Optical anisotropic laminates and optical elements

Abstract

The optical anisotropic laminate of the present invention comprises at least one photocurable film stacked on an anisotropic pigment film. The anisotropic pigment film includes a pigment, a polymerizable liquid crystal compound, and a photopolymerization initiator. The photocurable film includes a curable resin and a photopolymerization initiator. The maximum absorption wavelength λ0 of the photopolymerization initiator included in the anisotropic pigment film and the maximum absorption wavelength λ1 of the photopolymerization initiator included in the photocurable film satisfy the following formula (1). The weight-average molecular weight (Mw) of the curable resin exceeds 10,000. λ0 < λ1…(1).

Description

Technical Field

[0001] This invention relates to an optical anisotropic laminate and optical element that exhibits high dichroism and is useful for display elements such as linear polarizing film and circular polarizing film in dimming elements, liquid crystal elements (LCDs) and organic light-emitting elements (OLEDs). Background Technology

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

[0003] Previously, such polarizing films have included, for example, polarizing films containing polyvinyl alcohol (PVA) dyed with a low concentration of iodine (iodine-PVA polarizing film) (Patent Document 1).

[0004] However, iodine-PVA polarizing films dyed with low concentrations of iodine may have problems such as color changes due to iodine sublimation or deterioration caused by the environment, or warping due to the relaxation of PVA stretching.

[0005] It is also known that anisotropic pigment films formed by coating a liquid crystal composition containing pigments can function as polarizing films (Patent Document 2).

[0006] However, polarizing films formed by coating liquid crystal compositions containing pigments have the following problems: they cannot achieve high light absorption selectivity, or if high light absorption selectivity is desired, there are sometimes process difficulties.

[0007] Patent Document 1: Japanese Patent Application Publication No. 1-105204

[0008] Patent Document 2: Japanese Patent Publication No. 2004-535483

[0009] Under these circumstances, a polarizing film with high light absorption selectivity is desired, even if it is a thin film.

[0010] A polarizing film comprising an anisotropic pigment film is used in the form of an optically anisotropic laminate when mounted on a display element. This optically anisotropic laminate laminates a functional photocurable film onto the polarizing film for protection, adhesion, and imparting electro-optical properties, etc. As a method for laminating a photocurable film onto a polarizing film, one example is 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.

[0011] In the process of forming a film by irradiating a polarizing film with light to polymerize a photocurable film in the above-described lamination method, when the photocurable film is directly irradiated, the polarizing film is exposed to the irradiation light transmitted through the photocurable film. When light is irradiated from the polarizing film side, the photocurable film is photopolymerized using the light transmitted through the polarizing film, thus the polarizing film is exposed to the irradiation light.

[0012] When the polarizing film is exposed to illumination light as described above, if the wavelength of the illumination light is equivalent to the wavelength at which the photopolymerization initiator of the polarizing film is sensitive, then after photopolymerization, the photopolymerization initiator remaining in the polarizing film will also undergo a second polymerization reaction within the polarizing film. If a second polymerization reaction occurs, the arrangement of the liquid crystal compounds and pigments immobilized along the optimal molecular orientation in the polarizing film will be disrupted, potentially leading to a decrease in the optical properties of the polarizing film, such as dichroism and transmittance.

[0013] In light of this, it is desirable to realize an optically anisotropic laminate that can maintain the high optical performance of the polarizing film in a laminated structure in which a photocurable film is stacked on top of the polarizing film.

[0014] The purpose of this invention is to provide an optical anisotropic laminate and an optical element that have anisotropic pigment films and photocurable films stacked together and can maintain the high optical performance of the anisotropic pigment films. Summary of the Invention

[0015] The problem the invention aims to solve

[0016] The inventors have discovered that the above-mentioned problem can be solved by ensuring that the maximum absorption wavelengths of the photopolymerization initiators contained in each anisotropic pigment film and photocurable film have an appropriate relationship.

[0017] That is, the present invention has the following aspects.

[0018] [1] An optically anisotropic laminate, wherein at least one photocurable film is laminated on an anisotropic pigment film.

[0019] The aforementioned anisotropic pigment film comprises a pigment, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0020] The aforementioned photocurable film comprises a curable resin and a photopolymerization initiator.

[0021] The maximum absorption wavelength λ0 of the photopolymerization initiator contained in the above anisotropic pigment film and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the above photocurable film satisfy the following equation (1).

[0022] The weight-average molecular weight (Mw) of the aforementioned curable resins exceeds 10,000.

[0023] λ0<λ1…(1).

[0024] [2] An optically anisotropic laminate, wherein at least one adhesive film is laminated on anisotropic pigment films.

[0025] The aforementioned anisotropic pigment film comprises a pigment, a polymerizable liquid crystal compound, and a photopolymerization initiator.

[0026] The aforementioned adhesive film contains a curable resin and a photopolymerization initiator.

[0027] The maximum absorption wavelength λ0 of the photopolymerization initiator contained in the above anisotropic pigment film and the maximum absorption wavelength λ1 of the photopolymerization initiator of the above adhesive film satisfy the following formula (1).

[0028] λ0<λ1…(1).

[0029] [3] According to the optical anisotropic laminate described in [1], at least one layer of the photocurable film is an adhesive film.

[0030] [4] According to the optical anisotropic laminate described in [1], at least one layer of the photocurable film is an outer coating film.

[0031] [5] According to the optical anisotropic laminate described in [2], at least one outer coating film is further laminated on the anisotropic pigment film.

[0032] [6] An optical anisotropic laminate according to any one of [1] to [5], wherein the difference between the above-mentioned λ1 and the above-mentioned λ0 is 5 nm or more.

[0033] [7] An optically anisotropic laminate according to any one of [1] to [6], wherein the curable resin is an acrylic resin having (meth)acryloyl groups.

[0034] [8] The optically anisotropic laminate according to [7], wherein the double bond equivalent of the acrylic resin is 0.1 to 10 mmol / g.

[0035] [9] An optically anisotropic laminate according to any one of [1] to [8], wherein the polymeric liquid crystal compound is a compound represented by the following formula (2),

[0036] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)

[0037] (In formula (2),)

[0038] -Q 1 Represents a hydrogen atom or a polymeric group;

[0039] -Q 2 Indicates a polymerizable group;

[0040] -R 1 -and-R 2 - Each represents a chain-like organic group independently;

[0041] -A 11 -and-A 13 - Represent independently the partial structures, divalent organic groups, or single bonds represented by the following formula (3);

[0042] -A 12 - represents a portion of the structure or a divalent organic group represented by the following formula (3);

[0043] -Y 1 -and-Y 2 - can represent single bonds, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-, respectively.

[0044] -A 11 -and-A 13 - One of them is a partial structure or a divalent organic group represented by the following formula (3);

[0045] k is 1 or 2;

[0046] When k is 2, there are 2 -Y 2 -A 13 - Choose either the same or different)

[0047] -Cy-X 2 -C≡CX 1 - …(3)

[0048] (In formula (3),)

[0049] -Cy- indicates a hydrocarbon cyclic group or a heterocyclic group;

[0050] -X 1- indicates -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0051] -X 2 - indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-)

[0052]

[10] An optically anisotropic laminate according to any one of [1] to [9], wherein the pigment is an azo dichromatic pigment.

[0053]

[11] An optically anisotropic laminate according to any one of [1] to

[10] , wherein the polymeric liquid crystal compound has a number (r) of ring structures. n1 The number of ring structures (r) possessed by the aforementioned pigments n2 The ratio of (r) n1 / r n2 The value ranges from 0.7 to 1.5.

[0054]

[12] An optical element having an optically anisotropic laminate as described in any of [1] to

[11] .

[0055] The effects of the invention

[0056] The optical anisotropic laminate of the present invention can maintain excellent optical performance, especially sufficient dichroism ratio and transmittance.

[0057] The optical element of the present invention comprises such an optical anisotropic laminate of the present invention, and therefore has excellent optical performance, especially a good dichroism ratio and transmittance. Detailed Implementation

[0058] The embodiments of the present invention will now be described in detail. The present invention is not limited to the following embodiments and can be implemented with various modifications within its scope.

[0059] [Optical anisotropic laminate]

[0060] The optical anisotropic laminate of the present invention has at least one photocurable film (hereinafter, sometimes referred to as "the photocurable film of the present invention") or adhesive film (hereinafter, sometimes referred to as "the adhesive film of the present invention") laminated on an anisotropic pigment film (hereinafter, sometimes referred to as "the anisotropic pigment film of the present invention").

