Optically anisotropic laminate and optical element

Abstract

An optically anisotropic laminate in which a protective layer is laminated on an anisotropic dye layer. The anisotropic dye layer is formed from a composition for forming an anisotropic dye film containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator. In the optically anisotropic laminate, the absolute value of the surface free energy difference between the anisotropic dye layer and the protective layer is 3 mN / m2 or more. Alternatively, in the optically anisotropic laminate, the surface free energy of a film obtained by curing the curable resin is 45 mN / m2 or less. Alternatively, in the optically anisotropic laminate, the protective layer is formed from a composition for forming a protective layer containing a photocurable resin, and the photocurable resin contains a photocurable silicone resin.

Description

Technical Field

[0001] The present invention relates to an optically anisotropic laminate and an optical element showing high dichroism, which are useful for linear polarizing films, circular polarizing films, etc. provided in display elements such as light control elements, liquid crystal elements (LCDs), and organic electroluminescent elements (OLEDs). Background Art

[0002] In LCD, linear polarizing films and circular polarizing films are used to control the optical rotation and birefringence in display. In OLED, circular polarizing films are also used to prevent external light from being reflected in bright places.

[0003] Conventionally, as such a polarizing film, for example, a polarizing film obtained by dyeing polyvinyl alcohol (PVA) with low-concentration iodine (iodine-PVA polarizing film) is known (Patent Document 1).

[0004] However, the iodine-PVA polarizing film dyed with low-concentration iodine has problems such as iodine sublimation or deterioration depending on the usage environment, resulting in color change, and warping due to relaxation of the stretching of PVA.

[0005] It is also known that an anisotropic dye film formed by applying a liquid crystal composition containing a dye functions as a polarizing film (Patent Document 2).

[0006] In this case, an optically anisotropic laminate is formed in which a protective layer is usually laminated on the anisotropic dye layer.

[0007] Prior art literature

[0008] Patent Literature

[0009] Patent Document 1: Japanese Patent Application Laid-Open No. 1-105204

[0010] Patent Document 2: Japanese Patent Application No. 2004-535483 Summary of the invention

[0011] Problem that the invention aims to solve

[0012] When an optically anisotropic laminate in which an anisotropic dye layer and a protective layer are laminated is used as a polarizer, there is a problem that the appearance and performance as a polarizer are degraded under heating conditions.

[0013] An object of the present invention is to provide an optically anisotropic laminate and an optical element, wherein the optically anisotropic laminate comprises an anisotropic dye layer and a protective layer, and can suppress the degradation of appearance and performance under heating conditions and maintain good appearance and performance.

[0014] Solutions for solving problems

[0015] The present inventors have found that by making the absolute value of the surface free energy difference between the anisotropic dye layer and the protective layer equal to or greater than a predetermined value, it is possible to provide an optically anisotropic laminate in which the compatibility of the anisotropic dye layer and the protective layer is suppressed, the two layers do not mix even in a heated environment, and the laminate exhibits good heat resistance, solvent resistance, and excellent appearance and performance.

[0016] The gist of the first invention of the present invention is as follows.

[0017] [1-1] An optically anisotropic laminate comprising a protective layer laminated on an anisotropic dye layer,

[0018] The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0019] The absolute value of the surface free energy difference between the anisotropic pigment layer and the protective layer is 3 mN / m 2 above.

[0020] [1-2] The optically anisotropic laminate according to [1-1], wherein the protective layer is a layer formed from a protective layer-forming composition containing a photocurable silicone resin.

[0021] [1-3] The optically anisotropic laminate according to [1-2], wherein the photocurable silicone resin has fluorine atoms.

[0022] [1-4] The optically anisotropic laminate according to any one of [1-1] to [1-3], wherein the polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

[0023] [1-5] The optically anisotropic laminate according to any one of [1-1] to [1-4], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (1).

[0024] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1)

[0025] (In formula (1),

[0026] -Q 1 represents a hydrogen atom or a polymerizable group;

[0027] -Q2 represents a polymerizable group;

[0028] -R 1 -and-R 2 - each independently represents a chain organic group;

[0029] -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond;

[0030] -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2);

[0031] -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0032] -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2);

[0033] k is 1 or 2.

[0034] When k is 2, 2 -Y 2 -A 13 - are optionally the same or different from each other. )

[0035] -Cy-X 2 -C≡CX 1 -…(2)

[0036] (In formula (2),

[0037] -Cy- represents a hydrocarbon ring group or a heterocyclic group;

[0038] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0039] -X 2- represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. )

[0040] [1-6] An optical element comprising the optically anisotropic laminate according to any one of [1-1] to [1-5].

[0041] The present inventors have found that, for a curable resin contained in a protective layer-forming composition, the surface free energy of a film obtained by curing the curable resin is below a predetermined value, and that it is possible to provide an optically anisotropic laminate that suppresses the compatibility of an anisotropic dye layer and a protective layer, does not mix the two layers even in a heated environment, exhibits good heat resistance, and has excellent solvent resistance, appearance, and performance.

[0042] The gist of the second invention of the present invention is as follows.

[0043] [2-1] An optically anisotropic laminate comprising a protective layer laminated on an anisotropic dye layer,

[0044] The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0045] The protective layer is a layer formed of a protective layer-forming composition containing a curable resin, and the surface free energy of a film obtained by curing the curable resin is 45 mN / m 2 the following.

[0046] [2-2] The optically anisotropic laminate according to [2-1], wherein the curable resin is a photocurable silicone resin.

[0047] [2-3] The optically anisotropic laminate according to [2-2], wherein the photocurable silicone resin has fluorine atoms.

[0048] [2-4] The optically anisotropic laminate according to any one of [2-1] to [2-3], wherein the polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

[0049] [2-5] The optically anisotropic laminate according to any one of [2-1] to [2-4], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (1).

[0050] Q 1 -R 1-A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1)

[0051] (In formula (1),

[0052] -Q 1 represents a hydrogen atom or a polymerizable group;

[0053] -Q 2 represents a polymerizable group;

[0054] -R 1 -and-R 2 - each independently represents a chain organic group;

[0055] -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond;

[0056] -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2);

[0057] -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0058] -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2);

[0059] k is 1 or 2.

[0060] When k is 2, 2 -Y 2 -A 13 - are optionally the same or different from each other. )

[0061] -Cy-X 2 -C≡CX 1 -…(2)

[0062] (In formula (2),

[0063] -Cy- represents a hydrocarbon ring group or a heterocyclic group;

[0064] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0065] -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. )

[0066] [2-6] An optical element comprising the optically anisotropic laminate according to any one of [2-1] to [2-5].

[0067] The present inventors have found that the protective layer is a layer formed from a protective layer-forming composition containing a photocurable resin, and by using a photocurable silicone resin as the photocurable resin, it is possible to provide an optically anisotropic laminate that suppresses the compatibility of the anisotropic dye layer and the protective layer, does not mix the two layers even in a heated environment, exhibits good heat resistance, and has solvent resistance, and is excellent in appearance and performance.

[0068] The gist of the third invention of the present invention is as follows.

[0069] [3-1] An optically anisotropic laminate comprising a protective layer laminated on an anisotropic dye layer,

[0070] The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0071] The protective layer is a layer formed of a protective layer-forming composition containing a photocurable resin.

[0072] The photocurable resin includes a photocurable silicone resin.

[0073] [3-2] The optically anisotropic laminate according to [3-1], wherein the molecular weight M of the photocurable silicone resin is 5000 or more.

[0074] [3-3] The optically anisotropic laminate according to any one of [3-1] to [3-2], wherein the photocurable silicone resin has fluorine atoms.

[0075] [3-4] The optically anisotropic laminate according to any one of [3-1] to [3-3], wherein the polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

[0076] [3-5] The optically anisotropic laminate according to any one of [3-1] to [3-4], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (1).

[0077] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1)

[0078] (In formula (1),

[0079] -Q 1 represents a hydrogen atom or a polymerizable group;

[0080] -Q 2 represents a polymerizable group;

[0081] -R 1 -and-R 2 - each independently represents a chain organic group;

[0082] -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond;

[0083] -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2);

[0084] -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0085] -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2);

[0086] k is 1 or 2.

[0087] When k is 2, 2 -Y 2 -A 13 - are optionally the same or different from each other. )

[0088] -Cy-X 2 -C≡CX 1 -…(2)

[0089] (In formula (2),

[0090] -Cy- represents a hydrocarbon ring group or a heterocyclic group;

[0091] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0092] -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. )

[0093] [3-6] An optical element comprising the optically anisotropic laminate according to any one of [3-1] to [3-5].

[0094] Effects of the Invention

[0095] The optically anisotropic laminate of the present invention is excellent in heat resistance and solvent resistance, can maintain a good appearance, and can maintain a high degree of polarization when used as a polarizer.

[0096] The optical element of the present invention includes the optically anisotropic laminate of the present invention, and thus can maintain excellent optical performance. DETAILED DESCRIPTION

[0097] Hereinafter, the embodiments of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be implemented with various modifications within the scope of the gist thereof.

[0098] [Optically anisotropic laminate]

[0099] The optically anisotropic laminate of the first invention of the present invention comprises a protective layer (hereinafter sometimes referred to as the "protective layer of the first invention") laminated on an anisotropic dye layer (hereinafter sometimes referred to as the "anisotropic dye film of the present invention" or simply the "anisotropic dye film"), wherein the anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator, and the absolute value of the surface free energy difference between the anisotropic dye layer and the protective layer is 3 mN / m 2 above.

[0100] The optically anisotropic laminate of the second invention of the present invention is characterized in that a protective layer (hereinafter sometimes referred to as "the protective layer of the second invention") is laminated on an anisotropic dye layer (hereinafter sometimes referred to as "the anisotropic dye film of the present invention" or simply "the anisotropic dye film"), the anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator, and the protective layer is a layer formed of a protective layer-forming composition containing a curable resin (hereinafter sometimes referred to as "the protective layer-forming composition of the second invention"). The surface free energy of the film obtained by curing the curable resin is 32 mN / m 2 the following.

[0101] The optically anisotropic laminate of the third invention of the present invention is characterized in that a protective layer (hereinafter sometimes referred to as the "protective layer of the third invention") is stacked on an anisotropic dye layer (hereinafter sometimes referred to as the "anisotropic dye film of the present invention" or simply referred to as the "anisotropic dye film"), the anisotropic dye layer is a layer formed from an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound and a photopolymerization initiator, the protective layer is a layer formed from a protective layer-forming composition containing a photocurable resin, and the photocurable resin is a photocurable silicone resin.

[0102] Hereinafter, the “optically anisotropic laminate of the first invention”, the “optically anisotropic laminate of the second invention” and the “optically anisotropic laminate of the third invention” are collectively referred to as “optically anisotropic laminate of the present invention”.

[0103] Furthermore, the “protective layer of the first invention”, the “protective layer of the second invention”, and the “protective layer of the third invention” are collectively referred to as “protective layer of the present invention”.

[0104] The anisotropic pigment coating referred to in the present invention is a pigment coating having anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system including the thickness direction of the anisotropic pigment coating and any two orthogonal in-plane directions. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.

[0105] The protective layer mentioned in the present invention is, for example, a layer for imparting wear resistance, scratch resistance, stress relaxation resistance, chemical resistance, gas resistance, water resistance, corrosion resistance, etc., and further imparting functionalities such as leakage prevention, flattening, easy adhesion, demolding, optical property adjustment, etc. The protective layer may be composed of a photocurable film or a non-polymerizable layer, and is preferably a photocurable film.

[0106] The total thickness (overall thickness) of the optically anisotropic laminate of the present invention is preferably 0.5 μm or more, more preferably 1 μm or more, and further preferably 1.5 μm or more. On the other hand, the total thickness (overall thickness) of the optically anisotropic laminate of the present invention is preferably 800 μm or less, more preferably 500 μm or less, and further preferably 300 μm or less. When the total thickness of the optically anisotropic laminate of the present invention is greater than the aforementioned lower limit, there is a tendency for the handling to become easier, and when it is less than the aforementioned upper limit, there is a tendency for the optically anisotropic laminate to be thinner and lighter when used as an optical element.

[0107] The optical anisotropic laminate of the present invention having an anisotropic dye layer and a protective layer can be laminated with a photocurable film other than the anisotropic dye layer and the protective layer, and a functional film without photopolymerizability. Other functional films include adhesive and / or tackifying adhesive films, antireflection films, phase difference films, light control films that absorb, reflect or scatter light, low refractive films, high refractive films, electrical insulating films, electrical conductive films, orientation films, release films, etc.

[0108] In the optically anisotropic laminate of the present invention, the anisotropic dye layer is usually produced by irradiating an anisotropic dye film-forming composition containing a dye described later, a polymerizable liquid crystal compound and a photopolymerization initiator (hereinafter sometimes referred to as "the anisotropic dye film-forming composition of the present invention") with active energy rays to cure the film formed by wet film formation.

[0109] At least a part of the polymerizable liquid crystal compound in the anisotropic dye film-forming composition is polymerized during the production process of the anisotropic dye film to form a polymer of the polymerizable liquid crystal compound and exist in the anisotropic dye film.

[0110] In the optically anisotropic laminate of the first and second inventions, the protective layer is preferably a layer formed from a protective layer-forming composition containing a photocurable silicone resin described below (hereinafter, sometimes referred to as “the protective layer-forming composition of the present invention”).

[0111] In the optically anisotropic laminate of the third invention, the protective layer is usually a layer formed of a protective layer-forming composition containing a photocurable silicone resin described later, that is, a protective layer-forming composition of the present invention.

[0112] [Features of the optically anisotropic laminate of the first invention]

[0113] The optically anisotropic laminate of the first invention is characterized in that the absolute value of the surface free energy difference between the anisotropic dye layer of the present invention and the protective layer of the first invention is 3 mN / m 2 If the absolute value of the surface free energy difference is 3mN / m 2 If the above conditions are met, the heat resistance and solvent resistance are excellent, and the appearance and performance as a polarizer or the like can be stably maintained.

[0114] That is, a large absolute value of the surface free energy difference between the anisotropic dye layer and the protective layer means that the anisotropic dye layer and the protective layer have low compatibility. Due to the low compatibility, the two layers are not easily mixed even when exposed to heat or solvents, so the heat resistance and solvent resistance become good.

[0115] From this viewpoint, the absolute value of the surface free energy difference between the anisotropic dye layer of the present invention and the protective layer of the first invention is preferably 5 mN / m 2 More preferably 8mN / m 2 More preferably, 12 mN / m 2 above.

[0116] The upper limit of the absolute value of the surface free energy difference is not particularly limited, but is usually 60 mN / m due to the influence of intermolecular interactions and the like. 2 the following.

[0117] Examples of a method for making the absolute value of the surface free energy difference between the anisotropic dye layer of the present invention and the protective layer of the first invention equal to or greater than the above lower limit include the following methods (1) and / or (2).

[0118] (1) Reducing the surface free energy of the protective layer. In order to reduce the surface energy of the protective layer, by using the protective layer-forming composition of the present invention containing a photocurable silicone resin described later, particularly a photocurable silicone resin having fluorine atoms as the photocurable resin, it is possible to suppress the intermolecular interaction and reduce the dispersion component of the surface free energy, thereby reducing the surface energy of the protective layer.

[0119] (2) Increasing the surface free energy of the anisotropic dye layer: In order to increase the surface free energy of the anisotropic dye layer, there are methods of adjusting the surface free energy by utilizing the structure of the polymerizable liquid crystal compound or additives such as a leveling agent.

[0120] The surface free energy of the anisotropic dye layer formed using the anisotropic dye film-forming composition suitable for the present invention described later is usually 20 to 50 mN / m 2 About 30 to 40 mN / m is preferred 2 The surface free energy of the protective layer formed using the protective layer-forming composition suitable for the present invention described below is usually 15 to 45 mN / m 2 About 20 to 35 mN / m is preferred 2 Therefore, the surface free energy of the anisotropic dye layer of the present invention is preferably 3 to 30 mN / m greater than the surface free energy of the protective layer of the first invention. 2 The value of left and right.

[0121] In the first invention, the surface free energy is measured by the method described in the Examples section described later on the surface of the anisotropic dye film and the surface of the protective layer after curing.

[0122] [Features of the optically anisotropic laminate of the second invention]

[0123] The optically anisotropic laminate of the second invention is characterized in that it comprises a protective layer formed of a protective layer-forming composition containing a curable resin, and the surface free energy of a film obtained by curing the curable resin is 45 mN / m 2 The surface free energy of the film obtained by providing a protective layer formed of a protective layer-forming composition containing a curable resin and curing the curable resin is 45 mN / m 2 If the heat resistance and solvent resistance are excellent, the appearance and performance as a polarizer and the like can be stably maintained.

[0124] That is, regarding the curable resin contained in the protective layer forming composition, the low surface free energy of the film obtained by curing the curable resin means that there is a tendency for the wettability to other substances to be reduced. Since the affinity with the anisotropic pigment film as other substances is low, the two layers are difficult to mix even when exposed to heat or solvents, so the heat resistance and solvent resistance become good.

