Compounds, compositions, optical anisotropes and optical elements

Abstract

A compound represented by the following general formula (I). Z 1 -R sp1 -S-(T) 1 -L 1 ) m -A-(L 2 -T 2 ) n -L 3 -R sp2 -Z 2 (The symbols in general formula (I) are as described in the specification.)

Description

Technical Field

[0001] This disclosure relates to a compound suitable for manufacturing liquid crystal compositions, compositions using the compound, optical anisotropy, and optical elements. Background Technology

[0002] Liquid crystal compounds (hereinafter also referred to as "liquid crystal compounds") and liquid crystal compositions (hereinafter also referred to as "liquid crystal compositions") can be used for a variety of applications.

[0003] For example, Patent Document 1 describes a compound having a 2,6-naphthyl group, which provides a compound suitable for manufacturing liquid crystal compositions, the compound having high birefringence properties and a sufficiently large phase width for processing in itself or in the form of the composition.

[0004] In addition, Patent Document 2 describes a diphenylacetylene compound having a diphenylacetylene skeleton and containing sulfur atoms, which provides a compound with high refractive index anisotropy Δn.

[0005] Liquid crystal compounds with high refractive index anisotropy Δn are useful in a variety of applications. Furthermore, even if a compound with high refractive index anisotropy Δn itself does not possess liquid crystal properties, it can be mixed with other liquid crystal compounds to form liquid crystal compositions with high refractive index anisotropy Δn, which are useful in various applications.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Publication No. 2008-544954

[0009] Patent Document 2: Japanese Patent Application Publication No. 2023-3351 Summary of the Invention

[0010] The problem that the invention aims to solve

[0011] However, the compounds with 2,6-naphthyl groups specifically described in Patent Document 1 have problems such as insufficient refractive index anisotropy Δn (hereinafter also referred to as "Δn") or high phase transition temperature.

[0012] The diphenylacetylene compound described in Patent Document 2 suffers from light-induced degradation and discoloration due to the influence of its triple bond. The diphenylacetylene skeleton containing the triple bond may be oxidized and decomposed in the presence of oxygen, similar to the process of diphenylacetylene → diketone → carboxylic acid. Patent Document 2 describes good lightfastness under oxygen-barrier conditions, but in practical applications, lightfastness in an air atmosphere (in the presence of oxygen) is required.

[0013] Furthermore, the cured films of liquid crystal compositions with high refractive index anisotropy Δn tend to be hard and brittle, which is a problem. In liquid crystal compositions with high refractive index anisotropy Δn, multiple triple bonds or aromatic rings are present along the long axis of the molecules, resulting in partial structural aggregation originating from their rigid molecular structure. Therefore, it is believed that their cured films tend to be hard and brittle. Hard and brittle films have poor bending resistance, and cracks are easily generated during processes such as lamination with other optically anisotropic layers, substrate peeling after transfer of other optically anisotropic layers, and processing.

[0014] Thus, high refractive index anisotropy and flexibility are incompatible.

[0015] The cured film of the liquid crystal composition containing a compound having a 2,6-naphthyl group, as specifically described in Patent Document 1, and the cured film of the liquid crystal composition containing a diphenylacetylene compound, as described in Patent Document 2, are hard and brittle films that are prone to cracking.

[0016] In view of the actual situation described above, the first objective of this disclosure is to provide a compound with improved refractive index anisotropy Δn and lightfastness in air atmosphere and reduced phase transition temperature, a composition containing the compound, an optical anisotropy, and an optical element.

[0017] In view of the actual situation described above, the second objective of this disclosure is to provide an optical anisotropy body and optical element having improved refractive index anisotropy Δn and suppressing crack generation.

[0018] Methods for solving problems

[0019] The inventors conducted in-depth research and discovered that the above-mentioned problems can be solved by the following means.

[0020] That is, in order to achieve the first objective, the first disclosure includes the following method.

[0021] [1] A compound represented by the following general formula (I).

[0022] [Chemical Formula 1]

[0023] General Formula (I)

[0024] (In general formula (I), Z) 1 and Z 2 Each can independently represent a hydrogen atom, -CN, -NCS, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, or a polymeric group.

[0025] R sp1 and R sp2 Each can independently represent an alkylene group or single bond with 1 to 20 carbon atoms that can be independently replaced by O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, or -CH=CH-.

[0026] S represents a sulfur atom.

[0027] L 1 L 2 and L 3 Each independently represents -O-, -S-, -CHR-, -CHRCHR-, -OCHR-, -CHRO-, -SO-, -SO2-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR-, -NR-CO-, -SCHR-, -CH RS-, -SO-CHR-, -CHR-SO-, -SO2-CHR-, -CHR-SO2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -OCHRCHRO-, -SCHRCHRS-, -SO-CHRCHR-SO-, -SO2-CHRCH R-SO2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHRCHR-, -OCO-CHRCHR-, -CHRCHR-COO-, -CHRCHR-OCO-, -COO-CHR-, -OCO-CHR-, -CHR-COO-, -CHR-OCO-, -CR=CR-, -CR=N-, -N=CR-, -N=N-, -CR=NN=CR-, -CF=CF- or a single bond, where R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. When multiple Rs exist, they can be the same or different.

[0028] T 1 and T 2 Each of these groups independently represents an aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 20 divalent carbon atoms that is unsubstituted or can be substituted by one or more substituents E, wherein any carbon atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted by a heteroatom.

[0029] A represents a group represented by any of the following formulas (A-1) to (A-4), which can be replaced by one or more substituents E.

[0030] Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymerizable group. Wherein, if the above-described group described as substituent E has -CH2-, a group formed by replacing at least one of the -CH2- groups contained in the above-described group with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the group described as substituent E has hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms contained in the group with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E.

[0031] m and n each independently represent integers from 0 to 3, and m+n represents integers greater than or equal to 1.

[0032] L 1 L 2 T 1 and T 2 When multiple E exist, they can be the same or different.

[0033] [Chemical Formula 2]

[0034] (In formulas (A-1) to (A-4), W) 1 ~W 16 Each represents CR independently. 1 Or N, R 1 This represents a hydrogen atom or the substituent E.

[0035] Y 1 ~Y 2 Each represents NR independently. 2 O or S, R 2 This represents a hydrogen atom or the substituent E.

[0036] Indicates with L 1 L 2 L 3 Or the bonding position of S.

[0037] [2] According to the compound described in [1] above, m in the general formula (I) represents 0, A represents a group represented by the formula (A-1), and the group represented by the formula (A-1) can be replaced by one or more substituents E.

[0038] [3] The compounds described in [1] or [2] above are represented by the following general formula (I-1).

[0039] [Chemical Formula 3]

[0040] General formula (I-1)

[0041] (In general formula (I-1), Z) 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 Each of the groups, k1 and E, independently represents a group defined by general formula (I). In general formula (I-1), the 2,6-naphthyl group can be substituted by one or more substituents E, k1 represents an integer from 0 to 6, n' represents an integer from 0 to 2, and L... 2 and T 2 When multiple E exist, they can be the same or different.

[0042] [4] The compound according to any one of [1] to [3] above is represented by the following general formula (I-2).

[0043] [Chemical Formula 4]

[0044] General formula (I-2)

[0045] (In general formula (I-2), Z) 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 E and k1 independently represent groups defined by general formula (I). In general formula (I-2), 2,6-naphthyl and phenyl can be substituted by more than one substituent E, k1 represents an integer from 0 to 6, and k2 represents an integer from 0 to 4.

[0046] n' represents an integer from 0 to 2, L 2 and T 2 When multiple E exist, they can be the same or different.

[0047] [5] The compound according to any one of [1] to [4] above has liquid crystal properties.

[0048] [6] A composition comprising any one of the compounds described in [1] to [5].

[0049] [7] The composition according to [6] above further comprises a polymerization initiator.

[0050] [8] The composition according to [6] or [7] further comprises a chiral agent.

[0051] [9] An optical anisotropy obtained by orienting the compound represented by the general formula (I) in any one of the compositions described in [6] to [8] above.

[0052]

[10] An optical anisotropy, which is a cured product of the composition described above [7].

[0053]

[11] An optical element having an optical anisotropic layer formed using any one of the compositions described in [6] to [8] above.

[0054]

[12] An optical element having an optically anisotropic layer formed using any one of the compositions described in [6] to [8] above, The optical anisotropic layer has an orientation pattern. The orientation pattern is an orientation pattern derived from the orientation of the optical axis of the liquid crystal compound contained in the composition, which is continuously rotated and changed along at least one direction in the plane.

[0055] In addition, in order to achieve the second objective, the second disclosure includes the following methods.

[0056]

[14] An optical anisotropy is a cured product of a polymeric liquid crystal composition comprising a partial structure of the following general formula (Ia).

[0057] [Chemical Formula 5]

[0058] General formula (Ia)

[0059] (In general formula (Ia), 2,6-naphthyl can be replaced by more than one substituent E, and k1 represents an integer from 0 to 6.)

[0060] Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymerizable group. Wherein, if the above-described group described as substituent E has -CH2-, a group formed by replacing at least one of the -CH2- groups contained in the above-described group with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the group described as substituent E has hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms contained in the group with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E.

[0061] This indicates the bonding positions with other atoms.

[0062]

[15] The optical anisotropy according to

[14] is a cured product of a polymeric liquid crystal composition containing 4% by mass or more of a compound comprising a partial structure of the general formula (Ia).

[0063]

[16] According to the optical anisotropy described in

[14] or

[15] above, wherein the anisotropy located at 1205 cm⁻¹ is determined by the ATR method and using a Fourier transform infrared spectrophotometer (FT-IR). -1 ~1225cm -1 The peak intensity (P1) of the SC bond is located at 1600 cm⁻¹ -1 ~1650cm -1 The ratio of the peak intensity (P2) of the C=C bond (P1 / P2) is greater than 0.30 and less than 1.80.

[0064]

[17] An optical element having an optical anisotropic body as an optical anisotropic layer as described in any one of

[14] to

[16] above.

[0065]

[18] An optical element having an optical anisotropic body as described in any one of

[14] to

[16] above as an optical anisotropic layer, The optical anisotropic layer has an orientation pattern. The orientation pattern is an orientation pattern derived from the orientation of the optical axis of the liquid crystal compound contained in the composition, which rotates continuously along at least one direction in the plane.

[0066] Invention Effects

[0067] According to the first disclosed embodiment, it is possible to provide a compound with improved refractive index anisotropy Δn and lightfastness in air atmosphere and reduced phase transition temperature, a composition containing the compound, an optical anisotropy, and an optical element.

[0068] According to the second disclosed embodiment, it is possible to provide an optical anisotropy body and optical element with improved refractive index anisotropy Δn and suppression of crack generation. Detailed Implementation

[0069] Hereinafter, embodiments and examples of the present disclosure will be described with reference to the accompanying drawings. However, the present disclosure can be implemented in many different ways and is not limited to the description of the embodiments and examples illustrated below. Furthermore, in order to make the explanation clearer, the drawings sometimes schematically show the width, thickness, shape, etc. of various parts compared to the actual embodiment; however, these are merely examples and do not limit the interpretation of the present disclosure. Additionally, in this specification and the drawings, the same reference numerals are sometimes used for elements that are the same as those described with respect to previously presented figures, and detailed descriptions are appropriately omitted. Furthermore, for ease of explanation, phrases such as "above" or "below" are sometimes used, but the vertical direction can be reversed.

[0070] "In this specification, when a component or region is located 'above (or below)' other components or regions or other structures, unless otherwise specified, this includes not only the case where it is located directly above (or directly below) other structures, but also the case where it is located above (or below) other structures, that is, the case where other structural elements are included between the above (or below) other structures."

[0071] In this disclosure, orientation confinement force refers to the force that causes the liquid crystal compounds in the retardation layer to align in a specific direction.

[0072] In this disclosure, (meth)acrylic acid refers to acrylic acid or methacrylic acid, and (meth)acrylate refers to acrylate or methacrylate.

[0073] Furthermore, in this specification, the terms "plate," "sheet," and "membrane" are not distinguished from each other solely based on different names. "Membrane surface (plate surface, sheet surface)" refers to the surface that is aligned with the planar direction of the membrane-like (plate-like, sheet-like) component being viewed as a whole and globally.

[0074] Furthermore, in this disclosure, the "~" signifying a numerical range is used to encompass the numerical values ​​preceding and following it as both the lower and upper limits.

[0075] Furthermore, in this disclosure, the refractive index along the axis direction with the highest refractive index in the plane of the layer, namely the X-axis direction, is defined as Nx, the refractive index along the direction in the plane of the layer and orthogonal to the X-axis, is defined as Ny, and the refractive index in the thickness direction of the layer is defined as Nz. The in-plane phase difference (Re) can be calculated from Nx, Ny, Nz and the thickness d (nm) of the phase difference layer by the following formula.

[0076] In-plane phase difference (Re) = (Nx - Ny) × d

[0077] Unless otherwise specified, measurements of in-plane phase difference and other measurements and evaluations in this specification shall be performed in an atmosphere with a temperature of 23℃ ± 5℃ and a humidity of 40% or higher and 65% or lower. Furthermore, the sample shall be exposed to the aforementioned atmosphere for at least 30 minutes prior to the measurement and evaluation.

[0078] I. The First Public Edition

[0079] A. Compound

[0080] The compounds disclosed herein are those represented by the following general formula (I).

[0081] [Chemical Formula 6]

[0082] General Formula (I)

[0083] (In general formula (I), Z) 1 and Z 2 Each can independently represent a hydrogen atom, -CN, -NCS, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, or a polymeric group.

[0084] R sp1 and R sp2 Each can independently represent an alkylene group or single bond with 1 to 20 carbon atoms that can be independently replaced by O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, or -CH=CH-.

[0085] S represents a sulfur atom.

[0086] L 1 L 2 and L 3Each independently represents -O-, -S-, -CHR-, -CHRCHR-, -OCHR-, -CHRO-, -SO-, -SO2-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR-, -NR-CO-, -SCHR-, -CH RS-, -SO-CHR-, -CHR-SO-, -SO2-CHR-, -CHR-SO2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -OCHRCHRO-, -SCHRCHRS-, -SO-CHRCHR-SO-, -SO2-CHRCH R-SO2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHRCHR-, -OCO-CHRCHR-, -CHRCHR-COO-, -CHRCHR-OCO-, -COO-CHR-, -OCO-CHR-, -CHR-COO-, -CHR-OCO-, -CR=CR-, -CR=N-, -N=CR-, -N=N-, -CR=NN=CR-, -CF=CF- or a single bond, where R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. When multiple Rs exist, they can be the same or different.

[0087] T 1 and T 2 Each of these groups independently represents an aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 20 divalent carbon atoms that is unsubstituted or can be substituted by one or more substituents E, wherein any carbon atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted by a heteroatom.

[0088] A represents a group represented by any of the following formulas (A-1) to (A-4), which can be replaced by one or more substituents E.

[0089] Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymerizable group. Wherein, if the above-described group described as substituent E has -CH2-, a group formed by replacing at least one of the -CH2- groups contained in the above-described group with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the group described as substituent E has hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms contained in the group with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E.

[0090] m and n each independently represent integers from 0 to 3, and m+n represents integers greater than or equal to 1.

[0091] L 1 L 2 T 1 and T 2 When multiple E exist, they can be the same or different.

[0092] [Chemical Formula 7]

[0093] (In formulas (A-1) to (A-4), W) 1 ~W 16 Each represents CR independently. 1 Or N, R 1 This represents a hydrogen atom or the substituent E.

[0094] Y 1 ~Y 2 Each represents NR independently. 2 O or S, R 2 This represents a hydrogen atom or the substituent E.

[0095] Indicates with L 1 L 2 L 3 Or the bonding position of S.

[0096] The compound represented by general formula (I) disclosed herein is a compound that, by including a group represented by any one of the formulas (A-1) to (A-4) as a partial structure and including -S- (sulfur atom) as a bonding part, thereby improving the refractive index anisotropy Δn and the lightfastness in air environment, and reducing the phase transition temperature.

[0097] The group represented by any of the formulas (A-1) to (A-4) included as part of the structure is an anisotropic molecular structure with abundant electrons and a large difference in molecular length between the long and short axes. Therefore, it is presumed that the refractive index anisotropy Δn is increased, and that the refractive index anisotropy Δn is increased through the synergistic effect of the polarizability of sulfur atoms and the SS interaction. The compound represented by the general formula (I) of this disclosure can have oxygen atoms in the molecule, so it is believed that the increase in orientation order based on SO interaction also increases the refractive index anisotropy Δn.

[0098] The groups represented by any of the formulas (A-1) to (A-4) included as part of the structure are rigid, thus leading to a tendency for the phase transition temperature to be high. To address this, by including -S- (sulfur atoms) as bonding elements within the molecule, the carbon-sulfur-carbon bond angle is significantly bent, thereby suppressing stacking caused by intermolecular interactions and reducing crystallinity. As a result, coating adaptability is improved by increasing solubility and lowering the phase transition temperature.

[0099] Furthermore, the compound represented by general formula (I) of this disclosure does not contain triple bonds, thus suppressing the visible coloration and light-induced degradation under oxygen conditions in diphenylacetylene compounds as described in Patent Document 2. Therefore, the lightfastness of the compound represented by general formula (I) of this disclosure in an air atmosphere is improved.

[0100] In cholesterol-type liquid crystal phases formed using compounds with high refractive index anisotropy Δn, there are advantages such as a wider reflection bandwidth and improved reflection efficiency.

[0101] Furthermore, optical anisotropy bodies can typically be fabricated using compounds with high refractive index anisotropy Δn, enabling thin-film fabrication. That is, by using the compounds disclosed herein as optical anisotropy bodies, thin-film optical elements with excellent lightfastness can be fabricated. Additionally, the compounds disclosed herein have the advantage of a wider range of substrate options for setting optical anisotropy bodies due to their lower phase transition temperature.

[0102] The symbols in general formula (I) are explained in detail below.

[0103] Z 1 and Z 2Each can independently represent a hydrogen atom, -CN, -NCS, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, or a polymeric group.

[0104] Examples of alkoxy groups with 1 to 10 carbon atoms include straight-chain or branched alkoxy groups, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, tert-butoxy, and n-pentoxy. Alkoxy groups with 1 to 10 carbon atoms can also be alkoxy groups with 1 to 5 carbon atoms or alkoxy groups with 1 to 4 carbon atoms.