[0061] The anisotropic pigment film mentioned in this invention refers to a pigment film whose electromagnetic properties are anisotropic in any two of three directions selected from a total of three directions: the thickness direction of the anisotropic pigment film and any two directions in an arbitrary orthogonal in-plane three-dimensional coordinate system. Examples of electromagnetic properties include optical properties such as absorption and refraction; and electrical properties such as resistance and capacitance. The adhesive film mentioned in this invention is a film with adhesive and / or bonding properties, as described below, and is one type of photocurable film.

[0062] The total thickness (overall thickness) of the optical 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. By making the total thickness of the optical anisotropic laminate of the present invention at or above the above-mentioned lower limit, there is a tendency to make operation easier, and by making it at or below the above-mentioned upper limit, there is a tendency to make it thinner and lighter when used as an optical element.

[0063] The optical anisotropic laminate of the present invention, which comprises an anisotropic pigment film and a photocurable film, can also be laminated with a non-photopolymerizable functional film other than a photocurable film. Examples of non-photopolymerizable functional films include: non-photopolymerizable coating films that have protective (e.g., abrasion resistance, scratch resistance, stress relief, chemical resistance, gas resistance, water resistance, corrosion resistance), anti-seepage, planarization, easy adhesion, and mold release functions; adhesive films with adhesive and / or bonding properties; anti-reflective films; phase difference films; light control films that absorb light or reflect or scatter light; low-refractive-index films; high-refractive-index films; electrically insulating films; electrically conductive films; alignment films; and mold release films.

[0064] In addition, at least one layer of the photocurable film can be an adhesive film or an external coating film.

[0065] In the optical anisotropic laminate of the present invention, the anisotropic pigment film is typically manufactured by irradiating a film formed by wet deposition of the following anisotropic pigment film composition with active energy rays to cure it. The anisotropic pigment film in the optical anisotropic laminate of the present invention is a broad definition of anisotropic pigment film that includes both the uncured film before irradiation with active energy rays and the cured film after irradiation with active energy rays.

[0066] In the manufacturing process of anisotropic pigment films, at least a portion of the polymerizable liquid crystal compound polymerizes to form a polymer of the polymerizable liquid crystal compound, which is present in the anisotropic pigment film. In this invention, the polymer of the polymerizable liquid crystal compound in the anisotropic pigment film is also included and referred to as "polymerizable liquid crystal compound".

[0067] Furthermore, the photocurable film (including the adhesive film) of the optical anisotropic laminate of the present invention is generally manufactured by irradiating a film formed from the following photocurable film composition with active energy rays to cure it. The photocurable film in the optical anisotropic laminate of the present invention is a broadly defined photocurable film that includes both the uncured film before irradiation with active energy rays and the cured film after irradiation with active energy rays.

[0068] In the manufacturing process of a photocurable film, at least a portion of the curing resin polymerizes to become a polymer of the curing resin and is present in the photocurable film. In this invention, the polymer of the curing resin in the photocurable film is also included and referred to as "curing resin". Similarly, regarding the polyfunctional (meth)acrylate in the adhesive film described below, it also forms a cross-linked structure after film formation. It is not included in the adhesive film as a monomer of the polyfunctional (meth)acrylate. In this invention, substances that are incorporated into the reaction products in the reaction after film formation are also included and described as monomers before the reaction.

[0069] Furthermore, in the optical anisotropic laminate of the present invention, the adhesive film and the outer coating film are included as a type of photocurable film.

[0070] In the optical anisotropic laminate of the present invention, when the maximum absorption wavelength of the photopolymerization initiator contained in the anisotropic pigment film is set to λ0, and the maximum absorption wavelength of the photopolymerization initiator contained in the photocurable film (including the adhesive film) is set to λ1, λ0 and λ1 satisfy the following formula (1).

[0071] λ0<λ1 …(1)

[0072] λ0 and λ1 are both wavelengths above 250 nm that exhibit upward-convex inflection points in the absorption spectrum. Furthermore, in the case of multiple maximum absorption wavelengths, they become the maximum absorption wavelengths on the long wavelength side.

[0073] As long as equation (1) is satisfied, there are no particular limitations. The difference between λ1 and λ0 is preferably 5 nm or more, more preferably 10 nm or more, even more preferably 15 nm or more, and particularly preferably 30 nm or more. In addition, the difference is preferably 100 nm or less, more preferably 80 nm or less.

[0074] The reason why this invention can maintain excellent optical performance is as follows.

[0075] As a method for forming an optically anisotropic laminate, one possible step is to first photopolymerize an anisotropic pigment film to form a film, and then photopolymerize a photocurable film (including an adhesive film) on the anisotropic pigment film to form another film. To ensure that both the anisotropic pigment film and the photocurable film achieve a high degree of polymerization, it is ideal to irradiate with light of a wavelength suitable for the absorption wavelength of the photopolymerization initiator contained in each film. If the maximum absorption wavelength λ0 of the photopolymerization initiator in the anisotropic pigment film and the maximum absorption wavelength λ1 of the photopolymerization initiator in the photocurable film satisfy the relationship of equation (1), then the wavelength of light suitable for irradiating the photocurable film can be set to a wavelength longer than the wavelength of light suitable for irradiating the anisotropic pigment film. By lengthening the wavelength of light irradiating the photocurable film in this way, a wavelength range with lower sensitivity and lower energy density of the photopolymerization initiator contained in the anisotropic pigment film is achieved, thus suppressing the reaction of the residual photopolymerization initiator in the anisotropic pigment film. Therefore, after the photocurable film is formed, the molecular orientation of the polymeric liquid crystal compound and the pigment in the anisotropic pigment film is also maintained in the optimal state, and the anisotropic pigment film can maintain high optical performance.

[0076] It should be noted that the method for determining the maximum absorption wavelength of the photopolymerization initiator in this invention is not particularly limited, and methods such as using a spectrophotometer can be cited as examples.

[0077] Anisotropic pigment membrane

[0078] An anisotropic pigment film, as described above, is a pigment film whose electromagnetic properties are anisotropic in any two of three directions selected from the thickness direction of the anisotropic pigment film and any two directions in an arbitrary orthogonal in-plane three-dimensional coordinate system. Examples of electromagnetic properties include, for instance, optical properties such as absorption and refraction; and electrical properties such as resistance and capacitance.

[0079] Examples of films exhibiting optical anisotropy, such as absorption and refraction, include: linear polarizing films, circular polarizing films, and other polarizing films; phase retardation films and conductive anisotropic pigment films. These anisotropic pigment films are preferably used as polarizing films or conductive anisotropic pigment films, and more preferably as polarizing films.

[0080] In addition to functioning as a polarizing film that utilizes the anisotropy of light absorption to obtain linear polarized light, circular polarized light, elliptical polarized light, etc., the aforementioned anisotropic pigment films can also function as various anisotropic pigment films such as refractive anisotropy and conductive anisotropy by selecting the film forming process, substrate, and composition containing organic compounds (pigments or transparent materials).

[0081] When the optical anisotropic laminate of the present invention is used in a liquid crystal display or as a polarizing element in an anti-reflective film for an OLED, the orientation characteristics of the anisotropic pigment film can be expressed using the dichroism ratio. As long as the dichroism ratio is 8 or higher, it functions as a polarizing element; preferably 15 or higher, more preferably 20 or higher, even more preferably 25 or higher, particularly preferably 30 or higher, and even more preferably 40 or higher.

[0082] By setting the dichroism ratio to a value above the aforementioned lower limit, it becomes useful as an optical element, especially a polarizing element. A higher dichroism ratio is preferred.

[0083] When polarizing elements are used as antireflective films for OLEDs, even if the performance of peripheral materials such as retardation films is low, the characteristics of the antireflective film will be improved as long as the performance of the polarizing element is high. Therefore, as long as the performance of the polarizing element is high, the layer structure can be simplified, and even a thin film structure can easily exhibit sufficient functionality, making it suitable for applications involving deformation, including bending and flexing. In addition, the cost can be kept low.

[0084] When the pigment is uniformly oriented, the dichroic ratio (D) mentioned in this invention is expressed by the following formula.

[0085] D = Az / Ay

[0086] Here, Az is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is parallel to the orientation direction of the anisotropic pigment. Ay is the absorbance observed when the polarization direction of the light incident on the anisotropic pigment film is perpendicular to the polarization direction.

[0087] There are no particular restrictions as long as the same wavelength is used for each absorbance value, and any wavelength can be selected depending on the purpose. When indicating the degree of orientation of anisotropic pigment films, it is preferable to use the value obtained by correcting the specific wavelength region of 380nm to 780nm of the anisotropic pigment film using visual sensitivity, or the value at the maximum absorption wavelength in the visible region.

