Liquid crystal composition, light-absorbing anisotropic film, optical laminate, and image display device

Abstract

The present invention addresses the problem of providing: a liquid crystal composition in which a dichroic substance exhibits excellent solubility and which can increase the degree of orientation of an obtained light-absorbing anisotropic film; a light-absorbing anisotropic film; an optical laminate; and an image display device. A liquid crystal composition according to the present invention contains a liquid crystal compound and two or more dichroic substances. Among the dichroic substances, there is at least one combination of two dichroic substances satisfying the relationship in which the Tanimoto coefficient is 0.830-0.920. In the combination of two dichroic substances satisfying said relationship, when a dichroic substance having a larger molecular weight is represented by (ZA) and a dichroic substance having a smaller molecular weight is represented by (ZB), the melting points of both dichroic substances (ZA) and (ZB) are 200°C or less, at least one of the dichroic substances (ZA) and (ZB) is a dichroic substance having only one polymerizable group or not having a polymerizable group, and the dichroic substances (ZA) and (ZB) do not have any of a hydroxyl group, a carboxy group, or a sulfonic acid group.

Description

Liquid crystal composition, light-absorbing anisotropic film, optical laminate, and image display device.

[0001] The present invention relates to liquid crystal compositions, light-absorbing anisotropic films, optical laminates, and image display devices.

[0002] Conventionally, liquid crystal displays (LCDs) have used linear and circular polarizers to control optical rotation and birefringence in display. Similarly, organic light-emitting diodes (OLEDs) also use circular polarizers to prevent reflection of ambient light. While iodine has been widely used as the dichroic material in these polarizers (polarizing elements), light-absorbing anisotropic films using organic dyes as the dichroic material instead of iodine are also being investigated (Patent Document 1).

[0003] Furthermore, in recent years, techniques have been developed to use optically anisotropic films with an absorption axis in the thickness direction in conjunction with image display devices to prevent overlooking or to control the viewing angle. For example, optically anisotropic films formed from liquid crystal compositions containing liquid crystalline compounds or dichroic substances are known.

[0004] International Publication No. 2017 / 090668

[0005] The present inventors investigated light-absorbing anisotropic films described in Patent Document 1 and other documents, and found that there is room for improvement in balancing the solubility of the dichroic substance with the degree of orientation in the resulting light-absorbing anisotropic film.

[0006] Therefore, the object of the present invention is to provide a liquid crystal composition, a light-absorbing anisotropic film, an optical laminate, and an image display device that have good solubility of dichroic substances and can achieve a high degree of orientation of the resulting light-absorbing anisotropic film.

[0007] As a result of diligent research into the above-mentioned problems, the inventors have discovered that by using a liquid crystal composition containing specific amounts of two or more dichroic substances that satisfy various conditions such as the Tanimoto coefficient, the solubility of the dichroic substances improves, and the degree of orientation of the resulting light-absorbing anisotropic film increases, thus completing the present invention. In other words, the inventors have found that the above-mentioned problems can be solved by the following configuration.

[0008] [1] A liquid crystal composition containing a liquid crystal compound and two or more dichroic substances, wherein at least one combination of two dichroic substances satisfies the relationship that the Tanimoto coefficient is 0.830 to 0.920, and in the combination of two dichroic substances satisfying the above relationship, when the dichroic substance with a larger molecular weight is (ZA) and the dichroic substance with a smaller molecular weight is (ZB), the mass ratio of the content of the dichroic substance (ZA) to the content of the dichroic substance (ZB) in the total solid content of the liquid crystal composition is 0.33 to 3.00, the melting points of the dichroic substances (ZA) and (ZB) are both 200°C or less, and at least one of the dichroic substances (ZA) and (ZB) has only one polymerizable group or is a dichroic substance without polymerizable groups. [1] A liquid crystal composition in which the above-mentioned dichroic substances (ZA) and (ZB) do not have any hydroxyl groups, carboxyl groups, or sulfonic acid groups. [2] The liquid crystal composition according to [1], wherein the above-mentioned Tanimoto coefficient is 0.860 to 0.920. [3] The liquid crystal composition according to [1] or [2], wherein the above-mentioned dichroic substances (ZA) and (ZB) are both dichroic azo dye compounds. [4] The liquid crystal composition according to any one of [1] to [3], wherein the above-mentioned dichroic substances (ZA) and (ZB) both have a substructure represented by formula (1) described later. [5] The liquid crystal composition according to any one of [1] to [4], wherein the above-mentioned dichroic substances (ZA) and (ZB) both have a structure represented by formula (2) described later. [6] A liquid crystal composition according to any one of [1] to [5], further containing a solvent, wherein the difference in solubility parameters between the dichroic substance (ZA) and the solvent, and the difference in solubility parameters between the dichroic substance (ZB) and the solvent are both 3.0 or less. [7] A liquid crystal composition according to any one of [1] to [6], wherein the solubility of at least one of the dichroic substances (ZA) and (ZB) is less than 0.7%. [8] A light-absorbing anisotropic film obtained by fixing the orientation state of the liquid crystal composition according to any one of [1] to [7]. [9] A light-absorbing anisotropic film according to [8], wherein the angle θ between the transmittance center axis of the light-absorbing anisotropic film and the normal direction of the surface of the light-absorbing anisotropic film is 0° or more and 45° or less.

[10] The light-absorbing anisotropic film according to [8] or [9], wherein the absorption axis of the light-absorbing anisotropic film is parallel to the in-plane direction of the light-absorbing anisotropic film.

[11] An optical laminate having the light-absorbing anisotropic film according to any one of [8] to

[10] .

[12] An image display device having the light-absorbing anisotropic film according to any one of [8] to

[10] .

[0009] As shown below, the present invention provides a liquid crystal composition, a light-absorbing anisotropic film, an optical laminate, and an image display device that exhibit good solubility of dichroic substances and can achieve a high degree of orientation of the resulting light-absorbing anisotropic film.

[0010] Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, a numerical range represented by "~" means a range including the numerical values described before and after "~" as the lower limit value and the upper limit value. Also, in this specification, for a numerical range described stepwise, the upper limit value or the lower limit value described in a certain numerical range may be replaced with the upper limit value or the lower limit value of another numerically described stepwise range. Further, the upper limit value or the lower limit value described in a certain numerical range in the numerical range described in this specification may be replaced with the value shown in the examples. Also, in this specification, each component may be used alone as one kind of substance corresponding to each component, or two or more kinds may be used in combination. Here, 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. Also, in this specification, "(meth)acrylate" is a notation representing "acrylate" or "methacrylate", "(meth)acrylic" is a notation representing "acrylic" or "methacrylic", "(meth)acryloyl" is a notation representing "acryloyl" or "methacryloyl", and "(meth)acrylic acid" is a notation representing "acrylic acid" or "methacrylic acid". Also, in this specification, the bonding direction of the divalent group (for example, -COO-) described is not particularly limited unless the bonding position is specified. For example, when L in X-L-Y is -COO-, if the position bonded to the X side is *1 and the position bonded to the Y side is *2, L may be *1-O-CO-*2 or *1-CO-O-* with the position bonded to the Y side being *X側に結合している位置を*1、Y側に結合している位置を*2とすると、Lは*1-O-CO-*2であってもよく、*1-CO-O-*2であってもよい。

[0011] Also, in this specification, "orthogonal" and "parallel" regarding an angle mean a strict angle range of ±10°, and "identical" and "different" regarding an angle can be judged based on whether the difference is less than 5°. Also, in this specification, "visible light" refers to 380 to 780nm. Also, in this specification, when there is no particular note regarding the measurement wavelength, the measurement wavelength is 550nm.

[0012] In this specification, the "slow axis" refers to the direction in which the refractive index is maximum within the plane. When referring to the slow axis of a light-absorbing anisotropic film, it refers to the slow axis of the entire light-absorbing anisotropic film.

[0013] In this specification, "Re(λ)" and "Rth(λ)" represent the in-plane retardation and thickness-direction retardation at wavelength λ, respectively. Here, the values ​​for in-plane retardation and thickness-direction retardation are those measured using an AxoScan OPMF-1 (manufactured by OptoScience Co., Ltd.) with light at the measurement wavelength. Specifically, by inputting the average refractive index ((nx + ny + nz) / 3) and film thickness (d) into the AxoScan OPMF-1, the following can be calculated: Late axis direction (°) Re(λ) = R0(λ) Rth(λ) = ((nx + ny) / 2 - nz) × d Note that R0(λ) is displayed as a numerical value calculated by the AxoScan OPMF-1, but it means Re(λ).

