Composition, optically anisotropic film, circularly polarizing plate, display device

Abstract

The present application provides a composition capable of forming an optically anisotropic film exhibiting reverse wavelength dispersion and having a Nz coefficient of about 0.50 (0.40-0.60), an optically anisotropic film, a circularly polarizing plate, and a display device. The composition of the present application exhibits lyotropic liquid crystallinity and contains: a non-colored rod-like compound having an acid group or a salt thereof; a non-colored discotic compound having an acid group or a salt thereof; and a salt composed of a cation and an anion, wherein the ratio W calculated from formula (W) is 0.25-1.75, and the maximum absorption wavelength of the rod-like compound in the wavelength range of 230-400 nm is shorter than the maximum absorption wavelength of the discotic compound in the wavelength range of 230-400 nm.

Description

Technical Field

[0001] This invention relates to a composition, an optical anisotropic film, a circular polarizer, and a display device. Background Technology

[0002] Phase retardation films (optical anisotropic films) with refractive index anisotropy are used in various applications such as anti-reflective films for display devices and optical compensation films for liquid crystal display devices.

[0003] For example, Patent Document 1 proposes a biaxial optical anisotropic film formed using a composition exhibiting lyotropic liquid crystal properties. Here, biaxiality means that the refractive index nx in the slow axis direction, the refractive index ny in the fast axis direction, and the refractive index nz in the thickness direction of the optical anisotropic film satisfy the relationship nx>nz>ny.

[0004] Previous technical documents

[0005] Patent documents

[0006] Patent Document 1: Japanese Patent Publication No. 2012-500316 Summary of the Invention

[0007] The technical problem to be solved by the invention

[0008] On the other hand, in recent years, there has been a demand for optical anisotropic films to exhibit reverse wavelength dispersion.

[0009] The inventors studied the characteristics of the biaxial optical anisotropic film described in Patent Document 1 and found that it did not show reverse wavelength dispersion, which requires further improvement.

[0010] In view of the above-mentioned actual situation, the object of the present invention is to provide a composition capable of forming an optical anisotropic film exhibiting reverse wavelength dispersion and having an Nz coefficient of about 0.50 (0.40 to 0.60).

[0011] Furthermore, the present invention also aims to provide an optical anisotropic film, a circular polarizer, and a display device.

[0012] means for solving technical problems

[0013] Based on in-depth research into the problems of the prior art, the inventors discovered that the above-mentioned issues can be solved through the following structure.

[0014] (1) A composition comprising:

[0015] Non-coloring rod-shaped compounds having an acid group or its salt;

[0016] Non-coloring plate-like compounds having an acid group or its salt; and

[0017] A salt composed of cations and anions, wherein the composition,

[0018] The ratio W obtained from the following formula (W) is 0.25 to 1.75.

[0019] The maximum absorption wavelength of rod-shaped compounds in the wavelength range of 230–400 nm is shorter than that of plate-shaped compounds in the same range.

[0020] (2) The composition according to (1), wherein the ratio W is 0.75 to 1.15.

[0021] (3) The composition according to (1) or (2), wherein the rod-shaped compound and the plate-shaped compound are both lyotropic liquid crystal compounds.

[0022] (4) The composition according to any one of (1) to (3), wherein the salt is a lithium salt.

[0023] (5) The composition according to any one of (1) to (4), wherein the rod-shaped compound is a polymer having repeating units represented by the formula (X) described later.

[0024] (6) The composition according to any one of (1) to (5), wherein the plate-like compound is a compound represented by the formula (Y) described later.

[0025] (7) The composition according to any one of (1) to (6), wherein the content of the rod-shaped compound is more than 50% by mass relative to the total mass of the rod-shaped compound and the plate-shaped compound.

[0026] (8) An optically anisotropic film formed using any one of (1) to (7).

[0027] (9) A circular polarizer having:

[0028] (8) The optical anisotropic film described above; and

[0029] Polarizer.

[0030] (10) The circular polarizer according to (9), wherein the angle between the in-plane slow axis of the optical anisotropic film and the absorption axis of the polarizer is in the range of 45±5°.

[0031] (11) A display device having:

[0032] The circular polarizer described in (9) or (10); and

[0033] Display element.

[0034] (12) The display device according to (11), wherein the display element is an organic electroluminescent display element.

[0035] Invention Effects

[0036] According to the present invention, a composition capable of forming an optically anisotropic film exhibiting reverse wavelength dispersion and having an Nz coefficient of about 0.50 (0.40 to 0.60) can be provided.

[0037] Furthermore, according to the present invention, optical anisotropic films, circular polarizers, and display devices can also be provided. Attached Figure Description

[0038] Figure 1 This is a schematic diagram illustrating the structure of the optical anisotropic film of the present invention.

[0039] Figure 2 This is a schematic diagram used to illustrate the optical properties of non-colored rod-shaped compounds and non-colored plate-shaped compounds.

[0040] Figure 3 This is a schematic diagram illustrating the optical properties of the optical anisotropic film of the present invention.

[0041] Figure 4 This is a graph showing a comparison of the wavelength dispersion of the anomalous light refractive index ne of the optical anisotropic film of the present invention, which exhibits reverse wavelength dispersion, with that of the normal light refractive index no. Detailed Implementation

[0042] The present invention will now be described in detail.

[0043] In addition, in this specification, the numerical range indicated by “~” refers to the range included by taking the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0044] Furthermore, unless otherwise specified, the slow axis and fast axis are defined at a wavelength of 550 nm. That is, unless otherwise specified, for example, the direction of the slow axis refers to the direction of the slow axis at a wavelength of 550 nm.

[0045] In this invention, Re(λ) and Rth(λ) represent the in-plane delay and the thickness direction delay at wavelength λ, respectively. Unless otherwise specified, wavelength λ is 550 nm.

[0046] In this invention, Re(λ) and Rth(λ) are values ​​measured at wavelength λ using an AxoScan OPMF-1 (manufactured by Opto Science, Inc.). The values ​​are calculated by inputting the average refractive index ((nx+ny+nz) / 3) and film thickness (d(μm)) into the AxoScan.

[0047] Slow axis direction (°)

[0048] Re(λ)=R0(λ)

[0049] Rth(λ)=((nx+ny) / 2-nz)×d.

[0050] Additionally, R0(λ) is shown as a value calculated using AxoScan OPMF-1, representing Re(λ).

[0051] In this specification, the refractive indices nx, ny, and nz are measured using an Abbe refractometer (NAR-4T, manufactured by ATAGO CO.,LTD.) and a sodium lamp (λ = 589 nm) as the light source. Furthermore, when measuring wavelength dependence, measurements can be performed using a multi-wavelength Abbe refractometer DR-M2 (manufactured by ATAGO CO.,LTD.) combined with an interference filter.

[0052] Furthermore, values ​​from the Polymer Handbook (JOHN WILEY & SONS, INC) and various optical film catalogs can be used. The average refractive index values ​​of the main optical films are exemplified below: cellulose acylate (1.48), cyclic olefin polymer (1.52), polycarbonate (1.59), polymethyl methacrylate (1.49), and polystyrene (1.59).

[0053] Furthermore, in this specification, the Nz coefficient is given by Nz = (nx - nz) / (nx - ny).

[0054] When calculating the Nz coefficient of an optical anisotropic film, nx is the refractive index of the film in the slow axis direction, ny is the refractive index of the film in the fast axis direction, and nz is the refractive index of the film in the thickness direction.

[0055] In addition, nx, ny, and nz when calculating the Nz coefficient are the refractive indices at a wavelength of 550 nm.

[0056] In addition, in this specification, "visible light" refers to light with a wavelength of 400 to 700 nm. Furthermore, "ultraviolet light" refers to light with a wavelength of 10 nm or more but less than 400 nm.

[0057] Furthermore, in this specification, the terms relating to angles (e.g., "orthogonal", "parallel", etc.) include the range of errors permissible in the technical field to which this invention pertains. For example, it may mean within a tight angle of ±5°, and the error from the tight angle is preferably within a range of ±3°.

[0058] The bonding direction of the divalent group (e.g., -COO-) described in this specification is not particularly limited. For example, if L in XLY is -COO-, and the position bonded to the X side is set as *1 and the position bonded to the Y side is set as *2, then L can be *1-O-CO-*2 or *1-CO-O-*2.

[0059] As a characteristic feature of the compositions of the present invention, one can cite the fact that they contain rod-shaped compounds and plate-shaped compounds, as well as salts, in a prescribed proportion to satisfy a prescribed optical relationship.

[0060] The compositions of the present invention are compositions exhibiting lyotropic liquid crystal properties, for example, formed in an orientation state along a predetermined shear direction during the formation of an optically anisotropic film. Specifically, such as... Figure 1 As shown, when the composition is coated onto the support 10 and sheared along the x-axis, the rod-shaped compound 12, which functions as the main component on the support 10, is arranged with its molecular axis (the direction in which the rod-shaped compound 12 extends) along the x-axis. Furthermore, the plate-shaped compound 14 has a ring structure within it, resulting in an overall plate-like structure. Therefore, as... Figure 1 As shown, multiple plate-like compounds 14 are arranged with their plate-like structures facing each other (in other words, with their internal ring structures facing each other). Furthermore, the columnar aggregates formed by the association of the plate-like compounds 14 are arranged along the molecular axis of the rod-like compounds 12, which are predominantly located along the extension direction of the aggregates. At this time, as... Figure 1 As shown, the plate-shaped compound 14 is configured to stand upright relative to the support 10. That is, the plate-shaped compound 14 is configured such that its major axis is aligned with the normal direction (z-axis direction) of the support 10.

