydrous magnesium sulfate. After drying, the anhydrous magnesium sulfate was filtered off, and the filtrate was concentrated to obtain a crude product as a light brown oil. The crude product was purified by silica gel column chromatography (gradient from hexane alone to hexane / ethyl acetate = 93 / 7) to obtain 8.6 g of compound (S-1-b) as a colorless oil.

[0246] <Synthesis of Compound (S-1-c)> 8.6 g of compound (S-1-b), 0.5 g of sodium dihydrogen phosphate, and 36 mg of tetrabutylammonium hydrogen sulfate were added to 50 mL of ethyl acetate. 1.4 mL of hydrogen peroxide and an aqueous sodium chlorite solution (1.4 g of sodium chlorite dissolved in 3.5 mL of water) were added dropwise, successively, and the mixture was stirred at 40°C for 1 hour. After stirring, the aqueous layer was removed from the reaction solution, and the organic layer was washed with a 5% aqueous sodium sulfite solution and 10% saline solution and then dried over anhydrous sodium sulfate. After drying, the anhydrous sodium sulfate was filtered off, and the filtrate was concentrated to obtain 8.0 g of compound (S-1-c) as a white solid.

[0247] <Synthesis of Compound (D-1)> Under a nitrogen stream, 6.0 g of 4-phenylbenzoyl chloride, 30.5 g of methyl gentisate, 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 contents of the three-necked flask, and the mixture was allowed to react 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 compound (D-1) as a white solid (yield 62%).

[0248] <Synthesis of Compound B-1> 0.26 g of compound (D-1), 0.65 g of compound (S-1-c), and 9 mg of 4-dimethylaminopyridine were dissolved in 4 mL of dichloromethane, and 0.43 g of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 60 μL of 1-methylimidazole were added thereto and stirred at room temperature for 1 hour. After stirring, the reaction solution was purified by silica gel column chromatography (gradient from hexane alone to hexane / ethyl acetate = 95 / 5), yielding 0.81 g of compound B-1 as a white solid. The results of MALDI-MS measurement of the obtained compound B-1 are shown below. m / z: 1156.40 (100.0%), 1157.40 (96.9%), 1158.40 (56.8%), 1159.40 (29.8%), 1158.41 (19.8%), 1159.41 (12.6%), 1160.40 (11.5%), 1160.41 (8.3%), 1161.40 (4.6%), 1161.41 (2.2%), 1157.41 (1.5%), 1162.40 (1.5%), 1161.39 (1.0%)

[0249] [Synthesis of Compound B-2] Compound B-2 was synthesized according to the following procedure.

[0250]

[0251] <Synthesis of Compound (D-2-a)> 2.96 g of 4-hydroxybenzaldehyde and 5.00 g of 4-phenylbenzoyl chloride were dissolved in 50 mL of tetrahydrofuran and cooled to 5°C. 0.18 mL of 1-methylimidazole and 4.32 mL of N,N-diisopropylamine were added dropwise thereto, and the mixture was stirred at 5°C or below for 2 hours. 100 mL of methanol was added to the reaction solution, and the mixture was stirred for 5 minutes. The precipitated solid was collected by filtration and washed with methanol. The obtained solid was dried under reduced pressure, yielding 3.28 g of compound (D-2-a) as a white solid.

[0252] <Synthesis of Compound (D-2-b)> Compound (D-2-b) was obtained in a yield of 91% by the same procedure as in <Synthesis of Compound (S-1-c)>.

[0253] <Synthesis of Compound (S-4-b)> 2.90 g of 5-(benzyloxy)isophthalic acid, 4.42 g of potassium carbonate, and 10.89 g of compound (S-1-a) were added to 250 mL of 1-methyl-2-pyrrolidone, and the mixture was stirred at 55°C for 2 hours. The reaction solution was cooled to room temperature, and 300 mL of ethyl acetate and 150 mL of 1 N aqueous hydrochloric acid were added. After stirring, the organic layer was separated. The organic layer was washed twice with 100 mL of 10% brine and dried over anhydrous sodium sulfate. The desiccant was filtered off, and the organic layer was concentrated to obtain a crude product as a brown oil. The obtained crude product was purified by silica gel chromatography (hexane / ethyl acetate = 95 / 5), and 6.7 g of compound (S-4-b) was obtained as a colorless oil.