[0125] From this viewpoint, the surface free energy of a film obtained by curing the curable resin contained in the protective layer-forming composition of the second invention is 45 mN / m 2 Below, preferably 40mN / m 2 Below, more preferably 35mN / m 2Below, more preferably 30mN / m 2 Regarding the curable resin contained in the protective layer forming composition of the second invention, there is no particular restriction on the lower limit of the surface free energy of the film obtained by curing the curable resin. In order to stack other layers on the protective layer, it is preferably 10 mN / m 2 More preferably 15mN / m 2 More preferably, 18 mN / m 2 above.

[0126] Regarding the curable resin contained in the protective layer forming composition of the second invention, the surface free energy components of the film obtained by curing the protective layer resin may be in any range as long as the surface free energy is within the above range. The dispersion component γ d Preferably 35mN / m 2 Below, more preferably 30mN / m 2 Below, preferably 10mN / m 2 More preferably 15mN / m 2 More preferably, 18 mN / m 2 In addition, the polar component γ h Preferably 5.0 mN / m 2 Below, more preferably 3.0 mN / m 2 Below. γ d The lower limit is not particularly limited, but is usually 0.0 mN / m 2 above.

[0127] As a method for making the surface free energy of the film obtained by curing the curable resin contained in the protective layer forming composition of the second invention below the above upper limit, there can be cited a method of using the protective layer forming composition of the present invention containing a photocurable silicone resin described later, particularly a photocurable silicone resin having fluorine atoms, as the photocurable resin in the formation of the protective layer. That is, the photocurable silicone resin described later, particularly a photocurable silicone resin having fluorine atoms, can reduce the surface free energy by suppressing the intermolecular interaction and reducing the dispersion component of the surface free energy.

[0128] The surface free energy of the protective layer formed using the protective layer-forming composition suitable for the present invention described later is usually 10 to 32 mN / m 2 About 15 to 30 mN / m is preferred 2 .

[0129] In the second invention, the surface free energy is measured by the method described in the Examples section below on the surface of the cured resin layer, the surface of the anisotropic dye film, and the surface of the protective layer.

[0130] [Features of the optically anisotropic laminate of the third invention]

[0131] The optically anisotropic laminate according to the third invention is characterized in that the protective layer is a layer formed from the protective layer-forming composition of the present invention containing a photocurable silicone resin described later.

[0132] When the protective layer-forming composition contains a photocurable silicone resin, good curability can be obtained, and sufficient protective performance can be exhibited as a protective layer.

[0133] [Anisotropic pigment layer]

[0134] As described above, the anisotropic pigment layer is a pigment film having anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system including the thickness direction and any two orthogonal in-plane directions. Examples of electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance.

[0135] Examples of films having optical anisotropy such as absorption and refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye film is preferably used as a polarizing film or a conductive anisotropic dye film, and more preferably as a polarizing film.

[0136] The anisotropic pigment film can function as a polarizing film that utilizes the anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, etc., and can also function as various anisotropic pigment films such as refractive anisotropy and conductive anisotropy by selecting a film formation process and a substrate, and a composition containing an organic compound (pigment or transparent material).

[0137] When the optical anisotropic laminate of the present invention is used for a liquid crystal display or as a polarizing element of an anti-reflection film for OLED, the orientation characteristics of the anisotropic dye film can be represented by a dichroic ratio. As long as the dichroic ratio is more than 8, it functions as a polarizing element. The dichroic ratio is preferably more than 15, more preferably more than 20, more preferably more than 25, particularly preferably more than 30, and more preferably more than 40.

[0138] When the dichroic ratio is equal to or greater than the above lower limit, the optical element described below, particularly a polarizing element, is useful. The higher the dichroic ratio, the more preferred.

[0139] In the case of a polarizing element used as an anti-reflection film for OLED, even if the performance of the peripheral materials such as the phase difference film is low, as long as the performance of the polarizing element is high, the characteristics of the anti-reflection film will also be improved. Therefore, as long as the performance of the polarizing element is high, it is easy to simplify the layer structure, and even if it is a thin film structure, it is easy to show sufficient functions, and it can also be suitable for use after deformation including bending and curvature. In addition, the cost can be suppressed to a low level.

[0140] In the case where the dye is uniformly oriented, the dichroic ratio (D) referred to in the present invention is represented by the following formula.

[0141] D=Az / Ay

[0142] Here, Az is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is parallel to the orientation direction of the anisotropic dye, and Ay is the absorbance observed when the polarization direction of light incident on the anisotropic dye film is perpendicular.

[0143] As long as the same wavelength is used for each absorbance, there is no particular limitation, and any wavelength may be selected depending on the purpose. When indicating the degree of orientation of an anisotropic dye film, it is preferred to use a value corrected for a specific wavelength region of 380 nm to 780 nm of the anisotropic dye film using visual sensitivity, or a value at a maximum absorption wavelength in the visible region.

[0144] The transmittance of the anisotropic dye film of the present invention in the visible light wavelength region is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. The transmittance can be as long as it is the upper limit corresponding to the purpose. For example, in the case of increasing the degree of polarization, the transmittance is preferably 50% or less. By making the transmittance within the above range, it is useful as the following optical element, especially as an optical element for a liquid crystal display used for color display, and an anti-reflection film composed of a combination of an anisotropic dye film and a phase difference film.

[0145] The film thickness of the anisotropic dye film of the present invention is preferably 10 nm or more, more preferably 100 nm or more, and further preferably 500 nm or more, as a dry film thickness. On the other hand, the film thickness of the anisotropic dye film of the present invention is preferably 30 μm or less, more preferably 10 μm or less, and further preferably 5 μm or less, as a dry film thickness. When the film thickness of the anisotropic dye film is within the above range, there is a tendency to obtain uniform orientation of the dye and uniform film thickness in the film.

[0146] [Anisotropic dye film-forming composition]

[0147] The anisotropic dye film of the present invention is formed using the anisotropic dye film-forming composition of the present invention containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0148] The anisotropic dye film-forming composition of the present invention may contain additives other than the dye, the polymerizable liquid crystal compound, and the photopolymerization initiator, and a solvent.

[0149] <Pigment>

[0150] In the present invention, the pigment refers to a substance or compound that absorbs at least a part of the wavelength in the visible light region (380 nm to 780 nm).

[0151] As the pigment that can be used in the present invention, dichroic pigments can be cited. Dichroic pigments refer to pigments with properties that the absorbance in the long axis direction of the molecule is different from the absorbance in the short axis direction. The pigment may be a pigment with liquid crystal properties or may not have liquid crystal properties. Having liquid crystal properties means that a liquid crystal phase is exhibited at any temperature.

[0152] As the pigment contained in the anisotropic dye film-forming composition of the present invention, that is, the pigment contained in the anisotropic dye film of the present invention, there can be mentioned azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), stilbene pigments, cyanine pigments, phthalocyanine pigments, indigo pigments, condensed polycyclic pigments (including perylene pigments, oxazine pigments, acridine pigments, etc.), etc. Among these pigments, azo pigments are preferred in order to make the ratio of the molecular major and minor axes larger and obtain a higher molecular arrangement in the anisotropic dye film.

[0153] An azo dye refers to a dye having at least one azo group (-N=N-), and from the viewpoint of solubility in solvents, compatibility with liquid crystal compounds, color tone and ease of manufacture, the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, preferably 6 or less, more preferably 4 or less, and further preferably 3 or less.

[0154] Examples of the azo dye include compounds represented by formula (A).

[0155] R 11 -D 1 -N=N-(D 2 -N=N)pD 3 -R 12 …(A)

[0156] In formula (A),

[0157] D 1 , D 2 and D 3Each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.

[0158] p represents an integer from 0 to 4;

[0159] When p is an integer greater than 2, multiple D 2 Optionally the same or different from each other;

[0160] R 11 and R 12 Each independently represents a monovalent organic group.

[0161] D 1 , D 2 and D 3 Each independently represents a phenylene group which may have a substituent, a naphthylene group which may have a substituent, or a divalent heterocyclic group which may have a substituent.

[0162] As the substitution position of the phenylene group, 1,4-phenylene group is preferred in order to increase the linearity of the molecule.

[0163] As the substitution position of the naphthylene group, in order to make the linearity of the molecule higher, a 1,4-naphthylene group or a 2,6-naphthylene group is preferable.

[0164] The divalent heterocyclic group is a heterocyclic group having a carbon number of preferably 3 or more and 14 or less, more preferably 10 or less, constituting a ring. A monocyclic or bicyclic heterocyclic group is particularly preferred.

[0165] As the atom other than carbon constituting the divalent heterocyclic group, at least one selected from a nitrogen atom, a sulfur atom and an oxygen atom can be mentioned. When the heterocyclic group has a plurality of atoms constituting the ring other than carbon, these atoms may be the same or different.

[0166] Specific examples of the divalent heterocyclic group include a pyridinediyl group, a quinolinediyl group, an isoquinolinediyl group, a thiazolediyl group, a benzothiazolediyl group, a thienothiazolediyl group, a thienothiphenediyl group, a benzimidazolidinonediyl group, a benzofurandiyl group, a phthalimidediyl group, an oxazolediyl group, and a benzoxazolediyl group.

[0167] As D 1 , D 2 and D 3The substituents that the phenylene, naphthylene, and divalent heterocyclic groups in the group may optionally have include: alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms such as methoxy, ethoxy, and butoxy; fluoroalkyl groups having 1 to 4 carbon atoms such as trifluoromethyl; cyano; nitro; hydroxyl; halogen atoms; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl. Here, the so-called substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 4 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 8 carbon atoms. The unsubstituted amino group is -NH2. Examples of alkyl groups having 1 to 4 carbon atoms of the substituted amino group include methyl, ethyl, and butyl. Examples of the alkane diyl group having 2 to 8 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0168] In terms of molecular linearity, D 1 , D 2 and D 3 When the phenylene group, naphthylene group, and divalent heterocyclic group in are unsubstituted or substituted, they are preferably substituted with a methyl group, a methoxy group, a hydroxyl group, a fluorine atom, a chlorine atom, a dimethylamino group, a pyrrolidinyl group, or a piperidinyl group.

[0169] p represents an integer of 0 to 4. From the viewpoint of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, p is preferably 1 or more, preferably 4 or less, and more preferably 3 or less.

[0170] R 11 and R 12 Each independently represents a monovalent organic group.

[0171] As R 11 and R 12The monovalent organic group in the formula (a) includes a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may be branched, an alicyclic alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms which may be branched, such as a methoxy group, an ethoxy group, and a butoxy group, an alkoxy group having 1 to 20 carbon atoms which may be branched, such as a trifluoromethyl group, an alkyl group having 1 to 20 carbon atoms which may be branched, a cyano group, a nitro group, a hydroxyl group, a halogen atom, an amino group, a diethylamino group, a substituted or unsubstituted amino group, such as a pyrrolidinyl group, a carboxyl group, an alkyloxycarbonyl group having 1 to 20 carbon atoms which may be branched, such as a butoxycarbonyl group, an alkyloxycarbonyl group having 1 to 20 carbon atoms which may be branched, such as a vinyl group, 20 alkenyl; alkylphenylalkenyl such as 2-(4-butylphenyl)vinyl; carbamoyl; alkylcarbamoyl such as butylcarbamoyl and having 1 to 20 carbon atoms, which may be branched; sulfamoyl; alkylsulfamoyl such as butylsulfamoyl and having 1 to 20 carbon atoms, which may be branched; acylamino such as butylcarbonylamino and having 1 to 20 carbon atoms, which may be branched; acyloxy such as butylcarbonyloxy and having 1 to 20 carbon atoms, which may be branched; sulfanyl; alkylthio such as butylthio and having 1 to 20 carbon atoms; R in the following liquid crystal compounds 1 and R 2 A chain organic group having a polymerizable group. The so-called substituted amino group is an amino group having one or two alkyl groups with 1 to 20 carbon atoms which may have a branch, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkane diyl group with 2 to 20 carbon atoms. The unsubstituted amino group is -NH2. Examples of the alkyl group with 1 to 20 carbon atoms of the substituted amino group include methyl, ethyl, and butyl. Examples of the alkane diyl group with 2 to 20 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0172] As R 11 and R 12 , which may include: hydrogen atoms, chain groups, aliphatic organic groups ("aliphatic organic groups" include chain groups and cyclic groups), aliphatic organic groups in which a portion of carbon is substituted with nitrogen and / or oxygen ("aliphatic organic groups in which a portion of carbon is substituted with nitrogen and / or oxygen" include chain groups and cyclic groups, and include aliphatic organic groups in which a portion of methyl groups is substituted with hydroxyl groups, oxo groups (=O), amino groups, imino groups, etc.). In one embodiment, as R 11 and R 12 , preferably a hydrogen atom or a chain group. 11 and R 12 , preferably a hydrogen atom or an aliphatic organic group. 11 and R 12 , preferably an aliphatic organic group in which a portion of hydrogen atoms or carbon atoms are substituted with nitrogen atoms and / or oxygen atoms.

[0173] Examples of the chain group include: the aforementioned alkyl group having 1 to 20 carbon atoms which may be branched; an alkoxy group having 1 to 20 carbon atoms which may be branched; a fluoroalkyl group having 1 to 20 carbon atoms which may be branched; a substituted or unsubstituted amino group (the so-called substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 20 carbon atoms which may be branched. The unsubstituted amino group is -NH2); a carboxyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may be branched; a carbamoyl group; an alkylcarbamoyl group having 1 to 20 carbon atoms which may be branched; a sulfamoyl group; an alkylsulfamoyl group having 1 to 20 carbon atoms which may be branched; an acylamino group having 1 to 20 carbon atoms which may be branched; an acyloxy group having 1 to 20 carbon atoms which may be branched; a thiol group; an alkylthio group having 1 to 20 carbon atoms, and the like.

[0174] Examples of the aliphatic organic group include the above-mentioned optionally branched alkyl group having 1 to 20 carbon atoms, and alicyclic alkyl group having 1 to 20 carbon atoms.

[0175] Examples of the aliphatic organic group in which a part of the carbon atoms are substituted with nitrogen atoms and / or oxygen atoms include: the aforementioned alkoxy group having 1 to 20 carbon atoms which may be branched; substituted or unsubstituted amino group; carboxyl group; alkyloxycarbonyl group having 1 to 20 carbon atoms which may be branched; carbamoyl group; alkylcarbamoyl group having 1 to 20 carbon atoms which may be branched; acylamino group having 1 to 20 carbon atoms which may be branched; acyloxy group having 1 to 20 carbon atoms which may be branched. The aforementioned substituted amino group refers to an amino group having 1 or 2 alkyl groups having 1 to 20 carbon atoms which may be branched, or an amino group in which two substituted alkyl groups are bonded to each other to form an alkanediyl group having 2 to 20 carbon atoms. The unsubstituted amino group is -NH2. Examples of the alkyl group having 1 to 20 carbon atoms of the substituted amino group include methyl, ethyl, and butyl. Examples of the alkane diyl group having 2 to 20 carbon atoms include ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0176] In terms of high molecular linearity, R 11 and R 12 , are each independently preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as butyl, pentyl, hexyl, heptyl, octyl, etc.; an alkoxy group having 1 to 10 carbon atoms, such as butoxy, pentyloxy, hexyloxy, heptyloxy, octyloxy, etc.; a diethylamino, pyrrolidinyl, and piperidinyl group. In addition, R in the liquid crystal compound described below is also preferably 1 and R 2 It is preferably one of the chain organic groups having a polymerizable group.

[0177] The dye contained in the anisotropic dye film of the present invention is not particularly limited, and a known dye may be used.

[0178] Examples of known pigments include pigments (dichroic pigments, dichroic dyes) described in Patent Document 1, Japanese Patent No. 5982762, Japanese Patent Application Laid-Open No. 2017-025317, and Japanese Patent Application Laid-Open No. 2014-095899.

[0179] Specifically, the pigments described below are exemplified, but the pigments are not limited to these.

[0180]

[0181]

[0182]

[0183]

[0184] The molecular weight of these pigments is preferably 300 or more, more preferably 350 or more, further preferably 380 or more, preferably 1500 or less, more preferably 1200 or less, further preferably 1000 or less. Specifically, the molecular weight of the pigment of the present invention is preferably 300 to 1500, more preferably 350 to 1200, further preferably 380 to 1000. The molecular weight of the pigment is the sum of the atomic weights contained in the pigment molecule.

[0185] The content of the pigment (dichroic pigment) in the anisotropic pigment film is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 10 parts by mass or less, for example, relative to the anisotropic pigment film (100 parts by mass). Specifically, the content of the pigment (dichroic pigment) in the anisotropic pigment film is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and further preferably 0.05 to 10 parts by mass relative to the anisotropic pigment film (100 parts by mass). If the content of the pigment (dichroic pigment) is within the above range, there is a tendency to polymerize the polymerizable liquid crystal compound while maintaining a high orientation in the anisotropic pigment film of the present invention. If the content of the pigment (dichroic pigment) is above the above lower limit, there is a tendency to obtain sufficient light absorption, thereby obtaining sufficient polarization performance. When the content of the dye (dichroic dye) is at most the above upper limit, there is a tendency to easily suppress the disturbance of the alignment of the liquid crystal molecules.