[0061] As will be described later, by keeping the ratio W within a specified range, such as Figure 1 As shown, the plate-like compound 14 readily forms an associative compound in an upright manner. Furthermore, as described later, the ratio W represents the range of cations in excess relative to the plate-like compound.

[0062] like Figure 1 As shown, when the molecular axis of rod-shaped compound 12 is aligned along the x-axis, the refractive index nx along the x-axis, the refractive index ny along the y-axis, and the refractive index nz along the z-axis of rod-shaped compound 12 are as follows: Figure 2 As shown, nx is the largest. And, as... Figure 1 As shown, when the plate-like compound 14 is disposed, the refractive index nx in the x-axis direction, the refractive index ny in the y-axis direction, and the refractive index nz in the z-axis direction of the plate-like compound 14 are as follows: Figure 2As shown, nz is the largest. The refractive indices nx, ny, and nz of an optical anisotropic film along the x-axis depend on the refractive indices nx, ny, and nz of each component contained in the optical anisotropic film. Therefore, as... Figure 1 As shown, when rod-shaped compound 12 and plate-shaped compound 14 are configured, the refractive index nx along the x-axis, the refractive index ny along the y-axis, and the refractive index nz along the z-axis of the optical anisotropic film are as follows: Figure 3 As shown, Figure 1 In this context, the x-axis is the slow axis, and the refractive indices nx, ny, and nz of the optical anisotropic film satisfy the relationship nx > nz > ny. That is, it is easy to satisfy the requirement of the specified Nz coefficient (0.40 to 0.60).

[0063] Furthermore, in this invention, the maximum absorption wavelength of the rod-shaped compound in the wavelength range of 230–400 nm is shorter than that of the plate-shaped compound in the same wavelength range. That is, the rod-shaped compound has a maximum absorption wavelength at a shorter wavelength, while the plate-shaped compound has a maximum absorption wavelength at a longer wavelength; the maximum absorption wavelength of the rod-shaped compound is located at a wavelength shorter than that of the plate-shaped compound. For example… Figure 1 As shown, rod-shaped compound 12 aligns its absorption axis along the x-axis, and plate-shaped compound 14 aligns its absorption axis along the y-axis. Therefore, as Figure 4 As shown, since the refractive index of nx decreases earlier than that of ny, the refractive index of nx decreases more slowly than that of ny in the region indicated by the arrow, thus achieving reverse wavelength dispersion.

[0064] exist Figure 1 For the sake of simplicity, only two rod-shaped compounds 12 and four plate-shaped compounds 14 are shown in the diagram, but the number of rod-shaped and plate-shaped compounds in the optical anisotropic film is not limited to this. Figure 1 In this way.

[0065] The compositions of the present invention are lyotropic liquid crystal compositions (hereinafter also simply referred to as "compositions") containing a non-coloring rod-shaped compound having an acid group or a salt thereof and a non-coloring plate-shaped compound having an acid group or a salt thereof.

[0066] The following sections will first describe in detail the materials contained in the composition, and then describe in detail the optical anisotropic film formed using the composition.

[0067] (Rod-shaped compound)

[0068] The composition contains a non-coloring rod-shaped compound having an acid group or a salt thereof (hereinafter also simply referred to as "rod-shaped compound"). As described above, the rod-shaped compound readily orients in a prescribed direction.

[0069] Non-coloration refers to the absence of absorption in the visible light region. More specifically, it means that when measuring the UV-Vis absorption spectrum of a solution obtained by dissolving a rod-shaped compound at a concentration where the absorbance at the maximum absorption wavelength in the ultraviolet region (230–400 nm) is 1.0, the absorbance in the visible light region (wavelength 400–700 nm) is less than 0.1.

[0070] Rod-shaped compounds preferably exhibit lyotropic liquid crystal properties. That is, rod-shaped compounds are preferably non-coloring lyotropic liquid crystal compounds (non-coloring lyotropic liquid crystal rod-shaped compounds). Lyotropic liquid crystal properties refer to the property of inducing an isotropic phase-liquid phase transition by changing the temperature and concentration in a solution state dissolved in a solvent.

[0071] From the viewpoint of easily controlling liquid crystal properties, the rod-shaped compound is preferably water-soluble. A water-soluble rod-shaped compound is defined as a rod-shaped compound that dissolves in water at a rate of 1% or more by mass, preferably at a rate of 5% or more by mass.

[0072] In addition, rod-shaped compounds refer to compounds with ring structures (aromatic rings and non-aromatic rings, etc.) that are one-dimensionally linked by single bonds or divalent connecting groups, representing a group of compounds that have the property of being oriented in a way that their long axes are aligned with each other in a solvent.

[0073] The rod-shaped compound preferably has a maximum absorption wavelength in the range below 300 nm. That is, the rod-shaped compound preferably has a maximum absorption peak in the range below 300 nm.

[0074] Furthermore, the maximum absorption wavelength of the aforementioned rod-shaped compound refers to the wavelength at which its absorbance reaches its maximum value within the absorption spectrum of the rod-shaped compound (measurement range: wavelength range of 230–400 nm). When there are multiple maximum absorbance values ​​in the absorption spectrum of the rod-shaped compound, the wavelength with the longest wavelength in the measurement range is selected.

[0075] From the viewpoint of the superior effects of the present invention, the rod-shaped compound preferably has a maximum absorption wavelength in the range of 230 to 300 nm, and more preferably has a maximum absorption wavelength in the range of 250 to 290 nm.

[0076] The method for measuring the maximum absorption wavelength is as follows.

[0077] The absorption spectrum of the solution was measured using a spectrophotometer (MPC-3100 (manufactured by SHIMADZU)) after dissolving 5–50 mg of the rod-shaped compound in 1000 mL of pure water.

[0078] In this invention, the maximum absorption wavelength of the rod-shaped compound in the wavelength range of 230–400 nm is smaller than that of the maximum absorption wavelength of the plate-shaped compound in the wavelength range of 230–400 nm.

[0079] There is no particular limitation on the difference between the maximum absorption wavelength of the rod-shaped compound and the maximum absorption wavelength of the plate-shaped compound, but it is preferably 50 nm or more, and more preferably 70 nm or more.

[0080] Furthermore, as mentioned above, the maximum absorption wavelength of a rod-shaped compound refers to the wavelength at which its absorbance reaches its maximum value in the absorption spectrum of the rod-shaped compound (measurement range: wavelength range of 230–400 nm). When there are multiple maximum absorbance values ​​in the absorption spectrum of a rod-shaped compound, the wavelength with the longest wavelength in the measurement range is selected.

[0081] Furthermore, as described later, the maximum absorption wavelength of a plate-like compound refers to the wavelength at which its absorbance reaches its maximum value within the absorption spectrum of the plate-like compound (measurement range: wavelength range of 230–400 nm). When there are multiple maximum absorbance values ​​in the absorption spectrum of a plate-like compound, the wavelength with the longest wavelength in the measurement range is selected.

[0082] From the viewpoint of achieving superior effects of the present invention, the wavelength dispersity D of the rod-shaped compound, represented by formula (R), is... R Preferably, the wavelength dispersion D is 1.05 or higher and less than 1.20. As described later, the wavelength dispersion D... R It refers to the optical properties of the optically anisotropic film of the rod-shaped compound, which correspond to the optical properties exhibited by the rod-shaped compound in the optically anisotropic film.

[0083] Equation (R) Wavelength Dispersion D R =Re(450) R / Re(550) R

[0084] Re(450) R Re(550) represents the in-plane retardation of an optically anisotropic film R formed using a mixture R obtained by mixing 10 parts by mass of a rod-shaped compound with 90 parts by mass of water at a wavelength of 450 nm. R This indicates the in-plane retardation of the optical anisotropic film R at a wavelength of 550 nm.

[0085] As described above, the wavelength dispersity D of the rod-shaped compound, represented by formula (R), is... R This represents the in-plane retardation relationship of an optical anisotropic film R formed using a rod-shaped compound.

[0086] As a method for fabricating an optical anisotropic film R, the above-mentioned mixture R is coated on a glass substrate using a No. 4 wire rod (moving speed: 100cm / s), and then naturally dried at room temperature (20°C) to fabricate an optical anisotropic film R (film thickness approximately 240nm).

[0087] In addition, the type of rod-shaped compound contained in the mixture R is the same as that used in the composition.

[0088] In addition, the aforementioned wavelength dispersion D R With wavelength dispersion D discussed later P The preferred values ​​are different.

[0089] The Nz coefficient of an optical anisotropic film R is typically 1.

[0090] The Nz coefficient (Nz) of an anisotropic optical film R R It is usually 1.

[0091] The Nz coefficient of the optical anisotropic film R is determined by Nz R =(nx R -nz R ) / (nx R -ny R The value given.

