Polymerizable liquid crystal composition, optically anisotropic film, and optical component

Abstract

The present invention provides a polymerizable liquid crystal composition that improves liquid crystal alignment and suppresses alignment defects, an optically anisotropic film with improved appearance quality using the polymerizable liquid crystal composition, and optical components such as phase difference plates and diffractive optical elements using the optically anisotropic film. [Solution] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having at least one (meth)acryloyloxy group at one end, wherein the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition, and the polymerizable liquid crystal composition contains halogen, and an optically anisotropic film using the composition.

Description

[Technical Field]

[0001] This disclosure relates to polymerizable liquid crystal compositions, optically anisotropic films, and optical components. [Background technology]

[0002] It has been proposed to form an optically anisotropic polymer film (optically anisotropic film) by polymerizing a polymerizable liquid crystal composition, and to use this optically anisotropic film as a phase difference layer (for example, Patent Documents 1 and 2). Furthermore, Patent Document 3 discloses a diffractive optical element formed by patterning a thin film containing a liquid crystal compound and having optical anisotropy.

[0003] An optically anisotropic film using a polymerizable liquid crystal composition is formed by applying a coating solution of the polymerizable liquid crystal composition onto a substrate that has undergone an alignment treatment, such as a photo-alignment film or a resin layer having an uneven surface structure, aligning the polymerizable liquid crystal composition, and then polymerizing the polymerizable liquid crystal composition to fix the alignment state. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2000-98133 [Patent Document 2] Patent No. 5652412 [Patent Document 3] Special Publication No. 2017-522601 [Overview of the project] [Problems that the invention aims to solve]

[0005] In optically anisotropic films using polymerizable liquid crystal compositions, if the molecular orientation of the liquid crystal compound is disrupted, causing orientation defects, problems arise such as reduced performance or deterioration of the appearance of the optically anisotropic film. Patent Document 2 describes how, in order to improve the fact that the orientation of liquid crystal compounds is inhibited by charging, a polymerizable liquid crystal composition containing a quaternary ammonium salt as an antistatic agent is used to mitigate the charging and improve the orientation state and appearance defects. However, conventional technology is still insufficient to obtain uniform liquid crystal alignment, and further improvements in liquid crystal alignment and technologies to suppress alignment defects are needed.

[0006] This disclosure has been made in view of the above-mentioned problems, and aims to provide a polymerizable liquid crystal composition that improves liquid crystal alignment and suppresses alignment defects, an optically anisotropic film with improved appearance quality using the polymerizable liquid crystal composition, and optical components such as phase difference plates and diffractive optical elements. [Means for solving the problem]

[0007] The aspects of this disclosure relate to the following [1] to [9]. [1] A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having at least one terminal (meth)acryloyloxy group, A polymerizable liquid crystal composition containing halogens, wherein the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition. [2] The polymerizable liquid crystal composition according to [1], which does not contain a quaternary ammonium salt. [3] The polymerizable liquid crystal composition according to [1] or [2], wherein the halogen content is 0.001% by mass or more with respect to the total solid content of the polymerizable liquid crystal composition. [4] A polymerizable liquid crystal composition according to any one of the above [1] to [3], comprising a liquid crystal compound having a group represented by the following general formula (A) at its terminal end.

[0008] [ka] (In general formula (A), R x1 R is a hydrogen atom, a methyl group, or a halogen atom. x2 is a hydrogen atom or a halogen atom, and R x1 and Rx2 One of these is a halogen atom. (* indicates the bonding position with the liquid crystal compound.)

[0009] [5] An optically anisotropic film obtained by curing a polymerizable liquid crystal composition according to any one of the above items [1] to [4]. [6] An optical component comprising the optical anisotropy film described in [5] above. [7] An optical member having an orientation film having an uneven surface structure, on which the optical anisotropy film described in [5] is laminated. [8] An optical member having an optical anisotropy film described in [5] laminated on a photo-alignment film. [9] The optical member according to any one of the above [6] to [8], wherein the optical member is a phase difference plate, a polarizing plate, or a diffractive optical element. [Effects of the Invention]

[0010] This disclosure provides a polymerizable liquid crystal composition in which liquid crystal alignment is improved and alignment defects are suppressed, an optically anisotropic film with improved appearance quality using the polymerizable liquid crystal composition, and optical components such as phase difference plates, polarizers, and diffractive optical elements. [Modes for carrying out the invention]

[0011] In this disclosure, orientation-regulating force refers to the effect of aligning the liquid crystal compounds in the phase difference layer in a specific direction. In this disclosure, (meth)acrylic means acrylic or methacrylic, respectively, and (meth)acrylate means acrylate or methacrylate, respectively. Furthermore, in this specification, the terms "plate," "sheet," and "film" are not distinguished from each other solely based on differences in name. "Film surface (plate surface, sheet surface)" refers to the surface that coincides with the planar direction of the film-like (plate-like, sheet-like) member in question when viewed holistically and from a broad perspective. Furthermore, in this disclosure, the "~" indicating a numerical range is used to mean that the numbers written before and after it are included as the lower and upper limits, respectively.

[0012] I. Polymerizable liquid crystal composition This disclosure relates to a polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having at least one terminal (meth)acryloyloxy group, The present invention provides a polymerizable liquid crystal composition containing halogens, wherein the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition. In this disclosure, "solids" refers to components in the composition other than the solvent. Any component other than the solvent, even if its properties are liquid, is considered a solid. The total solids of a polymerizable liquid crystal composition refer to all components in the polymerizable liquid crystal composition excluding the solvent.

[0013] The polymerizable liquid crystal composition of this disclosure contains a polymerizable liquid crystal compound having at least one (meth)acryloyloxy group at one end, and a halogen whose halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition, thereby improving liquid crystal orientation and suppressing orientation defects. On a film subjected to alignment treatment (hereinafter referred to as the alignment film), liquid crystal compounds become aligned in a specific direction due to their interaction with the alignment film interface. However, polymerizable liquid crystal compounds having (meth)acryloyloxy groups with π electrons have a problem in that their liquid crystal orientation is easily disrupted and alignment defects occur due to the influence of the charging of the alignment film. In the polymerizable liquid crystal composition of this disclosure, the halogen added in a specific amount has polarity and is attracted to the charged alignment film interface, making it more susceptible to the orientation-regulating force of the alignment film, and as a result, the liquid crystal orientation is improved and alignment defects are suppressed. Furthermore, it is presumed that by adding a specific amount of halogen, an appropriate excluded volume effect is obtained compared to the intermolecular interactions between liquid crystal compounds having (meth)acryloyloxy groups with π electrons. However, if the halogen is included in an amount greater than the specific amount, the order between the liquid crystal compositions is disrupted and the orientation is worsened.

[0014] The polymerizable liquid crystal composition of this disclosure comprises at least a polymerizable liquid crystal compound having at least one (meth)acryloyloxy group at one end, and a halogen, but may further contain other components. The polymerizable liquid crystal composition of this disclosure may contain a polymerization initiator and may contain a solvent. Furthermore, other components may be included as long as they do not impair the effects of the present invention. As shown in the examples described later, the polymerizable liquid crystal composition of this disclosure does not contain quaternary ammonium salts, and even while maintaining chargeability, liquid crystal alignment is improved and alignment defects are suppressed. Therefore, the polymerizable liquid crystal composition of this disclosure does not need to contain quaternary ammonium salts. The following describes each component constituting the polymerizable liquid crystal composition of this disclosure in order.

[0015] <Polymerizable liquid crystal compound> The polymerizable liquid crystal compounds used in this disclosure are polymerizable liquid crystal compounds having at least one (meth)acryloyloxy group at one terminal, and can be appropriately selected from conventionally known polymerizable liquid crystal compounds having at least one (meth)acryloyloxy group at one terminal. The polymerizable liquid crystal compounds used in this disclosure have at least one (meth)acryloyloxy group at one end, which allows the liquid crystal compounds to be polymerized and immobilized, resulting in excellent arrangement stability and reduced likelihood of changes in phase difference over time. The polymerizable liquid crystal compound used in this disclosure may be a polymerizable liquid crystal compound having two or more (meth)acryloyloxy groups in one molecule. Having two or more (meth)acryloyloxy groups in one molecule makes the three-dimensional orientation of the liquid crystal compound more stable, and improves the hardness and durability of the coating film.

[0016] Examples of polymerizable liquid crystal compounds used in this disclosure include disc-shaped liquid crystal materials and rod-shaped liquid crystal materials. Examples of polymerizable liquid crystal compounds used in this disclosure include the compound represented by general formula (I) described in Japanese Patent Publication No. 2008-297210, the compound represented by general formula (1) described in Japanese Patent Publication No. 2010-84032, liquid crystal compound A0 described in Japanese Patent Publication No. 2016-53709, and polymerizable liquid crystal compounds described in paragraphs 0057 to 0064 of International Publication No. 2018 / 003498.

[0017] The polymerizable liquid crystal compounds used in this disclosure may be polymerizable liquid crystal compounds exhibiting reverse dispersion. For example, in addition to the polymerizable liquid crystal compound represented by the following general formula (1) described in Japanese Patent No. 6473537, liquid crystal compounds represented by the general formula (II) of International Publication No. WO2017 / 043438, Japanese Patent No. 5463666, Japanese Patent No. 4186981, Japanese Patent No. 5962760, and Japanese Patent No. 5826759, Japanese Patent No. 6568103, Japanese Patent No. 6427340, Japanese Patent Publication No. 2016-166344, and polymerizable liquid crystal compounds described in Recueil des Travaux Chimiques des Pays-Bas (1996), 115(6), 321-328 can be used.

[0018] Specifically, the polymerizable liquid crystal compounds used in this disclosure may be polymerizable liquid crystal compounds having two or more ring structures in the main chain, preferably three or more ring structures, and having a (meth)acryloyloxy group at at least one end of the main chain, or polymerizable liquid crystal compounds having (meth)acryloyloxy groups at both ends of the main chain. In the liquid crystal compounds of this disclosure, the main chain refers to the main carbon chain in the molecular chain of the liquid crystal compound, and means the stem portion with the largest number of carbon atoms.

[0019] The ring structures that may be included in the main chain of the polymerizable liquid crystal compound include alicyclic hydrocarbon groups, aromatic hydrocarbon groups, aromatic heterocyclic groups, and the like. These ring structures may be monocyclic or polycyclic. In the case of polycyclic structures, they may be condensed polycyclic structures or aggregated polycyclic structures.

