Optically anisotropic laminate and optical element

Abstract

This optically anisotropic laminate is obtained by laminating at least one photocurable film on an anisotropic dye film, wherein: the anisotropic dye film contains a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator; the photocurable film contains a curable resin and a photopolymerization initiator; the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film satisfy expression (1); and the weight-average molecular weight (Mw) of the curable resin is greater than 10,000.　(1): λ0<λ1

Description

[Technical Field]

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

[0002] In LCDs, linear and circular polarizing films are used to control the optical rotation and birefringence of the display. OLEDs also use circular polarizing films to prevent reflection of external light in bright places.

[0003] Conventionally, examples of such polarizing films include a polarizing film (iodine-PVA polarizing film) made by dyeing polyvinyl alcohol (PVA) with low concentration of iodine (Patent Document 1). However, iodine-PVA polarizing films dyed with low concentrations of iodine can have problems such as discoloration due to iodine sublimation or deterioration depending on the usage environment, and warping due to relaxation of the PVA stretching.

[0004] 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). However, polarizing films formed by applying a liquid crystal composition containing a dye have the problem that high light absorption selectivity cannot be obtained, or when attempting to obtain high light absorption selectivity, difficulties may arise in the process.

[0005] [Patent Document 1] Japanese Patent Application Publication No. 1-105204 [Patent Document 2] Special Publication No. 2004-535483

[0006] Under such circumstances, there is a demand for a polarizing film that has high light absorption selectivity even when it is a thin film.

[0007] When a polarizing film made of an anisotropic dye film is mounted on a display element, it is used in the form of an optically anisotropic laminate in which a photocurable film having functionality for the purposes of protection, adhesion, imparting electro-optical properties, etc. is laminated on the polarizing film. As a method for laminating the photocurable film on the polarizing film, there can be mentioned a method in which the polarizing film is first photopolymerized to form a film, and then the photocurable film is photopolymerized on the polarizing film to form a film.

[0008] In the step of forming a film by irradiating light on a polarizing film to polymerize the photocurable film in the lamination method, when the photocurable film is irradiated directly, the polarizing film is exposed to the irradiated light that has passed through the photocurable film, whereas when the light is irradiated from the polarizing film side, the polarizing film is exposed to the irradiated light because the photocurable film is photopolymerized by the light that has passed through the polarizing film.

[0009] When a polarizing film is exposed to irradiated light in this way, if the wavelength of the irradiated light corresponds to a wavelength to which the photopolymerization initiator in the polarizing film is sensitive, the photopolymerization initiator remaining in the polarizing film even after photopolymerization will cause a re-polymerization reaction in the polarizing film. If a re-polymerization reaction occurs, the alignment of the liquid crystal compound and dye that have been fixed in the optimal molecular orientation direction in the polarizing film will be disturbed, and the optical performance of the polarizing film, such as the dichroic ratio and transmittance, may be reduced.

[0010] For these reasons, it is desired to realize an optically anisotropic laminate in which a photocurable film is laminated on a polarizing film, and which can maintain the high optical performance of the polarizing film.

[0011] The present invention aims to provide an optically anisotropic laminate in which an anisotropic dye film and a photocurable film are laminated, and an optical element in which the high optical performance of the anisotropic dye film can be maintained. Summary of the Invention

[0012] The present inventors have found that the above-mentioned problems can be solved by ensuring that the maximum absorption wavelengths of the photopolymerization initiators contained in the anisotropic dye film and the photocurable film have an appropriate relationship. That is, the present invention has the following aspects.

[0013] [1] An optically anisotropic laminate in which at least one photocurable film is laminated on an anisotropic dye film, the anisotropic dye film contains a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator; the photocurable film contains a curable resin and a photopolymerization initiator; the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film satisfy the following formula (1): The optically anisotropic laminate, wherein the curable resin has a weight average molecular weight (Mw) of more than 10,000. λ0<λ1 …(1)

[0014] [2] An optically anisotropic laminate in which at least one adhesive film is laminated on an anisotropic dye film, the anisotropic dye film contains a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator; the adhesive film contains a curable resin and a photopolymerization initiator; An optically anisotropic laminate, wherein the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the adhesive film satisfy the following formula (1): λ0<λ1 …(1)

[0015] [3] The optically anisotropic laminate according to [1], wherein at least one layer of the photocurable film is an adhesive film.

[0016] [4] The optically anisotropic laminate according to [1], wherein at least one layer of the photocurable film is an overcoat film.

[0017] [5] The optically anisotropic laminate according to [2], wherein at least one overcoat film is further laminated on the anisotropic dye film.

[0018] [6] The optically anisotropic laminate according to any one of [1] to [5], wherein the difference between λ1 and λ0 is 5 nm or more.

[0019] [7] The optically anisotropic laminate according to any one of [1] to [6], wherein the curable resin is an acrylic resin having a (meth)acryloyl group.

[0020] [8] The optically anisotropic laminate according to [7], wherein the acrylic resin has a double bond equivalent of 0.1 to 10 mmol / g.

[0021] [9] The optically anisotropic laminate according to any one of [1] to [8], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (2): Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2) (In formula (2), -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 (3), a divalent organic group, or a single bond; -A 12 - represents a partial structure represented by the following formula (3) or a divalent organic group; -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)-, -CHCH-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-; -A 11 -and-A 13- is a partial structure represented by the following formula (3) or a divalent organic group: k is 1 or 2. If k is 2, two -Y 2 -A 13 - may be the same or different.) -Cy-X 2 -C≡CX 1 - ...(3) (In formula (3), -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)-, -C2O-, -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)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHHO-, -OCH-, -CHS-, or -SCH-.

[0022]

[10] The optically anisotropic laminate according to any one of [1] to [9], wherein the dye is an azo-based dichroic dye.

[0023]

[11] The number of ring structures (r n1 ) and the number of ring structures (r n2 ) and the ratio (r n1 / r n2 ) is 0.7 to 1.5.

[0024]

[12] An optical element having the optically anisotropic laminate according to any one of [1] to

[11] . [Effects of the Invention]

[0025] The optically anisotropic laminate of the present invention can maintain excellent optical performance, particularly sufficient dichroic ratio and transmittance. The optical element of the present invention includes the optically anisotropic laminate of the present invention, and therefore has excellent optical performance, particularly a sufficient dichroic ratio and transmittance. DETAILED DESCRIPTION OF THE INVENTION

[0026] The present invention will be described in detail below with reference to the following embodiments. The present invention is not limited to the following embodiments, and various modifications can be made within the scope of the present invention.

[0027] [Optical anisotropic laminate] The optically anisotropic laminate of the present invention is obtained by laminating at least one layer of a photocurable film (hereinafter sometimes referred to as a "photocurable film of the present invention") or a pressure-sensitive adhesive film (hereinafter sometimes referred to as a "pressure-sensitive adhesive film of the present invention") on an anisotropic dye film (hereinafter sometimes referred to as an "anisotropic dye film of the present invention"). The anisotropic dye film referred to in the present invention is a dye film that has anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system: the thickness direction of the anisotropic dye film 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. The adhesive film referred to in the present invention is a film that has adhesive and / or tackiness, and is a type of photocurable film, as described below.

[0028] The total thickness (total thickness) of the optically anisotropic laminate of the present invention is preferably 0.5 μm or more, more preferably 1 μm or more, and even more preferably 1.5 μm or more. On the other hand, it is preferably 800 μm or less, more preferably 500 μm or less, and even more preferably 300 μm or less. When the total thickness of the optically anisotropic laminate of the present invention is not less than the above lower limit, it becomes easy to handle, and when it is not more than the above upper limit, it tends to be thin and lightweight when used as an optical element.

[0029] The optically anisotropic laminate of the present invention having an anisotropic dye film and a photocurable film may be laminated with a non-photopolymerizable functional film other than the anisotropic dye film and the photocurable film. Examples of the non-photopolymerizable functional film include a non-photopolymerizable overcoat film having functions such as protection (e.g., abrasion resistance, scratch resistance, stress relaxation resistance, chemical resistance, gas resistance, water resistance, and corrosion resistance), bleeding prevention, flattening, easy adhesion, and release, a pressure-sensitive adhesive film having adhesiveness and / or cohesiveness, an anti-reflection film, a retardation film, a light control film that absorbs, reflects, or scatters light, a low refractive index film, a high refractive index film, an electrical insulating film, an electrically conductive film, an alignment film, and a release film. At least one layer of the photocurable film may be an adhesive film or an overcoat film.

[0030] In the optically anisotropic laminate of the present invention, the anisotropic dye film is usually produced by irradiating with active energy rays a film formed by wet film-forming of a composition for an anisotropic dye film, which will be described later, to cure it. The anisotropic dye film in the optically anisotropic laminate of the present invention is an anisotropic dye film in a broad sense, including both an uncured film before irradiation with active energy rays and a cured film after irradiation with active energy rays. The polymerizable liquid crystal compound in the anisotropic dye film is at least partially polymerized during the manufacturing process of the anisotropic dye film, and the polymerized liquid crystal compound is present in the anisotropic dye film. In the present invention, the polymerized liquid crystal compound in the anisotropic dye film is also referred to as the "polymerizable liquid crystal compound."

[0031] The photocurable film (including the adhesive film) of the optically anisotropic laminate of the present invention is usually produced by irradiating a film formed from the photocurable film composition described below with active energy rays to cure it. The photocurable film in the optically anisotropic laminate of the present invention is a photocurable film in a broad sense, including both the uncured film before irradiation with active energy rays and the cured film after irradiation with active energy rays. At least a portion of the curable resin in the photocurable film is polymerized during the production process of the photocurable film, and the polymerized curable resin is present in the photocurable film. In the present invention, the polymerized curable resin in the photocurable film is also referred to as the "curable resin." Similarly, the polyfunctional (meth)acrylate in the adhesive film described below forms a crosslinked structure after film formation, and is therefore no longer contained as a polyfunctional (meth)acrylate simple substance in the adhesive film. However, in the present invention, the polyfunctional (meth)acrylate is described as a simple substance before the reaction, including the one that is incorporated into the reaction product in the reaction after film formation.

[0032] In the optically anisotropic laminate of the present invention, the adhesive film and the overcoat film are included as embodiments of the photocurable film.

[0033] In the optically anisotropic laminate of the present invention, when the maximum absorption wavelength of the photopolymerization initiator contained in the anisotropic dye film is λ0 and the maximum absorption wavelength of the photopolymerization initiator contained in the photocurable film (including the adhesive film) is λ1, λ0 and λ1 satisfy the following formula (1): λ0<λ1 …(1) Both λ0 and λ1 are wavelengths that show upward inflection points in the absorption spectrum at wavelengths of 250 nm or more. In addition, when there are multiple maximum absorption wavelengths, they are the maximum absorption wavelengths on the long wavelength side.

[0034] Although there are no particular limitations as long as formula (1) is satisfied, the difference between λ1 and λ0 is preferably 5 nm or more, more preferably 10 nm or more, further preferably 15 nm or more, and particularly preferably 30 nm or more, and this difference is preferably 100 nm or less, more preferably 80 nm or less.

[0035] The reason why the present invention can maintain excellent optical performance is as follows. One method for forming an optically anisotropic laminate involves first photopolymerizing an anisotropic dye film to form a film, and then photopolymerizing a photocurable film (including a pressure-sensitive adhesive film) onto the anisotropic dye film to form a film. To achieve a high degree of polymerization for both the anisotropic dye film and the photocurable film, it is desirable to irradiate them with light of a wavelength that matches the absorption wavelength of the photopolymerization initiator contained in each film. If the maximum absorption wavelength λ0 of the photopolymerization initiator in the anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator in the photocurable film satisfy the relationship shown in Equation (1), the wavelength of light suitable for irradiating the photocurable film can be longer than the wavelength of light suitable for irradiating the anisotropic dye film. By using longer wavelength light to irradiate the photocurable film, the sensitivity of the photopolymerization initiator contained in the anisotropic dye film falls within a wavelength range with low energy density, thereby suppressing the reaction of the photopolymerization initiator remaining in the anisotropic dye film. Therefore, even after the photocurable film is formed, the molecular orientation of the polymerizable liquid crystal compound and the dye in the anisotropic dye film is maintained in an optimal state, and the anisotropic dye film can maintain high optical performance.

[0036] The method for measuring the maximum absorption wavelength of the photopolymerization initiator in the present invention is not particularly limited, and examples thereof include measurement using a spectrophotometer.

[0037] [Anisotropic dye film] As mentioned above, an anisotropic dye film is a dye film that has anisotropy in electromagnetic properties in any two directions selected from a total of three directions in a three-dimensional coordinate system: the thickness direction of the anisotropic dye film and any two orthogonal in-plane directions. Electromagnetic properties include optical properties such as absorption and refraction, and electrical properties such as resistance and capacitance. Examples of films having optical anisotropy such as absorption or refraction include polarizing films such as linear polarizing films and circular polarizing films, retardation films, and conductive anisotropic dye films. The anisotropic dye films are preferably used as polarizing films or conductive anisotropic dye films, and more preferably as polarizing films. The anisotropic dye film can function as a polarizing film that obtains linearly polarized light, circularly polarized light, elliptically polarized light, etc. by utilizing the anisotropy of light absorption. In addition, depending on the film formation process and the selection of the substrate and composition containing the organic compound (dye or transparent material), it can also function as a variety of anisotropic dye films with refractive anisotropy, conductive anisotropy, etc.

[0038] When the optically anisotropic laminate of the present invention is used as a polarizing element for a liquid crystal display or an antireflection film for an OLED, the orientation characteristics of the anisotropic dye film can be expressed by the dichroic ratio. A dichroic ratio of 8 or more functions as a polarizing element, but a dichroic ratio of 15 or more is preferred, a dichroic ratio of 20 or more is more preferred, a dichroic ratio of 25 or more is even more preferred, a dichroic ratio of 30 or more is particularly preferred, and a dichroic ratio of 40 or more is especially preferred. When the dichroic ratio is equal to or greater than the lower limit, the film is useful as an optical element, particularly a polarizing element, as described below.

[0039] When used as a polarizing element in an anti-reflection film for OLEDs, even if the performance of peripheral materials such as retardation films is low, the properties of the anti-reflection film are improved as long as the polarizing element has high performance. Therefore, if the polarizing element has high performance, it is easy to simplify the layer structure, and even a thin film structure can easily exhibit sufficient functionality, making it suitable for use in applications where it is used while being deformed, including folding and bending. It also makes it possible to keep costs low.

[0040] The dichroic ratio (D) referred to in the present invention is expressed by the following formula when the dyes are uniformly oriented. D=Az / Ay 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 to the orientation direction of the anisotropic dye.

[0041] The absorbances are not particularly limited as long as they are measured at the same wavelength, and any wavelength may be selected depending on the purpose. When expressing the degree of orientation of an anisotropic dye film, it is preferable to use a value corrected for luminosity in a specific wavelength range of 380 nm to 780 nm of the anisotropic dye film, or a value at the maximum absorption wavelength in the visible range.

[0042] The transmittance of the anisotropic dye film of the present invention in the visible light wavelength range is preferably 25% or more, more preferably 35% or more, and particularly preferably 40% or more. The transmittance may be set to the upper limit depending on the application. For example, when a high degree of polarization is required, the transmittance is preferably 50% or less. When the transmittance is in the above range, the film is useful as an optical element, as described below, and is particularly useful as an optical element for a liquid crystal display used for color display or as an antireflection film combining an anisotropic dye film and a retardation film.