[0088] The anisotropic pigment film of the present invention preferably has a transmittance of 25% or more in the visible light wavelength region, more preferably 35% or more, and particularly preferably 40% or more. The transmittance need only be at the upper limit corresponding to the application. For example, when increasing the polarization, the transmittance is preferably 50% or less. By achieving a transmittance within the above range, it is useful as an optical element, especially as an optical element for an anti-reflective film composed of an anisotropic pigment film and a retardation film used in liquid crystal displays for color displays.

[0089] The thickness of the anisotropic pigment film, measured in terms of dry film thickness, is 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. By keeping the thickness of the anisotropic pigment film within the above range, there is a tendency to obtain uniform pigment orientation and uniform film thickness within the film.

[0090] The anisotropic pigment film of the present invention comprises a pigment, a polymerizable liquid crystal compound and a photopolymerization initiator, and may also contain other components (other additives described below).

[0091] (Photopolymerization initiator)

[0092] The photopolymerization initiator in the anisotropic pigment film of the present invention is a polymerization initiator that generates active free radicals through the action of light, and is a compound that can initiate the polymerization reaction of polymerizable liquid crystal compounds.

[0093] The maximum absorption wavelength λ0 of the photopolymerization initiator contained in the anisotropic pigment film is not particularly limited, as long as it satisfies formula (1), preferably 260 nm or more, more preferably 280 nm or more, and even more preferably 300 nm or more. Furthermore, 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. Within this range, the photopolymerization reaction proceeds sufficiently, resulting in an anisotropic pigment film with good curing properties.

[0094] Examples of usable photopolymerization initiators include: titanium ether derivatives; biimidazole derivatives; halomethylated oxadiazole derivatives; halomethyl-triazine derivatives; alkyl phenyl ketone derivatives; oxime ester derivatives; benzoin derivatives; benzophenone derivatives; acylphosphine oxide derivatives; iodonium salts; sulfonium salts; anthraquinone derivatives; thioxanthone derivatives; acridine derivatives; phenazine derivatives; anthrone derivatives; benzoyl carbamate derivatives; ketone sulfone derivatives; and organic peroxides.

[0095] Among these photopolymerization initiators, alkyl phenyl ketone derivatives, oxime ester derivatives, bimidazole derivatives, and thioxanone derivatives are more preferred in order to obtain films with high curing degree through sufficient photopolymerization reaction.

[0096] Specifically, examples of titanium bis(cyclopentadienyl)titanium 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-(pyrrole-1-yl)phenyl]titanium, etc.

[0097] Examples of biimidazole derivatives include: 2-(2'-chlorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-chlorophenyl)-4,5-bis(3'-methoxyphenyl)imidazolium dimer, 2-(2'-fluorophenyl)-4,5-diphenylimidazolium dimer, 2-(2'-methoxyphenyl)-4,5-diphenylimidazolium dimer, 2-(4'-methoxyphenyl)-4,5-diphenylimidazolium dimer, etc.

[0098] Examples of halomethylated oxadiazole derivatives include: 2-(2-benzofuranyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-[2-(2-benzofuranyl)vinyl]-5-trichloromethyl-1,3,4-oxadiazole, 2-trichloromethyl-5-furanyl-1,3,4-oxadiazole, 2-phenyl-5-trichloromethyl-1,3,4-oxadiazole, 2-(1-naphthyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-(2-naphthyl)-5-trichloromethyl-1,3,4-oxadiazole, 2-styryl-5-trichloromethyl-1,3,4-oxadiazole, and 2-(4-methoxystyryl)-5-trichloromethyl-1,3,4-oxadiazole.

[0099] Examples of halomethyl-triazine derivatives include: 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-ethoxynaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-(4-ethoxycarbonylnaphthyl)-4,6-bis(trichloromethyl)-triazine, 2-[2-(4-methoxyphenyl)vinyl]-4,6-bis(trichloromethyl)-triazine, 2-(3,4-dimethoxyphenyl)-4,6-bis(trichloromethyl)-triazine, and 2-[2-(2-furanyl)vinyl]-4,6-bis(trichloromethyl)-triazine, etc.

[0100] Examples of alkyl phenyl ketone derivatives include: 2,2-diethoxyacetophenone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinylphenyl)butane-1-one, 2-dimethylamino-2-(4-methylbenzyl)-1-(4-morpholinylphenyl)butane-1-one, and 3,6-bis(2-methyl-2-morpholinylpropionyl)-9-octylcarbazole. Benzoyl dimethyl ketal, 2-hydroxy-2-methylphenylacetone, 1-hydroxycyclohexylphenyl ketone, 2-hydroxy-4'-(2-hydroxyethoxy)-2-methylphenylacetone, 2-hydroxy-1-{4-[4-(2-hydroxy-2-methylpropanoyl)benzyl]phenyl}-2-methylpropane-1-one, 2-hydroxy-2-methyl-1-(4-isopropylphenyl)propanone, 2-hydroxy-2-methyl-1-(4-dodecylphenyl)propanone, etc.

[0101] Examples of oxime ester derivatives include: 2-(benzoyloxyimino)-1-[4-(phenylthio)phenyl]-1-octanone, O-acetyl-1-[6-(2-methylbenzoyl)-9-ethyl-9H-carbazole-3-yl] acetoketone oxime, (9-ethyl-6-nitrocarbazole-3-yl)-[2-methyl-4-(3-methoxyprop-2-acyloxy)phenyl]-methyleneamino ester, Japanese Patent Application Publication No. 2000-80068, Japanese Patent Application Publication No. 2006-36750, Japanese Patent Application Publication No. 2008-179611, and Japanese Patent Application Publication No. 2. Oxime ester derivatives described in Japanese Patent Publication No. 011-132215, Japanese Patent Publication No. 2012-526185, International Publication No. 2008 / 078678, International Publication No. 2009 / 131189, International Publication No. 2012 / 045736, International Publication No. 2012 / 068879, International Publication No. 2013 / 165207, International Publication No. 2014 / 121701, International Publication No. 2016 / 036910, International Publication No. 2017 / 030005, and International Publication No. 2018 / 097580, etc.

[0102] Examples of benzoin derivatives include: benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin phenyl ether, benzoin isobutyl ether, benzoin isopropyl ether, etc.

[0103] Examples of benzophenone derivatives include: benzophenone, Mischel 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, etc.

[0104] Examples of acylphosphine oxide derivatives include: 2,4,6-trimethylbenzoyl diphenylphosphine oxide, bis(2,6-dimethoxybenzoyl)-2,4,4-trimethylpentylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, and ethyl(2,4,6-trimethylbenzoyl)phenylphosphine ester.

[0105] Examples of iodonium salts include: diphenyliodonium tetra(pentafluorophenyl)borate, diphenyliodonium hexafluorophosphate, diphenyliodonium hexafluoroantimonate, di(4-nonylphenyl)iodonium hexafluorophosphate, and 4-(methylphenyl)[4-(2-methylpropyl)phenyl]iodonium hexafluorophosphate.

[0106] Examples of sulfonium salts include: triphenylsulfonium hexafluorophosphate, triphenylsulfonium hexafluoroantimonate, triphenylsulfonium tetra(pentafluorophenyl)borate, diphenyl[4-(phenylthio)phenyl]sulfonium hexafluorophosphate, 4,4'-bis[diphenyldihydrosulfo]diphenyl sulfide bishexafluorophosphate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrosulfo]diphenyl sulfide bishexafluoroantimonate, 4,4'-bis[bis(β-hydroxyethoxy)phenyldihydrosulfo]diphenyl sulfide bishexafluorophosphate, 7-[bis(p-toluyl)dihydrosulfo]-2-isopropylthioxanthone hexafluoroantimonate, 7- [Di(p-toluyl)dihydrothio]-2-isopropylthioxanthone tetra(pentafluorophenyl)borate, 4-phenylcarbonyl-4'-diphenyldihydrothio-diphenyl sulfide hexafluorophosphate, 4-(p-tert-butylphenylcarbonyl)-4'-diphenyldihydrothio-diphenyl sulfide hexafluoroantimonate, 4-(p-tert-butylphenylcarbonyl)-4'-di(p-toluyl)dihydrothio-diphenyl sulfide tetra(pentafluorophenyl)borate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium hexafluorophosphate, tris[4-(4-acetylphenyl)thiophenyl]sulfonium tetra(pentafluorophenyl)borate, etc.

[0107] Anthraquinone derivatives include: 2-methylanthraquinone, 2-ethylanthraquinone, 2-tert-butylanthraquinone, 1-chloroanthraquinone, etc.