[0186] Therefore, the content of the pigment (dichroic pigment) in the anisotropic dye film-forming composition of the present invention is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and further preferably 10 parts by mass or less, for example, relative to the solid content (100 parts by mass) in the anisotropic dye film-forming composition. Specifically, the content of the pigment (dichroic pigment) in the solid content in the anisotropic dye film-forming composition is preferably 0.01 to 50 parts by mass, more preferably 0.05 to 30 parts by mass, and further preferably 0.05 to 10 parts by mass relative to the solid content (100 parts by mass). If the content of the pigment (dichroic pigment) is within the above range, the anisotropic dye film-forming composition of the present invention has a tendency to polymerize the polymerizable liquid crystal compound while maintaining a high orientation. If the content of the pigment (dichroic pigment) is above the above lower limit, sufficient light absorption can be obtained, thereby obtaining a sufficient polarization performance. When the content of the dye (dichroic dye) is at most the above upper limit, there is a tendency to easily suppress the disturbance of the alignment of the liquid crystal molecules.

[0187] Here, the solid content in the anisotropic dye film-forming composition corresponds to the total of all components other than the solvent in the anisotropic dye film-forming composition, and corresponds to the mass of the anisotropic dye film formed from the anisotropic dye film-forming composition.

[0188] The anisotropic dye film-forming composition of the present invention and the anisotropic dye film of the present invention may contain only one dye, or may contain two or more dyes.

[0189] <Polymerizable liquid crystal compound>

[0190] In the present invention, liquid crystal compounds refer to substances that exhibit a liquid crystal state. Specifically, as described on pages 1 to 28 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000), it refers to a compound that does not directly transform from a crystal to a liquid, but becomes a liquid after passing through an intermediate state that exhibits the properties of both a crystal and a liquid.

[0191] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is a liquid crystal compound having the following polymerizable group.

[0192] In the polymerizable liquid crystal compound, the polymerizable group may be arranged at any position in the liquid crystal compound molecule. In the polymerizable liquid crystal compound, the polymerizable group is preferably substituted at the terminal of the liquid crystal compound molecule from the viewpoint of ease of polymerization.

[0193] In the polymerizable liquid crystal compound, one or more polymerizable groups may be present in the liquid crystal compound molecule. When two or more polymerizable groups are present, they are preferably present at both ends of the liquid crystal compound molecule from the viewpoint of ease of polymerization.

[0194] The polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. When it is a compound having a carbon-carbon triple bond, the carbon-carbon triple bond can perform rotational motion and can become the core of the liquid crystal molecule, and there is a tendency that the mobility of the molecule is improved, the intermolecular interaction between the liquid crystal molecules or with the compound having a π conjugated system such as a pigment molecule becomes stronger, and the molecular orientation is improved.

[0195] When the polymerizable liquid crystal compound is a low molecular weight liquid crystal compound having no repeating structure including a unit showing liquid crystallinity, a high dichroic ratio is easily obtained, which is preferred.

[0196] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention is not particularly limited, and a liquid crystal compound having a polymerizable group can be used.

[0197] For example, examples of the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention include compounds represented by the following formula (1) (hereinafter, sometimes referred to as “polymerizable liquid crystal compound (1)”).

[0198] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1)

[0199] (In formula (1),

[0200] -Q 1 represents a hydrogen atom or a polymerizable group;

[0201] -Q 2 represents a polymerizable group;

[0202] -R 1 -and-R 2 - each independently represents a chain organic group;

[0203] -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group, or a single bond;

[0204] -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2);

[0205] -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0206] -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2);

[0207] k is 1 or 2.

[0208] When k is 2, 2 -Y 2 -A 13 - are optionally the same or different from each other. )

[0209] -Cy-X 2 -C≡CX 1 -…(2)

[0210] (In formula (2),

[0211] -Cy- represents a hydrocarbon ring group or a heterocyclic group;

[0212] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0213] -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. )

[0214] -A 11 When - is a partial structure represented by formula (2), formula (1) may be the following formula (1A) or the following formula (1B).

[0215] Q 1 -R 1 -Cy-X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1A)

[0216] Q 1 -R 1 -X 1 -C≡CX 2 -Cy-Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1B)

[0217] -A 12 When - is a partial structure represented by formula (2), formula (1) may be the following formula (1C) or the following formula (1D).

[0218] Q 1 -R 1 -A 11 -Y 1 -Cy-X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1C)

[0219] Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -Cy-(Y 2 -A 13 ) k -R 2 -Q 2 …(1D)

[0220] -A 13 When - is a partial structure represented by formula (2), formula (1) may be the following formula (1E) or the following formula (1F).

[0221] Q 1 -R1 -A 11 -Y 1 -A 12 -(Y 2 -Cy-X 2 -C≡CX 1 ) k -R 2 -Q 2 …(1E)

[0222] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -Cy) k -R 2 -Q 2 …(1F)

[0223] Similarly, in -A 11 -、-A 12 -and-A 13 When two or more of - are partial structures represented by formula (2), the directions of the partial structures represented by formula (2) may be reversed independently of each other.

[0224] As mentioned above, -A 11 -、-A 12 -and-A 13 - are each independently a partial structure represented by formula (2) or a divalent organic group. 11 -and-A 13 - can be a single bond, -A 11 -and-A 13 -Not a single bond at the same time.

[0225] (-Cy-)

[0226] The hydrocarbon ring group in -Cy- includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0227] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0228] The non-linked aromatic hydrocarbon ring group is a monocyclic or condensed divalent aromatic hydrocarbon ring group, and the carbon number is preferably 6 to 20 because the molecular orientation is improved by a core of an appropriate size. The carbon number of the non-linked aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0229] The connecting aromatic hydrocarbon ring group is a divalent group in which multiple monocyclic or condensed aromatic hydrocarbon rings are bonded by a single bond and have a connecting bond on the atoms constituting the ring. For the reason that the molecular orientation becomes good by being a core of suitable size, the carbon number of the monocyclic or condensed ring is preferably 6 to 20. The carbon number of the monocyclic or condensed ring is more preferably 6 to 15. As the connecting aromatic hydrocarbon ring group, for example, a monocyclic or condensed aromatic hydrocarbon ring with a first carbon number of 6 to 20 and a monocyclic or condensed aromatic hydrocarbon ring with a second carbon number of 6 to 20 are bonded by a single bond, and a first connecting bond is present on the atom constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring with a first carbon number of 6 to 20, and a divalent group having a second connecting bond is present on the atom constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring with a second carbon number of 6 to 20. As the connecting aromatic hydrocarbon ring group, specifically, biphenyl-4,4'-diyl can be cited.

[0230] As the aromatic hydrocarbon ring group, a non-bonding aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular orientation.

[0231] Among these, as an aromatic hydrocarbon ring group, a divalent group of a benzene ring, a divalent group of a naphthalene ring is preferred, and a divalent group of a benzene ring (phenylene) is more preferred. As a phenylene group, 1,4-phenylene is preferred. By making -Cy- these groups, the linearity of the liquid crystal molecules is improved, and there is a tendency to obtain an effect of improving the molecular orientation.

[0232] The non-aromatic hydrocarbon ring group includes a non-bonded non-aromatic hydrocarbon ring group and a bonded non-aromatic hydrocarbon ring group.

[0233] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number thereof is preferably 3 to 20 because the molecular orientation is improved by being a core of an appropriate size. The carbon number of the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetralin ring, and a bicyclo[2.2.2]octane ring.

[0234] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0235] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and have a connecting bond on the atoms constituting the ring; or is a divalent group in which one or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded by a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring and have a connecting bond on the atoms constituting the ring.

[0236] The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20 because the molecular orientation is improved by using a core of an appropriate size.

[0237] As examples of the linked non-aromatic hydrocarbon ring group, there can be mentioned a divalent group in which a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, a first bond is present on an atom constituting the ring of the first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second bond is present on an atom constituting the ring of the second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Furthermore, there can be mentioned a divalent group in which a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, a first bond is present on an atom constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second bond is present on an atom constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0238] Specific examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0239] As the non-aromatic hydrocarbon ring group, a non-bonding non-aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular alignment.

[0240] As the non-linked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl) is preferred. As the cyclohexanediyl, cyclohexane 1,4-diyl is preferred. By making -Cy- these groups, the linearity of the liquid crystal molecules is improved, and there is a tendency to obtain an effect of improving the molecular orientation.

[0241] The heterocyclic group in -Cy- includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0242] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0243] The non-linked aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and the carbon number of the non-linked aromatic heterocyclic group is preferably 4 to 20 because the molecular orientation is improved by a core of an appropriate size. The carbon number of the non-linked aromatic heterocyclic group is more preferably 4 to 15.

[0244] Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an isothiazole ring, an oxadiazole ring, a thiadiazole ring, a triazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0245] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and has a connecting bond on the atoms constituting the ring. For the reason that the molecular orientation is improved by a core of an appropriate size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0246] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, a first linking bond is present on an atom constituting the ring of the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and a second linking bond is present on an atom constituting the ring of the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0247] The non-aromatic heterocyclic group includes a non-bonded non-aromatic heterocyclic group and a bonded non-aromatic heterocyclic group.

[0248] The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and the carbon number is preferably 4 to 20 because the molecular orientation is improved by a core of an appropriate size. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0249] Examples of the non-aromatic heterocyclic ring which is a monocyclic ring or a condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinacridone ring.

[0250] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a linking bond on the atoms constituting the ring. For the reason that the molecular orientation is improved by a core of an appropriate size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0251] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, the first linking bond being on an atom constituting the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second linking bond being on an atom constituting the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0252] The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- may be selected from -R k 、-OH、-OR k 、-OC(=O)-R k 、-NH2、-NH-R k 、-N(R k ')-R k , -C(=O)-R k 、-C(=O)-OR k , -C(=O)-NH2, -C(=O)-NH-R k 、-C(=O)-N(R k ')-R k , -SH, -SR k , trifluoromethyl, sulfamoyl, carboxyl, sulfonyl, cyano, nitro, and halogen. k and-R k ' each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0253] In terms of high linearity of the molecular structure and the polymerizable liquid crystal compounds (1) being easily associated with each other and easily exhibiting a liquid crystal state, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in -Cy- are each independently preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a bromine atom, and more preferably unsubstituted.

[0254] The substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- may be the same or different. In addition, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be all substituted or all unsubstituted, or may be partially substituted and the other partially unsubstituted.

[0255] As -Cy-, a hydrocarbon ring group is preferred, and a phenylene group and a cyclohexanediyl group are more preferred, in terms of improving the molecular orientation of the polymerizable liquid crystal compound (1). As -Cy-, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are further preferred, and a 1,4-phenylene group is particularly preferred, in terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (1).

[0256] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S- or -SCH2-. In particular, -X represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S- or -SCH2-. 1 -, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH2O-, -OCH2-, -CH2S-, -SCH2-, etc., which have relatively small π bonds, are preferred. Among these, -C(=O)O-, -OC(=O)-, -CH2CH2-, -CH2O-, -OCH2-, and -X are more preferred. 1 - is -C(=O)O- or -OC(=O)-. In another embodiment, -X 1 -Preferably -CH2CH2-, -CH2O- or -OCH2-.

[0257] -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

[0258] From the viewpoint of increasing the core of the polymerizable liquid crystal compound (1) and the dichroism of the anisotropic dye film, it is preferred to connect -Cy- and -C≡C- with a highly linear group. Specifically, -X 2 -, preferably a single bond or -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH- or -NHC(=O)- having a π bond, and a single bond is more preferred in terms of higher linearity.

[0259] -Q 1 and-Q 2 The polymerizable group in is a group having a partial structure that can be polymerized by light, heat, and / or radiation, and is a functional group or atomic group required for ensuring the polymerization function. From the viewpoint of production of anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

[0260] Examples of the polymerizable group include acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, vinyl, vinyloxy, ethynyl, ethynyloxy, 1,3-butadienyl, 1,3-butadienyloxy, oxiranyl, oxetanyl, glycidyl, glycidyloxy, styryl, styryloxy, etc. Among these, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, oxiranyl, glycidyl, and glycidyloxy are preferred, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl, and glycidyloxy are more preferred, and acryloyloxy, methacryloyloxy, acryloyloxy, methacryloylamino, glycidyl, and glycidyloxy are still more preferred.

[0261] -R 1 -and-R 2 The chain organic group in - is a divalent organic group that does not contain a cyclic structure such as the aforementioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, or non-aromatic heterocycle.

[0262] Examples of such chain organic groups include -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, -N(alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, and -C(=O)O-(alkylene)-.

[0263] Examples of the alkylene groups in these chain organic groups include linear or branched alkylene groups having 1 to 25 carbon atoms. A portion of the carbon-carbon bonds of the alkylene groups may be unsaturated bonds. One or more methylene groups contained in the alkylene groups may be linked to -O-, -S-, -NH-, -N(R m )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, -CCl2-. Here, R m It represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0264] As the alkylene group in these chain organic groups, a part of the carbon atoms of the alkylene group may form an unsaturated bond from the aspect of high molecular linearity, and may also form a structure in which one or more methylene groups contained in the alkylene group are displaced by the aforementioned groups, and preferably a linear alkylene group having 1 to 25 carbon atoms.

[0265] The number of atoms in the main chain (the longest chain portion in the chain organic group) of the chain organic group is preferably 3-25, more preferably 5-20, and even more preferably 6-20.

[0266] As the chain organic group, -(CH2) is preferred. r -CH2-, -O-(CH2) r -CH2-、-(O) r1 -(CH2CH2O) r2 -(CH2) r3 -、-(O) r1 -(CH2) r2 -(CH2CH2O) r3 -. It should be noted that r in these formulas is an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and further preferably an integer of 5 to 19. In addition, r1, r2, and r3 in these formulas each independently represent an integer, and are appropriately adjusted so that the number of atoms in the main chain (referring to the longest chain part in the chain organic group) in the chain organic group is preferably 3 to 25, more preferably 5 to 20, and further preferably 6 to 20.

[0267] -R 1 -and-R 2 - are each independently preferably -(alkylene)- or -O-(alkylene)-. In one embodiment, -R 1 -and-R 2 The chain organic group in - is -(alkylene)-, and in another embodiment, is -O-(alkylene)-.

[0268] In the above formula (1B) and formula (1E), -X 1 -with-R 1 -or-X 1 -with-R 2 -bonded, in the above formula (1B) -A 13 - is a single bond or in the above formula (1E) -A 11 - is a single bond and -R 1 -or-R 2 -with-Y 1 -or-Y 2 -Bonded case, with -X 1 -、-Y 1 -or-Y 2 -Direct Bonding-R 1 -or-R 2 - is preferably -(alkylene)-.

[0269] Other than the above, not with -X 1 -、-Y 1 -or-Y 2 -Direct Bonded-R 1 -or-R 2 - is preferably -O-(alkylene)-.

[0270] -A 11 -、-A 12 -and-A 13 The divalent organic group in - is preferably a group represented by the following formula (3).

[0271] -Q 3 -…(3)

[0272] (In formula (3), Q 3 represents a hydrocarbon ring group or a heterocyclic ring group. )

[0273] -Q 3 The hydrocarbon ring group in - includes an aromatic hydrocarbon ring group and a non-aromatic hydrocarbon ring group.

[0274] The aromatic hydrocarbon ring group includes a non-bonded aromatic hydrocarbon ring group and a bonded aromatic hydrocarbon ring group.

[0275] The non-linked aromatic hydrocarbon ring group is a monocyclic or condensed divalent aromatic hydrocarbon ring group, and the carbon number is preferably 6 to 20 because the molecular orientation is improved by a core of an appropriate size. The carbon number of the non-linked aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzopyrene ring, Ring, triphenylene ring, acenaphthene ring, fluoranthene ring, fluorene ring, etc.

[0276] The connecting aromatic hydrocarbon ring group is a divalent group in which multiple monocyclic or condensed aromatic hydrocarbon rings are bonded by single bonds and have a connecting bond on the atoms constituting the ring. In order to make the orientation good by a core of suitable size, the carbon number of the monocyclic or condensed ring is preferably 6 to 20. The carbon number of the connecting aromatic hydrocarbon ring group is more preferably 6 to 15. As the connecting aromatic hydrocarbon ring group, for example, a monocyclic or condensed aromatic hydrocarbon ring with a first carbon number of 6 to 20 and a monocyclic or condensed aromatic hydrocarbon ring with a second carbon number of 6 to 20 are bonded by a single bond, and a first connecting bond is formed on the atoms of the ring of the monocyclic or condensed aromatic hydrocarbon ring with a first carbon number of 6 to 20, and a divalent group with a second connecting bond is formed on the atoms of the ring of the monocyclic or condensed aromatic hydrocarbon ring with a second carbon number of 6 to 20. As the connecting aromatic hydrocarbon ring group, specifically, biphenyl-4,4'-diyl can be cited.

[0277] As the aromatic hydrocarbon ring group, a non-bonding aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular orientation.

[0278] Among these, the aromatic hydrocarbon ring group is preferably a divalent group of a benzene ring or a divalent group of a naphthalene ring, and more preferably a divalent group of a benzene ring (phenylene). As the phenylene group, 1,4-phenylene is preferred. 3 - These groups tend to improve the linearity of liquid crystal molecules and to provide an effect of improving the molecular orientation.

[0279] The non-aromatic hydrocarbon ring group includes a non-bonded non-aromatic hydrocarbon ring group and a bonded non-aromatic hydrocarbon ring group.

