Liquid crystal assembly, hardening film, polarizing plate, image display device

Abstract

The present invention provides a liquid crystal composition, in which the transition temperature from a liquid crystal phase to a isotropic phase is high and the generation of crystals is inhibited in a solution that is obtained when the composition is mixed with a solvent. Also provided are a cured film, a polarizing plate, and an image display device. The liquid crystal composition contains: a polymerizable liquid crystal compound (A) having three ring structures in the direction of the molecular major axis; a polymerizable liquid crystal compound (B) which has at least four ring structures in the direction of the molecular major axis and has a transition temperature from the liquid crystal phase to the isotropic phase of 150℃ or higher; and a polymerizable compound (C) which is a compound that is different from the polymerizable liquid crystal compound (A), has three ring structures in the direction of the molecular major axis, and has a melting point of 65 to 120℃.

Description

[Technical Field]

[0001] The present invention relates to liquid crystal compositions, cured films, polarizing plates, and image display devices. [Background technology]

[0002] Liquid crystal compositions are used to form various components, such as optically anisotropic films. In terms of handling, it is preferable that the liquid crystal composition suppresses crystal precipitation and other processes. For example, Patent Document 1 discloses a liquid crystal composition containing a predetermined compound as a liquid crystal composition with high performance in suppressing crystallization. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2014-198814 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present inventors investigated the crystal suppression properties of the liquid crystal composition described in Patent Document 1 and found that while crystals generated after coating a substrate with a solution obtained by mixing the liquid crystal composition and a solvent can be suppressed, the suppression of crystal generation in the solution before coating is not always sufficient, and further improvements are needed. Furthermore, in liquid crystal compositions containing a specific liquid crystal compound, a high transition temperature from the liquid crystal phase to the isotropic phase is desirable in order to maintain liquid crystal properties even when heated.

[0005] In view of the above circumstances, the present invention aims to provide a liquid crystal composition that has a high transition temperature from the liquid crystal phase to the isotropic phase and suppresses the generation of crystals in a solution obtained by mixing with a solvent. Furthermore, the present invention also aims to provide a cured film, a polarizing plate, and an image display device. [Means for solving the problem]

[0006] As a result of intensive studies on the above problem, the present inventors have found that the above problem can be solved by the following constitution.

[0007] (1) A polymerizable liquid crystal compound (A) having three ring structures in the major axis direction of the molecule, and a polymerizable liquid crystal compound (B) having four or more ring structures in the major axis direction of the molecule, and having a transition temperature from a liquid crystal phase to an isotropic phase of 150° C. or higher, and a polymerizable compound (C) which is a compound different from the polymerizable liquid crystal compound (A), has three ring structures in the major axis direction of the molecule, and has a melting point of 65 to 120° C.; a liquid crystal composition comprising the same. (2) The liquid crystal composition according to (1), which has a melting enthalpy of 35 mJ / mg or less. (3) The polymerizable liquid crystal compound (A) is a compound represented by formula (1) described below, and the polymerizable liquid crystal compound (B) is a compound represented by formula (2) described below, which has a transition temperature from a liquid crystal phase to an isotropic phase of 150° C. or higher, and the polymerizable compound (C) is a compound represented by formula (3) described below, which has a melting point of 65 to 120° C.; the liquid crystal composition according to (1) or (2). (4) In formula (3), L9, L 10 , L 11 , and L 12 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, or an acyl group having 2 to 12 carbon atoms, and at least one of L9, L 10 , L 11 , and L 12 represents a group other than a hydrogen atom and a methyl group, the liquid crystal composition according to (3). (5) In formula (3), L9, L 10 , L 11 , and L 12 each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and L9, L 10 , L 11 , and L 12The liquid crystal composition according to (3) or (4), wherein at least one of the groups represents a group other than a hydrogen atom and a methyl group. (6) The liquid crystal composition according to any one of (3) to (5), wherein the polymerizable liquid crystal compound (A) is a compound represented by formula (1-1) described later. (7) The liquid crystal composition according to (6), wherein L1, L2, L3, and L4 each independently represent a hydrogen atom or a methyl group, and at least one of L1, L2, L3, and L4 represents a methyl group. (8) In formula (2), Q1 and Q2 each independently represent an aromatic ring which may have substituents having 1 to 12 carbon atoms; X2 represents the base shown in equation (2B) described later; A liquid crystal composition according to any one of (3) to (7), wherein x and y each independently represent 0 or 1, and x + y is 1 or 2. (9) The liquid crystal composition according to any one of (3) to (8), wherein the polymerizable liquid crystal compound (B) comprises at least one compound selected from the group consisting of the compound represented by formula (2-1) described later and the compound represented by formula (2-2) described later. (10) The liquid crystal composition according to (9), wherein L5, L6, L7, and L8 each independently represent a hydrogen atom or a methyl group, and at least one of L5, L6, L7, and L8 represents a methyl group. (11) The total content of the compound represented by formula (1) and the compound represented by formula (2) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 50 to 95% by mass. A liquid crystal composition according to any one of (3) to (10), wherein the content of the compound represented by formula (3) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 5 to 50% by mass. (12) The total content of the compound represented by formula (1) and the compound represented by formula (2) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 60 to 90% by mass. A liquid crystal composition according to any one of (3) to (11), wherein the content of the compound represented by formula (3) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 10 to 40% by mass. (13) The liquid crystal composition according to any one of (1) to (12), further comprising a polymerizable compound different from any of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C). (14) The liquid crystal composition according to any one of (1) to (13), further comprising a polymerization initiator. (15) A cured film obtained by curing any of the liquid crystal compositions described in (1) to (14). (16) The cured film described in (15), which is an optically anisotropic film. (17) The cured film according to (15), which is a film formed by fixing a torsion-oriented liquid crystal phase. (18) A polarizing plate comprising the cured film described in (15) and a polarizer. (19) An image display device comprising the cured film described in (15) or the polarizing plate described in (18). [Effects of the Invention]

[0008] According to the present invention, a liquid crystal composition can be provided that has a high transition temperature from the liquid crystal phase to the isotropic phase, and in which the formation of crystals is suppressed in the solution obtained by mixing with a solvent. Furthermore, according to the present invention, a cured film, a polarizing plate, and an image display device can also be provided. [Modes for carrying out the invention]

[0009] The present invention will be described in detail below. The following description of the constituent elements may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.

[0010] In this specification, a numerical range represented by "~" means a range that includes the numbers written before and after "~" as the lower and upper limits, respectively. In this specification, each component may be represented by a single substance or by a combination of two or more substances. When two or more substances are used in combination for each component, the content of that component refers to the total content of the combined substances unless otherwise specified.

[0011] In this specification, the bonding direction of divalent groups is not limited unless otherwise specified. For example, in a compound represented by the general formula "XMY", if M is -COO-(-CO-O-), and the bonded position on the X side is *1 and the bonded position on the Y side is *2, then M may be *1-CO-O-*2 or *1-O-CO-*2.

[0012] The liquid crystal composition of the present invention comprises a polymerizable liquid crystal compound (A) having three ring structures in the direction of the molecular long axis, a polymerizable liquid crystal compound (B) having four or more ring structures in the direction of the molecular long axis and having a transition temperature from the liquid crystal phase to the isotropic phase of 150°C or higher, and a polymerizable compound (C) that is different from polymerizable liquid crystal compound (A), having three ring structures in the direction of the molecular long axis and having a melting point of 65 to 120°C. In the liquid crystal composition of the present invention, it has been found that the desired effect can be obtained by combining the specific compounds described above. The following provides a detailed description of each compound.

[0013] <Polymerizable liquid crystal compound (A)> Polymerizable liquid crystal compound (A) is a polymerizable liquid crystal compound having three ring structures along the long axis of the molecule. Polymerizable liquid crystal compound (A) only needs to have three ring structures along the long axis of the molecule, and the ring structures may be directly bonded to each other or bonded via divalent linking groups. The ring structure can be an aromatic ring or a non-aromatic ring, with the aromatic ring being preferred. Aromatic rings include aromatic hydrocarbon rings and aromatic heterocycles. The aromatic hydrocarbon ring may be a monoring or a fused ring. The number of carbon atoms in the aromatic hydrocarbon ring is preferably 6 to 18, and more preferably 6 to 10. Examples of aromatic hydrocarbon rings include benzene rings, naphthalene rings, and anthracene rings. In this specification, a fused ring composed of multiple rings is considered as a single ring structure. The aromatic heterocycle may be a monocycle or a fused ring. The number of members in the aromatic heterocycle is preferably 5 to 10. The heteroatoms contained in the aromatic heterocycle are not particularly limited, but examples include nitrogen, oxygen, and sulfur atoms. The aromatic heterocycle is not particularly limited, but examples include pyridine, pyridazine, pyrimidine, pyrazine, triazine, thiophene, thiazole, and imidazole rings. Examples of non-aromatic rings include aliphatic hydrocarbon rings and aliphatic heterocycles. The aliphatic hydrocarbon ring may be a monocyclic or fused ring. The number of carbon atoms in the aliphatic hydrocarbon ring is not particularly limited, but 3 to 20 is preferred, and 3 to 10 is more preferred. Examples of aliphatic hydrocarbon rings include cyclopropane rings, cyclobutane rings, cyclopentane rings, and cyclohexane rings. The aliphatic heterocycle may be a monocycle or a fused ring. The number of members in the aliphatic heterocycle is preferably 5 to 10. The heteroatoms contained in the aliphatic heterocycle are not particularly limited, but examples include nitrogen, oxygen, and sulfur atoms. The aliphatic heterocycle is not particularly limited, but examples include pyrazoline rings, piperidine rings, and morpholine rings.