[0092] nx R ny is the in-plane refractive index along the slow axis of the anisotropic optical film R. R It is the in-plane fast axis refractive index of the optical anisotropic film R, nz R It is the refractive index along the thickness direction of the optically anisotropic film R. nx R ny R and nz R These are the refractive indices at a wavelength of 550nm.

[0093] Rod-shaped compounds contain an acid group or its salt (an acid group or a salt of an acid group). Furthermore, a salt is a salt formed when the hydrogen ion of an acid is replaced by another cation, such as a metal. That is, a salt of an acid group is a salt formed when the hydrogen ion of an acid group, such as the -SO3H group, is replaced by another cation.

[0094] Examples of acid groups or their salts include, for instance, sulfonyl groups (-SO3H) or their salts (-SO3H). - M + M + This indicates a cation and a carboxyl group (-COOH) or its salt (-COO). - M + M + (This indicates a cation.) From the viewpoint of achieving better results in this invention, a sulfonyl group or its salt is preferred.

[0095] As cations in salts of acid groups (e.g., cations in salts of sulfonates and salts of carboxyl groups), examples include Na... + K + Li + 、Rb + Cs + Ba 2+ Ca 2+ Mg 2+ 、Sr 2+ Pb 2+ Zn 2+ La 3+ Ce 3+ Y 3+ Yb 3+ Gd 3+ Zr 4+ or NH 4- k Q k + (Q represents a straight-chain or branched alkyl, alkenyl, alkynyl, or aryl group with 6 to 20 carbon atoms, and k represents an integer from 1 to 4). From the viewpoint of achieving better results with this invention, alkali metal ions are preferred, and Na is more preferred. + Or Li + Further optimization of Li + .

[0096] From the viewpoint of achieving better results with the present invention, as a rod-shaped compound, a polymer having repeating units represented by formula (X) is preferred.

[0097] [Chemical Formula 1]

[0098]

[0099] R x1 This indicates a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof, or a group represented by formula (X1). In formula (X1), * indicates a bonding position.

[0100] Formula (X1)*-R x3 -L x3 -R x4 -*

[0101] R x3 and R x4 R can be independently represented as a divalent aromatic ring group that may have substituents containing an acid group or its salt, or a divalent non-aromatic ring group that may have substituents containing an acid group or its salt. x3 and R x4At least one of them represents a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, or a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof.

[0102] L x3 It represents a single bond, -O-, -S-, alkylene, alkenyl, or ynylene.

[0103] By R x1 The divalent aromatic ring group and divalent non-aromatic ring group represented have substituents containing an acid group or its salt.

[0104] Examples of substituents containing an acid group or its salt include the groups described above, with an acid group or its salt being preferred.

[0105] As a substituent containing an acid group or its salt, it is preferably a group represented by formula (H). In formula (H), * indicates a bonding position.

[0106] Formula (H)R H -L H -*

[0107] R H This refers to an acid group or its salt. The definition of an acid group or its salt is as described above.

[0108] L H This indicates a single bond or a divalent linking group. There are no particular limitations on the divalent linking group; examples include divalent hydrocarbon groups (e.g., divalent aliphatic hydrocarbon groups such as alkylene groups with 1-10 carbon atoms, alkenyl groups with 1-10 carbon atoms, and alkyne groups with 1-10 carbon atoms, as well as divalent aromatic hydrocarbon groups such as arylene groups), divalent heterocyclic groups, -O-, -S-, -NH-, -CO-, or groups formed by combining them (e.g., -CO-O-, -O-divalent hydrocarbon-, -(O-divalent hydrocarbon-)). m -O- (m represents an integer greater than 1) and -2-valent hydrocarbon groups such as -O-CO-.

[0109] There is no particular limitation on the number of substituents containing an acid group or its salt in the divalent aromatic ring group, but from the viewpoint of better effect of the present invention, 1 to 3 is preferred, and more preferably 1.

[0110] There is no particular limitation on the number of substituents containing an acid group or its salt in the divalent non-aromatic ring group, but from the viewpoint of better effect of the present invention, 1 to 3 is preferred, and more preferably 1.

[0111] Composed of R x1 The aromatic ring represented by the substituent containing an acid group or its salt can be a monocyclic or polycyclic structure.

[0112] As the aromatic ring constituting the aforementioned divalent aromatic ring group, examples include aromatic hydrocarbon rings or aromatic heterocycles. That is, as R... x1 Examples include divalent aromatic hydrocarbon cycloalloys having substituents containing an acid group or its salt, and divalent aromatic heterocyclic cycloalloys having substituents containing an acid group or its salt.

[0113] Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0114] As a structure having only a substituent containing an acid group or its salt, a divalent aromatic hydrocarbon cyclic moiety, examples include the following groups. * indicates a bonding position.

[0115] [Chemical Formula 2]

[0116]

[0117] Examples of aromatic heterocycles include pyridine rings, thiophene rings, pyrimidine rings, thiazole rings, furan rings, pyrrole rings, imidazole rings, and indole rings.

[0118] As a structure having only a divalent aromatic heterocyclic group containing a substituent of an acid group or its salt, examples of divalent aromatic heterocyclic groups include the following groups. * indicates a bonding position.

[0119] [Chemical Formula 3]

[0120]

[0121] Composed of R x1 The non-aromatic ring represented by a divalent non-aromatic ring group containing a substituent of an acid group or its salt can be a monocyclic structure or a polycyclic structure.

[0122] As the non-aromatic ring constituting the aforementioned divalent non-aromatic ring group, examples include aliphatic rings and non-aromatic heterocycles. From the viewpoint of superior performance of the present invention, aliphatic rings are preferred, cycloalkanes are more preferred, and cyclohexane is even more preferred. That is, as R... x1 Examples include divalent aliphatic cyclic groups having substituents containing an acid group or its salt, and divalent non-aromatic heterocyclic groups having substituents containing an acid group or its salt, preferably divalent cycloalkylene groups having substituents containing an acid group or its salt.

[0123] Aliphatic rings can be either saturated or unsaturated.

[0124] As a structure having only a divalent aliphatic cyclic group containing a substituent of an acid group or its salt, examples of divalent aliphatic cyclic groups include the following groups. * indicates a bonding position.

[0125] [Chemical Formula 4]

[0126]

[0127] There are no particular restrictions on the heteroatoms contained in non-aromatic heterocycles; for example, oxygen, nitrogen, and sulfur atoms can be included.

[0128] There is no particular limitation on the number of heteroatoms contained in a non-aromatic heterocycle; for example, 1 to 3 can be cited.

[0129] As a structure having only a divalent non-aromatic heterocyclic group containing a substituent of an acid group or its salt, examples of divalent non-aromatic heterocyclic groups include the following groups. * indicates a bonding position.

[0130] [Chemical Formula 5]

[0131]

[0132] By R x1 The divalent aromatic ring group represented by the substituent containing an acid group or its salt, and the divalent non-aromatic ring group represented by the substituent containing an acid group or its salt, may also have substituents other than those containing an acid group or its salt.

[0133] Substituents are not particularly limited, and examples include alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, aromatic heterocyclic oxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, amide, alkoxycarbonylamino, aryloxycarbonylamino, alkylthio, arylthio, aromatic heterocyclic thio, ureyl, halogen atom, cyano, hydrazyl, heterocyclic groups (e.g., heteroaryl), silyl, and groups formed by combining them. Furthermore, the above substituents can be further substituted by other substituents.

[0134] R x3 and R x4 R can be independently represented as a divalent aromatic ring group that may have substituents containing an acid group or its salt, or a divalent non-aromatic ring group that may have substituents containing an acid group or its salt. x3 and R x4 At least one of them represents a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, or a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof.

[0135] By R x3 and R x4 The divalent aromatic ring group may have substituents containing an acid group or its salt as defined above.

[0136] Furthermore, it constitutes R x3 and R x4The definition of an aromatic ring, which may contain a divalent aromatic ring group with a substituent containing an acid group or its salt, is consistent with the above-described structure consisting of R. x1 The definition of an aromatic ring is the same as that of a divalent aromatic ring group containing a substituent of an acid group or its salt.

[0137] By R x3 and R x4 The substituents that a divalent nonaromatic ring group may have, which contain an acid group or its salt, are defined as described above.

[0138] Furthermore, it constitutes R x3 and R x4 The definition of a non-aromatic ring, which may contain a substituent of an acid group or its salt, is the same as described above, consisting of R. x1 The definition of a non-aromatic ring having a substituent containing an acid group or its salt is the same.

[0139] R x3 and R x4 At least one of them represents a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, or a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof, R x3 and R x4 Both can represent a divalent aromatic ring group having a substituent containing an acid group or its salt, or a divalent non-aromatic ring group having a substituent containing an acid group or its salt.

[0140] By R x3 and R x4 The definition of a divalent aromatic ring group having a substituent containing an acid group or its salt is the same as that of R above. x1 The definition of a divalent aromatic ring group having a substituent containing an acid group or its salt is the same.

[0141] Furthermore, by R x3 and R x4 The definition of a divalent nonaromatic ring group having a substituent containing an acid group or its salt is the same as that of R above. x1 The definition of a divalent nonaromatic ring group having a substituent containing an acid group or its salt is the same.