[0020] Examples of monocyclic ring structures include alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or aromatic heterocyclic groups with 3 to 20 members, preferably alicyclic hydrocarbon groups, aromatic hydrocarbon groups, or aromatic heterocyclic groups with 4 to 10 members, more preferably 5-membered or 6-membered rings, and even more preferably 6-membered rings. Specifically, examples include benzene rings, cyclohexane rings, pyrimidine rings, pyridazine rings, pyrazine rings, pyridine rings, piperidine rings, tetrahydropyran rings, dioxane rings, and thiazine rings.

[0021] Examples of polycyclic ring structures include polycyclic aromatic groups, aromatic heterocyclic groups, and polycyclic alicyclic hydrocarbon groups, with polycyclic aromatic groups having heterocyclic rings being preferred. Specifically, examples include indole groups, benzimidazole groups, benzofuran groups, benzothiophene groups, and benzothiazole groups.

[0022] As polymerizable liquid crystal compounds used in this disclosure, from the standpoint of availability, polymerizable liquid crystal compounds selected from the group consisting of compounds represented by the following general formula (1) are mentioned.

[0023] [ka] (In general formula (1), L 1 and L 2 These are each independent of -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -C H=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, or represents a single bond. A 1 and A2 Each independently represents an optionally substituted divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms, where any carbon atom of the aromatic hydrocarbon group and the alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom. n1 and n2 each independently represent an integer from 0 to 3, provided that n1 + n2 is 1 or more, and L 1 , L 2 , A 1 , and A 2 When there are a plurality of each, they may be the same or different from each other. R 1 and R 2 each independently represent a group selected from the following general formula (R-1), General formula (R-1): -L r1 -R sp1 -Z 1 In the general formula (R-1), L r1 represents -O-, -S-, -COO-, -OCO-, -OCOO-, or a single bond, R sp1 represents an alkylene group having 1 to 20 carbon atoms or a single bond in which one -CH2- or two or more non-adjacent -CH2- are each independently replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, or -CH=CH-, and Z 1 represents a hydrogen atom, -CN, -NCS, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a (meth)acryloyloxy group, and at least one Z 1 represents a (meth)acryloyloxy group. Ar is an optionally substituted divalent aromatic group, and the aromatic group may contain at least one nitrogen atom, oxygen atom or sulfur atom. 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 2 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkylthiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfo group, an amide group, a cyano group, a nitro group, a halogen atom, or a (meth)acryloyloxy group. However, if the group described as substituent E has -CH2-, a group obtained by replacing at least one of the -CH2- in the above group with -O-, -CO-, or -CH=CH- is also included as substituent E.

[0024] L 1 and L 2 In terms of liquid crystalline properties, ease of raw material availability, and ease of synthesis, these can be independently identified as -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -SCH2-, -CH2S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2 -, -CH2-COO-, -CH2-OCO-, -CH=CH-, or representing a single bond is preferred, and -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -SCH2-, -CH2S-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, or representing a single bond is more preferred. 1 and L 2From the viewpoint of solubility and orientation, it is preferable that each independently represents -O-, -S-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, or a single bond, and more preferably that they represent -O-, -S-, -COO-, -OCO-, -O-CO-O-, or a single bond. Note L 1 and L 2 If there are multiple instances of each independently, they may be identical or different.

[0025] A 1 and A 2 Each of these independently represents a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms, which may be unsubstituted or substituted with one or more substituents E. Any carbon atom in the aromatic hydrocarbon group or alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom, or a sulfur atom. The above aromatic hydrocarbon group may be an aromatic heterocyclic group, may have a fused ring structure, or may be a structure in which an alicyclic hydrocarbon group and an aromatic hydrocarbon group are fused. Note that A 1 and A 2 If there are multiple instances of each independently, they may be identical or different. Similarly, if there are multiple instances of E, they may be identical or different.

[0026] Aromatic hydrocarbon rings that constitute an aromatic hydrocarbon group, which may be substituted with nitrogen, oxygen, or sulfur atoms, include, for example, benzene rings, naphthalene rings, anthracene rings, and phenanthrene rings, while aromatic heterocycles include furan rings, pyridine rings, pyrimidine rings, pyrazine rings, and thiazine rings.

[0027] Examples of divalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cycloalkanediyl groups with 3 to 20 carbon atoms and alicyclic fused ring groups with 10 to 20 carbon atoms. Divalent cycloalkanediyl groups with 3 to 20 carbon atoms include: cyclopropanediyl group; cyclobutanediyl groups such as cyclobutane-1,2-diyl group and cyclobutane-1,3-diyl group; cyclopentanediyl groups such as cyclopentane-1,2-diyl group and cyclopentane-1,3-diyl group; cyclohexane-1,2-diyl group, cyclohexane-1,3-diyl group, and cyclohexane-1,4- Cyclohexanediyl groups such as diyl groups; cycloheptanediyl groups such as cycloheptane-1,2-diyl, cycloheptane-1,3-diyl, and cycloheptane-1,4-diyl; cyclooctanediyl groups such as cyclooctane-1,2-diyl, cyclooctane-1,3-diyl, cyclooctane-1,4-diyl, and cyclooctane-1,5-diyl; cyclodecane-1,2-diyl groups Examples include cyclodecanediyl groups such as cyclodecane-1,3-diyl group, cyclodecane-1,4-diyl group, and cyclodecane-1,5-diyl group; cyclododecanediyl groups such as cyclododecane-1,2-diyl group, cyclododecane-1,3-diyl group, cyclododecane-1,4-diyl group, and cyclododecane-1,5-diyl group; cyclotetradecanediyl groups such as cyclotetradecane-1,2-diyl group, cyclotetradecane-1,3-diyl group, cyclotetradecane-1,4-diyl group, cyclotetradecane-1,5-diyl group, and cyclotetradecanediyl groups such as cycloeicosane-1,2-diyl group and cycloeicosane-1,10-diyl group; and the cycloalkanediyl group may be unsubstituted or substituted with one or more substituents E. The cycloalkanediyl group may have any carbon atom substituted with an oxygen atom, a sulfur atom, or a nitrogen atom. Examples include the tetrahydropyran-2,5-diyl group, the 1,3-dioxane-2,5-diyl group, and the tetrahydrothiopyran-2,5-diyl group.

[0028] Examples of divalent alicyclic condensed ring groups having 10 to 20 carbon atoms include decalindiyl groups such as decahydronaphthalene-2,5-diyl, decahydronaphthalene-2,6-diyl, and decahydronaphthalene-2,7-diyl; adamantanediyl groups such as adamantane-1,2-diyl and adamantane-1,3-diyl; and bicyclo[2.2.1]heptanediyl groups such as bicyclo[2.2.1]heptane-2,3-diyl, bicyclo[2.2.1]heptane-2,5-diyl, and bicyclo[2.2.1]heptane-2,6-diyl. The alicyclic condensed ring groups may be unsubstituted or substituted with one or more substituents E. Furthermore, any carbon atom in the alicyclic condensed ring group may be substituted with an oxygen atom, a sulfur atom, or a nitrogen atom.

[0029] A divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms may be unsubstituted or substituted with one or more substituents E, and may be substituted with oxygen atoms, sulfur atoms or nitrogen atoms, may be a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 18 carbon atoms, may be a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 12 carbon atoms, or may be a divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having a 5-membered ring or a 6-membered ring.

[0030] A 1 and A 2 From the standpoint of ease of availability and ease of synthesis, these may be independently a 1,4-phenylene group, a cyclohexane-1,4-diyl group, or a naphthalene-2,6-diyl group, each of which may be unsubstituted or substituted with one or more substituents E. Furthermore, the cyclohexane-1,4-diyl group may have cis and trans stereoisomers. The 1,4-cyclohexylene may be in the cis or trans form, or a mixture of cis and trans isomers, but it is preferable to be in the trans or cis form, and more preferably a trans-cyclohexane-1,4-diyl group, due to its good orientation.

[0031] 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 2 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkylthiocarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, an amino group, a mercapto group, a carboxyl group, a sulfo group, an amide group, a cyano group, a nitro group, a halogen atom, or a (meth)acryloyloxy group. However, if the group described as substituent E has -CH2-, a group obtained by replacing at least one of the -CH2- in the above group with -O-, -CO-, or -CH=CH- is also included in substituent E. Note that the number of carbon atoms in substituent E includes, for example, the number of carbon atoms in the carbonyl (C=O) group in an alkanoyl group or an alkyloxycarbonyl group.

[0032] From the viewpoint of solvent solubility, substituent E may be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, a hydroxyl group, a carboxyl group, a cyano group, or a nitro group, and may be an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkanoyl group having 2 to 10 carbon atoms, an alkanoyloxy group having 2 to 10 carbon atoms, or an alkyloxycarbonyl group having 2 to 10 carbon atoms. From the viewpoint of solvent solubility and availability of materials, 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, or an alkyloxycarbonyl group having 2 to 6 carbon atoms; more preferably an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkanoyl group having 2 to 5 carbon atoms, an alkanoyloxy group having 2 to 5 carbon atoms, or an alkyloxycarbonyl group having 2 to 5 carbon atoms; and even more preferably a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a methoxy group, an ethoxy group, an n-propoxy group, an i-propoxy group, a methoxycarbonyl group, or an ethoxycarbonyl group.

[0033] n1 and n2 each independently represent integers from 0 to 3, but n1 + n2 is 1 or greater. n1 and n2 are each independently preferably 1 or 2, and more preferably 1. Furthermore, from the viewpoint of facilitating the production of polymerizable liquid crystal compounds and suppressing manufacturing costs, n1 and n2 may be the same integer. n1 + n2 is an integer less than or equal to 6, but it may also be an integer less than or equal to 4, or an integer less than or equal to 3.

[0034] R 1 and R 2 Each of these independently represents a base selected from the following general formula (R-1), General formula (R-1): -L r1 -R sp1 -Z 1 In general formula (R-1), L r1 -O-, -S-, -COO-, -OCO-, -OCOO-, or a single bond, R sp1 This represents an alkylene group or single bond having 1 to 20 carbon atoms, in which one -CH2- or two or more non-adjacent -CH2- may each be independently replaced by -O-, -COO-, -OCO-, -OCO-O-, -CO-NH-, -NH-CO-, or -CH=CH-. 1represents a hydrogen atom, -CN, -NCS, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a (meth)acryloyloxy group, and at least one Z 1 represents a (meth)acryloyloxy group.