[0105] Examples of alkylthio groups with 1 to 10 carbon atoms include straight-chain or branched alkylthio groups, such as methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, tert-butylthio, and n-pentylthio. Alkylthio groups with 1 to 10 carbon atoms can also be alkylthio groups with 1 to 5 carbon atoms or alkylthio groups with 1 to 4 carbon atoms.

[0106] When an optical anisotropy is made from a composition containing a compound represented by general formula (I), the orientation state of the compound represented by general formula (I) can be fixed, or the durability of the optical anisotropy can be improved. From this point of view, Z is preferred. 1 and Z 2 At least one of them represents a polymerizable group. From the viewpoint of superior reactivity, Z 1 and Z 2 Both of these can represent polymeric groups.

[0107] From the perspective of the ease of obtaining raw materials and the ease of synthesis, Z 1 and Z 2 One of them can be a polymerizable group, and the other can be an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, or -CN (cyano).

[0108] As a polymerizable group, groups previously used in polymerizable compounds can be applied without restriction.

[0109] The polymerizable groups preferably each independently represent groups selected from formulas (Z-1) to (Z-12) below. It should be noted that in formulas (Z-1) to (Z-12) below, (Astro) indicates that it is related to R sp1 Or R sp2 The bonding positions.

[0110] [Chemical Formula 8]

[0111] (In equations (Z-1) to (Z-12), R) zEach atom can be independently a hydrogen atom, fluorine atom, chlorine atom, bromine atom, iodine atom, methyl, ethyl, or trifluoromethyl atom.

[0112] When performing ultraviolet polymerization as a polymerization method, Z 1 Preferably, formulas (Z-1), (Z-2), (Z-4), (Z-6), and (Z-9) are used; more preferably, formulas (Z-1), (Z-4), and (Z-9) are used; even more preferably, formula (Z-1) is used; and in formula (Z-1), R is particularly preferred. z In the case of hydrogen atoms, methyl groups, or trifluoromethyl groups.

[0113] R sp1 and R sp2 Each can independently represent an alkylene group or single bond with 1 to 20 carbon atoms that can be independently replaced by O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO- or -CH=CH-.

[0114] From the perspective of the ease of obtaining raw materials and the ease of synthesis, R sp1 and R sp2 More preferably, each of the following is an alkylene group or single bond with 1 to 12 carbon atoms, which can be independently represented by one -CH2- or two or more non-adjacent -CH2- atoms, and can be independently replaced by O-, -COO-, or -OCO-. More preferably, each of the following is an alkylene group or single bond with 1 to 12 carbon atoms, and even more preferably, each of the following is an alkylene group or single bond with 1 to 10 carbon atoms. Particularly preferred are alkylene groups or single bonds with 1 to 6 carbon atoms. When multiple alkylene groups or single bonds exist, they can be the same or different.

[0115] In Z 1 and Z 2 When each is independently a hydrogen atom, -CN, -NCS, an alkoxy group with 1 to 10 carbon atoms, or an alkathio group with 1 to 10 carbon atoms, the adjacent R sp1 and R sp2 Ideally, each bond should be a single bond, independent of the others. On the other hand, in Z... 1 and Z 2 When each independently represents a polymerizable group, adjacent R sp1 and R sp2 Preferably, each is an alkylene group independently.

[0116] L 1 L 2 and L 3Each independently represents -O-, -S-, -CHR-, -CHRCHR-, -OCHR-, -CHRO-, -SO-, -SO2-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR-, -NR-CO-, -SCHR-, -CHR S-, -SO-CHR-, -CHR-SO-, -SO2-CHR-, -CHR-SO2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -OCHRCHRO-, -SCHRCHRS-, -SO-CHRCHR-SO-, -SO2-CHRCHR -SO2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHRCHR-, -OCO-CHRCHR-, -CHRCHR-COO-, -CHRCHR-OCO-, -COO-CHR-, -OCO-CHR-, -CHR-COO-, -CHR-OCO-, -CR=CR-, -CR=N-, -N=CR-, -N=N-, -CR=NN=CR-, -CF=CF- or a single bond, where R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. When multiple Rs exist, they can be the same or different.

[0117] In addition, L 1 and L 2 When multiple instances exist, they can be the same or different.

[0118] R preferably represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and even more preferably a hydrogen atom.

[0119] As L 1 and L 2More specifically, from the viewpoints of liquid crystal properties, ease of obtaining raw materials, and ease of synthesis, it is preferable that each of the following can be independently represented as -COO-, -OCO-, -OCH2-, -CH2O-, -CF2O-, -OCF2-, -CH2CH2-, -CF2CF2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -CH=CH-, -CF=CF-, or a single bond; more preferably, they can be represented as -COO-, -OCO-, -OCH2-, -CH2O-, or -CF2O-. -OCF2-, -CH2CH2-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -CH=CH- or a single bond, further preferably represented by -COO-, -OCO-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -CH=CH- or a single bond, even more preferably represented by -COO-, -OCO-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO- or a single bond, particularly preferably represented by -COO- or -OCO-.

[0120] From the perspective of the ease of obtaining raw materials and the ease of synthesis, L 3 Preferably, it represents -O-, -S-, -OCH2-, -CH2O-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO- or a single bond, more preferably it represents -O-, -S-, -COO-, -OCO-, -O-CO-O- or a single bond.

[0121] From the perspective of increasing Δn, L 3 The preferred option is indicated by -S-.

[0122] R sp2 When representing a single bond, L 3 It can be a single key.

[0123] T 1 and T 2Each of these terms independently represents an unsubstituted or divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may be substituted by one or more substituents E. Any carbon atom of this aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted with a heteroatom; more specifically, any carbon atom of this aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. The aforementioned aromatic hydrocarbon group can be an aromatic heterocyclic group, can have a fused ring structure, or can be a structure formed by the condensation of an alicyclic hydrocarbon group and an aromatic hydrocarbon group. It should be noted that T... 1 and T 2 When multiple instances of E exist independently, they can be the same or different. Furthermore, when multiple instances of E exist, they can be the same or different.

[0124] Examples of divalent aromatic hydrocarbon groups that can be substituted with heteroatoms include aromatic hydrocarbon groups with 6 to 20 divalent carbon atoms. Examples of aromatic hydrocarbon rings constituting these heteroatom-substituted aromatic hydrocarbon groups include benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings. Examples of aromatic heterocycles include furan rings, pyridine rings, pyrimidine rings, and pyrazine rings.

[0125] Examples of alicyclic hydrocarbon groups with 3 to 20 carbon atoms that are divalent include cycloalkane dimethyl groups with 3 to 20 carbon atoms and alicyclic fused ring groups with 10 to 20 carbon atoms.

[0126] Examples of divalent cycloalkane dimethyl groups with 3 to 20 carbon atoms include cyclopropane dimethyl; cyclobutane-1,2-dimethyl, cyclobutane-1,3-dimethyl, etc.; cyclopentane-1,2-dimethyl, cyclopentane-1,3-dimethyl, etc.; cyclohexane-1,2-dimethyl, cyclohexane-1,3-dimethyl, cyclohexane-1,4-dimethyl, etc.; cycloheptane-1,2-dimethyl, cycloheptane-1,3-dimethyl, cycloheptane-1,4-dimethyl, etc.; cyclooctane-1,2-dimethyl, cyclooctane-1,3-dimethyl, cyclooctane-1,4-dimethyl, cyclooctane-1,5-dimethyl, etc.; and cyclodecane-1,2-dimethyl. Cyclodecane-1,3-diyl, cyclodecane-1,4-diyl, cyclodecane-1,5-diyl, etc.; cyclododecane-1,2-diyl, cyclododecane-1,3-diyl, cyclododecane-1,4-diyl, cyclododecane-1,5-diyl, etc.; cyclotetradecane-1,2-diyl, cyclotetradecane-1,3-diyl, cyclotetradecane-1,4-diyl, cyclotetradecane-1,5-diyl, cyclotetradecane-1,7-diyl, etc.; cycloeicosyl-1,2-diyl, cycloeicosyl-1,10-diyl, etc.; etc., wherein the cycloalkane diyl group may be unsubstituted or substituted with one or more substituents E.

[0127] Any carbon atom in the cycloalkane diene can be replaced by an oxygen atom, a sulfur atom, or a nitrogen atom, for example, tetrahydropyran-2,5-diyl, 1,3-dioxane-2,5-diyl, tetrahydrothiaran-2,5-diyl, etc.

[0128] Examples of alicyclic fused-ring groups with 10 to 20 divalent carbon atoms include decahydronaphthalene-2,5-diyl, decahydronaphthalene-2,6-diyl, decahydronaphthalene-2,7-diyl, etc.; adamantane-1,2-diyl, adamantane-1,3-diyl, etc.; bicyclo[2.2.1]heptane-2,3-diyl, bicyclo[2.2.1]heptane-2,5-diyl, bicyclo[2.2.1]heptane-2,6-diyl, etc.; etc., wherein the alicyclic fused-ring group is unsubstituted or can be substituted by one or more substituents E. Furthermore, any carbon atom of the alicyclic fused-ring group can be substituted by an oxygen atom, a sulfur atom, or a nitrogen atom.

[0129] The divalent aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 20 carbon atoms that is unsubstituted or can be substituted by one or more substituents E, and can be substituted by oxygen, sulfur or nitrogen atoms, can be a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 18 carbon atoms, or a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 12 carbon atoms.

[0130] Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymerizable group. Wherein, if the above-described group described as substituent E has -CH2-, a group formed by replacing at least one of the -CH2- groups contained in the above-described group with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the substituent E described above has a hydrogen atom, a group formed by replacing at least one of the hydrogen atoms in the above group with at least one group selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E. It should be noted that the polymerizable group here can be related to the Z described above. 1 and Z 2 The polymerizable groups described herein are the same.

[0131] It should be noted that the number of carbon atoms in substituent E also includes the number of carbon atoms in the carbonyl group (C=O) in, for example, alkanoyl or alkoxycarbonyl groups.

[0132] From the viewpoint of solvent solubility, the substituent E can be an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkanoyl group with 1 to 10 carbon atoms, an alkanoyloxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 2 to 10 carbon atoms, a trifluoromethyl group, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, or a halogen atom.

[0133] From the viewpoint of liquid crystal properties and visible light transmittance, the substituent E is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkanoyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a trifluoromethyl group, a fluorine atom, or a chlorine atom.

[0134] In addition, T 1 and T 2 Each can independently represent a group represented by any one of the following general formulas (B-1) to (B-10), or a group formed by linking two or more but no more than three groups represented by any one of the following general formulas (B-1) to (B-10). Multiple existing T 1 and T 2 They can be the same or different.

[0135] [Chemical Formula 9]

[0136] (In formulas (B-1) to (B-10), W) 21 ~W 48 Each represents CR independently. 1 Or N, R 1 This represents a hydrogen atom or the substituent E.

[0137] Y 11 ~Y 18 Each represents NR independently. 2 O or S, R 2 This represents a hydrogen atom or the substituent E.

[0138] V 1 ~V 4 Each represents CR independently. 3 R 4 NR 5 O or S, R 3 ~R 5 Each of these independently represents a hydrogen atom or the substituent E.

[0139] Indicates with L 1 L 2 L 3 Or the bonding position of S.

[0140] A group formed by linking two or more but no more than three groups represented by any of the general formulas (B-1) to (B-10) can be a group formed by linking groups with the same structure or a group formed by linking groups with different structures. For example, as a group formed by linking two groups represented by general formula (B-2), the group represented by the following general formula (B-2-2) can be cited.

[0141] [Chemical Formula 10]

[0142] (In formula (B-2-2), W) 27 ~W 30 Each represents CR independently. 1 Or N, R 1 Representing a hydrogen atom or the substituent E, and multiple W atoms present. 27 ~W 30 Each can be the same or different. Adjacent substituents E can bond together to form a ring.

[0143] Furthermore, the groups represented by the general formulas (B-1) to (B-10) and (B-2-2) can be exemplified by those represented by formulas (b-1-1) to (b-1-7), (b-2-1) to (b-2-7), (b-2-2-1) to (b-2-2-3), (b-3-1) to (b-3-6), (b-4-1) to (b-4-6), (b-5-1) to (b-5-6), (b-6-1) to (b-6-8), (b-7-1) to (b-7-6), (b-8-1) to (b-8-6), (b-9-1) to (b-9-4), and (b-10-1) to (b-10-8). In these formulas, CR 1 R in 1 and CR 3 R 4 R in 3 and R 4 It is represented by hydrogen atoms, but each hydrogen atom may also be replaced by the substituent E.

[0144] [Chemical Formula 11]

[0145] [Chemical Formula 12]

[0146] [Chemical Formula 13]

[0147] In general formulas (B-1) to (B-10), W 21 ~W 48 Each represents CR independently. 1 Or N, from the viewpoint of ease of obtaining raw materials and ease of synthesis, preferably represents CR. 1 There are multiple R's in the general formulas (B-1) to (B-10). 1 In certain circumstances, they can be the same or different.

[0148] Y 11 ~Y 18 Each represents NR independently. 2 , O or S, can represent O or S. R 2 When multiple instances exist, they can be the same or different.

[0149] V 1 ~V 4 Each represents CR independently. 3 R 4 NR 5 O or S, preferably representing CR 3 R 4 In general formula (B-10), R 3 R 4 R 5 When multiple instances exist, they can be the same or different.

[0150] From the viewpoint of visible light transmittance, W in the above general formula (B-1) is preferred among the groups shown. 22 and W 23 Neither of these represents N; W is preferred. 25 and W 26 Neither of these represents N; W is preferred. 21 Representing N and W 22 ~W 26 CR 1 、 or W 21 ~W 26 All represent CR 1 W is preferred 21 ~W 26 All represent CR 1 .

[0151] From the viewpoint of visible light transmittance, W in the above general formula (B-2) is preferred among the groups shown. 27 and W 28Neither of these represents N; W is preferred. 29 and W 30 Neither of these represents N; W is preferred. 27 Representing N and W 28 ~W 30 CR 1 、 or W 27 ~W 30 All represent CR 1 W is preferred 27 ~W 30 All represent CR 1 .

[0152] In the groups represented by the above general formulas (B-3) or (B-4), from the viewpoint of ease of obtaining raw materials and ease of synthesis, Y in the above general formulas (B-3) and (B-4) is preferred. 11 and Y 12 Each can be represented independently as O or S, W 31 and W 32 Each of them represents N independently.

[0153] From the viewpoint of ease of obtaining raw materials and ease of synthesis, Y in the above general formulas (B-5) or (B-6) is preferred among the groups shown. 13 and Y 14 Each can be represented independently as O or S, W 33 W 34 W 35 and W 36 Each represents CR independently. 1 .

[0154] Among the groups represented by the above general formula (B-7) or (B-8), from the viewpoint of solvent solubility, Y in the above general formula (B-7) is preferred. 15 and Y 16 One of them represents NR 2 The other represents O or S, or Y. 15 and Y 16 These two represent NR 2 W 37 and W 38 Each represents CR independently. 1 Preferably, Y in the above general formula (B-8) 17 and Y 18 One of them represents NR 2 The other represents O or S, or Y. 17 and Y 18 These two represent NR 2 W 39 and W 40 Each represents CR independently.1 .

[0155] From the viewpoint of visible light transmittance, W in the above general formula (B-9) is preferred among the groups shown. 41 W 42 and W 43 Neither of these represents N; W is preferred. 44 W 45 and W 46 Neither of these represents N; W is preferred. 46 Representing N and W 41 ~W 45 CR 1 、 or W 41 ~W 46 All represent CR 1 W is preferred 41 ~W 46 All represent CR 1 .

[0156] In the groups represented by the above general formula (B-10), from the viewpoint of solvent solubility, in the above general formula (B-10), W 47 ~W 48 Ideally, each should be represented independently. 1 V 1 ~V 4 Ideally, each should be represented independently. 3 R 4 .

[0157] In general formulas (B-1) to (B-10), R 1 ~R 6 Each of these independently represents a hydrogen atom or the substituent E.

[0158] The substituent E can be the same as described above.

[0159] In general formulas (B-1) to (B-10), the substituent E is preferably 0 to 2, more preferably 0 to 1.

[0160] In general formulas (B-1) to (B-10), when each formula contains a substituent E, it has advantages such as improved solvent solubility and orientation.

[0161] From the viewpoint of the ease of obtaining the starting materials and the ease of synthesis of the compound represented by general formula (I), T is preferred. 1 and T 2 Each of the above general formulas (B-1), (B-2), (B-2-2), (B-3) or (B-4) represents a group independently, and more preferably a group represented by the above general formula (B-1) or (B-2).

[0162] In general formula (I), A represents any of the groups shown in formulas (A-1) to (A-4) below, which can be replaced by one or more substituents E.

[0163] [Chemical Formula 14]

[0164] (In formulas (A-1) to (A-4), W) 1 ~W 16 Each represents CR independently. 1 Or N, R 1 This represents a hydrogen atom or the substituent E.

[0165] Y 1 ~Y 2 Each represents NR independently. 2 O or S, R 2 This represents a hydrogen atom or the substituent E.

[0166] Indicates with L 1 L 2 L 3 Or the bonding position of S.

[0167] From the viewpoint of visible light transmittance, W in the above general formula (A-1) is preferred among the groups shown. 2 and W 3 Neither of these represents N; W is preferred. 5 and W 6 Neither of these represents N; W is preferred. 1 Representing N and W 2 ~W 6 CR 1 、 or W 1 ~W 6 All represent CR 1 W is preferred 1 ~W 6 All represent CR 1 .

[0168] From the viewpoint of visible light transmittance, W in the above general formula (A-2) is preferred among the groups shown. 7 and W 8 Neither of these represents N; W is preferred. 9 and W 10 Neither of these represents N; W is preferred. 11 and W 12 Neither of these represents N; W is preferred. 13 and W 14 Neither of these represents N; W is preferred. 14 Representing N and W 7 ~W13 CR 1 、 or W 7 ~W 14 All represent CR 1 W is preferred 7 ~W 14 All represent CR 1 .

[0169] In the groups represented by the above general formulas (A-3) or (A-4), from the viewpoint of ease of obtaining raw materials and ease of synthesis, Y in the above general formulas (A-3) and (A-4) is preferred. 1 and Y 2 Each can be represented independently as O or S, W 15 and W 16 Each of them represents N independently.

[0170] In equations (A-1) to (A-4), R 1 When multiple instances exist, they can be the same or different.

[0171] In general formulas (A-1) to (A-4), R 1 Each of these independently represents a hydrogen atom or the substituent E.

[0172] The substituent E can be the same as described above.