[0254] <Synthesis of Compound (S-4-c)> 6.00 g of compound (S-4-b) was dissolved in 30 mL of tetrahydrofuran, and the mixture was purged with nitrogen. 1.35 g of 10% palladium carbon was added thereto, and the atmosphere was purged with hydrogen and stirred at room temperature for 1 hour. The reaction solution was filtered through Celite, and the filtrate was concentrated under reduced pressure to obtain 5.2 g of compound (S-4-c) as a colorless oil.

[0255] <Synthesis of Compound B-2> Compound B-2 was obtained in a yield of 76% by the same procedure as in <Synthesis of Compound B-1>. The results of MALDI-MS measurement of the obtained Compound B-2 are shown below. m / z: 1154.39 (100.0%), 1155.39 (98.3%), 1156.39 (49.4%), 1157.39 (28.8%), 1156.38 (26.8%), 1158.39 (13.2%), 1157.38 (10.3%), 1158.38 (4.6%), 1159.39 (4.2%), 1157.40 (3.3%), 1159.38 (2.9%), 1158.40 (2.1%), 1160.39 (1.4%), 1160.38 (1.0%)

[0256] [Synthesis of Compound B-3] Compound B-3 was obtained in a yield of 61% by the same procedure as in <Synthesis of Compound (D-1)>, except that methyl gentisate was replaced with benzoquinone and 3,5-dihydroxybenzaldehyde was replaced with 3,4-dihydroxybenzaldehyde. The results of MALDI-MS measurement of the obtained Compound B-3 are shown below. m / z: 950.36 (100.0%), 951.36 (81.4%), 952.36 (41.5%), 953.36 (16.8%), 952.37 (12.7%), 954.36 (6.3%), 953.35 (5.1%), 953.37 (3.3%), 954.35 (2.2%), 955.36 (2.1%), 954.37 (1.5%)

[0257] [Synthesis of Compound B-4] Compound B-4 was synthesized according to the following procedure.

[0258]

[0259] <Synthesis of Compound (S-5-b)> Compound (S-5-b) was obtained in a yield of 52% by the same procedure as in <Synthesis of Compound (S-1-b)>, except that the raw materials were changed as described above.

[0260] <Synthesis of Compound (S-5-c)> Compound (S-5-c) was obtained in a yield of 94% by the same procedure as in <Synthesis of Compound (S-1-c)>, except that the raw materials were changed as described above.

[0261] <Synthesis of Compound B-4> Compound B-4 was obtained in a yield of 72% by the same procedure as in <Synthesis of Compound B-1>, except that the raw materials were changed as described above. The results of MALDI-MS measurement of the obtained Compound B-4 are shown below. m / z: 1509.54 (100.0%), 1510.54 (79.1%), 1508.54 (76.4%), 1511.54 (52.2%), 1512.54 (27.4%), 1510.55 (19.7%), 1511.55 (18.0%), 1513.54 (13.5%), 1512.55 (8.9%), 1514.54 (5.9%), 1512.53 (5.7%), 1513.55 (4.1%), 1513.53 (3.5%), 1514.55 (2.1%), 1515.54 (2.1%), 1514.53 (1.4%), 1509.55 (1.0%)

[0262] [Synthesis of Compound B-5] Compound B-5 was obtained in a yield of 69% by the same procedure as in [Synthesis of Compound B-2], except that 4-hydroxybenzaldehyde was replaced with 6-hydroxynaphthaldehyde. The results of MALDI-MS measurement of the obtained Compound B-5 are shown below. m / z: 1205.40 (100.0%), 1204.40 (98.8%), 1206.40 (57.9%), 1207.40 (30.9%), 1206.41 (22.2%), 1207.41 (14.3%), 1208.40 (11.8%), 1208.41 (9.7%), 1209.40 (4.9%), 1209.41 (2.5%), 1210.40 (1.6%), 1205.41 (1.5%), 1210.41 (1.0%)

[0263] [Synthesis of Compound B-6] Compound B-6 was synthesized according to the following procedure.

[0264]

[0265] <Synthesis of Compound (S-7-b)> Compound (S-7-b) was obtained in a yield of 89% by the same procedure as in <Synthesis of Compound (S-4-b)>, except that the raw materials were changed as described above.