[0035] In general formula (R-1), R sp1 Specifically, from the viewpoint of ease of obtaining raw materials and ease of synthesis, it is preferable that each independently represents an alkylene group or single bond having 1 to 12 carbon atoms, in which one -CH2- or two or more non-adjacent -CH2- may each independently be replaced with -O-, -COO-, or -OCO-; more preferably that each independently represents an alkylene group or single bond having 1 to 12 carbon atoms; even more preferably that each independently represents an alkylene group or single bond having 2 to 10 carbon atoms; and even more preferably that each independently represents an alkylene group or single bond having 2 to 6 carbon atoms. 1 and R 2 In R sp1 These may be the same or different.

[0036] In general formula (R-1), L r1 R represents -O-, -S-, -COO-, -OCO-, -OCOO-, or a single bond, but from the viewpoint of ease of obtaining raw materials and ease of synthesis, it is preferable that each independently represents -O-, -COO-, -OCO-, -OCOO-, or a single bond. 1 and R 2 In L r1 These may be the same or different. R sp1 When represents a single bond, adjacent L r1 It can be a single bond.

[0037] In general formula (R-1), Z 1 R represents a hydrogen atom, -CN, -NCS, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a (meth)acryloyloxy group. 1 and R 2 In this case, at least one Z 1represents a (meth)acryloyloxy group. Examples of alkoxy groups having 1 to 10 carbon atoms include linear or branched alkoxy groups, such as methoxy, ethoxy, n-propoxy, i-propoxy, n-butoxy, t-butoxy, and n-pentoxy groups. The alkoxy group having 1 to 10 carbon atoms may also be an alkoxy group having 1 to 5 carbon atoms, or an alkoxy group having 1 to 4 carbon atoms. Examples of alkylthio groups having 1 to 10 carbon atoms include linear or branched alkylthio groups, such as methylthio group, ethylthio group, n-propylthio group, i-propylthio group, n-butylthio group, t-butylthiooxy group, and n-pentylthio group. The alkylthio group having 1 to 10 carbon atoms may also be an alkylthio group having 1 to 5 carbon atoms, or an alkylthio group having 1 to 4 carbon atoms. From the standpoint of improving the hardness and durability of the coating, R 1 and R 2 In this case, two Z 1 This may be a (meth)acryloyloxy group. From the standpoint of solubility and orientation, R 1 and R 2 In this case, one Z 1 is a (meth)acryloyloxy group, and the other Z 1 This may be an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a -CN (cyano group).

[0038] Ar is a divalent aromatic group which may be substituted with one or more substituents E, and which may contain at least one nitrogen atom, oxygen atom, or sulfur atom. Ar may be an aromatic hydrocarbon group or an aromatic heterocyclic group, and A 1 and A 2 The aromatic hydrocarbon group or aromatic heterocyclic group described in [reference] may be the same as those described in [reference]. Ar may be a 1,4-phenylene group, a cyclohexane-1,4-diyl group, a naphthalene-2,6-diyl group, or a 4,4'-biphenylene group, depending on the availability of the materials.

[0039] Mesogenic groups contained in polymerizable liquid crystal compounds, or -(A 1 -L 1 ) n1 -Ar-(L 2 -A 2 ) n2 -The substructures represented by the following chemical formulas (m-1) to (m-11) are preferably used, and among them, from the viewpoint of solvent solubility, the substructures represented by at least one selected from the group consisting of the following chemical formulas (m-2), (m-3), (m-5), (m-7), (m-8), and (m-10) are preferably used. The hydrogen atoms in the phenylene group and naphthylene group in the substructures represented by the following chemical formulas (m-1) to (m-11) are the substituent E 1 It may be replaced by this.

[0040] [ka]

[0041] The polymerizable liquid crystal compounds used in this disclosure include, but are not limited to, the polymerizable liquid crystal compounds shown in formulas (1) to (19) below.

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] Furthermore, when the polymerizable liquid crystal compound used in this disclosure is an inverse-dispersive liquid crystal compound, examples include, but are not limited to, the polymerizable liquid crystal compounds shown in formulas (21) to (23) below.

[0046] [ka]

[0047] Furthermore, the polymerizable liquid crystal compound used in this disclosure is preferably solvable in 10% by mass or more in at least one solvent selected from the group consisting of methyl ethyl ketone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone, in order to broaden the range of usable substrates, and is more preferably solvable in 20% by mass or more.

[0048] The polymerizable liquid crystal compounds used in this disclosure can be produced by conventionally known methods. For example, they can be produced by appropriately combining known organic synthesis reactions (e.g., condensation reactions, esterification reactions, Williamson reactions, Ullmann reactions, Wittig reactions, Schiff base formation reactions, benzylation reactions, Sonogashira reactions, Suzuki-Miyaura reactions, Negishi reactions, Kumada reactions, Hiyama reactions, Buchwald-Hartwig reactions, Friedelcraft reactions, Heck reactions, aldol reactions, Daff reactions, etc.) described in Methoden der Organischen Chemie, Organic Reactions, Organic Syntheses, Comprehensive Organic Synthesis, Shin Jikken Koryu, etc., depending on their structure. The polymerizable liquid crystal compound used in this disclosure may be a commercially available product selected as appropriate.

[0049] The polymerizable liquid crystal compounds used in this disclosure can be used individually or in combination of two or more. The content of the polymerizable liquid crystal compound used in this disclosure is not limited, and may be adjusted as appropriate to adjust the desired optical anisotropy, etc., but may be 69.0% by mass or more, 80.0% by mass or more, 90.0% by mass or more, or 99.9% by mass or less, based on the total solid content (total amount of solids) of the polymerizable liquid crystal composition.

[0050] <Halogen> The polymerizable liquid crystal composition of this disclosure has a halogen content of 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition, and the inclusion of halogen improves liquid crystal alignment and suppresses alignment defects. Liquid crystal compounds having (meth)acryloyloxy groups with π electrons have a problem in that their liquid crystal orientation is easily disrupted and orientation defects occur due to the influence of the charging of the alignment film. In contrast, in the polymerizable liquid crystal composition of this disclosure, the halogen is presumed to improve the orientation of the liquid crystal compounds by imparting an excluded volume effect and polarity to the intermolecular interactions between liquid crystal compounds having (meth)acryloyloxy groups with π electrons.

[0051] The form of halogen contained in the polymerizable liquid crystal composition of this disclosure is not particularly limited. In the polymerizable liquid crystal composition of this disclosure, it is preferable that the halogen is bonded to the liquid crystal compound in order to improve the orientation of the liquid crystal compound and to suppress orientation defects. Since halogens are preferable to be bonded to the liquid crystal compound in order to improve the orientation of the liquid crystal compound and to suppress orientation defects, the halogen source may be a liquid crystal compound containing a halogen. A liquid crystal compound containing a halogen may be included as at least one of the polymerizable liquid crystal compounds.

[0052] In particular, it is more preferable that the halogen is bonded to the end of the liquid crystal compound, as this improves the orientation of the liquid crystal compound and makes it easier to suppress orientation defects. The halogen source may be a liquid crystal compound containing a halogen at its end. The end of the liquid crystal compound may be the end of the main chain of the liquid crystal compound.

[0053] As a halogen-containing liquid crystal compound, it may be a liquid crystal compound having a group represented by the following general formula (A) at its terminal end, as this improves the orientation of the liquid crystal compound and makes it easier to suppress orientation defects.

[0054] [ka] (In general formula (A), R x1 R is a hydrogen atom, a methyl group, or a halogen atom. x2 is a hydrogen atom or a halogen atom, and R x1 and R x2 One of these is a halogen atom. (* indicates the bonding position with the liquid crystal compound.)

[0055] The group represented by the general formula (A) above includes at least one group selected from the group consisting of the groups represented by (a-1), (a-2), and (a-3) below.

[0056] [ka] (In the formula, X represents a halogen atom, and * indicates the bonding position with the liquid crystal compound.)

[0057] In the case of a liquid crystal compound having a group represented by the general formula (A) at its terminal, heating during drying or orientation when forming a cured film (optically anisotropic film) using a polymerizable liquid crystal composition can cause HX (where X is a halogen atom) to detach from the liquid crystal compound and be converted to a (meth)acryloyloxy group. Therefore, a liquid crystal compound having a group represented by the general formula (A) at its terminal can improve the orientation of the liquid crystal compound through the action of the halogen present at the terminal, and then the converted (meth)acryloyloxy group can be cured by light irradiation to fix good orientation and contribute to improved durability.

[0058] [ka]

[0059] The liquid crystal compound having a group represented by the general formula (A) at its terminal end may be a liquid crystal compound represented by the following general formula (2).

[0060] [ka] (In general formula (2), L 1 and L 2 each independently represents -O-, -S-, -OCH2-, -CH2O-, -CH2CH2-, -CO-, -COO-, -OCO-, -CO-S-, -S-CO-, -O-CO-O-, -CO-NH-, -NH-CO-, -OCO-NH-, -NH-COO-, -NH-CO-NH-, -NH-O-, -O-NH-, -SCH2-, -CH2S-, -CH=CH-COO-, -CH=CH-OCO-, -COO-CH=CH-, -OCO-CH=CH-, -COO-CH2CH2-, -OCO-CH2CH2-, -CH2CH2-COO-, -CH2CH2-OCO-, -COO-CH2-, -OCO-CH2-, -CH2-COO-, -CH2-OCO-, -CH=CH-, or a single bond, A 1 and A 2 each independently represents an optionally substituted divalent aromatic hydrocarbon group or alicyclic hydrocarbon group having 3 to 20 carbon atoms, provided that any carbon atom of the aromatic hydrocarbon group and alicyclic hydrocarbon group may be substituted with a nitrogen atom, an oxygen atom or a sulfur atom. n1 and n2 each independently represent an integer of 0 to 3, provided that n1 + n2 is 1 or more, and L 1 L 2 A 1 and A 2 when there are a plurality of each of L, L, A, and A, they may be the same or different from each other. R 3 and R 4 each independently represents a group selected from the following general formula (R-2), General formula (R-2): -L r2 -R sp2 -Z 2 In general formula (R-2), L r2 represents -O-, -S-, -COO-, -OCO-, -OCOO-, or a single bond, and R sp2represents an alkylene group having 1 to 20 carbon atoms or a single bond in which one -CH2- or two or more non - adjacent -CH2- may each independently be replaced by -O-, -COO-, -OCO-, -OCO - O-, -CO - NH-, -NH - CO-, or -CH = CH-, and Z 2 represents a hydrogen atom, -CN, -NCS, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a (meth)acryloyloxy group, or a group represented by the general formula (A), and at least one Z 2 represents a group represented by the general formula (A). Ar is a divalent aromatic group which may be substituted by one or more substituents E, and the aromatic group may contain at least one nitrogen atom, oxygen atom or sulfur atom. The substituents E are each independently an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylamino group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkanoyl group having 1 to 10 carbon atoms, an alkanoyloxy group having 1 to 10 carbon atoms, an alkanoylamino group having 1 to 10 carbon atoms, an alkanoylthio group having 1 to 10 carbon atoms, an alkyloxycarbonyl group having 2 to 10 carbon atoms, an alkylaminocarbonyl group having 2 to 10 carbon atoms, an alkylthiocarbonyl group having 2 to 10 carbon atoms, a hydroxy group, an amino group, a mercapto group, a carboxy group, a sulfo group, an amide group, a cyano group, a nitro group, a halogen atom or a (meth)acryloyloxy group. However, when the above - mentioned groups described as substituents E have -CH2-, a group obtained by replacing at least one of -CH2- contained in the above - mentioned groups with -O-, -CO-, or -CH = CH- is also included in the substituents E.)