[0043] The anisotropic dye film has a dry thickness of preferably 10 nm or more, more preferably 100 nm or more, and even more preferably 500 nm or more. On the other hand, it is preferably 30 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. A thickness of the anisotropic dye film within the above range tends to result in uniform orientation of the dye within the film and a uniform film thickness.

[0044] The anisotropic dye film of the present invention contains a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator, and may contain other components (other additives described below).

[0045] (Photopolymerization initiator) The photopolymerization initiator in the anisotropic dye film of the present invention is a polymerization initiator that generates active radicals by the action of light, and is a compound that can initiate the polymerization reaction of a polymerizable liquid crystal compound.

[0046] The maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic dye film is not particularly limited as long as it satisfies formula (1), but is preferably 260 nm or more, more preferably 280 nm or more, and even more preferably 300 nm or more. Also, it is preferably 440 nm or less, more preferably 420 nm or less, even more preferably 400 nm or less, and even more preferably 380 nm or less. By keeping it within this range, the photopolymerization reaction proceeds sufficiently, resulting in an anisotropic dye film with a good degree of curing.

[0047] Examples of photopolymerization initiators that can be used include titanocene derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-s-triazine derivatives; alkylphenone derivatives; oxime ester derivatives; benzoins; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; thioxanthone derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives; phenylglyoxylate derivatives; ketosulfone derivatives, organic peroxides, and the like.

[0048] Among these photopolymerization initiators, alkylphenone derivatives, oxime ester derivatives, biimidazole derivatives and thioxanthone derivatives are more preferred because they allow the photopolymerization reaction to proceed sufficiently and result in a film with a high degree of cure.

[0049] Specific examples of 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.

[0050] 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.

[0051] Examples of halomethylated oxadiazole derivatives include 2-(2-benzofuranyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-[2-(2-benzofuranyl)ethenyl]-5-trichloromethyl-1,3,4-oxadiazole, 2-trichloromethyl-5-furyl-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-styryl-5-trichloromethyl-1,3,4-oxadiazole, and 2-(4-methoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole.

[0052] Examples of 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)ethenyl]-4,6-bis(trichloromethyl)-s-triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, and 2-[2-(2-furanyl)ethenyl]-4,6-bis(trichloromethyl)-s-triazine.

[0053] Examples of alkylphenone derivatives include 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinophenyl)butan-1-one, 3,6-bis(2-methyl-2-morpholinopropionyl)-9-octylcarbazole, benzyl dimethyl ketal, Examples include 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-methylpropan-1-one, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, and 2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone.

[0054] Examples of 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-methoxypropyl-2-yloxy)phenyl]-methylideneaminoacetate, and those disclosed in JP-A-2000-80068, JP-A-2006-36750, and JP-A-2008-179 611, JP 2011-132215 A, JP 2012-526185 A, WO 2008 / 078678, WO 2009 / 131189, WO 2012 / 045736, WO 2012 / 068879, WO 2013 / 165207, WO 2014 / 121701, WO 2016 / 036910, WO 2017 / 030005, WO 2018 / 097580, and the like.

[0055] Examples of benzoins include benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin isobutyl ether, and benzoin isopropyl ether.

[0056] Examples of 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.

[0057] 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)phenylphosphineate.

[0058] 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.

[0059] Sulfonium salts include triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetrakis(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-bis[diphenylsulfonio]diphenyl sulfide bishexafluorophosphate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[di(β-hydroxyethoxy)phenylsulfonio]diphenyl sulfide bishexafluorophosphate, 7-[di(p-toluyl)sulfonio]-2-isopropylthioxanthone hexafluoroantimonate, 7- Examples include [di(p-toluyl)sulfonio]-2-isopropylthioxanthone tetrakis(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenylsulfonio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenylsulfonio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)sulfonio-diphenyl sulfide tetrakis(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)sulfanylphenyl]sulfonium hexafluorophosphate, and tris[4-(4-acetylphenyl)sulfanylphenyl]sulfonium tetrakis(pentafluorophenyl)borate.

[0060] Examples of the anthraquinone derivatives include 2-methylanthraquinone, 2-ethylanthraquinone, 2-t-butylanthraquinone, and 1-chloroanthraquinone.

[0061] 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.

[0062] 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.

[0063] Examples of phenazine derivatives include 9,10-dimethylbenzphenazine.

[0064] Examples of anthrone derivatives include benzanthrone.

[0065] Phenyl glyoxylate derivatives include methyl benzoyl formate and the like.

[0066] Examples of the ketosulfone derivatives include 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone.

[0067] Examples of 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.

[0068] The photopolymerization initiator may be used alone or in combination of two or more. When using multiple photopolymerization initiators, it is sufficient that the photopolymerization initiators satisfying formula (1) are contained in the film, and the maximum absorption wavelength of the photopolymerization initiators used in combination is not limited to formula (1).

[0069] As the photopolymerization initiator, commercially available products can also be used. Commercially available products include, for example, 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 The Dow Chemical Company); ADEKA Arcles ARKLS® 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 Corporation); TAZ-A and TAZ-PP (manufactured by DKSH Japan Co., Ltd.); and TAZ-104 (manufactured by Sanwa Chemical Co., Ltd.); TRONLYTR-PBG-304, TRONLYTR-PBG-309, TRONLYTR-PBG-305, TRONLYTR-PBG-3057, TRONLYTR-PBG-314, TRONLYTR-PBG-326, and TRONLYTR-PBG-345 (manufactured by Changzhou TRONLY NEW ELECTRONIC MATERIALS CO., LTD.). CO.LTD); Pardual (registered trademark) TA-30G, TA-70H, TX (manufactured by NOF Corporation).

[0070] The content of the photopolymerization initiator in the anisotropic dye film of the present invention 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 polymerizable liquid crystal compound, from the viewpoint of obtaining a sufficiently polymerized anisotropic dye film. Furthermore, from the viewpoint of preventing the alignment of the polymerizable liquid crystal compound from being disturbed, the content is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more 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.

[0071] If necessary, a polymerization accelerator, a polymerization aid, etc. may be used in combination with the photopolymerization initiator. Examples of the polymerization accelerator and polymerization aid that can be used include amine compounds such as triethanolamine, N-methyldiethanolamine, ethyl-4-dimethylaminobenzoate, 2-(dimethylamino)ethylbenzoate, 2-ethylhexyl-4-dimethylaminobenzoate, octyl-4-dimethylaminobenzoate, and N-(2-hydroxyethyl)-N-methyl-p-toluidine; 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2- Examples of mercapto compounds include mercapto compounds having a heterocycle such as 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 trimellilolpropane tris(3-mercaptobutyrate).

[0072] The polymerization accelerator and polymerization aid may be used alone or in combination of two or more kinds.

[0073] If necessary, a sensitizing dye or other sensitizer may be used in combination for the purpose of increasing sensitivity. Sensitizing dyes that are appropriate for the wavelength of the exposure light source are used, including xanthene dyes described in JP-A-4-221958 and JP-A-4-219756, coumarin dyes having a heterocycle described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin dyes described in JP-A-3-239703 and JP-A-5-289335, 3-ketocoumarin dyes described in JP-A-6-19240, and pyrromethene dyes described in JP-A-6-19240, and JP-A-7-2528 and JP-A-7-155292. and dyes having a dialkylaminobenzene skeleton described in JP-B No. 45-37377, JP-A No. 48-84183, JP-A No. 52-112681, JP-A No. 58-15503, JP-A No. 60-88005, JP-A No. 59-56403, JP-A No. 2-69, JP-A No. 57-168088, JP-A No. 5-107761, JP-A No. 5-210240, and JP-A No. 4-288818.

[0074] Other sensitizers include the above-mentioned benzophenone derivatives and thioxanthone derivatives, as well as anthracene derivatives, phenothiazine derivatives, and perylene derivatives.

[0075] Examples of the anthracene derivatives include anthracene, 9,10-diethoxyanthracene, and 9,10-dibutoxyanthracene.

[0076] Examples of phenothiazine derivatives include phenothiazine, 10-methylphenothiazine, 10-phenylphenothiazine, 2-methoxyphenothiazine, 2-chlorophenothiazine, and 2-acetylphenothiazine.

[0077] Examples of perylene derivatives include perylene and 2,5,8,11-tetra-tert-butylperylene.

[0078] The sensitizing dyes and other sensitizers may be used alone or in combination of two or more.

[0079] (dye) In the present invention, a dye is a substance or compound that absorbs at least part of the wavelengths in the visible light region (380 nm to 780 nm). Dyes that can be used in the present invention include dichroic dyes. A dichroic dye is a dye that has different absorbance in the long axis direction of the molecule and absorbance in the short axis direction. The dye may or may not have liquid crystallinity. Having liquid crystallinity means that a liquid crystal phase is exhibited at any temperature.

[0080] Examples of dyes that can be contained in the anisotropic dye film of the present invention include azo dyes, quinone dyes (including naphthoquinone dyes, anthraquinone dyes, etc.), stilbene dyes, cyanine dyes, phthalocyanine dyes, indigo dyes, condensed polycyclic dyes (including perylene dyes, oxazine dyes, acridine dyes, etc.), etc. Among these dyes, azo dyes are preferred because they have a large molecular long-to-short axis ratio and can achieve high molecular alignment in the anisotropic dye film.

[0081] The azo dye refers to a dye having at least one azo group (-N=N-), and the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, and is preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less, from the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production.

[0082] Examples of azo dyes include compounds represented by formula (A). R 11 -D 1 -N=N-(D 2 -N=N)pD 3 -R 12 …(A) In formula (A), D 1 , D 2 and D 3 each independently represents an optionally substituted phenylene group, an optionally substituted naphthylene group, or an optionally substituted divalent heterocyclic group; p represents an integer of 0 to 4; If p is an integer greater than or equal to 2, multiple D 2 may be the same or different from each other; R 11 and R 12 each independently represents a monovalent organic group.

[0083] 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. The substitution position of the phenylene group is preferably a 1,4-phenylene group because the molecule has high linearity. The substitution position of the naphthylene group is preferably a 1,4-naphthylene group or a 2,6-naphthylene group because the molecule has high linearity.

[0084] The divalent heterocyclic group is a heterocyclic group having a ring containing preferably 3 to 14 carbon atoms, more preferably 10 or less. Monocyclic or bicyclic heterocyclic groups are particularly preferred.

[0085] The atom other than carbon constituting the divalent heterocyclic group is at least one selected from a nitrogen atom, a sulfur atom, and an oxygen atom. When the heterocyclic group has multiple atoms other than carbon constituting the ring, these atoms may be the same or different.

[0086] 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 thienothiophenediyl group, a benzimidazolidinonediyl group, a benzofurandiyl group, a phthalimidodiyl group, an oxazolediyl group, and a benzoxazolediyl group.

[0087] D 1 , D 2 and D 3In the above, optional substituents on the phenylene group, naphthylene group, and divalent heterocyclic group include alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, and butoxy; fluorinated alkyl groups having 1 to 4 carbon atoms, such as trifluoromethyl; cyano; nitro; hydroxyl; halogen atoms; and substituted or unsubstituted amino groups, such as amino, diethylamino, and pyrrolidino. Here, the term "substituted amino group" refers to an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or an amino group in which two substituted alkyl groups are bonded to form an alkanediyl group having 2 to 8 carbon atoms. An unsubstituted amino group is -NH2. Examples of alkyl groups having 1 to 4 carbon atoms in the substituted amino group include methyl, ethyl, and butyl. Examples of the alkanediyl group having 2 to 8 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group.

[0088] Due to its high molecular linearity, D 1 , D 2 and D 3 The phenylene group, naphthylene group, and divalent heterocyclic group in the formula (I) are unsubstituted, or if substituted, 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.

[0089] p represents an integer of 0 to 4. From the viewpoints of solubility in a solvent, compatibility with a liquid crystal compound, color tone, and ease of production, p is preferably 1 or more and 4 or less, and more preferably 3 or less.

[0090] R 11 and R 12 each independently represents a monovalent organic group. R 11 and R 12Examples of the monovalent organic group in the formula (I) include a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a branch; an alicyclic alkyl group having 1 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms which may have a branch, such as a methoxy group, an ethoxy group, and a butoxy group; a fluorinated alkyl group having 1 to 20 carbon atoms which may have a branch, such as a trifluoromethyl group; a cyano group; a nitro group; a hydroxyl group; a halogen atom; a substituted or unsubstituted amino group, such as an amino group, a diethylamino group, and a pyrrolidino group; a carboxy group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branch, such as a butoxycarbonyl group; an alkyloxycarbonyl group having 1 to 20 carbon atoms which may have a branch, such as an ethenyl group. an alkenyl group having 1 to 20 carbon atoms, such as a 2-(4-butylphenyl)ethenyl group; an alkylphenylalkenyl group such as a 2-(4-butylphenyl)ethenyl group; a carbamoyl group; an alkylcarbamoyl group having 1 to 20 carbon atoms, which may be branched, such as a butylcarbamoyl group; a sulfamoyl group; an alkylsulfamoyl group having 1 to 20 carbon atoms, which may be branched, such as a butylsulfamoyl group; an acylamino group having 1 to 20 carbon atoms, which may be branched, such as a butylcarbonylamino group; an acyloxy group having 1 to 20 carbon atoms, which may be branched, such as a butylcarbonyloxy group; a sulfanyl group; an alkylsulfanyl group having 1 to 20 carbon atoms, such as a butylsulfanyl group; 1 and R 2 Examples of the substituted amino group include a chain organic group having a polymerizable group such as the above. The substituted amino group refers to an amino group having one or two 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 form an alkanediyl group having 2 to 20 carbon atoms. An unsubstituted amino group is -NH2. Examples of the alkyl group having 1 to 20 carbon atoms of the substituted amino group include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 20 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group.

[0091] R 11 and R12 Examples of the alkyl group include a hydrogen atom, a chain group, an aliphatic organic group ("aliphatic organic group" includes chain and cyclic groups), and an aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen and / or oxygen ("aliphatic organic group in which some of the carbon atoms have been replaced with nitrogen and / or oxygen" includes chain and cyclic groups, and includes aliphatic organic groups in which some of the methyl groups have been replaced with hydroxyl groups, oxo groups (=O), amino groups, imino groups, etc.). In one embodiment, R 11 and R 12 As the alkyl group, a hydrogen atom or a chain group is preferable, and in another embodiment, a hydrogen atom or an aliphatic organic group is preferable, and in yet another embodiment, a hydrogen atom or an aliphatic organic group in which a portion of the carbon atoms has been replaced with a nitrogen atom and / or an oxygen atom is preferable.

[0092] Examples of the chain group include the above-mentioned alkyl group having 1 to 20 carbon atoms, which may be branched; alkoxy group having 1 to 20 carbon atoms, which may be branched; fluorinated alkyl group having 1 to 20 carbon atoms, which may be branched; substituted or unsubstituted amino group (a substituted amino group means an amino group having one or two alkyl groups having 1 to 20 carbon atoms, which may be branched. An unsubstituted amino group is -NH2); carboxy 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; sulfamoyl group; alkylsulfamoyl 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; sulfanyl group; alkylsulfanyl group having 1 to 20 carbon atoms, etc.

[0093] Examples of the aliphatic organic group include the above-mentioned alkyl groups having 1 to 20 carbon atoms, which may be branched, and alicyclic alkyl groups having 1 to 20 carbon atoms.