[0280] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and the carbon number thereof is preferably 3 to 20 because the molecular orientation is improved by being a core of an appropriate size. The carbon number of the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of the non-aromatic hydrocarbon ring include a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, a cycloheptane ring, a cyclooctane ring, a cyclohexene ring, a norbornane ring, a bornane ring, an adamantane ring, a tetralin ring, and a bicyclo[2.2.2]octane ring.

[0281] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group having no unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group having an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring. As the non-linked non-aromatic hydrocarbon ring group, an alicyclic hydrocarbon ring group is preferred from the viewpoint of productivity.

[0282] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or condensed non-aromatic hydrocarbon rings are bonded by a single bond and have a connecting bond on the atoms constituting the ring; or is a divalent group in which one or more rings selected from the group consisting of a monocyclic aromatic hydrocarbon ring, a condensed aromatic hydrocarbon ring, a monocyclic non-aromatic hydrocarbon ring, and a condensed non-aromatic hydrocarbon ring are bonded by a single bond to a monocyclic or condensed non-aromatic hydrocarbon ring and have a connecting bond on the atoms constituting the ring.

[0283] The number of carbon atoms in the monocyclic or condensed ring is preferably 3 to 20 because the molecular orientation is improved by using a core of an appropriate size.

[0284] As examples of the linked non-aromatic hydrocarbon ring group, there can be mentioned a divalent group in which a first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, a first bond is present on an atom constituting the ring of the first monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second bond is present on an atom constituting the ring of the second monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Furthermore, there can be mentioned a divalent group in which a monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms is bonded to a monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms by a single bond, a first bond is present on an atom constituting the ring of the monocyclic or condensed aromatic hydrocarbon ring having 3 to 20 carbon atoms, and a second bond is present on an atom constituting the ring of the monocyclic or condensed non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0285] Specific examples of the linking non-aromatic hydrocarbon ring group include a bis(cyclohexane)-4,4'-diyl group and a 1-cyclohexylbenzene-4,4'-diyl group.

[0286] As the non-aromatic hydrocarbon ring group, a non-bonding non-aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction between the liquid crystal compounds and improves the molecular alignment.

[0287] As the non-linked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl group) is preferred. As the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred.

[0288] -Q 3 The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0289] The aromatic heterocyclic group includes a non-bonded aromatic heterocyclic group and a bonded aromatic heterocyclic group.

[0290] The non-linked aromatic heterocyclic group is a monocyclic or condensed divalent aromatic heterocyclic group, and the carbon number of the non-linked aromatic heterocyclic group is preferably 4 to 20 because the molecular orientation is improved by a core of an appropriate size. The carbon number of the non-linked aromatic heterocyclic group is more preferably 4 to 15.

[0291] Examples of the aromatic heterocyclic ring include a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, a pyrrole ring, a pyrazole ring, an imidazole ring, a thiazole ring, an oxadiazole ring, an indole ring, a carbazole ring, a pyrroloimidazole ring, a pyrrolopyrazole ring, a pyrrolopyrrole ring, a thienopyrrole ring, a thienothiophene ring, a furanopyrrole ring, a furanofuran ring, a thienofuran ring, a thienothiazole ring, a benzisoxazole ring, a benzisothiazole ring, a benzimidazole ring, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a cinnoline ring, a quinoxaline ring, a phenanthridine ring, a quinazoline ring, a quinazolinone ring, and an azulene ring.

[0292] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by a single bond and has a connecting bond on the atoms constituting the ring. For the reason that the molecular orientation is improved by a core of an appropriate size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0293] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, a first linking bond is present on an atom constituting the ring of the first monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms, and a second linking bond is present on an atom constituting the ring of the second monocyclic or condensed aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0294] The non-aromatic heterocyclic group includes a non-bonded non-aromatic heterocyclic group and a bonded non-aromatic heterocyclic group.

[0295] The non-linked non-aromatic heterocyclic group is a monocyclic or condensed non-aromatic heterocyclic divalent group, and the carbon number is preferably 4 to 20 because the molecular orientation is improved by a core of an appropriate size. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0296] Examples of the non-aromatic heterocyclic ring which is a monocyclic ring or a condensed non-aromatic heterocyclic divalent group having 4 to 20 carbon atoms include a tetrahydrofuran ring, a tetrahydropyran ring, a dioxane ring, a tetrahydrothiophene ring, a tetrahydrothiopyran ring, a pyrrolidine ring, a piperidine ring, a dihydropyridine ring, a piperazine ring, a tetrahydrothiazole ring, a tetrahydrooxazole ring, an octahydroquinoline ring, a tetrahydroquinoline ring, an octahydroquinazoline ring, a tetrahydroquinazoline ring, a tetrahydroimidazole ring, a tetrahydrobenzimidazole ring, and a quinacridone ring.

[0297] The linked non-aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed non-aromatic heterocyclic rings are bonded by a single bond and have a linking bond on the atoms constituting the ring. For the reason that the molecular orientation is improved by a core of an appropriate size, the number of carbon atoms in the monocyclic or condensed ring is preferably 4 to 20. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0298] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms is bonded to a second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms by a single bond, the first linking bond being on an atom constituting the first monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms, and the second linking bond being on an atom constituting the second monocyclic or condensed non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0299] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - may also be selected from -R n 、-OH、-OR n 、-OC(=O)-R n 、-NH2、-NH-R n 、-N(R n ')-R n , -C(=O)-R n 、-C(=O)-OR n , -C(=O)-NH2, -C(=O)-NH-R n 、-C(=O)-N(R n ')-R n , -SH, -SR n , trifluoromethyl, sulfamoyl, carboxyl, sulfonyl, cyano, nitro, and halogen. n and-R n' Each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0300] Since the molecular structure has high linearity, the polymerizable liquid crystal compounds (1) are easily associated with each other and easily exhibit a liquid crystal state, -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - are each independently preferably unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom or a bromine atom, and more preferably unsubstituted.

[0301] -Q 3The substituents possessed by the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group in - may be the same or different. Furthermore, the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may all be substituted or all be unsubstituted, or may be partially substituted and the other partially unsubstituted.

[0302] -A 11 -、-A 12 -and-A 13 The substituents of the divalent organic group in - may be the same or different, 11 -、-A 12 -and-A 13 The divalent organic groups in - may be all substituted or all unsubstituted, or may be partially substituted and the other partially unsubstituted.

[0303] AS-Q 3 - is preferably a hydrocarbon ring group, more preferably a phenylene group or a cyclohexanediyl group. 3 -, and more preferably 1,4-phenylene and cyclohexane-1,4-diyl.

[0304] AS-A 11 -、-A 12 -and-A 13 -a divalent organic group, preferably, -Q 3 - is a hydrocarbon ring group, that is, as a divalent organic group, it is a hydrocarbon ring group. As the divalent organic group, phenylene and cyclohexanediyl are more preferred, and 1,4-phenylene and cyclohexane-1,4-diyl are further preferred in terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (1).

[0305] As the polymerizable liquid crystal compound (1), preferably: -A 11 -、-A 12 -and-A 13 -One of them is a partial structure represented by formula (2), and the other two are independently divalent organic groups. -A 11 -、-A 12 -and-A 13 -Cy- in the partial structure represented by formula (2) in - is preferably a hydrocarbon ring group, and it is particularly preferred that the divalent organic group is a hydrocarbon ring group. It is further preferred that the hydrocarbon ring group is 1,4-phenylene or cyclohexane-1,4-diyl. In addition, it is preferred that -A 11 -and-A 13 -One of them is cyclohexane-1,4-diyl.

[0306] More preferably -A 11 -and-A13 - one of them is a partial structure represented by formula (2), and the other and -A 12 - is a divalent organic group. In this case, -A 11 -and-A 13 The divalent organic group in - is preferably cyclohexane-1,4-diyl, and -A is particularly preferred. 12 - is 1,4-phenylene.

[0307] -Y 1 -and-Y 2 - independently represent a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; in terms of the linearity of the polymerizable liquid crystal compound (1) and the tendency to easily rotate around the minor axis of the molecule, -Y 1 -and-Y 2 -are each independently preferably a single bond with a smaller π bond property, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S- or -SCH2-, and more preferably a single bond, -C(=O)O-, -OC(=O)-, -CH2CH2-, -CH2O- or -OCH2-.

[0308] In the above formula (1A), formula (1C), formula (1D), formula (1F), -X 1 -with-Y 1 -or-X 1 -with-Y 2 -Bonded case, with -X 1 -Bonded-Y 1 -or with -X 1 -Bonded-Y 2 - is preferably a single bond. -X 1 -with-Y 1 -and-Y 2 The other of - is preferably -C(=O)O- or -OC(=O)-.

[0309] In the above formula (1B) and formula (1E), -X 1 -Not with -Y 1 -and-Y 2 - When any one of - is bonded, -X1 - preferably -CH2CH2-, -CH2O- or -OCH2-, -Y 1 -and-Y 2 - is preferably -C(=O)O- or -OC(=O)-.

[0310] k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2.

[0311] When k is 2, each -Y 2 - are optionally the same or different from each other, each -A 13 - are optionally the same as or different from each other.

[0312] The polymerizable liquid crystal compound (1) is preferably a compound represented by the above formula (1A), (1B), (1E) or (1F) because it optimizes the intermolecular interaction between the liquid crystal compounds and becomes a core of an appropriate size to improve the molecular orientation.

[0313] As the polymerizable liquid crystal compound (1), as described above, it is preferably a low molecular weight compound that does not have a repeating structure containing a unit showing liquid crystallinity, and therefore, it is preferably a compound structure represented by the aforementioned formula (1). Here, "does not have a repeating structure containing a unit showing liquid crystallinity" refers to a structure consisting of two or more units showing liquid crystallinity that are not represented by a polymer liquid crystal compound.

[0314] The molecular weight of the polymerizable liquid crystal compound (1) is preferably 2000 or less, more preferably 1500 or less, and further preferably 1000 or less. The lower limit is not particularly limited, but is preferably 400 or more, and more preferably 500 or more. The molecular weight of the polymerizable liquid crystal compound (1) is, for example, preferably 400 to 2000, more preferably 400 to 1500, and particularly preferably 500 to 1000. The molecular weight of the polymerizable liquid crystal compound is the sum of the atomic weights contained in the polymerizable liquid crystal compound molecule.

[0315] (Specific examples of polymerizable liquid crystal compounds)

[0316] Specifically, the polymerizable liquid crystal compound included in the anisotropic dye film of the present invention includes the polymerizable liquid crystal compounds described below, but is not limited to these. In the following exemplary formula, C6H 13 Refers to n-hexyl. C5H 11 It refers to n-pentyl.

[0317]

[0318]

[0319]

[0320]

[0321]

[0322]

[0323]

[0324]

[0325]

[0326]

[0327]

[0328]

[0329]

[0330] The liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention preferably includes a polymerizable liquid crystal compound (1). The anisotropic dye film-forming composition of the present invention may include only one polymerizable liquid crystal compound or two or more polymerizable liquid crystal compounds in any combination and ratio.

[0331] The content of the liquid crystal compound in the anisotropic dye film-forming composition of the present invention (when two or more liquid crystal compounds are used in combination, the sum of the contents of each) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, and preferably 99 parts by mass or less, more preferably 98 parts by mass or less, relative to the solid content (100 parts by mass) of the anisotropic dye film-forming composition. If the content of the liquid crystal compound is within the above range, there is a tendency for the orientation of the liquid crystal molecules to be improved.

[0332] The anisotropic dye film-forming composition of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (1). In view of more effectively obtaining the effect of the present invention brought about by using the polymerizable liquid crystal compound (1), the ratio of the polymerizable liquid crystal compound (1) in the total amount (100% by mass) of the liquid crystal compounds contained in the anisotropic dye film-forming composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and particularly preferably 15 to 100% by mass.

[0333] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention preferably has an isotropic phase appearance temperature of 160°C or less, more preferably 140°C or less, further preferably 115°C or less, further preferably 110°C or less, and particularly preferably 105°C or less, from a process point of view.

[0334] Here, the isotropic phase appearance temperature refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In the present invention, it is preferred that at least one of these phase transition temperatures is below the aforementioned upper limit, and it is more preferred that both phase transition temperatures are below the aforementioned upper limit.

[0335] (Relationship between polymerizable liquid crystal compounds and pigments)

[0336] The number of ring structures (r n1 ) and the number of ring structures possessed by the pigment (r n2 ) ratio (r n1 / r n2 ) is not particularly limited, and is preferably 0.7 to 1.5. The reason is that, from the viewpoint of easily improving the orientation of the anisotropic dye film, in order to make the molecular interaction between the liquid crystal molecules and the dye molecules stronger and make it less likely for the dye molecules to hinder the association of the liquid crystal molecules, it is preferred that the difference between the molecular length of the polymerizable liquid crystal compound and the molecular length of the dye is smaller.

[0337] In addition, a condensed ring formed by condensing two or more rings is counted as one ring structure.

[0338] Here, taking the compound represented by the above formula (A) as an example, the number of ring structures (r n2 ) is used for illustration. The number of ring structures is D in formula (A) 1 , D 2 and D 3 Specifically, when p is 0, r n2 is 2; when p is 1, r n2 is 3; when p is 4, r n2 is 6.

[0339] It should be noted that even if -R 11 and-R 12 is a cyclic functional group such as pyrrolidinyl or piperidinyl, -R 11 and-R 12 The number of ring structures contained in the compound represented by formula (A) is not included in the number of ring structures (r n2 )middle.

[0340] In addition, the number of ring structures (r n1 ) does not contain a ring structure (such as an oxirane ring or an oxetane ring, etc.) contained in the polymerizable group in the polymerizable liquid crystal compound.

[0341] (Method for producing polymerizable liquid crystal compound)

[0342] The polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be produced by combining known chemical reactions such as alkylation reaction, esterification reaction, amidation reaction, etherification reaction, ipso substitution reaction, and coupling reaction using a metal catalyst.

[0343] For example, the polymerizable liquid crystal compound contained in the anisotropic dye film-forming composition of the present invention can be synthesized by the method described in the Examples described below or by the method described in “Liquid Crystal Handbook” (Maruzen Co., Ltd., published on October 30, 2000, pp. 449 to 468).

[0344] <Photopolymerization initiator>

[0345] The photopolymerization initiator of the present invention is a polymerization initiator that generates active radicals by the action of light, and is a compound that can initiate a polymerization reaction of a polymerizable liquid crystal compound.

[0346] The maximum absorption wavelength of the photopolymerization initiator is preferably 260 nm or more, more preferably 280 nm or more, and further preferably 300 nm or more. The maximum absorption wavelength of the photopolymerization initiator is preferably 440 nm or less, more preferably 420 nm or less, further preferably 400 nm or less, and further more preferably 380 nm or less. By making the maximum absorption wavelength within this range, the photopolymerization reaction is fully carried out to obtain an anisotropic dye film with good curing degree.

[0347] Usable photopolymerization initiators include, for example, titanocene derivatives; biimidazole derivatives; halomethyl oxadiazole derivatives; halomethyl-s-triazine derivatives; alkyl phenone derivatives; oxime ester derivatives; benzoin; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; thioxanthone derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives; benzoylformate derivatives; ketosulfone derivatives, organic peroxides, and the like.

[0348] Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives, and thioxanthone derivatives are more preferable because the photopolymerization reaction proceeds sufficiently and a film having a high degree of curing is obtained.

[0349] Specifically, examples of the titanocene derivatives include dichlorobis(cyclopentadienyl)titanium, bis(cyclopentadienyl)diphenyltitanium, bis(cyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,3,5,6-tetrafluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4,6-trifluorophenyl)titanium, bis(cyclopentadienyl)bis(2,6-difluorophenyl)titanium, bis(cyclopentadienyl)bis(2,4-difluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,3,4,5,6-pentafluorophenyl)titanium, bis(methylcyclopentadienyl)bis(2,6-difluorophenyl)titanium, and bis(cyclopentadienyl)bis[2,6-difluoro-3-(pyrrol-1-yl)phenyl]titanium.

[0350] Examples of biimidazole derivatives include 2-(2'-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazole dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazole dimer, and 2-(4'-methoxyphenyl)-4,5-diphenylimidazole dimer.

[0351] Examples of the halomethylated oxadiazole derivatives include 2-(2-benzofuranyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-[2-(2-benzofuranyl)vinyl]-5-trichloromethyl-1,3,4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-(1-naphthyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(2-naphthyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-phenylvinyl-5-trichloromethyl-1,3,4-oxadiazole, and 2-(4-methoxyphenylvinyl)-5-trichloromethyl-1,3,4-oxadiazole.

[0352] Examples of the halomethyl-s-triazine derivatives include 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-[2-(4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(2-furyl)vinyl]-4,6-bis(trichloromethyl)-s-triazine.

[0353] Examples of the alkylphenone derivatives include 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butane-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole, Benzil dimethyl ketal, 2-hydroxy-2-methylpropiophenone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylpropiophenone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropionyl)benzyl]phenyl}-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone, and the like.