[0266] <Synthesis of Compound (S-7-c)> Compound (S-7-c) was obtained in a yield of 92% by the same procedure as in <Synthesis of Compound (S-1-c)>, except that the raw materials were changed as described above.

[0267] <Synthesis of Compound B-6> Compound B-6 was obtained in a yield of 70% by the same procedure as in [Synthesis of Compound B-1], except that the raw materials were changed as described above. The results of MALDI-MS measurement of the obtained Compound B-6 are shown below. m / z: 1351.39 (100.0%), 1350.39 (86.2%), 1352.39 (76.1%), 1353.39 (46.5%), 1354.39 (22.1%), 1352.40 (16.4%), 1353.40 (14.1%), 1355.39 (10.4%), 1354.40 (6.4%), 1354.38 (5.3%), 1356.39 (4.2%), 1355.40 (3.1%), 1355.38 (2.4%), 1356.40 (1.4%), 1357.39 (1.4%), 1356.38 (1.0%)

[0268] [Synthesis of Compound B-7] Compound B-7 was obtained in a yield of 69% by the same procedure as in [Synthesis of Compound B-2], except that 4-phenylbenzoyl chloride was changed to pyridine-3-carbonyl chloride hydrochloride. The results of MALDI-MS measurement of the obtained Compound B-7 are shown below. m / z: 1079.35 (100.0%), 1080.35 (90.2%), 1081.35 (57.2%), 1082.35 (28.5%), 1081.36 (12.6%), 1083.35 (10.9%), 1082.36 (8.5%), 1084.35 (4.3%), 1083.34 (3.2%), 1083.36 (3.0%), 1085.35 (1.4%), 1084.36 (1.2%), 1084.34 (1.0%)

[0269] [Synthesis of Compound B-8] Compound B-8 was obtained in a yield of 71% by the same procedure as in [Synthesis of Compound B-2], except that 4-phenylbenzoyl chloride was replaced with p-toluyl chloride. The results of MALDI-MS measurement of the obtained Compound B-8 are shown below. m / z: 1092.37 (100.0%), 1093.37 (92.0%), 1094.37 (57.7%), 1095.37 (29.1%), 1094.38 (13.8%), 1096.37 (11.3%), 1095.38 (9.2%), 1097.37 (4.5%), 1096.38 (3.3%), 1096.36 (3.1%), 1098.37 (1.4%), 1097.38 (1.4%), 1097.36 (1.0%)

[0270] [Synthesis of Compound B-9] Compound B-9 was synthesized according to the following procedure.

[0271]

[0272] <Synthesis of Compound (S-8-b)> Compound (S-8-b) was obtained in a yield of 83% by the same procedure as in <Synthesis of Compound (S-4-b)>, except that the raw materials were changed as described above.

[0273] <Synthesis of Compound (S-8-c)> Compound (S-8-c) was obtained in a yield of 90% by the same procedure as in <Synthesis of Compound (S-1-c)>, except that the raw materials were changed as described above.

[0274] <Synthesis of Compound B-9> Compound B-9 was obtained in a yield of 78% by the same procedure as in [Synthesis of Compound B-6], except that the raw materials were changed as described above. The results of MALDI-MS measurement of the obtained Compound B-9 are shown below. m / z: 1543.46 (100.0%), 1544.46 (72.1%), 1542.46 (69.5%), 1545.46 (54.5%), 1544.45 (37.2%), 1546.46 (36.6%), 1545.45 (28.3%), 1546.45 (19.4%), 1547.46 (17.6%), 1547.45 (14.5%), 1548.46 (8.1%), 1548.45 (8.0%), 1545.47 (4.9%), 1549.46 (3.7%), 1549.45 (3.7%), 1546.47 (3.4%), 1547.47 (2.0%), 1550.45 (1.6%), 1550.46 (1.3%), 1548.47 (1.2%)

[0275] [Formation of Optically Anisotropic Film] [Preparation of Photo-Alignment Film] A glass substrate was prepared as a support. The coating liquid for forming a photo-alignment film was applied onto the support at 2500 rpm for 30 seconds using a spin coater. Next, the support coated with the coating liquid for forming a photo-alignment film was dried on a hot plate at 60°C for 60 seconds to form a dried film on the support.