[0108] 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.

[0109] Examples of acridine derivatives include: 9-phenylacridine, 9-(p-methoxyphenyl)acridine, 1,5-bis(9-acridyl)pentane, and 1,7-bis(9-acridyl)heptane.

[0110] Examples of phenazine derivatives include 9,10-dimethylbenzophenazine.

[0111] Examples of anthrone derivatives include benzoanthrone.

[0112] Examples of benzoyl carbamate derivatives include methyl benzoate.

[0113] Examples of ketone sulfone derivatives include 1-[4-[(4-benzoylphenyl)thio]phenyl]-2-methyl-2-[(4-methylphenyl)sulfonyl]-1-propanone, etc.

[0114] Examples of organic peroxides include: 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2-(1-tert-butylperoxy-1-methylethyl)-9H-thioxanth-9-one, triazine peroxide derivatives, etc.

[0115] A single photopolymerization initiator can be used alone, or two or more can be used in combination. When using multiple photopolymerization initiators, as long as the film contains a photopolymerization initiator that satisfies formula (1), the maximum absorption wavelength of the combined photopolymerization initiators is not limited to formula (1).

[0116] Commercially available products can also be used as photopolymerization initiators.

[0117] Commercially available products include, for example: Omnicat (registered trademark, hereinafter the same) 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 and DETX-S; UVI-6992 (manufactured by Dow Chemical Co., Ltd.); ADEKA ARKLS (registered trademark) SP-150, SP-152, 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 (DKSH (Manufactured by 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, TRONLYTR-PBG-345 (manufactured by Changzhou TRONLY NEW ELECTRONIC MATERIALS CO.LTD); PERDUAL (registered trademark) TA-30G, TA-70H, TX (manufactured by Nichiyu Co., Ltd.).

[0118] From the viewpoint of obtaining a fully polymerized anisotropic pigment film, the content of the photopolymerization initiator in the anisotropic pigment 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. Furthermore, from the viewpoint of not easily disrupting the orientation of the polymerizable liquid crystal compound, the content is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, further preferably 8 parts by mass or less, and particularly preferably 3 parts by mass or less, relative to 100 parts by mass of the polymerizable liquid crystal compound.

[0119] Polymerization accelerators, polymerization aids, etc., can also be used in combination with photopolymerization initiators as needed. Examples of polymerization accelerators and polymerization aids used include: amine compounds such as triethanolamine, N-methyldiethanolamine, ethyl 4-dimethylaminobenzoate, 2-(dimethylamino)ethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, octyl 4-dimethylaminobenzoate, and N-(2-hydroxyethyl)-N-methyl-p-toluidine; heterocyclic thiol compounds such as 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, and 2-mercaptobenzimidazole; and aliphatic multifunctional thiol compounds such as pentaerythritol tetra(3-mercaptobutyrate), 1,4-bis(3-mercaptobutyryloxy)butane, 1,3,5-tris(3-mercaptobutyryloxyethyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, and trimethylolpropane tri(3-mercaptobutyrate).

[0120] Polymerization accelerators and polymerization aids can be used alone or in combination of two or more.

[0121] To improve sensor sensitivity, sensitizing pigments and other sensitizers may be used in combination as needed.

[0122] Sensitized pigments are selected according to the appropriate wavelength of the exposure light source. Examples include: xanthannaphthalene-based pigments described in Japanese Patent Application Publications No. 4-221958 and 4-219756; heterocyclic coumarin-based pigments described in Japanese Patent Application Publications No. 3-239703 and 5-289335; 3-ketocoumarin-based pigments described in Japanese Patent Application Publications No. 3-239703 and 5-289335; pyrrole methylene-based pigments described in Japanese Patent Application Publications No. 6-19240; and Japanese Patent Application Publications No. 47-2528 and 54-155292. Pigments having a dialkylaminobenzene skeleton, as described in Japanese Patent Publication No. 45-37377, Japanese Patent Publication No. 48-84183, Japanese Patent Publication No. 52-112681, Japanese Patent Publication No. 58-15503, Japanese Patent Publication No. 60-88005, Japanese Patent Publication No. 59-56403, Japanese Patent Publication No. 2-69, Japanese Patent Publication No. 57-168088, Japanese Patent Publication No. 5-107761, Japanese Patent Publication No. 5-210240, and Japanese Patent Publication No. 4-288818.

[0123] Other sensitizers include the aforementioned benzophenone derivatives and thioxanone derivatives. Furthermore, other sensitizers include anthracene derivatives, phenothiazine derivatives, and perylene derivatives.

[0124] Examples of anthracene derivatives include: anthracene, 9,10-diethoxyanthracene, and 9,10-diebutoxyanthracene.

[0125] Examples of phenothiazine derivatives include: phenothiazine, 10-methylphenothiazine, 10-phenylphenothiazine, 2-methoxyphenothiazine, 2-chlorophenothiazine, and 2-acetylphenothiazine.

[0126] Examples of perylene derivatives include: perylene, 2,5,8,11-tetratert-butylperylene, etc.

[0127] Sensitized pigments and other sensitizers can be used alone or in combination of two or more.

[0128] (pigment)

[0129] In this invention, a pigment is a substance or compound that absorbs at least a portion of the wavelengths in the visible light region (380 nm to 780 nm).

[0130] Dichroic pigments can be cited as examples of pigments that can be used in this invention. A dichroic pigment is a pigment that has the property that the absorbance along the long axis of the molecule differs from the absorbance along the short axis. The pigment may or may not be liquid crystal soluble. Liquid crystal soluble means that it exhibits a liquid crystal phase at any temperature.

[0131] Examples of pigments contained in the anisotropic pigment film of the present invention include: azo pigments, quinone pigments (including naphthoquinone pigments, anthraquinone pigments, etc.), violet pigments, anthocyanin pigments, phthalocyanine pigments, indigo pigments, and fused polycyclic pigments (including perylene pigments, oxazine pigments, acridine pigments, etc.). Among these pigments, azo pigments are preferred in order to achieve a large molecular length-to-short axis ratio and a high molecular arrangement in the anisotropic pigment film.

[0132] Azo pigments refer to pigments having at least one azo group (-N=N-). From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, hue, and ease of manufacture, the number of azo groups in one molecule is preferably 1 or more, more preferably 2 or more, more preferably 6 or less, more preferably 4 or less, and even more preferably 3 or less.

[0133] As azo pigments, for example, compounds represented by formula (A) can be listed.

[0134] R 11 -D 1 -N=N-(D 2 -N=N)pD 3 -R 12 …(A)

[0135] In formula (A),

[0136] D 1 D 2 and D 3 Each can be independently represented as a phenylene group that may have substituents, a naphthylene group that may have substituents, or a divalent heterocyclic group that may have substituents;

[0137] p represents an integer from 0 to 4;

[0138] When p is an integer greater than 2, multiple D 2 Choose either the same or different;

[0139] R 11 and R 12 Each can be used to represent a monovalent organic group independently.

[0140] D 1 D 2 and D 3Each can be independently represented as a phenylene group that may have substituents, a naphthylene group that may have substituents, or a divalent heterocyclic group that may have substituents.

[0141] As for the substitution position of the phenylene group, 1,4-phenylene is preferred due to the high linearity of the molecule.

[0142] As for the substitution position of the naphthyl group, 1,4-naphthyl or 2,6-naphthyl is preferred due to the high linearity of the molecule.

[0143] The divalent heterocyclic group is preferably a heterocyclic group with 3 or more and 14 or less carbon atoms forming the ring, more preferably 10 or less. It is particularly preferred to be a monocyclic or bicyclic heterocyclic group.

[0144] The atoms other than carbon that constitute the divalent heterocyclic group can be selected from at least one of nitrogen, sulfur, and oxygen atoms. In the case where the heterocyclic group has multiple atoms other than carbon that constitute the ring, these atoms may be the same or different.

[0145] As divalent heterocyclic groups, specific examples include: pyridinediyl, quinolinediyl, isoquinolinediyl, thiazolediyl, benzothiazolediyl, thienothiazolediyl, thienothienodiyl, benzimidazolinonediyl, benzofurandiyl, phthalimidediyl, oxazolediyl, benzooxazolediyl, etc.