[0094] Examples of aliphatic organic groups in which some of the carbon atoms have been replaced with nitrogen and / or oxygen atoms include the above-mentioned alkoxy groups having 1 to 20 carbon atoms, which may be branched; substituted or unsubstituted amino groups; carboxy groups; alkyloxycarbonyl groups having 1 to 20 carbon atoms, which may be branched; carbamoyl groups; alkylcarbamoyl groups having 1 to 20 carbon atoms, which may be branched; acylamino groups having 1 to 20 carbon atoms, which may be branched; and acyloxy groups having 1 to 20 carbon atoms, which may be branched. The above-mentioned substituted amino group refers to an amino group having one or two 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 form an alkanediyl group having 2 to 20 carbon atoms. An unsubstituted amino group is -NH2. Examples of the alkyl group having 1 to 20 carbon atoms in the substituted amino group include a methyl group, an ethyl group, and a butyl group. Examples of the alkanediyl group having 2 to 20 carbon atoms include an ethylene group, a propane-1,3-diyl group, a butane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, a hexane-1,6-diyl group, a heptane-1,7-diyl group, and an octane-1,8-diyl group.

[0095] Due to its high molecular linearity, R 11 and R 12 are each independently substituted with a hydrogen atom, an alkyl group having 1 to 10 carbon atoms such as a butyl group, a pentyl group, a hexyl group, a heptyl group, or an octyl group; an alkoxy group having 1 to 10 carbon atoms such as a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, or an octyloxy group; a diethylamino group, a pyrrolidino group, or a piperidinyl group. 1 and R 2 The preferred chain organic groups having a polymerizable group are also preferred.

[0096] The dye contained in the anisotropic dye film of the present invention is not particularly limited, and known dyes can be used. Examples of known dyes include the dyes (dichroic dyes, dichroic dyes) described in the aforementioned Patent Document 1, Japanese Patent No. 5982762, JP 2017-025317 A, and JP 2014-095899 A.

[0097] Specific examples include, but are not limited to, the dyes listed below.

[0098] [ka]

[0099] [ka]

[0100] [ka]

[0101] [ka]

[0102] The molecular weight of the dye contained in the anisotropic dye film of the present invention is preferably 300 or more, more preferably 350 or more, and even more preferably 380 or more, and is preferably 1500 or less, more preferably 1200 or less, and even more preferably 1000 or less. Specifically, the molecular weight of the dye contained in the anisotropic dye film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000.

[0103] The content of the dye (dichroic dye) in the anisotropic dye film is, for example, preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, and preferably 50 parts by mass or less, more preferably 30 parts by mass or less, and even more preferably 10 parts by mass or less, relative to 100 parts by mass of the anisotropic dye film. Specifically, the content of the dye (dichroic dye) in the anisotropic dye film is, for example, 0.01 to 50 parts by mass, preferably 0.05 to 30 parts by mass, and more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the anisotropic dye film. When the content of the dye (dichroic dye) is within the above range, the polymerizable liquid crystal compound tends to be polymerized while maintaining high alignment in the anisotropic dye film of the present invention. When the content of the dye (dichroic dye) is equal to or greater than the above lower limit, sufficient light absorption and sufficient polarization performance tend to be obtained. When the content of the dye (dichroic dye) is equal to or less than the upper limit, the alignment of the liquid crystal molecules tends to be more easily inhibited from being hindered.

[0104] The anisotropic dye film of the present invention may contain only one type of dye, or may contain two or more types of dyes.

[0105] (Polymerizable liquid crystal compound) In the present invention, the liquid crystal compound refers to a substance that exhibits a liquid crystal state, and specifically refers to a compound that does not directly transition from crystal to liquid, but becomes liquid via an intermediate state that exhibits properties of both crystal and liquid, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0106] The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is a liquid crystal compound having a polymerizable group, which will be described later.

[0107] In the polymerizable liquid crystal compound, the polymerizable group can be positioned at any position within the liquid crystal compound molecule, but it is preferable that the polymerizable group is substituted at the end of the liquid crystal compound molecule from the viewpoint of ease of polymerization. In a polymerizable liquid crystal compound, one or more polymerizable groups can be present in the liquid crystal compound molecule. When two or more polymerizable groups are present, it is preferable that they are present at both ends of the liquid crystal compound molecule from the viewpoint of ease of polymerization.

[0108] The polymerizable liquid crystal compound is preferably a compound having a carbon-carbon triple bond in the liquid crystal compound molecule. When the compound has a carbon-carbon triple bond, the carbon-carbon triple bond can rotate and serve as the core of the liquid crystal molecule, resulting in high molecular mobility and strong intermolecular interactions between the liquid crystal molecules and with compounds having a π-conjugated system such as dye molecules, which tends to result in high molecular orientation.

[0109] The polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention is not particularly limited, and any liquid crystal compound having a polymerizable group can be used.

[0110] For example, the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention may be a compound represented by the following formula (2) (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (2)").

[0111] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2) (In formula (2), -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 (3), a divalent organic group, or a single bond: -A 12 - represents a partial structure represented by the following formula (3) or a divalent organic group; -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)-, -CHCH-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-; -A 11 -and-A 13 - is a partial structure represented by the following formula (3) or a divalent organic group: k is 1 or 2. If k is 2, two -Y 2 -A 13 - may be the same or different.)

[0112] -Cy-X 2 -C≡CX 1 - ...(3) (In formula (3), -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)-, -C2O-, -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)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-.

[0113] In addition, -A 11 When - is a partial structure represented by formula (3), formula (2) may be the following formula (2A) or the following formula (2B). Q1 -R 1 -Cy-X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2A) Q 1 -R 1 -X 1 -C≡CX 2 -Cy-Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2B)

[0114] Also, -A 12 When - is a partial structure represented by formula (3), formula (2) may be the following formula (2C) or the following formula (2D). Q 1 -R 1 -A 11 -Y 1 -Cy-X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2C) Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -Cy-(Y 2 -A 13 ) k -R 2 -Q 2 …(2D)

[0115] Also, -A 13When - is a partial structure represented by formula (3), formula (2) may be the following formula (2E) or the following formula (2F). Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -Cy-X 2 -C≡CX 1 ) k -R 2 -Q 2 …(2E) Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -Cy) k -R 2 -Q 2 …(2F)

[0116] Similarly, -A 11 -, -A 12 -and-A 13 - When two or more of the partial structures are the partial structure represented by formula (3), the orientation of each partial structure represented by formula (3) may be inverted.

[0117] As mentioned above, -A 11 -, -A 12 -and-A 13 - is independently a partial structure represented by formula (3) or a divalent organic group, and -A 11 -and-A 13 - may be a single bond, but -A 11 -and-A 13 -, but neither of them is a single bond.

[0118] (-Cy-) The hydrocarbon ring group in -Cy- includes aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups. The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

[0119] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0120] The linked aromatic hydrocarbon ring group is a divalent group in which multiple monocyclic or fused aromatic hydrocarbon rings are bonded by single bonds and have a bond on an atom constituting the ring. The monocyclic or fused ring preferably has 6 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The monocyclic or fused ring more preferably has 6 to 15 carbon atoms. Examples of the linked aromatic hydrocarbon ring group include a divalent group in which a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, and the divalent group has a first bond on an atom constituting the first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

[0121] As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction acting between liquid crystal compounds, thereby improving molecular alignment. 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 group). As the phenylene group, a 1,4-phenylene group is preferred. When -Cy- is one of these groups, the linearity of the liquid crystal molecules is enhanced, and the effect of improving molecular alignment tends to be obtained.

[0122] The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0123] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic hydrocarbon ring group more preferably has 3 to 15 carbon atoms. 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 tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0124] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group that has 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.

[0125] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused non-aromatic hydrocarbon rings are bonded together with single bonds and which has a bond on an atom constituting the ring; or a divalent group in which one or more rings selected from the group consisting of monocyclic aromatic hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and fused non-aromatic hydrocarbon rings are bonded together with a monocyclic or fused non-aromatic hydrocarbon ring with a single bond and which has a bond on an atom constituting the ring. The number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 because an appropriate core size provides good molecular orientation.

[0126] Examples of linked non-aromatic hydrocarbon ring groups include divalent groups in which a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further examples include divalent groups in which a monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0127] 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.

[0128] The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group, because it optimizes the intermolecular interactions acting between liquid crystal compounds, thereby improving molecular alignment.

[0129] The non-linked non-aromatic hydrocarbon ring group is preferably a divalent group of cyclohexane (cyclohexanediyl group), and the cyclohexanediyl group is preferably a cyclohexane-1,4-diyl group. When -Cy- is one of these groups, the linearity of the liquid crystal molecules is enhanced, and the effect of improving molecular alignment tends to be obtained.

[0130] The heterocyclic group in -Cy- includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0131] The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

[0132] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0133] Examples of the aromatic heterocycle 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 furopyrrole ring, a furofuran 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.

[0134] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0135] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0136] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0137] The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0138] Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or fused non-aromatic heterocycle 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 quinuclidine ring.

[0139] 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 single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0140] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0141] The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- are each represented by -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 , a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen atom. k and -R k Each of the 's independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0142] The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- are each preferably independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted, in terms of having a highly linear molecular structure, facilitating association of the polymerizable liquid crystal compounds (2) with each other, and facilitating the development of a liquid crystal state.

[0143] 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, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group may all be substituted, all be unsubstituted, or some may be substituted and some unsubstituted.

[0144] As -Cy-, a hydrocarbon ring group is preferred, a phenylene group or a cyclohexanediyl group is more preferred, as it improves the molecular alignment of the polymerizable liquid crystal compound (2). As -Cy-, a 1,4-phenylene group or a cyclohexane-1,4-diyl group is even more preferred, and a 1,4-phenylene group is particularly preferred, as it can improve the linearity of the molecular structure of the polymerizable liquid crystal compound (2).

[0145] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-. Among these, -X 1 Preferred examples of - include -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -C2O-, -OCH2-, -CH2S-, and -SCH2-, which have a small π-bonding property. Among these, -C(=O)O-, -OC(=O)-, -CH2CH2-, -C2O-, and -OCH2- are more preferred, and -X 1 - is -C(=O)O- or -OC(=O)-. In another embodiment, -X 1 - is preferably -CH2CH2-, -CH2O- or -OCH2-.

[0146] -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)-, -C2O-, -OCH2-, -CH2S-, or -SCH2-.

[0147] From the viewpoint of increasing the core size of the polymerizable liquid crystal compound (2) and enhancing the dichroism of the anisotropic dye film, it is preferable to link -Cy- and -C≡C- with a highly linear group, specifically, -X 2 The - is 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-bonding property, and more preferably a single bond due to higher linearity.

[0148] -Q 1 and -Q 2 The polymerizable group in (1) 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 necessary to ensure the polymerization function. From the viewpoint of producing an anisotropic dye film, the polymerizable group is preferably a photopolymerizable group.

[0149] Specific examples of the polymerizable group include an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a vinyl group, a vinyloxy group, an ethynyl group, an ethynyloxy group, a 1,3-butadienyl group, a 1,3-butadienyloxy group, an oxiranyl group, an oxetanyl group, a glycidyl group, a glycidyloxy group, a styryl group, and a styryloxy group. Among these, an acryloyl group, a methacryloyl group, an acryloyloxy group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, an oxiranyl group, a glycidyl group, and a glycidyloxy group are preferred, an acryloyl group, a methacryloyloxy group, an acryloylamino group, a methacryloylamino group, a glycidyl group, and a glycidyloxy group are more preferred, and an acryloyloxy group, a methacryloyloxy group, and a glycidyloxy group are even more preferred.

[0150] -R 1 - and -R 2The chain organic group in - is a divalent organic group that does not contain a cyclic structure such as the above-mentioned aromatic hydrocarbon ring, non-aromatic hydrocarbon ring, aromatic heterocycle, or non-aromatic heterocycle. Examples of such a chain organic group include -(alkylene group)-, -O-(alkylene group)-, -S-(alkylene group)-, -NH-(alkylene group)-, -N(alkyl group)-(alkylene group)-, -OC(=O)-(alkylene group)-, and -C(=O)O-(alkylene group)-.

[0151] The alkylene group in these chain organic groups may be a straight-chain or branched alkylene group having 1 to 25 carbon atoms. The carbon-carbon bond of the alkylene group may be partially unsaturated. One or more methylene groups contained in the alkylene group may be -O-, -S-, -NH-, -N(R m )-, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, or -CCl2-. m represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0152] The alkylene group in these chain organic groups is preferably a linear alkylene group having 1 to 25 carbon atoms, in which some of the carbon atoms of the alkylene group may be unsaturated, or in which one or more methylene groups contained in the alkylene group may be replaced by the above-mentioned group, due to high molecular linearity.

[0153] The number of atoms in the main chain (meaning 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.

[0154] The chain organic group is -(CH2) r -CH2-, -O-(CH2) r -CH2-, -(O) r1 -(CH2CH2O) r2 -(CH2)r3 -, -(O) r1 -(CH2) r2 -(CH2CH2O) r3 - is preferred. In these formulas, r represents an integer of 1 to 24, preferably an integer of 2 to 24, more preferably an integer of 4 to 19, and even more preferably an integer of 5 to 19. In these formulas, r1, r2, and r3 each independently represent an integer, and are appropriately adjusted so that the number of atoms in the main chain of the chain organic group (meaning the longest chain portion in the chain organic group) is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

[0155] -R 1 - and -R 2 Preferably, each - is independently -(alkylene group)- or -O-(alkylene group)-. 1 - and -R 2 The chain organic group in - is -(alkylene group)-, and in another embodiment, is -O-(alkylene group)-.

[0156] As in the formula (2B) and formula (2E), -X 1 -and-R 1 -or-X 1 -and-R 2 - is bonded; in the formula (2B), -A 13 - is a single bond, or in the formula (2E), -A 11 - is a single bond, and -R 1 -or-R 2 -ga-Y 1 -or- Y 2 -X 1 -, -Y 1 -or- Y 2 - and directly bonded to -R 1 -or-R 2 - is preferably -(alkylene group)-.

[0157] Other than the above, -X 1 -, -Y 1 -or- Y 2-R not directly bonded to - 1 -or-R 2 - is preferably -O-(alkylene group)-.

[0158] -A 11 -, -A 12 -and-A 13 The divalent organic group in - is preferably a group represented by the following formula (4).

[0159] -Q 3 - …(4) (In formula (4), Q 3 represents a hydrocarbon ring group or a heterocyclic group.

[0160] -Q 3 The hydrocarbon ring group in - includes aromatic hydrocarbon ring groups and non-aromatic hydrocarbon ring groups.

[0161] The aromatic hydrocarbon ring group includes an unlinked aromatic hydrocarbon ring group and a linked aromatic hydrocarbon ring group.

[0162] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed aromatic hydrocarbon ring, and preferably has 6 to 20 carbon atoms because the appropriate core size provides good molecular orientation. The non-linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of aromatic hydrocarbon rings include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a perylene ring, a tetracene ring, a pyrene ring, a benzpyrene ring, a chrysene ring, a triphenylene ring, an acenaphthene ring, a fluoranthene ring, and a fluorene ring.

[0163] The linked aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused aromatic hydrocarbon rings are bonded by single bonds and which has a bond on an atom constituting the ring. The monocyclic or fused ring preferably has 6 to 20 carbon atoms because the appropriate core size provides good alignment. The linked aromatic hydrocarbon ring group more preferably has 6 to 15 carbon atoms. Examples of the linked aromatic hydrocarbon ring group include a divalent group in which a first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms is bonded to a second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms by a single bond, which has a first bond on an atom constituting the first monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic hydrocarbon ring having 6 to 20 carbon atoms. Specific examples of the linked aromatic hydrocarbon ring group include a biphenyl-4,4'-diyl group.

[0164] As the aromatic hydrocarbon ring group, a non-linked aromatic hydrocarbon ring group is preferred because it optimizes the intermolecular interaction acting between liquid crystal compounds, thereby improving molecular alignment. Of 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 group). As the phenylene group, a 1,4-phenylene group is preferred. -Q 3 When - is one of these groups, the linearity of the liquid crystal molecules increases, and the effect of improving molecular alignment tends to be obtained.