[0061] In the general formula (2), L 1 , L 2 , A 1 , A 2 , Ar, n1, and n2 may each be the same as L 1 , L 2 , A 1 , A 2 , Ar, n1, and n2 in the general formula (1).

[0062] In general formula (R-2), L r2 , and R sp2 These are L in general formula (1), respectively. r1 , and R sp1 It may be the same as that.

[0063] In general formula (R-2), Z 2 represents a hydrogen atom, -CN, -NCS, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, a (meth)acryloyloxy group, or a group represented by the general formula (A), and at least one Z 2 represents the group represented by the general formula (A) above. As for alkoxy groups with 1 to 10 carbon atoms and alkylthio groups with 1 to 10 carbon atoms, Z in general formula (R-1) 1 It may be the same as that. From the perspective of improving the hardness and durability of the coating, R 3 and R 4 In this case, one Z 2 is the group represented by the general formula (A) above, and the other Z 2 It is preferable that the group is a (meth)acryloyloxy group. From the standpoint of solubility and orientation, R 3 and R 4 In this case, one Z 2 is the group represented by the general formula (A) above, and the other Z 2 This may be an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, or a -CN (cyano group).

[0064] Liquid crystal compounds having a group represented by the general formula (A) at the terminal can be produced by using halogen-substituted propionic acid chloride instead of (meth)acrylate chloride in conventionally known methods for producing liquid crystal compounds having a (meth)acryloyloxy group at the terminal, but are not limited to this method.

[0065] The polymerizable liquid crystal composition of this disclosure comprises a polymerizable liquid crystal compound represented by the general formula (1) and a liquid crystal compound represented by the general formula (2), and may contain halogens such that the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition. In this case, the L of the liquid crystal compound represented by the general formula (2) 1 , L 2 , A 1 , A 2 Ar, n1, and n2 are, respectively, L of the polymerizable liquid crystal compound represented by the general formula (1). 1 , L 2 , A 1 , A 2 Ar, n1, and n2 may be the same or different.

[0066] In the polymerizable liquid crystal composition of this disclosure, the halogen can be fluorine, chlorine, bromine, or iodine. In the polymerizable liquid crystal composition of this disclosure, the halogen is preferably chlorine, bromine, or iodine, more preferably chlorine or bromine, and even more preferably chlorine, from the viewpoint of availability and durability.

[0067] The polymerizable liquid crystal composition of this disclosure contains halogens such that the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition. When the halogen content is below this upper limit, the order between liquid crystal compounds is not disrupted, and the effect of improving liquid crystal alignment by halogen addition is easily obtained. In the polymerizable liquid crystal composition of this disclosure, the halogen content measured by X-ray fluorescence analysis (XRF) is 0.300% by mass or less with respect to the total solid content of the polymerizable liquid crystal composition, but may be 0.280% by mass or less, 0.250% by mass or less, 0.200% by mass or less, 0.150% by mass or less, or 0.100% by mass or less. In the polymerizable liquid crystal composition of the present disclosure, the halogen content measured by X-ray fluorescence analysis (XRF) may be 0.001% by mass or more, and may be 0.002% by mass or more, based on the total solids of the polymerizable liquid crystal composition.

[0068] The halogen content of the polymerizable liquid crystal composition of the present disclosure shall be measured as follows. After preparing a coating solution of the polymerizable liquid crystal composition in which the liquid crystal compound is dissolved in a solvent, the solvent is volatilized by blowing nitrogen gas onto the coating solution at 25°C so as to leave only the solid content of the polymerizable liquid crystal composition, thereby obtaining a solid sample. Using a wavelength-dispersive X-ray fluorescence analyzer (manufactured by Rigaku Corporation, model "ZSX PrimusIV"), measure the halogen content of the solid content of the polymerizable liquid crystal composition under the following measurement conditions. The measurement sample is prepared by placing about 1 g of the solid sample in the aluminum ring for pressing attached to the wavelength-dispersive X-ray fluorescence analyzer, flattening it, protecting the top and bottom with filter paper, pressing it at 110 kN using a high-pressure press, and then removing the filter paper. For analysis, element identification is performed based on the peak position of the X-ray, and the concentration of each element is determined from the peak intensity of the X-ray using the semi-fundamental parameter method, and the halogen content relative to the total solids of the polymerizable liquid crystal composition is calculated. <XRF Measurement Conditions> X-ray source: Rh tube target · 3.8 kW (40 kV · 95 mA) Measurement vacuum degree: 13 Pa Measurement range (element): 6C~ 92 U (Full element analysis) Measurement diameter (X-ray irradiation range): 30 mmφ

[0069] In the polymerizable liquid crystal composition of the present disclosure, the halogen source may be appropriately adjusted and contained so that the halogen content measured by X-ray fluorescence analysis (XRF) is 0.300% by mass or less based on the total solids of the polymerizable liquid crystal composition and contains halogen.

[0070] <Polymerization initiator> The polymerizable liquid crystal composition used in the present disclosure preferably contains a polymerization initiator from the viewpoint of curability. The polymerization initiator is preferably a photopolymerization initiator that can initiate the polymerization reaction by ultraviolet irradiation. In this embodiment, the photopolymerization initiator can be appropriately selected from conventionally known ones. Specific examples of such photopolymerization initiators include, for example, aromatic ketones including thioxanthones, α-aminoalkylphenones, α-hydroxyketones, acylphosphine oxides, oxime esters, aromatic onium salts, organic peroxides, thio compounds, hexaarylbiimidazole compounds, ketooxime ester compounds, borate compounds, azinium compounds, metallocene compounds, active ester compounds, compounds having carbon-halogen bonds, and alkylamine compounds. Among these, at least one selected from the group consisting of acylphosphine oxide-based polymerization initiators, α-aminoalkylphenone-based polymerization initiators, α-hydroxyketone-based polymerization initiators, and oxime ester-based polymerization initiators is preferred because it hardens to the interior of the coating film and improves durability.

[0071] Examples of acylphosphine oxide polymerization initiators include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide (e.g., trade name: Omnirad819, manufactured by IGM RESINS BV), bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphenylphosphine oxide, and 2,4,6-trimethylbenzoyl-diphenylphosphine oxide (trade name: Omnirad TPO H, manufactured by IGM RESINS BV, etc.).

[0072] Examples of α-aminoalkylphenone polymerization initiators include 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (e.g., Omnirad907, manufactured by IGM RESINS BV), 2-benzyl-2-(dimethylamino)-1-(4-morpholinophenyl)-1-butanone (e.g., Omnirad369, manufactured by IGM RESINS BV), and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (Omnirad379EG, manufactured by IGM RESINS BV).

[0073] Examples of α-hydroxyketone polymerization initiators include 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)-benzyl]-phenyl}-2-methylpropan-1-one (e.g., trade name: Omnirad127, manufactured by IGM RESINS BV, etc.), 2-hydroxy-4'-hydroxyethoxy-2-methylpropiophenone (e.g., trade name: Omnirad2959, manufactured by IGM RESINS BV, etc.), 1-hydroxycyclohexylphenyl-ketone (e.g., trade name: Omnirad184, manufactured by IGM RESINS BV, etc.), and oligo{2-hydroxy-2-methyl-1-[4-(1-methylvinyl)phenyl]propanone} (e.g., trade name: ESACURE ONE, manufactured by IGM RESINS BV, etc.).

[0074] 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), ethanoone,1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name: Irgacure OXE-02, manufactured by BASF), and methanone,ethanoone,1-[9-ethyl-6-(1,3-dioxolane,4-(2-methoxyphenoxy)-9H-carbazol-3-yl]-,1-(o-acetyloxime) (trade name: ADEKA OPT-N-1919, manufactured by ADEKA).

[0075] If the polymerizable liquid crystal composition used in this disclosure contains a polymerization initiator, the content of the polymerization initiator in the composition is not particularly limited, but may be 0.1% by mass or more, 1.0% by mass or more, on the other hand, 20.0% by mass or less, 10.0% by mass or less, or 8.0% by mass or less, relative to the total mass of the liquid crystal compounds in the polymerizable liquid crystal composition (or, if the composition contains other liquid crystal compounds, relative to the total mass of the polymerizable liquid crystal compounds and other liquid crystal compounds). The polymerizable liquid crystal composition used in this disclosure may use one polymerization initiator alone or two or more initiators. When two or more initiators are used, it is preferable that their total content is within the above range.

[0076] <Other liquid crystal compounds> The polymerizable liquid crystal composition used in this disclosure may also include a liquid crystal compound that does not fall under the polymerizable liquid crystal compound and the halogen source, is halogen-free, and does not have a (meth)acryloyloxy group (also referred to as "other liquid crystal compounds"). As a liquid crystal compound different from the polymerizable liquid crystal compound, and which does not contain halogens, conventionally known liquid crystal compounds can be appropriately selected and used.

[0077] If the polymerizable liquid crystal composition used in this disclosure contains other liquid crystal compounds, the content of the other liquid crystal compounds in the composition is not particularly limited, but may be 10.0% by mass or less, 5.0% by mass or less, or 0.0% by mass, relative to the total mass of the liquid crystal compounds in the polymerizable liquid crystal composition (relative to the total mass of the polymerizable liquid crystal compounds and other liquid crystal compounds). The polymerizable liquid crystal composition used in this disclosure may use one other liquid crystal compound alone or two or more compounds. When two or more compounds are used, it is preferable that their total content is within the above range.