[0276] -------------------------------------------------- Coating liquid for forming photo-alignment film -------------------------------------------------- Photo-alignment material below: 1.00 parts by mass Water 16.00 parts by mass Butoxyethanol 42.00 parts by mass Propylene glycol monomethyl ether 42.00 parts by mass ------------------------------------------------------------------

[0277] Material for photo alignment

[0278]

[0279] The dried film was irradiated with 10 mW / cm through a wire grid polarizer using a 365 nm LED-UV irradiation device. ２ The film was irradiated with linearly polarized UV light at 1000 kJ / cm for 30 seconds to form a photo-alignment film.

[0280] Example 1 Coating liquid 1 for forming an optically anisotropic layer was prepared having the following composition. In Example 1, the silicon-containing compound shown in Table 1 below is Compound A-1. ------------------ Coating liquid 1 for forming an optically anisotropic layer ---------------------------------- 80.00 parts by mass of polymerizable liquid crystal compound 1 shown below; 3.00 parts by mass of Omnirad 819 (IGM Resins B.V.); 0.10 parts by mass of silicon-containing compound shown in Table 1; 2-butanone, amount to give a solids concentration of 30% by mass. ----------------------------------

[0281] Polymerizable liquid crystal compound 1 (mixture)

[0282]

[0283] 50 μL of the coating solution 1 for forming an optically anisotropic layer was measured out using a micropipette, dropped onto the prepared photo-alignment film, and spin-coated at a rotation speed of 1500 rpm. The resulting coating film was then subjected to a heat treatment at 80° C. for 1 minute, and then irradiated with 10 mW / cm 365 nm LED-UV light under a nitrogen atmosphere. ２ The film was then irradiated with UV light at 1000 kJ / min for 30 seconds to form an optically anisotropic layer 1A.

[0284] [Examples 2 to 20 and Examples 32 to 41] Optically anisotropic films were formed in the same manner as in Example 1, except that the silicon-containing compound in the coating liquid 1 for forming an optically anisotropic layer was changed to the compounds shown in Tables 1 and 2.

[0285] Example 21 Coating liquid 3 for forming an optically anisotropic layer was prepared having the following composition: Coating liquid 3 for forming an optically anisotropic layer ------------------------------------------------ 80 parts by mass of polymerizable discotic liquid crystal compound M4 described below 20 parts by mass of polymerizable discotic liquid crystal compound M5 described below Omnirad 819 (IGM Resins B.V.) 3 parts by mass Silicon-containing compound described in Table 1 0.50 parts by mass Methyl ethyl ketone (MEK) Amount sufficient to give a solids concentration of 33% by mass

[0286] Polymerizable discotic liquid crystal compound M4

[0287]

[0288] Polymerizable discotic liquid crystal compound M5

[0289]

[0290] 50 μL of Coating Solution 3 for Forming an Optically Anisotropic Layer was measured using a micropipette and dropped onto a glass substrate with an alignment film (PVA-103) and spin-coated to form a coating film. The resulting coating film was subjected to a heat treatment at 110°C for 2 minutes and then allowed to cool for 1 minute. The coating film after the cooling treatment was then irradiated with ultraviolet light (ultraviolet intensity: 500 mJ / cm2) in a nitrogen atmosphere to cure the coating film, yielding Optically Anisotropic Film 1B. The resulting optically anisotropic film had a thickness of approximately 1.1 μm.

[0291] Example 22 An optically anisotropic film was formed in the same manner as in Example 21, except that the silicon-containing compound in Coating Solution 3 for forming an optically anisotropic layer was changed to a compound shown in Table 1.

[0292] Example 23 Coating liquid 2 for forming an optically anisotropic layer was prepared having the following composition: Coating liquid 2 for forming an optically anisotropic layer ------------------------------------------------ 80 parts by mass of the above polymerizable discotic liquid crystal compound M4 20 parts by mass of the above polymerizable discotic liquid crystal compound M5 0.55 parts by mass of the above alignment film interface aligning agent 1 Omnirad 819 (IGM Resins B.V.) 3 parts by mass Silicon-containing compound shown in Table 1 0.10 parts by mass Methyl ethyl ketone (MEK) Amount to give a solids concentration of 33% by mass

[0293] 50 μL of the coating solution 2 for forming an optically anisotropic layer was measured out using a micropipette, dropped onto the prepared photo-alignment film, and spin-coated at a rotation speed of 1500 rpm. The resulting coating film was then subjected to a heat treatment at 80° C. for 1 minute, and then irradiated with 10 mW / cm 365 nm LED-UV light in a nitrogen atmosphere. ２ The film was then irradiated with UV light at 1000 kJ / min for 30 seconds to form an optically anisotropic layer 2A.