[0014] In this specification, examples of substituents (monovalent substituents) include the substituents listed in substituent group A below. In this specification, "may have substituents" includes not only embodiments without substituents but also embodiments having one or more substituents. <Substituent Group A> Substituents include, for example, halogen atoms (e.g., fluorine atom, chlorine atom, bromine atom, preferably chlorine atom, fluorine atom, more preferably fluorine atom); alkyl groups (preferably C1 to C48, more preferably C1 to C24, particularly preferably C1 to C8 alkyl groups, for example, C1 to C6 linear alkyl groups (e.g., methyl group, ethyl group, n-propyl group, n-butyl group, n-pentyl group, n-hexyl group), C3 to C6 branched alkyl groups (e.g., isopropyl group, isobutyl group, tert-butyl group, sec-butyl group, neopentyl group, isohexyl group, 3-methylpentyl group), C3 to C12 cyclic alkyl groups (e.g., cyclopropyl group, cyclopentyl group, cyclohexyl group, 1-norbornyl group, 1-adamantyl group)); Alkenyl groups (preferably 2 to 48 C12, more preferably 2 to 18 C12 alkenyl groups, for example vinyl groups, allyl groups, 1-butenyl groups, 2-butenyl groups); Alkynyl groups (preferably 2 to 6 C12 alkynyl groups, more preferably 2 to 4 C12 alkynyl groups, for example ethynyl groups, 1-propynyl groups, propargyl groups, 1-butynyl groups, 2-butynyl groups); Aryl groups (preferably 6 to 48 C12, more preferably 6 to 24 C12 aryl groups, for example phenyl groups, oligoaryl groups (naphthyl groups, anthryl groups), phenanthrenyl groups, fluorenyl groups, pyrenyl groups, triphenylenyl groups, biphenyl groups); Heteroaryl groups (preferably heterocyclic groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 2-thienyl group, 4-pyridyl group, 2-furyl group, 2-pyrimidinyl group, 1-pyridyl group, 2-benzothiazolyl group, 1-imidazolyl group, 1-pyrazolyl group, benzotriazole-1-yl group);Arylalkyl groups (preferably arylalkyl groups having 7 to 15 carbon atoms, for example, benzyl group, phenethyl group, methylbenzyl group, phenylpropyl group, 1-methylphenylethyl group, phenylbutyl group, 2-methylphenylpropyl group, tetrahydronaphthyl group, naphthylmethyl group, naphthylethyl group, indenyl group, fluorenyl group, anthracenylmethyl group (anthrylmethyl group), phenanthrylmethyl group (phenanthrylmethyl group)); silyl groups (preferably silyl groups having 3 to 38 carbon atoms, more preferably silyl groups having 3 to 18 carbon atoms, for example, trimethylsilyl group, triethylsilyl group, tributylsilyl group, t-butyldimethylsilyl group, t-hexyldimethylsilyl group); hydroxyl groups; cyano groups; nitro groups; morpholino groups; Alkoxy groups (preferably alkoxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methoxy group, ethoxy group, 1-butoxy group, 2-butoxy group, isopropoxy group, t-butoxy group, dodecyloxy group, cycloalkyloxy group (for example, cyclopentyloxy group, cyclohexyloxy group)); aryloxy groups (preferably aryloxy groups having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenoxy group, 1-naphthoxy group); alkenyloxy groups (preferably alkenyloxy groups having 2 to 6 carbon atoms, for example, vinyloxy group, 1-propenyloxy group, 2-n-propenyloxy group (allyloxy group), 1-n-butenyloxy group, prenyloxy group); Heterocyclic oxy groups (preferably heterocyclic oxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 1-phenyltetrazole-5-oxy group, 2-tetrahydropyranyloxy group); silyloxy groups (preferably silyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, trimethylsilyloxy group, t-butyldimethylsilyloxy group, diphenylmethylsilyloxy group); acyloxy groups (preferably acyloxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetoxy group, pivaloyloxy group, benzoyloxy group, dodecanoyloxy group, acryloyloxy group, methacryloyloxy group);Hydroxyalkylene oxy groups (preferably hydroxyalkylene oxy groups having 2 to 10 carbon atoms, for example, hydroxyethylene oxy groups); alkylcarbonyl oxy groups (preferably alkylcarbonyl oxy groups having 2 to 10 carbon atoms, for example, ethylcarbonyl oxy groups); alkoxycarbonyl oxy groups (preferably alkoxycarbonyl oxy groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, ethoxycarbonyl oxy groups, t-butoxycarbonyl oxy groups, cycloalkyloxycarbonyl oxy groups (for example, cyclohexyloxycarbonyl oxy groups)); aryloxycarbonyl oxy groups (preferably aryloxycarbonyl oxy groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl oxy groups); Carbamoyloxy groups (preferably carbamoyloxy groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-dimethylcarbamoyloxy group, N-butylcarbamoyloxy group, N-phenylcarbamoyloxy group, N-ethyl-N-phenylcarbamoyloxy group); sulfamoyloxy groups (preferably sulfamoyloxy groups having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, for example, N,N-diethylsulfamoyloxy group, N-propylsulfamoyloxy group); alkylsulfonyloxy groups (preferably alkylsulfonyloxy groups having 1 to 38 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methylsulfonyloxy group, hexadecylsulfonyloxy group, cyclohexylsulfonyloxy group); arylsulfonyloxy groups (preferably arylsulfonyloxy groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, phenylsulfonyloxy group); Acyl groups (preferably acyl groups having 1 to 48 carbon atoms, more preferably acyl groups having 1 to 24 carbon atoms, for example, formyl group, acetyl group, acryloyl group, methacryloyl group, pivaloyl group, benzoyl group, tetradecanoyl group, cyclohexanoyl group);Alkoxycarbonyl groups (preferably alkoxycarbonyl groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonyl group, ethoxycarbonyl group, octadecyloxycarbonyl group, cyclohexyloxycarbonyl group, 2,6-di-tert-butyl-4-methylcyclohexyloxycarbonyl group); aryloxycarbonyl groups (preferably aryloxycarbonyl groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonyl group); Carbamoyl groups (preferably carbamoyl groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, carbamoyl group, N,N-diethylcarbamoyl group, N-ethyl-N-octylcarbamoyl group, N,N-dibutylcarbamoyl group, N-propylcarbamoyl group, N-phenylcarbamoyl group, N-methylN-phenylcarbamoyl group, N,N-dicyclohexylcarbamoyl group); amino groups (preferably amino groups having 32 or fewer carbon atoms, more preferably 24 or fewer carbon atoms, for example, amino group, methylamino group, N,N-dimethylamino group, N,N-dibutylamino group, tetradecylamino group, 2-ethylhexylamino group, cyclohexylamino group); anilino groups (preferably anilino groups having 6 to 32 carbon atoms, more preferably 6 to 24 carbon atoms, for example, anilino group, N-methylanilino group); Heterocyclic amino groups (preferably heterocyclic amino groups having 1 to 32 carbon atoms, more preferably 1 to 18 carbon atoms, for example, 4-pyridylamino group); carbonamide groups (preferably carbonamide groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, acetamide group, benzamide group, tetradecaneamide group, pivaloylamide group, cyclohexaneamide group); ureido groups (preferably carbonamide groups having 1 to 32 carbon atoms, more preferably carbonamide groups having 1 to 24 carbon atoms, for example, ureido group, N,N-dimethylureido group, N-phenylureido group); imide groups (preferably imide groups having 36 carbon atoms or less, more preferably carbon atoms of 24 carbon atoms or less, for example, N-succinimide group, N-phthalimide group);Alkoxycarbonylamino groups (preferably alkoxycarbonylamino groups having 2 to 48 carbon atoms, more preferably 2 to 24 carbon atoms, for example, methoxycarbonylamino group, ethoxycarbonylamino group, t-butoxycarbonylamino group, octadecyloxycarbonylamino group, cyclohexyloxycarbonylamino group); aryloxycarbonylamino groups (preferably aryloxycarbonylamino groups having 7 to 32 carbon atoms, more preferably 7 to 24 carbon atoms, for example, phenoxycarbonylamino group); sulfonamide groups (preferably sulfonamide groups having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, for example, methanesulfonamide group, butanesulfonamide group, benzenesulfonamide group, hexadecanesulfonamide group, cyclohexanesulfonamide group); Sulfamoylamino groups (preferably C1-C48, more preferably C1-C24 sulfamoylamino groups, for example, N,N-dipropylsulfamoylamino group, N-ethyl-N-dodecylsulfamoylamino group); Azo groups (preferably C1-C32, more preferably C1-C24 azo groups, for example, phenylazo group, 3-pyrazolylazo group); Alkylthio groups (preferably C1-C48, more preferably C1-C24 alkylthio groups, for example, methylthio group, ethylthio group, octylthio group, cyclohexylthio group); Arylthio groups (preferably C6-C48, more preferably C6-C24 arylthio groups, for example, phenylthio group); Heterocyclic thio groups (preferably C1-C32, more preferably C1-C18 heterocyclic thio groups, for example, 2-benzothiazolylthio group, 2-pyridylthio group, 1-phenyltetrazolylthio group); Alkyl sulfinyl group (preferably an alkyl sulfinyl group having 1 to 32 carbon atoms, more preferably an alkyl sulfinyl group having 1 to 24 carbon atoms, for example, dodecane sulfinyl group); aryl sulfinyl group (preferably an aryl sulfinyl group having 6 to 32 carbon atoms, more preferably an aryl sulfinyl group having 6 to 24 carbon atoms, for example, phenyl sulfinyl group);An alkylsulfonyl group (preferably an alkylsulfonyl group having 1 to 48 carbon atoms, more preferably 1 to 24 carbon atoms, such as methylsulfonyl group, ethylsulfonyl group, propylsulfonyl group, butylsulfonyl group, isopropylsulfonyl group, 2-ethylhexylsulfonyl group, hexadecylsulfonyl group, octylsulfonyl group, cyclohexylsulfonyl group); an arylsulfonyl group (preferably an arylsulfonyl group having 6 to 48 carbon atoms, more preferably 6 to 24 carbon atoms, such as phenylsulfonyl group, 1-naphthylsulfonyl group); a sulfamoyl group (preferably a sulfamoyl group having 32 or fewer carbon atoms, more preferably 24 or fewer carbon atoms, such as sulfamoyl group, N,N-dipropylsulfamoyl group, N-ethyl-N-dodecylsulfamoyl group, N-ethyl-N-phenylsulfamoyl group, N-cyclohexylsulfamoyl group, N-(2-ethylhexyl)sulfamoyl group); a phosphonyl group (preferably a phosphonyl group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as phenoxyphosphonyl group, octyloxyphosphonyl group, phenylphosphonyl group); a phosphinoylamino group (preferably a phosphinoylamino group having 1 to 32 carbon atoms, more preferably 1 to 24 carbon atoms, such as diethoxyphosphinoylamino group, dioctyloxyphosphinoylamino group); an epoxy group; -NHCOCH; ３ ; -SO ２ NH C ２ H ４ OCH ３ ; -NHSO ２ CH ３ ; etc. may be mentioned, and two or more thereof may be combined. These substituents may further be substituted by these substituents. Also, when having two or more substituents, they may be the same or different from each other. Also, when possible, they may be bonded to each other to form a ring.

[0015] [Liquid Crystal Composition] The liquid crystal composition of the present invention (hereinafter also simply referred to as "this liquid crystal composition") is a liquid crystal composition containing a liquid crystal compound and two or more dichroic substances, wherein there is at least one combination of two dichroic substances that satisfies the relationship that the Tanimoto coefficient is 0.830 to 0.920. In the above combination of two dichroic substances that satisfies the Tanimoto coefficient relationship, the dichroic substance with a larger molecular weight is denoted as (ZA), and the dichroic substance with a smaller molecular weight is denoted as (ZB). In the above combination of two dichroic substances that satisfies the Tanimoto coefficient relationship, if the molecular weights are the same, the dichroic substance with a higher melting point is denoted as (ZA), and the dichroic substance with a lower melting point is denoted as (ZB). The mass ratio of the content of dichroic substance (ZA) to the content of dichroic substance (ZB) in the total solid content of the liquid crystal composition is 0.33 to 3.00. In addition, the melting points of the above dichroic substances (ZA) and (ZB) are both 200°C or lower. Furthermore, at least one of the above-mentioned dichroic substances (ZA) and (ZB) has only one polymerizable group or has no polymerizable groups. Also, the above-mentioned dichroic substances (ZA) and (ZB) do not have any hydroxyl groups, carboxyl groups, or sulfonic acid groups.

[0016] In the present invention, by using a liquid crystal composition containing specific amounts of two or more dichroic substances that satisfy the various conditions described above, such as the Tanimoto coefficient, the solubility of the dichroic substances is improved, and the degree of orientation of the resulting light-absorbing anisotropic film can be increased. The reason for this effect is not entirely clear, but the inventors speculate as follows: Dichroic substances that satisfy the Tanimoto coefficient have a moderate structural similarity to each other, which is thought to result in good solubility of the dichroic substances and allows the resulting light-absorbing anisotropic film to maintain a high degree of orientation.

[0017] The liquid crystal compounds and dichroic substances included in the liquid crystal composition of the present invention, as well as optional components, will be described in detail below.