[0165] The non-aromatic hydrocarbon ring group includes an unlinked non-aromatic hydrocarbon ring group and a linked non-aromatic hydrocarbon ring group.

[0166] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or condensed non-aromatic hydrocarbon ring, and preferably has 3 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic hydrocarbon ring group more preferably has 3 to 15 carbon atoms. 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 tetrahydronaphthalene ring, and a bicyclo[2.2.2]octane ring.

[0167] The non-linked non-aromatic hydrocarbon ring group includes an alicyclic hydrocarbon ring group that does not have an unsaturated bond as an interatomic bond constituting the non-aromatic hydrocarbon ring, and an unsaturated non-aromatic hydrocarbon ring group that has 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.

[0168] The linked non-aromatic hydrocarbon ring group is a divalent group in which a plurality of monocyclic or fused non-aromatic hydrocarbon rings are bonded together with single bonds and which has a bond on an atom constituting the ring; or a divalent group in which one or more rings selected from the group consisting of monocyclic aromatic hydrocarbon rings, fused aromatic hydrocarbon rings, monocyclic non-aromatic hydrocarbon rings, and fused non-aromatic hydrocarbon rings are bonded together with a monocyclic or fused non-aromatic hydrocarbon ring with a single bond and which has a bond on an atom constituting the ring. The number of carbon atoms in the single ring or condensed ring is preferably 3 to 20 because an appropriate core size provides good molecular orientation. Examples of linked non-aromatic hydrocarbon ring groups include divalent groups in which a first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the first monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Further examples include divalent groups in which a monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms are bonded by a single bond, the divalent groups having a first bond on an atom constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms and a second bond on an atom constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0169] 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.

[0170] The non-aromatic hydrocarbon ring group is preferably a non-linked non-aromatic hydrocarbon ring group, because it optimizes the intermolecular interactions acting between liquid crystal compounds, thereby improving molecular alignment.

[0171] As the unlinked non-aromatic hydrocarbon ring group, a divalent group of cyclohexane (cyclohexanediyl group) is preferred, and as the cyclohexanediyl group, a cyclohexane-1,4-diyl group is preferred.

[0172] -Q 3 The heterocyclic group in - includes an aromatic heterocyclic group and a non-aromatic heterocyclic group.

[0173] The aromatic heterocyclic group includes an unlinked aromatic heterocyclic group and a linked aromatic heterocyclic group.

[0174] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or condensed aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0175] Examples of the aromatic heterocycle 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 furopyrrole ring, a furofuran 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.

[0176] The linked aromatic heterocyclic group is a divalent group in which a plurality of monocyclic or condensed aromatic heterocyclic rings are bonded by single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked aromatic heterocyclic group is more preferably 4 to 15.

[0177] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0178] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0179] The non-linked non-aromatic heterocyclic group is a divalent group of a monocyclic or condensed non-aromatic heterocyclic ring, and preferably has 4 to 20 carbon atoms because an appropriate core size provides good molecular orientation. The non-linked non-aromatic heterocyclic group more preferably has 4 to 15 carbon atoms.

[0180] Examples of the non-aromatic heterocycle of a divalent group of a monocyclic or fused non-aromatic heterocycle 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 quinuclidine ring.

[0181] 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 single bonds and have bonds on atoms constituting the rings. The number of carbon atoms in the monocyclic or condensed rings is preferably 4 to 20 because the appropriate core size allows for good molecular orientation. The number of carbon atoms in the linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0182] Examples of the linked aromatic heterocyclic group include a divalent group in which a first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms are bonded by a single bond, and which has a first bond on an atom constituting the first monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms and a second bond on an atom constituting the second monocyclic or fused non-aromatic heterocyclic ring having 4 to 20 carbon atoms.

[0183] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are respectively represented by -R n , -OH, -OR n , -OC(=O)-R n , -NH2, -NH-Rn , -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 , a trifluoromethyl group, a sulfamoyl group, a carboxy group, a sulfo group, a cyano group, a nitro group, and a halogen atom. n and -R n’ each independently represents a linear or branched alkyl group having 1 to 6 carbon atoms.

[0184] -Q 3 The aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each preferably independently unsubstituted or substituted with a methyl group, a methoxy group, a fluorine atom, a chlorine atom, or a bromine atom, and more preferably unsubstituted, in terms of having a highly linear molecular structure, facilitating association of the polymerizable liquid crystal compounds (2) with each other, and facilitating the development of a liquid crystal state.

[0185] -Q 3 The 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, and the aromatic hydrocarbon ring group, non-aromatic hydrocarbon ring group, aromatic heterocyclic group and non-aromatic heterocyclic group may be entirely substituted, entirely unsubstituted, or partly substituted and partly unsubstituted.

[0186] -A 11 -, -A 12 -and-A 13 The substituents of the divalent organic group in -A may be the same or different, 11 -, -A 12 -and-A 13All of the divalent organic groups in - may be substituted, all may be unsubstituted, or some may be substituted and some may be unsubstituted.

[0187] -Q 3 As -, a hydrocarbon ring group is preferable, and a phenylene group or a cyclohexanediyl group is more preferable. Since the linearity of the molecular structure of the polymerizable liquid crystal compound (2) can be increased, -Q 3 As -, a 1,4-phenylene group and a cyclohexane-1,4-diyl group are more preferred.

[0188] -A 11 -, -A 12 -and-A 13 As the divalent organic group of -, -Q 3 Preferably, - is a hydrocarbon ring group, i.e., the divalent organic group is a hydrocarbon ring group. As the divalent organic group, a phenylene group or a cyclohexanediyl group is more preferred, and a 1,4-phenylene group or a cyclohexane-1,4-diyl group is even more preferred because they can increase the linearity of the molecular structure of the polymerizable liquid crystal compound (2).

[0189] The polymerizable liquid crystal compound (2) includes -A 11 -, -A 12 -and-A 13 -, one of which is a partial structure represented by formula (3), and the other two are each independently a divalent organic group; 11 -, -A 12 -and-A 13 Of these, -Cy- in the partial structure represented by formula (3) is preferably a hydrocarbon ring group, and it is particularly preferred that the divalent organic group is a hydrocarbon ring group. Furthermore, it is preferred that the hydrocarbon ring group is a 1,4-phenylene group or a cyclohexane-1,4-diyl group. 11 -and-A 13 Preferably, one of the groups is a cyclohexane-1,4-diyl group.

[0190] -A 11 -and-A 13-, one of which is a partial structure represented by formula (3), and the other one and -A 12 It is more preferable that - is a divalent organic group. 11 -and-A 13 Among -, one of the divalent organic groups is preferably a cyclohexane-1,4-diyl group, and -A12- is particularly preferably a 1,4-phenylene group.

[0191] -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)-, -CHCH-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS-, or -SCH-. Since the polymerizable liquid crystal compound (2) tends to be linear and to easily undergo rotational motion around the molecular minor axis, -Y 1 - and -Y 2 Each of the -'s independently represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CHCH-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHO-, -OCH-, -CHS- or -SCH-, which have little π-bonding property, and a single bond, -C(=O)O-, -OC(=O)-, -CHCH-, -CHO- or -OCH- is more preferred.

[0192] As in the formula (2A), formula (2C), formula (2D), and formula (2F), -X 1 - and -Y 1 -or-X 1 - and -Y 2 If - is bonded, -X 1 - Combines with -Y 1 - or -X 1 - Combines with -Y 2 - is preferably a single bond. 1 - and -Y 1 - and -Y 2The other of - is preferably -C(=O)O- or -OC(=O)-.

[0193] As in the formula (2B) and formula (2E), -X 1 -ga-Y 1 - and -Y 2 If it is not bound to any of -, -X 1 - is preferably -CH2CH2-, -CH2O- or -OCH2-; -Y 1 - and -Y 2 Each - is preferably -C(=O)O- or -OC(=O)-.

[0194] k is 1 or 2. In one embodiment, k is preferably 1. In another embodiment, k is preferably 2. When k is 2, each -Y 2 - may be the same or different, and each -A 13 - may be the same or different.

[0195] As the polymerizable liquid crystal compound (2), a compound represented by the formula (2A), (2B), (2E) or (2F) is preferred because it optimizes the intermolecular interactions acting between the liquid crystal compounds and provides an appropriate core size, resulting in good molecular orientation.

[0196] (Specific Examples of Polymerizable Liquid Crystal Compounds) Specific examples of the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention include, but are not limited to, the polymerizable liquid crystal compounds shown below. 13 means an n-hexyl group. 11 means an n-pentyl group.

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[0199]

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[0211] The liquid crystal compound contained in the anisotropic dye film of the present invention is preferably a polymerizable liquid crystal compound (2). The anisotropic dye film of the present invention may contain only one type of polymerizable liquid crystal compound alone, or may contain two or more types in any combination and ratio.

[0212] The content of the liquid crystal compound in the anisotropic dye film of the present invention (when two or more liquid crystal compounds are used in combination, the total content of each compound) 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 anisotropic dye film (100 parts by mass). If the content of the liquid crystal compound in the anisotropic dye film is within the above range, the alignment of the liquid crystal molecules tends to be high.

[0213] The anisotropic dye film of the present invention may contain one or more polymerizable or non-polymerizable liquid crystal compounds other than the polymerizable liquid crystal compound (2). However, from the viewpoint of more effectively obtaining the effects of the present invention by using the polymerizable liquid crystal compound (2), the proportion of the polymerizable liquid crystal compound (2) in 100% by mass of the total amount of liquid crystal compounds contained in the anisotropic dye film 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.

[0214] From the viewpoint of processing, the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention preferably has an isotropic phase appearance temperature of 160°C or less, more preferably 140°C or less, even more preferably 115°C or less, even more preferably 110°C or less, and particularly preferably 105°C or less. Here, the isotropic phase appearance temperature refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid crystal to liquid crystal. In the present invention, it is preferable that at least one of these phase transition temperatures is equal to or lower than the above upper limit, and it is more preferable that both of these phase transition temperatures are equal to or lower than the above upper limit.

[0215] (Method for producing polymerizable liquid crystal compound) The polymerizable liquid crystal compound contained in the anisotropic dye film 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. For example, the polymerizable liquid crystal compound contained in the anisotropic dye film of the present invention can be synthesized according to the method described in the examples below or the method described on pages 449 to 468 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0216] (Relationship between polymerizable liquid crystal compounds and dyes) The number of ring structures (r n1 ) and the number of ring structures that the dye has (r n2 ) and the ratio (r n1 / r n2 ) is not particularly limited, but is preferably 0.7 to 1.5. This is because, from the viewpoint of easily improving the alignment of the anisotropic dye film, it is preferable that the difference between the molecular length of the polymerizable liquid crystal compound and the molecular length of the dye is small, since this results in a strong intermolecular interaction between the liquid crystal molecules and the dye molecules and makes it difficult for the dye molecules to inhibit association of the liquid crystal molecules with each other. In addition, a fused ring in which two or more rings are fused is counted as one ring structure.

[0217] Here, taking the compound represented by the above formula (A) as an example, n2 The number of ring structures is the number of D in formula (A). 1 , D 2 and D 3 Specifically, if p is 0, then r n2 If p is 2; if p is 1, then r n2If p is 3; if p is 4, then r n2 is 6. In addition, -R 11 and -R 12 Even if -R is a cyclic functional group such as a pyrrolidinyl group or a piperidinyl group, 11 and -R 12 The number of ring structures contained in the compound represented by formula (A) (r n2 ) is not included.

[0218] The number of ring structures (r n1 ) does not include ring structures (such as oxirane rings and oxetane rings) contained in the polymerizable group in the polymerizable liquid crystal compound.

[0219] (Other additives) The anisotropic dye film of the present invention may further contain, as necessary, a non-polymerizable liquid crystal compound, a thermal polymerization initiator, a polymerization inhibitor, a polymerization aid, a polymerizable non-liquid crystal compound, a non-polymerizable non-liquid crystal compound, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an organic or inorganic filler, an organic or inorganic nanosheet, an organic or inorganic nanofiber, a metal oxide, or the like.

[0220] (Composition for anisotropic dye film) The anisotropic dye film of the present invention can be formed using a composition for an anisotropic dye film (hereinafter, sometimes referred to as "the composition for an anisotropic dye film of the present invention"). The composition for an anisotropic dye film of the present invention contains the dye, polymerizable liquid crystal compound, and photopolymerization initiator exemplified above for the anisotropic dye film, and may also contain the other additives mentioned above.

[0221] The composition for anisotropic dye film of the present invention may contain a solvent, if necessary. The solvent that can be used is not particularly limited as long as it can disperse or dissolve the polymerizable liquid crystal compound, dye and other additives sufficiently in the composition for anisotropic dye film. Examples of the solvent include alcohol solvents such as methanol, ethanol, ethylene glycol, isopropyl alcohol, 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; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene. These solvents may be used alone or in combination of two or more.

[0222] The solvent is preferably one that can dissolve the polymerizable liquid crystal compound and the dye, and more preferably one that completely dissolves the polymerizable liquid crystal compound and the dye. Furthermore, the solvent is preferably one that is inactive to the polymerization reaction of the polymerizable liquid crystal compound. Furthermore, from the viewpoint of coating the anisotropic dye film composition of the present invention described below, the solvent preferably has a boiling point in the range of 50 to 200°C.

[0223] When the composition for an anisotropic dye film of the present invention contains a solvent, the content of the solvent in the composition for an anisotropic dye film of the present invention is preferably 50 to 98 mass % relative to the total amount (100 mass %) of the composition for an anisotropic dye film of the present invention. In other words, the solid content in the composition for an anisotropic dye film of the present invention is preferably 2 to 50 mass %. When the solid content in the composition for anisotropic dye film is equal to or less than the upper limit, the viscosity of the composition for anisotropic dye film does not become too high, the thickness of the obtained anisotropic dye film becomes uniform, and unevenness tends to be less likely to occur in the anisotropic dye film. The solid content of the composition for an anisotropic dye film can be determined taking into consideration the thickness of the anisotropic dye film to be produced.

[0224] The viscosity of the composition for anisotropic dye film of the present invention is not particularly limited as long as a uniform film without unevenness in thickness can be produced by the coating method described below. From the viewpoints of achieving uniformity in thickness over a large area, productivity such as coating speed, and in-plane uniformity in optical properties, the viscosity is preferably 0.1 mPa·s or more, and is preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0225] The method for producing the composition for anisotropic dye film of the present invention is not particularly limited. For example, a dye, a polymerizable liquid crystal compound, a photopolymerization initiator, and optionally a solvent and other additives are mixed, and the mixture is stirred or shaken at 0 to 80° C. to dissolve the dye. If the dye is poorly soluble, a homogenizer, a bead mill disperser, or the like may be used.

[0226] The method for producing the composition for anisotropic dye film of the present invention may include a filtration step for the purpose of removing foreign matter and the like from the composition.

[0227] The composition for anisotropic dye films of the present invention, obtained by removing the solvent from the composition for anisotropic dye films, may or may not be liquid crystal at any temperature, but it is preferable that the composition exhibits liquid crystallinity at any temperature. From the viewpoint of the coating process described below, the composition obtained by removing the solvent from the anisotropic dye film composition generally has an isotropic phase appearance temperature of less than 200°C, preferably less than 160°C, more preferably less than 140°C, even more preferably less than 115°C, even more preferably less than 110°C, and particularly preferably less than 105°C.