[0146] As D 1 D 2 and D 3 The phenylene, naphthylene, and divalent heterocyclic groups in the amino group may optionally contain substituents, such as: alkyl groups having 1 to 4 carbon atoms; alkoxy groups having 1 to 4 carbon atoms, such as methoxy, ethoxy, and butoxy; fluoroalkyl groups having 1 to 4 carbon atoms, such as trifluoromethyl; cyano; nitro; hydroxyl; halogen atom; substituted or unsubstituted amino groups, such as amino, diethylamino, and pyrrolidinyl. Here, a substituted amino group refers to an amino group having one or two alkyl groups having 1 to 4 carbon atoms, or an amino group having two substituted alkyl groups bonded together to form an alkane diene having 2 to 8 carbon atoms. An unsubstituted amino group is -NH2. Examples of alkyl groups having 1 to 4 carbon atoms that are substituted amino groups include methyl, ethyl, and butyl. Examples of alkane dimethyl groups with 2 to 8 carbon atoms include: ethylene, propane-1,3-dimethyl, butane-1,3-dimethyl, butane-1,4-dimethyl, pentane-1,5-dimethyl, hexane-1,6-dimethyl, heptane-1,7-dimethyl, octane-1,8-dimethyl, etc.

[0147] In terms of the high linearity of molecules, D 1 D 2 and D 3When the phenylene, naphthylene, and divalent heterocyclic groups are unsubstituted or substituted, they are preferably substituted with methyl, methoxy, hydroxyl, fluorine, chlorine, dimethylamino, pyrrolyl, or piperidinyl groups.

[0148] p represents an integer from 0 to 4. From the viewpoints of solubility in solvents, compatibility with liquid crystal compounds, color tone, and ease of manufacture, p is preferably 1 or more, preferably 4 or less, and more preferably 3 or less.

[0149] R 11 and R 12 Each can be used to represent a monovalent organic group independently.

[0150] As R 11 and R 12 Monovalent organic groups in the group can include: hydrogen atoms; alkyl groups with 1 to 20 carbon atoms that may have branches; alicyclic alkyl groups with 1 to 20 carbon atoms; alkoxy groups with 1 to 20 carbon atoms such as methoxy, ethoxy, and butoxy; fluoroalkyl groups with 1 to 20 carbon atoms such as trifluoromethyl; cyano; nitro; hydroxyl; halogen atoms; substituted or unsubstituted amino groups such as amino, diethylamino, and pyrrolidinyl; carboxyl; alkyloxycarbonyl groups with 1 to 20 carbon atoms such as butoxycarbonyl; vinyl groups with 1 to 20 carbon atoms... 20-membered alkenyl group; 2-(4-butylphenyl)vinyl and other alkylphenyl alkenyl groups; carbamoyl group; butylcarbamoyl group and other alkylcarbamoyl groups having branches of 1 to 20 carbon atoms; aminosulfonyl group; butylaminosulfonyl group and other alkylaminosulfonyl groups having branches of 1 to 20 carbon atoms; butylcarbonylamino group and other acylamino group having branches of 1 to 20 carbon atoms; butylcarbonyloxy group and other acyloxy group having branches of 1 to 20 carbon atoms; sulfanyl group; butylthio group and other alkylthio group having branches of 1 to 20 carbon atoms; R in the following liquid crystal compounds 1 and R 2 A substituted amino group is a chain-like organic group containing polymerizable groups. The term "substituted amino" refers to an amino group having one or two branched alkyl groups of 1 to 20 carbon atoms, or an amino group having two substituted alkyl groups bonded together to form an alkane dieny of 2 to 20 carbon atoms. An unsubstituted amino group is -NH₂. Examples of substituted alkyl groups of 1 to 20 carbon atoms include methyl, ethyl, and butyl. Examples of alkane dieny groups of 2 to 20 carbon atoms include: ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, and octane-1,8-diyl.

[0151] As R 11 and R 12Examples include: hydrogen atoms, chain groups, aliphatic organic groups (“aliphatic organic groups” include both chain-like and cyclic types), and aliphatic organic groups in which a portion of the carbon is replaced by nitrogen and / or oxygen (“aliphatic organic groups in which a portion of the carbon is replaced by nitrogen and / or oxygen” include both chain-like and cyclic types, and where a portion of the aliphatic organic group's methyl group is replaced by a hydroxyl group, a side oxygen group (=O), an amino group, an imino group, etc.). As one method, as R 11 and R 12 Preferably, it is a hydrogen atom or a chain-like group. Alternatively, it is a hydrogen atom or an aliphatic organic group. Yet another way, it is a hydrogen atom or an aliphatic organic group in which a portion of the carbon atom is replaced by a nitrogen atom and / or an oxygen atom.

[0152] Examples of chain-like groups include: alkyl groups having branches of 1 to 20 carbon atoms; alkoxy groups having branches of 1 to 20 carbon atoms; fluoroalkyl groups having branches of 1 to 20 carbon atoms; substituted or unsubstituted amino groups (a substituted amino group is an amino group having one or two alkyl groups having branches of 1 to 20 carbon atoms. An unsubstituted amino group is -NH2); carboxyl groups; alkyloxycarbonyl groups having branches of 1 to 20 carbon atoms; carbamoyl groups; alkylcarbamoyl groups having branches of 1 to 20 carbon atoms; aminosulfonyl groups; alkylaminosulfonyl groups having branches of 1 to 20 carbon atoms; acylamino groups having branches of 1 to 20 carbon atoms; acyloxy groups having branches of 1 to 20 carbon atoms; thio groups; alkylthio groups having 1 to 20 carbon atoms, etc.

[0153] Examples of aliphatic organic groups include: alkyl groups with 1 to 20 carbon atoms that can have branches, and alkyl groups with 1 to 20 carbon atoms that are alicyclic.

[0154] Aliphatic organic groups in which a portion of a carbon atom is replaced by a nitrogen atom and / or an oxygen atom can be listed as follows: alkoxy groups having 1 to 20 carbon atoms that may have branches; substituted or unsubstituted amino groups; carboxyl groups; alkyloxycarbonyl groups having 1 to 20 carbon atoms that may have branches; carbamoyl groups; alkylcarbamoyl groups having 1 to 20 carbon atoms that may have branches; acylamino groups having 1 to 20 carbon atoms that may have branches; acyloxy groups having 1 to 20 carbon atoms, etc. The substituted amino group refers to an amino group having one or two alkyl groups having 1 to 20 carbon atoms that may have branches, or an amino group having two substituted alkyl groups bonded together to form an alkane diene having 2 to 20 carbon atoms. Unsubstituted amino groups are -NH2. Alkyl groups having 1 to 20 carbon atoms that are substituted amino groups can be listed as methyl, ethyl, and butyl, etc. Examples of alkane dimethyl groups with 2 to 20 carbon atoms include: ethylene, propane-1,3-diyl, butane-1,3-diyl, butane-1,4-diyl, pentane-1,5-diyl, hexane-1,6-diyl, heptane-1,7-diyl, octane-1,8-diyl, etc.

[0155] In terms of the high linearity of molecules, as R 11 and R 12 Preferably, each of the following is independently substituted with a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, such as butyl, pentyl, hexyl, heptyl, or octyl; an alkoxy group having 1 to 10 carbon atoms, such as butoxy, pentoxy, hexoxy, heptoxy, or octoxy; or a diethylamino, pyrrolidinyl, or piperidinyl group. Furthermore, R from the following liquid crystal compounds is also preferred. 1 and R 2 The preferred type is the chain-like organic group with polymerizable groups.

[0156] The pigment contained in the anisotropic pigment film of the present invention is not particularly limited, and known pigments may also be used.

[0157] As well-known pigments, examples include the pigments (dichroic pigments, dichroic dyes) described in the aforementioned patent document 1, Japanese Patent No. 5982762, Japanese Patent Application Publication No. 2017-025317, and Japanese Patent Application Publication No. 2014-095899.

[0158] Specifically, the following pigments may be listed, but are not limited to these.

[0159]

[0160]

[0161]

[0162]

[0163] The molecular weight of the pigment contained in the anisotropic pigment film of the present invention is preferably 300 or more, more preferably 350 or more, even more preferably 380 or more, preferably 1500 or less, more preferably 1200 or less, and even more preferably 1000 or less. Specifically, the molecular weight of the pigment contained in the anisotropic pigment film of the present invention is preferably 300 to 1500, more preferably 350 to 1200, and even more preferably 380 to 1000.

[0164] The content of the pigment (dichroic pigment) in the anisotropic pigment film is preferably 0.01 parts by mass or more, more preferably 0.05 parts by mass or more, more 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 pigment film. Specifically, the content of the pigment (dichroic pigment) in the anisotropic pigment film is, for example, 0.01 to 50 parts by mass, preferably 0.05 to 30 parts by mass, more preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the anisotropic pigment film. If the content of the pigment (dichroic pigment) is within the above range, there is a tendency to polymerize the polymerizable liquid crystal compound while maintaining a high orientation in the anisotropic pigment film of the present invention. If the content of the pigment (dichroic pigment) is above the above lower limit, there is a tendency to obtain sufficient light absorption, thereby obtaining sufficient polarization performance. If the content of pigment (dichroic pigment) is below the above-mentioned upper limit, there is a tendency to easily suppress the orientation of liquid crystal molecules.