[0078] <Solvent> The polymerizable liquid crystal composition used in this disclosure may contain a solvent as needed for coating purposes. In this disclosure, a polymerizable liquid crystal composition containing a solvent for coating purposes may be referred to as a "coating solution for polymerizable liquid crystal composition." As the solvent, it is appropriate to select from conventionally known solvents that can dissolve or disperse each component contained in the polymerizable liquid crystal 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); alkyl halogenated 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. As the solvent, at least one selected from the group consisting of ketone solvents, ester solvents, ether solvents, and amide solvents is preferred, and at least one selected from the group consisting of ketone solvents and ether solvents is more preferred. In this embodiment, the solvent can be used alone or in combination of two or more solvents as a mixed solvent. When the polymerizable liquid crystal composition used in this disclosure contains a solvent, the amount of solvent in the composition is preferably such that the solid content concentration of the composition is 0.5% to 30% by mass, and more preferably 1% to 20% by mass. The polymerizable liquid crystal composition used in this disclosure may use one solvent alone or two or more solvents. When two or more solvents are used, it is preferable that their total content is within the above range.

[0079] In addition to the above, the polymerizable liquid crystal composition used in this disclosure may also contain other components such as chiral agents, antioxidants, ultraviolet absorbers, sensitizers, stabilizers, plasticizers, chain transfer agents, polymerization inhibitors, defoamers, leveling agents, thickeners, flame retardants, surfactants, dispersants, dyes, and pigments. The polymerizable liquid crystal composition used in this disclosure may use one other component alone or two or more components. The content of the other components in the composition may be conventionally known and is not particularly limited. The total content of the other components in the composition may be 15.0% by mass or less, 10.0% by mass or less, 5.0% by mass or less, or 0.0% by mass, relative to the total mass of the liquid crystal compounds in the polymerizable liquid crystal composition (or, if the composition contains other liquid crystal compounds, relative to the total mass of the polymerizable liquid crystal compounds and other liquid crystal compounds).

[0080] II. Optically Anisotropic Films The optically anisotropic film of the present disclosure is a cured film of the polymerizable liquid crystal composition of the present disclosure. The method for curing the polymerizable liquid crystal composition used in this disclosure is not particularly limited, and known methods can be employed. For example, one embodiment includes a step of bringing an alignment film provided on a support described later into contact with the polymerizable liquid crystal composition to form a composition layer on the alignment film provided on the support (composition layer formation step), a step of applying a heat treatment to the composition layer to align the liquid crystal compounds in the polymerizable liquid crystal composition (alignment step), and a step of applying a curing treatment thereafter (curing step). According to this embodiment, the liquid crystal compounds in the polymerizable liquid crystal composition can be immobilized in an oriented state, and an optically anisotropic film can be formed.

[0081] The composition layer formation step involves bringing an alignment film provided on a support into contact with the polymerizable liquid crystal composition to form a composition layer on the alignment film provided on the support. The support and alignment film used will be described later. The method for bringing the alignment film provided on the support into contact with the composition is not particularly limited, and one example is a method of coating the composition onto the support. The coating method can be any method that can accurately form a film of the desired thickness, and can be selected as appropriate. Examples include gravure coating, reverse coating, knife coating, dip coating, spray coating, air knife coating, spin coating, roll coating, printing, immersion and pull-up, curtain coating, die coating, casting, bar coating, extrusion coating, and E-type coating methods.

[0082] The orientation step involves heat-treating the composition layer to orient the liquid crystal compounds in the polymerizable liquid crystal composition. The polymerizable liquid crystal compound, the optionally included halogen-containing liquid crystal compound, and other liquid crystal compounds contained in the composition layer are heated to a temperature at which orientation is possible. This heat treatment allows the polymerizable liquid crystal compound, the optionally included halogen-containing liquid crystal compound, and other liquid crystal compounds to be oriented and dried, and then fixed in the oriented state. The temperature at which orientation is possible varies depending on each substance in the composition, and therefore needs to be adjusted accordingly. For example, it is preferable to carry out the process within the range of 40°C to 200°C, and more preferably within the range of 60°C to 150°C. As a heating method, known heating and drying methods can be appropriately selected and used. Furthermore, the heating time can be selected as appropriate, but for example, it is selected within the range of 10 seconds to 2 hours, preferably 20 seconds to 30 minutes.

[0083] By heat-treating the composition layer, the liquid crystal compounds in the polymerizable liquid crystal composition become oriented, and a liquid crystal phase is formed. For example, if the composition layer contains a chiral agent, a cholesteric liquid crystal phase is formed.

[0084] After the orientation step, a curing step is performed. The curing method is not particularly limited and includes photocuring and thermocuring. Since the polymerizable liquid crystal compound of the present invention has a (meth)acryloyloxy group, photoirradiation treatment is preferred, and ultraviolet irradiation treatment is more preferred. For light irradiation, ultraviolet (UV) irradiation is preferably used. UV irradiation can be provided from sources such as ultra-high pressure mercury lamps, high-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, xenon arcs, and metal halide lamps. The irradiation dose from the energy source can be appropriately selected, for example, 10 mJ / cm² as the integrated exposure dose at an UV wavelength of 365 nm. 2 More than 10000mJ / cm 2 The following range is preferable.

[0085] The cured product obtained by the above process corresponds to a layer in which the liquid crystal phase is fixed. For example, a layer in which the nematic liquid crystal phase is fixed is formed. Furthermore, if the polymerizable liquid crystal composition contains a chiral agent, a layer in which the cholesteric liquid crystal phase is fixed is formed. Furthermore, these layers no longer need to exhibit liquid crystalline properties. More specifically, for example, the most typical and preferred embodiment of a state in which the cholesteric liquid crystal phase is "immobilized" is a state in which the orientation of the liquid crystal compound that constitutes the cholesteric liquid crystal phase is maintained. More specifically, it is preferable that the layer is non-fluid in a temperature range of 0°C to 50°C, and under more severe conditions of -30°C to 70°C, and that the immobilized orientation can be stably maintained without causing changes in the orientation due to external fields or external forces.

[0086] The thickness of the optically anisotropic film can be appropriately selected according to the application and is not particularly limited. The film thickness of the optically anisotropic film may be 0.80 μm or more, with an upper limit of 10.00 μm or less, or 5.00 μm or less, from the viewpoint of ease of coating, productivity, and substrate warpage.

[0087] The optically anisotropic film may have a refractive index anisotropy Δn measured with light of a wavelength of 550 nm of 0.16 to 0.24, may be 0.17 or greater, or may be 0.23 or less, from the viewpoint of orientation. The refractive index anisotropy Δn measured with light of wavelength 550 nm is calculated using the following formula, based on the in-plane retardation value (Re(550)) and film thickness d (nm) at wavelength 550 nm: 550 We seek. Δn 550 =Re(550) / film thickness d(nm)

[0088] The thickness of an optically anisotropic film is determined by taking a cross-sectional image of the optically anisotropic film using a scanning transmission electron microscope (STEM) (Hitachi High-Technologies Corporation, S-4800), measuring the thickness of the optically anisotropic film at 10 locations in the cross-sectional image, and taking the arithmetic mean of the thicknesses at those 10 locations. Cross-sectional images of optically anisotropic films are taken as follows. First, a block is prepared by embedding a 1mm x 10mm sample in embedding resin. From this block, uniform sections with a thickness of 70nm to 100nm, free from holes or other defects, are cut using a general sectioning method. An ultramicrotome (EM UC7, Leica Microsystems Co., Ltd.) is used to prepare the sections. These uniform sections, free from holes or other defects, are then used as the measurement sample. Subsequently, a cross-sectional image of the measurement sample is taken using a scanning transmission electron microscope (STEM). When taking these cross-sectional images, the detector is set to "TE", the acceleration voltage to "30kV", and the emission current to "10μA" for STEM observation. The magnification is adjusted as appropriate between 5000x and 200,000x while adjusting the focus and observing whether each layer can be distinguished. Furthermore, refractive index anisotropy Δn 550This involves applying a polymerizable liquid crystal composition onto an alignment film for retardation measurement, which has a recess formed in one direction, and drying it at 100°C for 60 seconds to orient the liquid crystal compound so that its director (optical axis) is horizontal to the surface of the support, after which it is irradiated with ultraviolet light (integrated light intensity of 150 mJ / cm²). 2 The polymerizable liquid crystal compound is immobilized to form a cured film of the polymerizable liquid crystal composition. The in-plane retardation value (Re) and layer thickness of the obtained optical anisotropy film are measured to determine the following. The in-plane retardation value (Re) is measured at a wavelength of 550 nm using the "RETS-100" product manufactured by Otsuka Electronics Co., Ltd., following the procedure (A1) to (A4) below. (A1) First, to stabilize the light source of the RETS-100, leave it for at least 60 minutes after turning on the light source. Then, select the rotational analyzer method and select single-point measurement. (A2) Next, the following measurement conditions were applied to the RETS-100. (Measurement conditions) • Retardation measurement range: Rotational analyzer method • Measurement spot diameter: φ5mm • Inclination angle range: 0° • Measurement wavelength range: 400nm~800nm (A3) Next, background data is obtained without placing a sample in the apparatus. The apparatus is a closed system, and this is done each time the light source is turned on. (A4) After that, the sample is placed on the stage inside the device and measured. From the obtained in-plane retardation value at a wavelength of 550 nm (Re(550)) and layer thickness d (nm), the refractive index anisotropy Δn is calculated using the following formula. 550 We seek. Δn 550 =Re(550) / layer thickness d(nm)

[0089] The presence of the polymerizable liquid crystal compound and / or halogen source in the optically anisotropic film can be confirmed by sampling and analyzing the material from the optically anisotropic film. Suitable analytical methods include NMR, IR, GC-MS, XPS, TOF-SIMS, XRF, and combinations thereof.

[0090] III. Optical Components The optical component of this disclosure is characterized by comprising an optically anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure. The optical members of this disclosure are members that have optical properties (e.g., polarizing properties, light refraction properties, light scattering properties, light reflectivity, light transmittance, light absorption properties, light diffraction properties, etc.) by comprising an optically anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure. The optical members are not particularly limited as long as they have optical properties, but examples include display devices (image display devices), input devices and other equipment (optical equipment), or members used in such equipment, such as phase difference plates, polarizers, reflectors, or diffractive optical elements.