[0142] L x3 It represents a single bond, -O-, -S-, alkylene, alkenyl, or ynylene.

[0143] There is no particular limitation on the number of carbon atoms in the alkylene group, but from the viewpoint of achieving better results in this invention, 1 to 3 is preferred, and more preferably 1.

[0144] There is no particular limitation on the number of carbon atoms in the alkenyl and alkyne groups, but from the viewpoint of achieving better results in this invention, 2 to 5 is preferred, and more preferably 2 to 4.

[0145] R x2 This indicates a divalent non-aromatic ring group or a group represented by formula (X2). In formula (X2), * indicates a bonding position.

[0146] Formula (X2)*-Z x1 -Z x2 -*

[0147] Z x1 and Z x2 Each group represents a divalent non-aromatic ring group independently. * indicates a bonding position.

[0148] Composed of R x2 The non-aromatic ring represented by the divalent non-aromatic ring group can be a monocyclic structure or a polycyclic structure.

[0149] As the non-aromatic ring constituting the aforementioned divalent non-aromatic ring group, examples include aliphatic rings and non-aromatic heterocycles. From the viewpoint of superior performance of the present invention, aliphatic rings are preferred, cycloalkanes are more preferred, and cyclohexane is even more preferred. That is, as R... x2 Examples of divalent aliphatic cyclic groups and divalent non-aromatic heterocyclic groups include divalent cycloalkyl groups, with divalent cycloalkylene groups being preferred.

[0150] Aliphatic rings can be either saturated or unsaturated.

[0151] Examples of divalent aliphatic cyclic groups include the following. * indicates the bonding position.

[0152] [Chemical Formula 6]

[0153]

[0154] There are no particular restrictions on the heteroatoms contained in non-aromatic heterocycles; for example, oxygen, nitrogen, and sulfur atoms can be included.

[0155] There is no particular limitation on the number of heteroatoms contained in a non-aromatic heterocycle; for example, 1 to 3 can be cited.

[0156] Examples of divalent non-aromatic heterocyclic groups include the following groups. * indicates the bonding position.

[0157] [Chemical Formula 7]

[0158]

[0159] Divalent non-aromatic ring groups can have substituents. There are no particular limitations on the types of substituents; for example, groups other than those derived from R... x1The groups represented are divalent aromatic ring groups having substituents containing an acid group or its salt, and divalent non-aromatic ring groups having substituents containing an acid group or its salt, and may have substituents other than those containing an acid group or its salt.

[0160] Z x1 and Z x2 Each of these groups represents a divalent non-aromatic ring group independently.

[0161] By Z x1 and Z x2 The definition of the divalent non-aromatic ring group is the same as that of R mentioned above. x2 The definition of the divalent non-aromatic ring group is the same.

[0162] L 1x and L 2x -CONH-, -COO-, -O-, or -S- can be represented independently. Among these, -CONH- is preferred from the viewpoint of achieving better results in this invention.

[0163] As the repeating unit represented by equation (X), the repeating unit represented by equation (X4) is preferred.

[0164] [Chemical Formula 8]

[0165]

[0166] The definitions of each group in formula (X4) are as described above.

[0167] The content of repeating units represented by formula (X) in a polymer having repeating units is not particularly limited, but is preferably 60 mol% or more, more preferably 80 mol% or more, relative to all repeating units in the polymer. As an upper limit, 100 mol% can be cited as an example.

[0168] The molecular weight of the polymer having repeating units represented by formula (X) is not particularly limited, but the number of repeating units represented by formula (X) in the polymer is preferably 2 or more, more preferably 10 to 100,000, and even more preferably 100 to 10,000.

[0169] Furthermore, the number-average molecular weight of the polymer having repeating units represented by formula (X) is not particularly limited, but is preferably 5,000 to 50,000, more preferably 10,000 to 30,000.

[0170] Furthermore, there are no particular limitations on the molecular weight distribution of the polymer having repeating units represented by formula (X), but it is preferably 1.0 to 12.0, and more preferably 1.0 to 7.0.

[0171] In this invention, the number-average molecular weight and molecular weight distribution are values ​​measured by gel permeation chromatography (GPC).

[0172] • Solvent (elution buffer): 20mM phosphoric acid (pH 7.0) / acetonitrile = 4 / 1

[0173] • Device Name: TOSOH HLC-8220GPC

[0174] • Columns: Connects to 3 G6000PWxL, 4500PWxL, and G2500pWwL steel rods manufactured by Tosoh Corporation.

[0175] Column temperature: 40℃

[0176] • Sample concentration: 2 mg / mL

[0177] • Flow rate: 1 mL / min

[0178] • Calibration curves: Calibration curves were used for 8 samples, with the range of polystyrene sulfonic acid (PSS) Mp = 891, 4.2k, 10.2k, 29.5k, 78.4k, 152k, 258k, and 462k.

[0179] (plate-like compound)

[0180] The composition contains a non-coloring plate-like compound having an acid group or a salt thereof (hereinafter also simply referred to as "plate-like compound").

[0181] Plate-like compounds exhibit non-coloring properties.

[0182] Non-coloration refers to the absence of absorption in the visible light region. More specifically, it means that when measuring the UV-Vis absorption spectrum of a solution obtained by dissolving a plate-like compound at a concentration where the absorbance at the maximum absorption wavelength in the ultraviolet region (230–400 nm) is 1.0, the absorbance in the visible light region (wavelength 400–700 nm) is less than 0.1.

[0183] In addition, "plate-like compounds" refer to compounds whose aromatic rings (aromatic hydrocarbon rings and aromatic heterocycles, etc.) have a two-dimensional diffusion structure through single bonds or appropriate linking groups, representing a group of compounds that have the property of forming columnar aggregates by associating with each other through planes in the compound in a solvent.

[0184] The plate-shaped compound preferably exhibits lyotropic liquid crystal properties. That is, the plate-shaped compound is preferably a non-coloring lyotropic liquid crystal compound (non-coloring lyotropic liquid crystal plate-shaped compound).

[0185] From the viewpoint of easily controlling liquid crystal properties, the plate-like compound is preferably water-soluble. A water-soluble plate-like compound is defined as a plate-like compound that dissolves in water at a rate of 1% or more by mass, and preferably at a rate of 5% or more by mass.

[0186] The plate-like compound preferably has a maximum absorption wavelength in the range of wavelengths exceeding 300 nm. That is, the plate-like compound preferably has a maximum absorption peak in the range of wavelengths exceeding 300 nm.

[0187] Furthermore, the maximum absorption wavelength of the aforementioned plate-like compound refers to the wavelength at which its absorbance reaches its maximum value within the absorption spectrum of the plate-like compound (measurement range: wavelength range of 230–400 nm). When there are multiple maximum absorbance values ​​in the absorption spectrum of the plate-like compound, the wavelength with the longest wavelength in the measurement range is selected.

[0188] From the viewpoint of the superior effects of the present invention, the plate-like compound preferably has a maximum absorption wavelength in the range of 320 to 400 nm, and more preferably in the range of 330 to 360 nm.

[0189] The method for measuring the maximum absorption wavelength is as follows.

[0190] The absorption spectrum of a solution obtained by dissolving a specific compound (0.01–0.05 mmol) in pure water (1000 ml) was measured using a spectrophotometer (MPC-3100 (manufactured by SHIMADZU)).

[0191] The Nz coefficient (Nz) of an optically anisotropic film P formed using a plate-like compound. P There are no particular limitations, but from the viewpoint of achieving better results in this invention, a negative value is preferred. That is, the Nz coefficient of the aforementioned optical anisotropic film P is preferably less than 0.

[0192] From the viewpoint of achieving better results with the present invention, the Nz coefficient of the optical anisotropic film P is preferably -0.45 to -0.10, more preferably -0.30 to -0.15, and even more preferably -0.25 to -0.19.

[0193] As will be discussed later, Nz P and wavelength dispersion D (described later) P It refers to the optical properties of the optically anisotropic film of the plate-like compound, which correspond to the optical properties exhibited by the plate-like compound in the optically anisotropic film.

[0194] Equation (N)Nz P =(nx P -nz P ) / (nx P -ny P )

[0195] Regarding nx P , representing the in-plane refractive index of the optically anisotropic film P formed using mixture P1 when the composition is salt-free and mixture P2 when the composition contains salt. Mixture P1 is obtained by mixing 10 parts by mass of a non-coloring plate-like compound with 90 parts by mass of water. Mixture P2 is obtained by mixing 10 parts by mass of the non-coloring plate-like compound, 90 parts by mass of water, and salt in an amount equal to the salt content of the plate-like compound in the composition. P This represents the in-plane refractive index along the fast axis of an optically anisotropic film P. (nz) P nx represents the refractive index along the thickness direction of the optically anisotropic film P. P ny P and nz P These are the refractive indices at a wavelength of 550nm.

[0196] That is, regarding the optically anisotropic film P, when the composition does not contain salt, it is an optically anisotropic film formed using a mixture P1 obtained by mixing 10 parts by mass of the plate-like compound and 90 parts by mass of water; when the composition contains salt, it is an optically anisotropic film formed using a mixture P2 obtained by mixing 10 parts by mass of the plate-like compound, 90 parts by mass of water, and a salt in an amount equal to the ratio of the salt content in the composition to the plate-like compound content.