[0018] [Dichroic Substances] The liquid crystal composition of the present invention contains two or more dichroic substances. Here, a dichroic substance means a dye whose absorbance differs depending on the direction. Furthermore, the dichroic substances may or may not exhibit liquid crystalline properties. In addition, the above-mentioned dichroic substances (ZA) and (ZB) do not have any hydroxyl groups, carboxyl groups, or sulfonic acid groups.

[0019] <Tanimoto Coefficient> The dichroic substances contained in this liquid crystal composition include at least one combination of two dichroic substances that satisfy a relationship in which the Tanimoto coefficient is between 0.830 and 0.920. The Tanimoto coefficient is an index used to quantitatively evaluate the structural coefficients between compounds, and is calculated by normalizing the number of common features between two datasets corresponding to two compounds by the total number of features in the two datasets. Specifically, the Tanimoto coefficient (T(A,B)) is calculated by dividing the number of common elements in datasets A and B (|A∩B|) by the sum of the number of unique elements contained in each dataset (|A∪B|). In the formula below, |A∩B| represents the number of common elements between set A and set B, |A∪B| represents the total number of elements in set A and set B, T(A,B) represents the Tanimoto coefficient, |A| represents the number of elements in set A, and |B| represents the number of elements in set B. T(A,B) = (|A∩B|) / (|A∪B|) = (|A∩B|) / (|A| + |B| - |A∩B|) The Tanimoto coefficient takes values ​​in the range of 0 to 1. A Tanimoto coefficient close to 1 indicates that the coefficients of the two compounds are high, and a Tanimoto coefficient close to 0 indicates that the coefficients of the two compounds are low.

[0020] The Tanimoto coefficient between dichroic substances is calculated by generating Topological torsion fingerprints that represent the molecular structure of the compounds using the chemical informatics software "RDKit," and then calculating based on these fingerprints.

[0021] If the liquid crystal composition contains three or more dichroic substances, it is sufficient that at least one combination of two dichroic substances satisfies the relationship of Tanimoto coefficient between 0.830 and 0.920. In other words, if the liquid crystal composition contains three or more dichroic substances, there may be combinations of two dichroic substances in which the Tanimoto coefficient does not satisfy the relationship of Tanimoto coefficient between 0.830 and 0.920. Specifically, if the liquid crystal composition contains dichroic substances A, B, and C, the combinations of dichroic substances include dichroic substances A and B, dichroic substances B and C, and dichroic substances A and C. For example, if the combination of dichroic substances A and B satisfies the relationship of Tanimoto coefficient between 0.830 and 0.920, it is not necessary for the combination of dichroic substances B and C, and the combination of dichroic substances A and C, to satisfy the relationship of Tanimoto coefficient between 0.830 and 0.920.

[0022] In the present invention, for the reason that the degree of orientation of the resulting light-absorbing anisotropic film is higher, it is preferable that at least one of the combinations of two dichroic substances in the liquid crystal composition satisfies the relationship that the Tanimoto coefficient is 0.860 to 0.920, and more preferably satisfies the relationship that is 0.890 to 0.920.

[0023] <Mass Ratio> In this liquid crystal composition, the mass ratio of the content of the dichroic substance (ZA) to the content of the dichroic substance (ZB) is 0.33 to 3.00, as described above. For the reason that the solubility of the dichroic substance is good, the mass ratio of the content of the dichroic substance (ZA) to the content of the dichroic substance (ZB) is preferably 0.40 to 2.50, and more preferably 0.45 to 2.22.

[0024] <Melting Point> In this liquid crystal composition, the melting points of the dichroic substances (ZA) and (ZB) described above are both 200°C or lower. However, for the reason that the planar surface of the resulting light-absorbing anisotropic film is improved, the melting points of both are preferably 195°C or lower, and more preferably 190°C or lower. Furthermore, for the reason that the degree of orientation of the resulting light-absorbing anisotropic film is increased, the melting points of the dichroic substances (ZA) and (ZB) are preferably 100°C or higher, and more preferably 120°C or higher.

[0025] <Polymerizable Groups> In this liquid crystal composition, at least one of the dichroic substances (ZA) and (ZB) described above is a dichroic substance having only one polymerizable group or having no polymerizable groups. However, for the reason that the degree of orientation of the resulting light-absorbing anisotropic film is high, it is preferable that both the dichroic substances (ZA) and (ZB) are dichroic substances having only one polymerizable group or having no polymerizable groups. As polymerizable groups, polymerizable groups that can be radically polymerized or cationically polymerized are preferred. As radical polymerizable groups, known radical polymerizable groups can be used, and preferred examples include acryloyloxy groups or methacryloyloxy groups. In this case, the polymerization rate of acryloyloxy groups is generally known to be faster, and from the viewpoint of improving productivity, acryloyloxy groups are preferred, but methacryloyloxy groups can also be used as polymerizable groups in the same way. Known cationic polymerizable groups can be used as the cationic polymerizable group, specifically including alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. Among these, alicyclic ether groups or vinyloxy groups are preferred, and epoxy groups, oxetanyl groups, or vinyloxy groups are particularly preferred.

[0026] In this liquid crystal composition, the total content of dichroic substances (ZA) and (ZB) is preferably more than 0% by mass and 30% by mass or less, more preferably 1 to 20% by mass, and even more preferably 1 to 15% by mass, because this results in a higher degree of orientation of the resulting light-absorbing anisotropic film. Here, when calculating the total content of dichroic substances (ZA) and (ZB), the content of a dichroic substance that falls under either (ZA) or (ZB) is counted as the content of either one of the dichroic substances (ZA) or (ZB). For example, if the liquid crystal composition contains three dichroic substances A, B, and C, and any combination of dichroic substances A and B, dichroic substances B and C, and dichroic substances A and C correspond to dichroic substances (ZA) and (ZB), then dichroic substance B corresponds to both dichroic substances (ZA) and (ZB). In this case, the total content of dichroic substances (ZA) and (ZB) shall be the total content of dichroic substances A, B, and C. Hereinafter, in this specification, "solid content of the liquid crystal composition" refers to the components excluding the solvent, and specific examples of solid content include dichroic substances, liquid crystal compounds, polymerization initiators, and surfactants.

[0027] The dichroic substances (ZA) and (ZB) are preferably dichroic azo dye compounds. A dichroic azo dye compound is an azo dye compound whose absorbance differs depending on the direction. The dichroic azo dye compound may or may not exhibit liquid crystalline properties. If the dichroic azo dye compound exhibits liquid crystalline properties, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystalline phase is exhibited is preferably room temperature (about 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoint of handling and manufacturing suitability. The dichroic azo dye compound is preferably a diazo dye compound having two azo bonds.

[0028] The dichroic substances (ZA) and (ZB) preferably both have a substructure represented by the following formula (1).

[0029] The dichroic substances (ZA) and (ZB) both preferably have a structure represented by the following formula (2).

[0030] In the above formulas (1) and (2), Ra １ and Ra ２ and Rb １１ and Rb １２ each independently represent a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a monovalent substituent, or a monovalent group in which -CH ２ - constituting the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is substituted with a divalent substituent.

[0031] Examples of the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include an alkyl group having 1 to 20 carbon atoms, etc. An alkyl group having 1 to 10 carbon atoms is preferable, and an alkyl group having 1 to 4 carbon atoms is more preferable. Further, examples of the divalent substituent that substitutes -CH ２ - constituting the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms include, for example, -O-, -CO-, -C(O)-O-, -O-C(O)-, -Si(CH ３ ) ２ -O-Si(CH ３ ) ２ -, -N(R)-, -N(R)-CO-, -CO-N(R)-, -N(R)-C(O)-O-, -O-C(O)-N(R)-, -N(R)-C(O)-N(R')-, -CH=CH-, -C≡C-, -N=N-, -C(R)=N-, -C(R)=CH-C(O)- or -O-C(O)-O-, etc. R and R' represent an alkyl group, and an alkyl group having 1 to 10 carbon atoms is preferable.

[0032] Ara and Arc each independently represent a divalent aromatic group which may have a monovalent substituent. Examples of divalent aromatic groups include divalent aromatic hydrocarbon groups and divalent aromatic heterocyclic groups. Examples of the above-mentioned divalent aromatic hydrocarbon groups include arylene groups having 6 to 12 carbon atoms, specifically phenylene groups, cumenylene groups, mesitylene groups, torylene groups, xylylene groups, etc. Among these, phenylene groups are preferred. Examples of the above-mentioned divalent aromatic heterocyclic groups include pyridylene groups (pyridine-diyl groups), pyridazine-diyl groups, imidazole-diyl groups, thienylene groups (thiophene-diyl groups), quinolylene groups (quinoline-diyl groups), etc. Ra １ Ra ２ , Rb １１ , Rb １２ Examples of "monovalent substituents" that Ara and Arc may have include the substituents listed in substituent group A above.

[0033] In equations (1) and (2) above, na and nc each independently represent integers from 0 to 3, and the sum of na and nc is 1 or greater. If there are multiple na, the multiple Ara values ​​may be the same or different. If there are multiple nc values, the multiple Arc values ​​may be the same or different.

[0034] In the present invention, the dichroic substances (ZA) and (ZB) preferably have a maximum absorption wavelength in the range of 560 nm to 700 nm, more preferably have a maximum absorption wavelength in the range of 560 to 650 nm, and even more preferably have a maximum absorption wavelength in the range of 560 to 640 nm. Here, the maximum absorption wavelength refers to the wavelength at which the absorbance of the dichroic substance takes its maximum value in the absorption spectrum (measurement range: wavelength 250 to 700 nm).

[0035] Examples of dichroic substances (ZA) and (ZB) include dichroic substances represented by the following formulas, from which two dichroic substances that satisfy the relationship of the Tanimoto coefficients described above are selected.

[0036] In this liquid crystal composition, for the effects of the present invention to become apparent, it is preferable that the solubility of at least one of the dichroic substances (ZA) and (ZB) be less than 0.7%, more preferably less than 0.6%, and even more preferably less than 0.5%.

[0037] [Other Dichroic Substances] The liquid crystal composition of the present invention may contain other dichroic substances other than the dichroic substances (ZA) and (ZB) described above.