[0014] The ring structure may have substituents. The type of substituent is not particularly limited and known substituents can be cited. The substituents are not particularly limited but can be, for example, halogen atoms, alkyl groups, alkenyl groups, alkynyl groups, hydroxyl groups, alkoxy groups, aryl groups, formyl groups, nitro groups, cyano groups, acyl groups, acyloxy groups, (meth)acryloyloxy groups, (meth)acryloylamino groups, dialkylamino groups, monoalkylamino groups, amino groups, maleimide groups, acetylamide groups, allyloxycarbamoyl groups, alkyloxycarbamoyl groups, N-((meth)acryloyloxyalkyl)carbamoyloxy groups, alkoxycarbonyl groups, carboxyl groups, sulfonamide groups, and groups combining these.

[0015] The polymerizable liquid crystal compound (A) preferably has a structure represented by formula (XA). Equation (XA) -(LY)3- L represents a single bond or a divalent linking group. The divalent linking group is not particularly limited, but examples include divalent aliphatic hydrocarbon groups (which may be linear, branched, or cyclic, preferably having 1 to 10 carbon atoms, such as alkylene, alkenylene, and alkynylene groups), divalent aromatic hydrocarbon groups, divalent heterocyclic groups, -O-, -S-, -SO2-, and -NR. A Examples include -, -CO-, -N=N-, -CH=N-, and groups formed by combining two or more of these. A This represents a hydrogen atom or an alkyl group (preferably with 1 to 5 carbon atoms). Y represents a divalent ring structure, and is a group obtained by abstracting two hydrogen atoms from the aforementioned ring structure. Specifically, this includes divalent aromatic ring groups and divalent non-aromatic ring groups. Aromatic rings that constitute a divalent aromatic ring group are the aromatic rings mentioned above. Non-aromatic rings that constitute a divalent non-aromatic ring group are the non-aromatic rings mentioned above.

[0016] As the polymerizable liquid crystal compound (A), a compound represented by formula (1) (hereinafter also simply referred to as "compound 1") is preferred because it provides at least one of the following effects: a higher transition temperature from the liquid crystal phase to the isotropic phase, and greater suppression of crystal formation in the solution obtained by mixing the liquid crystal composition with the solvent (hereinafter also simply referred to as "the advantage of the present invention").

[0017] [ka]

[0018] In formula (1), R1 represents a hydrogen atom or a methyl group. A1 represents an alkylene group having 2 to 18 carbon atoms, and one CH2 or two or more non-adjacent CH2 atoms in the alkylene group may be substituted with -O-. The number of carbon atoms in the alkylene group represented by A1 is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, in terms of achieving superior effects of the present invention.

[0019] Z1 and Z2 each independently represent -COO-, -O-, or a single bond. In particular, in terms of superior effects of the present invention, Z1 and Z2 are preferably -COO- or -O-, and more preferably -O-.

[0020] X1 represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group with 1 to 4 carbon atoms in the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a group represented by formula (1A) described later, and the group represented by formula (1A) is preferred in terms of the curability of the liquid crystal composition. Formula (1A) *-A2-P1 In formula (1A), A2 represents an alkylene group having 2 to 18 carbon atoms, and one CH2 or two or more non-adjacent CH2 atoms in the alkylene group may be substituted with -O-. The number of carbon atoms in the alkylene group represented by A2 is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, in terms of achieving superior effects of the present invention. P1 represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group, and an acryloyloxy group or a methacryloyloxy group is preferred in that the effects of the present invention are superior. * indicates the connection position.

[0021] L1, L2, L3, and L4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, and at least one of L1, L2, L3, and L4 represents a group other than a hydrogen atom. In particular, for the effects of the present invention to be superior, L1, L2, L3, and L4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, or a C2-C4 acyl group, and it is preferable that at least one of L1, L2, L3, and L4 represents a group other than a hydrogen atom, and it is more preferable that L1, L2, L3, and L4 each independently represent a hydrogen atom or a C1-C4 alkyl group, and at least one of L1, L2, L3, and L4 represents a group other than a hydrogen atom. In particular, it is even more preferable that L1, L2, L3, and L4 each independently represent a hydrogen atom or a methyl group, and at least one of L1, L2, L3, and L4 represents a methyl group, and it is especially preferable that L1, L2, and L3 are hydrogen atoms and L4 is a methyl group.

[0022] In particular, the polymerizable liquid crystal compound (A) is preferably a compound represented by formula (1-1) in terms of superior effects of the present invention.

[0023] [ka]

[0024] In formula (1-1) above, R1, A1, Z1, Z2, L1, L2, L3, and L4 are equivalent to R1, A1, A2, Z1, Z2, L1, L2, L3, and L4 in formula (1), respectively, and the preferred embodiment is as described above. In formula (1-1) above, A2 is equivalent to A2 in formula (1A), and the preferred embodiment is as described above. As mentioned above, in formula (1-1), at least one of L1, L2, L3, and L4 represents a group other than a hydrogen atom. R4 represents a hydrogen atom or a methyl group.

[0025] The transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (A) is not particularly limited, but it is preferable that it be greater than 120°C in that the effects of the present invention are superior. Furthermore, the upper limit of the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (A) is not particularly limited, but it is often 250°C or less, and more often 200°C or less. The method for measuring the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (A) (hereinafter, this method is also referred to as the "specification method") is as follows. Two polarizers of an optical microscope (Nikon ECLIPSE E600 POL) are positioned orthogonally to each other, and a sample stage is placed between the two polarizers. Next, a small amount of polymerizable liquid crystal compound (A) is placed on a glass slide, and the glass slide is placed on a hot stage on the sample stage. While observing the state of the sample with a microscope, the temperature of the hot stage is increased at 5°C / min, and the temperature at which the transition from the liquid crystal phase to the isotropic phase is recorded.

[0026] <Polymerizable liquid crystal compound (B)> Polymerizable liquid crystal compound (B) is a polymerizable liquid crystal compound having four or more ring structures along the long axis of the molecule and a transition temperature from the liquid crystal phase to the isotropic phase of 150°C or higher. Polymerizable liquid crystal compound (B) only needs to have four or more ring structures along the long axis of the molecule, and the ring structures may be directly bonded to each other or bonded via divalent linking groups. Examples of ring structures that polymerizable liquid crystal compound (B) may have include the ring structures that polymerizable liquid crystal compound (A) has described above. The number of ring structures that polymerizable liquid crystal compound (B) may have should be four or more, preferably four to six, and more preferably four or five. The transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (B) is 150°C or higher, and 150 to 400°C is preferred, and 150 to 300°C is more preferred, as the effects of the present invention are more superior in this respect. The method for measuring the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (B) is the same as the method for measuring the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound described above.

[0027] The polymerizable liquid crystal compound (B) preferably has a structure represented by formula (XB). Formula(XB) -(LY) n - In equation (XB), L and Y are equivalent to L and Y in equation (XA), respectively. n represents an integer greater than or equal to 4, preferably an integer between 4 and 6.

[0028] As the polymerizable liquid crystal compound (B), a compound represented by formula (2) (hereinafter also simply referred to as "compound 2") is preferred in that it has a transition temperature of 150°C or higher from the liquid crystal phase to the isotropic phase, which is superior to the effects of the present invention. In other words, compound 2 means a compound represented by formula (2) and having a transition temperature of 150°C or higher from the liquid crystal phase to the isotropic phase. The transition temperature range from the liquid crystal phase to the isotropic phase of compound 2 is the same as that of the polymerizable liquid crystal compound (B) described above, and the preferred embodiment is as described above.

[0029] [ka]

[0030] In formula (2), R2 represents a hydrogen atom or a methyl group. A3 represents an alkylene group having 2 to 18 carbon atoms, and one CH2 or two or more non-adjacent CH2 atoms in the alkylene group may be substituted with -O-. The number of carbon atoms in the alkylene group represented by A3 is preferably 2 to 10, and more preferably 2 to 8, in terms of achieving superior effects of the present invention.

[0031] Z3, Z4, Z5, and Z6 each independently represent -COO-, -O-, or a single bond. Among these, Z3, Z4, Z5, and Z6 are preferably each independently -COO- or -O- in terms of superior effects of the present invention.

[0032] Q1 and Q2 each independently represent an aromatic ring group or an alicyclic group which may have substituents having 1 to 12 carbon atoms. Aromatic ring groups include aromatic hydrocarbon ring groups and aromatic heterocyclic groups. Aromatic hydrocarbon rings constituting aromatic heterocyclic groups include the rings exemplified above as aromatic hydrocarbon rings that the aforementioned ring structure can take. Aromatic heterocyclic rings constituting aromatic heterocyclic groups include the rings exemplified above as aromatic heterocyclic rings that the aforementioned ring structure can take. Examples of alicyclic groups include aliphatic hydrocarbon ring groups and aliphatic heterocyclic groups. Examples of aliphatic hydrocarbon rings constituting an aliphatic hydrocarbon ring group include the rings exemplified above as possible aliphatic hydrocarbon rings that the ring structure can take. Examples of aliphatic heterocyclic groups constituting an aliphatic heterocyclic group include the rings exemplified above as possible aliphatic heterocyclic rings that the ring structure can take. The substituents that the above aromatic ring group and alicyclic group may have have 1 to 12 carbon atoms, preferably 1 to 10, more preferably 1 to 8, and even more preferably 2 to 6. Examples of the substituents include alkyl groups, alkoxy groups, and alkoxycarbonyl groups. In particular, an aromatic ring group which may have substituents having 1 to 12 carbon atoms is preferred in terms of the superior effects of the present invention, and a phenylene group which may have substituents having 1 to 12 carbon atoms is even more preferred.