[0091] The optical component of this disclosure may be an optically anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure, but may further include an alignment film, a support, or other functional layers.

[0092] In the optical members of this disclosure, the optical anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure may be the same as described above, so its explanation is omitted here.

[0093] <Support> The support structure provides support for the alignment film and the optically anisotropic film. Various sheet-like materials (films, plates) can be used as the support, as long as they can support the alignment film and the optically anisotropic film. As the support, a transparent support is preferred, and examples include polyacrylic resin films such as polymethyl methacrylate, cellulose resin films such as cellulose triacetate, cycloolefin polymer films (for example, "Arton" manufactured by JSR Corporation, "Zeonor" manufactured by Nippon Zeon Corporation), polyethylene terephthalate (PET), polycarbonate, and polyvinyl chloride. The support is not limited to a flexible film, but may also be a non-flexible substrate such as a glass substrate.

[0094] There are no restrictions on the thickness of the support; the appropriate thickness should be set to accommodate the alignment film and the optical anisotropy film, depending on the application of the optical component and the material used to form the support. The thickness of the support may be 1 μm to 1000 μm, 3 μm to 250 μm, or 5 μm to 150 μm.

[0095] In the optical component of this disclosure, the support is provided with an optically anisotropic film in a preferred manner during manufacturing, and is not an essential component. For example, since it is possible to peel off the support after forming the optical anisotropy film, the optical component does not necessarily need to include a support.

[0096] <Orientation film> When forming at least an optically anisotropic film, it is preferable to provide an orientation film on the surface of the support. The alignment film is a film used to orient the liquid crystal compound containing the polymerizable liquid crystal compound into a predetermined liquid crystal alignment pattern when forming an optically anisotropic film.

[0097] Various known alignment films can be used. The alignment film may be, for example, a photo-alignment film obtained by irradiating a photo-alignment material with polarized or unpolarized light to form an alignment film. Polarized light irradiation can be applied perpendicularly or obliquely to the photo-alignment film, while unpolarized light irradiation can be applied obliquely to the photo-alignment film.

[0098] As the photo-alignment material used in the photo-alignment film, conventionally known photo-alignment materials can be appropriately selected and used. Examples of photo-alignment materials include those described in Japanese Patent Publication No. 2006-285197, Japanese Patent Publication No. 2007-76839, Japanese Patent Publication No. 2007-138138, Japanese Patent Publication No. 2007-94071, Japanese Patent Publication No. 2007-121721, Japanese Patent Publication No. 2007-140465, Japanese Patent Publication No. 2007-156439, Japanese Patent Publication No. 2007-133184, and Japanese Patent Publication No. Azo compounds described in Japanese Patent Publication No. 2009-109831, Japanese Patent Publication No. 3883848 and Japanese Patent Publication No. 4151746, aromatic ester compounds described in Japanese Patent Application Publication No. 2002-229039, maleimides and / or alkeni having photo-orienting units described in Japanese Patent Application Publication No. 2002-265541 and Japanese Patent Application Publication No. 2002-317013 Examples of preferred materials include ru-substituted nadiimide compounds, photocrosslinkable silane derivatives described in Japanese Patent No. 4205195 and Japanese Patent No. 4205198, photocrosslinkable polyimides, photocrosslinkable polyamides and photocrosslinkable esters described in Japanese Patent Publication No. 2003-520878, Japanese Patent Publication No. 2004-529220 and Japanese Patent No. 4162850, and photodimerizable compounds described in Japanese Patent Publication No. 9-118717, Japanese Patent Publication No. 10-506420, Japanese Patent Publication No. 2003-505561, International Publication No. 2010 / 150748, Japanese Patent Publication No. 2013-177561 and Japanese Patent Publication No. 2014-12823, particularly cinnamate compounds, chalcone compounds and coumarin compounds. Among these, azo compounds, photocrosslinkable polyimides, photocrosslinkable polyamides, photocrosslinkable esters, cinnamate compounds, and chalcone compounds are particularly suitable for use.

[0099] There are no limitations on the method for forming the alignment film, and various known methods can be used depending on the material used to form the alignment film. For example, one method involves coating the alignment film onto the surface of a support, drying it, and then exposing the alignment film with laser light to form an alignment pattern. For example, as a method and exposure apparatus for exposing an alignment film to form an alignment pattern, refer to paragraphs 0078-0080 and Figure 5, paragraphs 0098-0107 and Figures 8-10 of International Publication No. 2020 / 022496, paragraphs 0075-0076 and Figure 1 of Japanese Patent Publication No. 2015-532468, etc.

[0100] Furthermore, the orientation film may be, for example, a rubbing-treated film made of an organic compound such as a polymer, an obliquely vapor-deposited film of an inorganic compound, a film having microgrooves, or a film obtained by accumulating LB (Langmuir-Blodgett) films of organic compounds such as ω-tricosanoic acid, dioctadecylmethylammonium chloride, and methyl stearylate using the Langmuir-Blodgett method.

[0101] An oriented film formed by rubbing can be created by rubbing the surface of a polymer layer several times in a specific direction with paper or cloth. Preferred materials for use in the orientation film include polyimide, polyvinyl alcohol, polymers having polymerizable groups as described in Japanese Patent Publication No. 9-152509, materials used for forming orientation films as described in Japanese Patent Publication No. 2005-97377, Japanese Patent Publication No. 2005-99228, and Japanese Patent Publication No. 2005-128503.

[0102] Furthermore, the orientation film may be an orientation film of a resin layer on which an uneven shape has been transferred to its surface. An orientation film of a resin layer on which an uneven shape has been transferred to its surface can be obtained, for example, by applying an ultraviolet-curable resin to the support, then using a roll plate with an uneven shape formed around it to transfer the uneven shape to the ultraviolet-curable resin on the support, and curing the ultraviolet-curable resin by ultraviolet irradiation to obtain a cured film of the ultraviolet-curable resin. A conventionally known method can be used to form an orientation film of a resin layer on which an uneven shape has been transferred to its surface, for example, paragraphs 0041 to 0043 and Figures 3 to 4 of Japanese Patent Application Publication No. 2022-147451. As the UV-curable resin, conventionally known UV-curable resins can be used, such as (meth)acrylate resins and epoxy resins. The alignment film may be an alignment film having an uneven surface structure, such as an alignment film produced by rubbing treatment or an alignment film of a resin layer on which an uneven shape has been transferred to the surface.

[0103] There are no restrictions on the thickness of the alignment film; the appropriate thickness should be set according to the material used to form the alignment film, so as to obtain the required alignment function. The thickness of the photo-alignment film is preferably 0.01 μm to 2 μm, and more preferably 0.05 μm to 1 μm. In the case of a resin layer with an uneven surface transferred to it, the thickness of the alignment film is preferably 0.5 μm to 20 μm, and more preferably 1 μm to 10 μm.

[0104] The optical member of this disclosure may be an optical member in which an optically anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure is laminated on an alignment film having an uneven surface structure. Furthermore, the optical member of this disclosure may be an optical member in which an optically anisotropic film obtained by curing the polymerizable liquid crystal composition of this disclosure is laminated on a photo-alignment film. Laminating an optically anisotropic film, which is made by curing a polymerizable liquid crystal composition, onto an alignment film having an uneven surface structure has the problem that liquid crystal alignment tends to be poor and alignment defects tend to occur. However, by using the polymerizable liquid crystal composition of this disclosure, even when an optically anisotropic film, which is made by curing a polymerizable liquid crystal composition, is laminated onto an alignment film having an uneven surface structure, the liquid crystal alignment tends to be improved and alignment defects tend to occur less easily.

[0105] In the optical components of this disclosure, the alignment film is provided as a preferred embodiment and is not an essential component. For example, since it is possible to peel off the alignment film after forming the optical anisotropy film, the optical component does not necessarily need to contain an alignment film. Furthermore, polymerizable liquid crystal compounds can be oriented by forming an orientation pattern on the support, for example, by rubbing the support or processing the support with laser light.

[0106] <Other components and functional layers of optical elements> The optical components of this disclosure may have other configurations and other functional layers, to the extent that they do not impede the effects of this disclosure. Examples of other functional layers include phase difference layers different from the optical anisotropy film of this disclosure, gas barrier layers, adhesive layers, surface protection layers, and other alignment films for phase difference layers. These other layers can be selected and used from conventionally known layers as appropriate.

[0107] If the optical component of this disclosure is a polarizing plate, it further comprises a polarizer. Conventional polarizers can be used as polarizers, including, for example, sheet-type polarizers such as polyvinyl alcohol film, polyvinyl formal film, polyvinyl acetal film, and ethylene-vinyl acetate copolymer saponified film dyed with iodine or the like and stretched; wire grid-type polarizers consisting of numerous parallel metal wires; coated polarizers coated with lyotropic liquid crystal or dichroic guest-host materials; and multilayer thin-film polarizers. These polarizers may also be reflective polarizers that have the function of reflecting polarization components that are not transmitted.

[0108] Furthermore, when the optical member of this disclosure is a diffractive optical element, the orientation pattern of the optical anisotropy layer is an orientation pattern in which the orientation of the optical axis derived from the liquid crystal compound contained in the polymerizable liquid crystal composition changes continuously along at least one direction in the plane. For diffractive 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.

[0109] This disclosure is not limited to the embodiments described above. The embodiments described above are illustrative, and any configuration that is substantially identical to the technical idea described in the claims of this disclosure and achieves similar effects is included within the technical scope of this disclosure. [Examples]

[0110] Examples and comparative examples are shown below to further illustrate this disclosure. In this specification, unless otherwise specified, all parameters shall be values ​​measured at a temperature of 25°C ± 2°C and a relative humidity of 40% to 65%. Furthermore, before starting each measurement, the target sample shall be exposed to the above atmosphere for at least 30 minutes before measurement and evaluation. Each compound produced was processed using the JEOL JNM-LA400WB manufactured by JEOL Ltd. 1 The chemical structure was confirmed by 1H NMR measurement.