[0294] Examples 24 to 31 Optically anisotropic films were formed in the same manner as in Example 23, except that the silicon-containing compound in the coating liquid 2 for forming an optically anisotropic layer was changed to a compound shown in Table 1.

[0295] Comparative Examples 1 and 2 Optically anisotropic films were formed in the same manner as in Example 24, except that the silicon-containing compound in Coating Solution 2 for forming an optically anisotropic layer was changed to a compound shown in Table 1.

[0296] Comparative Examples 3 to 7 Optically anisotropic films were formed in the same manner as in Example 1, except that the silicon-containing compound in Coating Solution 1 for forming an optically anisotropic layer was changed to a compound shown in Table 1.

[0297] [Evaluation] The optically anisotropic layers obtained in each of the Examples and Comparative Examples were observed under an optical microscope and evaluated for visual unevenness and alignment unevenness according to the following criteria: In practice, a rating of "B" or higher is preferred for visual unevenness and alignment unevenness.

[0298] [Evaluation criteria for visual unevenness] "A": Almost no visual unevenness. "B": Slight visual unevenness. "C": Visual unevenness. "D": Significant visual unevenness.

[0299] (Evaluation criteria for alignment unevenness) "A": Almost no alignment defects. "B": Slight alignment defects. "C": Alignment defects. "D": Significant alignment defects.

[0300] [Results] The table shows the silicon-containing compound used in forming each optically anisotropic film, the type of optically anisotropic layer-forming coating liquid used in forming each optically anisotropic film, and the evaluation results. In the table, the silicon-containing compound contained in the optically anisotropic layer-forming coating liquid is the silicon-containing compound listed in the table. For example, the optically anisotropic layer-forming coating liquid used in Example 2 is a composition in which the silicon-containing compound in the optically anisotropic layer-forming coating liquid 1 described above is Compound A-2; the optically anisotropic layer-forming coating liquid used in Example 22 is a composition in which the silicon-containing compound in the optically anisotropic layer-forming coating liquid 2 described above is Compound A-2; and the optically anisotropic layer-forming coating liquid used in Example 24 is a composition in which the silicon-containing compound in the optically anisotropic layer-forming coating liquid 3 described above is Compound B-2. In the table, the "Si-Me / Mw" column indicates the value obtained by dividing the total number of methyl groups bonded to silicon atoms in the silicon-containing compound by the molecular weight of the compound.

[0301]

[0302]

[0303] From the results shown in the above table, it was confirmed that the composition of the present invention can form an optically anisotropic film in which visual unevenness and alignment unevenness are suppressed.

[0304] Comparison of Examples 4, 6, 7, and 19 with other Examples confirmed that when the silicon-containing group having an Si—O—Si structure in Compound A has a group represented by Formula (C-2) or a group represented by Formula (C-3), the visual unevenness suppression performance is more excellent. Comparison of Examples 1 to 20 and 32 to 41 confirmed that when the silicon-containing group having an Si—O—Si structure contains 5 or more silicon atoms, the visual unevenness suppression performance is more excellent. Comparison of Example 20 with Examples 1 to 19 and 32 to 41 confirmed that the effect of the present invention is more excellent when the molecular weight of Compound A is 700 or more. Comparison of Examples 1 to 20 and 32 to 41 confirmed that the effect of the present invention is more excellent when the value obtained by dividing the total number of methyl groups bonded to silicon atoms by the molecular weight of the compound in Compound A is 0.017 to 0.025. Comparison of Examples 26 and 31 with other Examples confirmed that B ｂ１ In the group represented by the formula: ｂ１ -X ｂ１ The number of groups represented by -L ｂ１ -X ｂ１ -L in a group having two or more groups represented by ｂ１ -X ｂ１ It was confirmed that when the number of groups represented by Z is 2, the alignment unevenness suppression performance is more excellent. ａ１ It was confirmed that when is —O—, —CO—, —CO—O—, or —NH—CO—O—, the alignment unevenness suppression performance is more excellent.