[0354] Examples of the oxime ester derivatives include 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazol-3-yl]ethanone oxime, (9-ethyl-6-nitrocarbazol-3-yl)-[2-methyl-4-(3-methoxyprop-2-yloxy)phenyl]-methyleneaminoacetate, JP-A-2000-80068, JP-A-2006-36750, JP-A-2008-179611, JP-A-2011- -132215, JP-A-2012-526185, International Publication No. 2008 / 078678, International Publication No. 2009 / 131189, International Publication No. 2012 / 045736, International Publication No. 2012 / 068879, International Publication No. 2013 / 165207, International Publication No. 2014 / 121701, International Publication No. 2016 / 036910, International Publication No. 2017 / 030005, International Publication No. 2018 / 097580, etc.

[0355] Examples of the benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

[0356] Examples of the benzophenone derivatives include benzophenone, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(methylethylamino)benzophenone, 2-methylbenzophenone, 3-methylbenzophenone, 4-methylbenzophenone, 2-chlorobenzophenone, 4-bromobenzophenone, 2-carboxybenzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 2,4,6-trimethylbenzophenone.

[0357] Examples of the acylphosphine oxide derivatives include 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine oxide.

[0358] Examples of the iodonium salts include diphenyliodonium tetrakis(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and 4-(methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate.

[0359] Examples of the sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-bis[diphenylsulfonium]diphenyl sulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonium]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonium]diphenyl sulfide bishexafluorophosphate, 7-[di(p-toluoyl)sulfonium]-2-isopropylthioxanthone hexafluoroantimonate, 7- [Di(p-toluoyl)sulfonium]-2-isopropylthioxanthone·tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonium-diphenyl sulfide·hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonium-diphenyl sulfide·hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluoyl)sulfonium-diphenyl sulfide·tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium·hexafluorophosphate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium·tetrakis(pentafluorophenyl)borate, and the like.

[0360] Examples of the anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, and 1-chloroanthraquinone.

[0361] Examples of thioxanthone derivatives include thioxanthone, 2-ethylthioxanthone, 4-ethylthioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2-chlorothioxanthone, 2,4-dimethylthioxanthone, 2,4-diethylthioxanthone, 2,4-diisopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 1-methoxycarbonylthioxanthone, and 2-ethoxycarbonylthioxanthone.

[0362] Examples of the acridine derivatives include 9-phenylacridine, 9-(p-methoxyphenyl)acridine, 1,5-bis(9-acridinyl)pentane, and 1,7-bis(9-acridinyl)heptane.

[0363] Examples of phenazine derivatives include 9,10-dimethylbenzophenazine and the like.

[0364] Examples of the anthrone derivatives include benzanthrone and the like.

[0365] Examples of the benzoylformate derivatives include methyl benzoylformate and the like.

[0366] Examples of the ketosulfone derivatives include 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone and the like.

[0367] Examples of the organic peroxides include 3,3′,4,4′-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1-methylethyl)-9H-thioxanthen-9-one, and triazine peroxide derivatives.

[0368] The photopolymerization initiator may be used alone or in combination of two or more.

[0369] As the photopolymerization initiator, a commercially available product may be used.

[0370] Examples of commercially available products include Omnicat (registered trademark; the same applies hereinafter) 250, Omnicat 270, Omnirad (registered trademark) 651, Omnirad 184, Omnirad 1173, Omnirad 2959, Omnirad 127, Omnirad 907, Omnirad 369, Omnirad 379EG, Omnirad TPO H, Omnirad 819, Omnirad 784, Omnirad MBF, Omnirad 754 (IGM Resins), IRGACURE (registered trademark) OXE01, IRGACURE OXE02, IRGACURE OXE03, IRGACURE OXE04, IRGACURE 290, IRGACURE 369 (manufactured by BASF); SEIKUOL (registered trademark) BZ, Z, and BEE (manufactured by Seiko Chemical Co., Ltd.); Kayacure (registered trademark) BP100, DETX-S; UVI-6992 (manufactured by Dow Chemical Company); ADEKA ARKLS (registered trademark) SP-150, SP-152, and SP-170, N-1414, N-1717, N-1919, NCI-100, NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Co., Ltd.); TAZ-A and TAZ-PP (manufactured by DKSH Japan Co., Ltd.); and TAZ-104 (manufactured by Sanhe Chemical Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-3057, TRONLYTR-PBG-314, TRONLYTR-PBG-326, TRONLYTR-PBG-345 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd. CO.LTD)); PERDUAL (registered trademark) TA-30G, TA-70H, TX (manufactured by NOF Corporation).

[0371] From the viewpoint of obtaining a fully polymerized anisotropic dye film, the content of the photopolymerization initiator in the anisotropic dye film-forming composition of the present invention is preferably 0.1 parts by mass or more, and more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the polymerizable liquid crystal compound. In addition, from the viewpoint of not easily disturbing the orientation of the polymerizable liquid crystal compound, the content of the photopolymerization initiator is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0372] The anisotropic dye film-forming composition of the present invention may contain a polymerization accelerator, a polymerization aid, and the like in order to use them in combination with the photopolymerization initiator as necessary.

[0373] Examples of the polymerization accelerator and polymerization aid used include amine compounds such as triethanolamine, N-methyldiethanolamine, ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, octyl 4-dimethylaminobenzoate, and N-(2-hydroxyethyl)-N-methyl-p-toluidine; mercapto compounds having a heterocyclic ring such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole; and mercapto compounds such as aliphatic polyfunctional mercapto compounds such as pentaerythritol tetrakis(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H, 3H, 5H)-trione and trimethylolpropane tris(3-mercaptobutyrate).

[0374] The polymerization accelerator and the polymerization aid may be used alone or in combination of two or more.

[0375] The anisotropic dye film-forming composition of the present invention may contain a sensitizing dye, other sensitizers, and the like in order to improve the sensing sensitivity as necessary.

[0376] The sensitizing pigment is a suitable substance according to the wavelength of the exposure light source. For example, the sensitizing pigment includes: xanthene pigments described in Japanese Patent Laid-Open Nos. 4-221958 and 4-219756; coumarin pigments with heterocyclic rings described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; 3-ketocoumarin pigments described in Japanese Patent Laid-Open Nos. 3-239703 and 5-289335; pyrromethene pigments described in Japanese Patent Laid-Open Nos. 6-19240; and pyrrolemethine pigments described in Japanese Patent Laid-Open Nos. 47-2528 and 54-155292. The pigments having a dialkylaminobenzene skeleton described in Japanese Patent Publication No. 45-37377, Japanese Patent Application Laid-Open No. 48-84183, Japanese Patent Application Laid-Open No. 52-112681, Japanese Patent Application Laid-Open No. 58-15503, Japanese Patent Application Laid-Open No. 60-88005, Japanese Patent Application Laid-Open No. 59-56403, Japanese Patent Application Laid-Open No. 2-69, Japanese Patent Application Laid-Open No. 57-168088, Japanese Patent Application Laid-Open No. 5-107761, Japanese Patent Application Laid-Open No. 5-210240, Japanese Patent Application Laid-Open No. 4-288818, etc.

[0377] Examples of other sensitizers include the above-mentioned benzophenone derivatives and thioxanthone derivatives, and examples of other sensitizers include anthracene derivatives, phenothiazine derivatives, and perylene derivatives.

[0378] Examples of the anthracene derivatives include anthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

[0379] Examples of the phenothiazine derivatives include phenothiazine, 10-methylphenothiazine, 10-phenylphenothiazine, 2-methoxyphenothiazine, 2-chlorophenothiazine, and 2-acetylphenothiazine.

[0380] Examples of the perylene derivatives include perylene and 2,5,8,11-tetra-tert-butylperylene.

[0381] The sensitizing dye and other sensitizers may be used alone or in combination of two or more.

[0382] <Other additives>

[0383] The anisotropic dye film-forming composition of the present invention may further contain non-polymerizable liquid crystal compounds, thermal polymerization initiators, polymerization inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, non-polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic / inorganic fillers, organic / inorganic nanosheets, organic / inorganic nanofibers, metal oxides, etc. as needed.

[0384] <Solvent>

[0385] The anisotropic dye film-forming composition of the present invention may contain a solvent as necessary.

[0386] The solvent that can be used is not particularly limited as long as it can sufficiently disperse or dissolve the polymerizable liquid crystal compound, the dye, and other additives in the anisotropic dye film-forming composition. Examples include: alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorinated solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorinated solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.

[0387] These solvents may be used alone or in combination of two or more.

[0388] The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and the pigment, and more preferably a solvent that can completely dissolve the polymerizable liquid crystal compound and the pigment. In addition, the solvent is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. In addition, from the perspective of applying the anisotropic dye film-forming composition of the present invention as described later, a solvent having a boiling point in the range of 50 to 200° C. is preferred.

[0389] When the anisotropic dye film-forming composition of the present invention contains a solvent, the content ratio of the solvent in the anisotropic dye film-forming composition is preferably 50 to 98% by mass relative to the total amount (100% by mass) of the anisotropic dye film-forming composition of the present invention. In other words, the solid content in the anisotropic dye film-forming composition of the present invention is preferably 2 to 50% by mass.

[0390] When the solid content in the anisotropic dye film-forming composition is below the above upper limit, the viscosity of the anisotropic dye film-forming composition does not become too high, the thickness of the obtained anisotropic dye film becomes uniform, and the anisotropic dye film tends to be less prone to unevenness.

[0391] The solid content of the anisotropic dye film-forming composition can be determined in consideration of the thickness of the anisotropic dye film to be produced.

[0392] <Viscosity of Anisotropic Dye Film-Forming Composition>

[0393] The viscosity of the anisotropic dye film-forming composition of the present invention is not particularly limited as long as a uniform film without uneven thickness can be produced by the coating method described below. From the viewpoint of obtaining uniform thickness over a large area, productivity such as coating speed, and in-plane uniformity of optical properties, the viscosity of the anisotropic dye film-forming composition of the present invention is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and further preferably 50 mPa·s or less.

[0394] <Method for Producing Anisotropic Dye Film-Forming Composition>

[0395] The method for producing the anisotropic dye film-forming composition of the present invention is not particularly limited. For example, a dye, a polymerizable liquid crystal compound, a photopolymerization initiator, a solvent as required, other additives, etc. are mixed, and stirred and shaken at 0 to 80° C. to dissolve the dye. In the case where these are poorly soluble, a homogenizer, a bead mill disperser, etc. may also be used.

[0396] The method for producing the anisotropic dye film-forming composition of the present invention may include a filtration step in order to remove foreign matter and the like in the composition.

[0397] The anisotropic dye film-forming composition of the present invention may or may not be a liquid crystal at any temperature, but preferably exhibits liquid crystallinity at any temperature.

[0398] Regarding the composition obtained by removing the solvent from the anisotropic dye film-forming composition, from the viewpoint of the coating process described below, its isotropic phase appearance temperature is generally less than 200°C, preferably less than 160°C, more preferably less than 140°C, further preferably less than 115°C, further more preferably less than 110°C, and particularly preferably less than 105°C.

[0399] [Method for producing anisotropic dye film]

[0400] The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the anisotropic dye film-forming composition of the present invention.

[0401] The wet film-forming method mentioned in the present invention is a method of applying an anisotropic dye film-forming composition on a substrate and orienting it by a certain method. Therefore, the anisotropic dye film-forming composition may or may not contain a solvent as long as it has fluidity. From the perspective of viscosity or film uniformity during coating, it is preferred to contain a solvent.

[0402] The liquid crystal compound and the pigment in the anisotropic dye film can be oriented by shearing during the coating process, or can be oriented during the solvent drying process. In addition, the liquid crystal compound, the pigment, etc. can be oriented and stacked on the substrate by heating after coating and drying to re-orient the liquid crystal compound, the pigment, etc. In the wet film forming method, when the anisotropic dye film forming composition is applied to the substrate, the pigment and the liquid crystal compound are self-associated (molecular association state such as liquid crystal state) in the anisotropic dye film forming composition, or in the process of solvent drying, or after the solvent is completely removed, so as to form an orientation in a small area. By applying an external field to this state, it can be oriented in a fixed direction in a large area to obtain an anisotropic dye film with the desired performance. In this regard, it is different from the method of orienting the pigment only by the stretching process after dyeing a polyvinyl alcohol (PVA) film or the like with a solution containing a pigment. Here, the so-called external field can be listed as the influence of the orientation treatment layer pre-applied to the substrate, shear force, magnetic field, electric field, heat, etc. These may be used alone or in combination of two or more. The mixture may be subjected to a heating step as required.

[0403] The process of applying the anisotropic dye film-forming composition to the substrate to form a film, the process of applying an external field to perform alignment, and the process of drying the solvent may be performed sequentially or simultaneously.

[0404] As a method of imparting the anisotropic dye film-forming composition to a substrate in a wet film-forming method, for example, a coating method, a dip coating method, an LB film formation method, a known printing method, etc. In addition, there is also a method of transferring the anisotropic dye film obtained in the above manner to another substrate.

[0405] Among these, it is preferable to apply the anisotropic dye film-forming composition to the substrate by a coating method.

[0406] The orientation direction of the anisotropic dye film may be different from the coating direction. In the present invention, the orientation direction of the anisotropic dye film is, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film. In the case of a retardation film, the orientation direction is the fast axis or the slow axis.

[0407] The method for obtaining an anisotropic dye film by applying the anisotropic dye film-forming composition is not particularly limited, and examples thereof include the method described in pages 253 to 277 of "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published on March 20, 1971), the method described in pages 118 to 149 of "Creation and Application of Molecular Coordination Materials" edited by Kunihiro Ichimura (published by CMC Co., Ltd., published on March 3, 1998), and the method of applying the composition to a substrate having a height difference structure (which may have been previously subjected to an orientation treatment) by slit die coating, spin coating, spray coating, rod coating, roll coating, knife coating, curtain coating, injection, dip coating, etc. Among them, the slit die coating method or the rod coating method is preferred because a highly uniform anisotropic dye film can be obtained.

[0408] The die coater used in the slot die coating method is usually equipped with a coating machine that ejects a coating liquid, a so-called slot die. The slot die is disclosed in, for example, Japanese Patent Laid-Open No. 2-164480, Japanese Patent Laid-Open No. 6-154687, Japanese Patent Laid-Open No. 9-131559, "Basics and Applications of Dispersion, Coating and Drying" (2014, TECHNO SYSTEMS Co., Ltd., ISBN9784924728707C 305), "Wet Coating Technology in Display and Optical Components" (2007, Information Agency, ISBN9784901677752), "Precision Coating and Drying Technology in the Electronic Field" (2007, Technology Information Association, ISBN9784861041389), etc. These well-known slot dies can be applied even to flexible components such as films or belts, and relatively hard components such as glass substrates.

[0409] Examples of the substrate for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose, and urethane films.

[0410] In order to control the orientation direction of the dye, the substrate surface may be subjected to an orientation treatment (orientation film) by a known method described in pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) (rubbing method, method of forming grooves (fine groove structure) on the surface of the orientation film, method of using polarized ultraviolet light / polarized laser (photo-orientation method), orientation method based on LB film formation, orientation method based on inclined evaporation of inorganic substances, etc.). In particular, the rubbing method and orientation treatment based on the photo-orientation method are preferably listed. As materials used in the rubbing method, polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, acrylic resin, etc. are listed. As materials used in the photo-orientation method, polycinnamate system, polyamic acid / polyimide system, azobenzene system, etc. are listed. In the case where an orientation treatment layer is provided, it is believed that the liquid crystal compound and the dye are oriented by the influence of the orientation treatment of the orientation treatment layer and the shear force applied to the anisotropic dye film-forming composition during coating.

[0411] The supply method and supply interval of the anisotropic dye film forming composition when applying the anisotropic dye film forming composition are not particularly limited. Since the supply operation of the coating liquid becomes complicated and the coating film thickness may vary when the coating liquid is started and stopped, when the thickness of the anisotropic dye film is thin, it is ideal to apply the anisotropic dye film while continuously supplying the anisotropic dye film forming composition.

[0412] The speed of applying the anisotropic dye film forming composition is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, further preferably 1.0 m / min or more, and particularly preferably 5.0 m / min or more. The speed of applying the anisotropic dye film forming composition is usually 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and further preferably 50 m / min or less. By making the coating speed within the above range, there is a tendency to obtain anisotropy of the anisotropic dye film and to be able to apply uniformly.

[0413] The coating temperature of the anisotropic dye film-forming composition is usually 0° C. or higher and 100° C. or lower, preferably 80° C. or lower, and more preferably 60° C. or lower.

[0414] The humidity during application of the anisotropic dye film-forming composition is preferably 10% RH or more and preferably 80% RH or less.

[0415] The anisotropic dye film may be subjected to an insolubilization treatment. Insolubilization refers to a treatment for improving the stability of the film by reducing the solubility of the compound in the anisotropic dye film to control the dissolution of the compound from the anisotropic dye film.

[0416] Specifically, film polymerization, overcoating, and the like are preferred in terms of ease of subsequent steps, durability of the anisotropic dye film, and the like.

[0417] When polymerizing the film, light and / or radiation are used to polymerize the film in which the liquid crystal molecules and the pigment molecules are aligned.

[0418] When polymerization is performed using light or radiation, it is preferred to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm.

[0419] The light source of the active energy ray with a wavelength of 190 to 450 nm is not particularly limited. For example, it can be a xenon lamp, a halogen lamp, a tungsten lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, a medium-pressure mercury lamp, a low-pressure mercury lamp, a carbon arc, a fluorescent lamp, and other lamp light sources; an argon ion laser, a YAG laser, an excimer laser, a nitrogen laser, a helium-cadmium laser, a semiconductor laser, and other laser light sources. When used after irradiation with light of a specific wavelength, an optical filter can also be used.