[0173] In general formulas (A-1) to (A-4), the substituent E preferably includes 0 to 1, but may also be 0.

[0174] In general formulas (A-1) to (A-4), R 1 It can consist entirely of hydrogen atoms.

[0175] From the perspective of superior refractive index anisotropy, A can be the formula (A-1), in which W is preferred. 1 Representing N, W 2 ~W 6 CR 1 , or W 1 ~W 6 All represent CR 1 W is preferred 1 ~W 6 All represent CR 1 .

[0176] From the viewpoint of improving the solvent solubility and orientation of the compound represented by general formula (I), T in general formula (I) is preferred. 1 T 2 At least one of A and B has the substituent E.

[0177] m and n each independently represent integers from 0 to 3. m+n is an integer greater than or equal to 1.

[0178] m+n is an integer less than 6, less than 4, or less than 2.

[0179] From the viewpoint that it is easy to increase Δn and easy to improve lightfastness in air, it is preferable that S and A are adjacent, and m can be 0.

[0180] From the perspective of superior refractive index anisotropy, A can be expressed as equation (A-1).

[0181] m represents 0, and A represents the group shown in formula (A-1). When the group shown in formula (A-1) can be replaced by one or more substituents E, the presence of a group such as naphthyl group and S (sulfur atom) bonded to it makes it easier to increase Δn and lightfastness in air, which is preferred from this point of view.

[0182] It is believed that when sulfur atoms are substituted on the group represented by formula (A-1), the interaction between sulfur atoms and the group represented by formula (A-1) is weaker and their electron-donating ability is weaker than that of oxygen atoms. Therefore, it is possible to suppress the oxidation of the group represented by formula (A-1). In addition, the valence of sulfur atoms can take on high valence states of 2 → 4 → 6. Therefore, it is believed that sulfur atoms can capture oxidation caused by air and also have the effect of protecting the group represented by formula (A-1) which is important for optical properties.

[0183] From the viewpoint of easily increasing Δn and easily increasing lightfastness in air, the compound represented by the general formula (I) can be a compound represented by the following general formula (I-1).

[0184] [Chemical Formula 15]

[0185] General formula (I-1)

[0186] (In general formula (I-1), Z) 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 Each of the groups, k1 and E, independently represents a group defined by general formula (I). In general formula (I-1), the 2,6-naphthyl group can be substituted by more than one substituent E, k1 represents an integer from 0 to 6, and n' represents an integer from 0 to 2. L 2 and T 2When multiple E exist, they can be the same or different.

[0187] In the general formula (I-1), from the viewpoint of liquid crystallization, the T bonded to the -COO- group bonded to the naphthyl group... 2 Preferably, it is a group represented by any one of the general formulas (B-1) to (B-10), and more preferably a group represented by any one of the general formulas (B-1), (B-2), (B-2-2), (B-3) or (B-4).

[0188] From the viewpoint that the compounds represented by the general formula (I) can easily improve Δn, easily improve lightfastness in air, and have excellent solvent solubility, the compounds represented by the following general formula (I-2) can be used.

[0189] [Chemical Formula 16]

[0190] General formula (I-2)

[0191] (In general formula (I-2), Z) 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 E and k1 independently represent the groups defined by general formula (I). In general formula (I-2), 2,6-naphthyl and phenyl can be substituted by more than one substituent E, k1 represents an integer from 0 to 6, and k2 represents an integer from 0 to 4.

[0192] n' represents an integer from 0 to 2. L 2 and T 2 When multiple E exist, they can be the same or different.

[0193] In the general formulas (I-1) and (I-2), k1 represents an integer from 0 to 6. From the perspective of the ease of obtaining raw materials and the ease of synthesis, k1 can be an integer from 0 to 3, an integer from 0 to 2, 0 or 1, or 0.

[0194] In the general formula (I-2), k2 represents an integer from 0 to 4. From the perspective of the ease of obtaining raw materials and the ease of synthesis, k2 can be an integer from 0 to 2, and can be 0 or 1. When k2 is 1, it is preferred from the perspective of orientation.

[0195] In the general formulas (I-1) and (I-2), n' represents an integer from 0 to 2. From the viewpoint of solvent solubility and phase transition temperature, n' can be 1 or 2, or it can be 1.

[0196] In the general formulas (I-1) and (I-2), Z 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 E and E each independently represent the groups defined in general formula (I), as described above.

[0197] In the general formulas (I-1) and (I-2), from the viewpoint of fixing the orientation state of the compound represented by general formula (I) and improving the durability of optical anisotropy, Z 1 Preferably, it represents a polymerizable group. From a reactivity point of view, Z 1 A further preferred embodiment is formula (Z-1), in which R is particularly preferred. z In the case of hydrogen atoms, methyl groups, or trifluoromethyl groups.

[0198] In the general formulas (I-1) and (I-2), from the viewpoint of the ease of obtaining raw materials, R sp1 Preferably, it represents an alkylene group having 1 to 6 carbon atoms, and more preferably, it represents an alkylene group having 2 to 6 carbon atoms.

[0199] In the general formulas (I-1) and (I-2), the substituent E can be the same as described above. From the viewpoint of liquid crystal properties and visible light transmittance, it is preferable to have an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, an alkanoyl group with 2 to 6 carbon atoms, an alkanoyloxy group with 2 to 6 carbon atoms, an alkoxycarbonyl group with 2 to 6 carbon atoms, a trifluoromethyl group, a fluorine atom, or a chlorine atom. More preferably, it is preferably an alkyl group with 1 to 6 carbon atoms, an alkoxy group with 1 to 6 carbon atoms, an alkanoyloxy group with 2 to 6 carbon atoms, an alkoxycarbonyl group with 2 to 6 carbon atoms, or a fluorine atom.

[0200] In general formula (I-1), as a specific example when k1 is 0, the compounds represented by Lc-1 to Lc-80 below can be cited. R sp1 and R sp2 In this context, n represents 1 to 20, and n is preferably 2 or more, more preferably 4 or more. On the other hand, n is preferably 12 or less, more preferably 10 or less, and may also be 6 or less.

[0201] Additionally, in Z 1 and Z 2 In equation (Z-1), R is... zEach of them is preferably a hydrogen atom or a methyl group, and more preferably a hydrogen atom.

[0202] In the following chemical formulas, Me represents methyl.

[0203] [Table 1]

[0204] [Table 2]

[0205] Furthermore, the following examples illustrate representative structural formulas of compounds represented by general formula (I), but are not limited to these.

[0206] [Chemical Formula 17]

[0207] [Chemical Formula 18]

[0208] [Chemical Formula 19]

[0209] [Chemical Formula 20]

[0210] [Chemical Formula 21]

[0211] Compounds represented by general formula (I) can be manufactured, for example, by the following method. As a method, they can be manufactured by appropriately combining well-known organic synthesis reactions (such as condensation reactions, esterification reactions, Williamson reactions, Ulmann reactions, Wittsch reactions, Schiff base formation reactions, benzylation reactions, sago reactions, Suzuki-Miyaura reactions, Negishi reactions, Kumada reactions, Hiyama reactions, Buchwald-Hartwig reactions, Friedrich-Cleift reactions, Heck reactions, aldol condensation reactions, Duff reactions, etc.) as described in Method der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, and New Experimental Chemistry Lectures, depending on their structure.

[0212] Specific synthetic examples of compounds represented by general formula (I) are shown in the examples described later.

[0213] In addition, the intermediates used in the manufacturing process can be commercially available products or synthesized using previously known methods.

[0214] In this disclosure, the structure of the compound can be analyzed by a combination of nuclear magnetic resonance (NMR), thermal decomposition gas chromatography-mass spectrometry (Py-GC-MS), and matrix-assisted laser desorption / ionization time-of-flight mass spectrometry (MALDI-TOFMS).

[0215] The compound represented by general formula (I) may or may not be liquid crystal soluble, but is preferably liquid crystal soluble.

[0216] When the compound represented by general formula (I) has liquid crystal properties, it is preferable to align the compound represented by general formula (I) when making an optical anisotropic layer from a composition containing the compound represented by general formula (I), as it is easy to make the desired orientation pattern.

[0217] However, even if the compound represented by general formula (I) does not have liquid crystal properties, it can be mixed with other liquid crystal compounds to form a liquid crystal composition, thereby creating the desired orientation pattern.

[0218] The term "liquidity" refers to the property of a compound to exhibit an intermediate phase between a crystalline phase (low-temperature side) and an isotropic phase (high-temperature side) when the temperature is changed. As a specific observation method, the optical anisotropy and fluidity originating from the liquid crystal phase can be confirmed by observing the compound under a polarizing microscope while heating or cooling it using a hot stage or similar device.

[0219] From the viewpoint of expanding the selection of usable substrates and processing, the phase transition temperature of the compound represented by the general formula (I) can be above 40°C and below 110°C, below 100°C, and further below 90°C. If the liquid crystal compound is solid at room temperature, the drying process in the manufacturing process, the weighing during ink production, and the stability during storage are all excellent.

[0220] It should be noted that when the compound represented by the general formula (I) has liquid crystal properties, the phase transition temperature is the solid-liquid crystal phase transition temperature; when the compound represented by the general formula (I) does not have liquid crystal properties, the phase transition temperature is the solid-liquid phase transition temperature.

[0221] In this disclosure, the phase transition temperature of the compound represented by general formula (I) is determined using a differential scanning calorimeter (DSC). The determination is performed in accordance with section 8 of JIS K7121-1987. The phase transition temperature is the extrapolated melting start temperature (Tim) according to section 9.1(2) of JIS K7121-1987. The heating and cooling procedures (heating rate, cooling rate, heating start temperature, and cooling end temperature) are as follows.

[0222] After sealing 5 mg of the test sample into an aluminum sample pan, the sample was placed in a DSC (Digital Subtraction Angiography) chamber and cooled from 25°C to -10°C at a rate of -25°C / min under a nitrogen atmosphere, and maintained at -10°C for 15 minutes. Then, as the first heating, the temperature was increased from -10°C to 150°C at a rate of 10°C / min, and maintained at 150°C for 1 minute. As the first cooling, the temperature was reduced from 150°C to -10°C at a rate of -10°C / min, and maintained at -10°C for 10 minutes. Then, as the second heating, the temperature was increased from -10°C to 150°C at a rate of 10°C / min, and maintained at 150°C for 1 minute. As the second cooling, the temperature was reduced from 150°C to 25°C at a rate of -10°C / min. The endothermic onset temperature detected during the second heating, which is the temperature at the intersection of the straight line obtained by extending the baseline from the low temperature side to the high temperature side and the tangent line drawn from the point with the largest slope in the curve on the low temperature side of the melting peak, is the extrapolated melting onset temperature (Tim) and is taken as the phase transition temperature.

[0223] It should be noted that the upper limit temperature for DSC measurements in this embodiment and the comparative example was set to 150°C. However, in the case of compounds that begin to polymerize at 150°C, the upper limit temperature for DSC measurements was changed to be lower than the polymerization initiation temperature of the compound.

[0224] At this point, observe whether the compound polymerizes by following steps i) to iii) to determine the upper limit temperature for DSC measurement.

[0225] i) Set the first heating temperature to 150°C for measurement. If no peak is detected or the peak area is significantly reduced in the second heating, repeat the DSC measurement by lowering the first heating temperature by 5°C.

[0226] ii) If no peak is detected or the peak area is significantly reduced in the second heating even if the arrival temperature of the first heating is reduced by 5°C, DSC measurement shall be performed again under the condition that the arrival temperature of the first heating is further reduced by 5°C.

[0227] iii) Repeat ii) above until a peak is detected in the second heating. Set the temperature at which a peak can be detected in the second heating as the upper limit temperature for DSC measurement (the upper limit of the heating temperature).

[0228] The compound represented by the general formula (I) is a compound with increased birefringence (Δn). When the composition is prepared by the method shown in the examples described later, a cured film (optical anisotropic layer) is formed, and the refractive index anisotropy (Δn) is measured, it is preferably 0.25 or higher.

[0229] Furthermore, from the viewpoint of expanding the range of usable substrates, it is preferable that the compound represented by the general formula (I) is dissolved in at least 10% by mass in a solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone and cyclohexanone, and it is even more preferable that it is dissolved in at least 20% by mass.

[0230] B. Composition

[0231] Regarding the compositions of this disclosure, compositions comprising compounds represented by the general formula (I) (hereinafter also referred to as "compositions of this disclosure") are described.

[0232] The content of the compound represented by general formula (I) in the composition disclosed herein is not particularly limited, and may be 4% by mass or more, 9% by mass or more, 20% by mass or more, 30% by mass or more, 40% by mass or more, or on the other hand, may be 100% by mass or less, or 99% by mass or less, relative to the total mass of the solid components in the composition.

[0233] It should be noted that solid components refer to components other than solvents in the composition (non-volatile components). If it is a component other than a solvent, then even if its physical state is liquid, it is considered a solid component.

[0234] The composition may use one compound of general formula (I) alone, or two or more compounds. When two or more compounds are used, their total content is preferably within the range described above.

[0235] The compositions disclosed herein preferably have liquid crystal properties.

[0236] When the composition disclosed herein has liquid crystal properties, it is easy to orient the compounds in the composition when an optical anisotropic layer is made from the composition, and the desired orientation pattern can be easily made, which is therefore preferred.

[0237] The term "liquidity" in a composition refers to the property of the composition to exhibit an intermediate phase between a crystalline phase (low-temperature side) and an isotropic phase (high-temperature side) when the temperature is changed. As a specific observation method, the optical anisotropy and fluidity originating from the liquid crystal phase can be confirmed by observing the composition under a polarizing microscope while heating or cooling it using a hot stage or the like.

[0238] The compositions disclosed herein are preferably compositions for forming optically anisotropic layers.

[0239] In addition to the compounds represented by general formula (I), the compositions disclosed herein may also contain other components.

[0240] The other ingredients are described below.

[0241] <Other Liquid Crystal Compounds>

[0242] The compositions disclosed herein may contain liquid crystal compounds (also referred to as "other liquid crystal compounds") that are different from those represented by general formula (I).

[0243] Other liquid crystal compounds can be rod-shaped or disk-shaped, but rod-shaped liquid crystal compounds are preferred. Furthermore, other liquid crystal compounds are preferably liquid crystal compounds having polymerizable groups (other polymerizable liquid crystal compounds).

[0244] Examples of rod-shaped liquid crystal compounds, such as rod-shaped nematic liquid crystal compounds, can be cited. Preferably, these rod-shaped nematic liquid crystal compounds are methylimine derivatives, azo derivatives, cyanobiphenyl derivatives, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexane derivatives, cyano-substituted phenylpyrimidine derivatives, alkoxy-substituted phenylpyrimidine derivatives, phenyl dioxane derivatives, diphenylacetylene derivatives, or alkenylcyclohexylbenzylnitrile derivatives. Other liquid crystal compounds can be used, including not only low-molecular-weight liquid crystal compounds but also high-molecular-weight liquid crystal compounds.

[0245] Liquid crystal compounds having polymerizable groups are obtained by introducing polymerizable groups into a liquid crystal compound. Examples of polymerizable groups include Z of the above general formula (I). 1 and Z 2 Polymer groups are illustrated in the example.

[0246] The number of polymerizable groups in the liquid crystal compound is preferably 1 to 6, more preferably 1 to 3, and even more preferably 1 or 2.

[0247] Other liquid crystal compounds preferably have high refractive index anisotropy Δn. Specifically, the refractive index anisotropy Δn of the other liquid crystal compounds used in combination is preferably 0.15 or more, more preferably 0.18 or more, and even more preferably 0.22 or more. There is no particular upper limit to the refractive index anisotropy Δn, and it is mostly below 0.60.

[0248] In addition, by mixing the compound represented by general formula (I) with other liquid crystal compounds, the crystallization temperature of the whole can be significantly reduced.

[0249] Examples of other liquid crystal compounds include those described in Makromol. Chem., Vol. 192, p. 59 (1991), Makromol. Chem., Vol. 190, p. 2255 (1989), Advanced Materials, Vol. 5, p. 107 (1993), U.S. Patent No. 4,683,327, U.S. Patent No. 5,622,648, U.S. Patent No. 5,770,107, Japanese Patent Application Publication No. 11-513,019, 2001-505,879, 2001-527,570, 6-16,616, 7-110,469, 11-80081, and 2001-328,973.

[0250] Alternatively, polymeric liquid crystal compounds exhibiting anti-dispersion properties may be used. Specifically, examples include polymeric liquid crystal compounds represented by general formula (1) as described in International Publication No. 2019 / 074007, liquid crystal compounds represented by general formula (II) as described in International Publication No. 2017 / 043438, Japanese Patent Nos. 5463666, 4186981, 5962760, 5826759, 6568103, 6427340, Japanese Patent Application Publication No. 2016-166344, or polymeric liquid crystal compounds described in Recueil des Travaux Chimiques des Pays-Bas (1996), 115(6), 321-328.

[0251] Examples of other liquid crystal compounds include those represented by the general formula (II) below, which are different from those represented by formula (I).

[0252] [Chemical Formula 22]

[0253] General Formula (II)

[0254] (In general formula (II), Z) 1 Z 2 R sp1 and R sp2 Each of them independently represents a group defined in the above general formula (I).

[0255] L 4 and L 5Each independently represents -O-, -S-, -CHR-, -CHRCHR-, -OCHR-, -CHRO-, -SO-, -SO2-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR-, -NR-CO-, -SCHR-, -CHRS -, -SO-CHR-, -CHR-SO-, -SO2-CHR-, -CHR-SO2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -OCHRCHRO-, -SCHRCHRS-, -SO-CHRCHR-SO-, -SO2-CHRCHR-S O2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHRCHR-, -OCO-CHRCHR-, -CHRCHR-COO-, -CHRCHR-OCO-, -COO-CHR-, -OCO-CHR-, -CHR-COO-, -CHR-OCO-, -CR=CR-, -CR=N-, -N=CR-, -N=N-, -CR=NN=CR-, -CF=CF-, -C≡C- or a single bond, where R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. When multiple Rs exist, they can be the same or different.

[0256] T 3 Each of these groups independently represents an unsubstituted aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 20 divalent carbon atoms, which may be substituted by one or more substituents E or groups selected from the general formula (D-1) below, wherein any carbon atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted by a heteroatom.

[0257] Substituent E represents a group defined by the general formula (I).

[0258] p represents an integer from 2 to 6. L 4 and T 3 When multiple substituents E or groups selected from the following general formula (D-1) are present, they may be the same or different.