[0033] X2 represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, an optionally substituted aromatic ring group, a cyclohexyl group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 4 carbon atoms in the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a group represented by formula (2A) described later. The group represented by formula (2A) is preferred in terms of superior effects of the present invention, and the group represented by formula (2B) is more preferred. Formula (2A) *-A4-P2 In formula (2A), A4 represents an alkylene group having 2 to 18 carbon atoms, and one CH2 or two or more non-adjacent CH2 atoms in the alkylene group may be substituted with -O-. The number of carbon atoms in the alkylene group represented by A4 is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, in terms of achieving superior effects of the present invention. P2 represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group, and an acryloyloxy group or a methacryloyloxy group is preferred in that the effects of the present invention are superior. * indicates the connection position.

[0034] [ka]

[0035] In formula (2B), R5 represents a hydrogen atom or a methyl group. A4 in equation (2B) is equivalent to A4 in equation (2A). * indicates the connection position.

[0036] L5, L6, L7, and L8 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, and at least one of L5, L6, L7, and L8 represents a group other than a hydrogen atom. In particular, for superior effects of the present invention, it is preferable that L5, L6, L7, and L8 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, or a C2-C4 acyl group, with at least one of L5, L6, L7, and L8 representing a group other than a hydrogen atom, and more preferably that L5, L6, L7, and L8 each independently represent a hydrogen atom or a methyl group, with at least one of L5, L6, L7, and L8 representing a methyl group. In particular, it is even more preferable that L5, L6, and L7 are hydrogen atoms and L8 is a methyl group.

[0037] x and y each independently represent 0, 1, or 2, and at least one of x and y represents 1 or 2. In particular, in terms of superior effects of the present invention, it is preferable that x and y each independently represent 0 or 1, and that x + y is 1 or 2.

[0038] In particular, in terms of superior effects of the present invention, it is preferable that the polymerizable liquid crystal compound (B) contains at least one compound selected from the group consisting of compounds represented by formula (2-1) and compounds represented by formula (2-2).

[0039] [ka]

[0040] R2, A3, Z4, L5, L6, L7, and L8 in formulas (2-1) and (2-2) are synonymous with R2, A3, Z4, L5, L6, L7, and L8 in formula (2), and the preferred embodiment is as described above. A4 in formulas (2-1) and (2-2) is synonymous with A4 in formula (2A), and the preferred embodiment is as described above. R5 in formulas (2-1) and (2-2) is synonymous with R5 in formula (2B), and the preferred embodiment is as described above. As mentioned above, in equations (2-1) and (2-2), at least one of L5, L6, L7, and L8 represents a group other than a hydrogen atom.

[0041] <Polymerizable compound (C)> Polymerizable compound (C) is a different compound from polymerizable liquid crystal compound (A), having three ring structures along the long axis of the molecule and a melting point of 65 to 120°C. Note that if polymerizable compound (C) does not exhibit liquid crystalline properties, the above melting point represents the transition temperature from the solid state to the liquid state; if polymerizable compound (C) exhibits liquid crystalline properties, the above melting point represents the transition temperature from the liquid crystal phase to the isotropic phase. Polymerizable compound (C) only needs to have three ring structures along the long axis of the molecule, and the ring structures may be directly bonded to each other or bonded via divalent linking groups. Examples of ring structures possessed by polymerizable liquid crystal compound (C) include the ring structures possessed by polymerizable liquid crystal compound (A) described above. The melting point of polymerizable compound (C) is 65 to 120°C, and 70 to 110°C is preferred, and 80 to 110°C is more preferred, in terms of achieving superior effects of the present invention. If polymerizable compound (C) exhibits liquid crystalline properties, the method for measuring the melting point of polymerizable compound (C) is the same as the method for measuring the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (A) described above. If polymerizable compound (C) does not exhibit liquid crystalline properties, the same procedure as the method for measuring the transition temperature from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (A) is followed, and the temperature at which polymerizable compound (C) changes from a solid state to a liquid state is defined as the melting point.

[0042] The polymerizable compound (C) may be a compound that exhibits liquid crystalline properties, or a compound that does not exhibit liquid crystalline properties, but it is preferable that it is a compound that exhibits liquid crystalline properties.

[0043] The polymerizable compound (C) preferably has a structure represented by formula (XC). Formula (XC) -(LY)3- In equation (XC), L and Y are equivalent to L and Y in equation (XA), respectively.

[0044] As the polymerizable compound (C), a compound represented by formula (3) (hereinafter also simply referred to as "compound 3") is preferred, as it has a melting point of 65 to 120°C, which is superior to the effects of the present invention. In other words, compound 3 means a compound represented by formula (3) and having a melting point of 65 to 120°C. The melting point range of compound 3 is the same as that of the polymerizable liquid crystal compound (C) described above, and the preferred embodiment is as described above.

[0045] [ka]

[0046] In formula (3), R3 and R6 represent a hydrogen atom or a methyl group. A5 and A6 each independently represent an alkylene group having 2 to 18 carbon atoms, and one CH2 or two or more non-adjacent CH2 atoms in the alkylene group may be substituted with -O-. The number of carbon atoms in the alkylene groups represented by A5 and A6 is preferably 2 to 10, more preferably 2 to 8, and even more preferably 2 to 6, in terms of achieving superior effects of the present invention.

[0047] Z7 and Z8 each independently represent -COO-, -O-, or a single bond. In particular, in terms of superior effects of the present invention, Z7 and Z8 are preferably -COO- or -O-, and -O- is more preferred.

[0048] L9, L 10 , L11 , and, L 12 Each of these independently represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, an alkoxy group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 12 carbon atoms, an acyl group having 2 to 12 carbon atoms, a formyl group, a cyano group, a nitro group, an N-alkylamide group having 1 to 12 carbon atoms in the alkyl group, an N,N-dialkylamino group having 1 to 12 carbon atoms in the alkyl group, a maleimide group, an acryloylamino group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 12 carbon atoms in the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a halogen atom, L9, L 10 , L 11 , and, L 12 At least one of these represents a group other than a hydrogen atom or a methyl group. In particular, L9 and L offer superior effects compared to the present invention. 10 , L 11 , and, L 12 Each of these independently represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C2-C12 alkoxycarbonyl group, or a C2-C12 acyl group, L9, L 10 , L 11 , and, L 12 Preferably, at least one of them represents a group other than a hydrogen atom and a methyl group, and represents a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, L9, L 10 , L 11 , and, L 12 It is more preferable that at least one of them represents a group other than a hydrogen atom and a methyl group. In particular, L9, L 10 , and, L 11 is a hydrogen atom, L 12 It is even more preferable that the alkyl group has 2 to 12 carbon atoms. Furthermore, the number of carbon atoms in the alkyl group is preferably 2 to 10, more preferably 2 to 7, and even more preferably 3 to 4, in terms of achieving superior effects of the present invention. The number of carbon atoms in the above alkoxy group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2, in terms of achieving superior effects of the present invention. The number of carbon atoms in the above-mentioned alkoxycarbonyl group is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2, in terms of achieving superior effects of the present invention. The number of carbon atoms in the acyl group described above is preferably 1 to 8, more preferably 1 to 5, and even more preferably 1 to 2, in terms of achieving superior effects of the present invention.

[0049] The liquid crystal composition of the present invention may contain other compounds besides the polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) described above. Other compounds may include, for example, polymerizable liquid crystal compounds different from polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C). The polymerizable compound may also be a polymerizable liquid crystal compound. Other compounds include polymerization initiators. The polymerization initiator used is selected according to the type of polymerization reaction, and examples include thermal polymerization initiators and photopolymerization initiators. Other compounds include, for example, chiral agents, surfactants, adhesion improvers, vertical alignment agents, horizontal alignment agents, and crosslinking agents.

[0050] The liquid crystal composition of the present invention is preferably substantially solvent-free. "Substantially solvent-free" means that the solvent content relative to the total mass of the liquid crystal composition is 1% by mass or less. The lower limit is not particularly limited, but could be 0% by mass.

[0051] In the liquid crystal composition of the present invention, the content of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is not particularly limited, but in terms of achieving superior effects of the present invention, the total content of polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 50 to 95% by mass. Preferably, the total content of polymerizable compound (C) relative to the total amount is 5 to 50% by mass, the total content of polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 60 to 90% by mass, and more preferably, the total content of polymerizable compound (C) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 10 to 40% by mass. Furthermore, when the liquid crystal composition of the present invention contains compound 1, compound 2, and compound 3, it is preferable that the total content of compound 1 and compound 2 relative to the total amount of compound 1, compound 2, and compound 3 is 50 to 95% by mass, the total content of compound 3 relative to the total amount of compound 1, compound 2, and compound 3 is 5 to 50% by mass, it is more preferable that the total content of compound 1 and compound 2 relative to the total amount of compound 1, compound 2, and compound 3 is 60 to 90% by mass, and the total content of compound 3 relative to the total amount of compound 1, compound 2, and compound 3 is 10 to 40% by mass.