[0420] The exposure amount of the active energy ray is preferably 1 to 100,000 J / m 2 , more preferably 10 to 10,000 J / m 2 .

[0421] Although polymerization can be performed using light and / or radiation, photopolymerization or a combination of photopolymerization and thermal polymerization is preferred in terms of a shorter film formation process time and a simpler device. In the case of thermal polymerization, it is preferably performed at a temperature in the range of 50 to 200° C., and more preferably at a temperature in the range of 60 to 150° C.

[0422] [Protective layer]

[0423] The protective layer is a film for protecting the anisotropic dye film (for example, imparting or improving abrasion resistance, scratch resistance, stress relaxation resistance, chemical resistance, gas resistance, water resistance, and corrosion resistance), and is preferably a photocurable film.

[0424] The protective layer may also serve as an outer coating film having the functions of preventing leakage (preventing low molecular weight components from seeping out), flattening, easy bonding, demolding, optical property adjustment, etc. As long as the protective layer can show the function of protecting the anisotropic film, the stacking position with the anisotropic dye film is not limited. From the viewpoint of effectively protecting the anisotropic dye film, it is preferably a stacking structure in which the protective layer is adjacent to the anisotropic dye film of the present invention, and more preferably a stacking structure in which the protective layer is adjacent to the surface of the anisotropic dye film on the opposite side of the substrate.

[0425] The protective layer of the first invention is preferably formed using a protective layer-forming composition described below.

[0426] The protective layer of the second invention is formed using a protective layer-forming composition containing a curable resin.

[0427] The protective layer of the third invention is formed using a protective layer-forming composition described below containing a photocurable resin.

[0428] From the viewpoint of enhancing the mechanical strength and fully demonstrating the protective effect, the thickness of the protective layer of the present invention is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, and further more preferably 1 μm or more. In addition, from the viewpoint of being able to reduce the thickness of the obtained optically anisotropic laminate, the thickness of the protective layer of the present invention is preferably 175 μm or less, more preferably 120 μm or less, further preferably 100 μm or less, further preferably 80 μm or less, particularly preferably 60 μm or less, particularly preferably 50 μm or less, particularly preferably 20 μm or less, and most preferably 10 μm or less.

[0429] From the viewpoint of suppressing the degradation of the protective layer due to light, the light transmittance of the protective layer of the present invention at a wavelength of 380 nm or less is preferably less than 50%, more preferably less than 30%, and further preferably less than 20%. On the other hand, from the viewpoint of suppressing the degradation of the optical element due to light, the light transmittance at a wavelength of 400 nm or less is preferably less than 30%, more preferably less than 25%, further preferably less than 22%, and particularly preferably less than 20%.

[0430] From the viewpoint of visibility when used in an image display device, the light transmittance of the protective layer of the present invention at a wavelength of 430 nm is preferably 60% or more, more preferably 70% or more, further preferably 75% or more, and particularly preferably 80% or more.

[0431] [Protective layer forming composition]

[0432] The protective layer-forming composition used for forming the protective layer of the first invention (hereinafter sometimes referred to as "the protective layer-forming composition of the first invention") preferably contains at least a photocurable resin, more preferably further contains a photopolymerization initiator, and may contain other components.

[0433] The protective layer-forming composition of the second invention for forming the protective layer of the second invention contains at least a curable resin, preferably further contains a photopolymerization initiator, and may contain other components.

[0434] The protective layer-forming composition for forming the protective layer of the third invention (hereinafter sometimes referred to as the "protective layer-forming composition of the third invention") preferably contains at least a photocurable silicone resin, preferably further contains a photopolymerization initiator, and may contain other components.

[0435] Hereinafter, the “protective layer-forming composition of the first invention”, “protective layer-forming composition of the second invention” and “protective layer-forming composition of the third invention” may be collectively referred to as “protective layer-forming composition of the present invention”.

[0436] <Curing resin>

[0437] As the photocurable resin of the protective layer forming composition of the first invention, various conventionally known resins can be used, for example, acrylic resins, polyester resins, urethane resins, polyethylene resins, epoxy resins, silicone resins, vinyl acetate resins, fluorine resins, nitrile rubber, chloroprene rubber, styrene-butadiene rubber, etc.

[0438] The protective layer-forming composition of the first invention preferably contains a photocurable silicone resin as the photocurable resin.

[0439] As the curable resin of the protective layer forming composition of the second invention, various conventionally known resins can be used, for example, acrylic resins, polyester resins, urethane resins, polyethylene resins, epoxy resins, silicone resins, vinyl acetate resins, fluorine resins, nitrile rubber, chloroprene rubber, styrene-butadiene rubber, etc. can be cited.

[0440] The protective layer-forming composition of the second invention preferably contains a photocurable resin as the curable resin, and more preferably contains a photocurable silicone resin.

[0441] The protective layer-forming composition of the third invention contains a photocurable silicone resin as the photocurable resin.

[0442] By making the protective layer-forming composition of the present invention contain a photocurable silicone resin, good curability can be obtained, and sufficient protective performance as a protective layer can be expressed.

[0443] Hereinafter, the photocurable silicone resin will be described.

[0444] <Photocurable silicone resin>

[0445] From the viewpoint of suppressing the compatibility of the anisotropic dye layer and the protective layer and preventing the two layers from mixing even when heated and exhibiting good heat resistance, the photocurable silicone resin preferably contains a siloxane unit, more preferably a dimethylsiloxane unit, in the main chain skeleton.

[0446] The photocurable silicone resin preferably contains fluorine atoms from the viewpoint of suppressing the compatibility of the anisotropic dye layer and the protective layer, and preventing the two layers from mixing even when heated and exhibiting good heat resistance.

[0447] The photocurable silicone resin used in the present invention preferably has a siloxane unit represented by the following formula (B) from the viewpoint of suppressing the compatibility of the anisotropic dye layer and the protective layer and preventing the two layers from mixing even when heated and exhibiting good heat resistance.

[0448] (R 21 R 22 R 23 SiO 1 / 2 ) n1 (R 24 R 25 SiO 2 / 2 ) n2 (R 26 SiO 3 / 2 ) n3 (SiO 4 / 2 ) n4 (O 1 / 2 R 27 ) n5 (B)

[0449] (Where R 21 ~R 26 are each independently a monovalent aliphatic hydrocarbon group which may have a substituent or a monovalent aromatic hydrocarbon group which may have a substituent, R 21 ~R 26 Any of them has a polymerizable group as a substituent.

[0450] R 27 is a hydrogen atom or an alkyl group.

[0451] n1 to n5 are each independently an average of 0 or more and 1 or less, and the total of n1, n2, n3 and n4 is 1.)

[0452] R 21 ~R 26The monovalent aliphatic hydrocarbon group is preferably a monovalent aliphatic hydrocarbon group having 1 to 6 carbon atoms. Examples thereof include methyl, ethyl, propyl, butyl, pentyl, hexyl, and cyclohexyl. In the case of an alkyl structure, it may be a linear structure or a branched structure.

[0453] The monovalent aromatic hydrocarbon group is preferably a monovalent aromatic hydrocarbon group having 6 to 10 carbon atoms, and examples thereof include a phenyl group, a tolyl group, a phenylethyl group, a xylyl group, and a naphthyl group.

[0454] R 27 Among them, the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms. Examples thereof include methyl group, ethyl group, propyl group and butyl group, and the alkyl group may be a linear structure or a branched structure.

[0455] As R 21 ~R 26 The polymerizable group possessed by any one of the above-mentioned may include, for example, a (meth)acryloyl group, a (meth)acryloyloxy group, a (meth)acryloylamino group, a vinyl group, a vinyloxy group, a group containing an epoxy structure, a mercapto group, an isocyanate group, an ethynyl group, an ethynyloxy group, a 1,3-butadienyl group, a 1,3-butadienyloxy group, an oxirane group, a glycidyl group, a glycidyloxy group, a styryl group, a styryloxy group, etc. Among them, from the aspect of obtaining good curability, a (meth)acryloyl group and a (meth)acryloyloxy group are preferred, and a (meth)acryloyloxy group is more preferred.

[0456] From the viewpoint of making the protective layer exhibit a protective function, the siloxane unit having a substituent containing a polymerizable group is preferably 0.01 mol% or more, more preferably 0.05 mol% or more, and further preferably 0.1 mol% or more relative to the total siloxane units. In addition, from the viewpoint of avoiding deformation such as curing shrinkage, the siloxane unit having a substituent containing a polymerizable group is preferably 95 mol% or less, more preferably 90 mol% or less, and further preferably 85 mol% or less relative to the total siloxane units.

[0457] As R 21 ~R 26 The substituent other than the aforementioned polymerizable group optionally possessed may include, for example, a fluorine atom, a chlorine atom, a bromine atom, a phenyl group, an amino functional group, a perfluoroalkyl group, a group containing a poly(hexafluoropropylene oxide) structure, etc. Substituents containing fluorine atoms. Among them, from the viewpoint of suppressing the compatibility of the anisotropic dye layer and the protective layer, preferably a fluorine atom, a substituent containing fluorine atoms, more preferably a fluorine atom.

[0458] From the viewpoint of suppressing the compatibility of the anisotropic dye layer and the protective layer, and showing good heat resistance without mixing the two layers even when heated, the siloxane unit having a fluorine atom or a substituent containing a fluorine atom of the aforementioned formula (B) is preferably 0.01 mol% or more, more preferably 0.05 mol% or more relative to the total siloxane unit. In addition, from the viewpoint of facilitating the provision of other functional layers on the protective layer, the siloxane unit having a fluorine atom or a substituent containing a fluorine atom of the aforementioned formula (B) is preferably 90 mol% or less, more preferably 80 mol% or less, and further preferably 70 mol% or less relative to the total siloxane unit.

[0459] In the first and third inventions, the dimethylsiloxane unit is preferably 0.5 mol% to 95 mol%, and more preferably 1 mol% to 90 mol%, based on all siloxane units.

[0460] In the second invention, the dimethylsiloxane unit is preferably 0.5 mol% to 60 mol%, and more preferably 1 mol% to 50 mol%, based on all siloxane units.

[0461] As the photocurable silicone resin used in the photocurable silicone resin, a commercially available product may be used.

[0462] Commercially available photocurable silicone resins not containing fluorine atoms include X-40-2761 (manufactured by Shin-Etsu Chemical Co., Ltd.) Commercially available photocurable silicone resins containing fluorine atoms include X-12-2430C (manufactured by Shin-Etsu Chemical Co., Ltd.).

[0463] The molecular weight M of the photocurable silicone resin used in the first and third inventions is preferably 5,000 or more, more preferably 10,000 or more, further preferably 12,000 or more, particularly preferably 15,000 or more, preferably 500,000 or less, more preferably 300,000 or less, and further preferably 100,000 or less. When the molecular weight M of the photocurable silicone resin is above the aforementioned lower limit, the curing shrinkage can be reduced and the optical properties of the optically anisotropic laminate can be improved. On the other hand, when the molecular weight M of the photocurable silicone resin is below the aforementioned upper limit, film formation tends to be easy.

[0464] The molecular weight M of the photocurable silicone resin used in the second invention is preferably 1000 or more, more preferably 5000 or more, further preferably 10000 or more, particularly preferably 15000 or more, preferably 500000 or less, more preferably 300000 or less, further preferably 100000 or less. When the molecular weight M of the photocurable silicone resin is above the aforementioned lower limit, the curing shrinkage can be reduced and the optical properties of the optically anisotropic laminate can be improved. On the other hand, when the molecular weight M of the photocurable silicone resin is below the aforementioned upper limit, film formation tends to be easy.

[0465] The molecular weight M of a resin such as a photocurable silicone resin can be determined using the value of the dynamic viscosity. Specific measurement conditions are shown in the following examples.

[0466] These curable silicone resins may be used alone or in combination of two or more.

[0467] The protective layer forming composition of the present invention may contain a photocurable resin other than a photocurable silicone resin as a photocurable resin or a curable resin. As a photocurable resin other than a photocurable silicone resin, for example, an acrylic resin can be cited in terms of the ease of introduction of curable carbon-carbon double bonds such as (meth)acryloyl groups.

[0468] By controlling the amount of curable carbon-carbon double bonds such as the (meth)acryloyl group, the degree of crosslinking can be controlled, and the adjustment of the exudation of low molecular weight components becomes easy. Furthermore, the bending properties of such photocurable resins are also excellent. It is speculated that the reason is that by making the resin component contain an appropriate amount of crosslinking groups, flexibility and curability can be achieved at the same time.

[0469] As the curable functional group contained in the photocurable resin, active energy ray curable functional groups such as carbon-carbon double bonds can be cited. For example, (meth)acryloyl and vinyl ether compounds can be cited. Among these, considering the ease of introduction and reactivity, (meth)acryloyl is preferred, and acryloyl is particularly preferred.

[0470] The polymerization reaction of the raw materials of the resin is generally a radical polymerization, and the polymerization can be carried out under conventionally known conditions.

[0471] Examples of monomers that can be used in combination as raw materials include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, cyclohexyl (meth)acrylate, phenyl (meth)acrylate, methoxy (poly)ethylene glycol (meth)acrylate, methoxy (poly)propylene glycol (meth)acrylate, methoxy (poly)ethylene glycol (poly)propylene glycol (meth)acrylate, octoxy (poly)ethylene glycol (meth)acrylate, octoxy (poly)propylene glycol (meth)acrylate. (Meth)acrylates such as esters, octyloxytetramethylene glycol (meth)acrylate, dodecyloxy (poly)ethylene glycol (meth)acrylate, and stearyloxy (poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl (meth)acrylamide, n-butyl (meth)acrylamide, isobutyl (meth)acrylamide, tert-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; styrene monomers such as styrene, p-chlorostyrene, and p-bromostyrene, etc. These may be used alone or in combination of two or more.

[0472] The acrylic resin can be produced by a radical polymerization reaction using the above-mentioned raw material vinyl monomers. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0473] From the viewpoint of showing the function of the protective layer or obtaining a smooth protective layer, the content of the photocurable resin in the protective layer is preferably 50% by mass or more, more preferably 60% by mass or more, and further preferably 70% by mass or more in 100% by mass of the protective layer. In addition, the content of the photocurable resin in the protective layer is preferably 99.99% by mass or less, and more preferably 99.9% by mass or less in 100% by mass of the protective layer.

[0474] Therefore, from the viewpoint of expressing the function of the protective layer or obtaining a smooth protective layer, the content of the photocurable resin in the protective layer-forming composition for forming the protective layer is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and further preferably 70 parts by mass or more relative to 100 parts by mass of the solid content of the protective layer-forming composition. In addition, the content of the photocurable resin in the protective layer-forming composition is preferably 99.99 parts by mass or less, and more preferably 99.9 parts by mass or less relative to 100 parts by mass of the solid content of the protective layer-forming composition.

[0475] Here, the solid content in the protective layer forming composition corresponds to the total of all components other than the solvent in the protective layer forming composition, and corresponds to the mass of the protective layer formed from the protective layer forming composition.

[0476] The content of the photocurable silicone resin in the protective layer-forming composition used in forming the protective layer is preferably 20 parts by mass or more, more preferably 30 parts by mass or more, and further preferably 35 parts by mass or more, relative to 100 parts by mass of the solid content of the protective layer-forming composition, from the viewpoint of expressing the function of the protective layer or obtaining a smooth protective layer. In addition, the content of the photocurable silicone resin is preferably 99.5 parts by mass or less, and more preferably 99 parts by mass or less, relative to 100 parts by mass of the solid content of the protective layer-forming composition.

[0477] <Photopolymerization initiator>

[0478] The protective layer-forming composition of the present invention preferably contains a photopolymerization initiator.

[0479] The maximum absorption wavelength of the photopolymerization initiator contained in the protective layer forming composition of the present invention is preferably 300 nm or more, more preferably 320 nm or more, and further preferably 340 nm or more. In addition, the maximum absorption wavelength of the photopolymerization initiator is preferably 450 nm or less, more preferably 430 nm or less, and further preferably 410 nm or less. By being within this range, the photopolymerization reaction is fully carried out, and an effect of obtaining a protective layer with a good degree of curing can be achieved.

[0480] As the photopolymerization initiator, the photopolymerization initiators listed in the above-mentioned anisotropic dye film-forming composition can be used.

[0481] From the viewpoint of obtaining a protective layer with good curing degree, the content of the photopolymerization initiator in the protective layer is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, in 100% by mass of the protective layer. In addition, the content of the photopolymerization initiator is preferably 30% by mass or less, more preferably 10% by mass or less, further preferably 8% by mass or less, particularly preferably 5% by mass or less, and particularly preferably 3% by mass or less, in 100% by mass of the protective layer.

[0482] Therefore, from the viewpoint of obtaining a protective layer with a good degree of curing, the content of the photopolymerization initiator in the protective layer-forming composition for forming the protective layer is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, relative to 100 parts by mass of the solid content of the protective layer-forming composition. In addition, the content of the photopolymerization initiator is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the solid content of the protective layer-forming composition.