[0228] (Method for manufacturing anisotropic dye film) The anisotropic dye film of the present invention is preferably produced by a wet film-forming method using the composition for anisotropic dye film of the present invention.

[0229] The wet film-forming method referred to in the present invention is a method of applying and orienting a composition for an anisotropic dye film onto a substrate by some method. Therefore, the composition for an anisotropic dye film only needs to have fluidity, and may or may not contain a solvent. From the viewpoint of viscosity during application and film uniformity, it is preferable that the composition contains a solvent.

[0230] The liquid crystal compounds and dyes in anisotropic dye films can be aligned by shear during the coating process or by the drying process of the solvent. Alternatively, the liquid crystal compounds and dyes can be aligned and laminated on a substrate through a process of heating after coating and drying to realign them. In wet film-forming methods, when an anisotropic dye film composition is applied to a substrate, the dyes and liquid crystal compounds self-associate (a molecular association state such as a liquid crystal state) within the anisotropic dye film composition, or during the drying process of the solvent, or after the solvent is completely removed, resulting in alignment over a small area. Applying an external field to this state can induce a uniform orientation in a macroscopic region, resulting in an anisotropic dye film with the desired performance. In this respect, this method differs from methods that rely on dyeing a polyvinyl alcohol (PVA) film or the like with a dye-containing solution and stretching it to align the dye solely through the stretching process. Here, external fields include the influence of an alignment treatment layer previously applied to the substrate, shear force, magnetic field, electric field, heat, etc., and these can be used alone or in combination. If necessary, a heating step may be carried out.

[0231] The process of applying the composition for anisotropic dye film onto a substrate to form a film, the process of orienting by applying an external field, and the process of drying the solvent may be carried out sequentially or simultaneously.

[0232] In the wet film-forming method, the composition for an anisotropic dye film can be applied to a substrate by, for example, a coating method, a dip coating method, an LB film formation method, a known printing method, etc. Alternatively, the anisotropic dye film thus obtained can be transferred to another substrate.

[0233] Among these, it is preferable to apply the composition for anisotropic dye film onto a substrate by using a coating method.

[0234] 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 refers to, for example, the transmission axis (polarization axis) or absorption axis of polarized light in the case of a polarizing film, or the fast axis or slow axis in the case of a retardation film.

[0235] The method for applying the composition for anisotropic dye film to obtain an anisotropic dye film is not particularly limited, and examples thereof include the method described in "Coating Engineering" by Harasaki Yuji (Asakura Shoten Co., Ltd., published March 20, 1971), pages 253-277, and the method described in "Creation and Application of Molecular Cooperative Materials" edited by Ichimura Kunihiro (CMC Publishing Co., Ltd., published March 3, 1998), pages 118-149, as well as coating a substrate having a stepped structure (which may have been previously subjected to an orientation treatment) by slot die coating, spin coating, spray coating, bar coating, roll coating, blade coating, curtain coating, fountain coating, dipping, etc. Among these, slot die coating and bar coating are preferred because they can produce highly uniform anisotropic dye films.

[0236] The die coater used in the slot die coating method is generally equipped with a coating machine that ejects the coating liquid, a so-called slit die. Slit dies are disclosed, for example, in Japanese Patent Application Laid-Open Nos. 2-164480, 6-154687, and 9-131559, "Fundamentals and Applications of Dispersion, Coating, and Drying" (2014, Techno System Co., Ltd., ISBN 9784924728707 C 305), "Wet Coating Technology for Displays and Optical Components" (2007, Information Organization, ISBN 9784901677752), and "Precision Coating and Drying Technology in the Electronics Field" (2007, Technical Information Association, ISBN 9784861041389). These known slit dies can be used to coat flexible materials such as films and tapes, as well as hard materials such as glass substrates.

[0237] Examples of substrates that can be used for forming the anisotropic dye film of the present invention include glass, triacetate, acrylic, polyester, polyimide, polyetherimide, polyether ether ketone, polycarbonate, cycloolefin polymer, polyolefin, polyvinyl chloride, triacetyl cellulose, and urethane-based films.

[0238] To control the orientation direction of the dye, the substrate surface may be subjected to an alignment treatment (alignment film) using a known method, such as rubbing, forming grooves (fine groove structures) on the alignment film surface, using polarized ultraviolet light or polarized laser (photoalignment), forming an LB film, or oblique deposition of inorganic materials, as described on pages 226 to 239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000). The preferred alignment treatments are rubbing and photoalignment. Materials used in rubbing include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Materials used in photoalignment include polycinnamate, polyamic acid / polyimide, and azobenzene. When an alignment layer is provided, the liquid crystal compound and dye are thought to be aligned due to the effects of the alignment treatment layer and the shear force applied to the anisotropic dye film composition during application.

[0239] The method and interval for supplying the composition for anisotropic dye film when coating the composition for anisotropic dye film are not particularly limited. Since the operation of supplying the coating liquid may become complicated and the thickness of the coating film may vary when the coating liquid is started and stopped, when the thickness of the anisotropic dye film is thin, it is desirable to apply the composition for anisotropic dye film while continuously supplying it.

[0240] The coating speed of the composition for an anisotropic dye film is usually 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, even more preferably 1.0 m / min or more, and particularly preferably 5.0 m / min or more. The coating speed of the composition for an anisotropic dye film is usually 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and even more preferably 50 m / min or less. When the coating speed is within the above range, the anisotropy of the anisotropic dye film is obtained and the coating tends to be uniform.

[0241] The coating temperature of the composition for anisotropic dye film is usually 0° C. or higher and 100° C. or lower, preferably 80° C. or lower, and more preferably 60° C. or lower.

[0242] The humidity during application of the composition for anisotropic dye film is preferably 10% RH or higher and preferably 80% RH or lower.

[0243] The anisotropic dye film may be subjected to an insolubilization treatment. Insolubilization refers to a treatment that reduces the solubility of the compound in the anisotropic dye film, thereby controlling the elution of the compound from the anisotropic dye film and increasing the stability of the film. Specifically, film polymerization and overcoating are preferred in terms of ease of post-processing and durability of the anisotropic dye film.

[0244] When polymerizing the film, the film in which the liquid crystal molecules and dye molecules are oriented is polymerized using light and / or radiation.

[0245] When polymerization is carried out using light or radiation, it is preferable to irradiate with active energy rays having a wavelength in the range of 190 to 450 nm. The light source of the actinic energy ray with a wavelength of 190 to 450 nm is not particularly limited, but examples thereof include lamp light sources such as xenon lamps, halogen lamps, tungsten lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, medium-pressure mercury lamps, low-pressure mercury lamps, carbon arcs, and fluorescent lamps; and laser light sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium cadmium lasers, and semiconductor lasers. When using light with a specific wavelength, an optical filter can also be used. The exposure dose of the actinic energy ray is 1 to 100,000 J / m 2 is preferred, and 10 to 10,000 J / m 2 is more preferred.

[0246] Although polymerization may be carried out using light and / or radiation, photopolymerization or a combination of photopolymerization and thermal polymerization is preferred because it shortens the film formation process time and requires simple equipment. When thermal polymerization is carried out, it is preferably carried out at a temperature in the range of 50 to 200°C, more preferably in the range of 60 to 150°C.

[0247] [Photocurable film] The photocurable film referred to in the present invention is a functional film having photopolymerization properties. Examples of functional films include overcoat films having functions such as protection (e.g., abrasion resistance, scratch resistance, stress relaxation resistance, chemical resistance, gas resistance, water resistance, and corrosion resistance), bleeding prevention, flattening, easy adhesion, and mold release, as well as adhesive and / or cohesive films, anti-reflection films, retardation films, light control films that absorb, reflect, or scatter light, low-refractive films, high-refractive films, electrically insulating films, electrically conductive films, and alignment films. As the photocurable film to be laminated on the anisotropic dye film, an overcoat film is preferred in terms of being able to protect the anisotropic dye film as a protective film, and an adhesive film is preferred in terms of being able to easily form an optical element using an optically anisotropic laminate.

[0248] The optically anisotropic laminate of the present invention has at least one photocurable film laminated on an anisotropic dye film. The photocurable film is appropriately selected depending on the application, and may be a single layer or a multi-layer laminate. For example, the photocurable film may be a tacky adhesive film and an overcoat film, and in this case, a laminate structure of anisotropic dye film / overcoat film / tacky adhesive film is preferred. Other layers may be laminated between the anisotropic dye film, the overcoat film, and the tacky adhesive film. When the overcoat film has the function of protecting the anisotropic dye film, it is preferred that the overcoat film be laminated on the anisotropic dye film from the viewpoint of effective protection.

[0249] (Photopolymerization initiator) The photocurable film of the present invention contains a photopolymerization initiator.

[0250] The maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film of the present invention is not particularly limited as long as it satisfies formula (1), but is preferably 300 nm or more, more preferably 320 nm or more, and even more preferably 340 nm or more. Also, it is preferably 450 nm or less, more preferably 430 nm or less, and even more preferably 410 nm or less. By keeping it within this range, the photopolymerization reaction proceeds sufficiently, resulting in the effect of obtaining a photocurable film with a good degree of cure. As the photopolymerization initiator for the photocurable film, the photopolymerization initiators exemplified for the anisotropic dye film can be used.

[0251] To obtain a photocurable film with a good degree of curing, the content of the photopolymerization initiator in the photocurable film is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, based on 100% by mass of the photocurable film, and is preferably 30% by mass or less, more preferably 10% by mass or less, even more preferably 8% by mass or less, and particularly preferably 3% by mass or less.

[0252] Therefore, from the viewpoint of obtaining a photocurable film with a good degree of curing, the content of the photopolymerization initiator in the photocurable film-forming composition described below used to form the photocurable film 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 photocurable film composition, and is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less.

[0253] (curable resin) The photocurable film of the present invention contains a curable resin as a polymerizable component that is cured by photopolymerization.

[0254] As the curable resin, various conventionally known resins can be used, such as acrylic resin, polyester resin, urethane resin, polyvinyl resin, epoxy resin, silicone resin, vinyl acetate resin, nitrile rubber, chloroprene rubber, styrene-butadiene rubber, etc. Among these, acrylic resin is particularly preferred in terms of ease of introduction of a curable carbon-carbon double bond such as a (meth)acryloyl group. By controlling the amount of curable carbon-carbon double bonds such as (meth)acryloyl groups, the degree of crosslinking can be controlled, making it easier to adjust the bleed-out of low-molecular-weight components. Furthermore, such curable resins also have excellent bending properties. This is presumably because the inclusion of an appropriate amount of crosslinking groups in the resin component allows for both flexibility and curability.

[0255] Examples of the curable functional group contained in the curable resin include active energy ray-curable functional groups such as carbon-carbon double bonds, for example, (meth)acryloyl groups and vinyl ether compounds. Among these, (meth)acryloyl groups, particularly acryloyl groups, are preferred in terms of ease of introduction and reactivity.

[0256] As a method for introducing the double bond into an acrylic resin having an active energy ray-curable functional group such as a carbon-carbon double bond, the following methods 1 to 6 can be mentioned. Method 1: A method of reacting an acrylic resin having an epoxy group with a compound having a double bond and a carboxyl group Method 2: A method of reacting an acrylic resin having a carboxyl group with a compound having a double bond and an epoxy group Method 3: Reacting an acrylic resin having a hydroxyl group with a compound having a double bond and a carboxyl group Method 4: Reacting an acrylic resin having a carboxyl group with a compound having a double bond and a hydroxyl group Method 5: Reacting an acrylic resin having an isocyanate group with a compound having a double bond and a hydroxyl group Method 6: Reacting an acrylic resin having a hydroxyl group with a compound having a double bond and an isocyanate group The above methods may be used in combination. Hereinafter, a radically polymerizable monomer having a carbon-carbon double bond may be referred to as a vinyl monomer.

[0257] In Method 1, examples of vinyl monomers having epoxy groups used to obtain acrylic resins having epoxy groups include glycidyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, and 3,4-epoxycyclohexylmethyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred, and glycidyl methacrylate is particularly preferred, in consideration of good reactivity and ease of use of the material. These may be used alone or in combination of two or more.

[0258] Examples of the compound having a double bond and a carboxyl group in Method 1 include (meth)acrylic acid, carboxyethyl (meth)acrylate, an adduct of glycerin di(meth)acrylate and succinic anhydride, an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride, and an adduct of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, (meth)acrylic acid and an adduct of pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. Only one type of compound having a double bond and a carboxyl group may be used, or two or more types may be combined.

[0259] In Method 2, examples of vinyl monomers having a carboxyl group used to obtain an acrylic resin having a carboxyl group include (meth)acrylic acid, carboxyethyl (meth)acrylate, and polybasic acid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. These may be used alone or in combination of two or more.

[0260] In Method 2, examples of the compound having a double bond and an epoxy group include glycidyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate glycidyl ether. Among these, glycidyl (meth)acrylate is preferred. These compounds may be used alone or in combination of two or more.

[0261] In Method 3, examples of vinyl monomers having a hydroxyl group used to obtain an acrylic resin having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0262] In Method 3, the same compounds as those in Method 1 can be used as the compound having a double bond and a carboxyl group.

[0263] In Method 4, the same acrylic resin having a carboxyl group as in Method 2 can be used.

[0264] In Method 4, examples of the compound having a double bond and a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0265] In Method 5, examples of vinyl monomers having an isocyanate group that can be used to obtain an acrylic resin having an isocyanate group include isocyanate ethyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0266] In Method 5, the compound having a double bond and a hydroxyl group may be, for example, the same compound as that mentioned in Method 4.

[0267] In Method 6, the same compounds as those in Method 3 can be used as the acrylic resin having a hydroxyl group.

[0268] In Method 6, examples of the compound having a double bond and an isocyanate group include isocyanate ethyl (meth)acrylate, etc. These may be used alone or in combination of two or more.

[0269] Among the above methods, method 1 is preferred because the reaction is easy to control. In method 1, the double bond is introduced by a ring-opening addition reaction between the epoxy group of the acrylic resin having an epoxy group and the carboxyl group of the compound having a double bond and a carboxyl group.

[0270] In Method 1, the epoxy group-containing monomer in the epoxy group-containing acrylic resin preferably accounts for 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more of the total amount of monomers constituting the epoxy group-containing acrylic resin. There is no particular upper limit, but it is preferably 99.9% by mass or less, more preferably 80% by mass or less, even more preferably 70% by mass or less, particularly preferably 50% by mass or less, and most preferably 40% by mass or less. By using within this range, an overcoat film with excellent bleed-out prevention and bending properties is obtained.

[0271] In Method 1, the ratio of the compound having a double bond and a carboxyl group to the epoxy groups in the acrylic resin having an epoxy group is preferably 10 to 150 mol %, more preferably 30 to 130 mol %, and even more preferably 50 to 110 mol %. Using the compound in this range is preferable from the viewpoints of allowing the reaction to proceed just right and reducing the amount of raw material residue.

[0272] The acrylic resin, such as the above-mentioned acrylic resin having an epoxy group, may be a copolymer of (meth)acrylates other than those mentioned above or other vinyl monomers.

[0273] The polymerization reaction of these raw materials is usually radical polymerization, and can be carried out under conventionally known conditions.

[0274] 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 octoxytetramethylene glycol (meth)acrylate, lauroxy(poly)ethylene glycol (meth)acrylate, and stearoxy(poly)ethylene glycol (meth)acrylate; acrylamides such as ethyl(meth)acrylamide, n-butyl(meth)acrylamide, i-butyl(meth)acrylamide, t-butyl(meth)acrylamide, N-hydroxyethyl(meth)acrylamide, N-hydroxypropyl(meth)acrylamide, and N,N-dihydroxyethyl(meth)acrylamide; and styrene-based monomers such as styrene, p-chlorostyrene, and p-bromostyrene. These may be used alone or in combination of two or more.