[0165] The anisotropic pigment membrane of the present invention may contain only one pigment or two or more pigments.

[0166] (polymeric liquid crystal compound)

[0167] In this invention, liquid crystal compound refers to a substance that exhibits a liquid crystal state. Specifically, as described on pages 1 to 28 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000), it refers to a compound that does not directly transform from crystal to liquid, but rather becomes liquid after passing through an intermediate state exhibiting the properties of both crystal and liquid.

[0168] The polymerizable liquid crystal compound contained in the anisotropic pigment film of the present invention is a liquid crystal compound having the following polymerizable groups.

[0169] In polymerizable liquid crystal compounds, polymerizable groups can be positioned at any position within the liquid crystal compound molecule, but from the viewpoint of ease of polymerization, polymerizable groups are preferably substituted at the ends of the liquid crystal compound molecule.

[0170] In a polymerizable liquid crystal compound, there may be more than one polymerizable group within the liquid crystal compound molecule. In the case of two or more such groups, from the viewpoint of ease of polymerization, it is preferable that they are respectively present at both ends of the liquid crystal compound molecule.

[0171] The polymerizable liquid crystal compound is preferably a compound with carbon-carbon triple bonds within the liquid crystal compound molecule. When it is a compound with carbon-carbon triple bonds, these carbon-carbon triple bonds can undergo rotational motion and can become the nucleus of the liquid crystal molecule. This increases the molecular mobility and strengthens the intermolecular interactions between liquid crystal molecules or with compounds such as pigment molecules that have a π-conjugation system, thus increasing the molecular orientation.

[0172] The polymeric liquid crystal compound contained in the anisotropic pigment film of the present invention is not particularly limited, and liquid crystal compounds having polymeric groups can be used.

[0173] For example, as a polymerizable liquid crystal compound contained in the anisotropic pigment film of the present invention, the following compound represented by formula (2) can be listed (hereinafter, sometimes referred to as "polymerizable liquid crystal compound (2)").

[0174] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2 …(2)

[0175] (In formula (2),)

[0176] -Q 1 Represents a hydrogen atom or a polymeric group;

[0177] -Q 2 Indicates a polymerizable group;

[0178] -R 1 -and-R 2 - Each represents a chain-like organic group independently;

[0179] -A 11 -and-A 13 - Represent independently the partial structures, divalent organic groups, or single bonds represented by the following formula (3);

[0180] -A 12 - represents a portion of the structure or a divalent organic group represented by the following formula (3);

[0181] -Y 1 -and-Y 2 - can represent single bonds, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-, respectively.

[0182] -A 11 -and-A 13 - One of them is a partial structure or a divalent organic group represented by the following formula (3);

[0183] k is 1 or 2;

[0184] When k is 2, there are 2 -Y 2 -A 13 - Choose either the same or different.

[0185] -Cy-X 2 -C≡CX 1 - …(3)

[0186] (In formula (3),)

[0187] -Cy- indicates a hydrocarbon cyclic group or a heterocyclic group;

[0188] -X 1 - indicates -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-;

[0189] -X 2 - indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

[0190] It should be noted that in -A 11 - In the case of a partial structure represented by equation (3), equation (2) can be either equation (2A) or equation (2B).

[0191] Q 1 -R 1 -Cy-X 2 -C≡CX 1 -Y 1 -A 12 -(Y 2 -A 13 ) k -R 2 -Q 2

[0192] …(2A)

[0193] Q 1 -R 1 -X 1 -C≡CX 2 -Cy-Y 1 -A12 -(Y 2 -A 13 ) k -R 2 -Q 2

[0194] …(2B)

[0195] In addition, in -A 12 - In the case of a partial structure represented by equation (3), equation (2) can be either equation (2C) or equation (2D).

[0196] Q 1 -R 1 -A 11 -Y 1 -Cy-X 2 -C≡CX 1 -(Y 2 -A 13 ) k -R 2 -Q 2

[0197] …(2C)

[0198] Q 1 -R 1 -A 11 -Y 1 -X 1 -C≡CX 2 -Cy-(Y 2 -A 13 ) k -R 2 -Q 2

[0199] …(2D)

[0200] In addition, in -A 13 - In the case of a partial structure represented by equation (3), equation (2) can be either equation (2E) or equation (2F).

[0201] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -Cy-X 2 -C≡CX 1 ) k -R 2 -Q 2

[0202] …(2E)

[0203] Q 1 -R 1 -A 11 -Y 1 -A 12 -(Y 2 -X 1 -C≡CX 2 -Cy) k -R 2 -Q 2

[0204] …(2F)

[0205] Similarly, in -A 11 -、-A 12 -and-A 13 In the case where two or more of the structures represented by equation (3) are partial structures, the orientation of the partial structures represented by equation (3) can also be flipped independently.

[0206] As mentioned above, -A 11 -、-A 12 -and-A 13 - Each independently represents a partial structure or divalent organic group as shown in formula (3), in addition, -A 11 -and-A 13 - can also be a single key, but -A 11 -and-A 13 - Not both are single keys.

[0207] (-Cy-)

[0208] The hydrocarbon cyclic groups in -Cy- include both aromatic and non-aromatic hydrocarbon cyclic groups.

[0209] Aromatic hydrocarbon cyclic groups include non-linked aromatic hydrocarbon cyclic groups and linked aromatic hydrocarbon cyclic groups.

[0210] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or fused aromatic hydrocarbon ring, and its carbon number is preferably 6 to 20 for the reason that good molecular orientation is achieved through a appropriately sized nucleus. The carbon number of the non-linked aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of aromatic hydrocarbon rings include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, benzo[a]pyrene rings, etc. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, fluorene rings, etc.

[0211] The linking aromatic hydrocarbon cyclic group is a divalent group consisting of multiple monocyclic or fused aromatic hydrocarbon rings bonded by single bonds, with a connecting bond on the atom of the ring. For the reason that molecular orientation is good due to a suitable-sized nucleus, the number of carbon atoms in the monocyclic or fused ring is preferably 6 to 20. More preferably, the number of carbon atoms in the monocyclic or fused ring is 6 to 15. Examples of linking aromatic hydrocarbon cyclic groups include: a divalent group consisting of a monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms bonded by single bonds to a monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms, having a first connecting bond on the atom of the ring constituting the monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms, and having a second connecting bond on the atom of the ring constituting the monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms. Specifically, a biphenyl-4,4'-diyl group is an example of a linking aromatic hydrocarbon cyclic group.

[0212] As an aromatic hydrocarbon cyclic group, a non-linked aromatic hydrocarbon cyclic group is preferred for the reason that it optimizes the intermolecular interactions between liquid crystal compounds and thus improves molecular orientation.

[0213] Among these, the preferred aromatic hydrocarbon cyclic groups are divalent groups of benzene rings and naphthalene rings, and more preferably divalent groups of benzene rings (phenylene). 1,4-phenylene is preferred as the phenylene group. By using these groups as -Cy-, there is a tendency to obtain improved linearity and molecular orientation of the liquid crystal molecules.

[0214] Non-aromatic hydrocarbon cyclic groups include unlinked non-aromatic hydrocarbon cyclic groups and linked non-aromatic hydrocarbon cyclic groups.

[0215] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or fused non-aromatic hydrocarbon ring, and its carbon number is preferably 3 to 20 for the reason that the molecular orientation becomes good by having a suitable-sized nucleus. The carbon number of the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of non-aromatic hydrocarbon rings include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norcamphene ring, camphene ring, adamantane ring, tetrahydronaphthalene ring, bicyclic [2.2.2]octane ring, etc.

[0216] Non-linked non-aromatic hydrocarbon cyclic groups include alicyclic hydrocarbon cyclic groups that do not have unsaturated bonds as interatomic bonds constituting the non-aromatic hydrocarbon ring, and unsaturated non-aromatic hydrocarbon cyclic groups that have unsaturated bonds as interatomic bonds constituting the non-aromatic hydrocarbon ring. From the viewpoint of productivity, alicyclic hydrocarbon cyclic groups are preferred as non-linked non-aromatic hydrocarbon cyclic groups.