[0197] As a method for fabricating an optical anisotropic film P, the above-mentioned mixture P1 or mixture P2 is coated on a glass substrate using a No. 4 wire rod (moving speed: 100cm / s), and then naturally dried at room temperature (20°C) to fabricate an optical anisotropic film P (film thickness approximately 240nm).

[0198] Furthermore, as described above, when the composition contains salt, the mixture P2 also contains a specified amount of salt. Specifically, an optically anisotropic film P is prepared by adding an amount of salt to the mixture P2 in the same ratio as the salt content of the plate-like compound in the composition.

[0199] That is, when the composition contains a plate-like compound and a salt, the mixture P2 contains 10 parts by mass of the plate-like compound, 90 parts by mass of water, and a specified amount of salt (parts by mass) in the same ratio as the salt content to the plate-like compound content in the composition (mass content of salt / mass content of plate-like compound). More specifically, when the salt content to the plate-like compound content in the composition (mass content of salt / mass content of plate-like compound) is 1 / 10, the mixture P2 contains 10 parts by mass of the plate-like compound, 90 parts by mass of water, and 1 part by mass of salt.

[0200] In addition, the types of plate-like compounds contained in mixtures P1 and P2 are the same as those in the composition.

[0201] In addition, the salts contained in mixture P2 are the same types used as those in the composition.

[0202] From the viewpoint of achieving superior results in this invention, the wavelength dispersion D of the optically anisotropic film P is improved. P The preferred value is 1.20 to 1.30.

[0203] Equation (P) Wavelength Dispersion D P =Re(450) P / Re(550) P

[0204] Re(450) P Re(550) represents the in-plane retardation of the optically anisotropic film P at a wavelength of 450 nm. P This indicates the in-plane retardation of the optical anisotropic film P at a wavelength of 550 nm.

[0205] As described above, the wavelength dispersion D P This represents the in-plane retardation relationship of an optically anisotropic film P formed using a plate-like compound.

[0206] From the viewpoint of achieving better results with the present invention, the plate-like compound preferably has an acid group or a salt thereof.

[0207] The acid group or its salt is defined as described above.

[0208] The plate-like compound may have only one acid group or its salt, or it may have multiple acid groups or their salts. When the plate-like compound has multiple acid groups or their salts, the number is preferably 2 to 4, more preferably 2.

[0209] From the viewpoint of achieving better results with the present invention, the compound represented by formula (Y) is preferred as a plate-like compound.

[0210] Formula(Y)R y2 -L y3 -L y1 -R y1 -L y2 -L y4 -R y3

[0211] R y1 This indicates a divalent monocyclic group or a divalent fused polycyclic group.

[0212] Examples of rings included in a divalent monocyclic group include monocyclic hydrocarbon rings and monocyclic heterocycles. A monocyclic hydrocarbon ring can be a monocyclic aromatic hydrocarbon ring or a monocyclic non-aromatic hydrocarbon ring. A monocyclic heterocycle can be a monocyclic aromatic heterocycle or a monocyclic non-aromatic heterocycle.

[0213] From the viewpoint of achieving better results with a divalent monocyclic group, a divalent monocyclic aromatic hydrocarbon cyclic group or a divalent monocyclic aromatic heterocyclic group is preferred.

[0214] There is no particular limitation on the number of ring structures contained in the divalent fused polycyclic group, but from the viewpoint of better performance of the present invention, it is preferred to be 3 to 10, more preferably 3 to 6, and even more preferably 3 to 4.

[0215] Examples of rings included in a divalent fused polycyclic group include hydrocarbon rings and heterocycles. The hydrocarbon ring can be an aromatic or non-aromatic hydrocarbon ring. The heterocycle can be an aromatic or non-aromatic heterocycle.

[0216] From the viewpoint of achieving better results with this invention, the divalent fused polycyclic group is preferably composed of an aromatic hydrocarbon ring and a heterocycle. The divalent fused polycyclic group is preferably a conjugated linker group. That is, a conjugated divalent fused polycyclic group is preferred.

[0217] Examples of rings constituting divalent fused polycyclic groups include, for example, dibenzothiophene-S,S-dioxide (represented by formula (Y2)), dinaphthalene[2,3-b:2',3'-d]furan (represented by formula (Y3)), 12H-benzo“b”phenoxazine (represented by formula (Y4)), dibenzo[b,i]dibenzo-p-dioxin (represented by formula (Y5)), benzo[b]naphthalene[2',3':5,6]dioxane[2,3-i]dibenzo-p-dioxin (represented by formula (Y6)), acenaphthene[1,2-b]benzo[g]quinoxaline (represented by formula (Y7)), 9H-acenaphthene[1,2-b]imidazol[4,5-g]quinoxaline (represented by formula (Y8)), and dibenzo[b,def] (Chrysene)-7,14-dione (a ring represented by formula (Y9)) and acetylquinoxaline (a ring represented by formula (Y10)).

[0218] That is, as a divalent fused polycyclic group, examples can be given of divalent groups formed by removing two hydrogen atoms from the rings represented by formulas (Y2) to (Y10).

[0219] [Chemical Formula 9]

[0220]

[0221] [Chemical Formula 10]

[0222]

[0223] Divalent monocyclic groups and divalent fused polycyclic groups can have substituents. There are no particular restrictions on the types of substituents; for example, groups other than those derived from R... x1 The group represented is a divalent aromatic ring group having a substituent containing an acid group or its salt, and a divalent non-aromatic ring group having a substituent containing an acid group or its salt, and is exemplified by substituents other than the substituent containing an acid group or its salt.

[0224] R y2 and R y3 Each can independently represent a hydrogen atom or an acid group or its salt, R y2 and R y3 At least one of them represents an acid group or its salt. Ry 2 and R y3 Both are preferably represented by an acid group or its salt.

[0225] By R y2 and R y3 The acid group or its salt is defined as described above.

[0226] L y1 and L y2 Each can independently represent a single bond, a divalent aromatic ring group, or a group represented by formula (Y1). Wherein, when R... y1 When L is a divalent monocyclic group, y1 and L y2 All of these represent divalent aromatic ring groups or groups represented by formula (Y1). In formula (Y1), * indicates a bonding position.

[0227] Formula (Y1)*-R y4 -(R y5 ) n -*

[0228] R y4 and R y5 Each of these groups represents a divalent aromatic ring group independently.

[0229] n represents 1 or 2.

[0230] Composed of L y1 and L y2 The aromatic ring represented by the divalent aromatic ring group can be a monocyclic structure or a polycyclic structure.

[0231] As the aromatic ring constituting the aforementioned divalent aromatic ring group, examples include aromatic hydrocarbon rings or aromatic heterocycles. That is, as a group composed of L... y1 and L y2Examples of divalent aromatic ring groups include divalent aromatic hydrocarbon ring groups and divalent aromatic heterocyclic groups.

[0232] Examples of aromatic hydrocarbon rings include benzene rings and naphthalene rings.

[0233] Examples of divalent aromatic hydrocarbon cyclic groups include the following. * indicates the bonding position.

[0234] [Chemical Formula 11]

[0235]

[0236] Examples of aromatic heterocycles include pyridine rings, thiophene rings, pyrimidine rings, thiazole rings, furan rings, pyrrole rings, imidazole rings, and indole rings.

[0237] Examples of divalent aromatic heterocyclic groups include the following groups. * indicates the bonding position.

[0238] [Chemical Formula 12]

[0239]

[0240] By R y4 and R y5 The definition of the divalent aromatic ring group is also consistent with that of L y1 and L y2 The divalent aromatic ring groups are the same.

[0241] L y3 and L y4 Each can independently represent a single bond, -O-, -S-, alkylene, alkenylene, alkyneylene, or a combination thereof.

[0242] Examples of groups that combine these groups include, for example, -O-alkylene and -S-alkylene.

[0243] There is no particular limitation on the number of carbon atoms in the alkylene group, but from the viewpoint of achieving better results in this invention, 1 to 3 is preferred, and more preferably 1.

[0244] There is no particular limitation on the number of carbon atoms in the alkenyl and alkyne groups, but from the viewpoint of achieving better results in this invention, 2 to 5 is preferred, and more preferably 2 to 4.

[0245] <salt>

[0246] The composition contains a salt consisting of cations and anions.

[0247] Furthermore, the salt described above does not contain the aforementioned rod-shaped and plate-shaped compounds. That is, the salt described above is a compound different from the aforementioned rod-shaped and plate-shaped compounds.

[0248] There are no particular limitations on the salt; it can be an inorganic salt or an organic salt. From the viewpoint of better performance of the present invention, an inorganic salt is preferred. Examples of inorganic salts include alkali metal salts, alkaline earth metal salts, and transition metal salts. From the viewpoint of better performance of the present invention, an alkali metal salt is preferred.

[0249] Alkali metal salts are salts whose cations are alkali metal ions. Lithium ions or sodium ions are preferred as alkali metal ions, and lithium ions are more preferred. That is, lithium salts or sodium salts are preferred as salts, and lithium salts are more preferred.