[0038] Other dichroic materials are not particularly limited and include visible light absorbing materials (dichroic dyes), luminescent materials (fluorescent materials, phosphorescent materials), ultraviolet absorbing materials, infrared absorbing materials, nonlinear optical materials, carbon nanotubes, and inorganic materials (e.g., quantum rods). Conventionally known dichroic materials (dichroic dyes) can also be used. Specifically, for example, paragraphs

[0067] to

[0071] of JP 2013-228706, paragraphs

[0008] to

[0026] of JP 2013-227532, paragraphs

[0008] to

[0015] of JP 2013-209367, paragraphs

[0045] to

[0058] of JP 2013-14883, paragraphs

[0012] to

[0029] of JP 2013-109090, paragraphs

[0009] to

[0017] of JP 2013-101328, JP Paragraphs

[0051] to

[0065] of Japanese Patent Publication No. 2013-37353, paragraphs

[0049] to

[0073] of Japanese Patent Publication No. 2012-63387, paragraphs

[0016] to

[0018] of Japanese Patent Publication No. Hei 11-305036, paragraphs

[0009] to

[0011] of Japanese Patent Publication No. 2001-133630, paragraphs

[0030] to

[0169] of Japanese Patent Publication No. 2011-215337, paragraphs

[0021] to

[0075] of Japanese Patent Publication No. 2010-106242, and paragraphs [0010-215846] Paragraphs

[0011] to

[0025] of JP 2011-048311, paragraphs

[0017] to

[0069] of JP 2011-213610, paragraphs

[0013] to

[0133] of JP 2011-237513, paragraphs

[0074] to

[0246] of JP 2016-006502, paragraphs

[0005] to

[0051] of JP 2018-053167, paragraphs

[0014] to

[0032] of JP 2020-11716 Paragraphs

[0005] to

[0041] of International Publication No. 2016 / 060173, paragraphs

[0008] to

[0062] of International Publication No. 2016 / 136561, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154835, paragraphs

[0014] to

[0033] of International Publication No. 2017 / 154695, paragraphs

[0013] to

[0037] of International Publication No. 2017 / 195833, paragraphs

[0014] to

[0034] of International Publication No. 2018 / 164252,Examples include paragraphs

[0021] to

[0030] of International Publication No. 2018 / 186503, paragraphs

[0043] to

[0063] of International Publication No. 2019 / 189345, paragraphs

[0043] to

[0085] of International Publication No. 2019 / 225468, paragraphs

[0050] to

[0074] of International Publication No. 2020 / 004106, and paragraphs

[0015] to

[0038] of International Publication No. 2021 / 044843.

[0039] Other preferred dichroic substances include dichroic azo dye compounds. Dichroic azo dye compounds refer to azo dye compounds whose absorbance differs depending on the direction. Dichroic azo dye compounds may or may not exhibit liquid crystalline properties. If a dichroic azo dye compound exhibits liquid crystalline properties, it may exhibit either nematic or smectic properties. The temperature range in which the liquid crystalline phase is exhibited is preferably room temperature (about 20 to 28°C) to 300°C, and more preferably 50 to 200°C from the viewpoint of handling and manufacture suitability.

[0040] In the present invention, it is preferable that the other dichroic substance has a maximum absorption wavelength in the range of 350 nm to 560 nm.

[0041] If the liquid crystal composition of the present invention contains other dichroic substances, the total content of the dichroic substances (ZA), (ZB), and other dichroic substances (i.e., all dichroic substances contained in the liquid crystal composition) is not particularly limited, but is preferably 4 to 80% by mass, more preferably 8 to 60% by mass, and even more preferably 10 to 40% by mass, based on the total mass of solids of the liquid crystal composition.

[0042] [Liquid Crystal Compound] This liquid crystal composition contains a liquid crystal compound. This allows for the orientation of dichroic substances to a higher degree while suppressing the deposition of dichroic substances.

[0043] As the liquid crystal compound, either polymer liquid crystal compounds or low-molecular-weight liquid crystal compounds can be used, but polymer liquid crystal compounds are preferred because they allow for a high degree of orientation. Furthermore, polymer liquid crystal compounds and low-molecular-weight liquid crystal compounds may be used in combination. Here, "polymer liquid crystal compound" refers to a liquid crystal compound having repeating units in its chemical structure. "Low-molecular-weight liquid crystal compound" refers to a liquid crystal compound that does not have repeating units in its chemical structure. Examples of polymer liquid crystal compounds include the thermotropic liquid crystal polymer described in Japanese Patent Application Publication No. 2011-237513 and the polymer liquid crystal compounds described in paragraphs

[0012] to

[0042] of International Publication No. 2018 / 199096. Examples of low-molecular-weight liquid crystal compounds include the liquid crystal compounds described in paragraphs

[0072] to

[0088] of Japanese Patent Application Publication No. 2013-228706, among which liquid crystal compounds exhibiting smectic properties are preferred. Examples of such liquid crystal compounds are those described in paragraphs

[0019] to

[0140] of International Publication No. 2022 / 014340, which are incorporated herein by reference. Preferably, the liquid crystal compound is one that does not exhibit dichroism in the visible light region.

[0044] Side-chain polymer liquid crystal compounds are preferred because they allow for a higher degree of orientation. Side-chain polymer liquid crystal compounds are liquid crystal compounds having repeating units. Suitable examples of side-chain polymer liquid crystal compounds include liquid crystal compounds having repeating units represented by the following formula (L1), as described in paragraph

[0014] of International Publication No. 2018 / 199096.

[0045] In the above formula (L1), R １ L represents a hydrogen atom or a methyl group. １ and L ２ Each of these independently represents a single bond or a divalent linking group, M １ represents a mesogenic group, T １ This represents a terminal group.

[0046] Furthermore, as a low-molecular-weight liquid crystal compound, the compound represented by the following formula (L2) described in paragraph

[0074] of Japanese Patent Application Publication No. 2013-228706 is a suitable example. １ -V １ -W １ -X １ -Y １ -X ２ -Y ２ -X ３ -W ２ -V ２ -U ２ (L2) In formula (L2), X １ , X ２ and X ３ Each of these independently represents an optionally substituted 1,4-phenylene group or an optionally substituted cyclohexane-1,4-diyl group. However, X １ , X ２ and X ３ At least one of these is a substituted 1,4-phenylene group. A substituted cyclohexane-1,4-diyl group is formed by -CH ２ The - may be replaced with -O-, -S-, or NR-. R is an alkyl group or phenyl group having 1 to 6 carbon atoms. １ and Y ２ These are, independently of each other, -CH ２ CH ２ -ien-CH ２ O-, -COO-, -OCOO-, single bond, -N=N-, -CR ａ =CR ｂ -, -C≡C- or CR ａ = represents N-. ａ and R ｂ Each of these independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. １ U represents a hydrogen atom or a polymerizable group. ２ This represents a polymerizable group. １ and W ２ These independently represent a single bond, -O-, -S-, -COO-, or OCOO-. １ and V ２Each of these independently represents an alkanediyl group having 1 to 20 carbon atoms, which may have substituents, and the -CH group constitutes the alkanediyl group. ２ The dash may be replaced with -O-, -S-, or NH-.

[0047] From the viewpoint of increasing the degree of orientation, it is preferable that the liquid crystal compound has at least one group selected from the group consisting of a fluorine atom, a cyano group, a trifluoromethyl group, and a nitro group.

[0048] From the viewpoint of ease of handling, the weight-average molecular weight (Mw) of the polymer liquid crystal compound is preferably 1,000 to 500,000, and more preferably 2,000 to 300,000. Furthermore, from the viewpoint of suppressing cracks during coating, the weight-average molecular weight (Mw) of the polymer liquid crystal compound is preferably 10,000 or more, and more preferably 10,000 to 300,000. Furthermore, from the viewpoint of the temperature latitude of the degree of orientation, the weight-average molecular weight (Mw) of the polymer liquid crystal compound is preferably less than 100,000, and more preferably 2,000 or more and less than 100,000. Here, the weight-average molecular weight of the polymer liquid crystal compound is the value measured by gel permeation chromatography (GPC). • Solvent (eluent): N-methylpyrrolidone • Instrument name: TOSOH HLC-8220GPC • Column: Three TOSOH TSKgelSuperAWM-H (6mm x 15cm) columns connected together • Column temperature: 25°C • Sample concentration: 0.1% by mass • Flow rate: 0.35 mL / min • Calibration curve: Calibration curve using seven TOSOH TSK standard polystyrene samples with Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06) was used.

[0049] The liquid crystal compound content is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass, based on 100 parts by mass of the total content of all dichroic substances in the liquid crystal composition. Having a liquid crystal compound content within the above range further improves the degree of orientation of the dichroic substances. Furthermore, the liquid crystal compound content is preferably 50 to 99% by mass, more preferably 65 to 95% by mass, and even more preferably 75 to 90% by mass, based on the total mass of solids in the liquid crystal composition. Note that the liquid crystal compound may be present as a single compound or as two or more compounds. If two or more liquid crystal compounds are present, the above-mentioned liquid crystal compound content refers to the total content of the liquid crystal compounds.

[0050] [Other Components] This liquid crystal composition may contain components other than the dichroic substances (ZA) and (ZB) described above, other dichroic substances, and liquid crystal compounds (hereinafter also referred to as "other components"). Examples of other components include orientation agents, polymerization initiators, interface modifiers, and solvents.

[0051] <Orientation Agents> The liquid crystal composition of the present invention may contain orientation agents. Examples of orientation agents include boronic acid compounds and onium salts. Boronic acid compounds function as horizontal or vertical orientation agents. Onium salts function as vertical orientation agents. One type of orientation agent may be used alone, or two or more types may be used in combination.

[0052] As the boronic acid compound, the compound represented by formula (30) is preferred.

[0053] Formula (30)

[0054] In formula (30), R １ and R ２ Each of these independently represents a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group. ３represents a substituent containing a (meth)acrylic group. Specific examples of boronic acid compounds include the boronic acid compounds represented by general formula (I) described in paragraphs 0023 to 0032 of Japanese Patent Application Publication No. 2008-225281. The following examples of boronic acid compounds are also preferred.

[0055]

[0056] Specific examples of onium salts include the onium salts described in paragraphs 0052 to 0058 of Japanese Patent Publication No. 2012-208397, the onium salts described in paragraphs 0024 to 0055 of Japanese Patent Publication No. 2008-026730, and the onium salts described in Japanese Patent Publication No. 2002-37777.

[0057] When the liquid crystal composition of the present invention contains an alignment agent, the content of the alignment agent is preferably 0.01 to 30% by mass, and more preferably 0.1 to 10% by mass, based on the total mass of the solids of the liquid crystal composition.

[0058] <Polymerization Initiator> The liquid crystal composition of the present invention may contain a polymerization initiator. There are no particular restrictions on the polymerization initiator, but it is preferable that it be a photosensitive compound, i.e., a photopolymerization initiator. Various compounds can be used as photopolymerization initiators without particular restrictions. Examples of photopolymerization initiators include α-carbonyl compounds (US Patent Nos. 2,367,661 and 2,367,670), acyloin ethers (US Patent No. 2,448,828), α-hydrocarbon-substituted aromatic acyloin compounds (US Patent No. 2,722,512), polynuclear quinone compounds (US Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazole dimer and p-aminophenyl ketone (US Patent No. 3,549,367). Examples of photopolymerization initiators include acridine and phenazine compounds (Japanese Patent Publication No. 60-105667 and U.S. Patent No. 4239850), oxadiazole compounds (U.S. Patent No. 4212970), o-acyloxime compounds (Japanese Patent Publication No. 2016-27384

[0065] ), and acylphosphine oxide compounds (Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Patent Publication No. 10-95788 and Japanese Patent Publication No. 10-29997). Commercially available products can also be used as such photopolymerization initiators, including Irgacure 184, Irgacure 907, Irgacure 369, Irgacure 651, Irgacure 819, Irgacure OXE-01 and Irgacure OXE-02 from BASF. Polymerization initiators may be used individually or in combination of two or more.