[0217] The non-aromatic hydrocarbon ring group is a divalent group consisting of multiple monocyclic or fused non-aromatic hydrocarbon rings bonded by single bonds, with connecting bonds on the atoms constituting the ring; or a divalent group consisting of 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 bonded by single bonds to monocyclic or fused non-aromatic hydrocarbon rings, with connecting bonds on the atoms constituting the ring.

[0218] For the reason that molecular orientation becomes good by using a nucleus of suitable size, the number of carbon atoms in a monocyclic or fused ring is preferably 3 to 20.

[0219] As a linking non-aromatic hydrocarbon ring group, examples include monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms bonded to monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms by a single bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and having a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Furthermore, examples include monocyclic or fused aromatic hydrocarbon rings having 3 to 20 carbon atoms bonded to monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms by a single bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms, and having a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0220] As a linking cyclic group to a non-aromatic hydrocarbon, examples include bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl.

[0221] As a non-aromatic hydrocarbon cyclic group, it is preferred to be a non-linked non-aromatic hydrocarbon cyclic group for the reason that it optimizes the intermolecular interactions between liquid crystal compounds and thus improves molecular orientation.

[0222] As a non-linked, non-aromatic hydrocarbon cyclic group, a divalent group of cyclohexane (cyclohexanediyl) is preferred, and cyclohexane-1,4-diyl is more preferred. By making -Cy- these groups, there is a tendency to obtain the effect of improved linearity and molecular orientation of liquid crystal molecules.

[0223] The heterocyclic groups in -Cy- include aromatic heterocyclic groups and non-aromatic heterocyclic groups.

[0224] Aromatic heterocyclic groups include non-linked aromatic heterocyclic groups and linked aromatic heterocyclic groups.

[0225] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or fused aromatic heterocyclic group, and its carbon number is preferably 4 to 20 for the reason that molecular orientation is good due to a suitable-sized nucleus. The carbon number of the non-linked aromatic heterocyclic group is more preferably 4 to 15.

[0226] Examples of aromatic heterocycles include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, isothiazole ring, oxadiazole ring, thiadiazole ring, triazole ring, indole ring, carbazole ring, pyrroloimidazol ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanolopyrrole ring, furanolofuran ring, thienofuran ring, thienothiazole ring, benzoisoxazole ring, benzoisothiazole ring, benzimidazole ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, borazolinite ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazolinone ring, azulene ring, etc.

[0227] The connecting aromatic heterocyclic group is a divalent group consisting of multiple monocyclic or fused aromatic heterocycles bonded by single bonds, with connecting bonds on the atoms constituting the rings. For the reason that molecular orientation is good due to a suitable-sized nucleus, the number of carbon atoms in the monocyclic or fused rings is preferably 4 to 20. The number of carbon atoms connecting the aromatic heterocyclic group is more preferably 4 to 15.

[0228] As a linking aromatic heterocyclic group, examples include a monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms in the first ring bonded to a monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms in the second ring bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms, and a divalent group having a second linking bond on the atom of the ring constituting the monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms.

[0229] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0230] The non-linked non-aromatic heterocyclic group is a monocyclic or fused non-aromatic heterocyclic divalent group, and its carbon number is preferably 4 to 20 for the reason that molecular orientation is good due to a suitable-sized nucleus. The carbon number of the non-linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0231] Examples of non-aromatic heterocycles that are monocyclic or fused non-aromatic heterocycles with 4 to 20 carbon atoms include: tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothioran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazolium ring, tetrahydrobenzimidazole ring, quinacrine ring, etc.

[0232] The non-aromatic heterocyclic group is a divalent group consisting of multiple monocyclic or fused non-aromatic heterocycles bonded by single bonds, forming a linking bond on the atoms constituting the ring. For the reason that molecular orientation is good due to a suitable-sized nucleus, the number of carbon atoms in the monocyclic or fused ring is preferably 4 to 20. The number of carbon atoms in the non-aromatic heterocyclic group is more preferably 4 to 15.

[0233] As a linking aromatic heterocyclic group, examples include monocyclic or fused non-aromatic heterocycles having 4 to 20 carbon atoms in the first ring and monocyclic or fused non-aromatic heterocycles having 4 to 20 carbon atoms in the second ring, which are bonded by a single bond, have a first linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms in the first ring and a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms in the second ring.

[0234] The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- can also be selected from -R. k -OH, -OR k -OC(=O)-R k -NH2, -NH-R k -N(R) k ')-R k -C(=O)-R k -C(=O)-OR k , -C(=O)-NH2, -C(=O)-NH-R k -C(=O)-N(R) k ')-R k -SH, -SR k It is substituted with one or more groups from the group consisting of trifluoromethyl, aminosulfonyl, carboxyl, sulfonyl, cyano, nitro, and halogen. Here, -R k and -R k Each can be used independently to represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0235] In terms of the high linearity of the molecular structure and the ease with which polymerizable liquid crystal compounds (2) can associate with each other and exhibit a liquid crystal state, the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in -Cy- are each preferably unsubstituted or substituted with methyl, methoxy, fluorine, chlorine, or bromine atoms, and more preferably unsubstituted.

[0236] In -Cy-, the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group may have the same or different substituents. In addition, the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group may be completely substituted, completely unsubstituted, or partially substituted and partially unsubstituted.

[0237] As for -Cy-, in terms of improving the molecular orientation of the polymerizable liquid crystal compound (2), a hydrocarbon cyclic group is preferred, and more preferably a phenylene or cyclohexane-diyl group. In terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), as for -Cy-, 1,4-phenylene or cyclohexane-1,4-diyl group is even more preferred, and 1,4-phenylene is particularly preferred.

[0238] -X 1 - represents -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. Among these, -X represents the linearity of the polymerizable liquid crystal compound (2) or its tendency to easily rotate around its short molecular axis. 1 - Examples of preferred compounds with relatively weak π-bond properties include -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH2O-, -OCH2-, -CH2S-, and -SCH2-. Among these, -C(=O)O-, -OC(=O)-, -CH2CH2-, -CH2O-, and -OCH2- are more preferred, and -X is even more preferred. 1 - can be -C(=O)O- or -OC(=O)-. Additionally, as another way, -X 1 - Preferably -CH2CH2-, -CH2O-, or -OCH2-.

[0239] -X 2 - indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

[0240] From the viewpoint of increasing the core of the polymerizable liquid crystal compound (2) and increasing the dichroism of the anisotropic pigment film, it is preferable to use a group with higher linearity to connect -Cy- and -C≡C-, specifically, as -X 2 - Preferably, it is a single bond or a π bond -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH=CH-, -C(=O)NH- or -NHC(=O)-, and for the sake of higher linearity, it is even more preferred to be a single bond.

[0241] -Q 1 and -Q 2 The polymerizable group in the image is a group having a partial structure capable of polymerization by light, heat, and / or radiation, and is a functional group or atomic group required to ensure the polymerization function. From the viewpoint of manufacturing anisotropic pigment films, this polymerizable group is preferably a photopolymerizable group.

[0242] As polymerizable groups, examples include acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, vinyl, ethoxy, ethynyl, 1,3-butadienyl, 1,3-butadienyloxy, ethylene oxide, oxetyl, glycidyl, glycidyloxy, styrene, styreneoxy, etc. Among these, acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, ethylene oxide, glycidyl, glycidyl, glycidyloxy, etc. are preferred; more preferably acryloyl, methacryloyl, acryloyloxy, methacryloyloxy, acryloylamino, methacryloylamino, glycidyl, glycidyl, glycidyloxy, etc.; and even more preferably acryloyloxy, methacryloyloxy, glycidyloxy, etc.

[0243] -R 1 -and-R 2 - The chain-like organic groups in - are divalent organic groups that do not contain the above-mentioned aromatic hydrocarbon rings, non-aromatic hydrocarbon rings, aromatic heterocycles, non-aromatic heterocycles, and other cyclic structures.

[0244] Examples of such chain-like organic groups include: -(alkylene)-, -O-(alkylene)-, -S-(alkylene)-, -NH-(alkylene)-, -N(alkyl)-(alkylene)-, -OC(=O)-(alkylene)-, and -C(=O)O-(alkylene)-.

[0245] Alkyl groups, including those with 1 to 25 carbon atoms, can be either straight-chain or branched. A portion of the carbon-carbon bond in an alkyl group may also be unsaturated. One or more methylene groups within an alkyl group may be derived from or derived from -O-, -S-, -NH-, or -N(R) groups. m The structures are substituted with -, -C(=O)-, -C(=O)-O-, -C(=O)-NH-, -CHF-, -CF2-, -CHCl-, and -CCl2-. Here, R... m It refers to a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0246] As for the alkylene groups in these chain-like organic groups, in terms of higher molecular linearity, a portion of the carbon in the alkylene group can be an unsaturated bond. In addition, one or more methylene groups contained in the alkylene group can also be structures with the above-mentioned group displacements, preferably straight-chain alkylene groups with 1 to 25 carbons.