[0052] Furthermore, if the total content of polymerizable liquid crystal compound (C) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 5 to 50% by mass, the viscosity of the liquid crystal composition of the present invention can be increased compared to a liquid crystal composition containing polymerizable liquid crystal compound (A) alone. In particular, it is possible to suppress repellency defects that tend to occur when the cured film after curing the liquid crystal composition of the present invention is a layer in which a twisted-oriented liquid crystal phase is fixed. A "repulsion defect" refers to a defect that occurs when a liquid crystal composition is applied to a substrate, resulting in areas where the liquid crystal composition is repelled from the substrate, leaving uncoated areas within the cured film.

[0053] The mixing ratio of polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B) in the liquid crystal composition of the present invention is not particularly limited, but the content of polymerizable liquid crystal compound (A) relative to the total content of polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B) is preferably 50 to 97% by mass, and more preferably 70 to 95% by mass.

[0054] The total content of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) relative to the total mass of the liquid crystal composition of the present invention is preferably 60% by mass or more, and more preferably 70% by mass or more, in terms of superior effects of the present invention. There is no particular upper limit, and it is 100% by mass, but it is often 99% by mass or less.

[0055] When the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 20% by mass, and more preferably 0.5 to 10% by mass, based on the total mass of the liquid crystal composition.

[0056] In the liquid crystal composition, polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) may each be included individually or in combination of two or more types. Furthermore, if the liquid crystal composition contains two or more compounds that fall under both polymerizable liquid crystal compound (A) and polymerizable compound (C), at least one shall be polymerizable liquid crystal compound (A) and at least one shall be polymerizable compound (C).

[0057] The enthalpy of melting of the liquid crystal composition is not particularly limited, but it is preferably 35 mJ / mg or less, and more preferably 30 mJ / mg or less, in terms of achieving superior effects of the present invention. The lower limit of the enthalpy of melting is not particularly limited, but it is often 20 mJ / mg or more. The method for measuring the enthalpy of melting of a liquid crystal composition is as follows: First, a solution is prepared by mixing polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), polymerizable compound (C), polymerization inhibitor (Irganox 1010, manufactured by BASF Japan), and solvent (e.g., acetone) contained in the liquid crystal composition. The content ratio of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) in the solution is the same as the content ratio of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) in the liquid crystal composition. The content of the polymerization inhibitor in the solution is 1% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), polymerizable compound (C), and polymerization inhibitor. The content of the solvent in the solution is 88% by mass relative to the total mass of the solution. The obtained solution is dried under reduced pressure at 30°C for 2 hours to remove the solvent from the solution. The resulting solid sample is then heated from 25°C to 140°C at a rate of 5°C / min using a differential scanning calorimeter (Hitachi High-Tech Science X-DSC7000) and measured to calculate the enthalpy of fusion.

[0058] The method for manufacturing the liquid crystal composition is not particularly limited, and known methods can be employed.

[0059] <Cured film> The cured film of the present invention is a film obtained by curing the above-described liquid crystal composition. The method for forming the cured film described above is not particularly limited, but one method involves applying a liquid crystal composition to form a coating film, applying an orientation treatment to the coating film to orient the polymerizable liquid crystal compound, and then applying a curing treatment. The object to which the liquid crystal composition is coated is not particularly limited, and examples include the support described later and the polarizer described later. Furthermore, if the cured film is an optically anisotropic film, the object to which the liquid crystal composition is applied may be subjected to a rubbing treatment in order to align the in-plane slow axis of the optically anisotropic film to a predetermined direction. For example, a support that has been subjected to a rubbing treatment may be used.

[0060] Methods for applying liquid crystal compositions include curtain coating, dip coating, spin coating, print coating, spray coating, slot coating, roll coating, slide coating, blade coating, gravure coating, and wire bar coating.

[0061] Next, the formed coating film is subjected to an orientation treatment to orient the polymerizable liquid crystal compounds within the coating film. The polymerizable liquid crystal compounds in the coating film include at least polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B). If polymerizable compound (C) exhibits liquid crystalline properties, polymerizable compound (C) is also considered a polymerizable liquid crystal compound. Orientation treatment can be performed by drying the coating film at room temperature or by heating the coating film. The liquid crystal phase formed by the orientation treatment can generally be transitioned by changes in temperature or pressure. The conditions for heating the coating film are not particularly limited, but the heating temperature is preferably 50 to 250°C, more preferably 50 to 150°C, and the heating time is preferably 10 seconds to 10 minutes. Furthermore, after heating the coating film, it may be cooled as needed before the curing treatment (light irradiation treatment) described later. The cooling temperature is preferably 20 to 200°C, and more preferably 30 to 150°C. The type of liquid crystal phase formed in the above orientation process is not particularly limited and can be appropriately adjusted depending on the components contained in the liquid crystal composition. Examples of liquid crystal phases include nematic phase, smectic phase, and torsion-aligned liquid crystal phase. A torsion-oriented liquid crystal phase refers to a phase in which the liquid crystal compound is twisted and oriented along a helical axis extending in the thickness direction. The twist angle is not particularly limited; for example, a torsion-oriented liquid crystal phase may have a twist angle greater than 0° and less than or equal to 360°. A cholesteric liquid crystal phase is one type of torsion-oriented liquid crystal phase. In this specification, a cholesteric liquid crystal phase refers to a form in which the twist angle is greater than 360°.

[0062] Next, the coating film in which the polymerizable liquid crystal compound is oriented is subjected to a curing treatment. The curing treatment method applied to a coating film on which polymerizable liquid crystal compounds are oriented is not particularly limited and includes, for example, light irradiation treatment and heat treatment. Among these, light irradiation treatment is preferred from the viewpoint of manufacturability, and ultraviolet irradiation treatment is more preferred. There are no particular restrictions on the irradiation conditions for the light irradiation treatment, but 50-1000 mJ / cm² is recommended. 2 A certain irradiation dose is preferred. The atmosphere during the light irradiation treatment is not particularly limited, but a nitrogen atmosphere is preferred.

[0063] The cured film obtained by the method described above is a film in which a predetermined liquid crystal phase is fixed. The cured film may be, for example, a film in which a nematic phase is fixed, or a film in which a torsion-oriented liquid crystal phase is fixed. Furthermore, the cured film may have multiple regions along the thickness direction in which different orientation states of liquid crystal compounds are fixed. For example, the cured film may have regions along the thickness direction in which homogeneously oriented liquid crystal compounds are fixed and regions in which torsion-oriented liquid crystal compounds are fixed. Furthermore, the cured film may be an optically anisotropic film. An optically anisotropic film is a film having a predetermined in-plane retardation and / or retardation in the thickness direction. As an optically anisotropic film, it may be a so-called λ / 4 plate or λ / 2 plate, as it can be applied to a variety of uses. A λ / 4 plate is a plate that has the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). More specifically, it is a plate in which the in-plane retardation Re at a given wavelength λnm is λ / 4 (or an odd multiple thereof). The in-plane retardation (Re(550)) of the λ / 4 plate at a wavelength of 550 nm is centered around the ideal value (137.5 nm), with an error of about 25 nm acceptable. For example, it is preferably between 110 and 160 nm, and more preferably between 120 and 150 nm. Furthermore, a λ / 2 plate refers to an optically anisotropic film in which the in-plane retardation Re(λ) at a specific wavelength λnm satisfies Re(λ) ≈ λ / 2. This equation only needs to be achieved at any wavelength in the visible light region (for example, 550 nm). In particular, it is preferable that the in-plane retardation Re(550) at a wavelength of 550 nm satisfies the following relationship. 210nm ≤ Re(550) ≤ 300nm

[0064] The thickness of the cured film is not particularly limited, and the optimal thickness is selected as appropriate depending on the application. However, from the standpoint of ease of handling, 0.05 to 10 μm is preferred, and 0.1 to 8.0 μm is more preferred.

[0065] <Optical film> The optical film of the present invention comprises a support and a cured film disposed on the support. The characteristics of the cured film are as described above.

[0066] A transparent support is preferred as the support material. A transparent support refers to a support material with a visible light transmittance of 60% or more, preferably 80% or more, and more preferably 90% or more.

[0067] The support may be a long, rectangular support (long support). While the length of the long support in the longitudinal direction is not particularly limited, supports of 10m or more are preferred, and from a productivity standpoint, 100m or more is preferred. However, the length in the longitudinal direction is not particularly limited and is often 10,000m or less. The width of the long support structure is not particularly limited, but it is often between 150 and 3000 mm, and preferably between 300 and 2000 mm.

[0068] As the material for forming the support, a polymer with excellent optical performance, transparency, mechanical strength, thermal stability, moisture shielding properties, and isotropy is preferred. Examples of polymer films that can be used as supports include cellulose acylate films (e.g., cellulose triacetate film, cellulose diacetate film, cellulose acetate butyrate film, and cellulose acetate propionate film), polyolefin films such as polyethylene and polypropylene, polyester films such as polyethylene terephthalate and polyethylene naphthalate, polyacrylic films such as polymethyl methacrylate, polyethersulfone films, polyurethane films, polycarbonate films, polysulfone films, polyether films, polymethylpentene films, polyetherketone films, (meth)acrylonitrile films, and films of polymers having an alicyclic structure (norbornene-based resins (Arton: trade name, manufactured by JSR Corporation, amorphous polyolefins (Zeonex: trade name, manufactured by Nippon Zeon Co., Ltd.))). Among these, triacetylcellulose, polyethylene terephthalate, or polymers having an alicyclic structure are preferred as materials for the polymer film.