[0059] When the liquid crystal composition of the present invention contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass, based on the total mass of the solids of the liquid crystal composition.

[0060] <Interface Modifier> The liquid crystal composition of the present invention may contain an interface modifier. There are no particular restrictions on the interface modifier; polymer-based interface modifiers and low-molecular-weight interface modifiers can be used, and compounds described in paragraphs

[0253] to

[0293] of Japanese Patent Application Publication No. 2011-237513 can be used. Silicon-based polymers can also be used as interface modifiers. Furthermore, fluorine (meth)acrylate-based polymers described in paragraphs

[0018] to

[0043] of Japanese Patent Application Publication No. 2007-272185 can also be used as interface modifiers. Furthermore, as interface modifiers, the compounds described in paragraphs

[0079] to

[0102] of Japanese Patent Publication No. 2007-069471, polymerizable liquid crystal compounds represented by formula (4) described in Japanese Patent Publication No. 2013-047204 (particularly the compounds described in paragraphs

[0020] to

[0032] ), polymerizable liquid crystal compounds represented by formula (4) described in Japanese Patent Publication No. 2012-211306 (particularly the compounds described in paragraphs

[0022] to

[0029] ), and liquid crystal alignment promoters represented by formula (4) described in Japanese Patent Publication No. 2002-129162 (particularly paragraphs Compounds described in paragraphs

[0076] to

[0078] and paragraphs

[0082] to

[0084] ), compounds represented by formulas (4), (II), and (III) described in Japanese Patent Publication No. 2005-099248 (particularly the compounds described in paragraphs

[0092] to

[0096] ), compounds described in paragraphs

[0013] to

[0059] of Japanese Patent No. 4385997, compounds described in paragraphs

[0018] to

[0044] of Japanese Patent No. 5034200, and compounds described in paragraphs

[0019] to

[0038] of Japanese Patent No. 4895088 can also be used. The interface modifier may be used alone or in combination of two or more types.

[0061] When the liquid crystal composition of the present invention contains an interface modifier, the content of the interface modifier is preferably 0.005 to 15% by mass, more preferably 0.01 to 5% by mass, and even more preferably 0.015 to 3% by mass, based on the total mass of the solids of the liquid crystal composition. When multiple interface modifiers are used in combination, it is preferable that the total amount of the multiple interface modifiers is within the above range.

[0062] <Solvent> The liquid crystal composition of the present invention preferably contains a solvent from the viewpoint of workability, etc. Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, and cyclohexanone), ethers (e.g., dioxane, tetrahydrofuran, tetrahydropyran, dioxolane, tetrahydrofurfuryl alcohol, and cyclopentyl methyl ether), aliphatic hydrocarbons (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., benzene, toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, trichloromethane (chloroform), dichloroethane, dichlorobenzene, and chlorothol). Examples of organic solvents include esters (e.g., methyl acetate, ethyl acetate, and butyl acetate, diethyl carbonate, etc.), alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol, etc.), cellosolves (e.g., methyl cellosolve, ethyl cellosolve, and 1,2-dimethoxyethane, etc.), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide and dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, etc.), and heterocyclic compounds (e.g., pyridine, etc.), as well as water.

[0063] These solvents may be used individually or in combination of two or more. For better solubility of the dichroic substance contained in this liquid crystal composition, it is preferable that the difference in solubility parameters between the dichroic substance (ZA) and the solvent, and between the dichroic substance (ZB) and the solvent, is 3.0 or less. More preferably, it is 2.8 or less, and even more preferably 2.5 or less, for even better solubility. Solubility parameters (HSP values) are explained in Hansen, Charles (2007). Hansen Solubility P16 parameters: A user's handbook, Second Edition. Boca Raton, Fla: CRC Press. ISBN 9780849372483. The HSP value of each dichroic substance in this invention is calculated by inputting the structural formula of the compound into the following software, and more specifically, it corresponds to the δtotal value. The software used is HSPiP (Hansen Solubility Parameters in Practice) ver4.1.07. Furthermore, the HSP value of a solvent when two or more solvents are mixed can be determined from the mass ratio of the solvents. For example, in the case of a mixture of two solvents, if the mass fractions of each solvent are W1 and W2, and the HSP values ​​of each solvent are HSP1 and HSP2, then the HSP value of the mixed solvent can be calculated by the following formula: HSP = W1 × HSP1 + W2 × HSP2

[0064] If the liquid crystal composition of the present invention contains a solvent, the solvent content is preferably 70 to 99% by mass, more preferably 83 to 97% by mass, and even more preferably 85 to 95% by mass, based on the total mass of the liquid crystal composition.

[0065] [Light-absorbing anisotropic film] The light-absorbing anisotropic film of the present invention is a light-absorbing anisotropic film obtained by fixing the orientation state of the liquid crystal composition of the present invention as described above. The orientation state of the liquid crystal composition (especially the liquid crystal compound) may be any of the following: horizontal orientation, vertical orientation, tilted orientation, or twisted orientation.

[0066] The method for producing the light-absorbing anisotropic film of the present invention is not particularly limited, but a method comprising the steps of applying the above-described liquid crystal composition of the present invention onto an alignment film to form a coating film (hereinafter also referred to as the "coating film formation step") and aligning the liquid crystal components contained in the above-described coating film (hereinafter also referred to as the "alignment step") in this order (hereinafter also referred to as the "present production method") is preferred for the reason that the degree of orientation of the resulting light-absorbing anisotropic film is higher. Note that the liquid crystal components include not only the above-described liquid crystal compounds but also components that are dichroic substances having liquid crystal properties. Each step will be described below.

[0067] [Coated Film Formation Process] The coated film formation process is a process of forming a coated film by applying the liquid crystal composition of the present invention described above onto the alignment film. By using a liquid crystal composition containing the solvent described above, or by using a liquid liquid such as a molten liquid obtained by heating or the like, it becomes easier to apply the liquid crystal composition onto the alignment film. Known methods for applying the liquid crystal composition include roll coating, gravure printing, spin coating, wire bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray, and inkjet methods.

[0068] <Orientation Film> An orientation film can be formed by means such as rubbing treatment of an organic compound (preferably a polymer) onto the film surface, 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, etc.) by the Langmuir-Bludget method (LB film). Furthermore, orientation films that exhibit orientation function by applying an electric field, a magnetic field, or light irradiation are also known. Among these, in the present invention, an orientation film formed by rubbing treatment is preferred in terms of ease of controlling the pre-tilt angle of the orientation film, and a photo-oriented orientation film formed by light irradiation is also preferred in terms of uniformity of orientation.

[0069] (Rubbing-treated orientation film) Numerous polymer materials are described in the literature and many commercially available products can be used for the orientation film formed by rubbing treatment. In the present invention, polyvinyl alcohol or polyimide, and its derivatives are preferably used. For the orientation film, refer to the description on pages 43, line 24 to 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the orientation film is preferably 0.01 to 10 μm, and more preferably 0.01 to 1 μm.

[0070] (Photo-aligned film) Numerous publications describe photo-alignment materials used in alignment films formed by light irradiation. In the present invention, for example, azo compounds described in Japanese Patent Publication No. 2006-285197, Japanese Patent Publication No. 2007-76839, Japanese Patent Publication No. 2007-138138, Japanese Patent Publication No. 2007-94071, Japanese Patent Publication No. 2007-121721, Japanese Patent Publication No. 2007-140465, Japanese Patent Publication No. 2007-156439, Japanese Patent Publication No. 2007-133184, Japanese Patent Publication No. 2009-109831, Japanese Patent No. 3883848, Japanese Patent No. 4151746, and Japanese Patent Publication No. 2002-229039 Preferred examples include aromatic ester compounds, maleimides and / or alkenyl-substituted nadiimide compounds having photo-orienting units as described in Japanese Patent Publication No. 2002-265541 and Japanese Patent Publication No. 2002-317013, photocrosslinkable silane derivatives as described in Japanese Patent No. 4205195 and Japanese Patent No. 4205198, photocrosslinkable polyimides, polyamides or esters as described in Japanese Patent Publication No. 2003-520878 and Japanese Patent Publication No. 2004-529220, or photocrosslinkable polyimides, polyamides or esters as described in Japanese Patent No. 4162850. More preferably are azo compounds, photocrosslinkable polyimides, polyamides or esters.

[0071] A photo-alignment film is manufactured by irradiating a photo-alignment film formed from the above materials with linearly polarized or unpolarized light. In this specification, "linearly polarized light irradiation" and "unpolarized light irradiation" refer to operations that cause a photoreaction in the photo-alignment material. The wavelength of light used varies depending on the photo-alignment material used and is not particularly limited as long as it is the wavelength necessary for the photoreaction. The peak wavelength of the light used for irradiation is preferably 200 nm to 700 nm, and ultraviolet light with a peak wavelength of 400 nm or less is more preferred.

[0072] Light sources used for light irradiation include commonly used light sources such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury xenon lamps, and carbon arc lamps; various lasers [e.g., semiconductor lasers, helium-neon lasers, argon ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers]; light-emitting diodes; and cathode ray tubes.

[0073] Methods for obtaining linearly polarized light include using polarizers (e.g., iodine polarizers, dichroic polarizers, and wire grid polarizers), using prism-type elements (e.g., Grant-Thomson prisms) or reflective polarizers utilizing the Brewster angle, or using light emitted from a polarized laser light source. Alternatively, filters or wavelength conversion elements may be used to selectively irradiate only the light of the required wavelength.

[0074] When linearly polarized light is used, the light is irradiated from the top or back surface of the alignment film, perpendicular or oblique to the surface of the alignment film. The angle of incidence of the light varies depending on the photo-alignment material, but is preferably 0 to 90° (perpendicular), and more preferably 40 to 90°. When unpolarized light is used, the alignment film is irradiated with unpolarized light from an oblique angle. The angle of incidence is preferably 10 to 80°, more preferably 20 to 60°, and even more preferably 30 to 50°. The irradiation time is preferably 1 to 60 minutes, and more preferably 1 to 10 minutes.

[0075] If patterning is required, a method can be employed in which light irradiation using a photomask is performed the number of times necessary to create the pattern, or a method can be employed in which the pattern is written by laser scanning.

[0076] [Orientation Step] The orientation step is a step in which the dichroic substance contained in the coating film is oriented. This gives rise to the light-absorbing anisotropic film of the present invention. In the orientation step, it is thought that the dichroic substance is oriented along the liquid crystal compound oriented by the orientation film. The orientation step may include a drying treatment. The drying treatment can remove components such as solvents from the coating film. The drying treatment may be carried out by leaving the coating film at room temperature for a predetermined time (for example, natural drying), or by heating and / or blowing air. Here, the dichroic substance contained in the liquid crystal composition may be oriented by the coating film formation step or drying treatment described above. For example, in an embodiment in which the liquid crystal composition is prepared as a coating solution containing a solvent, the dichroic substance contained in the coating film may be oriented by drying the coating film to remove the solvent from the coating film, thereby giving rise to the light-absorbing anisotropic film of the present invention.