[0275] The acrylic resin can be produced by radical polymerization using the above-mentioned vinyl monomers as raw materials. The radical polymerization reaction is preferably carried out in an organic solvent in the presence of a radical polymerization initiator.

[0276] Examples of organic solvents used in radical polymerization include ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropyl alcohol (IPA), and isobutanol; ether solvents such as ethylene glycol dimethyl ether and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, propylene glycol monomethyl ether acetate, and 2-ethoxyethyl acetate; and aromatic hydrocarbon solvents such as toluene. These organic solvents may be used alone or in combination of two or more.

[0277] Examples of radical polymerization initiators used in radical polymerization include organic peroxides such as benzoyl peroxide and di-t-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile). These radical polymerization initiators may be used alone or in combination of two or more. The radical polymerization initiator is preferably used in an amount of 0.01 to 5 parts by mass per 100 parts by mass of the total of the vinyl monomers used as raw materials.

[0278] During radical polymerization, a chain transfer agent can be used for the purpose of controlling the weight average molecular weight of the acrylic resin. Examples of the chain transfer agent include butanethiol, octanethiol, decanethiol, dodecanethiol, hexadecanethiol, octadecanethiol, cyclohexyl mercaptan, thiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, 2,2-(ethylenediaminetetraacetic acid)-2-methylpropanol, methyl-3-mercaptopropionate ... Examples of suitable thiol compounds include thiol compounds such as mercaptoacetate, 4-methylbenzenethiol, octanoic acid 2-mercaptoethyl ester, 1,8-dimercapto-3,6-dioxaoctane, decantrithiol, dodecyl mercaptan, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimethylmercapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid. These may be used alone or in combination of two or more.

[0279] The amount of the chain transfer agent used is preferably 0.1 to 25 parts by mass, more preferably 0.5 to 20 parts by mass, and even more preferably 1.0 to 15 parts by mass, per 100 parts by mass of the total of the vinyl monomers as raw materials.

[0280] The reaction time for the radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours. The reaction temperature is preferably 40 to 120°C, more preferably 50 to 100°C.

[0281] To react an acrylic resin with a compound having a double bond and a carboxyl group, the compound having a double bond and a carboxyl group is added to the acrylic resin obtained as described above, and the reaction is carried out in the presence of one or more catalysts, such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, or triethylamine, typically at a temperature of 90 to 140°C, preferably 100 to 120°C, for typically 3 to 9 hours. The catalyst is preferably used in an amount of approximately 0.5 to 3 parts by mass per 100 parts by mass of the combined starting materials (meth)acrylic acid ester polymer and the compound having a double bond and a carboxyl group. This reaction may be carried out immediately after the acrylic resin is produced by polymerization, or the acrylic resin may be separated from the reaction system and then the compound having a double bond and a carboxyl group may be added.

[0282] The double bond equivalent of the acrylic resin is preferably 0.1 to 10 mmol / g, more preferably 0.2 to 7.0 mmol / g, even more preferably 0.5 to 6.0 mmol / g, particularly preferably 1.0 to 5.5 mmol / g, and most preferably 2.0 to 5.0 mmol / g. By adjusting the double bond equivalent within this range, it becomes easier to achieve both bleed-out prevention and bending properties. The double bond equivalent refers to the concentration of (meth)acryloyl groups in the acrylic resin, i.e., the amount of (meth)acryloyl groups introduced.

[0283] The weight average molecular weight (Mw) of the curable resin contained in the photocurable film of the present invention is usually 5000 or more, preferably 7000 or more, more preferably 9000 or more, and usually 200000 or less, preferably 100000 or less, more preferably 70000 or less, and even more preferably 50000 or less. When it is within the above range, it becomes easier to form surface irregularities. However, from the viewpoint of the optical performance of the optically anisotropic laminate of the present invention, the weight average molecular weight (Mw) of the curable resin contained in the photocurable film of the present invention is preferably more than 10,000, more preferably at least 12,000, even more preferably at least 14,000, and particularly preferably at least 15,000. If it is at least the above lower limit, it is possible to reduce cure shrinkage and improve the optical performance of the optically anisotropic laminate.

[0284] The weight-average molecular weight (Mw) of the resin can be determined by gel permeation chromatography (GPC) using a polystyrene standard. Specific measurement conditions are shown in the Examples below.

[0285] The content of the curable resin in the photocurable film is preferably 50% by mass or more, more preferably 60% by mass or more, and even more preferably 70% by mass or more, based on 100% by mass of the photocurable film, from the viewpoint of exhibiting the functions of the photocurable film or obtaining a smooth photocurable film, and is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.

[0286] Therefore, from the viewpoint of exhibiting the functions of the photocurable film or obtaining a smooth photocurable film, the content of the curable resin in the photocurable film-forming composition described below used to form the photocurable film is preferably 50 parts by mass or more, more preferably 60 parts by mass or more, and even more preferably 70 parts by mass or more, relative to 100 parts by mass of the solid content of the photocurable film composition, and is preferably 99.99 parts by mass or less, more preferably 99.9 parts by mass or less.

[0287] (Other components) The photocurable film of the present invention may contain a polymerizable liquid crystal compound or the like in addition to a curable resin as a polymerizable component that is cured by photopolymerization.

[0288] As the polymerizable liquid crystal compound, various conventionally known polymerizable liquid crystal compounds can be used. For example, the polymerizable liquid crystal compounds exemplified in the anisotropic dye film are described on pages 408-410, 521-524, 562-563, etc. of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published October 30, 2000).

[0289] The photocurable film of the present invention may further contain a non-polymerizable resin, a non-polymerizable liquid crystal compound, a thermal polymerization initiator, a polymerization inhibitor, a polymerization aid, a surfactant, a leveling agent, a coupling agent, a pH adjuster, a dispersant, an antioxidant, an antistatic agent, an ultraviolet absorber, a light stabilizer, a thickener, an antifoaming agent, a pigment, an organic or inorganic filler, an organic or inorganic nanosheet, an organic or inorganic nanofiber, a metal oxide, or the like.

[0290] (Thickness of photocurable film) The thickness of the photocurable film of the present invention is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, and even more preferably 1 μm or more, from the viewpoint of increasing the mechanical strength and exhibiting functionality. Also, from the viewpoint of reducing the thickness of the obtained optically anisotropic laminate, it is preferably 175 μm or less, more preferably 120 μm or less, even more preferably 80 μm or less, even more preferably 60 μm or less, particularly preferably 20 μm or less, and even particularly preferably 10 μm or less.

[0291] (Composition for photocurable film) The photocurable film of the present invention can be formed using a photocurable film composition (hereinafter, sometimes referred to as "photocurable film composition of the present invention"). The photocurable film composition contains the photopolymerization initiator and curable resin exemplified above for the photocurable film, and may also contain other components.

[0292] The photocurable film composition may contain a solvent, if necessary. The solvent that can be used is not particularly limited as long as it can sufficiently disperse or dissolve the photopolymerization initiator, curable resin, and other components contained in the photocurable film composition. Examples of the solvent include alcohol solvents such as water, methanol, ethanol, ethylene glycol, isopropyl alcohol, 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; fluorine-containing solvents such as perfluorobenzene, perfluorotoluene, perfluorodecalin, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorine-containing solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene. These solvents may be used alone or in combination of two or more.

[0293] The solvent preferably has a boiling point in the range of 50 to 200°C from the viewpoint of coating the photocurable film composition.

[0294] When the photocurable composition for a film of the present invention contains a solvent, the content of the solvent in the photocurable composition for a film of the present invention is preferably 50 to 98 mass% relative to the total amount (100 mass%) of the photocurable composition for a film of the present invention. In other words, the content of solids in the photocurable composition for a film of the present invention is preferably 2 to 50 mass%. When the solid content in the photocurable film composition is equal to or less than the upper limit, the viscosity of the photocurable film composition does not become too high, the thickness of the obtained photocurable film becomes uniform, and unevenness in the photocurable film tends to be less likely to occur. The solid content can be determined in consideration of the thickness of the photocurable film to be produced.

[0295] The viscosity of the photocurable film composition is not particularly limited as long as it can produce a uniform film without unevenness in thickness. However, from the viewpoint of obtaining uniform thickness over a large area and productivity such as coating speed using the coating method described below, the viscosity is preferably 0.1 mPa·s or more, and is preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0296] The method for producing the photocurable film composition of the present invention is not particularly limited. For example, a curable resin, a photopolymerization initiator, and optionally a solvent and other components are mixed. A filtration step may be included to remove foreign matter from the composition.

[0297] (Method for producing photocurable film) The method for producing the photocurable film of the present invention is not particularly limited, but examples thereof include a method in which the photocurable film composition of the present invention is formed into a sheet, and a method in which the film is produced by a wet film-forming method.

[0298] The method of forming into a sheet as referred to in the present invention is a method in which a photocurable film composition is formed into a molded body, for example, a sheet body, by some method, and then irradiated with heat and / or active energy rays to cure the photocurable film composition. As a method for forming into a sheet, known methods can be used, such as wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendaring, inflation, injection molding, and liquid injection curing, etc. Among these, wet lamination, extrusion casting, and extrusion lamination are preferred.

[0299] The wet film-forming method referred to in the present invention is a method in which a photocurable film-forming composition is applied to a substrate by some method, and then the photocurable film-forming composition is cured by polymerization using active energy rays. Thermal polymerization may be used in combination with the polymerization using active energy rays.

[0300] The substrate may be a substrate containing an anisotropic dye film or a substrate not containing an anisotropic dye film. In the case of a substrate not containing an anisotropic dye film, a photocurable film can be produced by transferring a photocurable film composition coated on the substrate to a substrate containing an anisotropic film, or by transferring an anisotropic dye film coated on the substrate to a substrate containing a photocurable film composition, and then irradiating the composition with active energy rays to cure it.

[0301] Examples of methods for applying the photocurable film composition to a substrate include reverse coating, gravure coating, rod coating, bar coating, Mayer bar coating, die coating, and spray coating.

[0302] The photocurable film composition may be dried at 40° C. or higher and 130° C. or lower, if necessary, before being polymerized by irradiation with active energy rays. The active energy rays include light and radiation, of which ultraviolet light and visible light are preferred from the viewpoint of ease of controlling polymerization.

[0303] When curing by ultraviolet irradiation, a xenon lamp, a high-pressure mercury lamp, a metal halide lamp, an LED-UV lamp, etc. can be used as the light source of the ultraviolet irradiation device. The amount of ultraviolet irradiation is determined appropriately depending on the photocurable film composition, but is usually 10 mJ / cm. 2 More than 10000mJ / cm 2 From the viewpoint of degree of cure, it is 15 mJ / cm 2 More than 5000mJ / cm 2 Less than 20 mJ / cm is preferred 2 More than 3000mJ / cm 2 The following is more preferred:

[0304] (Overcoat film) An overcoat film may be provided as the photocurable film. The overcoat film is not particularly limited, but can be produced using an overcoat film composition having the same composition as the photocurable film composition of the present invention.

[0305] As with the photocurable film composition, the overcoat film composition contains a curable resin, which can protect the anisotropic dye film and prevent low-molecular-weight components from bleeding out from each layer. The curable resins preferred for the overcoat film composition are the same as those for the photocurable film composition described above.

[0306] The thickness of the overcoat film is preferably 0.1 μm or more, more preferably 0.3 μm or more, even more preferably 0.5 μm or more, and particularly preferably 1 μm or more, in order to provide functions such as protection, bleeding prevention, flattening, easy adhesion, and mold releasability. On the other hand, the upper limit of the thickness is preferably 100 μm or less, more preferably 50 μm or less, and even more preferably 30 μm or less, in order to make the optically anisotropic laminate thinner.

[0307] The overcoat film contains a photopolymerization initiator, and the photopolymerization initiators exemplified for the photocurable film can be used as the photopolymerization initiator for the overcoat film.

[0308] (Adhesive film) As the photocurable film, a tacky and / or adhesive film having tackiness and / or adhesiveness may be provided. The tacky and adhesive film can be produced using a composition for a tacky and adhesive film corresponding to the photocurable film composition for forming the tacky and adhesive film.

[0309] The adhesive film preferably has a light transmittance at wavelengths of 400 nm or less of less than 30%, more preferably less than 25%, even more preferably less than 22%, and particularly preferably less than 20%. When the light transmittance at wavelengths of 400 nm is less than the upper limit, deterioration of the coated optical element due to light can be suppressed.

[0310] Furthermore, from the viewpoint of visibility when used in an image display device, the adhesive film preferably has a light transmittance at a wavelength of 430 nm of 60% or more, more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more.

[0311] The thickness of the adhesive film is preferably 3 μm or more, more preferably 10 μm or more, even more preferably 20 μm or more, particularly preferably 30 μm or more, and especially preferably 40 μm or more, from the viewpoint of ensuring adhesiveness. On the other hand, the upper limit of the thickness is preferably 175 μm or less, more preferably 120 μm or less, even more preferably 80 μm or less, and particularly preferably 60 μm or less, from the viewpoint of contributing to the thinning of the optically anisotropic laminate.

[0312] The adhesive film contains a curable resin and a photopolymerization initiator. The photopolymerization initiator for the adhesive film can be any of the photopolymerization initiators listed above for the photocurable film.

[0313] The content of the photopolymerization initiator in the adhesive film is not particularly limited, but from the viewpoint of sufficiently progressing the polymerization reaction and improving the shape stability of the adhesive film, it is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more, even more preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more, relative to 100 parts by mass of the curable resin. Furthermore, from the viewpoint of ensuring adhesiveness, the upper limit of the content of the photopolymerization initiator in the adhesive film is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, even more preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less, relative to 100 parts by mass of the curable resin.

[0314] The curable resin contained in the adhesive film has adhesive and / or adhesive properties. As the curable resin, various conventionally known resins can be used, such as acrylic resin, epoxy resin, urethane resin, silicone resin, vinyl acetate resin, nitrile rubber, chloroprene rubber, styrene-butadiene rubber, etc. Among them, acrylic resin is preferred because of its excellent adhesive properties.

[0315] The acrylic resin is not particularly limited, but examples of the (meth)acrylic polymer (A) include a homopolymer of alkyl(meth)acrylate and a copolymer obtained by polymerizing a monomer component copolymerizable therewith. A preferred example of the copolymer is a (meth)acrylic resin (A) obtained by copolymerizing an alkyl(meth)acrylate (a1) having 4 to 18 carbon atoms in the side chain as the main component with a monomer component copolymerizable therewith. The above-mentioned main component means a component that has a significant effect on the properties of the (meth)acrylic polymer (A), and the content of the component is usually 30% by mass or more, preferably 35% by mass or more, of the total (meth)acrylic polymer (A). The (meth)acrylic polymer (A) may contain two or more (meth)acrylic polymers having different glass transition temperatures from the viewpoints of processability, adhesive strength, stress relaxation property, heat resistance reliability, and wet heat haze resistance.