Claims

1. A composition comprising a silicon-containing compound selected from the group consisting of compound A satisfying requirements (a1) to (a3) ​​and compound B satisfying requirements (b1) to (b4), and a liquid crystal compound. (a1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. (a2) Represented by formula (A1). Formula (A1) A-(Z ａ１ -Y ａ１ - (X ａ１ ) ｍ ) ｎ In formula (A1), A is an aromatic ring or an aliphatic ring which may have a substituent; １ -L Ａ -A ２ A represents a group represented by the formula: １ and A ２ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. Ａ is -C≡C- or -CH ２ - represents ａ１ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, and -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ａ１ each independently represents a silicon-containing group having a Si-O-Si structure; n represents an integer of 2 or more; each independently represents an integer of 1 or more; (a3) ​​the molecular weight is 500 to 8000; (b1) the value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more; (b2) -L ｂ１ -X ｂ１ L ｂ１ each independently represents an alkylene group which may have a heteroatom or -O-. ｂ１ represents a monovalent group selected from the group consisting of groups represented by formulas (C-1) to (C-3): In formula (C-1), R Ｃ１ ~R Ｃ３ each independently represents an alkyl group having 1 to 10 carbon atoms; and k represents an integer of 2 to 20. In formula (C-2), R Ｃ４ represents an alkyl group having 1 to 10 carbon atoms. Ｃ５ and R Ｃ６ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X). In formula (C-3), R Ｃ７ ~R Ｃ９ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X). In formula (C-1X), R Ｃ１０ ~R Ｃ１２ each independently represents an alkyl group having 1 to 10 carbon atoms; and l represents an integer of 0 to 20. (b3) *-(Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１ The symbol * represents a bonding position. Z ｂ１ each independently represents an alkylene group, —O—, —CO—, or —NR Ｎ R represents a group consisting of a substituted or unsubstituted aryl group, or a combination thereof. Ｎ represents a hydrogen atom or a substituent. ｂ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ｂ１ represents a substituent not containing a hydrogen atom or a silicon atom, and s represents an integer of 1 or greater. (b4) The molecular weight is 500 to 8,000.

2. The composition according to claim 1, wherein the compound A is a compound represented by formula (A2) or a compound represented by formula (A3). ａ１ - (Y ａ２ -Z ａ２ ) ｒ -Y ａ３ - (T ａ１ ) ｍ１ ) ｎ Formula (A3) A-(Z ａ１ -Y ａ１ - (Z ａ３ -B ａ１ ) ｍ２ ) ｎ In formula (A2) and formula (A3), A, Z ａ１ , Y ａ１ and n represents A, Z in formula (A1). ａ１ , Y ａ１ In formula (A2), Z ａ２ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, and -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ２ and Y ａ３ Each of T independently represents an aromatic ring or an aliphatic ring which may have a substituent. Each of r independently represents an integer of 0 or more. ａ１ represents a monovalent substituent T having a siloxane structure containing three or more silicon atoms. ａ３ The site of bonding to the group represented by the formula: Ｎ m1 represents an integer of 1 or more. ａ３ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, or -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ represents a monovalent aromatic ring group substituted with one or more monovalent substituents T having a siloxane structure containing three or more silicon atoms, provided that the site at which the substituent T bonds to the aromatic ring constituting the aromatic ring group is not one of -O-, -CO-, -NR Ｎ m2 represents an integer of 2 or greater.

3. The composition according to claim 1, wherein the compound B is a compound represented by formula (B1). ｂ１ - (Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１ In formula (B1), Z ｂ１ , Y ｂ１ , W ｂ１ and s is Z in the partial structure in the requirement (b3). ｂ１ , Y ｂ１ , W ｂ１ , and s. ｂ１ Is, -L ｂ１ -X ｂ１ or -L ｂ１ -X ｂ１ [0043] The aromatic ring is substituted with one or more groups having two or more groups represented by the following formula:

4. In the formula (A2), Y in the substituent T ａ３ and in the formula (A3), a site in the substituent T that bonds to an aromatic ring constituting the aromatic ring group is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-.