[0069] The support may contain various additives (e.g., optical anisotropy modifiers, wavelength dispersion modifiers, fine particles, plasticizers, UV inhibitors, degradation inhibitors, and release agents).

[0070] The retardation value in the thickness direction of the support at a wavelength of 550 nm (Rth(550)) is not particularly limited, but -110 to 110 nm is preferred, and -80 to 80 nm is more preferred. The in-plane retardation value (Re(550)) of the support at a wavelength of 550 nm is not particularly limited, but is preferably 0 to 50 nm, more preferably 0 to 30 nm, and even more preferably 0 to 10 nm.

[0071] The thickness of the support is not particularly limited, but is preferably 10 to 200 μm, more preferably 10 to 100 μm, and even more preferably 20 to 90 μm. Furthermore, the support may consist of multiple layers stacked together. To improve adhesion between the support and the layer provided thereon, the surface of the support may be subjected to surface treatment (e.g., glow discharge treatment, corona discharge treatment, ultraviolet (UV) treatment, and flame treatment). Alternatively, an adhesive layer (primer layer) may be provided on the support. The support may be a so-called temporary support, or it may be a peelable support.

[0072] Alternatively, a rubbing treatment may be applied directly to the surface of the support. In other words, a support that has been rubbed may be used. The direction of the rubbing treatment is not particularly limited, and the optimal direction can be appropriately selected depending on the direction in which the liquid crystal compound is to be oriented. The rubbing process can be applied to a treatment method widely used as a liquid crystal alignment process for LCDs (liquid crystal displays). Specifically, a method can be used in which the surface of a support is rubbed in a certain direction using paper, gauze, felt, rubber, nylon fibers, or polyester fibers to obtain alignment.

[0073] In optical films, other components besides the support and cured film may be included. For example, an optical film may have an orientation film between the support and the cured film. The oriented film can be formed by means such as rubbing of an organic compound (preferably a polymer), oblique deposition of an inorganic compound, formation of a layer having microgrooves, or accumulation of an organic compound (e.g., ω-tricosanoic acid, dioctadecylmethylammonium chloride, methyl stearylate) by the Langmuir-Bludget method (LB film). Furthermore, orientation films are known in which orientation functions are generated by the application of an electric field, a magnetic field, or light irradiation (preferably polarized light).

[0074] Furthermore, the optical film may have an adhesive layer or a tack layer. Examples of adhesives that constitute the adhesive layer include well-known adhesives. Examples of adhesives that constitute the adhesive layer include well-known adhesives.

[0075] <Application> The cured film and optical film of the present invention can be applied to a variety of uses. For example, the cured film or optical film of the present invention may be combined with a polarizer to form a polarizing plate. A circular polarizing plate is preferred as the polarizing plate.

[0076] Furthermore, the cured film, optical film, or polarizing plate of the present invention may be included in a display device. For example, a more specific application of the cured film and optical film of the present invention is an optical compensation film for optically compensating liquid crystal cells, and a more specific application of the polarizing plate of the present invention is an anti-reflective film used in display devices such as organic electroluminescent display devices. In particular, a preferred embodiment is a circular polarizer comprising a cured film which is an optically anisotropic film and a polarizer. This circular polarizer can be suitably used as the anti-reflective film. In other words, in a display device having a display element (for example, an organic electroluminescent display element) and a circular polarizer disposed on the display element, the reflective color can be further suppressed. A polarizer can be any component that has the function of converting light into a specific linear polarization (linear polarizer), and mainly absorbing polarizers can be used. Absorption polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based and dye-based polarizers include coated polarizers and stretched polarizers, both of which are applicable, but polarizers made by adsorbing iodine or a dichroic dye onto polyvinyl alcohol and then stretching it are preferred. The relationship between the absorption axis of the polarizer and the slow axis of the hardened film, which is an optically anisotropic film, is not particularly limited. However, when the optically anisotropic film (hardened film) is a λ / 4 plate and the optical film is used as a circularly polarizing film, the angle between the absorption axis of the polarizer and the slow axis of the optically anisotropic film (hardened film) is preferably 45°±10°. The cured film may also be used as an optical laminate in combination with other optically anisotropic films. The optical laminate containing the cured film of the present invention may also be used as a circularly polarized film in combination with a polarizer, in which case an optimal angular relationship is appropriately selected between the slow axis of each layer in the optical laminate and the absorption axis of the polarizer. Furthermore, as described above, if the cured film has regions along its thickness direction in which the orientation states of different liquid crystal compounds are fixed, such a cured film and a polarizer may be combined and used as a circularly polarized film. In this case, an optimal angular relationship is appropriately selected between the slow axis of each region in the cured film and the absorption axis of the polarizer.

[0077] Furthermore, the cured film of the present invention is suitably used as an optical compensation film for liquid crystal display devices, such as IPS (In-Plane Switching) type liquid crystal display devices, and can improve color changes when viewed from an oblique direction and light leakage when displaying black. [Examples]

[0078] The features of the present invention will be further described below with reference to examples and comparative examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the following examples can be modified as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be interpreted restrictively by the specific examples shown below.

[0079] <Example 1> Solution 1 was prepared by mixing the following compounds. Polymerizable liquid crystal compound (1-1) 74 parts by mass Polymerizable liquid crystal compound (2-1) 11 parts by mass Polymerizable compound (3-1) 15 parts by mass Methyl isobutyl ketone 117 parts by mass 39 parts by mass of ethyl propionate

[0080] Polymerizable liquid crystal compounds (1-1) (see chemical formula below) (corresponds to compounds represented by formula (1). Transition temperature from liquid crystal phase to isotropic phase: 123°C)

[0081] [ka]

[0082] Polymerizable liquid crystal compounds (2-1) (see chemical formula below) (corresponds to compounds represented by formula (2). Transition temperature from liquid crystal phase to isotropic phase: 236°C)

[0083] [ka]

[0084] Polymerizable compound (3-1) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 107°C). Note that Me represents a methyl group. Note that polymerizable compound (3-1) does not exhibit liquid crystalline properties, and the above melting point refers to the transition temperature from the solid state to the liquid state.

[0085] [ka]

[0086] <Examples 2-10, Comparative Examples 1-4> Solutions 2-10 and solutions C1-C4 were prepared in the same manner as in Example 1, except that the compounds and their compositional ratios were changed as shown in Table 1. The compounds used in Table 1 are as follows:

[0087] Polymerizable liquid crystal compounds (2-2) (see chemical formula below) (corresponds to compounds represented by formula (2). Transition temperature from liquid crystal phase to isotropic phase: 300°C)

[0088] [ka]

[0089] Polymerizable compound (3-2) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 91°C). Note that polymerizable compound (3-2) exhibits liquid crystalline properties, and the above melting point represents the transition temperature from the liquid crystalline phase to the isotropic phase.

[0090] [ka]

[0091] Polymerizable compound (3-3) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 87°C) Note that polymerizable compound (3-3) exhibits liquid crystalline properties, and the above melting point represents the transition temperature from the liquid crystal phase to the isotropic phase.

[0092] [ka]

[0093] Polymerizable compounds (3-4) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 100°C). Note that polymerizable compounds (3-4) do not exhibit liquid crystalline properties, and the above melting point refers to the transition temperature from the solid state to the liquid state.

[0094] [ka]

[0095] Polymerizable compounds (3-5) (see chemical formula below) (corresponds to compounds represented by formula (3). Melting point: 78°C). Note that polymerizable compounds (3-5) do not exhibit liquid crystalline properties, and the above melting point refers to the transition temperature from the solid state to the liquid state.

[0096] [ka]

[0097] Polymerizable compound (3-6) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 66°C). Note that polymerizable compound (3-6) does not exhibit liquid crystalline properties, and the above melting point represents the transition temperature from the solid state to the liquid state.

[0098] [ka]

[0099] Polymerizable compound (3-7) (see chemical formula below) (corresponds to the compound represented by formula (3). Melting point: 107°C). Note that polymerizable compound (3-7) does not exhibit liquid crystalline properties, and the above melting point refers to the transition temperature from the solid state to the liquid state.

[0100] [ka]

[0101] The polymerizable liquid crystal compounds used in the examples, as well as the transition temperatures from the liquid crystal phase to the isotropic phase and from the solid state to the liquid state of the polymerizable compounds, were determined by the identification method described above.