[0259] [Chemical Formula 23]

[0260] General formula (D-1)

[0261] (In general formula (D-1), G) 1 The alkyl group represents an alkyl group having 1 to 6 hydrogen atoms or carbon atoms, wherein the alkyl group is unsubstituted or may be substituted by one or more of the said substituents E. Q 1This refers to an organic group having 2 to 30 carbon atoms and an aromatic hydrocarbon group, wherein any carbon atom of the aromatic hydrocarbon group may be substituted with a heteroatom, and the aromatic hydrocarbon group may be unsubstituted or substituted with one or more of the said substituents E. J 1 This represents -O-, -S-, -COO-, -OCO-, -OCO-O-, and -NQ. 2 -、-N=CQ 2 -、-CO-NQ 2 -、-OCO-NQ 2 -or-O-NQ 2 -, where Q 2 The following can represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, a cycloalkenyl group having 3 to 12 carbon atoms, an organic group having 2 to 30 carbon atoms having an aromatic hydrocarbon group (any carbon atom of which may be replaced by a heteroatom), or -L 6 -R sp2 -Z 2 The alkyl, cycloalkyl, cycloalkenyl, and aromatic hydrocarbon groups are each unsubstituted or can be substituted by one or more of the said substituents E. The alkyl group can be substituted by the cycloalkyl or cycloalkenyl group. One -CH2- or two or more non-adjacent -CH2- groups in the alkyl group can be independently substituted by -O-, -S-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -SO2-, -O-CO-O-, -CO-NH-, -NH-CO-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -CH=CH-, -CF=CF-, or -C≡C-. One -CH2- or two or more non-adjacent -CH2- groups in the cycloalkyl or cycloalkenyl group can be independently substituted by -O-, -CO-, -COO-, -OCO-, or -O-CO-O-. 6 R sp2 and Z 2 Respectively represent the L 5 R sp2 and Z 2 Groups that are the same as the groups defined in [the original text], respectively with the L 5 R sp2 and Z 2 They can be the same or different. Also, Q... 1 With Q 2 They can also be bonded to form rings. For a detailed description of the groups selected from the general formula (D-1), the detailed description of the groups selected from the general formula (D-1) as described in International Publication No. 2019 / 074007 can be incorporated into this application specification. Furthermore, as a polymerizable liquid crystal compound having groups selected from the general formula (D-1) as substituents, the detailed description of the polymerizable liquid crystal compound represented by general formula (1) as described in International Publication No. 2019 / 074007 can be incorporated into this application specification.

[0262] In general formula (II), Z 1 Z 2 R sp1 R sp2 Each of the substituents E can be independently the same as the group described in the above general formula (I).

[0263] L 4 In and R sp1 bonded L 4 and L 5 Preferably, it can be used with L in the general formula (I) 3 The same as recorded in the text.

[0264] Not with R sp1 bonded L 4 Preferably, it can be used with L in the general formula (I) 1 and L 2 The same as recorded in the text.

[0265] T 3 In this context, "T" represents an aromatic hydrocarbon group or alicyclic hydrocarbon group with 3 to 20 divalent carbon atoms that is unsubstituted or can be substituted by one or more substituents E, wherein any carbon atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group can be replaced by a heteroatom T. 3 It can be used with T in the general formula (I) 1 and T 2 The same as described in [the original text]. From the viewpoint of the ease of obtaining the starting materials and the ease of synthesis of the compound represented by general formula (II), T 3 Each group is preferably represented independently by the group represented by the general formula (B-1), (B-2), (B-2-2), (B-3), (B-4) or (B-10), and more preferably by the group represented by the general formula (B-1), (B-2), (B-2-2) or (B-10).

[0266] p is preferably an integer greater than or equal to 3, but can also be an integer less than or equal to 5.

[0267] When the compositions disclosed herein contain other liquid crystal compounds, the content of the other liquid crystal compounds in the composition is not particularly limited, and can be 95% by mass or less, 90% by mass or less, 80% by mass or less, or 60% by mass or less relative to the total mass of the solid components in the composition. The content of the other liquid crystal compounds in the composition can be 0% by mass or more, or 1% by mass or more, relative to the total mass of the solid components in the composition.

[0268] The compositions disclosed herein may use one or more other liquid crystal compounds alone. When using two or more compounds, their total content is preferably within the range described above.

[0269] <Polymerization initiator>

[0270] The compositions disclosed herein may contain a polymerization initiator.

[0271] The polymerization initiator can be appropriately selected based on the polymerizable groups contained in the composition.

[0272] The polymerization initiator is preferably a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation. In this embodiment, the photopolymerization initiator can be appropriately selected from conventionally known substances. Specific examples of such photopolymerization initiators include, for instance, aromatic ketones such as thioxanthone, α-aminoalkylphenyl ketones, α-hydroxy ketones, acylphosphine oxides, oxime esters, aromatic onium salts, organic peroxides, thiolated compounds, hexaaryl biimidazole compounds, ketoxime esters, borate compounds, acridine onium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds. To improve durability by curing to the interior of the coating, at least one of acylphosphine oxide-based polymerization initiators, α-aminoalkylphenyl ketone-based polymerization initiators, α-hydroxy ketone-based polymerization initiators, and oxime ester-based polymerization initiators is preferred.

[0273] Examples of acylphosphine oxide polymerization initiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (e.g., trade name: Omnirad 819, manufactured by IGM RESINS BV), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethyl-pentylphenylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM RESINS BV, etc.).

[0274] In addition, examples of α-aminoalkyl phenyl ketone polymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one (e.g., Omnirad 907, manufactured by IGM RESINS BV), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g., Omnirad 369, manufactured by IGM RESINS BV), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholino)phenyl]-1-butanone (Omnirad 379EG, manufactured by IGM RESINS BV).

[0275] In addition, examples of α-hydroxy ketone polymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methyl-propanoyl)-benzyl]-phenyl}-2-methyl-propane-1-one (e.g., trade names: Omnirad 127, manufactured by IGM RESINS BV, etc.), 2-hydroxy-4'-hydroxyethoxy-2-methylphenylacetone (e.g., trade names: Omnirad 2959, manufactured by IGM RESINS B.V., etc.), 1-hydroxy-cyclohexyl-phenyl-one (e.g., trade names: Omnirad 184, manufactured by IGM RESINS BV, etc.), and oligomeric {2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} (e.g., trade names: ESACUREONE, manufactured by IGM RESINS BV, etc.).

[0276] Examples of oxime ester polymerization initiators include 1,2-octanedione, 1-[4-(phenylthio)-,2-(O-benzoyl oxime)] (trade name: Irgacure OXE-01, manufactured by BASF), ethyl ketone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (trade name: Irgacure OXE-02, manufactured by BASF), methyl ketone, ethyl ketone, 1-[9-ethyl-6-(1,3-dioxacyclopentane,4-(2-methoxyphenoxy)-9H-carbazole-3-yl]-,1-(O-acetyl oxime) (trade name: ADEKAOPT-N-1919, manufactured by ADEKA), etc.

[0277] When the composition disclosed herein contains a polymerization initiator, the content of the polymerization initiator in the composition is not particularly limited, but is preferably 0.1% to 20% by mass relative to the total mass of the compound represented by general formula (I) (when the composition contains other liquid crystal compounds, the total mass of the compound represented by general formula (I) and other liquid crystal compounds). More preferably, it is 1% to 8% by mass.

[0278] The compositions disclosed herein may use one polymerization initiator alone, or two or more initiators. When two or more initiators are used, their total content is preferably within the range described above.

[0279] Chiral reagents

[0280] The compositions disclosed herein may contain chiral agents. When the compositions disclosed herein contain chiral agents, a cholesterol phase can be formed.

[0281] There are no particular limitations on the type of chiral reagent. Chiral reagents can be liquid crystal or non-liquid crystal. Chiral reagents typically contain asymmetric carbon atoms. However, axially asymmetric or planar asymmetric compounds that do not contain asymmetric carbon atoms can also be used as chiral reagents. Examples of axially asymmetric or planar asymmetric compounds include naphthalene, helicene, p-cycloaranes, and their derivatives. Chiral reagents can have polymerizable groups. Specific examples of chiral reagents include those described in Japanese Patent Application Publication No. 08-245960, EP1816180, Japanese Patent No. 5284735, and Japanese Patent No. 4871139.

[0282] When the composition of this disclosure contains a chiral agent, the content of the chiral agent in the composition is not particularly limited, but is preferably 0.1% to 15% by mass, more preferably 1.0% to 10% by mass, relative to the total mass of the compound represented by general formula (I) (or, when the composition contains other liquid crystal compounds, relative to the total mass of the compound represented by general formula (I) and other liquid crystal compounds).

[0283] The compositions disclosed herein may use one chiral reagent alone, or two or more. When two or more are used, their total content is preferably within the range described above.

[0284] Solvent

[0285] From a coating point of view, the compositions disclosed herein may include solvents as needed. As solvents, appropriate solvents can be selected from conventionally known solvents capable of dissolving or dispersing the components contained in the polymerizable composition. Specifically, examples include hydrocarbon solvents such as hexane, cyclohexane, and toluene; ketone solvents such as methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone; ether solvents such as tetrahydrofuran, 1,3-dioxolane, and propylene glycol monoethyl ether (PGME); halogenated alkyl solvents such as chloroform and dichloromethane; ester solvents such as ethyl acetate and propylene glycol monomethyl ether acetate; amide solvents such as N,N-dimethylformamide and N-methylpyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; and alcohol solvents such as methanol, ethanol, and propanol. In this embodiment, one solvent may be used alone, or two or more may be used in combination as a mixed solvent.

[0286] When the composition disclosed herein contains a solvent, the solvent content in the composition is preferably an amount that makes the solid component concentration of the composition 0.5% to 20% by mass, more preferably 1% to 10% by mass.

[0287] The compositions disclosed herein can be used with one solvent alone, or with two or more solvents. When two or more solvents are used, their total content is preferably within the range described above.

[0288] <surfactants>

[0289] The compositions disclosed herein may contain surfactants that facilitate the formation of stable or rapid liquid crystal phases (e.g., nematic phases, cholesterol phases).

[0290] Examples of surfactants include fluorinated (meth)acrylate polymers, compounds represented by general formulas (X1) to (X3) as described in WO2011 / 162291, compounds represented by general formula (I) as described in paragraphs 0082 to 0090 of Japanese Patent Application Publication No. 2014-119605, and compounds described in paragraphs 0020 to 0031 of Japanese Patent Application Publication No. 2013-47204.

[0291] As fluorinated (meth)acrylate polymers that can be used as surfactants, the polymers described in paragraphs 0018 to 0043 of Japanese Patent Application Publication No. 2007-272185 can also be cited.

[0292] When the composition disclosed herein contains a surfactant, the content of the surfactant is not particularly limited, but is preferably 0.001% to 10% by mass relative to the total mass of the compound represented by general formula (I) (or, when the composition contains other liquid crystal compounds, the total mass of the compound represented by general formula (I) and other liquid crystal compounds). More preferably, it is 0.05% to 3% by mass.

[0293] The compositions disclosed herein may use one surfactant alone or two or more surfactants. When two or more surfactants are used, their total content is preferably within the range described above.

[0294] In addition to the above, the compositions disclosed herein may also contain antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, defoamers, leveling agents, thickeners, flame retardants, surfactants, dispersants, dyes and pigments, and other color materials.

[0295] C. Optical anisotropic bodies

[0296] The optical anisotropy of this disclosure is an optical anisotropy obtained by orienting the compound represented by general formula (I) in the composition of this disclosure.

[0297] The optical anisotropy of this disclosure can be an optical anisotropy as a cured product of the composition containing the polymerization initiator of this disclosure.

[0298] Furthermore, the optical anisotropy of this disclosure can be an optical anisotropy as the composition containing the chiral reagent of this disclosure or a cured product thereof. The composition containing the chiral reagent of this disclosure as an optical anisotropy can be a cured product.

[0299] There are no particular limitations on the method for immobilizing the composition disclosed herein, and known methods can be used. For example, a method comprising the following steps can be described: a step of contacting a specified substrate with the composition to form a composition layer on a support (composition layer forming step); a step of subjecting the composition layer to heat treatment to orient the compound represented by general formula (I) (orientation step); and then, a step of subjecting a curing treatment as needed (curing step). Preferably, an orientation film is provided on the support, which may be a step of contacting the orientation film provided on the support with the composition to form a composition layer on the orientation film provided on the support (composition layer forming step); and a step of subjecting the composition layer to heat treatment to orient the compound represented by general formula (I) (orientation step).

[0300] According to this method, it is possible to immobilize the compound in the orientation state represented by general formula (I) and form an optical anisotropy (e.g., an optical anisotropy layer).

[0301] It should be noted that an optically anisotropic material refers to a substance that exhibits optical anisotropy. Optical anisotropy means that the refractive index varies depending on the polarization direction. For example, it can be confirmed by placing an optically anisotropic material between two polarizing plates in a crossed Nicol configuration, rotating it, and allowing incident light to pass through at a specific angle during observation, while observing the disappearance of incident light at other angles.

[0302] The composition layer formation process is a process in which a specified support is brought into contact with the composition to form a composition layer on the support. There are no particular limitations on the type of support used; known substrates (e.g., resin substrates, glass substrates, ceramic substrates, semiconductor substrates, and metal substrates) are examples.

[0303] There are no particular limitations on the method of bringing the support into contact with the composition; for example, the method of coating the composition onto the support can be cited.

[0304] As described above, it is preferable to provide an alignment film on the support body, and the alignment film can be provided by conventionally known methods.

[0305] Any coating method that can form a film with high precision at the desired thickness can be used; an appropriate method can be selected. Examples include gravure coating, reverse coating, doctor blade coating, dip coating, spray coating, air knife coating, spin coating, roller coating, printing, dip-coating, curtain coating, mold coating, casting, rod coating, extrusion coating, and E-type coating.

[0306] The orientation process is a process of heat-treating the composition layer to orient the compound represented by general formula (I).

[0307] The compound represented by general formula (I) contained in the composition layer is adjusted to an oriented temperature and heated. Through this heat treatment, the compound represented by general formula (I) and other liquid crystal compounds further contained as needed can be oriented and dried, and can be immobilized while maintaining the oriented state.

[0308] The orientation temperature varies depending on the substances in the composition, and therefore needs to be adjusted accordingly. For example, it is preferable to perform the experiment in a range of 60°C or higher and 200°C or lower, and more preferably in a range of 60°C or higher and 100°C or lower.

[0309] As a heating method, well-known heating and drying methods can be appropriately selected and used.

[0310] In addition, the heating time can be selected appropriately, for example, within the range of more than 10 seconds and less than 2 hours, preferably more than 20 seconds and less than 30 minutes.

[0311] By subjecting the composition layer to heat treatment, the compound represented by general formula (I) undergoes orientation to form a liquid crystal phase. For example, when a chiral reagent is included in the composition layer, a cholesterol-type liquid crystal phase is formed.

[0312] After the orientation process, a curing process is performed as needed.

[0313] There are no particular limitations on the curing method; examples include light curing and heat curing. Among these, light irradiation is preferred, and ultraviolet irradiation is even more preferred.

[0314] For light irradiation, ultraviolet (UV) irradiation is preferred. UV irradiation can be achieved using UV light emitted from ultra-high pressure mercury lamps, high pressure mercury lamps, low pressure mercury lamps, carbon arc lamps, xenon arc lamps, metal halide lamps, etc. The irradiation dose from the energy source can be appropriately selected; for example, a cumulative exposure dose at a UV wavelength of 365 nm is preferably 10 mJ / cm². 2 Above and 10000 mJ / cm 2 Within the following range.

[0315] The cured product obtained by the above treatment is equivalent to a layer formed by fixing a liquid crystal phase. In the case where the composition contains a chiral agent, a layer formed by fixing a cholesterol-type liquid crystal phase is formed.

[0316] It should be noted that these layers no longer need to exhibit liquid crystal properties. More specifically, for example, regarding the state of "immobilizing" a cholesterol-type liquid crystal phase, the state in which the orientation of the compound represented by the general formula (I) of the cholesterol-type liquid crystal phase is maintained is the most typical and preferred manner. More specifically, it is preferred that the layer does not have fluidity in a temperature range of -30°C to 70°C, typically at 0°C to 50°C, and even more severe conditions at -30°C to 70°C, and that the orientation morphology does not change due to external fields or forces, thus stably and continuously maintaining the immobilized orientation morphology.

[0317] The thickness of the optical anisotropic material (e.g., the optical anisotropic layer) can be selected appropriately according to the application and is not particularly limited. For example, the thickness of the optical anisotropic layer can be 0.1 μm or more and 10 μm or less, 0.1 μm or more and 5 μm or less, or 0.5 μm or more and 3 μm or less.

[0318] The compounds contained in the compositions of this disclosure within optical anisotropy can be identified by collecting and analyzing materials from the optical anisotropy. Analytical methods include HPLC, GPC, NMR, IR, thermal decomposition GC-MS, LC-MS, TOF-MS, TOF-SIMS, and combinations thereof. Furthermore, X-ray photoelectron spectrometry (XPS), infrared spectroscopy (IR), and Raman spectroscopy can be used to identify peaks or amounts of bonds and functional groups originating from the liquid crystal components contained in the optical anisotropy. By combining these analytical results, the structure of the components contained in the optical anisotropy can be analyzed.

[0319] D. Optical elements

[0320] The optical element disclosed herein is an optical element having an optical anisotropy layer formed using the composition of the present disclosure.

[0321] The optical element disclosed herein can be an optical element having an optical anisotropy layer formed using the composition of the present disclosure. The optical anisotropic layer has an orientation pattern. The orientation pattern is an orientation pattern derived from the orientation of the optical axis of the liquid crystal compound contained in the composition, which rotates continuously along at least one direction in the plane.

[0322] The orientation pattern is preferably one of the following: an orientation pattern in which the orientation of the optical axis of the compound represented by general formula (I) is continuously rotated along at least one direction in the plane, or an orientation pattern in which the orientation of the optical axis of the compound represented by general formula (I) and other liquid crystal compounds is continuously rotated along at least one direction in the plane.

[0323] The optical element disclosed herein enables light incident on the optical element to diffract through an orientation pattern having an optical axis whose orientation continuously rotates along at least one direction within the plane. The compound represented by general formula (I) is a compound with high refractive index anisotropy Δn, thus improving diffraction efficiency.

[0324] The optical elements disclosed herein can be suitably applied to conventionally known optical elements that include the optical anisotropy layer.