[0316] Examples of the alkyl(meth)acrylate (a1) having 4 to 18 carbon atoms in the side chain include linear alkyl(meth)acrylates such as n-butyl(meth)acrylate, pentyl(meth)acrylate, hexyl(meth)acrylate, heptyl(meth)acrylate, n-octyl(meth)acrylate, nonyl(meth)acrylate, decyl(meth)acrylate, undecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, tetradecyl(meth)acrylate, cetyl(meth)acrylate, and stearyl(meth)acrylate; isobutyl(meth)acrylate, sec-butyl(meth)acrylate, t-butyl(meth)acrylate; and isopentyl(meth)acrylate. Examples of suitable acrylates include branched alkyl (meth)acrylates such as butyl (meth)acrylate, neopentyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isooctyl (meth)acrylate, isononyl (meth)acrylate, isodecyl (meth)acrylate, and isostearyl (meth)acrylate, and alicyclic (meth)acrylates such as cyclohexyl (meth)acrylate, t-butylcyclohexyl (meth)acrylate, 3,5,5-trimethylcyclohexane (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and isobornyl (meth)acrylate. These may be used alone or in combination of two or more.

[0317] From the viewpoint of improving the stress relaxation property and heat resistance reliability of the adhesive film, the content of the alkyl (meth)acrylate (a1) is preferably 3% by mass or more, more preferably 5% by mass or more, even more preferably 8% by mass or more, particularly preferably 10% by mass or more, and most preferably 12% by mass or more, based on the total components of the (meth)acrylic polymer (A). Also, from the viewpoint of suppressing a decrease in adhesive strength, the content of the alkyl (meth)acrylate (a1) is preferably 80% by mass or less, more preferably 60% by mass or less, even more preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less, based on the total components of the (meth)acrylic polymer (A).

[0318] Examples of the monomer component copolymerizable with the alkyl (meth)acrylate (a1) having 4 to 18 carbon atoms in the side chain include a hydroxyl group-containing (meth)acrylate monomer (a2), a (meth)acrylate monomer or vinyl ester-based monomer (a3) ​​having 1 to 3 carbon atoms in the side chain, a functional group-containing ethylenically unsaturated monomer (a4), and other copolymerizable monomers (a5).

[0319] Examples of the hydroxyl group-containing monomer (a2) include hydroxyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 5-hydroxypentyl (meth)acrylate, 6-hydroxyhexyl (meth)acrylate, and 8-hydroxyoctyl (meth)acrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl (meth)acrylate; oxyalkylene-modified monomers such as diethylene glycol (meth)acrylate and polyethylene glycol (meth)acrylate; primary hydroxyl group-containing monomers such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate; secondary hydroxyl group-containing monomers such as 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, and 3-chloro-2-hydroxypropyl (meth)acrylate; and tertiary hydroxyl group-containing monomers such as 2,2-dimethyl-2-hydroxyethyl (meth)acrylate. These can be used alone or in combination of two or more.

[0320] Among the hydroxyl group-containing monomers (a2), primary hydroxyl group-containing monomers, particularly 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate, and especially 2-hydroxyethyl (meth)acrylate and 4-hydroxybutyl (meth)acrylate are preferred because they have an excellent balance between moist heat resistance and heat resistance.

[0321] From the viewpoint of improving moist heat resistance, the lower limit of the content of the hydroxyl group-containing monomer (a2) is usually 3 mass% or more, preferably 5 mass% or more, more preferably 8 mass% or more, even more preferably 10 mass% or more, and particularly preferably 12 mass% or more, based on the total components of the (meth)acrylic polymer (A). The upper limit of the content of the hydroxyl group-containing monomer (a2) is usually 60% by mass or less, preferably 45% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less, from the viewpoint of suppressing the self-crosslinking reaction of the (meth)acrylic polymer (A) and improving processability and heat resistance reliability.

[0322] Examples of the (meth)acrylate monomer or vinyl ester monomer (a3) ​​having 1 to 3 carbon atoms in the side chain include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, vinyl propionate, vinyl acetate, etc. These monomers (a3) ​​may be used alone or in combination of two or more. Of the above-mentioned components (a3), it is preferable to use methyl (meth)acrylate and ethyl (meth)acrylate from the viewpoint of improving cohesive strength when used as an adhesive.

[0323] When the component (a3) ​​is contained, the lower limit is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more, based on the total components of the (meth)acrylic polymer (A), from the viewpoint of improving cohesive strength when used as a tacky adhesive film. Also, when the component (a3) ​​is contained, the upper limit is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less, based on the total components of the (meth)acrylic polymer (A), from the viewpoint of improving processability.

[0324] Examples of the functional group-containing ethylenically unsaturated monomer (a4) include carboxyl group-containing monomers, nitrogen atom-containing functional group-containing monomers, acetoacetyl group-containing monomers, isocyanate group-containing monomers, and glycidyl group-containing monomers. Among these, functional group-containing monomers having a nitrogen atom are preferred in terms of imparting cohesive strength and crosslinking-promoting action, more preferably amino group-containing monomers and amide group-containing monomers, and even more preferably amino group-containing monomers.

[0325] Examples of carboxyl group-containing monomers include (meth)acrylic acid, carboxylethyl (meth)acrylate, 2-(meth)acryloyloxyethyl hexahydrophthalic acid, 2-(meth)acryloyloxypropyl hexahydrophthalic acid, 2-(meth)acryloyloxyethyl phthalic acid, 2-(meth)acryloyloxypropyl phthalic acid, 2-(meth)acryloyloxyethyl maleic acid, 2-(meth)acryloyloxypropyl maleic acid, 2-(meth)acryloyloxyethyl succinic acid, 2-(meth)acryloyloxypropyl succinic acid, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, and monomethyl itaconate.

[0326] Examples of amino group-containing monomers include primary amino group-containing (meth)acrylates such as aminomethyl (meth)acrylate and aminoethyl (meth)acrylate; secondary amino group-containing (meth)acrylates such as t-butylaminoethyl (meth)acrylate and t-butylaminopropyl (meth)acrylate; and tertiary amino group-containing (meth)acrylates such as ethylaminoethyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, dimethylaminopropyl (meth)acrylate, diethylaminopropyl (meth)acrylate, and dimethylaminopropylacrylamide.

[0327] Examples of the amide group-containing monomer include (meth)acrylamide; N-alkyl(meth)acrylamides such as N-methyl(meth)acrylamide, N-ethyl(meth)acrylamide, N-propyl(meth)acrylamide, Nn-butyl(meth)acrylamide, diacetone(meth)acrylamide, and N,N'-methylenebis(meth)acrylamide; N,N-dialkyl(meth)acrylamides such as N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N,N-dipropyl(meth)acrylamide, N,N-ethylmethylacrylamide, and N,N-diallyl(meth)acrylamide; hydroxyalkyl(meth)acrylamides such as N-hydroxymethyl(meth)acrylamide and N-hydroxyethyl(meth)acrylamide; and alkoxyalkyl(meth)acrylamides such as N-methoxymethyl(meth)acrylamide and N-(n-butoxymethyl)(meth)acrylamide.

[0328] Examples of acetoacetyl group-containing monomers include 2-(acetoacetoxy)ethyl (meth)acrylate and allyl acetoacetate.

[0329] Examples of isocyanate group-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof. The isocyanate group may be protected with a blocking agent such as methyl ethyl ketone oxime, 3,5-dimethylpyrazole, 1,2,4-triazole, or diethyl malonate.

[0330] Examples of the glycidyl group-containing monomer include glycidyl (meth)acrylate and allyl glycidyl (meth)acrylate.

[0331] These functional group-containing ethylenically unsaturated monomers (a4) may be used alone or in combination of two or more.

[0332] From the viewpoint of improving the heat resistance and light resistance of the adhesive film, the upper limit of the content of the functional group-containing ethylenically unsaturated monomer (a4) is preferably 30 mass % or less, more preferably 20 mass % or less, even more preferably 10 mass % or less, and particularly preferably 5 mass % or less, based on the total components of the (meth)acrylic polymer (A).

[0333] Examples of other copolymerizable monomers (a5) that can be used as needed include aromatic (meth)acrylic acid ester monomers such as phenyl(meth)acrylate, benzyl(meth)acrylate, phenoxyethyl(meth)acrylate, phenyldiethylene glycol(meth)acrylate, phenoxypolyethylene glycol(meth)acrylate, phenoxypolyethylene glycol-polypropylene glycol-(meth)acrylate, and nonylphenol ethylene oxide adduct (meth)acrylate; 4-acryloyloxybenzophenone, 4-acryloyloxyethoxybenzophenone, 4-acryloyloxy-4'-methoxybenzophenone, 4-acryloyloxyethoxy-4'-methoxybenzophenone, 4-acryloyloxy-4'-bromobenzophenone, 4-acryloyloxyethoxy-4'-bromobenzophenone, 4-methacryloyloxybenzophenone; Examples of the vinyl monomers include (meth)acrylic acid ester monomers having a benzophenone structure, such as 4-methacryloyloxyethoxybenzophenone, 4-methacryloyloxy-4'-methoxybenzophenone, 4-methacryloyloxyethoxy-4'-methoxybenzophenone, 4-methacryloyloxy-4'-bromobenzophenone, 4-methacryloyloxyethoxy-4'-bromobenzophenone, and mixtures thereof, and vinyl monomers such as acrylonitrile, methacrylonitrile, styrene, α-methylstyrene, vinyl stearate, vinyl chloride, vinylidene chloride, alkyl vinyl ethers, vinyltoluene, vinylpyridine, vinylpyrrolidone, dialkyl itaconate esters, dialkyl fumarate esters, allyl alcohol, acrylic chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinyl ketone. These may be used alone or in combination of two or more.

[0334] The (meth)acrylic polymer (A) may have a polymerizable carbon-carbon double bond group introduced into its side chain, which can enhance the crosslinking sensitivity of the (meth)acrylic polymer (A) and can crosslink the (meth)acrylic polymer (A) by irradiation with lower-energy active energy rays, thereby imparting cohesive strength and heat resistance.

[0335] Examples of a method for introducing a polymerizable carbon-carbon double bond group into the side chain of the (meth)acrylic polymer (A) include a method in which a copolymer containing the above-mentioned hydroxyl group-containing monomer (a2) or functional group-containing ethylenically unsaturated monomer (a4) is prepared, and then a compound (a6) having a polymerizable carbon-carbon double bond group and a functional group reactive with these functional groups is subjected to a condensation or addition reaction while maintaining the activity of the polymerizable carbon-carbon double bond group. Examples of combinations of these functional groups include epoxy groups (glycidyl groups) and carboxyl groups, amino groups and carboxyl groups, amino groups and isocyanate groups, epoxy groups (glycidyl groups) and amino groups, hydroxyl groups and epoxy groups, and hydroxyl groups and isocyanate groups. Among these combinations of functional groups, the combination of hydroxyl groups and isocyanate groups is preferred because of the ease of reaction control. Among these, a combination in which the copolymer has a hydroxyl group and the compound (a6) has an isocyanate group is preferred. Examples of the isocyanate compound having a polymerizable carbon double bond include the above-mentioned 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and alkylene oxide adducts thereof.

[0336] From the viewpoint of improving adhesiveness and stress relaxation properties, the amount of compound (a6) added is preferably 10 parts by mass or less, more preferably 8 parts by mass or less, even more preferably 5 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic polymer (A). The lower limit of the weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is preferably 100,000 or more, more preferably 300,000 or more, and even more preferably 500,000 or more, from the viewpoint of obtaining a pressure-sensitive adhesive film with high cohesive strength. The upper limit of the weight average molecular weight (Mw) of the (meth)acrylic polymer (A) is preferably 2,000,000 or less, more preferably 1,500,000 or less, and even more preferably 1,000,000 or less, from the viewpoint of obtaining an adhesive film with high fluidity and stress relaxation.

[0337] The adhesive film may contain a polyfunctional (meth)acrylate. Examples of the polyfunctional (meth)acrylate include a (meth)acrylic monomer or a (meth)acrylic oligomer having two or more functional groups. When the adhesive film contains a polyfunctional (meth)acrylate, a crosslinked structure is formed in the adhesive film, and cohesive strength and durability can be imparted to the adhesive film.

[0338] Examples of the (meth)acrylic monomer having two or more functional groups include 1,4-butanediol di(meth)acrylate, glycerin di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerin glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecane dimethanol di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol A polyethoxy di(meth)acrylate, bisphenol B polyethoxy di(meth)acrylate, bisphenol C ... Nol A polypropoxy di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane trioxyethyl (meth)acrylate, ε-caprolactone-modified tris(2-hydroxyethyl) isocyanurate tri(meth)acrylate, pentaerythritol tri(meth)acrylate, propoxylated pentaerythritol tri(meth)acrylate, ethoxylated pentaerythritol tri(meth)acrylate ) acrylate, pentaerythritol tetra(meth)acrylate, propoxylated pentaerythritol tetra(meth)acrylate, ethoxylated pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, (tris(acryloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate, dipenta Examples of the acrylate include erythritol penta(meth)acrylate, tripentaerythritol hexa(meth)acrylate, tripentaerythritol penta(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, di(meth)acrylate of an ε-caprolactone adduct of neopentyl glycol hydroxypivalate, trimethylolpropane tri(meth)acrylate, trimethylolpropane polyethoxytri(meth)acrylate, and ditrimethylolpropane tetra(meth)acrylate. Among these, (meth)acrylic monomers are preferred from the viewpoint of imparting appropriate toughness to the cured product, and among these, polyfunctional (meth)acrylic monomers having an alkylene glycol skeleton, such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and polytetramethylene glycol di(meth)acrylate, are more preferred.

[0339] The molecular weight of the polyfunctional (meth)acrylic monomer is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and particularly preferably 500 or more, from the viewpoint of imparting appropriate flexibility to the cured product.

[0340] Examples of the (meth)acrylic oligomer having two or more functional groups include polyfunctional (meth)acrylic oligomers such as polyester (meth)acrylate, epoxy (meth)acrylate, urethane (meth)acrylate, and polyether (meth)acrylate. Among these, urethane (meth)acrylate oligomers are preferred from the viewpoint of imparting appropriate toughness to the cured product. The molecular weight of the polyfunctional (meth)acrylic oligomer is preferably 300 or more, more preferably 400 or more, even more preferably 600 or more, and particularly preferably 800 or more, from the viewpoint of imparting appropriate flexibility to the cured product.

[0341] The lower limit of the content of the polyfunctional (meth)acrylate in the adhesive film is preferably 1 part by mass or more, more preferably 2 parts by mass or more, even more preferably 4 parts by mass or more, and particularly preferably 10 parts by mass or more, relative to 100 parts by mass of the (meth)acrylic polymer (A), from the viewpoint of imparting shape stability to the adhesive film and durability when formed into a laminate. The upper limit of the content of the polyfunctional (meth)acrylate is preferably 100 parts by mass or less, more preferably 60 parts by mass or less, even more preferably 40 parts by mass or less, and particularly preferably 30 parts by mass or less, relative to 100 parts by mass of the (meth)acrylic polymer (A), from the viewpoint of ensuring adhesiveness.

[0342] The adhesive film may contain an ultraviolet absorber, which can reduce deterioration of the optically anisotropic laminate due to light. Examples of ultraviolet absorbers include benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, triazine-based ultraviolet absorbers, salicylic acid-based ultraviolet absorbers, and cyanoacrylate-based ultraviolet absorbers. Among these, benzophenone-based ultraviolet absorbers, benzotriazole-based ultraviolet absorbers, and triazine-based ultraviolet absorbers are preferred from the viewpoint of easily achieving the ultraviolet absorption effect. Among these, benzophenone-based ultraviolet absorbers are more preferred from the viewpoint of excellent yellowing resistance. These ultraviolet absorbers can be used alone or in combination of two or more.