[0111] Furthermore, in this disclosure, unless otherwise specified, the various parameters in the evaluation items below refer to the average value of nine measurements. The nine measurement points are the intersections of lines drawn to divide the inner region of the measurement sample from the outer edge into four equal parts vertically and horizontally, with these points as the measurement centers. If the measurement sample is a rectangle, measurements are taken with the nine points as the centers, with the intersections of lines drawn to divide the inner region of the rectangle from the outer edge into four equal parts vertically and horizontally, and the average value is calculated. If the measurement sample is a shape other than a rectangle, such as a circle, ellipse, triangle, or pentagon, a rectangle with the largest area inscribed in that shape is drawn, and nine measurements are taken with respect to that rectangle using the method described above.

[0112] [Preparation of polymerizable liquid crystal compounds] As a polymerizable liquid crystal compound, polymerizable liquid crystal compound (A), represented by the following chemical formula, was synthesized with reference to Japanese Patent No. 6705548.

[0113] [ka]

[0114] [Preparing the halogen source] (Synthesis of liquid crystal compound (B-1)) Liquid crystal compound (B-1) was synthesized according to the following scheme.

[0115] [ka]

[0116] (1) Synthesis of compound 1 Dimethylacetamide (DMAc) (400 mL) was added to 4-hydroxybenzoic acid (13.8 g, 100.0 mmol), 4-chlorobutyl acetate (37.7 g, 250.0 mmol), potassium carbonate (41.5 g, 300.0 mmol), and potassium iodide (1.7 g, 10.0 mmol). The resulting mixture was stirred at 80°C for 3 hours. Sodium hydroxide (20.0 g, 500.0 mmol) solution (400 mL water, 100 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, methanol was removed by distillation under reduced pressure, and 1 M hydrochloric acid (1000 mL) was added to the resulting residue. Water and ethyl acetate were added to the resulting mixture, and then it was extracted with ethyl acetate. The solvent of the resulting organic layer was removed by distillation under reduced pressure. The obtained solid was purified with diisopropyl ether to obtain compound 1 (20.1 g, 95.5 mmol). The yield was 95.5%.

[0117] (2) Synthesis of compound 2 Compound 1 (16.8 g, 80.0 mmol) and N,N-dimethylaniline (14.5 g, 120.0 mmol) were dissolved in tetrahydrofuran (THF) (100 mL). The resulting solution was cooled to 10°C, acrylate chloride (9.1 g, 100.0 mmol) was added dropwise, and the mixture was stirred at 10°C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and then it was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. Compound 2 (20.7 g, 20.7 mmol) was obtained by recrystallization of the resulting residue using toluene. The yield was 98.0%.

[0118] [ka]

[0119] (3) Synthesis of compound 3 100 mL of thionyl chloride was added to 10.9 g of 3-chloropropionic acid (100.0 mmol). The resulting solution was stirred at room temperature for 1 hour. The residual thionyl chloride was removed from the resulting mixture by distillation, and 50 mL of THF was added to prepare a THF solution of 3-chloropropionic acid chloride. Compound 1 (16.8 g, 80.0 mmol) and N,N-dimethylaniline (14.5 g, 120.0 mmol) were dissolved in tetrahydrofuran (THF) (100 mL). The resulting solution was cooled to 10°C, and a THF solution of 3-chloropropionic acid chloride was added dropwise. The mixture was stirred at 10°C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and then it was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. Compound 3 (22.7 g, 75.4 mmol) was obtained by recrystallization of the resulting residue using toluene. The yield was 94.3%.

[0120] [ka]

[0121] (4) Synthesis of compound 4 Compound 2 (2.8 g, 10.5 mmol), methylhydroquinone (1.2 g, 10.0 mmol), and 4-dimethylaminopyridine (DMAP) (0.12 g, 1.0 mmol) were dissolved in CH2Cl2 (12 mL). The resulting solution was cooled to 15°C, and N,N-diisopropylcarbodiimide (DIC) (1.6 g, 12.0 mmol) was added dropwise. The mixture was stirred at 15°C for 3 hours. Methanol (240 mL) was added to the resulting mixture and it was filtered. The filtrate was washed with methanol to obtain compound 4 (3.6 g, 9.9 mmol). The yield was 98.5%.

[0122] (5) Synthesis of liquid crystal compound (B-1) Compound 4 (1.9 g, 5.0 mmol), Compound 3 (2.3 g, 7.5 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH2Cl2 (4 mL). The resulting solution was cooled to 15°C, DIC (1.3 g, 10.0 mmol) was added dropwise, and the mixture was stirred at 15°C for 3 hours. Methanol (40 mL) was added to the resulting mixture and it was filtered. The filtrate was washed with methanol to obtain liquid crystal compound (B-1) (3.0 g, 4.6 mmol). The yield was 91.5%.

[0123] 1 H-NMR(CDCl3):δ=1.93(m,8H),2.24(s,3H),2.76(t,2H),3.64(t,2H)4.14(t,4H),4.19(t,2H),4.33(t,2H), 5.84(dd,1H),6.15(dd,1H),6.41(dd,1H),6.98(m,4H),7.05(d,1H),7.13(d,1H),7.18(dd,1H),8.15(m,4H)

[0124] (Synthesis of liquid crystal compound (B-2)) Liquid crystal compound (B-2) was synthesized according to the following scheme.

[0125] [ka]

[0126] (1) Synthesis of compound 5 3-bromopropionic acid (15.3 g, 100.0 mmol) was mixed with thionyl chloride (100 mL). The resulting solution was stirred at room temperature for 1 hour. The residual thionyl chloride was removed from the resulting mixture by distillation, and THF (50 mL) was added to prepare a THF solution of 3-bromopropionic acid chloride. Compound 1 was prepared in the same manner as the synthesis of liquid crystal compound (B-1). Compound 1 (16.8 g, 80.0 mmol) and N,N-dimethylaniline (14.5 g, 120.0 mmol) were dissolved in tetrahydrofuran (THF) (100 mL). The resulting solution was cooled to 10°C, and a THF solution of 3-bromopropionate chloride was added dropwise. The mixture was stirred at 10°C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and then it was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. Compound 5 (24.5 g, 71.4 mmol) was obtained by recrystallization of the resulting residue using toluene. The yield was 88.8%.

[0127] [ka]

[0128] (2) Synthesis of liquid crystal compound (B-2) Compound 4 was prepared in the same manner as the synthesis of liquid crystal compound (B-1). Compound 4 (1.9 g, 5.0 mmol), Compound 5 (2.6 g, 7.5 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH2Cl2 (4 mL). The resulting solution was cooled to 15°C, DIC (1.3 g, 10.0 mmol) was added dropwise, and the mixture was stirred at 15°C for 3 hours. Methanol (40 mL) was added to the resulting mixture and it was filtered. The filtrate was washed with methanol to obtain liquid crystal compound (B-2) (3.3 g, 4.7 mmol). The yield was 93.5%.

[0129] 1 H-NMR(CDCl3):δ=1.88(m,8H),2.22(s,3H),3.03(t,2H),3.64(t,2H)4.12(t,4H),4.21(t,2H),4.31(t,2H), 5.82(dd,1H),6.17(dd,1H),6.43(dd,1H),6.99(m,4H),7.07(d,1H),7.11(d,1H),7.16(dd,1H),8.13(m,4H)

[0130] (Synthesis of liquid crystal compound (B-3)) Liquid crystal compound (B-3) was synthesized according to the following scheme.

[0131] [ka]

[0132] (1) Synthesis of compound 6 3-iodopropionic acid (20.0 g, 100.0 mmol) was mixed with thionyl chloride (100 mL). The resulting solution was stirred at room temperature for 1 hour. The residual thionyl chloride was removed from the resulting mixture by distillation, and THF (50 mL) was added to prepare a THF solution of 3-bromopropionate chloride. Compound 1 was prepared in the same manner as the synthesis of liquid crystal compound (B-1). Compound 1 (16.8 g, 80.0 mmol) and N,N-dimethylaniline (14.5 g, 120.0 mmol) were dissolved in tetrahydrofuran (THF) (100 mL). The resulting solution was cooled to 10°C, and a THF solution of 3-bromopropionate chloride was added dropwise. The mixture was stirred at 10°C for 1 hour. Water and ethyl acetate were added to the resulting mixture, and then it was extracted with ethyl acetate. The solvent in the resulting organic layer was removed by vacuum distillation. Compound 6 (26.9 g, 68.5 mmol) was obtained by recrystallization of the resulting residue using toluene. The yield was 85.6%.

[0133] [ka]

[0134] (2) Synthesis of liquid crystal compound (B-3) Compound 4 was prepared in the same manner as the synthesis of liquid crystal compound (B-1). Compound 4 (1.9 g, 5.0 mmol), Compound 6 (2.9 g, 7.5 mmol), and DMAP (0.06 g, 0.5 mmol) were dissolved in CH2Cl2 (4 mL). The resulting solution was cooled to 15°C, DIC (1.3 g, 10.0 mmol) was added dropwise, and the mixture was stirred at 15°C for 3 hours. Methanol (40 mL) was added to the resulting mixture and it was filtered. The filtrate was washed with methanol to obtain liquid crystal compound (B-3) (3.4 g, 4.6 mmol). The yield was 92.3%.

[0135] 1 H-NMR(CDCl3):δ=1.92(m,8H),2.24(s,3H),3.03(t,2H),3.41(t,2H)4.14(t,4H),4.29(m,4H),5.84( dd,1H),6.16(dd,1H),6.41(dd,1H),7.01(m,4H),7.08(d,1H),7.12(d,1H),7.18(dd,1H),8.16(m,4H)

[0136] [Preparation of a roll-shaped plate for alignment films having an uneven surface structure] A quartz matrix was fabricated using an electron beam lithography process with an electron beam lithography system and a dry etching system, employing a 6-inch square synthetic quartz plate. Next, UV-curable resin was poured into the mold, and then cured by irradiating the UV-curable resin with ultraviolet light. After that, the UV-curable resin was peeled off the mold to obtain a resin plate having a shape complementary to the surface shape of the mold. Then, multiple duplicate molds of the mold, which had a shape complementary to the shape of the resin plate, were produced by electroforming. Next, the multiple duplicate molds were wound onto a roll to produce a roll-shaped plate. The roll-shaped plate for the alignment film is a mold with a shape complementary to the shape of the alignment film. In order to form a recessed pattern on the alignment film, the pattern of the roll-shaped plate is a convex pattern. The roll-shaped plate has a pattern of convex portions, in which linear convex portions with a width of 25 nm and a height of 30 nm extend in the x direction, and linear convex portions are repeatedly arranged parallel to each other in the y direction with a spacing of 25 nm between them.