[0102] <Rating> (Transition temperature test) The solutions prepared in each example and comparative example were coated onto a rubbing-treated tack film using a bar, and the solvent was evaporated to prepare observation samples containing the liquid crystal composition. Two polarizers of an optical microscope (Nikon ECLIPSE E600 POL) were positioned orthogonally to each other, and a sample stage was set between the two polarizers. The prepared observation samples were then placed on a hot stage on the sample stage. While observing the state of the sample with a microscope, the temperature was increased at 20°C / min, and the transition temperature (Iso point) from the liquid crystal phase to the isotropic phase of the liquid crystal composition was measured. The obtained transition temperatures were evaluated according to the following criteria. The results are summarized in Table 1. A: Transition temperature is 110°C or higher B: Transition temperature is between 100°C and 110°C C: Transition temperature is between 95°C and 100°C D: Transition temperature less than 95°C

[0103] (Precipitation test) A stainless steel plate (SUS304, 2cm x 2cm) was immersed in the solution prepared in each example and comparative example for 30 seconds. After removing it with tweezers, it was dried at room temperature for 5 minutes. The above procedure was repeated 5 times, and the increase in weight from the stainless steel plate before the test was defined as the amount of precipitate (g). In solutions where crystals are easily formed, crystals easily precipitate on the stainless steel plate, resulting in a larger increase in weight compared to the stainless steel plate before the test. The amount of precipitate obtained was evaluated according to the following criteria. The results are summarized in Table 1. A: Precipitation amount is 0.012g or less B: Precipitation amount greater than 0.012g and less than or equal to 0.020g C: Precipitation amount greater than 0.020g and less than 0.025g D: Precipitation amount is 0.025g or more

[0104] (Measuring enthalpy of fusion) A solution for preparing measurement samples was prepared by mixing the polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) contained in the solutions prepared in each example and comparative example with a polymerization inhibitor (Irganox 1010, manufactured by BASF Japan) and acetone. The content ratio of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) in the solution for preparing measurement samples was the same as the content ratio of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) in the solutions of each example and comparative example. The content of the polymerization inhibitor in the solution for preparing measurement samples was 1% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), polymerizable compound (C), and polymerization inhibitor. The solvent content in the solution for preparing measurement samples was 88% by mass relative to the total mass of the solution. The obtained sample preparation solution was dried under reduced pressure at 30°C for 2 hours to remove the acetone from the sample preparation solution. The resulting solid sample was then heated from 25°C to 140°C at a rate of 5°C / min using a differential scanning calorimeter (Hitachi High-Tech Science X-DSC7000) and measured to calculate the enthalpy of fusion. The results are summarized in Table 1.

[0105] In Table 1, the "Transition Temperature (°C)" column under "Polymerizable Liquid Crystal Compound (B)" represents the transition temperature (°C) from the liquid crystal phase to the isotropic phase of polymerizable liquid crystal compound (B). In Table 1, the "Melting Point (°C)" column in the "Polymerizable Compound (C)" column represents the melting point (°C) of polymerizable compound (C). However, this "melting point" represents the transition temperature (°C) from the liquid crystal phase to the isotropic phase if polymerizable compound (C) exhibits liquid crystalline properties, and the transition temperature (°C) from the solid state to the liquid state if polymerizable compound (C) does not exhibit liquid crystalline properties. In Table 1, the "Functional group type" column in the "Polymerizable compound (C)" column refers to L9, L in formula (3). 10 , L 11 , and, L 12 This represents the type of functional group other than a hydrogen atom that falls under any of the following categories. In Table 1, the "Number of Functional Groups" column in the "Polymerizable Compound (C)" column refers to L9, L in formula (3). 10 , L 11 , and, L 12 This represents the number of functional groups other than hydrogen atoms that fall under any of the following categories. In Table 1, in the "Mass Ratio (A / B / C)" column, the value for A represents the percentage (mass%) of polymerizable liquid crystal compound (A) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C); the value for B represents the percentage (mass%) of polymerizable liquid crystal compound (B) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C); and the value for C represents the percentage (mass%) of polymerizable compound (C) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C). However, in Comparative Example 2, the content of polymerizable liquid crystal compound (2-1) was 14.7% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C), and the content of polymerizable liquid crystal compound (2-2) was 2.0% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C). Furthermore, in Example 10, the content of polymerizable liquid crystal compound (2-1) was 11.9% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C), and the content of polymerizable liquid crystal compound (2-2) was 1.7% by mass relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C). In Table 1, the "Transition Temperature Test" column shows the results of the transition temperature test described above, and the number in parentheses represents the transition temperature (°C) from the liquid crystal phase to the isotropic phase of the liquid crystal composition. In Table 1, the "Precipitation Test" column shows the results of the precipitation test described above, and the number in parentheses represents the amount of precipitate (g).

[0106] [Table 1]

[0107] As shown in Table 1 above, it was confirmed that the desired effect can be obtained with the liquid crystal composition of the present invention. The embodiment of Comparative Example 2 corresponds to the embodiment (Example 84) specifically disclosed in Patent Document 1. From a comparison of Examples 1 to 4, L9 and L in formula (3) 10 , L 11 , and, L 12 It was confirmed that a superior effect is obtained when the functional group other than the hydrogen atom corresponding to any of the above is an alkyl group. From a comparison of Examples 4 and 5, L9 and L in formula (3) 10 , L 11 , and, L 12 It was confirmed that a better effect can be obtained when the number of carbon atoms in the alkyl group other than the hydrogen atom that falls under any of the following categories is 7 or less. A comparison of Examples 6 and 7 with other examples confirmed that a superior effect can be obtained when there is only one substituent. From a comparison of Examples 4, 8, and 9, it was confirmed that a superior effect is obtained when the total content of polymerizable liquid crystal compound (A) and polymerizable liquid crystal compound (B) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 50-90% by mass, and when the content of polymerizable compound (C) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 10-50% by mass.

[0108] Furthermore, when the solution 1 obtained in Example 1 was mixed with the following example compounds (ethylene oxide-modified trimethylolpropane triacrylate, photopolymerization initiator, left-hand chiral agent (L), right-hand chiral agent (R), polymer (A), polymer (B)), and evaluated in the same manner as in Example 1 (transition temperature test, precipitation test), similar results were obtained. Furthermore, when the compounds exemplified below were further mixed with the solutions 2 to 10 obtained in Examples 2 to 10, similar results to those obtained in each example were obtained. The solution obtained by further mixing the following exemplary compounds with solution 10 obtained in Example 10 is referred to as solution 10A.

[0109] Ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 4 parts by mass Photopolymerization initiator (Irgacure 819, manufactured by BASF) 3 parts by mass Left-handed chiral agent (L) 0.45 parts by mass Right-handed chiral agent (R) 0.40 parts by mass Polymer (A) 0.08 parts by mass Polymer (B) 0.50 parts by mass

[0110] Left-handed chiral agent (L) (see chemical formula below)

[0111] [ka]

[0112] Right-handed chiral agent (R) (see chemical formula below)

[0113] [ka]

[0114] Polymer A (see chemical formula below)

[0115] [ka]

[0116] Polymer B (see chemical formula below)

[0117] [ka]

[0118] <Example 11> The components listed below (Cellulose Acylate Dope) were added to a mixing tank, stirred, and then heated at 90°C for 10 minutes. The resulting composition was then filtered through filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm to prepare the dope. The solid content concentration of the dope was 23.5% by mass, the amount of plasticizer added was a ratio to the cellulose acylate, and the solvent of the dope was methylene chloride / methanol / butanol = 81 / 18 / 1 (by mass ratio).

[0119] (Cellulose acylate doped) Cellulose acylate (acetyl substitution degree 2.86, viscosity-average degree of polymerization 310) 100 parts by mass Sugar ester compound 1 (shown by chemical formula (S4)) 6.0 parts by mass Sugar ester compound 2 (shown by chemical formula (S5)) 2.0 parts by mass Silica particle dispersion (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 0.1 parts by mass Solvents (methylene chloride / methanol / butanol)

[0120] [ka]

[0121] [ka]

[0122] The dope prepared above was cast using a drum film-making machine. The dope was cast from the die so that it was in contact with a metal support cooled to 0°C, and then the resulting web (film) was peeled off. The drum was made of stainless steel (SUS). After peeling the cast web (film) from the drum, it was dried for 20 minutes in a tenter device at 30-40°C during film transport, using a tenter device that clipped both ends of the web with clips during transport. Subsequently, the web was post-dried by zone heating while being transported on a roll. The resulting web was knurled and then wound up. The thickness of the resulting cellulose acylate film was 40 μm, the in-plane retardation Re(550) at a wavelength of 550 nm was 1 nm, and the thickness-direction retardation Rth(550) at a wavelength of 550 nm was 26 nm.

[0123] The cellulose acylate film prepared as described above was subjected to a continuous rubbing process. At this time, the longitudinal direction of the long film and the transport direction were parallel, and the angle between the longitudinal direction of the film (transport direction) and the rotation axis of the rubbing roller was set to 80°. If the longitudinal direction of the film (transport direction) is set to 90°, and when observed from the film side, with the film width direction as the reference (0°) and clockwise rotation represented as a positive value, the rotation axis of the rubbing roller is at 10°. In other words, the position of the rotation axis of the rubbing roller is the position obtained by rotating 80° counterclockwise with respect to the longitudinal direction of the film. Using the cellulose acylate film that underwent the above rubbing process as a substrate, the solution 10A prepared as described above was applied using a Gieser coating machine to form a composition layer. Next, the obtained composition layer was heated at 80°C for 60 seconds. Subsequently, under oxygen-containing air (oxygen concentration: approximately 20 vol%) at 30°C, ultraviolet light was irradiated onto the composition layer using a 365 nm LED lamp (manufactured by Acroedge Co., Ltd.) (irradiation dose: 35 mJ / cm²). 2 Next, the resulting composition layer was heated at 80°C for 10 seconds. After that, nitrogen purging was performed to adjust the oxygen concentration to 100 ppm by volume, and ultraviolet light was irradiated onto the composition layer at 80°C using a metal halide lamp (manufactured by iGraphics Co., Ltd.) (irradiation dose: 500 mJ / cm²). 2 An optically anisotropic film was formed in which the orientation state of the liquid crystal compound was fixed. In this way, an optical film was fabricated in which the optically anisotropic film was arranged on a cellulose acylate film, which served as a support. The resulting optically anisotropic film had a second region on the support side in which homogeneously oriented liquid crystal compounds were fixed, and a first region in which torsionally oriented liquid crystal compounds were fixed.