[0343] [Method for producing optically anisotropic laminate] The method for producing the optically anisotropic laminate of the present invention is not particularly limited, but examples thereof include the following methods (1) to (3). (1) A method for producing an optically anisotropic laminate by applying a photocurable film composition to a substrate on which an anisotropic dye film has been produced, and polymerizing the composition using active energy rays to produce a photocurable film. (2) A method for producing an optically anisotropic laminate by forming a photocurable film composition into a sheet on a substrate on which an anisotropic dye film has been produced, and polymerizing the composition using active energy rays to produce a photocurable film. (3) A method for producing an optically anisotropic laminate by applying a photocurable film composition to a substrate on which no anisotropic dye film has been formed, or forming the composition into a sheet, and then transferring the composition to a substrate on which an anisotropic dye film has been formed, and then curing the composition with active energy rays to form a photocurable film. (4) A method for producing an optically anisotropic laminate by applying an anisotropic dye film to a substrate on which no anisotropic dye film has been formed, or by transferring an anisotropic dye film from a substrate on which an anisotropic dye film has been formed to a photocurable film composition formed into a sheet, and then curing the composition with active energy rays to form a photocurable film. From the viewpoint of shortening the process, a preferred method is to produce an optically anisotropic laminate by applying a photocurable film composition to a substrate on which an anisotropic dye film has been produced, or by forming the composition into a sheet, and polymerizing the composition using active energy rays to form a photocurable film.

[0344] [Optical elements] The optical element of the present invention includes the optically anisotropic laminate of the present invention.

[0345] The optical element in the present invention refers to a polarizing element that utilizes the anisotropy of light absorption to obtain linearly polarized light, circularly polarized light, elliptically polarized light, etc., a retardation element, an optical compensation element, or an element having functions such as reflection, brightness improvement, refractive anisotropy, or conductive anisotropy. The optical element may have one or more functions. These functions can be appropriately adjusted by selecting the anisotropic dye film formation process and the composition containing the substrate and organic compound (dye or transparent material).

[0346] The optical element of the present invention is preferably used as a polarizing element or a polarizing element combined with other functions, and more preferably used as a polarizing element. The optical element of the present invention can be suitably used in applications such as flexible displays, since a polarizing element can be obtained by forming an anisotropic dye film on a substrate by coating or the like.

[0347] [Polarizing element] When the optical element of the present invention is used as a polarizing element, the polarizing element may have any other layer as long as it has the optically anisotropic laminate of the present invention.

[0348] The layers that can be used in combination with the polarizing element can be provided as appropriate in accordance with the manufacturing process, characteristics, and functions, and the positions and order of lamination thereof are not particularly limited. The layer having an optical function can be formed by the following method.

[0349] A layer having a function as a retardation film can be formed by applying or pasting a retardation film onto other layers constituting a polarizing element, etc. The retardation film can be formed, for example, by performing a stretching treatment described in JP-A Nos. 2-59703 and 4-230704, or by performing a treatment described in JP-A No. 7-230007.

[0350] A layer functioning as a brightness enhancement film can be formed by coating or laminating a brightness enhancement film onto other layers constituting a polarizing element, etc. The brightness enhancement film can be formed, for example, by forming micropores using the methods described in JP-A Nos. 2002-169025 and 2003-29030, or by superposing two or more cholesteric liquid crystal layers having different central wavelengths of selective reflection.

[0351] A layer that functions as a reflective film or a semi-transparent reflective film can be formed, for example, by applying or laminating a metal thin film obtained by vapor deposition or sputtering to other layers that constitute the polarizing element.

[0352] The layer functioning as a diffusion film can be formed, for example, by coating another layer constituting the polarizing element with a resin solution containing fine particles.

[0353] When the optical element of the present invention is used in various display elements such as LCDs and OLEDs, the optical element of the present invention may be formed directly on the surface of an electrode substrate or the like that constitutes these display elements, or the optical element of the present invention may be used as a constituent member of these display elements. [Example]

[0354] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples as long as it does not depart from the gist of the invention. In the following description, "parts" means "parts by mass."

[0355] [Transmittance measurement] The transmittance was measured using a total light transmittance value measured using a haze meter (manufactured by Nippon Denshoku Industries Co., Ltd., product name "NDH-5000SP") The transmittance before and after lamination of the photocurable film was compared, and if there was no decrease in transmittance after lamination, the optical performance of the optically anisotropic laminate was maintained and judged as "good (◯)", and if there was a decrease in transmittance after lamination, the optical performance of the optically anisotropic laminate was not sufficiently maintained and judged as "poor (×)".

[0356] [Measurement of weight average molecular weight (Mw)] The weight average molecular weight (Mw) was determined by measuring the molecular weight by gel permeation chromatography (GPC) using standard polystyrene standards.

[0357] Details of the polymerizable liquid crystal compounds and dyes contained in the anisotropic dye films used in the examples and comparative examples are as follows.

[0358] [Polymerizable liquid crystal compound] <Polymerizable liquid crystal compound (I-1)> The polymerizable liquid crystal compound (I-1) shown in the following structural formula was synthesized according to the description of JP-A-2020-042305. 11 H 22 means that 11 methylene chains are bonded in a linear fashion.

[0359] [ka]

[0360] <Polymerizable liquid crystal compound (I-2)> A polymerizable liquid crystal compound (I-2) represented by the following structural formula was synthesized according to the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). 11 H 22 means that 11 methylene chains are bonded in a linear fashion.

[0361] [ka]

[0362] [Pigment] The chemical structures of the dyes (II-1) and (II-2) used in the examples and comparative examples are shown below.

[0363] [ka]

[0364] [ka]

[0365] [Example 1] <Preparation of composition for anisotropic dye film> To 69.31 parts of cyclopentanone, 28.57 parts of polymerizable liquid crystal compound (I-1), 0.34 parts of dye (II-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of dye (II-2) (manufactured by Showa Kako Co., Ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF), and 0.34 parts of BYK-361N (manufactured by BYK-Chemie) were added, and the mixture was heated and stirred at 80°C, and then filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) to obtain composition 1 for anisotropic dye film.

[0366] <Production of anisotropic dye film> Anisotropic dye film composition 1 was applied by spin coating to a substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont Microsystems, alignment film formed by rubbing) had been formed on glass. The film was then dried by heating at 120°C for 2 minutes, and cooled to the liquid crystal phase. The film was then exposed to an exposure dose of 500 mJ / cm. 2 Polymerization was carried out at 365 nm (reference wavelength) to obtain anisotropic dye film 1 having a thickness of 3 μm. When the obtained anisotropic dye film 1 was observed by holding a polarizing plate over the anisotropic dye film side, light and dark appeared every time the polarizing plate was rotated by 90 degrees, indicating that the film had polarizing properties. The maximum absorption wavelength λ0 of the photopolymerization initiator (IRGACURE (registered trademark) 369) contained in this anisotropic dye film 1 was 319 nm.

[0367] <Preparation of overcoat film> An overcoat film was formed using a composition for an overcoat film on the anisotropic dye film 1. The curable resin (R-1) contained in the composition for an overcoat film was synthesized by the following method.

[0368] Propylene glycol monomethyl ether (157 parts), glycidyl methacrylate (98 parts), methyl methacrylate (1.0 part), ethyl acrylate (1.0 part), 2,2'-azobis(2,4-dimethylvaleronitrile) (1.0 part), and γ-trimethoxysilylpropanethiol (KBM-803, manufactured by Shin-Etsu Chemical Co., Ltd.) (1.9 parts) were placed in a flask equipped with a thermometer, a stirrer, and a reflux condenser, and the mixture was allowed to react at 65°C for 3 hours. Thereafter, 2,2'-azobis(2,4-dimethylvaleronitrile) (0.5 parts) was further added and reacted for 3 hours, after which propylene glycol monomethyl ether (138 parts) and p-methoxyphenol (0.45 parts) were added and the mixture was heated to 100°C. Next, acrylic acid (51 parts) and triphenylphosphine (3.1 parts) were added and reacted at 110°C for 6 hours to obtain a curable resin (R-1) that was a (meth)acryloyl copolymer with a carbon-carbon double bond content (acryloyl equivalent (amount of acryloyl group introduced)) of 4.6 mmol / g. The weight average molecular weight (Mw) of this curable resin (R-1) was 17,700.

[0369] 23.08 parts of a 65 mass% solution of curable resin (R-1) in propylene glycol monomethyl ether, 0.13 parts of a photopolymerization initiator (PI-1) represented by the following structural formula, 0.40 parts of BYK-3550 (manufactured by BYK-Chemie), and 76.39 parts of ethanol were mixed and stirred, and the mixture was filtered using a syringe equipped with a syringe filter (manufactured by Membrane Solutions, PTFE13045, diameter 0.45 μm) to obtain a composition for an overcoat film.

[0370] [ka]

[0371] The composition for the overcoat film was formed on the anisotropic dye film by spin coating, and after heating and drying at 50°C for 2 minutes, the film was exposed to light at an exposure dose of 5000 mJ / cm 2 (365 nm standard) to form an overcoat film, thereby obtaining an optically anisotropic laminate 1. The maximum absorption wavelength λ1 of the photopolymerization initiator (PI-1) contained in the overcoat film, which is a photocurable film, was 356 nm.

[0372] The evaluation result of the change in transmittance of the optically anisotropic laminate 1 before and after lamination of the photocurable film was ◯ (good), indicating that the optical performance was good even when the photocurable film was laminated.

[0373] [Comparative Example 1] An optically anisotropic laminate 2 was obtained in the same manner as in Example 1, except that the photopolymerization initiator contained in the overcoat film of Example 1 was changed to IRGACURE (registered trademark) 369. The evaluation result of the change in transmittance of the optically anisotropic laminate 2 before and after lamination of the photocurable film was × (poor), indicating that the optical performance was reduced by laminating the photocurable film.

[0374] The results of evaluating the change in λ0, λ1, and the transmittance before and after lamination of the photocurable film of the optically anisotropic laminate in Example 1 and Comparative Example 1 are shown in Table 1. The results demonstrate that the optically anisotropic laminate satisfying formula (1) has high optical performance.

[0375] [Table 1]

[0376] [Example 2] An optically anisotropic laminate 3 was obtained in the same manner as in Example 1, except that the polymerizable liquid crystal compound (I-1) contained in the composition for anisotropic dye film in Example 1 was changed to the polymerizable liquid crystal compound (I-2). The evaluation result of the change in transmittance of the optically anisotropic laminate 3 before and after lamination of the photocurable film was ◯ (good), indicating that the optical performance was good even when the photocurable film was laminated.

[0377] Comparative Example 2 An optically anisotropic laminate 4 was obtained in the same manner as in Comparative Example 1, except that the polymerizable liquid crystal compound (I-1) contained in the composition for anisotropic dye film in Comparative Example 1 was changed to the polymerizable liquid crystal compound (I-2). The evaluation result of the change in transmittance of the optically anisotropic laminate 4 before and after lamination of the photocurable film was × (poor), indicating that the optical performance was reduced by lamination of the photocurable film.

[0378] Table 2 shows the results of evaluating the change in λ0, λ1, and transmittance before and after lamination of the photocurable film of the optically anisotropic laminate in Example 2 and Comparative Example 2. The results demonstrate that the optically anisotropic laminate satisfying formula (1) has high optical performance.

[0379] [Table 2]

[0380] Comparative Example 3 An optically anisotropic laminate 5 was obtained in the same manner as in Example 1, except that the curable resin (R-1) contained in the overcoat film composition of Example 1 was replaced with UV-curable urethane acrylate Shikoh UV-7750B (manufactured by Mitsubishi Chemical Corporation, weight average molecular weight Mw = 2400).

[0381] The evaluation result of the change in transmittance of the optically anisotropic laminate 5 before and after lamination of the photocurable film was × (poor), indicating that the optical performance was reduced by laminating the photocurable film.

[0382] Table 3 shows the results of evaluating λ0, λ1, the weight average molecular weight (Mw) of the curable resin, and the change in transmittance before and after lamination of the photocurable film of the optically anisotropic laminate in Example 1 and Comparative Example 3. The results show that optically anisotropic laminates in which the weight average molecular weight (Mw) of the curable resin exceeds 10,000 have high optical performance.

[0383] [Table 3]

[0384] Although the present invention has been described in detail with reference to specific embodiments, it will be apparent to those skilled in the art that various modifications can be made without departing from the spirit and scope of the invention. This application is based on Japanese Patent Application No. 2020-197232 filed on November 27, 2020, the entire contents of which are incorporated by reference.

Claims

1. A method for producing an optically anisotropic laminate in which at least one photocurable film is laminated on an anisotropic dye film, comprising the steps of: a step of obtaining the anisotropic dye film by irradiating a film of a composition for an anisotropic dye film, which comprises a dye, a polymerizable liquid crystal compound, and a photopolymerization initiator, with active energy rays; and obtaining the photocurable film by irradiating a film of a photocurable film composition containing a curable resin and a photopolymerization initiator with active energy rays, the maximum absorption wavelength λ0 of the photopolymerization initiator contained in the composition for anisotropic dye film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the composition for photocurable film satisfy the following formula (1): The method for producing an optically anisotropic laminate, wherein the curable resin contained in the photocurable film composition has a weight average molecular weight (Mw) of more than 10,000. λ0<λ1... (1) However, both λ0 and λ1 are wavelengths that show upwardly convex inflection points in the absorption spectrum at wavelengths of 250 nm or more. In addition, when there are multiple maximum absorption wavelengths, the maximum absorption wavelengths are the longer wavelengths.

2. The method for producing an optically anisotropic laminate according to claim 1 , wherein at least one layer of the photocurable film is an adhesive film.

3. The method for producing an optically anisotropic laminate according to claim 1 , wherein at least one of the photocurable films is an overcoat film.

4. The method for producing an optically anisotropic laminate according to any one of claims 1 to 3, wherein the difference between λ1 and λ0 is 5 nm or more.

5. The method for producing an optically anisotropic laminate according to any one of claims 1 to 4, wherein the curable resin is an acrylic resin having a (meth)acryloyl group.

6. 6. The method for producing an optically anisotropic laminate according to claim 5, wherein the acrylic resin has a double bond equivalent of 0.1 to 10 mmol / g.

7. The method for producing an optically anisotropic laminate according to any one of claims 1 to 6, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (2): Q １ -R １ -A １１ -Y １ -A １２ -(Y ２ -A １３ ) ｋ -R ２ -Q ２ …(2) (In formula (2), -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 (3), a divalent organic group, or a single bond: -A １２ - represents a partial structure represented by the following formula (3) or a divalent organic group; -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)-, or -CH ２ CH ２ -, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH ２ O-, -OCH ２ -, -CH ２ S- or -SCH ２ represents -; -A １１ - and - A １３ One of the - is a partial structure represented by the following formula (3) or a divalent organic group: k is 1 or 2. When k is 2, two -Y ２ -A １３ - may be the same or different.) -Cy-X ２ -C≡C-X １ - …(3) (In formula (3), -Cy- represents a hydrocarbon ring group or a heterocyclic group; -X １ - is -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ２ CH ２ -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH ２ O-, -OCH ２ -, -CH ２ S- or -SCH ２ represents -; -X ２ - represents a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH ２ CH ２ -, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CHH ２ O-, -OCH ２ -, -CH ２ S- or -SCH ２ - represents.)

8. The method for producing an optically anisotropic laminate according to any one of claims 1 to 7, wherein the dye is an azo-based dichroic dye.

9. The number of ring structures (r ｎ１ ) and the number of ring structures that the dye has (r ｎ２ ) and the ratio (r ｎ１ / r ｎ２ 9. The method for producing an optically anisotropic laminate according to claim 1, wherein the value of (a) is 0.7 to 1.

5.

10. A method for producing an optical element, comprising producing an optically anisotropic laminate by the method for producing an optically anisotropic laminate according to any one of claims 1 to 9, and using the produced optically anisotropic laminate to produce an optical element.

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