[0077] The orientation step preferably includes a heat treatment. This further orients the dichroic substances contained in the coating film, resulting in a higher degree of orientation of the resulting light-absorbing anisotropic film. The heat treatment is preferably performed at 10 to 250°C, and more preferably at 25 to 190°C, from the viewpoint of machinability and other factors. The heating time is preferably 1 to 300 seconds, and more preferably 1 to 60 seconds.

[0078] The orientation step may include a cooling treatment performed after the heat treatment. The cooling treatment is a process of cooling the heated coating film to room temperature (20-25°C). This further fixes the orientation of the dichroic substances contained in the coating film, resulting in a higher degree of orientation of the resulting light-absorbing anisotropic film. The cooling method is not particularly limited and can be carried out by known methods. The light-absorbing anisotropic film of the present invention can be obtained by the above steps.

[0079] [Other steps] The present manufacturing method may include a step of curing the light-absorbing anisotropic film after the orientation step described above (hereinafter also referred to as the "curing step"). The curing step is carried out, for example, by heating and / or light irradiation (exposure). Among these, it is preferable that the curing step be carried out by light irradiation. Various light sources can be used for curing, such as infrared light, visible light or ultraviolet light, but ultraviolet light is preferred. In addition, ultraviolet light may be irradiated while heating during curing, or ultraviolet light may be irradiated through a filter that transmits only specific wavelengths. Furthermore, exposure may be carried out under a nitrogen atmosphere. When the curing of the light-absorbing anisotropic film proceeds by radical polymerization, it is preferable to expose under a nitrogen atmosphere because the inhibition of polymerization by oxygen is reduced.

[0080] The thickness of the light-absorbing anisotropic film of the present invention is not particularly limited, but is preferably 0.3 to 10 μm, and more preferably 0.5 to 9 μm.

[0081] In the light-absorbing anisotropic film of the present invention, the angle θ (hereinafter also abbreviated as "transmittance central axis angle θ") between the transmittance central axis of the light-absorbing anisotropic film and the normal direction of the surface of the light-absorbing anisotropic film is preferably 0° or more and 45° or less, more preferably 0° or more and less than 45°, even more preferably 0° or more and 35° or less, and particularly preferably 0° or more and less than 35°, because the effect of the present invention, which is a high degree of orientation, becomes apparent. A laminate having a light-absorbing anisotropic film with a transmittance central axis angle θ of 0° or more and 45° or less, and a polarizer having an absorption axis in the plane, is suitably used as a viewing angle control film.

[0082] Here, the transmittance center axis of a light-absorbing anisotropic film refers to the direction that exhibits the highest transmittance when the transmittance is measured while varying the tilt angle (polar angle) and tilt direction (azimuth angle) of the surface (principal surface) of the light-absorbing anisotropic film with respect to the normal direction. Specifically, the Müller matrix at a wavelength of 550 nm is measured using AxoScan (OPMF-2, Axometrics). More specifically, during the measurement, the azimuth angle at which the transmittance center axis is tilted is first found, and then, within the plane containing the normal direction of the light-absorbing anisotropic film along that azimuth angle (a plane containing the transmittance center axis and perpendicular to the film surface), the Müller matrix at a wavelength of 550 nm is measured while changing the polar angle, which is the angle of the surface of the light-absorbing anisotropic film with respect to the normal direction, from -70 to 70° in 1° increments, and the transmittance of the light-absorbing anisotropic film is derived. As a result, the direction with the highest transmittance is defined as the transmittance center axis. The transmittance center axis refers to the direction of the absorption axis (the long axis direction of the molecule) of the dichroic substance contained in the light-absorbing anisotropic film.

[0083] The transmittance center axis angle θ can be set to a desired value by, for example, adjusting the type and content of the orientation agent.

[0084] In order to demonstrate the effect of the present invention, which is a high degree of orientation, another preferred embodiment of the light-absorbing anisotropic film of the present invention is an embodiment in which the absorption axis is parallel to the in-plane direction of the light-absorbing anisotropic film (polarizer). A laminate having a light-absorbing anisotropic film (polarizer) in which the absorption axis is parallel to the in-plane direction of the light-absorbing anisotropic film and a λ / 4 plate (described later) is suitably used as a circular polarizer.

[0085] [Optical Laminate] The optical laminate of the present invention is an optical laminate having the light-absorbing anisotropic film of the present invention described above. The light-absorbing anisotropic film may also be arranged on a substrate. Furthermore, if the optical laminate of the present invention has a substrate, a specific layer and an orientation film may be provided between the substrate and the light-absorbing anisotropic film. The following describes each component constituting the laminate of the present invention.

[0086] [Substrate] A transparent support is preferred as the substrate. A transparent support refers to a support with a visible light transmittance of 60% or more, preferably 80% or more, and more preferably 90% or more. Known transparent resin films, transparent resin plates, transparent resin sheets, etc., can be used as the transparent support, and there are no particular limitations. Examples of transparent resin films that can be used include cellulose acylate films (e.g., cellulose triacetate film (refractive index 1.48), cellulose diacetate film, cellulose acetate butyrate film, cellulose acetate propionate film), polyethylene terephthalate film, polyethersulfone film, polyacrylic resin film, polyurethane resin film, polyester film, polycarbonate film, polysulfone film, polyether film, polymethylpentene film, polyetherketone film, (meth)acrylonitrile film, etc.

[0087] Among these, cellulose acylate film is preferred because it has high transparency, low optical birefringence, is easy to manufacture, and is commonly used as a protective film for polarizing plates, and cellulose triacetate film is more preferred. The thickness of the substrate is usually 20 to 100 μm. In the present invention, it is particularly preferred that the substrate is a cellulose ester film and that its film thickness is 20 to 70 μm. If a specific layer described later is not included between the substrate and the orientation film, it is preferable to saponify the surface of the substrate with an alkaline solution before use.

[0088] [Specific Layer] The specific layer is a layer formed from a composition containing a compound having a boronic acid structure and a surfactant. A preferred method for forming the specific layer is to coat the above composition onto a cellulose acylate film. The thickness of the specific layer is not particularly limited, but is often 10 μm or less, and is preferably 3.0 μm or less in terms of excellent bending resistance of the optical film. The lower limit is not particularly limited, but is often 0.1 μm or more.

[0089] [Light-absorbing anisotropic film] The light-absorbing anisotropic film of the present invention is as described above, so its explanation will be omitted.

[0090] [Orientation Layer] The orientation layer is as described in the method for manufacturing the light-absorbing anisotropic film, so its explanation will be omitted here.

[0091] [λ / 4 plate] One preferred embodiment of the glossy laminate of the present invention is an embodiment having a light-absorbing anisotropic film (particularly a light-absorbing anisotropic film in which the transmittance center axis angle θ is greater than 45° and less than or equal to 90°) and a λ / 4 plate. Such a laminate (optical film) can be suitably used as a circular polarizer.

[0092] A λ / 4 plate is a plate having λ / 4 functionality, specifically a plate that has the function of converting linearly polarized light of a certain wavelength into circularly polarized light (or circularly polarized light into linearly polarized light). For example, a single-layer λ / 4 plate can be a stretched polymer film or a phase difference film on which a light-absorbing anisotropic film having λ / 4 functionality is provided on a support. A multi-layer λ / 4 plate can be a broadband λ / 4 plate formed by laminating a λ / 4 plate and a λ / 2 plate. The λ / 4 plate and the light-absorbing anisotropic film may be in contact with each other, or other layers may be provided between the λ / 4 plate and the light-absorbing anisotropic film. Such layers may include adhesive layers and barrier layers to ensure adhesion.

[0093] [Polarizer] Another preferred embodiment of the optical laminate of the present invention is an embodiment having a light-absorbing anisotropic film (particularly a light-absorbing anisotropic film having a transmittance center axis angle θ of 0° or more and 45° or less) and a polarizer having an absorption axis in the plane. Such a laminate (optical film) is suitably used as a viewing angle control film for controlling the viewing angle. The polarizer is preferably positioned on the side of the light-absorbing anisotropic film opposite to the substrate. The polarizer may be positioned in contact with the surface of the light-absorbing anisotropic film, or it may be positioned on the surface of the light-absorbing anisotropic film via another layer (for example, a known adhesive layer or bonding layer).

[0094] The polarizer is not particularly limited as long as it is a component that has an absorption axis in its plane and has the function of converting light into a specific linear polarization; conventionally known polarizers can be used. Examples of polarizers include iodine-based polarizers, dye-based polarizers using dichroic dyes, and polyene-based polarizers. Iodine-based polarizers and dye-based polarizers include coated polarizers and stretched polarizers, both of which can be applied. As polarizers, polarizers in which dichroic organic dyes are oriented using the orientation of liquid crystal compounds are preferred, and as stretched polarizers, polarizers made by adsorbing iodine or dichroic dyes onto polyvinyl alcohol and stretching it are preferred. Examples include a light-absorbing anisotropic film containing a dichroic dye compound that does not contain a liquid crystal compound as described in Japanese Patent Application Publication No. 2010-152351 and is horizontally oriented (in a direction intersecting the thickness direction of the light-absorbing anisotropic film), and a light-absorbing anisotropic film containing a liquid crystal compound and a horizontally oriented dichroic dye compound as described in International Publication No. 2017 / 154907.

[0095] [Barrier Layer] The optical laminate of the present invention preferably has a barrier layer together with the light-absorbing anisotropic film. Here, the barrier layer is also called a gas barrier layer (oxygen barrier layer) and has the function of protecting the polarizing element of the present invention from gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers. For the reason that the durability of the optical laminate of the present invention is improved, the layer adjacent to the light-absorbing anisotropic film has an oxygen permeability coefficient of 200 cc / m ２ It is preferable that the barrier layer has a day atm of 50 cc / m³ or less, and that the oxygen permeability coefficient is 50 cc / m³. ２ It is more preferable to have a barrier layer with a permeability of 1 / day·atm or less. Here, the oxygen permeability coefficient is an index that represents the amount of oxygen that passes through the membrane per unit time and per unit area, and in the present invention, the value measured with an oxygen concentration device (for example, MODEL 3600 manufactured by Hack Ultra Analytical Corporation) under conditions of 25°C and 50% relative humidity (RH) is adopted.

[0096] [Adhesive Layer] The laminate of the present invention may or may not have an adhesive layer. Examples of adhesives constituting the adhesive layer include adhesives and adhesives. Examples of adhesives include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives, with acrylic-based adhesives (pressure-sensitive adhesives) being preferred. Examples of adhesives include polyvinyl alcohol adhesives (water-based adhesives), solvent-type adhesives, emulsion-type adhesives, solvent-free adhesives, active energy ray-curing adhesives, and thermosetting adhesives. Examples of active energy ray-curing adhesives include electron beam-curing adhesives, ultraviolet-curing adhesives, and visible light-curing adhesives, with ultraviolet-curing adhesives being preferred.