[0250] Examples of alkali metal salts include, for example, alkali metal hydroxides such as lithium hydroxide, sodium hydroxide, and potassium hydroxide; alkali metal carbonates such as lithium carbonate, sodium carbonate, and potassium carbonate; and alkali metal bicarbonates such as lithium bicarbonate, sodium bicarbonate, and potassium bicarbonate.

[0251] In addition to the above, as alkali metal salts, they can also be phosphates and chlorides, for example.

[0252] Examples of anions that can be used as salts include hydroxide ions, carbonate ions, chloride ions, sulfate ions, nitrate ions, phosphate ions, borate ions, tetrafluoroborate ions, hexafluorophosphate ions, perchlorate ions, toluenesulfonate ions, oxalate ions, formate ions, trifluoroacetate ions, trifluoromethanesulfonate ions, hexafluorophosphate ions, bis(fluoromethanesulfonyl)imide ions, bis(pentafluoroethanesulfonyl)imide ions, and bis(trifluoromethanesulfonyl)imide ions.

[0253] Furthermore, when the plate-like compound has a salt with an acid group, the cation in the salt with the acid group is preferably of the same type as the cation in the salt used above.

[0254] <Other Ingredients>

[0255] The composition may also contain other components besides rod-shaped compounds, plate-shaped compounds and salts.

[0256] The composition may also contain a solvent. Examples of solvents include polar solvents such as water, alcohols, and dimethylformamide, as well as non-polar solvents such as hexane. Among these, polar solvents are preferred, and water or alcohols are more preferred.

[0257] In addition to the above, other additives that may be included in the composition include polymerizable compounds, polymerization initiators, wavelength dispersion control agents, optical property modifiers, surfactants, adhesion modifiers, lubricants, orientation control agents, and ultraviolet absorbers.

[0258] <Composition of the composition>

[0259] The composition contains at least a rod-shaped compound, a plate-shaped compound, and a salt.

[0260] The composition is equivalent to a lyotropic liquid crystal composition.

[0261] Here, a lyotropic liquid crystal composition refers to a composition that exhibits the property of undergoing an isotropic phase-liquid phase transition in solution by changing the temperature and concentration. That is, a composition that, in a solution containing various components such as rod-shaped compounds, plate-shaped compounds, and solvents, can exhibit lyotropic liquid crystal properties by adjusting the concentration of each compound. Furthermore, even if the composition contains excess solvent and does not exhibit lyotropic liquid crystal properties in that state, but displays lyotropic liquid crystal properties upon concentration changes, such as during a drying process after coating, the composition is equivalent to the aforementioned lyotropic liquid crystal composition.

[0262] In the above composition, the ratio W obtained by formula (W) is 0.25 to 1.75, and from the viewpoint of better effect of the present invention, it is preferably 0.50 to 1.50, and more preferably 0.75 to 1.15.

[0263] [Formula 1]

[0264]

[0265] In formula (W), C1 represents the molar amount of cations contained in the salt of the acid group of the rod-shaped compound. Furthermore, in the case where the rod-shaped compound has only an acid group and no salt containing an acid group, the above C1 is 0.

[0266] C2 represents the molar amount of cations contained in the salt of the acid group of the plate-like compound. Furthermore, in the case where the plate-like compound has only an acid group and no salt containing an acid group, the above C2 is 0.

[0267] C3 represents the molar amount of cations contained in the salt.

[0268] A1 represents the total molar amount of an acid group or its salt in the rod-shaped compound. When the rod-shaped compound contains both an acid group and its salt, the above total molar amount represents the sum of the molar amounts of the acid group and its salt. When the rod-shaped compound contains only one of the acid group and its salt, the molar amount of the one that is not present is 0.

[0269] A2 represents the total molar amount of acid groups or their salts in the plate-like compound. When the plate-like compound contains both acid groups and their salts, the above total molar amount represents the sum of the molar amounts of the acid groups and their salts. When the plate-like compound contains only either an acid group or its salt, the molar amount of the non-existent group is 0.

[0270] For example, in a composition containing a rod-shaped compound having an SO3Li group, a plate-shaped compound having an SO3Li group, and LiOH, when the molar amount of the SO3Li group in the rod-shaped compound is 5 mmol, the molar amount of the SO3Li group in the plate-shaped compound is 8 mmol, and the molar amount of LiOH is 8 mmol, the molar amount of the cation contained in the salt of the acid group of the rod-shaped compound is calculated to be 5 mmol, the molar amount of the cation contained in the salt of the acid group of the plate-shaped compound is calculated to be 8 mmol, and the molar amount of the cation contained in LiOH is calculated to be 8 mmol, and the ratio W is calculated to be {(5+8+8)-(5+8)} / 8=1.

[0271] Assuming the above rod-shaped compound is a rod-shaped compound with SO3H group, when the molar amount of SO3H group in the rod-shaped compound is 5 mmol, the ratio W is calculated as {(8+8)-(5+8)} / 8=0.375.

[0272] The ratio W above represents the amount of cations from the excess salt in the composition relative to the amount of acid groups or their salts present in the plate-like compound. That is, ratio W represents the ratio of the amount of acid groups present in the rod-like and plate-like compounds and the amount of excess cations that do not form salts relative to the amount of acid groups or their salts present in the plate-like compound. As described above, when the composition contains a predetermined amount of cations relative to the acid groups or their salts present in the plate-like compound, the plate-like compound readily obtains a predetermined structure in the optical anisotropic film, thus obtaining the desired optical anisotropic film.

[0273] The content of rod-shaped and plate-shaped compounds in the composition is not particularly limited, but is preferably 60-100% by mass, more preferably 80-99% by mass, relative to the total solid content in the composition.

[0274] Total solids content refers to the components other than solvents that can form optically anisotropic films. Furthermore, even if these components are in liquid form, they are still counted as solids content.

[0275] The composition may contain only one rod-shaped compound or two or more rod-shaped compounds.

[0276] The composition may contain only one plate-like compound or two or more plate-like compounds.

[0277] The content of the rod-shaped compound is not particularly limited relative to the total mass of the rod-shaped and plate-shaped compounds in the composition, but from the viewpoint of achieving excellent results of the present invention, it is preferable to exceed 50% by mass, more preferably 55% by mass or more. There is no particular upper limit, but it is preferably 90% by mass or less, more preferably 80% by mass.

[0278] As described above, the compositions of the present invention may also contain a solvent.

[0279] There is no particular limitation on the concentration of solid components in the composition of the present invention, but from the viewpoint of achieving excellent results, it is preferably 1 to 50% by mass relative to the total mass of the composition, more preferably 3 to 30% by mass.

[0280] As described above, the composition is a lyotropic liquid crystal composition. Therefore, the composition can be a composition containing a specified amount of solvent and exhibiting lyotropic liquid crystal properties (a state exhibiting lyotropic liquid crystal properties), or a composition containing an excess of solvent and not exhibiting lyotropic liquid crystal properties in that state (a composition exhibiting an isotropic phase), or a composition in which the solvent evaporates during the formation of an optically anisotropic film and exhibits lyotropic liquid crystal properties during the formation of the coating film.

[0281] Furthermore, as described later, if an orientation film is disposed on the support, the orientation of the compound can be induced by exhibiting lyotropic liquid crystal properties during the drying process after the composition is coated, thereby forming an optically anisotropic film.

[0282] <Methods for manufacturing optical anisotropic films>

[0283] The method for manufacturing the optical anisotropic film of the present invention is not particularly limited as long as the above-described composition is used. For example, a method of coating the composition of the present invention and orienting the rod-shaped and plate-shaped compounds in the coating to form an optical anisotropic film is preferred.

[0284] The steps of the above method are explained in detail below.

[0285] First, the composition is coated. Typically, the composition is coated onto a support.

[0286] The support used is a component that functions as a substrate for coating the composition. The support can also be a so-called pseudo-support.

[0287] Examples of supports (pseudo-supports) include plastic substrates or glass substrates. Examples of materials constituting plastic substrates include polyester resins such as polyethylene terephthalate, polycarbonate resins, (meth)acrylic resins, epoxy resins, polyurethane resins, polyamide resins, polyolefin resins, cellulose resins, silicone resins, and polyvinyl alcohol.

[0288] The thickness of the support can be about 5 to 1000 μm, preferably 10 to 250 μm, and more preferably 15 to 90 μm.

[0289] Additionally, an orientation membrane can be disposed on the support as needed.

[0290] Alignment films are generally composed primarily of polymers. Polymers used in alignment films are documented in numerous publications, and many commercially available products are readily available. Polyvinyl alcohol, polyimide, or their derivatives are preferred polymers for alignment films.

[0291] In addition, it is preferable to apply a known friction treatment to the alignment film.

[0292] Furthermore, photoalignment films can also be used as alignment films.

[0293] The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 1 μm.

[0294] As coating methods, well-known methods can be cited, such as curtain coating, extrusion coating, roller coating, dip coating, spin coating, printing coating, spray coating, and sliding coating.

[0295] Furthermore, if a shearing coating method is used, both compound orientation and coating can be performed simultaneously.

[0296] Furthermore, continuous coating can be used to continuously orient rod-shaped and plate-shaped compounds during coating. Examples of continuous coating methods include curtain coating, extrusion coating, roller coating, and slide coating. As specific coating apparatus, die coaters, doctor blade coaters, or rod coaters are preferred.