[0483] <Other ingredients>

[0484] The protective layer-forming composition of the present invention may contain a polymerizable liquid crystal compound or the like in addition to the photocurable resin as a polymerizable component that is cured by photopolymerization.

[0485] As the polymerizable liquid crystal compound, various polymerizable liquid crystal compounds known in the past can be used, for example, the polymerizable liquid crystal compounds listed in the aforementioned anisotropic dye film-forming composition, and the records of pages 408 to 410, 521 to 524, 562 to 563 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000) can be cited.

[0486] The protective layer forming composition of the present invention may also contain non-polymerizable resins, non-polymerizable liquid crystal compounds, thermal polymerization initiators, inhibitors, polymerization aids, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers, thickeners, defoaming agents, pigments, organic-inorganic fillers, organic-inorganic nanosheets, organic-inorganic nanofibers, metal oxides, etc.

[0487] As the ultraviolet absorber optionally contained in the protective layer forming composition of the present invention, for example, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, triazine ultraviolet absorbers, salicylic acid ultraviolet absorbers, cyanoacrylate ultraviolet absorbers, etc. can be listed. Among these, from the viewpoint of easily obtaining the effect of ultraviolet absorption, benzophenone ultraviolet absorbers, benzotriazole ultraviolet absorbers, and triazine ultraviolet absorbers are preferred. Among them, from the viewpoint of excellent yellowing resistance, benzophenone ultraviolet absorbers are more preferred.

[0488] These ultraviolet absorbers can be used alone or in combination of two or more.

[0489] <Solvent>

[0490] The protective layer-forming composition of the present invention may contain a solvent as necessary.

[0491] The solvent that can be used is not particularly limited as long as it can sufficiently disperse or dissolve the photocurable resin, photopolymerization initiator, and other components contained in the protective layer-forming composition. Examples of the solvent include: alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorinated solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorinated solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.

[0492] From the viewpoint of being able to fully impart a protective function to the anisotropic pigment film, as the solvent, preferred are alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; and ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; and more preferred are alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether.

[0493] Furthermore, as the solvent, polar solvents are preferred from the viewpoint of compatibility with the anisotropic dye film. Among polar solvents, polar solvents having a relative dielectric constant of 10 or more are more preferred, polar solvents having a relative dielectric constant of 15 or more are further preferred, and polar solvents having a relative dielectric constant of 20 or more are particularly preferred.

[0494] These solvents may be used alone or in combination of two or more.

[0495] From the viewpoint of coating the protective layer-forming composition, the solvent preferably has a boiling point in the range of 50 to 200°C.

[0496] When the protective layer forming composition of the present invention contains a solvent, the content ratio of the solvent in the protective layer forming composition is preferably 50 to 98% by mass relative to the total amount (100% by mass) of the protective layer forming composition of the present invention. In other words, the content of the solid component in the protective layer forming composition of the present invention is preferably 2 to 50% by mass.

[0497] When the solid content in the protective layer forming composition is at most the above upper limit, the viscosity of the protective layer forming composition does not become too high, the thickness of the obtained protective layer becomes uniform, and the protective layer tends to be less prone to unevenness.

[0498] The solid content can be determined in consideration of the thickness of the protective layer to be produced.

[0499] <Viscosity of protective layer forming composition>

[0500] The viscosity of the protective layer forming composition of the present invention is not particularly limited as long as a uniform protective layer without uneven thickness can be produced. From the viewpoint of obtaining a large area of ​​thickness uniformity and productivity such as coating speed by the coating method described later, the viscosity of the protective layer forming composition of the present invention is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and further preferably 50 mPa·s or less.

[0501] <Method for producing protective layer-forming composition>

[0502] The method for producing the protective layer forming composition of the present invention is not particularly limited. For example, a photocurable resin, a photopolymerization initiator, a solvent as required, other components, etc. are mixed. In order to remove foreign matter, etc. in the composition, a filtering step may be included.

[0503] [Method for producing protective layer]

[0504] The method for producing the protective layer of the present invention is not particularly limited, and examples thereof include a method of forming the protective layer-forming composition of the present invention into a sheet shape and a method of producing the composition by a wet film-forming method.

[0505] The method of forming into a sheet mentioned in the present invention is a method of forming the protective layer forming composition into a formed body such as a sheet by some method and then curing the protective layer forming composition by irradiating heat and / or active energy rays.

[0506] As a method for forming into a sheet, a known method can be used, such as wet lamination, dry lamination, extrusion casting using a T die, extrusion lamination, calendaring or inflation, injection molding, liquid injection curing, etc. Among them, wet lamination, extrusion casting, and extrusion lamination are preferred.

[0507] The wet film forming method mentioned in the present invention is a method in which the protective layer forming composition is applied to a substrate by a certain method and then cured by polymerization using active energy rays. Thermal polymerization can also be used in combination with polymerization using active energy rays.

[0508] The substrate may be a substrate including an anisotropic dye film or a substrate not including an anisotropic dye film. In the case of a substrate not including an anisotropic dye film, the protective layer can be manufactured by transferring a protective layer-forming composition applied to a substrate to a substrate including an anisotropic dye film or by transferring an anisotropic dye film applied to a substrate to a substrate including a protective layer-forming composition, and curing the composition by irradiating the substrate with active energy rays.

[0509] Examples of a method for coating the protective layer-forming composition of the present invention on a substrate include reverse coating, gravure coating, rod coating, bar coating, Meyer bar coating, die coating, and spray coating.

[0510] The protective layer-forming composition of the present invention may be dried at 30° C. or higher and 150° C. or lower, if necessary, before being polymerized by irradiation with active energy rays.

[0511] Examples of the active energy rays include light and radiation, and among these, ultraviolet rays and visible light are preferred from the viewpoint of easy polymerization control.

[0512] When curing is performed by ultraviolet irradiation, a xenon lamp, a high pressure mercury lamp, a metal halide lamp, an LED-UV lamp, etc. can be used as a light source of the ultraviolet irradiation device. The irradiation amount of ultraviolet rays is appropriately determined according to the protective layer forming composition, and is generally 10 mJ / cm 2 Above and 10000mJ / cm 2 From the viewpoint of the degree of curing, the irradiation amount of ultraviolet rays is preferably 15 mJ / cm 2 Above and 5000mJ / cm 2 Less than 20 mJ / cm 2 Above and 3000mJ / cm 2 the following.

[0513] [Other functional films]

[0514] The optically anisotropic laminate of the present invention may include, in addition to the aforementioned anisotropic dye film and protective layer, an adhesive film having adhesion and / or tackiness, an antireflection film, a phase difference film, a light control film that absorbs, reflects or scatters light, a low refractive film, a high refractive film, an electrical insulating film, an electrical conductive film, an alignment film and other functional films. These functional films are preferably photopolymerizable photocurable films, but may also be films that are not photopolymerizable.

[0515] Among them, a tacky adhesive film is particularly preferred from the viewpoint of facilitating formation of an optical element using an optically anisotropic laminate.

[0516] The optically anisotropic laminate having an adhesive film and a protective layer preferably has a laminate structure of anisotropic dye film / protective layer / adhesive film. Other layers may be laminated between the anisotropic dye film, the protective layer, and the adhesive film.

[0517] (Adhesive film)

[0518] The pressure-sensitive adhesive film can be produced using the pressure-sensitive adhesive film-forming composition.

[0519] From the viewpoint of suppressing degradation of the adhesive film due to light, the light transmittance of the adhesive film at a wavelength of 380 nm or less is preferably less than 50%, more preferably less than 30%, and further preferably less than 20%. On the other hand, from the viewpoint of suppressing degradation of the optical element due to light, the light transmittance at a wavelength of 400 nm or less is preferably less than 30%, more preferably less than 25%, further preferably less than 22%, and particularly preferably less than 20%.

[0520] In terms of visibility when used in image display devices, the light transmittance of the adhesive film at a wavelength of 430 nm is preferably 60% or more, more preferably 70% or more, further preferably 75% or more, and particularly preferably 80% or more.

[0521] From the viewpoint of ensuring adhesiveness, the thickness of the adhesive film is preferably 3 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, particularly preferably 30 μm or more, and particularly preferably 40 μm or more. On the other hand, from the viewpoint of contributing to thinning of the optically anisotropic laminate, the upper limit of the thickness of the adhesive film is preferably 175 μm or less, more preferably 120 μm or less, further preferably 80 μm or less, and particularly preferably 60 μm or less.

[0522] The pressure-sensitive adhesive film-forming composition contains a curable resin and a photopolymerization initiator. As the photopolymerization initiator of the pressure-sensitive adhesive film-forming composition, the photopolymerization initiators listed in the protective layer-forming composition can be used.

[0523] The content of the photopolymerization initiator of the adhesive film-forming composition is not particularly limited. From the viewpoint of fully carrying out the polymerization reaction and improving the shape stability of the adhesive film, the content of the photopolymerization initiator of the adhesive film-forming composition is preferably 0.1 parts by mass or more relative to 100 parts by mass of the curable resin, more preferably 0.5 parts by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. In addition, from the viewpoint of ensuring adhesion, the upper limit of the content of the photopolymerization initiator of the adhesive film-forming composition is preferably 15 parts by mass or less relative to 100 parts by mass of the curable resin, more preferably 10 parts by mass or less, further preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0524] The curable resin contained in the adhesive film forming composition has the function of bonding and / or adhesiveness. As the curable resin, various resins known in the past can be used. For example, acrylic resins, epoxy resins, urethane resins, silicone resins, vinyl acetate resins, nitrile rubber, chloroprene rubber, styrene-butadiene rubber, etc. can be listed. Among them, acrylic resins are preferably used in terms of excellent bonding adhesiveness.

[0525] The pressure-sensitive adhesive film may contain a UV absorber. By containing a UV absorber, degradation of the optically anisotropic laminate due to light can be reduced.

[0526] As the ultraviolet absorber, the ultraviolet absorbers listed in the composition for forming a protective layer can be used.

[0527] [Method for producing optically anisotropic laminate]

[0528] The method for producing the optically anisotropic laminate of the present invention is not particularly limited, and examples thereof include the following methods (1) to (4).

[0529] (1) A method for producing an optically anisotropic laminate by coating a protective layer-forming composition on a substrate having an anisotropic dye film formed thereon and polymerizing the composition using active energy rays to form a protective layer

[0530] (2) A method for producing an optically anisotropic laminate by forming a protective layer-forming composition into a sheet on a substrate having an anisotropic dye film formed thereon and polymerizing the sheet using active energy rays to produce a protective layer.

[0531] (3) A method for producing an optically anisotropic laminate by transferring a protective layer-forming composition applied or formed in a sheet form on a substrate without an anisotropic dye film to a substrate with an anisotropic dye film, and then curing the composition using active energy rays to form a protective layer.

[0532] (4) A method for producing an optically anisotropic laminate by transferring an anisotropic dye film from a substrate on which an anisotropic dye film is produced to a protective layer-forming composition coated or formed in a sheet form on a substrate on which an anisotropic dye film is not produced, and then curing the composition using active energy rays to form a protective layer.

[0533] From the viewpoint of shortening the process, a method of producing an optically anisotropic laminate by applying or forming a sheet of the protective layer-forming composition on a substrate having an anisotropic dye film and polymerizing it using active energy rays to form a protective layer is preferred.

[0534] Functional films other than the protective layer can also be formed in the same manner as the protective layer.

[0535] [Optical components]

[0536] The optical element of the present invention includes the optically anisotropic laminate of the present invention.

[0537] The optical element in the present invention refers to a polarizing element, a phase difference element, an optical compensation element, an element having functions such as reflection, brightness improvement, refractive anisotropy or conductive anisotropy that utilizes the anisotropy of light absorption to obtain linear polarization, circular polarization, elliptical polarization, etc. The optical element may have a single function or multiple functions. These functions can be appropriately adjusted by the selection of the anisotropic pigment film forming process and the substrate or the composition containing the organic compound (pigment, transparent material).

[0538] The optical element of the present invention is preferably used as a polarizing element or a polarizing element combined with other functions, and is more preferably used as a polarizing element.

[0539] Since a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating, the optical element of the present invention can also be preferably used for applications such as flexible displays.

[0540] [Polarizing element]

[0541] When the optical element of the present invention is used as a polarizing element, the polarizing element may have any other layers as long as it has the optically anisotropic laminate of the present invention.

[0542] The layers that can be used in combination in the polarizing element can be appropriately arranged according to the manufacturing process, characteristics, and functions, and the position and order of lamination are not particularly limited.

[0543] The layer having an optical function can be formed by the following method.

[0544] The layer having the function of a phase difference film can be formed by coating or laminating the phase difference film on other layers constituting the polarizing element. The phase difference film can be formed, for example, by performing a stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, or performing a treatment described in Japanese Patent Laid-Open No. 7-230007.

[0545] The layer having the function of a brightness enhancement film can be formed by coating or laminating the brightness enhancement film on other layers constituting the polarizing element, etc. The brightness enhancement film can be formed, for example, by forming micropores using the method described in Japanese Patent Application Laid-Open Nos. 2002-169025 and 2003-29030, or by overlapping two or more cholesteric liquid crystal layers having different central wavelengths for selective reflection.

[0546] The layer having a function as a reflective film or a semi-transmitting reflective film can be formed by, for example, applying or laminating a metal thin film obtained by vapor deposition or sputtering to other layers constituting the polarizing element.

[0547] The layer having a function as a diffusion film can be formed by, for example, applying a resin solution containing fine particles to another layer constituting the polarizing element.

[0548] When the optical element of the present invention is used for various display elements such as LCD or OLED, the optical element of the present invention can be directly formed on the surface of an electrode substrate etc. constituting these display elements, and can also be used as a constituent member of these display elements.

[0549] Example

[0550] Hereinafter, the present invention will be described in more detail by way of examples. The present invention is not limited to the following examples unless it departs from the gist of the present invention.

[0551] In the following description, "parts" means "parts by mass".

[0552] [Measurement / Evaluation Method]

[0553] Various measurement / evaluation methods in the following Examples and Comparative Examples are as follows.

[0554] <Molecular weight M>

[0555] Substitute the kinematic viscosity η of the silicone resin into the AJ Barry formula (the following formula (4)) to find the approximate molecular weight M of dimethylsiloxane. (Reference: AJ Barry, J. Appl. Physics, 17, 1020,

[1946] )

[0556] logη=1.00+0.0123M 0.5(4)

[0557] When calculating the kinetic viscosity η from the viscosity μ, the following formula (5) is used (density: ρ).

[0558] η=μ / ρ (5)

[0559] <Surface free energy>

[0560] The surface free energy γ can be calculated by obtaining the static contact angle of water or diiodomethane with respect to the target surface at 25° C. using the theoretical formula described in DK Wendt and RC Wendt, J. Appl. Polym. Sci., 13, 1741 (1969).

[0561] The static contact angle was measured using a contact angle meter "DropMaster500" manufactured by Kyowa Interface Science Co., Ltd. The measurement temperature was set to 25°C, the drop amount was set to 2 μL, and the contact angles of distilled water and diiodomethane were evaluated 1 second after the droplet landed. Five points were measured respectively and the average value was calculated. Using the average value of the calculated static contact angle, the surface free energy was calculated using the theoretical formula described in the aforementioned non-patent literature.

[0562] γ d represents the dispersion component (dispersion term) of the surface free energy, γ h Represents the polar component (polar term) of surface free energy.

[0563] <Heat resistance evaluation>

[0564] As a heat resistance test, the optically anisotropic laminate was heated on a hot plate at 80° C. for 5 minutes, and then removed from the hot plate and left at room temperature. The appearance of the optically anisotropic laminate after the test was observed and evaluated according to the following criteria.

[0565] (Evaluation Criteria)

[0566] ○: Good appearance is maintained.

[0567] ×: White turbidity was observed.

[0568] <Evaluation of Solvent Resistance>

[0569] As a solvent resistance (ethanol) test, ethanol was dropped onto the optically anisotropic laminate for 1 minute, and then the laminate was wiped with a cotton swab. The appearance of the optically anisotropic laminate after the test was observed and evaluated according to the following criteria.

[0570] (Evaluation Criteria)

[0571] ○: Good appearance is maintained.

[0572] ×: Wiping traces with the cotton swab were observed.

[0573] [Polymerizable liquid crystal compounds and pigments]

[0574] The details of the polymerizable liquid crystal compound and the dye contained in the anisotropic dye film used in the following Examples and Comparative Examples are as follows.

[0575] [Polymerizable liquid crystal compound]

[0576] The polymerizable liquid crystal compound (I-1) (molecular weight: 828) represented by the following structural formula was synthesized according to the description of Japanese Patent Application Laid-Open No. 2020-042305. 11 H 22 It refers to 11 methylene chains bonded into a straight chain.

[0577]

[0578] <Pigment>

[0579] The chemical structures of the dyes (II-1) and (II-2) are shown below.

[0580]

[0581]

[0582] [Examples and Comparative Examples of the First Invention]

[0583] [Example I-1]

[0584] <Preparation of anisotropic dye film-forming composition>

[0585] To 69.31 parts of cyclopentanone were added 28.57 parts of a polymerizable liquid crystal compound (I-1), 0.34 parts of a pigment (II-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of a pigment (II-2) (manufactured by Showa Chemical Industry Co., Ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF) (maximum absorption wavelength 319 nm), and 0.34 parts of BYK-361N (manufactured by BYK-Chemie), and after heating and stirring at 80°C, the mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a composition for forming an anisotropic pigment film.