[0124] A polyvinyl alcohol (PVA) film with a thickness of 80 μm was stained by immersion in an iodine aqueous solution with an iodine concentration of 0.05 mass% at 30°C for 60 seconds. Next, the obtained film was stretched longitudinally to five times its original length while immersed in a boric acid aqueous solution with a boric acid concentration of 4 mass% for 60 seconds, and then dried at 50°C for 4 minutes to obtain a polarizer with a thickness of 20 μm.

[0125] A commercially available cellulose acylate film, Fujitac TG40UL (manufactured by Fujifilm Corporation), was prepared and immersed in a 1.5 mol / liter sodium hydroxide aqueous solution at 55°C. After that, the sodium hydroxide was thoroughly rinsed off with water. Subsequently, the resulting film was immersed in a 0.005 mol / liter dilute sulfuric acid aqueous solution at 35°C for 1 minute, and then immersed in water to thoroughly rinse off the dilute sulfuric acid solution. Finally, the resulting film was thoroughly dried at 120°C to produce a polarizer protective film with a saponified surface.

[0126] Similar to the preparation of the polarizer protective film described above, the optical film prepared above was saponified, and the polarizer and the polarizer protective film described above were continuously bonded to the support surface contained in the optical film using a polyvinyl alcohol-based adhesive to produce a long circular polarizer. In other words, the circular polarizer had the polarizer protective film, polarizer, support, and optical anisotropy film in this order. The absorption axis of the polarizer coincided with the longitudinal direction of the circular polarizer, the rotation angle of the in-plane slow axis of the second region with respect to the absorption axis of the polarizer was 10°, and the rotation angle of the in-plane slow axis of the surface of the first region opposite to the second region with respect to the absorption axis of the polarizer was 85°.

[0127] <Example 12> (Fabrication of cellulose acylate film (substrate)) A cellulose acylate film was prepared following the same procedure as in Example 11.

[0128] (Laminate formation of optically anisotropic layer (C) and optically anisotropic layer (B)) (Formation of optically anisotropic layer (1c)) On the cellulose acylate film prepared above, an optically anisotropic layer coating solution (1c) containing a rod-shaped liquid crystal compound of the following composition was applied using a Gieser coating machine to form a composition layer. Then, holding both ends of the film, a cooling plate (9°C) was placed on the side of the film where the coating was formed, at a distance of 5 mm from the film, and a heater (75°C) was placed on the opposite side of the film where the coating was formed, at a distance of 5 mm from the film, and the film was dried for 2 minutes. Next, the sample is heated with hot air at 60°C for 1 minute, and then, while purging with nitrogen to maintain an atmosphere with an oxygen concentration of 100 ppm by volume, a 365 nm UV-LED is used to irradiate it at a dose of 100 mJ / cm². 2 The material was irradiated with ultraviolet light. Subsequently, an optically anisotropic layer (1c) was formed by annealing with hot air at 120°C for 1 minute. The resulting optically anisotropic layer (1c) was exposed to UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) at room temperature, through a wire grid polarizer, at a rate of 7.9 mJ / cm². 2 By irradiating with a wavelength of 313 nm, an optically anisotropic layer (1c) with orientation control capability was formed on the surface. The thickness of the formed optically anisotropic layer (1c) was 0.5 μm. The in-plane retardation Re at a wavelength of 550 nm was 0 nm, and the retardation Rth in the thickness direction at a wavelength of 550 nm was -68 nm. The average tilt angle of the rod-shaped liquid crystal compound with respect to the film surface in the direction of the long axis was 90°, confirming that it was oriented perpendicular to the film surface.

[0129] ------------------------------------------------------------------ Composition for forming optically anisotropic layer (1c) ------------------------------------------------------------------ Polymerizable liquid crystal compound (1-1) 84 parts by mass Polymerizable liquid crystal compound (2-1) 14 parts by mass Polymerizable liquid crystal compound (2-2) 2 parts by mass Polymerizable compound (3-4) 30 parts by mass Polymerizable monomer (A-400, manufactured by Shin-Nakamura Chemical Industry Co., Ltd.) 4.0 parts by mass 5.0 parts by mass of the polymerization initiator S-1 (oxime type) listed below The following photoacid generator D-1: 3.0 parts by mass The following polymer M-1: 2.0 parts by mass The following vertical alignment agent S01: 2.0 parts by mass The following photo-oriented polymer A-1: ​​2.0 parts by mass Methyl ethyl ketone 42.3 parts by mass Methyl isobutyl ketone 627.5 parts by mass ------------------------------------------------------------------

[0130] Polymerization initiator S-1

[0131] [ka]

[0132] Photoacid Generator D-1

[0133] [ka]

[0134] Polymer M-1

[0135] [ka]

[0136] Vertical alignment agent S01

[0137] [ka]

[0138] Photo-oriented polymer A-1 (The numerical values ​​indicated within each repeating unit represent the content (mass%) of each repeating unit relative to the total number of repeating units. From left to right, the content was 43% by mass, 27% by mass, and 30% by mass. The weight-average molecular weight was 69800.) Polymer A-1, described below, was synthesized by changing the composition ratio using the method described in Example 1 of Japanese Patent Application No. 2020-128049.

[0139] [ka]

[0140] (Formation of optically anisotropic layer (1b)) Next, an optically anisotropic layer coating solution (1b) containing a rod-shaped liquid crystal compound of the following composition was applied to the optically anisotropic layer (1c) prepared above using a Gieser coating machine, and heated with 80°C hot air for 60 seconds. Subsequently, the resulting composition layer was irradiated with UV light (500 mJ / cm²) at 80°C. 2 The orientation of the liquid crystal compound was fixed by performing the following procedure, and an optically anisotropic layer (1b) was formed. The optically anisotropic layer (1b) had a thickness of 1.5 μm, Δnd at a wavelength of 550 nm was 164 nm, and the twist angle of the liquid crystal compound was -81°. When the width direction of the film was set to 0° (the longitudinal direction to 90°), the orientation axis angle of the liquid crystal compound, when viewed from the optically anisotropic layer (1b) side, was -14° on the air side and -95° on the side in contact with the optically anisotropic layer (1c). The orientation axis angle of the liquid crystal compound contained in the optical anisotropic layer is expressed by observing the substrate from the surface side of the optical anisotropic layer, with the substrate width direction set to 0° as the reference, and clockwise (rightward) rotation being negative and counterclockwise (leftward) rotation being positive. Furthermore, the twist angle of the liquid crystal compound is expressed by observing the substrate from the surface side of the optical anisotropy layer, with the orientation axis direction of the liquid crystal compound on the surface side (front side) as the reference, and a clockwise (rightward) orientation axis direction of the liquid crystal compound on the substrate side (back side) being considered negative, and a counterclockwise (leftward) orientation being considered positive.

[0141] ------------------------------------------------------------------ Composition for forming an optically anisotropic layer (1b) ------------------------------------------------------------------ Polymerizable liquid crystal compound (1-1) 59 parts by mass Polymerizable liquid crystal compound (2-1) 10 parts by mass Polymerizable liquid crystal compound (2-2) 1 part by mass Polymerizable compound (3-4) 30 parts by mass Ethylene oxide-modified trimethylolpropane triacrylate (V#360, manufactured by Osaka Organic Chemical Co., Ltd.) 4 parts by mass Photopolymerization initiator (Irgacure 819, manufactured by BASF) 3 parts by mass 0.60 parts by mass of the above left-handed chiral agent (L) 0.2 parts by mass of the following fluorine-containing compound D Methyl isobutyl ketone 156 parts by mass ------------------------------------------------------------------

[0142] Fluorine-containing compound D (The numerical values ​​within each repeating unit represent the content (mass%) relative to the total number of repeating units; the content of the repeating unit on the left was 76 mass%, and the content of the repeating unit on the right was 24 mass.)

[0143] [ka]

[0144] Following the procedure described above, a laminate (1c-1b) was fabricated in which an optically anisotropic layer (1c) and an optically anisotropic layer (1b) were directly laminated onto a long cellulose acylate film.

[0145] <Example 13> Laminates (1c-2b) were prepared in the same manner as in Example 12, except that the composition ratios of polymerizable liquid crystal compounds (1-1), polymerizable liquid crystal compounds (2-1), polymerizable liquid crystal compounds (2-2), and polymerizable compound (3-4) in the optical anisotropic layer forming composition (1b) were changed as shown in Table 2.

[0146] <Rating> (Removal defect) The above laminates (1c-1b) and (1c-2b) were cut to a size of 20 cm x 20 cm and placed in a light box with polarizing plates set up in crossed nicols. The number of repellent defects in the optically anisotropic layers (1b) and (2b), which were located on the opposite side from the cellulose acylate film, was counted by visual inspection. Repellent defects were defined as defects that appeared to be circular or elliptical. The evaluation of repellent defects was as follows: 5 or more repellent defects resulted in a C rating, 1 to 4 repellent defects resulted in a B rating, and no repellent defects resulted in an A rating. The results are summarized in Table 2.

[0147] In Table 2, the column "(1-1)+(2-1)+(2-2)" represents the ratio (mass%) of the total amount of polymerizable liquid crystal compound (1-1), polymerizable liquid crystal compound (2-1), polymerizable liquid crystal compound (2-2), and polymerizable compound (3-4) to the total amount of polymerizable liquid crystal compound (1-1), polymerizable liquid crystal compound (2-1), polymerizable liquid crystal compound (2-2), and polymerizable compound (3-4). The column "(3-4)" represents the ratio (mass%) of polymerizable compound (3-4) to the total amount of polymerizable liquid crystal compound (1-1), polymerizable liquid crystal compound (2-1), polymerizable liquid crystal compound (2-2), and polymerizable compound (3-4). The composition ratios of polymerizable liquid crystal compound (1-1), polymerizable liquid crystal compound (2-1), and polymerizable liquid crystal compound (2-2) were 84 / 14 / 2 in both Examples 12 and 13.