[0297] As a method for orienting rod-shaped and plate-shaped compounds in a coating film, as described above, a shearing method can be cited.

[0298] If necessary, the coating formed on the support can be subjected to heat treatment.

[0299] There are no particular restrictions on the conditions for heating the coating, but the heating temperature is preferably 50 to 250°C and the heating time is preferably 10 seconds to 10 minutes.

[0300] Furthermore, the coating can be cooled as needed after heating. The cooling temperature is preferably 20–200°C, more preferably 20–150°C.

[0301] As another method for orienting rod-shaped and plate-shaped compounds in a coating film, as mentioned above, the method of using an orientation film can be cited.

[0302] The orientation direction can be controlled by pre-treating the alignment film in a predetermined direction. This method is particularly advantageous when using an alignment film for continuous coating with a roller support, especially when the film is oriented in an inclined direction relative to the conveying direction.

[0303] In the method of using an alignment film, there is no particular limitation on the concentration of the solvent in the composition used; it can be the concentration of the solvent in which the composition exhibits lyotropic liquid crystal properties, or a concentration lower than that. As described above, since the composition is a lyotropic liquid crystal composition, even when the concentration of the solvent in the composition is high (when the composition itself exhibits an isotropic phase), by exhibiting lyotropic liquid crystal properties during the drying process after coating the composition, the orientation of the compound can be induced on the alignment film to form an optically anisotropic film.

[0304] In addition, after forming the optically anisotropic film, the orientation state of the rod-shaped and plate-shaped compounds can be fixed as needed.

[0305] There are no particular limitations on the method for fixing the orientation state of rod-shaped and plate-shaped compounds. As mentioned above, a method of cooling after heating the coating can be cited.

[0306] Furthermore, as a method for fixing the orientation state of rod-shaped and plate-shaped compounds, one example is contacting a solution containing polyvalent metal ions with the formed coating film. When the solution containing polyvalent metal ions is contacted with the formed coating film, polyvalent metal ions are supplied to the coating film. The polyvalent metal ions supplied to the coating film become crosslinking points between the acid groups or their salts present in the rod-shaped and / or plate-shaped compounds, forming a crosslinked structure in the coating film, thereby fixing the orientation state of the rod-shaped and plate-shaped compounds.

[0307] There are no particular restrictions on the types of polyvalent metal ions used, but from the viewpoint that the orientation state of rod-shaped and plate-shaped compounds is easy to fix, alkaline earth metal ions are preferred, and calcium ions are even more preferred.

[0308] Properties of Optical Anisotropic Films

[0309] The Nz coefficient of the optical anisotropic film satisfies the relationship of equation (1).

[0310] Equation (1) 0.40 ≤ Nz coefficient ≤ 0.60

[0311] The preferred value is 0.42 to 0.58, and the more preferred value is 0.45 to 0.54.

[0312] Optical anisotropic films exhibit reverse wavelength dispersion. Furthermore, reverse wavelength dispersion refers to the phenomenon where, when measuring the in-plane retardation (Re) value in at least a portion of the wavelength region of the visible light spectrum, the Re value remains constant or increases with increasing measurement wavelength. In this invention, the optical anisotropic film exhibits reverse wavelength dispersion only if it satisfies the relationships in equations (2) and (3).

[0313] Formula (2)Re(450) / Re(550)<1.00

[0314] Re(450) represents the in-plane retardation of an optical anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of an optical anisotropic film at a wavelength of 550 nm.

[0315] The Re(450) / Re(550) ratio is preferably 0.87 or less, more preferably 0.85 or less. Furthermore, the Re(450) / Re(550) ratio is preferably 0.60 or more, more preferably 0.72 or more, and more preferably 0.82 or more.

[0316] Formula (3)Re(650) / Re(550)>1.00

[0317] Re(650) represents the in-plane delay of an optical anisotropic film at a wavelength of 650 nm.

[0318] The Re(650) / Re(550) ratio is preferably 1.02 or higher, more preferably 1.05 or higher. There is no particular upper limit, but it is preferably 1.25 or lower, more preferably 1.20 or lower.

[0319] There are no particular limitations on the Re(550) of the optical anisotropic film, but from the viewpoint of its usefulness as a λ / 4 plate, it is preferably 110 to 160 nm, and more preferably 120 to 150 nm.

[0320] There is no particular limitation on the Rth(550) of the optical anisotropic film, but it is preferably -50 to 40 nm, and more preferably -40 to 30 nm.

[0321] There is no particular limitation on the thickness of the optical anisotropic film. From the viewpoint of thinning, it is preferably 10 μm or less, more preferably 0.5 to 8.0 μm, and even more preferably 0.5 to 6.0 μm.

[0322] Furthermore, in this specification, the thickness of the optical anisotropic film refers to the average thickness of the optical anisotropic film. This average thickness is calculated by measuring the thickness at any five or more points on the optical anisotropic film and then taking the arithmetic mean of these measurements.

[0323] <Applications>

[0324] The aforementioned optical anisotropic film can be used for various applications. For example, the in-plane retardation of the optical anisotropic film can be adjusted to use it as a so-called λ / 4 plate or λ / 2 plate.

[0325] In addition, a λ / 4 plate refers to a plate that has the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light). More specifically, it is a plate whose in-plane delay Re at a specified wavelength λnm is represented by λ / 4 (or an odd multiple thereof).

[0326] The in-plane delay (Re(550)) of the λ / 4 plate at a wavelength of 550nm can have an error of about 25nm centered on the ideal value (137.5nm), for example, preferably 110-160nm, more preferably 120-150nm.

[0327] Furthermore, the λ / 2 plate refers to an optically anisotropic film whose in-plane retardation Re(λ) at a specific wavelength λnm satisfies Re(λ)≈λ / 2. This formula can be implemented at any wavelength in the visible light region (e.g., 550nm). Preferably, the in-plane retardation Re(550) at a wavelength of 550nm satisfies the following relationship.

[0328] 210nm≤Re(550)≤300nm

[0329] <Optical film>

[0330] Optical anisotropic films can also be combined with other layers to be used as optical films. That is, the optical film of the present invention comprises the above-mentioned optical anisotropic film and other layers.

[0331] Other examples of layers include the aforementioned orientation film and support.

[0332] Furthermore, there are no particular restrictions on the placement of the optical anisotropic film in the optical film. For example, a configuration in which a support, an orientation film, and an optical anisotropic film are arranged in sequence can be cited.

[0333] <Polarizing plate>

[0334] The optical anisotropic film of the present invention is preferably applicable to polarizers.

[0335] That is, the polarizer (preferably a circular polarizer) of the present invention includes an optical anisotropic film or optical film and a polarizer. In addition, a circular polarizer refers to an optical element that converts unpolarized light into circularly polarized light.

[0336] A polarizer is any component that can convert light into linearly polarized light (a linear polarizer), and absorption polarizers can be used as the primary type.

[0337] Examples of absorption-type polarizers include iodine-based polarizers, dye-based polarizers utilizing 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 dichroic dyes onto polyvinyl alcohol and then stretching it are preferred.

[0338] There are no particular restrictions on the relationship between the slow axis of the optical anisotropic film and the absorption axis of the polarizer. However, when the optical anisotropic film is a λ / 4 plate and is used as a circularly polarized light thin film, the angle between the in-plane slow axis of the optical anisotropic film and the absorption axis of the polarizer is preferably in the range of 45 ± 10°. That is, the angle between the in-plane slow axis of the optical anisotropic film and the absorption axis of the polarizer is preferably in the range of 35 to 55°.

[0339] <Display Device>

[0340] The circular polarizer of the present invention is preferably applicable to display devices. That is, the circular polarizer of the present invention can be used as a so-called anti-reflective film.

[0341] The display device of the present invention includes a display element and the aforementioned circular polarizer. The circular polarizer is disposed on the visual recognition side, and a polarizer is disposed on the visual recognition side within the circular polarizer.

[0342] There are no particular limitations on the display device; examples include organic EL display elements and liquid crystal display elements, with organic EL display elements being preferred.

[0343] Example

[0344] The following examples and comparative examples further illustrate the features of the present invention. Regarding the materials, amounts, proportions, processing contents, and processing steps shown in the following examples, appropriate modifications can be made without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the specific examples shown below.

[0345] <Synthesis>

[0346] The following plate-shaped compounds I-1, I-1', I-2, II-1, II-1', and II-2 were synthesized using known methods. II-1, II-1', and II-2 are all polymers (n=2 or higher). The number-average molecular weight of II-1 is 24,000, and its molecular weight distribution is 6.8. The number-average molecular weight of II-1' is 30,000, and its molecular weight distribution is 5.7. The number-average molecular weight of II-2 is 25,000, and its molecular weight distribution is 5.1.

[0347] In addition, plate-like compound I-1, plate-like compound I-1', plate-like compound I-2, and rod-like compound II-1, rod-like compound II-1', and rod-like compound II-2 all exhibited lyotropic liquid crystal properties.