[0097] The thickness of the adhesive layer is not particularly limited, but from the viewpoint of thinning, it is preferably 25 μm or less, more preferably 15 μm or less, and even more preferably 5 μm or less. The lower limit is not particularly limited, but it is often 0.1 μm or more.

[0098] By imparting the function of improving the durability of the barrier layer to the adhesive layer, it is also preferable from the viewpoint of simplification and thinning to have a configuration in which the light-absorbing anisotropic film and the adhesive layer are adjacent to each other without a barrier layer. For example, a configuration in which the alignment film / light-absorbing anisotropic film / adhesive layer / phase difference layer are arranged adjacent to each other can be considered. In this case, as the adhesive layer, from the viewpoint of preventing the diffusion of dichroic substances in the light-absorbing anisotropic film during durability, for example, an adhesive mainly composed of polyvinyl alcohol, a UV (ultraviolet) adhesive with a low oxygen permeability coefficient, or an adhesive having a hydrophilic group-containing polymer is preferred.

[0099] [Image Display Device] The image display device of the present invention is an image display device having the light-absorbing anisotropic film of the present invention described above (preferably the optical laminate of the present invention described above). Examples of image display devices include liquid crystal displays, organic electroluminescent displays, plasma displays, micro-LED (Light Emitting Diode) displays, head-up displays, and head-mounted displays. Of these, liquid crystal cells or organic EL display panels are preferred. That is, the image display device of the present invention is preferably a liquid crystal display device using a liquid crystal cell as a display element, or an organic EL display device using an organic EL display panel as a display element. Some image display devices are thin and can be molded into curved surfaces. Since the light-absorbing anisotropic film of the present invention is thin and easily bendable, it can be suitably applied to image display devices with curved display surfaces. In addition, some image display devices have a pixel density exceeding 250 ppi and are capable of high-definition display. The light-absorbing anisotropic film used in the present invention can be suitably applied to such high-definition image display devices without causing moiré patterns.

[0100] The present invention will be described in more detail below based on the following 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 as being limited by the following examples.

[0101] [Example 1] The optical laminate of Example 1 was manufactured as follows.

[0102] [Preparation of Cellulose Acrylate Film 1] Cellulose acrylate film 1 was prepared as follows. The following components were placed in 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 a dope. The solid content concentration of the dope was 23.5% by mass, and the solvent of the dope was methylene chloride / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0103] -------------------------------------------------- Cellulose acylate dope -------------------------------------------------- Cellulose acylate (acetyl substitution degree 2.86, viscosity-average degree of polymerization 310) 100 parts by mass Sugar ester compound 1 (formula (S4) below) 6.0 parts by mass Sugar ester compound 2 (formula (S5) below) 2.0 parts by mass Silica particle dispersion (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 0.1 parts by mass Solvent (methylene chloride / methanol / butanol) 351.9 parts by mass

[0104]

[0105]

[0106] The dope prepared as described above was cast using a drum film-forming 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. The drum was made of SUS (stainless steel).

[0107] After the casting process, the obtained web (film) was peeled from the drum and dried for 20 minutes in a tenter device at 30-40°C during film transport, using clips to hold both ends of the web in place. Subsequently, the web was further dried by zone heating while being transported on a roll. The obtained web was knurled and then wound up to form cellulose acylate film A1. The thickness of the obtained cellulose acylate film A1 was 60 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 35 nm.

[0108] [Fabrication of Optical Laminate] An optical laminate 1 was fabricated comprising the cellulose acylate film 1, a specific layer UL1 (described later), a light-absorbing anisotropic film P1, and a protective layer B1 adjacent to each other in this order, as described below.

[0109] (Formation of specific layer UL1) The specific layer-forming composition UL1, described later, was continuously applied to the cellulose acylate film 1 using a wire bar. The cellulose acylate film with the coating was dried with 60°C hot air for 60 seconds, and then heated with 300 mJ / cm using an LED (light emitting diode) lamp (center wavelength 365 nm). 2 A specific layer UL1 was fabricated on the cellulose acylate film A1 by irradiation under the following irradiation conditions. The thickness of the specific layer UL1 was 0.4 μm. -------------------------------------------------- Composition of the specific layer-forming composition UL1 -------------------------------------------------- NK ester A-TMMT (manufactured by Shin Nakamura Chemical Co., Ltd.) 9.23 parts by mass Boronic acid compound B-1 (see below) 2.40 parts by mass IRGACUREOXE-02 (manufactured by BASF) 0.35 parts by mass Surfactant S-1 (see below) 0.024 parts by mass Butyl acetate 74.80 parts by mass Methyl ethyl ketone 13.20 parts by mass --------------------------------------------------

[0110] Boronic acid compound B-1

[0111] Surfactant S-1 (The numerical value indicated for each repeating unit represents the content (mass %) of each repeating unit relative to the total number of repeating units. n is 9. The weight-average molecular weight is 11000. Ac represents an acetyl group.)

[0112] (Formation of PVA-oriented film) On the obtained cellulose acylate film with a specific layer, the orientation film-forming composition 1 containing the following PVA was applied with a wire bar. After the film was formed, it was dried with hot air at 60°C for 60 seconds, and then with hot air at 100°C for 120 seconds to form an orientation film AL1 containing PVA. The thickness of the orientation film AL1 containing PVA was 0.15 μm.

[0113] ------------------------------------------------------------------- Composition 1 for forming an oriented film ------------------------------------------------------------------- Modified polyvinyl alcohol PVA-1 1.81 parts by mass Water 75.39 parts by mass Methanol 22.80 parts by mass -------------------------------------------------------------------

[0114] (Modified polyvinyl alcohol PVA-1) Note that the composition ratio of each repeating unit is based on mol%.

[0115] (Formation of light-absorbing anisotropic film) The following liquid crystal composition P1 was continuously applied to the obtained PVA-containing alignment film AL1 using a wire bar, and the coating was heated at 120°C for 60 seconds, then cooled to room temperature (23°C). Next, the coating was heated at 75°C for 60 seconds and cooled again to room temperature. After that, an LED lamp (center wavelength 365 nm) was used to illuminate the coating from the normal direction at an illuminance of 200 mW / cm². 2 A light-absorbing anisotropic film P1 was fabricated on an orientation film AL1 containing PVA by irradiating it for 2 seconds under the specified irradiation conditions. The thickness of the light-absorbing anisotropic film P1 was 3.5 μm.

[0116] ------------------------------------------------------------------- Liquid Crystal Composition P1 ------------------------------------------------------------------- • The following dichroic substance (X) D-1 0.76 parts by mass • The following dichroic substance (Y) D-2 0.04 parts by mass • The following dichroic substance (ZA) D-3 0.57 parts by mass • The following dichroic substance (ZB) D-4 0.57 parts by mass • The following polymer liquid crystal compound P-1 3.93 parts by mass • The following liquid crystal compound L-1 2.43 parts by mass • IRGACURE OXE-2 (manufactured by BASF) 0.13 parts by mass • The following orientation agent E-1 0.05 parts by mass • The following boronic acid compound B-2 0.28 parts by mass • The following surfactant S-2 0.008 parts by mass • Cyclopentanone 82.11 parts by mass • Benzyl alcohol 9.12 parts by mass ------------------------------------------------------------------

[0117] Dichroic substance (X) D-1

[0118] Dichroic substance (Y) D-2

[0119] Dichroic substance (ZA) D-3

[0120] Dichroic substance (ZB) D-4

[0121] Polymeric liquid crystal compound P-1 (The numerical values ​​indicated for each repeating unit ("59", "15", "26") represent the content (mass %) of each repeating unit relative to the total number of repeating units. The weight-average molecular weight is 21,000.)

[0122] Liquid crystal compound L-1 [A mixture of the following liquid crystal compounds (RA), (RB), and (RC) in a mass ratio of 84:14:2]

[0123] Orienting agent E-1

[0124] Boronic acid compound B-2

[0125] Surfactant S-2 [The numerical values ​​indicated for each repeating unit ("40", "40", "20") represent the content (mass %) of each repeating unit relative to the total number of repeating units. The weight-average molecular weight is 11,000.]

[0126] (Formation of protective layer B1) The protective layer-forming composition B1 described below was continuously applied to the obtained light-absorbing anisotropic film P1 using a wire bar to form a coating film. Next, the coating film was dried with hot air at 60°C for 60 seconds, and then with hot air at 100°C for 120 seconds to form protective layer B1, and an optical laminate 1 was fabricated. The thickness of the protective layer was 0.5 μm. --------------------------------------------------------------------------- Composition B1 for forming a protective layer --------------------------------------------------------------------------- Modified polyvinyl alcohol PVA-1 3.19 parts by mass IRGACURE 2959 (manufactured by BASF) 0.17 parts by mass BYK 348 (manufactured by BYK) 0.02 parts by mass The following mixed solution 1 2.26 parts by mass Water 70 parts by mass Methanol 30 parts by mass --------------------------------------------------------------------------- Composition B1 for forming a protective layer --------------------------------------------------------------------------- Modified polyvinyl alcohol PVA-1 3.19 parts by mass IRGACURE 2959 (manufactured by BASF) 0.17 parts by mass BYK 348 (manufactured by BYK) 0.02 parts by mass Mixed solution 1 2.26 parts by mass Water 70 parts by mass Methanol 30 parts by mass ---------------------------------------------------------------------------

[0127] -------------------------------------------------- Mixture 1 -------------------------------------------------- ・2,5-dimethoxytetrahydrofuran 0.80 parts by mass ・Pyridinium p-toluenesulfonate 0.24 parts by mass ・Water 8.96 parts by mass -------------------------------------------------- Mixture 1 was heated and stirred at 40°C for 4 hours, and then mixed with the other components to prepare protective layer forming composition B1.

[0128] [Examples 2-7 and Comparative Examples 1-9] Optical laminates 2-16 were manufactured in the same manner as in Example 1, except that the content or types of dichroic substances (ZA) and (ZB) were changed to those shown in Table 1 below.

[0129] [Evaluation] The following evaluations were performed using each of the fabricated optical laminates. Furthermore, the light-absorbing anisotropic film contained in each optical laminate of the example was evaluated for transmittance center axis, degree of orientation, and solubility, as described later.

[0130] [Transmittance Center Axis] The transmittance center axis of the light-absorbing anisotropic films prepared in each example and comparative example was measured using the method described above. The transmittance center axis angle θ of the light-absorbing anisotropic films was 0° in all cases.