[0137] [Example 1] (1) Production of polymerizable liquid crystal composition A coating solution for polymerizable liquid crystal composition 1 was prepared by dissolving 99.95 parts by mass of polymerizable liquid crystal compound (A), 0.05 parts by mass of liquid crystal compound (B-1) as a halogen source, and 4 parts by mass of a photopolymerization initiator (BASF, trade name: Irgacure OXE02) in 896 parts by mass of methyl ethyl ketone.

[0138] (2) Manufacturing of optically anisotropic films and optical components using an orientation film having an uneven surface structure (2-1) Fabrication of an oriented film having an uneven surface structure A primer layer with the following formulation was applied to a substrate layer (a cycloolefin polymer with a thickness of 40 μm, product name "Zeonor" from Nippon Zeon Co., Ltd.) and dried to form a primer layer with a thickness of 0.5 μm. <Coating solution for primer layer formation> • Polyolefin resin: 70 parts by mass (Manufactured by Mitsubishi Chemical Corporation, product name: Surflen P-1000) • Silica-based lubricant: 5 parts by mass (Manufactured by CIK Nanotech, product name: SIRMIBK15WT%-E65) Methyl ethyl ketone: 25 parts by mass Next, a coating solution for aligning the film according to the following formulation was applied to the primer layer and dried to form a layer containing uncured resin. <Coating solution for forming orientation films> Pentaerythritol triacrylate: 96 parts by mass (Manufactured by Nippon Kayaku Co., Ltd., product name: PET-30) • Photopolymerization initiator: 4 parts by mass (Manufactured by IGM RESINS BV, product name: Omnirad184)

[0139] Next, using the aforementioned roll-shaped plate for the alignment film, a layer containing uncured resin was formed using a roll-to-roll method, and at the same time, the formed resin-containing layer was cured by irradiating it with ultraviolet light from the substrate layer side. At this time, the integrated amount of ultraviolet light was 500 mJ / cm². 2 Next, the formed layer was peeled off from the plate, and a laminate was obtained having a primer layer and an orientation film having a surface with a shaped pattern and an uneven surface structure on the base layer.

[0140] (2-2) Manufacturing of optically anisotropic films and optical components The polymerizable liquid crystal composition 1 was applied to the orientation film having an uneven surface structure to form a film of polymerizable liquid crystal composition 1 such that the film thickness after curing was 1 μm. After drying at 100°C for 120 seconds, it was irradiated with ultraviolet (UV) light (cumulative light intensity 150 mJ / cm²). 2 An optical component was obtained by forming a cured film (optically anisotropic film) of a polymerizable liquid crystal composition.

[0141] (3) Manufacturing of optically anisotropic films and optical components using photoalignment films (3-1) Fabrication of photoalignment films Copolymer 1 was obtained by copolymerizing a photo-oriented monomer with hydroxyethyl methacrylate according to the description in Production Example 1 of Patent No. 5626493. A photo-alignment film composition with the following composition was prepared. ·Copolymer 1: 0.1 part by mass Hexamethoxymethylmelamine (HMM): 0.01 parts by mass • p-toluenesulfonic acid monohydrate (PTSA): 0.0015 parts by mass • Propylene glycol monomethyl ether (PGME): 2.1 parts by mass

[0142] The photo-alignment film composition was applied by bar coating to one side of a PET substrate (manufactured by Toyobo Co., Ltd., E5100, 38 μm thick) to a cured film thickness of 0.2 μm. The substrate was then heated in a 120°C oven for 1 minute to dry and heat-cur it, forming a cured film. Subsequently, polarized ultraviolet light containing a 313 nm emission line was applied to the surface of the cured film using a Hg-Xe lamp and a Gran-Taylor prism, perpendicular to the substrate normal, at an exposure dose of 100 mJ / cm². 2 By irradiating with this, a photo-aligned film was formed.

[0143] (3-2) Manufacturing of optically anisotropic films and optical components The polymerizable liquid crystal composition 1 coating solution was applied to the above-mentioned photo-alignment film so that the film thickness after curing would be 1 μm, thereby forming the polymerizable liquid crystal composition. After drying at 100°C for 120 seconds, ultraviolet (UV) light was irradiated (integrated light intensity 150 mJ / cm²). 2An optical component was obtained by forming a cured film (optically anisotropic film) of a polymerizable liquid crystal composition.

[0144] [Examples 2-9, Comparative Examples 1-2] (1) Production of polymerizable liquid crystal composition In Example 1(1), a coating solution for a polymerizable liquid crystal composition was prepared in the same manner as in Example 1, except that the polymerizable liquid crystal compound and halogen source listed in Table 1 were used in the parts by mass listed in Table 1.

[0145] (2) Manufacturing of optically anisotropic films and optical components using an orientation film having an uneven surface structure In Example 1(2), an optically anisotropic film and optical component were manufactured in the same manner as in Example 1, except that the coating solution of the polymerizable liquid crystal composition obtained in each example or comparative example was used instead of the coating solution of polymerizable liquid crystal composition 1.

[0146] (3) Manufacturing of optically anisotropic films and optical components using photoalignment films In Example 1(3), an optically anisotropic film and optical component were manufactured using a photo-alignment film in the same manner as in Example 1, except that the coating solution of the polymerizable liquid crystal composition obtained in each example or comparative example was used instead of the coating solution of polymerizable liquid crystal composition 1.

[0147] [evaluation] (1) Halogen content of polymerizable liquid crystal composition determined by XRF measurement After preparing a coating solution of the polymerizable liquid crystal composition, the solvent was evaporated by spraying nitrogen gas onto the coating solution at 25°C to obtain a solid sample containing only the solid components of the polymerizable liquid crystal composition. Using a wavelength-dispersive X-ray fluorescence analyzer (manufactured by Rigaku Corporation, model "ZSX PrimusIV"), the halogen content of the solid content of the polymerizable liquid crystal composition was measured under the following measurement conditions. The measurement sample was prepared by placing about 1-2 g of the solid sample in an aluminum ring for pressing attached to the wavelength-dispersive X-ray fluorescence analyzer, flattening it, protecting the top and bottom with medicine wrapping paper, pressing it at 110 kN using a high-pressure press, and then removing the medicine wrapping paper. For the analysis, element identification was performed based on the peak position of the X-ray, and the concentration of each element was determined from the peak intensity of the X-ray using the semi-fundamental parameter method, and the halogen content relative to the total solid content of the polymerizable liquid crystal composition was calculated. <XRF Measurement Conditions> X-ray source: Rh tube, 3.8 kW (40 kV, 95 mA) Measurement vacuum: 13 Pa Measurement range (elements): 6C~ 92 U (total element analysis) Measurement diameter (X-ray irradiation range): 30 mmφ

[0148] Note that according to the measurement by X-ray fluorescence analysis, the halogen content ratio relative to the total solid content of the polymerizable liquid crystal composition does not depend on the form of the solid sample before preparing the measurement sample, and the solid sample may be in the form of powder or broken coating film.

[0149] (2) Orientation For the optical member prepared using the photo-alignment film, the photo-alignment film and the optically anisotropic film were transferred onto the adhesive glass, the PET substrate was peeled off, and a measurement sample was prepared in the order of photo-alignment film / optically anisotropic film / adhesive glass. As the adhesive, an optical adhesive (manufactured by Panac Co., Ltd., Panaclean PD-S1, 25 μm, acrylic adhesive) was used. For the optical member prepared using the alignment film having an uneven structure on the surface, no transfer was performed, and the alignment defects were evaluated as the optical member. Using a polarizing microscope (BX-51 manufactured by Olympus Corporation), the number of alignment defects of the cured film of the polymerizable liquid crystal compound in a visual field of 1.20 mm × 1.28 mm was counted. Here, only the alignment defects caused by the measurement sample were counted, and the number of defects caused by environmental foreign matters, etc. was excluded and not counted. (Evaluation Criteria) A: The number of alignment defects is less than 10 B: The number of alignment defects is 10 or more and less than 20 C: The number of alignment defects is 20 or more and less than 50 D: The number of alignment defects is 50 or more

[0150]

Table 1

[0151] [Summary of Results] In the optical anisotropic film of Comparative Example 1, which is a cured film of a conventional polymerizable liquid crystal composition containing no halogen, many alignment defects were confirmed. On the other hand, in Examples 1 to 9 containing halogen at the content specified in the present invention, the liquid crystal alignment of the cured film of the polymerizable liquid crystal composition was improved, alignment defects were suppressed, and it was shown that an optical anisotropic film and an optical member with improved appearance quality could be obtained. It is speculated that by containing halogen at the content specified in the present invention, the interaction effect between liquid crystal compounds and the influence due to the polarity of halogen contributed like a horizontal alignment agent to the interface. In Comparative Example 2 containing more halogen than the content specified in the present invention, no improvement effect on liquid crystal alignment was observed. This is speculated to be because the ratio of halogen in the whole liquid crystal becomes high, the interaction between liquid crystals changes, and the alignment order collapses.

Claims

1. A polymerizable liquid crystal composition comprising a polymerizable liquid crystal compound having at least one terminal (meth)acryloyloxy group, A polymerizable liquid crystal composition containing halogens, wherein the halogen content, as measured by X-ray fluorescence analysis (XRF), is 0.300% by mass or less relative to the total solid content of the polymerizable liquid crystal composition.

2. A polymerizable liquid crystal composition according to claim 1, which does not contain a quaternary ammonium salt.

3. The polymerizable liquid crystal composition according to claim 1 or 2, wherein the halogen content is 0.001% by mass or more with respect to the total solid content of the polymerizable liquid crystal composition.

4. A polymerizable liquid crystal composition according to claim 1 or 2, comprising a liquid crystal compound having a group represented by the following general formula (A) at its terminal end. 【Chemistry 1】 (In general formula (A), R ｘ１ R is a hydrogen atom, a methyl group, or a halogen atom. ｘ２ is a hydrogen atom or a halogen atom, and R ｘ１ and R ｘ２ One of these is a halogen atom. (* indicates the bonding position with the liquid crystal compound.)

5. An optically anisotropic film obtained by curing the polymerizable liquid crystal composition according to claim 1 or 2.

6. An optical member comprising the optical anisotropy film described in claim 5.

7. An optical member comprising an orientation film having an uneven surface structure, on which the optical anisotropic film described in claim 5 is laminated.

8. An optical member having an optically anisotropic film according to claim 5 laminated on a photo-alignment film.

9. The optical member according to claim 6, wherein the optical member is a phase difference plate, a polarizing plate, or a diffractive optical element.

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