[0348] Furthermore, plate-shaped compound I-1, plate-shaped compound I-1', plate-shaped compound I-2, and rod-shaped compounds II-1, II-1', and II-2 all satisfy the aforementioned non-coloring requirement. More specifically, when measuring the UV-Vis absorption spectra of solutions obtained by dissolving the above compounds at a concentration of 1.0 with the absorbance at the maximum absorption wavelength in the ultraviolet region (230–400 nm), the absorbance in the visible light region (wavelength 400–700 nm) is 0.1 or less.

[0349] [Chemical Formula 13]

[0350]

[0351] [Chemical Formula 14]

[0352]

[0353] The plate-like compound I-1 has a maximum absorption wavelength of 345 nm in the wavelength range of 230–400 nm.

[0354] The plate-like compound I-1' has a maximum absorption wavelength of 345 nm in the wavelength range of 230–400 nm.

[0355] The plate-like compound I-2 has a maximum absorption wavelength of 345 nm in the wavelength range of 230–400 nm.

[0356] The rod-shaped compound II-1 has a maximum absorption wavelength of 260 nm in the wavelength range of 230–400 nm.

[0357] The rod-shaped compound II-1' has a maximum absorption wavelength of 260 nm in the wavelength range of 230–400 nm.

[0358] The rod-shaped compound II-2 has a maximum absorption wavelength of 290 nm in the wavelength range of 230–400 nm.

[0359] <Example 1>

[0360] An optically anisotropic film forming composition 1 with the following composition was prepared. Optically anisotropic film forming composition 1 is a composition exhibiting lyotropic liquid crystal properties.

[0361]

[0362] The optical anisotropic film forming composition 1 prepared above was coated onto a glass substrate using a wire rod (moving speed: 100 cm / s) and then allowed to dry naturally at room temperature (20°C). Next, the resulting coating was immersed in a 1 mol / L calcium chloride aqueous solution for 5 seconds, rinsed with deionized water, and then air-dried to fix the orientation state, thereby fabricating the optical anisotropic film 1.

[0363] <Examples 2-9, Comparative Examples 1-3>

[0364] The types of rod-shaped compounds, plate-shaped compounds, and salts were changed to the compounds shown in Table 1 below, and the amounts of each component were adjusted as shown in Table 1 below. Otherwise, optical anisotropic films 2-9, optical anisotropic film C1, and optical anisotropic film C3 were prepared by the same method as in Example 1.

[0365] No salt was used in Comparative Example 1 and Comparative Example 3.

[0366] In addition, regarding Comparative Example 2, the compound had no orientation and no optically anisotropic film was obtained.

[0367] <Evaluation>

[0368] The in-plane delay and Nz coefficient of the obtained optical anisotropic films 1-9, optical anisotropic film C1 and optical anisotropic film C3 were measured in the manner described above.

[0369] The results are summarized in Table 1.

[0370] In Table 1, “D” R The column indicates the wavelength dispersity D of the above rod-shaped compound, represented by formula (R). R Wavelength dispersion D R The measurement method is as described above. For example, in Example 1, an optically anisotropic film R was fabricated using a mixture R obtained by mixing rod-shaped compound II-1 (10 parts by mass) and water (90 parts by mass) by the above method, and wavelength dispersion D was obtained. R .

[0371] In Table 1, “λ” R The column indicates the maximum absorption wavelength of the rod-shaped compound.

[0372] In Table 1, “D” P The column indicates the wavelength dispersibility D of the above-mentioned plate-like compound, represented by formula (P). P .

[0373] In Table 1, “λ” P The column indicates the maximum absorption wavelength of the plate-like compound.

[0374] Wavelength Dispersion DR and Nz P The measurement method is as described above. For example, in Example 1, a mixture P2 obtained by mixing plate-like compound I-1 (10 parts by mass), water (90 parts by mass), and lithium hydroxide (0.93 parts by mass) was used to prepare an optically anisotropic film P by the above method, and wavelength dispersion D was obtained. P and Nz P .

[0375] The "ratio W" in Table 1 is the ratio W obtained from the above formula (W).

[0376] In Table 1, "LiOH" in the "Salt" column represents lithium hydroxide, "LiOTf" represents lithium trifluoromethanesulfonate, "LiTFSI" represents lithium bis(trifluoromethanesulfonyl)imide, "Li2SO4" represents lithium sulfate, and "NaOH" represents sodium hydroxide.

[0377]

[0378] As shown in Table 1, the optical anisotropic films formed using the compositions of the present invention exhibit the desired effects.

[0379] By comparing Examples 1 to 7, it was confirmed that better results could be obtained when W was 0.75 to 1.15.

[0380] In addition, better reverse wavelength dispersion means that the values ​​of Re(450) / Re(550) are closer to 0.82 and Re(650) / Re(550) are closer to 1.18.

[0381] Symbol Explanation

[0382] 10-Support, 12-Rod-shaped compound, 14-Specific compound.

Claims

1. A composition exhibiting lyotropic liquid crystal properties and comprising: Non-coloring rod-shaped compounds having an acid group or its salt; Non-coloring plate-like compounds having an acid group or its salt; and Salts composed of cations and anions. The anions are hydroxide ions, carbonate ions, chloride ions, sulfate ions, nitrate ions, phosphate ions, borate ions, tetrafluoroborate ions, hexafluorophosphate ions, perchlorate ions, toluenesulfonate ions, oxalate ions, formate ions, trifluoroacetate ions, trifluoromethanesulfonate ions, hexafluorophosphate ions, bis(fluoromethanesulfonyl)imide ions, bis(pentafluoroethanesulfonyl)imide ions, and bis(trifluoromethanesulfonyl)imide ions. The ratio W obtained from equation (W) is 0.25 to 1.

75. The maximum absorption wavelength of the rod-shaped compound in the wavelength range of 230–400 nm is smaller than that of the plate-shaped compound in the wavelength range of 230–400 nm. In formula (W), C1 represents the molar amount of cations contained in the salt of the acid group of the rod-shaped compound, C2 represents the molar amount of cations contained in the salt of the acid group of the plate-shaped compound, C3 represents the molar amount of cations contained in the salt, A1 represents the total molar amount of the acid group and the salt of the acid group in the rod-shaped compound, and A2 represents the total molar amount of the acid group and the salt of the acid group in the plate-shaped compound.

2. The composition according to claim 1, wherein, The ratio W is 0.75 to 1.

15.

3. The composition according to claim 1 or 2, wherein, Both the rod-shaped compound and the plate-shaped compound are lyotropic liquid crystal compounds.

4. The composition according to claim 1 or 2, wherein, The salt composed of cations and anions is a lithium salt.

5. The composition according to claim 1 or 2, wherein, The rod-shaped compound is a polymer having repeating units represented by formula (X). R x1 This refers to a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof, or a group represented by formula (X1). Formula (X1)*-R x3 -L x3 -R x4 -* R x3 and R x4 R can be independently represented as a divalent aromatic ring group that may have substituents containing an acid group or its salt, or a divalent non-aromatic ring group that may have substituents containing an acid group or its salt. x3 and R x4 At least one of them represents a divalent aromatic ring group having a substituent containing an acid group or a salt thereof, or a divalent non-aromatic ring group having a substituent containing an acid group or a salt thereof. L x3 Indicates a single bond, -O-, -S-, alkylene, alkenylene, or ynylene. R x2 This indicates a divalent non-aromatic ring group or a group represented by formula (X2). Formula (X2)*-Z x1 -Z x2 -*, Z x1 and Z x2 Each can be independently represented by a divalent non-aromatic ring group. L x1 and L x2 Each can be independently represented as -CONH-, -COO-, -O-, or -S-. In equation (X1), * represents the bonding position. In equation (X2), * represents the bonding position.

6. The composition according to claim 1 or 2, wherein, The plate-like compound is a compound represented by formula (Y). Formula(Y)R y2 -L y3 -L y1 -R y1 -L y2 -L y4 -R y3 , R y1 This indicates a divalent monocyclic group or a divalent fused polycyclic group. R y2 and R y3 Each can independently represent a hydrogen atom or an acid group or its salt, R y2 and R y3 At least one of them represents an acid group or its salt. L y1 and L y2 Each can independently represent a single bond, a divalent aromatic ring group, or a group represented by formula (Y1), wherein, when R y1 When L is a divalent monocyclic group, y1 and L y2 Both represent a divalent aromatic ring group or a group represented by formula (Y1). Formula (Y1)*-R y4 -(R y5 ) n -*, R y4 and R y5 Each of these groups independently represents a divalent aromatic ring group. n represents 1 or 2, L y3 and L y4 Each can independently represent a single bond, -O-, -S-, alkylene, alkenylene, ynylene, or a combination thereof. In formula (Y1), * represents the bonding position.

7. The composition according to claim 1 or 2, wherein, The content of the rod-shaped compound exceeds 50% by mass relative to the total mass of the rod-shaped compound and the plate-shaped compound.

8. An optically anisotropic film formed using the composition of any one of claims 1 to 7.

9. A circular polarizer, comprising: The optical anisotropic film of claim 8; and Polarizer.

10. The circular polarizer according to claim 9, wherein, The angle between the in-plane slow axis of the optical anisotropic film and the absorption axis of the polarizer is in the range of 45±5°.

11. A display device comprising: The circular polarizer as described in claim 9 or 10; and Display element.

12. The display device according to claim 11, wherein, The display element is an organic electroluminescent display element.

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