[0131] [Degree of Orientation] The degree of orientation of the obtained optical laminate at a wavelength of 550 nm was calculated by the following method. Using an AxoScan OPMF-1 (OptoScience Co., Ltd.), the Mueller matrix at a wavelength of 550 nm was measured at each pole angle, changing the pole angle, which is the angle with respect to the normal direction of the optical absorption anisotropy film, in 1° increments from -70° to 70°, and the minimum transmittance (Tmin) was derived. Next, after removing the effect of surface reflection, Tm(0) was defined as the Tmin at the pole angle where Tmin was highest, and Tm(40) was defined as the Tmin in the direction where the pole angle was increased by another 40° from the pole angle with the highest Tmin. Absorbance (A) was calculated from the obtained Tm(0) and Tm(40) using the following formula, and A(0) and A(40) were calculated. A = -log(Tm) Here, Tm represents transmittance and A represents absorbance. From the calculated A(0) and A(40), the degree of orientation SP at a wavelength of 550 nm, defined by the following formula, was calculated and evaluated according to the following criteria. The results are shown in Table 1 below. SP = (4.6 × A(40) - A(0)) / (4.6 × A(40) + 2 × A(0)) <Evaluation Criteria> A: Degree of orientation SP is 0.93 or higher B: Degree of orientation SP is 0.88 or higher and less than 0.93 C: Degree of orientation SP is less than 0.88

[0132] [Solubility of Mixed Dichroic Substances in Solvents] In Table 1 below, the solubility of mixed dichroic substances in solvents was measured by the following method. Solvents (4.43 parts by mass of cyclopentanone, 0.493 parts by mass of benzyl alcohol) and 0.0750 parts by mass of the dichroic substance were weighed into a sample tube. Here, the dichroic substance is a mixture of "Dichroic Substance (ZA)" and "Dichroic Substance (ZB), etc." as formulated in each example and comparative example and listed in Table 1 below, and was mixed in the mixing ratio of each example and comparative example. The above sample tube was stirred in a water bath set to 60°C for 1 hour, and then stirred at 30°C for 4 hours to prepare a solution. The above solution was filtered through a 0.45 μm hydrophobic filter, and the filtrate was dried at 100°C for 2 hours to obtain residual solids. Let M1 be the mass of the filtrate and M2 be the mass of the residual solids, and the solubility (mass%) was calculated based on the following formula (A) and evaluated in the following order. Formula (A) (M2 / M1) × 100 <Solubility Evaluation Criteria> A: Solubility of 1% by mass or more B: Solubility of 0.5% by mass or more and less than 1% by mass C: Solubility of less than 0.5% by mass

[0133] [Solubility of Dichroic Substances (D-3 to D-18)] In Table 1 below, the solubility of dichroic substances (D-3 to D-18) in the solvent was measured by the following method. 4.925 parts by mass of cyclopentanone as the solvent and 0.0750 parts by mass of the dichroic substances (D-3 to D-18) were weighed into a sample tube. The sample tube was stirred in a water bath set to 40°C for 2 hours, then filtered through a 0.45 μm hydrophobic filter, and the filtrate was dried at 100°C for 2 hours to obtain residual solids. Let M1 be the mass of the filtrate and M2 be the mass of the residual solids, and the solubility (mass%) was calculated based on the following formula (B). Formula (B) (M2 / M1) × 100 In Table 1 below, the solubility of the dichroic substances was evaluated according to the following criteria. <Solubility Evaluation Criteria> A: Solubility is less than 0.7% by mass B: Solubility is 0.7% by mass or more

[0134] In Table 1 below, the melting points of dichroic substances were evaluated according to the following criteria: <Criteria for evaluating melting points> A: Melting point of 200°C or less B: Melting point exceeding 200°C

[0135] In Table 1 below, the difference in solubility parameters between the solvent and the dichroic substance (ZA), and the difference in solubility parameters between the solvent and the dichroic substance (ZB) were calculated using the method described above and evaluated according to the following criteria: <Evaluation Criteria for Difference in Solubility Parameters> A: Difference in solubility parameters is 3 or less B: Difference in solubility parameters is greater than 3

[0136]

[0137] The structures of the dichroic substances shown in Table 1 are shown below.

[0138] Dichroic substance D-3

[0139] Dichroic substance D-4

[0140] Dichroic substance D-5

[0141] Dichroic substance D-6

[0142] Dichroic substance D-7

[0143] Dichroic substance D-8

[0144] Dichroic substance D-9

[0145] Dichroic substance D-10

[0146] Dichroic substance D-11

[0147] Dichroic substance D-12

[0148] Dichroic substance D-13

[0149] Dichroic substance D-14

[0150] Dichroic substance D-15

[0151] Dichroic substance D-16

[0152] Dichroic substance D-17

[0153] Dichroic substance D-18

[0154] As shown in Table 1, if a liquid crystal composition does not contain a dichroic substance that satisfies the relationship where the Tanimoto coefficient is 0.830 to 0.920, it was found that the solubility of the dichroic substance is poor or the degree of orientation of the resulting light-absorbing anisotropic film is low (Comparative Examples 1, 2, and 9). Furthermore, if the mass ratio of the content of dichroic substance (ZA) to the content of dichroic substance (ZB) in the total solid content of the liquid crystal composition does not meet the requirement of 0.33 to 3.00, it was found that the solubility of the dichroic substance is poor (Comparative Example 4). In addition, if the melting point of one of the dichroic substances (ZA) and (ZB) is above 200°C, it was found that the solubility of the dichroic substance is poor and the degree of orientation of the resulting light-absorbing anisotropic film is low (Comparative Examples 5, 6, and 8). Furthermore, if both the dichroic substances (ZA) and (ZB) have two polymerizable groups, it was found that the degree of orientation of the resulting light-absorbing anisotropic film is low (Comparative Example 7). Furthermore, it was found that when the dichroic substances (ZA) and (ZB) have hydroxyl groups, the solubility of the dichroic substances is poor, and the degree of orientation of the resulting light-absorbing anisotropic film is low (Comparative Example 3).

[0155] In contrast, when a dichroic substance satisfies a relationship such that the Tanimoto coefficient is 0.830 to 0.920, the mass ratio of the content of dichroic substance (ZA) to the content of dichroic substance (ZB) is 0.33 to 3.00, the melting points of both dichroic substances (ZA) and (ZB) are 200°C or lower, at least one of the dichroic substances (ZA) and (ZB) has only one polymerizable group or is a dichroic substance without polymerizable groups, and neither dichroic substance (ZA) nor (ZB) has a hydroxyl group, a carboxyl group, or a sulfonic acid group, it was found that the liquid crystal composition has good solubility of the dichroic substance and a high degree of orientation of the resulting light-absorbing anisotropic film (Examples 1 to 7). In particular, a comparison of Example 6 with Examples 1-5 and 7 revealed that when the Tanimoto coefficient is between 0.860 and 0.920, the orientation of the resulting light-absorbing anisotropic film is better. Furthermore, a comparison of Example 4 with Examples 1-3, 5 and 7 revealed that when the Tanimoto coefficient is between 0.890 and 0.920, the orientation of the resulting light-absorbing anisotropic film is better. Furthermore, comparison with Comparative Examples 5 and 6 revealed that under conditions where the melting point of the dichroic substance (ZB) exceeds 200°C, the solubility of the dichroic substance in the liquid crystal composition is poor, or the degree of orientation of the resulting light-absorbing anisotropic film is low, regardless of the Tanimoto coefficient. It was found that when the dichroic substances (ZA) and (ZB) have melting points of 200°C or lower, and the Tanimoto coefficient is between 0.830 and 0.920, the liquid crystal composition exhibits good solubility of the dichroic substance and a high degree of orientation of the resulting light-absorbing anisotropic film.

Claims

1. A liquid crystal composition containing a liquid crystal compound and two or more dichroic substances, wherein at least one combination of two dichroic substances satisfies the relationship that the Tanimoto coefficient is 0.830 to 0.920, and in the combination of two dichroic substances satisfying the said relationship, when the dichroic substance with a larger molecular weight is (ZA) and the dichroic substance with a smaller molecular weight is (ZB), the mass ratio of the content of the dichroic substance (ZA) to the content of the dichroic substance (ZB) in the total solid content of the liquid crystal composition is 0.33 to 3.00, the melting points of the dichroic substances (ZA) and (ZB) are both 200°C or less, and at least one of the dichroic substances (ZA) and (ZB) has only one polymerizable group or is a dichroic substance without polymerizable groups. A liquid crystal composition in which the dichroic substances (ZA) and (ZB) do not have any hydroxyl groups, carboxyl groups, or sulfonic acid groups.

2. The liquid crystal composition according to claim 1, wherein the Tanimoto coefficient is 0.860 to 0.

920.

3. The liquid crystal composition according to claim 1, wherein both the dichroic substance (ZA) and (ZB) are dichroic azo dye compounds.

4. The liquid crystal composition according to claim 1, wherein the dichroic substances (ZA) and (ZB) each have a substructure represented by the following formula (1). Here, in formula (1) above, Ra １ and Ra ２ Each of these independently constitutes a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a monovalent substituent, or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a monovalent substituent -CH ２ The - represents a monovalent group substituted with a divalent substituent. Ara and Arc each independently represent a divalent aromatic group which may have a monovalent substituent. na and nc each independently represent an integer from 0 to 3, and the sum of na and nc is 1 or greater. If there are multiple na, the multiple Ara may be the same or different. If there are multiple nc, the multiple Arc may be the same or different.

5. The liquid crystal composition according to claim 1, wherein the dichroic substances (ZA) and (ZB) each have a structure represented by the following formula (2). Here, in equation (2) above, Ra １ Ra ２ , Rb １１ and Rb １２ Each of these independently constitutes a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a monovalent substituent, or a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms which may have a monovalent substituent -CH ２ The hyphen (-) represents a monovalent group substituted with a divalent substituent. Ara and Arc each independently represent a divalent aromatic group which may have a monovalent substituent. na and nc each independently represent integers between 0 and 3, and the sum of na and nc is 1 or greater. If there are multiple na, the multiple Ara values ​​may be the same or different. If there are multiple ncs, the multiple Arcs may be the same or different.

6. The liquid crystal composition according to claim 1, further comprising a solvent, wherein the difference in solubility parameters between the dichroic substance (ZA) and the solvent, and the difference in solubility parameters between the dichroic substance (ZB) and the solvent are both 3.0 or less.

7. The liquid crystal composition according to claim 1, wherein the solubility of at least one of the dichroic substances (ZA) and (ZB) is less than 0.7%.

8. A light-absorbing anisotropic film obtained by fixing the orientation state of the liquid crystal composition according to any one of claims 1 to 7.

9. The light-absorbing anisotropic film according to claim 8, wherein the angle θ between the transmittance center axis of the light-absorbing anisotropic film and the normal direction of the surface of the light-absorbing anisotropic film is 0° or more and 45° or less.

10. The light-absorbing anisotropic film according to claim 8, wherein the absorption axis of the light-absorbing anisotropic film is parallel to the in-plane direction of the light-absorbing anisotropic film.

11. An optical laminate having the light-absorbing anisotropic film described in claim 8.

12. An image display device having the light-absorbing anisotropic film described in claim 8.

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