[0325] Furthermore, the optical element disclosed herein can be appropriately applied to conventionally known optical elements as long as the optical anisotropy layer has an orientation pattern and the orientation pattern is an orientation pattern derived from the optical axis of the liquid crystal compound contained in the composition that rotates continuously along at least one direction in the plane.

[0326] Regarding optical elements, for example, refer to paragraphs

[0067] to

[0107] of International Publication No. 2020 / 022496 or paragraphs

[0035] to

[0072] of Japanese Patent Application Publication No. 2017-31379.

[0327] The optical element disclosed herein can be used as an optical component in augmented reality (AR) image projection devices, etc.

[0328] Furthermore, the optical element disclosed herein can be used as a light guide element comprising the optical element and a light guide plate.

[0329] II. The Second Publication

[0330] The second disclosed optical anisotropy is a cured product of a polymeric liquid crystal composition comprising a partial structure of the following general formula (Ia).

[0331] [Chemical Formula 24]

[0332] General formula (Ia)

[0333] (In general formula (Ia), 2,6-naphthyl can be replaced by more than one substituent E, and k1 represents an integer from 0 to 6.)

[0334] Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymerizable group. Wherein, if the above-described group described as substituent E has -CH2-, a group formed by replacing at least one of the -CH2- groups contained in the above-described group with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the group described as substituent E has hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms contained in the group with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E.

[0335] This indicates the bonding positions with other atoms.

[0336] The second disclosed optical anisotropy is a cured polymeric liquid crystal composition, and is an optical anisotropy with improved refractive index anisotropy Δn and suppressed crack generation by including a partial structure of general formula (Ia).

[0337] The partial structure of general formula (Ia) has an electron-withdrawing group -COO- at the 2-position of naphthalene and an electron-donating group -S- at the 6-position of naphthalene, thus creating a structure that induces a wider π-conjugation resonance. The optical anisotropy disclosed in the second book includes a partial structure of general formula (Ia), therefore it is speculated that π electrons expand towards the 2- and 6-positions of naphthalene through the -S-naphthalene-COO- structure, increasing the refractive index at the 2- and 6-positions of naphthalene and raising the refractive index anisotropy Δn. Furthermore, it is speculated that the refractive index anisotropy Δn also increases due to the large polarizability of the sulfur atom or the synergistic effect of intermolecular SS interactions. Additionally, if the partial structure of general formula (Ia) is included, the bonding angle of the -S- adjacent to naphthalene is significantly bent, therefore it is presumed that even with deformation, sufficient elongation can be obtained through this bond. Therefore, it is speculated that by including a partial structure of general formula (Ia), the optical anisotropy disclosed in the second book has an increased refractive index anisotropy Δn and is less prone to cracking.

[0338] The second disclosed optical anisotropy exhibits improved bending resistance, making it less prone to cracking even when bent, and demonstrates excellent fit and processability.

[0339] The second disclosed optical anisotropy can have an in-plane phase difference Re and layer thickness (nm) measured by the method shown below and Δn calculated by the following formula, where Δn can be 0.25 or more.

[0340] Δn = Re / layer thickness (nm)

[0341] Re was measured using a phase difference measuring device (RETS-100, Otsuka Electronics Co., Ltd.) at a wavelength of 550 nm, with the temperature set at 25°C. The average of three measured values ​​was used as the measurement result. It should be noted that when an optical anisotropy is laminated with a substrate having a phase difference, such as polyethylene terephthalate (PET), the optical anisotropy is transferred onto a glass plate with an adhesive layer (optical adhesive, PANACLEAN PD-S1, PANAC Corporation) that does not have a phase difference to create a measurement sample, and the in-plane phase difference Re is measured.

[0342] (Re measurement conditions)

[0343] • Delay measurement range: Rotating analyzer method

[0344] • Measurement point diameter: 5mm

[0345] • Tilt angle range: 0°

[0346] • Measurement wavelength range: 400nm~800nm

[0347] (Layer thickness measurement)

[0348] Regarding the thickness of the optical anisotropic body (optical anisotropic layer), a cross-section of the optical anisotropic body was photographed using a scanning transmission electron microscope (STEM) (Hitachi High-Technologies Corporation, S-4800). The thickness of the optical anisotropic body at 10 points in the image of the cross-section was measured and set as the arithmetic mean of the thickness at these 10 points.

[0349] The cross-sectional photographs of the optical anisotropy are shown below. First, a block of sample 1mm × 10mm was prepared by embedding it in resin. Using standard slicing methods, a uniform slice with a thickness of 70nm to 100nm without pores was cut from this block. The slices were prepared using an ion milling apparatus (Hitachi High Technology Co., Ltd., IM-4000II). This uniform slice without pores was then used as the measurement sample. A cross-sectional photograph of the measurement sample was then taken using a scanning transmission electron microscope (STEM). When taking this cross-sectional photograph, the detector was set to "TE", the accelerating voltage to "30kV", and the emission current to "10μA" for STEM observation. Regarding magnification, the contrast and brightness were adjusted appropriately from 5000x to 200,000x while adjusting the focus and observing whether the layers could be distinguished.

[0350] The second disclosed optical anisotropy is an optical anisotropy that does not produce cracks when the curved portion of the mandrel with a diameter of 3 mm is observed using the cylindrical mandrel method according to JIS-K5600-5-1:1999 and with a 10x magnifying glass.

[0351] The second disclosed optical anisotropy is a cured product of a polymeric liquid crystal composition comprising a partial structure of the general formula (Ia).

[0352] Regarding the optical anisotropy disclosed in the second book, which includes a partial structure of the general formula (Ia), fragment ions of the partial structure of the general formula (Ia) and fragment ions of the structure containing the partial structure of the general formula (Ia) are analyzed by detecting time-of-flight secondary ion mass spectrometry (TOF-SIMS).

[0353] (TOF-SIMS measurement conditions)

[0354] TOF-SIMS device: TOF-SIMS manufactured by ION-TOF Company 5

[0355] Primary ion type: Bi3 ++

[0356] Primary ion acceleration voltage: 25kV

[0357] Primary ion current: 0.2 pA

[0358] Measurement area: 200μm × 200μm (using a neutralization gun for charge calibration)

[0359] Number of scans: 64

[0360] In the partial structure of the general formula (Ia), the substituent E may be the same as the substituent E described in the first disclosure. From the viewpoint of liquid crystal properties and visible light transmittance, the substituent E is preferably an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkanoyl group having 2 to 6 carbon atoms, an alkanoyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a trifluoromethyl group, a fluorine atom, or a chlorine atom; more preferably, it is an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an alkanoyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, or a fluorine atom.

[0361] In the partial structure of general formula (Ia), k1 represents an integer from 0 to 6. From the perspective of the ease of obtaining raw materials and the ease of synthesis, k1 can be an integer from 0 to 3, an integer from 0 to 2, 0 or 1, or 0.

[0362] The second disclosed optical anisotropy may be a cured product of a polymeric liquid crystal composition comprising a compound having a partial structure of the general formula (Ia).

[0363] Compounds containing a portion of the structure of the general formula (Ia) may not be liquid crystal oriented; they may be liquid crystal compounds or polymeric liquid crystal compounds.

[0364] The compound containing a partial structure of the general formula (Ia) in the second disclosed optical anisotropy may be a compound represented by the general formula (I-1) or a compound represented by the general formula (I-2).

[0365] The compounds represented by general formula (I-1) and general formula (I-2) may be the same as those described in the first disclosure.

[0366] As a second disclosed optical anisotropy, a polymeric liquid crystal composition comprising a partial structure of the general formula (Ia) includes, for example, a composition comprising a compound containing a partial structure of the general formula (Ia) and at least a polymeric liquid crystal compound. If the compound comprising a partial structure of the general formula (Ia) is a polymeric liquid crystal compound, it may not be necessary to further comprise other polymeric liquid crystal compounds.

[0367] The components and their contents that may be included in the polymeric liquid crystal composition containing a partial structure of the general formula (Ia) in the second disclosed optical anisotropy may be the same as the components and their contents described in the composition of the first disclosed invention.

[0368] Other liquid crystal compounds may be the same as those described in the compositions disclosed in the first publication. The compound represented by general formula (II) may be a compound represented by general formula (II) (but different from compounds containing a portion of the structure of general formula (Ia)).

[0369] In the cured product of the polymeric liquid crystal composition, which is the second disclosed optical anisotropy, the polymerization initiator sometimes decomposes, so it may not contain a polymerization initiator.

[0370] In the second disclosed optical anisotropy, from the viewpoint of refractive index anisotropy and crack suppression, it is preferable to contain 4% by mass or more of a compound comprising a partial structure of the general formula (Ia).

[0371] In the second disclosed optical anisotropy, the compound containing a portion of the structure of the general formula (Ia) can be 9% or more by mass, 30% or more by mass, 50% or more by mass, 70% or more by mass, or on the other hand, 100% or less by mass, 99% or less by mass, or 97% or less by mass.

[0372] In the second disclosed optical anisotropy, from the viewpoint of refractive index anisotropy and crack initiation suppression, the ATR method was used and Fourier transform infrared spectrophotometer (FT-IR) was used to measure the position at 1205 cm⁻¹. -1 ~1225cm -1 The peak intensity (P1) of the SC bond is located at 1600 cm⁻¹ -1 ~1650cm -1 The ratio of the peak intensity (P2) of the C=C bond (P1 / P2) can be greater than 0.30 and less than 1.8. The P1 / P2 ratio can be greater than 0.45, greater than 0.80, or greater than 1.00.

[0373] Located at 1205cm -1 ~1225cm -1 The peak representing the SC bond of the aromatic ring is located at 1600 cm⁻¹. -1 ~1650cm -1 The peaks representing C=C bonds indicate the C=C bonds of the aromatic ring. Therefore, P1 / P2, which is the ratio of their peak intensities, represents the relative amount of aromatic rings bonded to sulfur atoms. From the viewpoint of refractive index anisotropy and suppression of crack formation, it is preferable that P1 / P2 is 0.30 or higher. On the other hand, from the viewpoint of film surface hardness, it is preferable that P1 / P2 is 1.80 or lower.

[0374] Furthermore, from the perspective of refractive index anisotropy and suppressing crack initiation, the ATR method was used and Fourier transform infrared spectrophotometer (FT-IR) was used to measure the crack location at 1205 cm⁻¹. -1 ~1225cm -1 The peak intensity (P1) of the SC bond is located at 1700 cm⁻¹ -1 ~1750cm -1 The ratio of the peak intensity (P3) of the C=O bond (P1 / P3) can be greater than 0.10 and less than 0.80. The P1 / P3 ratio can be greater than 0.30 or greater than 0.50.

[0375] Furthermore, from the perspective of refractive index anisotropy and crack suppression, the ATR method was used, and Fourier transform infrared spectrophotometer (FT-IR) was used to measure the crack location at 1205 cm⁻¹. -1 ~1225cm -1 The peak intensity (P1) of the SC bond is located at 1600 cm⁻¹ -1 ~1650cm -1 The peak intensity (P2) of the C=C bond and its location at 1700 cm⁻¹ -1 ~1750cm -1 The ratio of the total peak intensities (P3) of the C=O bonds {P1 / (P2+P3)} can be greater than 0.10 and less than 0.80. The ratio P1 / (P2+P3) can be greater than 0.15 or greater than 0.30.

[0376] It should be noted that the peak intensity measured in FT-IR refers to the absorbance at the peak position (unitless). The peak intensity is calculated using the analytical software provided with the measuring device, which determines the height from the background to the peak in the obtained spectrum.

[0377] (FT-IR measurement conditions)

[0378] The surface of an optically anisotropic body was measured using the ATR method and a Fourier transform infrared spectrophotometer (FT-IR). Measurements were performed with the surface of the optically anisotropic body exposed as needed.

[0379] Measurement apparatus: Fourier transform infrared spectrophotometer (manufactured by Nippon Spectrophotometer Co., Ltd., with an ATR-PRO470-H device mounted on the FT-IR6100)

[0380] Light source: High-brightness ceramic light source

[0381] Detector: DLATGS

[0382] Beam splitter: Ge / KBr

[0383] Measurement mode: ATR method (diamond prism, incident angle 45°)

[0384] Wavenumber range for measurement: 4,000 cm⁻¹ -1 ~400cm -1

[0385] Resolution: 4cm -1

[0386] Determine the diameter of the light spot: 1.5mm

[0387] Total number of times: 32

[0388] The second disclosed optical anisotropy can be manufactured as follows: a polymeric liquid crystal composition comprising a portion of the structure of the general formula (Ia) is prepared, and the polymeric liquid crystal composition is used to manufacture the optical anisotropy in the same manner as described in the first disclosed optical anisotropy.

[0389] In the second disclosed optical anisotropy, the cured product of a polymeric liquid crystal composition comprising a portion of the structure of the general formula (Ia) is equivalent to a layer formed by fixing a liquid crystal phase. Wherein, in the case that the composition contains a chiral reagent, a layer formed by fixing a cholesterol-type liquid crystal phase is formed.

[0390] Furthermore, these layers no longer need to exhibit liquid crystal properties. More specifically, for example, regarding the state of "immobilization" of a cholesterol-type liquid crystal phase, the orientation of the compound containing a portion of the structure of the general formula (Ia) that forms the cholesterol-type liquid crystal phase is maintained is the most typical and preferred manner.

[0391] The thickness of the optical anisotropic body (e.g., optical anisotropic layer) disclosed in the second book can be appropriately selected according to the application, without any particular limitation. The thickness of the optical anisotropic layer can be, for example, 0.1 μm or more and 10 μm or less, 0.1 μm or more and 5 μm or less, or 0.5 μm or more and 3 μm or less.

[0392] The second disclosed optical anisotropy is a cured polymeric liquid crystal composition, and the orientation of its molecules can be analyzed by X-ray diffraction. Furthermore, the components contained in the second disclosed optical anisotropy can be identified by collecting and analyzing the material from the optical anisotropy. As analytical methods, HPLC, GPC, NMR, IR, thermal decomposition GC-MS, LC-MS, TOF-MS, TOF-SIMS, and combinations thereof can be applied. Furthermore, by X-ray photoelectron spectrometry (XPS), infrared spectroscopy (IR), or Raman spectroscopy, the peaks or amounts of bonds and functional groups originating from the liquid crystal components contained in the optical anisotropy can be identified. By combining these analytical results, the structure of the components contained in the optical anisotropy can be analyzed.

[0393] The second disclosed optical element is an optical element having the optical anisotropic body disclosed in the second disclosure as an optical anisotropic layer.

[0394] Additionally, the optical element disclosed in the second book may be an optical element having an optical anisotropy layer as an optical anisotropy layer having an orientation pattern derived from an orientation pattern in which the orientation of the optical axis of the liquid crystal compound contained in the composition is continuously rotated along at least one in-plane direction.

[0395] The second disclosed optical element can be suitably applied to conventionally known optical elements that include the optical anisotropy layer.

[0396] The optical element disclosed in the second book may be the same as the optical element disclosed in the first book.

[0397] Example

[0398] Using the AVANCE (400MHz) manufactured by Bruker... 1 ¹H NMR measurements were used to confirm the chemical structures of the manufactured compounds.

[0399] In this disclosure, unless otherwise specified, the in-plane phase difference Re and various FT-IR parameters in the following evaluation items refer to the average values ​​of the measurements at three locations. Regarding the three measurement locations, the three points where the lines dividing the longitudinal direction of the quadrilateral sample into four equal parts and the lines dividing the transverse direction into two equal parts are drawn are considered as the measurement centers. The longitudinal direction of the quadrilateral is the direction of its longer side. It should be noted that when the measurement sample is a shape other than a quadrilateral, such as a circle, ellipse, triangle, or pentagon, the quadrilateral with the largest area inscribed in these shapes is drawn, and for this quadrilateral, the three measurements are performed using the method described above.

[0400] Example 1 Series: First Disclosure

[0401] [Manufacturing Example 1: Manufacturing of Compound A-1]

[0402] Compound A-1 was synthesized according to the following procedure.

[0403] [Chemical Formula 25]

[0404] (1) Synthesis of Compound 1

[0405] 6-Hydroxy-2-naphthoic acid (7.5 g, 39.9 mmol) and 1,4-diazabicyclo[2.2.2]octane (DABCO) (13.4 g, 119.6 mmol) were dissolved in dimethylformamide (DMF) (75 mL). N,N-dimethylthiocarbamoyl chloride (14.5 g, 119.6 mmol) was added to the resulting solution, and the mixture was stirred at 65 °C for 3 hours. The resulting solution was cooled to room temperature, and 1 M hydrochloric acid (150 mL) was added. The resulting mixture was filtered and washed with water. The resulting solid was purified by re-slurrying with methanol to give compound 1 (10.6 g, 38.5 mmol). The yield was 96.5%.

[0406] (2) Synthesis of compound 2

[0407] Compound 1 (8.0 g, 29.1 mmol) was stirred at 230 °C for 3 hours. The residue was purified by rapid column chromatography to give compound 2 (7.9 g, 28.6 mmol). The yield was 98.5%.

[0408] (3) Synthesis of compound 3

[0409] Compound 2 (7.9 g, 28.6 mmol) was dissolved in methanol (40 mL). An aqueous solution of potassium hydroxide (4.3 g, 85.8 mmol) (water; 40 mL) was added to the resulting solution, and the mixture was stirred at 70 °C for 3 hours. The solution was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (120 mL) was added to the residue. The resulting mixture was filtered, and the residue was washed with water to give compound 3 (5.6 g, 27.3 mmol). The yield was 95.5%.

[0410] (4) Synthesis of compound 4

[0411] Dimethylacetamide (DMAc) (200 mL) was added to compound 3 (10 g, 47.0 mmol), 4-chlorobutyl acetate (21.2 g, 141.0 mmol), potassium carbonate (19.4 g, 141.0 mmol), and potassium iodide (0.8 g, 4.7 mmol). The resulting mixture was stirred at 80 °C for 3 hours. A sodium hydroxide solution (9.4 g, 235.0 mmol) (200 mL water, 50 mL methanol) was added to the resulting mixture, and the mixture was stirred at 80 °C for 3 hours. The resulting mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (500 mL) was added to the residue. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The solid was purified by re-slurrying with diisopropyl ether to give compound 4 (12.4 g, 44.9 mmol). The yield was 95.5%.

[0412] (5) Synthesis of compound 5

[0413] Compound 4 (10.0 g, 36.1 mmol) and N,N-dimethylaniline (6.6 g, 54.2 mmol) were dissolved in tetrahydrofuran (THF) (100 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (4.9 g, 54.2 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The residue was recrystallized from toluene to give compound 5 (11.8 g, 35.7 mmol). The yield was 98.0%.