5. An optically anisotropic film formed using the composition according to any one of claims 1 to 4.

6. A compound satisfying requirements (a1) to (a3). (a1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. (a2) The compound is represented by the formula (A1). Formula (A1) A-(Z ａ１ -Y ａ１ - (X ａ１ ) ｍ ) ｎ In formula (A1), A is an aromatic ring or an aliphatic ring which may have a substituent; １ -L Ａ -A ２ A represents a group represented by the formula: １ and A ２ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. Ａ is -C≡C- or -CH ２ - represents ａ１ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, and -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ａ１ each independently represents a silicon-containing group having a Si-O-Si structure. n represents an integer of 2 or more. each independently represents an integer of 1 or more. (a3) ​​The molecular weight is 500 to 8,000.

7. The compound according to claim 6, which is represented by formula (A2) or formula (A3). Formula (A2) A-(Z ａ１ - (Y ａ２ -Z ａ２ ) ｒ -Y ａ３ - (T ａ１ ) ｍ１ ) ｎ Formula (A3) A-(Z ａ１ -Y ａ１ - (Z ａ３ -B ａ１ ) ｍ２ ) ｎ In formula (A2) and formula (A3), A, Z ａ１ , Y ａ１ and n represents A, Z in formula (A1). ａ１ , Y ａ１ In formula (A2), Z ａ２ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, and -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ２ and Y ａ３ Each of T independently represents an aromatic ring or an aliphatic ring which may have a substituent. Each of r independently represents an integer of 0 or more. ａ１ represents a monovalent substituent T having a siloxane structure containing three or more silicon atoms. ａ３ The site of bonding to the group represented by the formula: Ｎ m1 represents an integer of 1 or more. ａ３ each independently represents a chain alkylene group, -O-, -CO-, or a chain alkylene group, -O-, -CO-, and -NR Ｎ R represents a group consisting of a combination of two or more selected from the group consisting of Ｎ represents a hydrogen atom or a substituent. ａ１ represents a monovalent aromatic ring group substituted with one or more monovalent substituents T having a siloxane structure containing three or more silicon atoms, provided that the site at which the substituent T bonds to the aromatic ring constituting the aromatic ring group is not one of -O-, -CO-, -NR Ｎ m2 represents an integer of 2 or greater.

8. In the formula (A2), Y in the substituent T ａ３ and in the formula (A3), a site in the substituent T that bonds to an aromatic ring constituting the aromatic ring group is -CO-O-, -O-CO-O-, -NH-CO-O-, or -CO-O-NH-.

9. A compound that satisfies requirements (b1) to (b4). (b1) The value obtained by dividing the total number of methyl groups bonded to silicon atoms in the molecule by the molecular weight of the compound is 0.0140 or more. (b2) -L ｂ１ -X ｂ１ L ｂ１ each independently represents an alkylene group which may have a heteroatom or -O-. ｂ１ represents a monovalent group selected from the group consisting of groups represented by formulas (C-1) to (C-3): In formula (C-1), R Ｃ１ ~R Ｃ３ each independently represents an alkyl group having 1 to 10 carbon atoms; and k represents an integer of 2 to 20. In formula (C-2), R Ｃ４ represents an alkyl group having 1 to 10 carbon atoms. Ｃ５ and R Ｃ６ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X). In formula (C-3), R Ｃ７ ~R Ｃ９ each independently represents an alkyl group having 1 to 10 carbon atoms or a group represented by formula (C-1X). In formula (C-1X), R Ｃ１０ ~R Ｃ１２ each independently represents an alkyl group having 1 to 10 carbon atoms; and l represents an integer of 0 to 20. (b3) *-(Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１ The symbol * represents a bonding position. Z ｂ１ each independently represents an alkylene group, —O—, —CO—, or —NR Ｎ R represents a group consisting of a substituted or unsubstituted aryl group, or a combination thereof. Ｎ represents a hydrogen atom or a substituent. ｂ１ each independently represents an aromatic ring or an aliphatic ring which may have a substituent. ｂ１ represents a substituent not containing a hydrogen atom or a silicon atom, and s represents an integer of 1 or greater. (b4) The molecular weight is 500 to 8,000.

10. The compound according to claim 9, represented by formula (B1). ｂ１ - (Z ｂ１ -Y ｂ１ ) ｓ -W ｂ１ In formula (B1), Z ｂ１ , Y ｂ１ , W ｂ１ and s is Z in the partial structure. ｂ１ , Y ｂ１ , W ｂ１ , and s. ｂ１ Is, -L ｂ１ -X ｂ１ or -L ｂ１ -X ｂ１ [0043] The aromatic ring is substituted with one or more groups having two or more groups represented by the following formula:

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