[0586] <Formation of anisotropic pigment film>

[0587] The anisotropic dye film-forming composition was formed into a film on a substrate having an oriented film of polyimide formed on glass (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, oriented film formed by rubbing method) by spin coating, and dried by heating at 120°C for 2 minutes, and then cooled to a liquid crystal phase, and then exposed to light at an exposure dose of 500 mj / cm 2 The polymerization was carried out at 365 nm (based on 365 nm) to obtain an anisotropic dye film with a film thickness of 3 μm.

[0588] When the obtained anisotropic dye film was observed by placing a polarizing plate on the anisotropic dye film side, clear light and dark appeared every time the polarizing plate was rotated 90 degrees, indicating that the film had good polarization performance.

[0589] The surface free energy measured for this anisotropic dye film is shown in Table 1 below.

[0590] <Preparation of protective layer forming composition>

[0591] As the photocurable silicone resin, the following fluorine-containing photocurable silicone resin X-12-2430C (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-1) was used. The molecular weight M of the fluorine-containing photocurable silicone resin was 24,000.

[0592] 40 parts of fluorine-containing photocurable silicone resin (R-1), 0.40 parts of photopolymerization initiator Omnirad 369 (manufactured by IGMRESINS), 1.20 parts of BYK-3550 (manufactured by BYK-Chemie), and 60 parts of ethanol were mixed and stirred, and filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a protective layer forming composition I-1.

[0593] <Formation of protective layer>

[0594] The protective layer-forming composition I-1 was formed into a film on the anisotropic dye film by spin coating, and after heating and drying at 50° C. for 2 minutes, an exposure dose of 500 mj / cm 2 The polymerization was carried out at 365 nm (based on 365 nm) to form a protective layer I-1 having a film thickness of 2 μm, thereby obtaining an optically anisotropic laminate I-1.

[0595] The surface free energy of the formed protective layer I-1 is shown in Table 1.

[0596] [Example I-2]

[0597] A protective layer I-2 was formed on the anisotropic dye film formed in the same manner as in Example I-1 except that the amount of the fluorine-containing photocurable silicone resin (R-1) was changed from 40 parts to 50 parts and the amount of the photopolymerization initiator Omnirad369 was changed from 0.40 parts to 0.50 parts, thereby obtaining an optically anisotropic laminate I-2. The surface free energy of the protective layer I-2 thus formed is shown in Table 1.

[0598] [Example I-3]

[0599] As the photocurable silicone resin of the protective layer forming composition, a fluorine-free photocurable silicone resin X-40-2761 (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-2) was used. In the same manner as in Example I-1, a protective layer I-3 was formed on the anisotropic dye film to obtain an optically anisotropic laminate I-3. The molecular weight M of the fluorine-free photocurable silicone resin (R-2) was 19000. The surface free energy of the formed protective layer I-3 is shown in Table 1.

[0600] [Comparative Example I-1]

[0601] As the photocurable resin of the protective layer forming composition, the following photocurable urethane acrylate resin, UV-7600B (manufactured by Mitsubishi Chemical Corporation) (R-3), was used. In the same manner as in Example I-1, a protective layer I-4 was formed on the anisotropic dye film to obtain an optically anisotropic laminate I-4. The weight average molecular weight (Mw) of the photocurable urethane acrylate resin (R-3) was 2000. The surface free energy of the formed protective layer I-4 is shown in Table 1.

[0602] [Evaluation results]

[0603] The optically anisotropic laminates I-1 to I-4 produced in Examples I-1 to I-3 and Comparative Example I-1 were evaluated for heat resistance and solvent resistance. The results are shown in Table 1.

[0604] [Table 1]

[0605]

[0606] As shown in Table 1, the absolute value of the surface free energy difference between the anisotropic pigment layer and the protective layer is 3 mN / m 2 The optically anisotropic laminate of the first invention described above is excellent in heat resistance and solvent resistance, and can maintain good appearance and performance in applications such as polarizers.

[0607] [Examples and Comparative Examples of the Second Invention]

[0608] [Example II-1]

[0609] <Preparation of anisotropic dye film-forming composition>

[0610] To 69.31 parts of cyclopentanone were added 28.57 parts of a polymerizable liquid crystal compound (I-1), 0.34 parts of a pigment (II-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of a pigment (II-2) (manufactured by Showa Chemical Industry Co., Ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF) (maximum absorption wavelength 319 nm), and 0.34 parts of BYK-361N (manufactured by BYK-Chemie), and after heating and stirring at 80°C, the mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a composition for forming an anisotropic pigment film.

[0611] <Formation of anisotropic pigment film>

[0612] The anisotropic dye film-forming composition was formed into a film on a substrate having an oriented film of polyimide formed on glass (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, oriented film formed by rubbing method) by spin coating, and dried by heating at 120°C for 2 minutes, and then cooled to a liquid crystal phase, and then exposed to light at an exposure dose of 500 mj / cm 2 The polymerization was carried out at 365 nm (based on 365 nm) to obtain an anisotropic dye film with a film thickness of 3 μm.

[0613] When the obtained anisotropic dye film was observed by placing a polarizing plate on the anisotropic dye film side, clear light and dark appeared every time the polarizing plate was rotated 90 degrees, indicating that the film had good polarization performance.

[0614] <Preparation of protective layer-forming composition>

[0615] As the photocurable silicone resin, the following fluorine-containing photocurable silicone resin X-12-2430C (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-1) was used. The molecular weight M of the fluorine-containing photocurable silicone resin was 24,000.

[0616] 40 parts of fluorine-containing photocurable silicone resin (R-1), 0.40 parts of photopolymerization initiator Omnirad 369 (manufactured by IGMRESINS), 1.20 parts of BYK-3550 (manufactured by BYK-Chemie), and 60 parts of ethanol were mixed and stirred, and filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a protective layer forming composition II-1.

[0617] <Formation of protective layer>

[0618] The protective layer-forming composition II-1 was formed into a film on the anisotropic dye film by spin coating, and after heating and drying at 50° C. for 2 minutes, an exposure dose of 500 mj / cm 2 The polymerization was carried out (365 nm basis) to form a protective layer II-1 having a film thickness of 2 μm, thereby obtaining an optically anisotropic laminate II-1.

[0619] <Surface free energy of a film obtained by curing the resin contained in the protective layer-forming composition>

[0620] A film of the R-1-containing resin composition obtained in the same manner as the protective layer-forming composition II-1 except that 1.20 parts of BYK-3550 was replaced with 0 parts was formed on glass by spin coating, and after heating and drying at 50° C. for 2 minutes, an exposure dose of 500 mj / cm 2 The surface free energy of the fluorine-containing photocurable silicone resin (R-1) was calculated as the surface free energy of the R-1 resin layer, as shown in Table 2.

[0621] [Example II-2]

[0622] A protective layer II-2 was formed on the anisotropic dye film formed in the same manner as in Example II-1 except that the fluorine-containing photocurable silicone resin (R-1) was changed from 40 parts to 50 parts and the photopolymerization initiator Omnirad 369 was changed from 0.40 parts to 0.50 parts, thereby obtaining an optically anisotropic laminate II-2.

[0623] [Example II-3]

[0624] As the photocurable silicone resin of the protective layer forming composition, a fluorine-free photocurable silicone resin X-40-2761 (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-2) was used. In the same manner as in Example II-1, a protective layer II-3 was formed on the anisotropic dye film to obtain an optically anisotropic laminate II-3. The molecular weight M of the fluorine-free photocurable silicone resin (R-2) was 19,000.

[0625] The R-2 resin layer was obtained in the same manner as in Example II-1 except that the photocurable silicone resin (R-1) was replaced by the fluorine-free photocurable silicone resin (R-2). The surface free energy of the fluorine-free photocurable silicone resin (R-2) was calculated as the surface free energy of the R-2 resin layer, as shown in Table 2.

[0626] [Comparative Example II-1]

[0627] As the photocurable resin of the protective layer forming composition, the following photocurable urethane acrylate resin, UV-7600B (manufactured by Mitsubishi Chemical Corporation) (R-3), was used. In the same manner as in Example II-1, a protective layer II-4 was formed on the anisotropic dye film to obtain an optically anisotropic laminate II-4. The weight average molecular weight (Mw) of the photocurable urethane acrylate resin (R-3) was 2000.

[0628] The R-3 resin layer was obtained in the same manner as in Example II-1 except that the photocurable silicone resin (R-1) was replaced by the photocurable urethane acrylate resin (R-3). The surface free energy of the photocurable urethane acrylate resin (R-3) was calculated as the surface free energy of the R-3 resin layer, as shown in Table 2.

[0629] [Evaluation results]

[0630] The heat resistance and solvent resistance of the optically anisotropic laminates II-1 to II-4 produced in Examples II-1 to II-3 and Comparative Example II-1 were evaluated. Table 2 shows the results.

[0631] [Table 2]

[0632]

[0633] As shown in Table 2, the surface free energy of the film obtained by curing the curable resin contained in the protective layer forming composition is 45 mN / m 2 The optically anisotropic laminate of the following second invention is excellent in heat resistance and solvent resistance, and can maintain good appearance and performance in applications such as polarizers.

[0634] [Examples and Comparative Examples of the Third Invention]

[0635] [Example III-1]

[0636] <Preparation of anisotropic dye film-forming composition>

[0637] To 69.31 parts of cyclopentanone were added 28.57 parts of a polymerizable liquid crystal compound (I-1), 0.34 parts of a pigment (II-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of a pigment (II-2) (manufactured by Showa Chemical Industry Co., Ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF) (maximum absorption wavelength 319 nm), and 0.34 parts of BYK-361N (manufactured by BYK-Chemie), and after heating and stirring at 80°C, the mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a composition for forming an anisotropic pigment film.

[0638] <Formation of anisotropic pigment film>

[0639] The anisotropic dye film-forming composition was formed into a film on a substrate having an oriented film of polyimide formed on glass (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, oriented film formed by rubbing method) by spin coating, and dried by heating at 120°C for 2 minutes, and then cooled to a liquid crystal phase, and then exposed to light at an exposure dose of 500 mj / cm 2 The polymerization was carried out at 365 nm (based on 365 nm) to obtain an anisotropic dye film with a film thickness of 3 μm.

[0640] When the obtained anisotropic dye film was observed by placing a polarizing plate on the anisotropic dye film side, clear light and dark appeared every time the polarizing plate was rotated 90 degrees, indicating that the film had good polarization performance.

[0641] <Preparation of protective layer-forming composition>

[0642] As the photocurable silicone resin, the following fluorine-containing photocurable silicone resin X-12-2430C (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-1) was used. The molecular weight M of the fluorine-containing photocurable silicone resin was 24,000.

[0643] 40 parts of fluorine-containing photocurable silicone resin (R-1), 0.40 parts of photopolymerization initiator Omnirad 369 (manufactured by IGMRESINS), 1.20 parts of BYK-3550 (manufactured by BYK-Chemie), and 60 parts of ethanol were mixed and stirred, and filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, caliber 0.45 μm) to obtain a protective layer forming composition III-1.

[0644] <Formation of protective layer>

[0645] The protective layer-forming composition III-1 was formed into a film on the anisotropic dye film by spin coating, and after heating and drying at 50° C. for 2 minutes, an exposure dose of 500 mj / cm 2 The polymerized layer was then polymerized (365 nm standard) to form a protective layer III-1 having a film thickness of 2 μm, thereby obtaining an optically anisotropic laminate III-1.

[0646] [Example III-2]

[0647] A protective layer III-2 was formed on the anisotropic dye film formed in the same manner as in Example III-1 except that the fluorine-containing photocurable silicone resin (R-1) was changed from 40 parts to 50 parts and the photopolymerization initiator Omnirad 369 was changed from 0.40 parts to 0.50 parts, thereby obtaining an optically anisotropic laminate III-2.

[0648] [Example III-3]

[0649] As the photocurable silicone resin of the protective layer forming composition, a fluorine-free photocurable silicone resin X-40-2761 (manufactured by Shin-Etsu Chemical Co., Ltd.) (R-2) was used. In the same manner as in Example III-1, a protective layer III-3 was formed on the anisotropic dye film to obtain an optically anisotropic laminate III-3. The molecular weight M of the fluorine-free photocurable silicone resin (R-2) was 19,000.

[0650] [Comparative Example III-1]

[0651] As the photocurable resin of the protective layer forming composition, the following photocurable urethane acrylate resin, UV-7600B (manufactured by Mitsubishi Chemical Corporation) (R-3), was used. In the same manner as in Example III-1, a protective layer III-4 was formed on the anisotropic dye film to obtain an optically anisotropic laminate III-4. The weight average molecular weight (Mw) of the photocurable urethane acrylate resin (R-3) was 2000.

[0652] [Evaluation results]

[0653] The heat resistance and solvent resistance of the optically anisotropic laminates III-1 to III-4 produced in Examples III-1 to III-3 and Comparative Example III-1 were evaluated. The results are shown in Table 3.

[0654] [Table 3]

[0655]

[0656] As can be seen from Table 3, the optically anisotropic laminate of the third invention having a protective layer formed of a protective layer-forming composition containing a photocurable silicone resin has excellent heat resistance and solvent resistance, and can maintain good appearance and performance in applications such as polarizers.

[0657] Although the present invention has been described in detail using specific embodiments, it is apparent to one skilled in the art that various modifications can be made within the scope of exhibiting the effects of the invention.

[0658] This application is based on Japanese Patent Application No. 2022-153906, Japanese Patent Application No. 2022-153907 and Japanese Patent Application No. 2022-153908 filed on September 27, 2022, the entireties of which are incorporated herein by reference.

Claims

1. An optically anisotropic laminate, wherein a protective layer is laminated on an anisotropic dye layer, The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator. The absolute value of the surface free energy difference between the anisotropic pigment layer and the protective layer is 3 mN / m 2 above.

2. The optically anisotropic laminate according to claim 1, wherein The protective layer is a layer formed from a protective layer-forming composition containing a photocurable silicone resin.

3. The optically anisotropic laminate according to claim 2, wherein The photocurable silicone resin has fluorine atoms.

4. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

5. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a compound represented by the following formula (1): Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1) In formula (1), -Q 1 represents a hydrogen atom or a polymerizable group; -Q 2 represents a polymerizable group; -R 1 -and-R 2 - each independently represents a chain organic group; -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond; -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2); -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2); k is 1 or 2, When k is 2, 2 -Y 2 -A 13 - are optionally the same as or different from each other, -Cy-X 2 -C≡C-X 1 -…(2) In formula (2), -Cy- represents a hydrocarbon ring group or a heterocyclic group; -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

6. An optically anisotropic laminate, comprising a protective layer laminated on an anisotropic dye layer, The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator. The protective layer is a layer formed of a protective layer-forming composition containing a curable resin. The surface free energy of the film obtained by curing the curable resin is 45 mN / m 2 the following.

7. The optically anisotropic laminate according to claim 1, wherein The curable resin is a photocurable silicone resin.

8. The optically anisotropic laminate according to claim 2, wherein The photocurable silicone resin has fluorine atoms.

9. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

10. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a compound represented by the following formula (1): Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1) In formula (1), -Q 1 represents a hydrogen atom or a polymerizable group; -Q 2 represents a polymerizable group; -R 1 -and-R 2 - each independently represents a chain organic group; -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond; -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2); -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2); k is 1 or 2, When k is 2, 2 -Y 2 -A 13 - are optionally the same as or different from each other, -Cy-X 2 -C≡C-X 1 -…(2) In formula (2), -Cy- represents a hydrocarbon ring group or a heterocyclic group; -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

11. An optically anisotropic laminate, comprising a protective layer laminated on an anisotropic dye layer, The anisotropic dye layer is a layer formed of an anisotropic dye film-forming composition containing a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator. The protective layer is a layer formed of a protective layer-forming composition containing a photocurable resin. The photocurable resin includes a photocurable silicone resin.

12. The optically anisotropic laminate according to claim 1, wherein The molecular weight M of the photocurable silicone resin is 5000 or more.

13. The optically anisotropic laminate according to claim 1, wherein The photocurable silicone resin has fluorine atoms.

14. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a low-molecular polymerizable liquid crystal compound having no repeating structure.

15. The optically anisotropic laminate according to claim 1, wherein The polymerizable liquid crystal compound is a compound represented by the following formula (1): Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(1) In formula (1), -Q 1 represents a hydrogen atom or a polymerizable group; -Q 2 represents a polymerizable group; -R 1 -and-R 2 - each independently represents a chain organic group; -A 11 -and-A 13 - each independently represents a partial structure represented by the following formula (2), a divalent organic group or a single bond; -A 12 - represents a partial structure or a divalent organic group represented by the following formula (2); -Y 1 -and-Y 2 - each independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -A 11 -and-A 13 - one of which is a partial structure or a divalent organic group represented by the following formula (2); k is 1 or 2, When k is 2, 2 -Y 2 -A 13 - are optionally the same as or different from each other, -Cy-X 2 -C≡C-X 1 -…(2) In formula (2), -Cy- represents a hydrocarbon ring group or a heterocyclic group; -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -X 2 - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. 16 . An optical element comprising the optically anisotropic laminate according to claim 1 .

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