[0414] (6) Synthesis of compound A-1

[0415] Compound 5 (4.1 g, 12.5 mmol), methylhydroquinone (0.6 g, 5.0 mmol), and 4-dimethylaminopyridine (DMAP) (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-1 (3.7 g, 5.0 mmol). The yield was 99.5%.

[0416] 1 H-NMR(CDCl3): δ=1.87(m,8H),2.31(s,3H),3.13(t,4H),4.21(t,4H),5.80(dd,2H),6.37(dd,2H),6.41(dd, 2H),7.24(m,5H),7.47(s,1H),7.49(s,1H),7.72(d,2H),7.85(d,2H),7.89(d,2H),8.20(m,2H),8.71(d,2H)

[0417] [Chemical Formula 26]

[0418] [Manufacturing Example 2: Manufacturing of Compound A-2]

[0419] Compound A-2 was synthesized according to the following procedure.

[0420] [Chemical Formula 27]

[0421] (1) Synthesis of compound 6

[0422] Compound 3 was synthesized in the same manner as in Example 1. DMAc (200 mL) was added to compound 3 (10 g, 47.0 mmol), 2-[2-(2-chloroethoxy)ethoxy]ethanol (7.9 g, 47.0 mmol), potassium carbonate (19.5 g, 141.0 mmol), and potassium iodide (0.8 g, 4.7 mmol). The resulting mixture was stirred at 80 °C for 3 hours. A sodium hydroxide solution (9.4 g, 235.0 mmol) (200 mL water, 50 mL methanol) was added to the resulting mixture, and the mixture was stirred at 80 °C for 3 hours. The resulting mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (500 mL) was added to the residue. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The solid was purified by re-slurrying with diisopropyl ether to give compound 6 (14.6 g, 43.5 mmol). The yield was 92.5%.

[0423] (2) Synthesis of compound 7

[0424] Compound 6 (10 g, 29.7 mmol) and N,N-dimethylaniline (5.4 g, 44.6 mmol) were dissolved in THF (200 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (4.0 g, 44.6 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and the reaction product was extracted with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The residue was recrystallized from toluene to give compound 7 (10.7 g, 24.5 mmol). The yield was 92.5%.

[0425] (8) Synthesis of compound A-2

[0426] Compound 7 (4.9 g, 12.5 mmol), methylhydroquinone (0.6 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-2 (4.2 g, 4.8 mmol). The yield was 96.5%.

[0427] 1H-NMR(CDCl3): δ=3.09(t,4H),4.05(m,16H),4.19(t,4H),5.76(dd,2H),6.34(dd,2H),6.39(dd,2H),7 .22(m,5H),7.45(s,1H),7.47(s,1H),7.70(d,2H),7.83(d,2H),7.87(d,2H),8.18(m,2H),8.69(d,2H)

[0428] [Manufacturing Example 3: Manufacturing of Compound A-3]

[0429] Compound 5 was synthesized in the same manner as in Example 1. Compound 5 (4.1 g, 12.5 mmol), 2-fluoro-1,4-benzenediol (0.6 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-3 (3.4 g, 4.5 mmol). The yield was 90.5%.

[0430] 1 H-NMR(CDCl3): δ=1.85(m,8H),3.12(t,4H),4.20(t,4H),5.81(dd,2H),6.34(dd,2H),6.42(dd,2H),7 .22(m,5H),7.40(s,1H),7.48(s,1H),7.72(d,2H),7.84(d,2H),7.88(d,2H),8.19(m,2H),8.70(d,2H)

[0431] [Chemical Formula 28]

[0432] [Manufacturing Example 4: Manufacturing of Compound A-4]

[0433] Compound 5 was synthesized in the same manner as in Example 1. Compound 5 (4.1 g, 12.5 mmol), methyl 2,5-dihydroxybenzoate (0.8 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-4 (3.6 g, 4.6 mmol). The yield was 91.5%.

[0434] 1 H-NMR(CDCl3): δ=1.87(m,8H),3.13(t,4H),3.74(s,3H),4.21(t,4H),5.80(dd,2H),6.07(dd,2H),6.36(dd,2H),7 .36(d,1H),7.47(m,2H),7.55(m,1H),7.73(s,2H),7.83(d,2H),7.89(d,2H),8.01(d,1H),8.17(m,2H),8.73(m,2H)

[0435] [Chemical Formula 29]

[0436] [Manufacturing Example 5: Manufacturing of Compound A-5]

[0437] Compound 5 was synthesized in the same manner as in Example 1. Compound 5 (4.1 g, 12.5 mmol), 2-(4-hydroxyphenyl)ethanol (0.7 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-5 (3.5 g, 4.7 mmol). The yield was 93.0%.

[0438] 1H-NMR(CDCl3): δ=1.93(m,8H),3.16(t,2H),3.14(t,4H),4.26(t,4H),4.61(t,3H),5.84(dd,2H),6.11(dd,2H),6.40(dd,2 H),7.20(m,6H),7.38(d,2H),7.75(d,1H),7.80(m,1H),7.83(m,2H),8.00(dd,1H),8.18(dd,1H),8.51(s,1H),8.69(s,1H)

[0439] [Chemical Formula 30]

[0440] [Manufacturing Example 6: Manufacturing of Compound A-6]

[0441] Compound A-6 was synthesized according to the following procedure.

[0442] [Chemical Formula 31]

[0443] (1) Synthesis of compound 8

[0444] 4-Hydroxybenzoic acid (1.4 g, 10 mmol) was dissolved in THF (14 mL) and cooled to 15 °C. Chloromethyl methyl ether (1.0 g, 12.0 mmol) and N,N-diisopropylethylamine (1.9 g, 15.0 mmol) were added to the resulting mixture, and the mixture was stirred at 15 °C for 1 hour. 4-Methylthiobenzoic acid (2.0 g, 12.0 mmol) and DMAP (0.1 g, 1.0 mmol) were added to the resulting mixture, followed by dropwise addition of N,N-diisopropylcarbodiimide (1.9 g, 15.0 mmol), and the mixture was stirred at 15 °C for 3 hours. 35% hydrochloric acid (10 mL) was added to the resulting mixture, and the mixture was stirred at 15 °C for 24 hours. Methanol (28 mL) was added to the resulting mixture, and the mixture was filtered and washed with methanol. The residue was recrystallized from DMF / methanol to give compound 8 (2.6 g, 9.0 mmol). The yield was 89.5%.

[0445] (2) Synthesis of compound 9

[0446] Compound 5 was synthesized in the same manner as in Example 1. Compound 5 (1.8 g, 5.5 mmol), methylhydroquinone (0.6 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (0.8 g, 6 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound 9 (2.1 g, 4.9 mmol). The yield was 98.5%.

[0447] (3) Synthesis of compound A-6

[0448] Compound 9 (0.4 g, 1.0 mmol), compound 8 (0.4 g, 1.5 mmol), and DMAP (0.01 g, 0.1 mmol) were dissolved in CH₂Cl₂ (2 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (0.3 g, 2.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (10 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-6 (0.7 g, 0.9 mmol). The yield was 91.5%.

[0449] 1 H-NMR(CDCl3): δ=1.96(m,4H),2.31(s,3H),2.65(s,3H),4.14(t,2H),4.27(t,2H),5.86(dd,1H),6.18(dd,1H),6.41(dd,1H),7.2 0(m,5H),7.34(dd,1H),7.42(dd,1H),7.58(dd,1H),7.79(d,1H),7.88(d,1H),7.95(d,1H),8.12(m,3H),8.20(d,2H),8.72(s,1H)

[0450] [Manufacturing Example 7: Manufacturing of Compound A-7]

[0451] Compound 9 was synthesized in the same manner as in Example 6. Compound 9 (0.4 g, 1.0 mmol), 6-methoxy-2-naphthoic acid (0.3 g, 1.5 mmol), and DMAP (0.01 g, 0.1 mmol) were dissolved in CH₂Cl₂ (2 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (0.3 g, 2.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (10 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-7 (0.6 g, 1.0 mmol). The yield was 98.0%.

[0452] 1 H-NMR(CDCl3): δ=1.96(m,4H),2.31(s,3H),2.65(s,3H),4.14(t,2H),4.27(t,2H),5.86(dd,1H),6.18(dd,1H),6.41(dd,1H),7.2 0(m,5H),7.34(dd,1H),7.42(dd,1H),7.58(dd,1H),7.79(d,1H),7.88(d,1H),7.95(d,1H),8.12(m,3H),8.20(d,2H),8.72(s,1H)

[0453] [Chemical Formula 32]

[0454] [Manufacturing Example 8: Manufacturing of Compound A-8]

[0455] Compound 9 was synthesized in the same manner as in Example 6. Compound 9 (0.4 g, 1.0 mmol), 4-cyanobenzoic acid (0.2 g, 1.5 mmol), and DMAP (0.01 g, 0.1 mmol) were dissolved in CH₂Cl₂ (2 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (0.3 g, 2.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (10 mL) was added to the resulting mixture, and the filtered residue was washed with methanol to give compound A-8 (0.5 g, 0.9 mmol). The yield was 93%.

[0456] 1 H-NMR (CDCl3): δ=1.89(m,4H),2.38(s,3H),3.23(t,2H),4.27(t,2H),5.81(dd,1H),6.11(dd,1H),6.41(dd,1H),7. 35(d,1H),7.36(dd,1H),7.42(dd,1H),7.79(s,1H),7.88(m,3H),7.98(s,1H),8.18(d,2H),8.35(d,2H),8.78(s,1H)

[0457] [Chemical Formula 33]

[0458] [Manufacturing Example 9: Manufacturing of Compound A-9]

[0459] Compound 5 was synthesized in the same manner as in Example 1. Compound 5 (1.5 g, 4.5 mmol), 4-cyano-4'-hydroxybiphenyl (0.6 g, 3.0 mmol), and DMAP (0.04 g, 0.3 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (0.8 g, 6.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-9 (1.4 g, 2.7 mmol). The yield was 91.5%.

[0460] [Chemical Formula 34]

[0461] [Manufacturing Example 10: Manufacturing of Compound A-10]

[0462] Compound A-10 was synthesized according to the following procedure.

[0463] 1 H-NMR(CDCl3): δ=1.87(m,4H),3.13(t,2H),4.21(t,2H),5.80(dd,1H),6.07(dd,1H),6.36(dd, 1H),7.38(t,2H),7.48(m,1H),7.66(m,7H),7.82(d,1H),7.88(d,1H),8.19(d,1H),8.73(s,1H)

[0464] [Chemical Formula 35]

[0465] (1) Synthesis of compound 10

[0466] 6-Hydroxy-2-quinolinecarboxylic acid (18.9 g, 100.0 mmol) and DABCO (33.7 g, 300.0 mmol) were dissolved in DMF (200 mL). N,N-Dimethylthiocarbamoyl chloride (37.1 g, 300.0 mmol) was added to the resulting solution, and the mixture was stirred at 65 °C for 3 hours. The resulting solution was cooled to room temperature, and 1 M hydrochloric acid (450 mL) was added. The resulting mixture was filtered, and the residue was washed with water. The resulting solid was purified by re-slurrying with methanol to give compound 10 (26.9 g, 97.5 mmol). The yield was 97.5%.

[0467] (2) Synthesis of compound 11

[0468] Compound 10 (26.9 g, 97.5 mmol) was stirred at 230 °C for 3 hours. The residue was purified by rapid column chromatography to give compound 11 (26.9 g, 97.5 mmol). The yield was 100%.

[0469] (3) Synthesis of compound 12

[0470] Compound 11 (22.1 g, 80.0 mmol) was dissolved in methanol (250 mL). An aqueous solution of potassium hydroxide (13.5 g, 240.0 mmol) (120 mL water) was added to the resulting solution, and the mixture was stirred at 70 °C for 3 hours. The solution was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (300 mL) was added to the residue. The resulting mixture was filtered, and the residue was washed with water to give compound 12 (15.8 g, 76.8 mmol). The yield was 96.0%.

[0471] (4) Synthesis of compound 13

[0472] DMAc (150 mL) was added to compound 12 (14.4 g, 70.0 mmol), 4-chlorobutyl acetate (31.6 g, 210.0 mmol), potassium carbonate (29.0 g, 210.0 mmol), and potassium iodide (1.2 g, 7.0 mmol). The resulting mixture was stirred at 80 °C for 3 hours. A sodium hydroxide solution (14.0 g, 350.0 mmol) (70 mL water, 70 mL methanol) was added to the resulting mixture, and the mixture was stirred at 80 °C for 3 hours. The resulting mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (700 mL) was added to the residue. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The solid was purified by re-slurrying with diisopropyl ether to give compound 13 (18.3 g, 66.1 mmol). The yield was 94.5%.

[0473] (5) Synthesis of compound 14

[0474] Compound 13 (16.6 g, 60 mmol) and N,N-dimethylaniline (9.1 g, 75.0 mmol) were dissolved in THF (200 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (6.8 g, 75.0 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, followed by extraction with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The residue was recrystallized from toluene to give compound 14 (19.5 g, 58.8 mmol). The yield was 98.0%.

[0475] (6) Synthesis of compound A-10

[0476] Compound 14 (16.6 g, 50 mmol), methylhydroquinone (2.5 g, 20 mmol), and DMAP (2.4 g, 2.0 mmol) were dissolved in CH₂Cl₂ (50 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (7.6 g, 60.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (1000 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-10 (14.2 g, 18.9 mmol). The yield was 94.5%.

[0477] 1 H-NMR(CDCl3): δ=1.98(m,8H),2.45(s,3H),3.64(t,4H),4.78(t,4H),5.87(dd,2H),6.44(dd,2H),6. 48(dd,2H),7.53(m,5H),7.61(s,1H),7.63(s,1H),7.86(d,2H),7.97(d,2H),8.03(d,2H),8.33(m,2H)

[0478] [Manufacturing Example 11: Manufacturing of Compound A-11]

[0479] Compound A-11 was synthesized according to the following procedure.

[0480] [Chemical Formula 36]

[0481] (1) Synthesis of compound 15

[0482] 4-(4-hydroxyphenyl)benzoic acid (6.4 g, 30.0 mmol) and DABCO (10.1 g, 90.0 mmol) were dissolved in DMF (300 mL). N,N-dimethylthiocarbamoyl chloride (11.1 g, 90 mmol) was added to the resulting solution, and the mixture was stirred at 65 °C for 3 hours. The resulting solution was cooled to room temperature, and 1 M hydrochloric acid (150 mL) was added. The resulting mixture was filtered, and the residue was washed with water. The resulting solid was purified by re-slurrying with methanol to give compound 15 (8.7 g, 28.8 mmol). The yield was 96.0%.

[0483] (2) Synthesis of compound 16

[0484] Compound 15 (8.7 g, 28.8 mmol) was stirred at 230 °C for 3 hours. The residue was purified by rapid column chromatography to give compound 16 (8.5 g, 28.1 mmol). The yield was 97.5%.

[0485] (3) Synthesis of compound 17

[0486] Compound 16 (7.5 g, 25.0 mmol) was dissolved in methanol (250 mL). An aqueous solution of potassium hydroxide (4.2 g, 75.0 mmol) (75 mL of water) was added to the resulting solution, and the mixture was stirred at 70 °C for 3 hours. The solution was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (100 mL) was added to the residue. The resulting mixture was filtered, and the residue was washed with water to give compound 17 (5.5 g, 18.9 mmol). The yield was 95.0%.

[0487] (4) Synthesis of compound 18

[0488] DMAc (35 mL) was added to compound 17 (3.5 g, 15.0 mmol), 4-chlorobutyl acetate (6.8 g, 45.0 mmol), potassium carbonate (6.2 g, 45.0 mmol), and potassium iodide (0.2 g, 1.5 mmol). The resulting mixture was stirred at 80 °C for 3 hours. A solution of sodium hydroxide (3.0 g, 75.0 mmol) (15 mL water, 15 mL methanol) was added to the resulting mixture, and the mixture was stirred at 80 °C for 3 hours. The resulting mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (150 mL) was added to the residue. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The solid was purified by re-slurrying with diisopropyl ether to give compound 18 (4.1 g, 13.7 mmol). The yield was 91.0%.

[0489] (5) Synthesis of compound 19

[0490] Compound 18 (3.6 g, 12.0 mmol) and N,N-dimethylaniline (1.8 g, 15.0 mmol) were dissolved in THF (35 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (1.4 g, 15.0 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, followed by extraction with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The residue was recrystallized from toluene to give compound 19 (4.0 g, 11.2 mmol). The yield was 93.0%.

[0491] (6) Synthesis of compound A-11

[0492] Compound 19 (2.7 g, 7.5 mmol), methylhydroquinone (0.4 g, 3.0 mmol), and DMAP (0.04 g, 0.3 mmol) were dissolved in CH₂Cl₂ (4 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.1 g, 9.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (40 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-11 (2.2 g, 2.7 mmol). The yield was 91.5%.

[0493] 1 H-NMR(CDCl3): δ=1.98(m,8H),2.33(s,3H),3.23(t,4H),4.09(t,4H),5.88(dd,2H ),6.41(dd,2H),6.45(dd,2H),7.24(m,7H),7.58(m,4H),7.68(m,4H),8.18(m,4H)

[0494] [Manufacturing Example 12: Manufacturing of Compound A-12]

[0495] Compound A-12 was synthesized according to the following procedure.

[0496] [Chemical Formula 37]

[0497] (1) Synthesis of compound 20

[0498] 4-Amino-3-hydroxybenzoic acid (7.7 g, 50.0 mmol) and potassium ethyl xanthate (12.0 g, 75.0 mmol) were dissolved in ethanol (200 mL). The resulting solution was stirred under reflux for 3 hours. The solution was cooled to room temperature, and the ethanol was removed by vacuum distillation. 1 M hydrochloric acid and ethyl acetate were added to the residue, and the mixture was extracted with ethyl acetate. The resulting organic layer was removed by distillation to give compound 20 (12.2 g, 45.5 mmol). The yield was 91.0%.