[0148] [Table 2]

[0149] The results in Table 2 show that when the total content of polymerizable liquid crystal compound (C) relative to the total amount of polymerizable liquid crystal compound (A), polymerizable liquid crystal compound (B), and polymerizable compound (C) is 5-50% by mass, repellent defects are further suppressed.

Claims

1. A polymerizable liquid crystal compound (A) having three ring structures along the long axis of the molecule, A polymerizable liquid crystal compound (B) having four or more ring structures along the long axis of the molecule and a transition temperature from the liquid crystal phase to the isotropic phase of 150°C or higher, A liquid crystal composition comprising a polymerizable compound (C) which is different from the polymerizable liquid crystal compound (A), having three ring structures in the direction of the long axis of the molecule and having a melting point of 65 to 120°C, The enthalpy of fusion is 35 mJ / mg or less. The polymerizable liquid crystal compound (A) is a compound represented by formula (1), The polymerizable liquid crystal compound (B) has a transition temperature from the liquid crystal phase to the isotropic phase of 150°C or higher, and is a compound represented by formula (2). A liquid crystal composition in which the polymerizable compound (C) has a melting point of 65 to 120°C and is a compound represented by formula (3). 【Chemistry 1】 In formula (1), R1 represents a hydrogen atom or a methyl group; A1 represents an alkylene group having 2 to 18 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- in the alkylene group may be substituted with -O-; Z1 and Z2 independently represent -COO-, -O-, or a single bond; X1 represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group with 1 to 4 carbon atoms in the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a group represented by formula (1A); L1, L2, L3, and L4 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, and at least one of L1, L2, L3, and L4 represents a group other than a hydrogen atom. Formula (1A) *-A 2 -P 1 In formula (1A), A2 represents an alkylene group having 2 to 18 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- in the alkylene group may be substituted with -O-; P1 represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group; * indicates the joining position. 【Chemistry 2】 In formula (2), R 2 represents a hydrogen atom or a methyl group; A3 represents an alkylene group having 2 to 18 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- in the alkylene group may be substituted with -O-; Z3, Z4, Z5, and Z6 each independently represent a -COO-, -O-, or single bond; Q1 and Q2 each independently represent an aromatic or alicyclic group which may have substituents having 1 to 12 carbon atoms; X2 represents a hydrogen atom, a halogen atom, a linear alkyl group having 1 to 4 carbon atoms, a methoxy group, an ethoxy group, an optionally substituted aromatic ring group, a cyclohexyl group, a vinyl group, a formyl group, a nitro group, a cyano group, an acetyl group, an acetoxy group, an N-acetylamide group, an acryloylamino group, an N,N-dimethylamino group, a maleimide group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group having 1 to 4 carbon atoms in the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a group represented by the following formula (2A); L5, L6, L7, and L8 each independently represent a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, and at least one of L5, L6, L7, and L8 represents a group other than a hydrogen atom; x and y each independently represent 0, 1, or 2, and at least one of x and y represents 1 or 2. Formula (2A) *-A 4 -P 2 In formula (2A), A4 represents an alkylene group having 2 to 18 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- in the alkylene group may be substituted with -O-; P2 represents a hydrogen atom, an acryloyloxy group, or a methacryloyloxy group; * indicates the joining position. 【Transformation 3】 In formula (3), R3 and R6 represent a hydrogen atom or a methyl group; A5 and A6 each independently represent an alkylene group having 2 to 18 carbon atoms, and one -CH2- or two or more non-adjacent -CH2- in the alkylene group may be substituted with -O-; Z7 and Z8 independently represent -COO-, -O-, or a single bond; L9, L10, L11, and L12 each independently represent a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C2-C12 alkoxycarbonyl group, a C2-C12 acyl group, a formyl group, a cyano group, a nitro group, an N-alkylamide group with 1-C12 C1 of the alkyl group, an N,N-dialkylamino group with 1-C12 C1 of the alkyl group, a maleimide group, an acryloylamino group, a methacryloylamino group, an allyloxy group, an allyloxycarbamoyl group, an N-alkyloxycarbamoyl group with 1-C12 C1 of the alkyl group, an N-(2-methacryloyloxyethyl)carbamoyloxy group, an N-(2-acryloyloxyethyl)carbamoyloxy group, or a halogen atom. At least one of these represents a group other than a hydrogen atom or a methyl group.

2. In formula (3), L ９ , L １０ , L １１ , and, L １２ Each of these independently represents a hydrogen atom, a C1-C12 alkyl group, a C1-C12 alkoxy group, a C2-C12 alkoxycarbonyl group, or a C2-C12 acyl group, L ９ , L １０ , L １１ , and, L １２ The liquid crystal composition according to claim 1, wherein at least one of the groups represents a group other than a hydrogen atom and a methyl group.

3. In formula (3), L ９ , L １０ , L １１ , and L １２ each independently represent a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and L ９ , L １０ , L １１ , and L １２ at least one of which represents a group other than a hydrogen atom and a methyl group. The liquid crystal composition according to claim 1 or 2.

4. The liquid crystal composition according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound (A) is a compound represented by formula (1-1). 【Chemistry 4】 In formula (1-1), R １ and R ４ represents a hydrogen atom or a methyl group; A １ and A ２ Each of these independently represents an alkylene group having 2 to 18 carbon atoms, and one of the -CH groups in the alkylene group ２ - or two or more non-adjacent - CH ２ The hyphen may be replaced by -O-; Z １ and Z ２ These independently represent -COO-, -O-, or a single bond; L １ , L ２ , L ３ , and, L ４ Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, L １ , L ２ , L ３ , and, L ４ At least one of them represents a group other than a hydrogen atom.

5. In formula (1-1), L １ , L ２ , L ３ , and, L ４ Each of these independently represents either a hydrogen atom or a methyl group, L １ , L ２ , L ３ , and, L ４ The liquid crystal composition according to claim 4, wherein at least one of them represents a methyl group.

6. In formula (2), Q １ and Q ２ Each of these independently represents an aromatic ring which may have substituents having 1 to 12 carbon atoms; X ２ represents the base expressed by formula (2B); The liquid crystal composition according to any one of claims 1 to 5, wherein x and y each independently represent 0 or 1, and x + y is 1 or 2. 【Transformation 5】 In formula (2B), R ５ represents a hydrogen atom or a methyl group; A ４ This represents an alkylene group having 2 to 18 carbon atoms, and one of the alkylene groups is -CH ２ - or two or more non-adjacent - CH ２ The dash may be replaced by -O-. * indicates the joining position.

7. The liquid crystal composition according to any one of claims 1 to 6, wherein the polymerizable liquid crystal compound (B) comprises at least one compound selected from the group consisting of compounds represented by formula (2-1) and compounds represented by formula (2-2). 【Transformation 6】 In equations (2-1) and (2-2), R ２ and R ５ Each of these independently represents either a hydrogen atom or a methyl group; A ３ and A ４ Each of these independently represents an alkylene group having 2 to 18 carbon atoms, and one of the -CH groups in the alkylene group ２ - or two or more non-adjacent - CH ２ The hyphen may be replaced by -O-; Z ４ and Z ５ These independently represent -COO-, -O-, or a single bond; L ５ , L ６ , L ７ , and, L ８ Each of these independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, a C2-C5 alkoxycarbonyl group, a C2-C4 acyl group, or a halogen atom, L ５ , L ６ , L ７ , and, L ８ At least one of them represents a group other than a hydrogen atom.

8. In equations (2-1) and (2-2), L ５ , L ６ , L ７ , and, L ８ Each of these independently represents either a hydrogen atom or a methyl group, L ５ , L ６ , L ７ , and, L ８ The liquid crystal composition according to claim 7, wherein at least one of them represents a methyl group.

9. The total content of the compound represented by formula (1) and the compound represented by formula (2) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 50 to 95% by mass. The liquid crystal composition according to any one of claims 1 to 8, wherein the content of the compound represented by formula (3) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 5 to 50% by mass.

10. The total content of the compound represented by formula (1) and the compound represented by formula (2) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 60 to 90% by mass. The liquid crystal composition according to any one of claims 1 to 9, wherein the content of the compound represented by formula (3) relative to the total amount of the compound represented by formula (1), the compound represented by formula (2), and the compound represented by formula (3) is 10 to 40% by mass.

11. Furthermore, the liquid crystal composition according to any one of claims 1 to 10, comprising a polymerizable compound different from any of the polymerizable liquid crystal compound (A), the polymerizable liquid crystal compound (B), and the polymerizable compound (C).

12. Furthermore, the liquid crystal composition according to any one of claims 1 to 11, comprising a polymerization initiator.

13. A cured film obtained by curing the liquid crystal composition according to any one of claims 1 to 12.

14. The cured film according to claim 13, which is an optically anisotropic film.

15. The cured film according to claim 13, wherein the film is formed by fixing a torsion-oriented liquid crystal phase.

16. A polarizing plate comprising the cured film according to claim 13 and a polarizer.

17. An image display device comprising the cured film according to claim 13, or the polarizing plate according to claim 16.

Images