[0499] (2) Synthesis of compound 21

[0500] DMAc (80 mL) was added to compound 20 (8.0 g, 30.0 mmol), 4-chlorobutyl acetate (13.6 g, 90.0 mmol), potassium carbonate (12.4 g, 90.0 mmol), and potassium iodide (0.5 g, 3.0 mmol). The resulting mixture was stirred at 80 °C for 3 hours. A sodium hydroxide solution (6.0 g, 150.0 mmol) (30 mL water, 30 mL methanol) was added to the resulting mixture, and the mixture was stirred at 80 °C for 3 hours. The resulting mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (300 mL) was added to the residue. Water and ethyl acetate were added to the resulting mixture, and the mixture was extracted with ethyl acetate. The solvent of the resulting organic layer was removed by vacuum distillation. The solid was purified by re-slurrying with diisopropyl ether to give compound 21 (9.2 g, 28.7 mmol). The yield was 95.5%.

[0501] (3) Synthesis of compound 22

[0502] Compound 21 (7.7 g, 24.0 mmol) and N,N-dimethylaniline (3.6 g, 30.0 mmol) were dissolved in THF (70 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (2.7 g, 30.0 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, followed by extraction with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The residue was recrystallized from toluene to give compound 22 (5.9 g, 22.2 mmol). The yield was 92.5%.

[0503] (4) Synthesis of compound A-12

[0504] Compound 22 (3.3 g, 12.5 mmol), methylhydroquinone (0.6 g, 5.0 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH₂Cl₂ (6 mL). The resulting solution was cooled to 15 °C, and N,N-diisopropylcarbodiimide (1.9 g, 15.0 mmol) was added dropwise. The mixture was stirred at 15 °C for 3 hours. Methanol (120 mL) was added to the resulting mixture, and the mixture was filtered. The residue was washed with methanol to give compound A-12 (3.6 g, 4.9 mmol). The yield was 98.0%.

[0505] 1H-NMR(CDCl3): δ=1.89(m,4H),1.99(m,4H),2.43(s,3H),3.42(t,4H),4.23(t,4H),5.82(dd,2H),6.13(dd,2H ),6.41(dd,2H),7.33(d,1H),7.41(d,1H),7.52(dd,1H),7.68(dd,1H),7.99(m,2H),8.27(d,1H),8.33(d,2H)

[0506] [Comparative Manufacturing Example 1: Manufacturing of Comparative Compound RA-1]

[0507] The comparative compound RA-1 was synthesized according to the following procedure.

[0508] [Chemical Formula 38]

[0509] (1) Synthesis of compound 23

[0510] DMAc (500 mL) was added to 4-iodophenol (22.0 g, 100.0 mmol), 3-chloro-1-propanol (14.2 g, 150.0 mmol), potassium carbonate (20.7 g, 150.0 mmol), and potassium iodide (1.7 g, 10.0 mmol). The resulting mixture was stirred at 100 °C for 3 hours. The mixture was cooled to room temperature, and methanol was removed by vacuum distillation. 1 M hydrochloric acid (200 mL) was added to the residue. Water and ethyl acetate were added to the mixture, and the mixture was extracted with ethyl acetate. The residue was purified by rapid column chromatography to give compound 23 (30.7 g, 95.5 mmol). The yield was 95.5%.

[0511] (2) Synthesis of compound 24

[0512] Et3N (1000 mL) was mixed in CuI (0.8 g, 4.0 mmol), triphenylphosphine (PPh3) (2.1 g, 8.0 mmol), Pd(PPh3)2Cl2 (2.8 g, 4.0 mmol), and butylated hydroxytoluene (BHT) (0.2 g, 1.0 mmol) under an inert gas atmosphere. The resulting mixture was cooled to 0 °C, and 5-bromo-2-iodotoluene (29.7 g, 100.0 mmol) and 4-ethynyl anisole (15.9 g, 120.0 mmol) were added. The mixture was stirred at room temperature for 18 hours. Water and ethyl acetate were added to the resulting mixture, and the mixture was then extracted with ethyl acetate. The solvent in the organic layer was removed by vacuum distillation. The residue was purified by rapid column chromatography to give compound 24 (27.3 g, 98.0 mmol). The yield was 98.0%.

[0513] (3) Synthesis of compound 25

[0514] Et3N (950 mL) was mixed in CuI (0.7 g, 3.8 mmol), PPh3 (2.0 g, 7.6 mmol), Pd(PPh3)2Cl2 (2.7 g, 3.8 mmol), and BHT (0.2 g, 1.0 mmol) under an inert gas atmosphere. The resulting mixture was cooled to 0 °C, and compound 24 (26.4 g, 95.5 mmol) and 2-methyl-3-butyn-2-ol (20.0 g, 237.5 mmol) were added. The mixture was stirred under reflux for 3 hours. Water and ethyl acetate were added to the resulting mixture, and the mixture was then extracted with ethyl acetate. The solvent in the organic layer was removed by vacuum distillation. The residue was purified by rapid column chromatography to give compound 25 (26.5 g, 87.9 mmol). The yield was 92.5%.

[0515] (4) Synthesis of compound 26

[0516] Compound 25 (15.1 g, 50.0 mmol) was dissolved in toluene (50 mL) and cooled to 0 °C. Sodium hydroxide (3.0 g, 75.0 mmol) was added to the resulting solution. The mixture was stirred under reflux for 3 hours. The mixture was cooled to room temperature, and 1 M hydrochloric acid (100 mL) and ethyl acetate were added, followed by extraction with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The residue was purified by rapid column chromatography to give compound 26 (12.2 g, 49.5 mmol). The yield was 95.5%.

[0517] (5) Synthesis of compound 27

[0518] Et3N (500 mL) was mixed in CuI (0.4 g, 2.0 mmol), PPh3 (1.1 g, 4.0 mmol), Pd(PPh3)2Cl2 (1.4 g, 2.0 mmol), and BHT (0.2 g, 1.0 mmol) under an inert gas atmosphere. The resulting mixture was cooled to 0 °C, and compound 23 (13.6 g, 50.0 mmol) and compound 26 (14.8 g, 60 mmol) were added. The mixture was stirred at room temperature for 18 hours. Water and ethyl acetate were added to the resulting mixture, and the mixture was then extracted with ethyl acetate. The solvent in the organic layer was removed by vacuum distillation. The residue was purified by rapid column chromatography to give compound 27 (19.0 g, 48.0 mmol). The yield was 96.0%.

[0519] (6) Compare the synthesis of compound RA-1

[0520] Compound 27 (15.9 g, 40 mmol) and N,N-dimethylaniline (5.8 g, 48.0 mmol) were dissolved in THF (100 mL). The resulting solution was cooled to 10 °C, and acryloyl chloride (4.3 g, 48.0 mmol) was added dropwise, with stirring at 10 °C for 1 hour. Water and ethyl acetate were added to the resulting mixture, followed by extraction with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. The residue was purified by rapid column chromatography to give the comparative compound RA-1 (17.6 g, 39.0 mmol). The yield was 97.5%.

[0521] 1 H-NMR(CDCl3): δ=2.14(m,2H),2.49(s,3H),3.83(s,3H),4.07(t,2H),4.35(t,2H),5.82 (dd,1H),6.09(dd,1H),6.39(dd,1H),6.85(m,4H),7.28(d,1H),7.38(s,1H),7.42(m,5H)

[0522] [Comparative Manufacturing Example 2: Manufacturing of Comparative Compound RA-2]

[0523] The comparative compound RA-2 was manufactured in accordance with Japanese Patent Publication No. 2008-544954.

[0524] [Chemical Formula 39]

[0525] [Comparative Manufacturing Example 3: Manufacturing of Comparative Compound RA-3]

[0526] The comparative compound RA-3 was manufactured in accordance with Japanese Patent Publication No. 2008-544954.

[0527] [Chemical Formula 40]

[0528] [Comparative Manufacturing Example 4: Manufacturing of Comparative Compound RA-4]

[0529] The comparative compound RA-4 was manufactured in accordance with Japanese Patent Application Publication No. 2008-179654.

[0530] [Chemical Formula 41]

[0531] [Comparative Manufacturing Example 5: Manufacturing of Comparative Compound RA-5]

[0532] The comparative compound RA-5 was manufactured with reference to Japanese Patent No. 5962760.

[0533] [Chemical Formula 42]

[0534] [Example 1]

[0535] As Example 1, compound A-1 was used, and the following evaluation was performed.

[0536] (1) Phase transition temperature determination

[0537] As the sample for determination, 5 mg of compound A-1 was sealed in an aluminum sample dish and placed in a differential scanning calorimeter (DSC) (Shimadzu DSC-60). Under a nitrogen atmosphere, the sample was cooled from 25°C to -10°C at a rate of -25°C / min and maintained at -10°C for 15 minutes. Then, as the first heating, the sample was heated from -10°C to 150°C at a rate of 10°C / min and maintained at 150°C for 1 minute. As the first cooling, the sample was cooled from 150°C to -10°C at a rate of -10°C / min and maintained at -10°C for 10 minutes. Then, as the second heating, the sample was heated from -10°C to 150°C at a rate of 10°C / min and maintained at 150°C for 1 minute. As the second cooling, the sample was cooled from 150°C to 25°C at a rate of -10°C / min. The endothermic onset temperature detected during the second heating, which is the temperature at the intersection of the straight line obtained by extending the baseline from the low temperature side to the high temperature side and the tangent line drawn from the point with the largest slope in the curve on the low temperature side of the melting peak, is the extrapolated melting onset temperature (Tim) and is taken as the phase transition temperature.

[0538] (Evaluation criteria for phase transition temperature)

[0539] A: Phase transition temperature is less than 90℃

[0540] B: Phase transition temperature is above 90℃ and below 110℃

[0541] C: Phase transition temperature is above 110℃

[0542] The lower the phase transition temperature, the better the coating adaptability.

[0543] (2) Manufacturing of the composition and optical anisotropy, and determination of Δn (refractive index anisotropy).

[0544] A composition comprising the following compounds is prepared, and an optically anisotropic layer is prepared using the composition to calculate the Δn of compound A-1. Since the optically anisotropic layer contains only compound A-1, which exhibits optical anisotropy, the Δn of the optically anisotropic layer is taken as the Δn of compound A-1.

[0545] <Composition>

[0546] 100 parts by weight of compound A-1

[0547] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) 5 parts by weight

[0548] 450 parts by weight of methyl ethyl ketone

[0549] <Optical Anisotropic Materials>

[0550] The composition was spin-coated onto the entire surface of a 50mm × 50mm glass substrate with an alignment film after abrasion treatment. After heating to a temperature at which the composition exhibits a nematic phase, a process of 244 mJ / cm² was performed. 2 Ultraviolet radiation is used to create an optical anisotropic layer.

[0551] <Determination of Δn (Refractive Index Anisotropy)>

[0552] For the fabricated optical anisotropic layer, the in-plane phase difference Re and layer thickness (nm) are measured, and Δn is calculated using the following formula.

[0553] Δn = Re / layer thickness (nm)

[0554] Re was measured at a wavelength of 550 nm using a phase difference measuring device (RETS-100 manufactured by Otsuka Electronics Co., Ltd.), with the temperature set at 25°C. The average value of the three measured values ​​was used as the measurement result.

[0555] (Re measurement conditions)

[0556] • Delay measurement range: Rotating analyzer method

[0557] • Measurement point diameter: 5mm

[0558] • Tilt angle range: 0°

[0559] • Measurement wavelength range: 400nm~800nm

[0560] Regarding the thickness of the optical anisotropic layer, a cross-section of the optical anisotropic layer was photographed using a scanning transmission electron microscope (STEM) (Hitachi High-Technologies Corporation, S-4800). The thickness of the optical anisotropic layer at 10 points in the image of this cross-section was measured and set as the arithmetic mean of the thickness at these 10 points.

[0561] The cross-sectional photographs of the optical anisotropic layer are shown below. First, a block of sample embedded in embedding resin and cut into 1mm × 10mm pieces was prepared. Using standard slicing methods, uniform slices with a thickness of 70nm to 100nm without pores were cut from this block. Slices were prepared using an ion milling apparatus (Hitachi High Technology Co., Ltd., IM-4000II). This uniform slice without pores was then used as the measurement sample. A cross-sectional photograph of the measurement sample was then taken using a scanning transmission electron microscope (STEM). When taking this cross-sectional photograph, the detector was set to "TE", the accelerating voltage to "30kV", and the emission current to "10μA" for STEM observation. Regarding magnification, the contrast and brightness were adjusted appropriately from 5000x to 200,000x while adjusting the focus and observing whether the layers could be distinguished.

[0562] (Evaluation criteria for refractive index anisotropy)

[0563] A: Δn is 0.25 or higher.

[0564] B: Δn is less than 0.25

[0565] (3) Evaluation of lightfastness

[0566] An ultraviolet-absorbing layer was stacked on an optical anisotropic layer fabricated for measuring refractive index anisotropy Δn, and a lightfastness test was conducted.

[0567] <Laminated material for lightfastness testing>

[0568] (Fabrication of the ultraviolet absorption layer)

[0569] Referring to paragraph 0110 of Japanese Patent Application Publication No. 2021-189224, 2-[2-(6-hydroxybenzo[1,3]dioxane-5-yl)-2H-benzotriazol-5-yl]ethyl methacrylate, which is used as an ultraviolet absorber, was synthesized.

[0570] A coating solution for forming an ultraviolet (UV) absorbing layer was applied to one side of a triacetyl cellulose (TAC) resin film substrate (Fujifilm Corporation, TD80UL, 80 μm thickness) to form a coating film. The UV absorbing layer forming coating solution was prepared by adding 5 parts by weight of a photopolymerization initiator (Omnirad 907, manufactured by IGM Resins BV) and 5 parts by weight of the UV absorber to 100 parts by weight of pentaerythritol triacrylate (trade name: PET-30) from Nippon Kayaku Co., Ltd. The formed coating film was then irradiated with ultraviolet light (cumulative light intensity: 150 mJ / cm²). 2 This forms a 3μm thick ultraviolet absorption layer.

[0571] (Preparation of laminates for lightfastness testing)

[0572] On an optical anisotropy layer fabricated for measuring refractive index anisotropy Δn, the TAC substrate side of the ultraviolet absorption layer is bonded using an optical adhesive. The optical adhesive used is a 25 μm thick optical adhesive (trade name: PANACLEAN PD-S1, 25 μm, manufactured by PANAC Corporation, acrylic adhesive).

[0573] <Lightfastness Test>

[0574] The optically anisotropic layer was irradiated from the UV-absorbing layer side of the manufactured lightfastness testing laminate using a UV carbon arc lightfastness testing machine (manufactured by Suga Test Instruments Co., Ltd., FadeMeter). The irradiation was performed in an air atmosphere with a tank temperature of 42°C, relative humidity of 50%, and illuminance of 500 W / m². 2 A lightfastness test was conducted with an irradiation time of 48 hours.

[0575] Similarly, the Re of the optical anisotropic layer before and after the lightfastness test was measured, and the Re change rate shown below was calculated.

[0576] Re change rate (%) = [100 × {|(Re after the experiment) - (Re before the experiment)|} / (Re before the experiment)]

[0577] (Evaluation Criteria)

[0578] A: The rate of change of Re is less than 10%.

[0579] B: The rate of change of Re is greater than 10% but less than 15%.

[0580] C: The rate of change of Re is above 15%.

[0581] The smaller the Re change rate, the better the lightfastness.

[0582] [Example 2]

[0583] As Example 2, compound A-2 was used, and the following evaluation was performed.

[0584] (1) Phase transition temperature determination

[0585] Compound A-2 was used instead of compound A-1 in Example 1, and the phase transition temperature was otherwise determined in the same manner as in Example 1.

[0586] (2) Manufacturing of the composition and optical anisotropy, and determination of Δn (refractive index anisotropy).

[0587] Since compound A-2 does not have a single orientation, a composition containing other liquid crystal compounds with the following composition was prepared, and Δn was determined using an optically anisotropic layer prepared using this composition, in the same manner as in Example 1.

[0588] Specifically, the refractive index anisotropy Δn of an optical anisotropy layer manufactured in the same manner as in Example 1 was measured using compositions 2-a, 2-b, and 2-c, which respectively contained 20 parts by mass, 10 parts by mass, and 0 parts by mass of compound A-2. Linear univariate regression analysis was performed on the obtained measurements to determine the refractive index anisotropy Δn when compound A-2 was 100 parts by mass.

[0589] When the refractive index anisotropy Δn is set as y and the mass fraction of compound A-2 is set as x, the regression coefficients a and b of the following regression equation are derived from the measured values ​​using the least squares method.

[0590] y=ax+b

[0591] Substituting x=100 into the derived regression equation, the resulting value is used as the extrapolated value of the refractive index anisotropy Δn of compound A-2.

[0592] <Composition 2-a>

[0593] 20 parts by weight of compound A-2

[0594] Polymerizable liquid crystal compound (B-1) (manufactured by TCI, CAS RN: 132900-75-5, product code: D5936) 80 parts by weight

[0595] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) (parts by weight)

[0596] 50 parts by weight of methyl ethyl ketone

[0597] <Composition 2-b>

[0598] 10 parts by weight of compound A-2

[0599] Polymerizable liquid crystal compound (B-1) (manufactured by TCI, CAS RN: 132900-75-5, product code: D5936) 90 parts by weight

[0600] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) 5 parts by weight

[0601] 450 parts by weight of methyl ethyl ketone

[0602] <Composition 2-c>

[0603] Polymerizable liquid crystal compound (B-1) (manufactured by TCI, CAS RN: 132900-75-5, product code: D5936) 100 parts by weight

[0604] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) 5 parts by weight

[0605] 450 parts by weight of methyl ethyl ketone

[0606] (3) Evaluation of lightfastness

[0607] In the lightfastness evaluation of Example 1, the optical anisotropic layer was changed to an optical anisotropic layer made using composition 2-a containing 20 parts by mass of compound A-2, and the lightfastness evaluation was otherwise performed in the same manner as in Example 1.

[0608] [Examples 3, 4, 6-10, Comparative Examples 2, 4 and 5]

[0609] In Examples 3, 4, 6-10, and Comparative Examples 2, 4 and 5, the compounds shown in Table 3 were used instead of compound A-1 in Example 1. Otherwise, the phase transition temperature determination, the manufacture of the composition and the optical anisotropic layer, the determination of Δn and the lightfastness test were performed in the same manner as in Example 1.

[0610] [Examples 5, 11, 12, Comparative Examples 1 and 3]

[0611] In Examples 5, 11, 12, Comparative Examples 1 and 3, the compounds shown in Table 3 were used instead of compound A-2 in Example 2. Otherwise, the phase transition temperature determination, the manufacture of the composition and the optical anisotropic layer, the determination of Δn, and the lightfastness test were performed in the same manner as in Example 2.

[0612] [Table 3]

[0613] Table 3.

[0614] As shown in Examples 1 to 12, the compound represented by general formula (I) of this disclosure is a compound with improved refractive index anisotropy Δn and lightfastness in air atmosphere and reduced phase transition temperature.

[0615] In contrast, the compound of Comparative Example 1, which is a diphenylacetylene compound, exhibits poor lightfastness in an air atmosphere.

[0616] The compound of Comparative Example 2, which is equivalent to the compound with 2,6-naphthyl group specifically described in Patent Document 1, has a high phase transition temperature, insufficient refractive index anisotropy Δn, and poor lightfastness.

[0617] Among the compounds containing 2,6-naphthyl groups specifically described in Patent Document 1, the compound of Comparative Example 3, which corresponds to a compound with high specificity of refractive index anisotropy Δn, has a high phase transition temperature and poor lightfastness. Compared to the compound of Comparative Example 3, the compound of Example 9, which has a structure in which the linking group adjacent to the naphthyl group -OCOO- is changed to -S-, shows a lower phase transition temperature.

[0618] In addition, the compound of Comparative Example 4, which has a 2,6-naphthyl group and whose adjacent linker is -O-, has a high phase transition temperature, insufficient refractive index anisotropy Δn, and poor lightfastness.

[0619] (Example 13: Manufacturing of optical components)

[0620] A composition comprising compound A-1 of Example 1 with the following composition is prepared, and an optical element comprising a layer consisting of a fixed cholesterol-type liquid crystal phase, i.e., an optical anisotropy layer, is prepared using the composition.

[0621] <Composition>

[0622] 24.5 parts by mass of compound A-1

[0623] Chiral reagent (compound (Ch-1) below) 0.5 parts by weight

[0624] Photopolymerization initiator (Omnirad 907, manufactured by IGM Resins BV) 1 part by weight

[0625] Leveling agent (acrylic surfactant, Polyflow No. 75, manufactured by Kyoei Chemicals) 0.01 parts by weight

[0626] Methyl ethyl ketone (MEK) 24 parts by weight

[0627] 50 parts by weight of methyl isobutyl ketone (MIBK)

[0628] It should be noted that the chiral reagent (compound (Ch-1) below) is synthesized by combining the methods described in Japanese Patent Application Publication No. 2005-263778, US Patent No. 5886242, and British Patent Application Publication No. 2298202. As compound (Ch-1), the binaphthyl group uses an R-body.

[0629] [Chemical Formula 43]

[0630] <Formation of Photo-aligned Film>

[0631] A composition for photoalignment film was prepared in the same manner as the photoalignment film material of Example 1 in Japanese Patent Application Publication No. 2021-103225.

[0632] The photo-alignment film composition was spin-coated onto one side of a PET substrate (Toyobo Co., Ltd., E5100, 38μm thickness) to a cured film thickness of 0.2μm. The substrate was then dried and thermally cured in an oven at 90°C for 2 minutes to form a cured coating. Next, using an Hg-Xe lamp and a Glan-Taylor prism, an exposure of 100mJ / cm was applied perpendicularly from the substrate normal. 2 The surface of the cured coating is irradiated with polarized ultraviolet light containing a bright line of 313 nm, thereby forming an alignment film.

[0633] <Fabrication of Optical Components>

[0634] The composition was coated onto the formed alignment film to achieve a cured film thickness of approximately 4 μm, thus forming a polymeric liquid crystal composition film. The film was then dried in an oven at 90°C for 2 minutes and irradiated under a nitrogen atmosphere using an H-lamp manufactured by Fusion Corporation at a dose of 400 mJ / cm². 2 Irradiation with ultraviolet (UV) light creates an optical anisotropic layer, which is then used to manufacture optical components.

[0635] The cross-section of the optical anisotropic layer of this optical element was observed using a scanning transmission electron microscope (STEM). By observing the repeating structure of the bright and dark parts, it was confirmed that the layer was formed by fixing a cholesterol-type liquid crystal layer.

[0636] Specifically, the central portion of the optical element sample was cut into strips (2mm × 5mm), embedded in thermosetting resin, and then sliced ​​using a microtome to create ultrathin sections (80nm thick) with smooth cross-sections. Using STEM, the obtained ultrathin sections were observed under the following measurement conditions (detector TE, accelerating voltage 30kV, emission current 10μA, magnification 5000x) to obtain cross-sectional images of the optical anisotropy layer of the optical element. The STEM cross-sectional images confirmed repeating structures of dark-bright-dark-bright or bright-dark-bright-dark regions.

[0637] Example II Series: Second Disclosure

[0638] In the series of Examples II, compounds A-1, A-4, A-5, A-7, RA-1, RA-2, RA-4, and RA-5 were prepared in the same manner as in the series of Examples I.

[0639] [Example II-1]

[0640] As in Example II-1, an optical anisotropy was manufactured using compound A-1 as a polymeric liquid crystal compound containing a partial structure represented by formula (Ia).

[0641] <Composition>

[0642] 100 parts by weight of compound A-1

[0643] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) 5 parts by weight

[0644] Leveling agent (acrylic surfactant, Polyflow No. 75, manufactured by Kyoei Chemicals) 0.01 parts by weight

[0645] 450 parts by weight of methyl ethyl ketone

[0646] <Optical Anisotropic Materials>

[0647] The above composition was applied to a 100 μm thick PET film (A4160: manufactured by Toyobo Co., Ltd.) that had undergone nylon friction treatment, using a rod coating method to cure the film to a thickness of 5 μm. After heating to a temperature at which the composition exhibits a nematic phase and drying, it was irradiated with a high-pressure mercury lamp at 240 mJ / cm². 2 Ultraviolet light is used to create an optical anisotropic layer.

[0648] (1) Bending resistance test

[0649] The test piece used in the bending resistance test was a 50mm × 20mm quadrilateral cut from near the center of the optical anisotropic body. With the aforementioned optical anisotropic layer of the test piece as the outer side, the long side was bent using the cylindrical mandrel method according to JIS-K5600-5-1:1999. The bent portion of the optical anisotropic layer with a mandrel diameter of 3mm was observed using a 10x magnifying glass to check for cracks. The fewer cracks, the better the bending resistance, and the better the fit and processability.

[0650] (Evaluation criteria for flexural resistance)

[0651] A: No cracks

[0652] B: There are cracks

[0653] (2) Determination of Δn (refractive index anisotropy)

[0654] The composition was spin-coated onto the entire surface of a 50mm × 50mm glass substrate with an alignment film after rubbing treatment. After heating to a temperature at which the composition exhibits a nematic phase, a 244mJ / cm² pressure was applied. 2 Ultraviolet radiation is used to create an optical anisotropic layer.

[0655] For the manufactured optical anisotropic layer, Δn is calculated in the same manner as the "Δn (refractive index anisotropy) measurement" described in Example 1 of the Example I series.

[0656] (Evaluation criteria for refractive index anisotropy)

[0657] A: Δn is 0.25 or higher.

[0658] B: Δn is less than 0.25

[0659] (3) FT-IR measurement

[0660] For the optical anisotropic body for which the above Δn measurement was performed, the infrared absorption spectrum was measured from the optical anisotropic side using the ATR method and a Fourier transform infrared spectrophotometer.

[0661] Peaks P1, P2, and P3, as specified below, are detected using the peak detection mode of the analysis software. The analysis software is then used to determine the height from the background to the peak apex for each peak, which is then taken as the peak intensity.

[0662] P1; located at 1205cm -1 ~1225cm -1 Peak intensity of SC bond

[0663] P2; located at 1600cm -1 ~1650cm -1 Peak intensity of C=C bond

[0664] P3; located at 1700cm -1 ~1750cm -1 Peak intensity of C=O bond

[0665] FT-IR measurements were performed at three different locations within the sample. The average value of P1 at the three locations was taken as the P1 of the sample. Similarly, the average values ​​of the measurements at the three locations were taken as P2 and P3 of the sample. P1 / P2, P1 / P3, and P1 / (P2+P3) were calculated from the obtained values ​​of P1, P2, and P3.

[0666] (Measurement conditions)

[0667] Measurement apparatus: Fourier transform infrared spectrophotometer (manufactured by Nippon Spectrophotometer Co., Ltd., with an ATR-PRO470-H device mounted on the FT-IR6100)

[0668] Light source: High-brightness ceramic light source

[0669] Detector: DLATGS

[0670] Beam splitter: Ge / KBr

[0671] Measurement mode: ATR method (diamond prism, incident angle 45°)

[0672] Wavenumber range for measurement: 4,000 cm⁻¹ -1 ~400cm -1

[0673] Resolution: 4cm -1

[0674] Determine the diameter of the light spot: 1.5mm

[0675] Total number of times: 32

[0676] Analysis: Spectra Manager Version 2 spectral analysis program

[0677] [Examples II-2 to II-4, Comparative Examples II-1 to II-4]

[0678] In Examples II-2 to II-4 and Comparative Examples II-1 to II-4, the compounds shown in Table 4 were used instead of compound A-1 used in Example II-1 as polymeric liquid crystal compounds containing a portion of the structure shown in formula (Ia). Otherwise, the composition and optical anisotropy were manufactured in the same manner as in Example II-1. Furthermore, in the same manner as in Example II-1, the obtained optical anisotropy was used to perform bending resistance tests and Δn (refractive index anisotropy) measurements. For Comparative Example II-1, in the same manner as in Example II-1, the obtained optical anisotropy was used to perform FT-IR measurements.

[0679] [Example II-5]

[0680] A composition comprising the following components, using compound A-1 as a partial structure of the polymeric liquid crystal compound shown in formula (Ia) and further comprising other polymeric liquid crystal compounds shown in Table 4, was prepared. An optical anisotropy was then manufactured using this composition. Furthermore, following the same procedure as in Example II-1, the resulting optical anisotropy was subjected to bending resistance tests, Δn (refractive index anisotropy) measurements, and FT-IR measurements.

[0681] <Composition>

[0682] 10 parts by mass of compound A-1

[0683] 90 parts by weight of compound RA-2

[0684] Photopolymerization initiator (2-methyl-1-(4-methylthiophenyl)-2-morpholinopropane-1-one: Omnirad 907, manufactured by IGMRESINS BV) 5 parts by weight

[0685] Leveling agent (acrylic surfactant, Polyflow No. 75, manufactured by Kyoei Chemicals) 0.01 parts by weight

[0686] 450 parts by weight of methyl ethyl ketone

[0687] [Example II-6]

[0688] In Example II-6, compound A-4 was used instead of compound A-1 in Example II-5. Otherwise, the composition was prepared in the same manner as in Example II-5, and the optical anisotropy was manufactured using the composition. In addition, the obtained optical anisotropy was subjected to bending resistance test, Δn (refractive index anisotropy) measurement, and FT-IR measurement in the same manner as in Example II-1.

[0689] [Example II-7]

[0690] In Example II-7, compound RA-1 was used instead of compound RA-2 in Example II-5. Otherwise, the composition was prepared in the same manner as in Example II-5, and the optical anisotropy was manufactured using the composition. In addition, the bending resistance test and Δn (refractive index anisotropy) measurement were performed using the obtained optical anisotropy in the same manner as in Example II-1.

[0691] [Example II-8]

[0692] In Example II-8, compound RA-5 was used instead of compound RA-2 in Example II-5. Otherwise, the composition was prepared in the same manner as in Example II-5, and the optical anisotropy was manufactured using the composition. In addition, the bending resistance test and Δn (refractive index anisotropy) measurement were performed using the obtained optical anisotropy in the same manner as in Example II-1.

[0693] [Table 4]

[0694] Table 4.

[0695] It should be noted that "n / a" in the table indicates that it was not measured.

[0696] As shown in Examples II-1 to II-8, the cured product of the polymeric liquid crystal composition containing the partial structure represented by formula (Ia) of this disclosure, namely the optical anisotropic layer, exhibits both improved refractive index anisotropy Δn and improved flexural strength.

[0697] In contrast, the optical anisotropic layer of Comparative Example II-1 containing a diphenylacetylene compound, the optical anisotropic layers of Comparative Examples II-2 and II-3 containing conventional compounds with 2,6-naphthyl groups, and the optical anisotropic layer of Comparative Example II-4 are all hard and brittle films with poor bending resistance.

Claims

1. A compound represented by the following general formula (I), [Chemical Formula 1] General Formula (I) In general formula (I), Z 1 and Z 2 Each can independently represent a hydrogen atom, -CN, -NCS, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, or a polymeric group. R sp1 and R sp2 Each independently represents one -CH2- or two or more non-adjacent -CH2- atoms, each independently substituted or unsubstituted by O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, or -CH=CH-, representing an alkylene group or single bond with 1 to 20 carbon atoms. S represents a sulfur atom. L 1 L 2 and L 3 Each independently represents -O-, -S-, -CHR-, -CHRCHR-, -OCHR-, -CHRO-, -SO-, -SO2-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NR-, -NR-CO-, -SCHR-, -CH RS-, -SO-CHR-, -CHR-SO-, -SO2-CHR-, -CHR-SO2-, -CF2O-, -OCF2-, -CF2S-, -SCF2-, -OCHRCHRO-, -SCHRCHRS-, -SO-CHRCHR-SO-, -SO2-CHRCH R-SO2-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CHRCHR-, -OCO-CHRCHR-, -CHRCHR-COO-, -CHRCHR-OCO-, -COO-CHR-, -OCO-CHR-, -CHR-COO-, -CHR-OCO-, -CR=CR-, -CR=N-, -N=CR-, -N=N-, -CR=NN=CR-, -CF=CF- or a single bond, where R represents a hydrogen atom or an alkyl group with 1 to 10 carbon atoms. Multiple Rs can exist and can be the same or different. T 1 and T 2 Each of these groups independently represents an unsubstituted or divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may be substituted by one or more substituents E. Any carbon atom of the aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted by a heteroatom. A represents a group represented by any of the following formulas (A-1) to (A-4), which is substituted by one or more substituents E or is not substituted. Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymeric group, wherein... When the substituent E contains -CH2-, a group formed by replacing at least one of the -CH2- atoms in the substituent E with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the substituent E contains hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms in the substituent E with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E. m and n each independently represent integers from 0 to 3, and m+n represents integers greater than or equal to 1. L 1 L 2 T 1 and T 2 When multiple instances exist, they can be the same or different. [Chemical Formula 2] In equations (A-1) to (A-4), W 1 ~W 16 Each represents CR independently. 1 Or N, R 1 Represents a hydrogen atom or the substituent E. Y 1 ~Y 2 Each represents NR independently. 2 O or S, R 2 Represents a hydrogen atom or the substituent E. Indicates with L 1 L 2 L 3 Or the bonding position of S.

2. The compound according to claim 1, wherein, In the general formula (I), m represents 0, A represents the group represented by the formula (A-1), and the group represented by the formula (A-1) is substituted by one or more substituents E or is not substituted.

3. The compound according to claim 1, represented by the following general formula (I-1), [Chemical Formula 3] General formula (I-1) In general formula (I-1), Z 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 Each of the groups, k1 and E, independently represents a group defined by general formula (I), in which the 2,6-naphthyl group is substituted by one or more substituents E or is not substituted, k1 represents an integer from 0 to 6, n' represents an integer from 0 to 2, and L... 2 and T 2 When multiple instances exist, they can be the same or different.

4. The compound according to claim 1, which is represented by the following general formula (I-2), [Chemical Formula 4] General formula (I-2) In general formula (I-2), Z 1 Z 2 R sp1 R sp2 S, L 2 L 3 T 2 Each of E independently represents a group defined by general formula (I). In general formula (I-2), 2,6-naphthyl and phenyl are substituted or unsubstituted by one or more substituents E. k1 represents an integer from 0 to 6, and k2 represents an integer from 0 to 4. n' represents an integer from 0 to 2, L 2 and T 2 When multiple instances exist, they can be the same or different.

5. The compound according to any one of claims 1 to 4, wherein it has liquid crystal properties.

6. A composition comprising the compound according to any one of claims 1 to 4.

7. The composition according to claim 6, further comprising a polymerization initiator.

8. The composition according to claim 6, further comprising a chiral agent.

9. An optical anisotropy obtained by orienting the compound represented by the general formula (I) in the composition of claim 6.

10. An optical anisotropy, which is a cured product of the composition of claim 7.

11. An optical anisotropy obtained by orienting the compound represented by the general formula (I) in the composition of claim 8.

12. An optical element having an optically anisotropic layer formed using the composition of claim 6.

13. An optical element having an optically anisotropic layer formed using the composition of claim 6, The optical anisotropic layer has an orientation pattern. The orientation pattern is an orientation pattern derived from the orientation of the optical axis of the liquid crystal compound contained in the composition, which rotates continuously along at least one direction in the plane.

14. An optical anisotropy, which is a cured product of a polymeric liquid crystal composition comprising a portion of the structure of the following general formula (Ia), [Chemical Formula 5] General formula (Ia) In general formula (Ia), the 2,6-naphthyl group is substituted by one or more substituents E or is not substituted, and k1 represents an integer from 0 to 6. Each substituent E independently represents an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkanothiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfonyl group, an amide group, a cyano group, a nitro group, a halogen atom, or a polymeric group, wherein... When the substituent E contains -CH2-, a group formed by replacing at least one of the -CH2- atoms in the substituent E with -O-, -CO-, or -CH=CH- is also included in substituent E. Furthermore, when the substituent E contains hydrogen atoms, a group formed by replacing at least one of the hydrogen atoms in the substituent E with at least one selected from the group consisting of fluorine atoms and polymerizable groups is also included in substituent E. It indicates the bonding position with other atoms.

15. The optical anisotropy according to claim 14, wherein it is a cured product of a polymeric liquid crystal composition containing 4% by mass or more of a compound comprising a partial structure of the general formula (Ia).

16. The optical anisotropy according to claim 14 or 15, wherein, The location at 1205 cm⁻¹ was determined using the ATR method and a Fourier transform infrared spectrophotometer (FT-IR). -1 ~1225cm -1 The peak intensity P1 of the SC bond is located at 1600 cm⁻¹ -1 ~1650cm -1 The ratio of the peak intensity P2 of the C=C bond to P1 / P2 is greater than 0.30 and less than 1.

80.

17. An optical element having an optical anisotropy body as described in claim 14 or 15 as an optical anisotropy layer.

18. An optical element having an optical anisotropic body as described in claim 14 or 15 as an optical anisotropic layer, The optical anisotropic layer has an orientation pattern. The orientation pattern is an orientation pattern derived from the orientation of the optical axis of the liquid crystal compound contained in the composition, which rotates continuously along at least one direction in the plane.

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