[0247] The number of atoms in the main chain (the longest chain portion of the chain organic group) of the chain organic group is preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

[0248] As a chain-like organic group, -(CH2) is preferred. r -CH2-, -O-(CH2) r -CH2-、-(O) r1 -(CH2CH2O) r2 -(CH2) r3 -、-(O) r1 -(CH2) r2 -(CH2CH2O) r3 It should be noted that r in these formulas is an integer from 1 to 24, preferably an integer from 2 to 24, more preferably an integer from 4 to 19, and even more preferably an integer from 5 to 19. Furthermore, r1, r2, and r3 in these formulas each independently represent an integer, and the number of atoms in the main chain (referring to the longest chain portion of the chain-like organic group) is appropriately adjusted in a manner preferably 3 to 25, more preferably 5 to 20, and even more preferably 6 to 20.

[0249] -R 1 -and-R 2 - Preferably, -(alkylene)- or -O-(alkylene)-, respectively. As one embodiment, -R 1 -and-R 2 The chain-like organic group in - is -(alkylene)-, or, alternatively, -O-(alkylene)-.

[0250] In the case of -X as described in equations (2B) and (2E) above 1 - and -R 1 -or-X 1 - and -R 2 - Bonding case; in equation (2B) above -A 13 - is a single bond or in the above equation (2E) -A 11 - represents a single bond, and -R 1 -or-R 2 -and-Y 1 -or-Y 2 In the case of -bonding, with -X 1 -、-Y 1 -or-Y 2 -Directly bonded-R 1 -or-R 2 - Preferably -(alkylene)-.

[0251] Other than those mentioned above are not related to -X 1 -、-Y 1 -or-Y 2 -Directly bonded-R 1 -or-R 2 - Preferably -O-(alkylene)-.

[0252] -A 11 -、-A 12 -and-A 13 The divalent organic group in - is preferably represented by the following formula (4).

[0253] -Q 3 -…(4)

[0254] (In equation (4), Q) 3 (Indicates a hydrocarbon cyclic group or a heterocyclic group)

[0255] -Q 3 The hydrocarbon cyclic groups in - include aromatic hydrocarbon cyclic groups and non-aromatic hydrocarbon cyclic groups.

[0256] Aromatic hydrocarbon cyclic groups include non-linked aromatic hydrocarbon cyclic groups and linked aromatic hydrocarbon cyclic groups.

[0257] The non-linked aromatic hydrocarbon ring group is a divalent group of a monocyclic or fused aromatic hydrocarbon ring, and its carbon number is preferably 6 to 20 for the reason that good molecular orientation is achieved through a appropriately sized nucleus. The carbon number of the non-linked aromatic hydrocarbon ring group is more preferably 6 to 15. Examples of aromatic hydrocarbon rings include: benzene rings, naphthalene rings, anthracene rings, phenanthrene rings, perylene rings, tetraphenylbenzene rings, pyrene rings, benzo[a]pyrene rings, etc. Rings, triphenylene rings, acenaphthene rings, fluoranthene rings, fluorene rings, etc.

[0258] The linking aromatic hydrocarbon cyclic group is a divalent group consisting of multiple monocyclic or fused aromatic hydrocarbon rings bonded by single bonds, with a connecting bond on the atom of the ring. For good orientation through a appropriately sized nucleus, the monocyclic or fused ring preferably has 6 to 20 carbon atoms. More preferably, the linking aromatic hydrocarbon cyclic group has 6 to 15 carbon atoms. Examples of linking aromatic hydrocarbon cyclic groups include a divalent group consisting of a first monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms bonded by single bonds to a second monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms, having a first connecting bond on the atom of the first monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms, and a second connecting bond on the atom of the second monocyclic or fused aromatic hydrocarbon ring with 6 to 20 carbon atoms. Specifically, a biphenyl-4,4'-diyl linking aromatic hydrocarbon cyclic group can be cited.

[0259] As an aromatic hydrocarbon cyclic group, a non-linked aromatic hydrocarbon cyclic group is preferred for the reason that it optimizes the intermolecular interactions between liquid crystal compounds and thus improves molecular orientation.

[0260] Among these, the preferred aromatic hydrocarbon cyclic group is a divalent group of a benzene ring or a divalent group of a naphthalene ring, more preferably a divalent group of a benzene ring (phenylene). The preferred phenylene group is 1,4-phenylene. By making -Q... 3 - These bases tend to improve the linearity and molecular orientation of liquid crystal molecules.

[0261] Non-aromatic hydrocarbon cyclic groups include unlinked non-aromatic hydrocarbon cyclic groups and linked non-aromatic hydrocarbon cyclic groups.

[0262] The non-linked non-aromatic hydrocarbon ring group is a divalent group of a monocyclic or fused non-aromatic hydrocarbon ring, and its carbon number is preferably 3 to 20 for the reason that the molecular orientation becomes good by having a suitable-sized nucleus. The carbon number of the non-linked non-aromatic hydrocarbon ring group is more preferably 3 to 15. Examples of non-aromatic hydrocarbon rings include: cyclopropane ring, cyclobutane ring, cyclopentane ring, cyclohexane ring, cycloheptane ring, cyclooctane ring, cyclohexene ring, norcamphene ring, camphene ring, adamantane ring, tetrahydronaphthalene ring, bicyclic [2.2.2]octane ring, etc.

[0263] Non-linked non-aromatic hydrocarbon cyclic groups include alicyclic hydrocarbon cyclic groups that do not have unsaturated bonds as interatomic bonds constituting the non-aromatic hydrocarbon ring, and unsaturated non-aromatic hydrocarbon cyclic groups that have unsaturated bonds as interatomic bonds constituting the non-aromatic hydrocarbon ring. From the viewpoint of productivity, alicyclic hydrocarbon cyclic groups are preferred as non-linked non-aromatic hydrocarbon cyclic groups.

[0264] The non-aromatic hydrocarbon ring group is a divalent group consisting of multiple monocyclic or fused non-aromatic hydrocarbon rings bonded by single bonds, forming a connecting bond on the atoms constituting the ring; or it is a divalent group consisting of 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, bonded by single bonds to monocyclic or fused non-aromatic hydrocarbon rings, forming a connecting bond on the atoms constituting the ring.

[0265] For the reason that molecular orientation becomes good by using a nucleus of suitable size, the number of carbon atoms in a monocyclic or fused ring is preferably 3 to 20.

[0266] As a linking non-aromatic hydrocarbon ring group, examples include monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms bonded to monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms by a single bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms, and having a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms. Furthermore, examples include monocyclic or fused aromatic hydrocarbon rings having 3 to 20 carbon atoms bonded to monocyclic or fused non-aromatic hydrocarbon rings having 3 to 20 carbon atoms by a single bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused aromatic hydrocarbon ring having 3 to 20 carbon atoms, and having a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic hydrocarbon ring having 3 to 20 carbon atoms.

[0267] As a linker to a non-aromatic hydrocarbon cyclic group, examples include: bis(cyclohexane)-4,4'-diyl and 1-cyclohexylbenzene-4,4'-diyl.

[0268] As a non-aromatic hydrocarbon cyclic group, it is preferred to be a non-linked non-aromatic hydrocarbon cyclic group for the reason that it optimizes the intermolecular interactions between liquid crystal compounds and thus improves molecular orientation.

[0269] As a non-linked non-aromatic hydrocarbon cyclo group, it is preferably a divalent group of cyclohexane (cyclohexanediol), and as a cyclohexanediol, it is preferably cyclohexane-1,4-diol.

[0270] -Q 3 The heterocyclic groups in - include aromatic heterocyclic groups and non-aromatic heterocyclic groups.

[0271] The aromatic heterocyclic group comprises non-linked aromatic heterocyclic groups and linked aromatic heterocyclic groups.

[0272] The non-linked aromatic heterocyclic group is a divalent group of a monocyclic or fused aromatic heterocyclic group, and its carbon number is preferably 4 to 20 for the reason that molecular orientation is good due to a suitable-sized nucleus. The carbon number of the non-linked aromatic heterocyclic group is more preferably 4 to 15.

[0273] Examples of aromatic heterocycles include: furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrrole ring, pyrazole ring, imidazole ring, thiazole ring, oxadiazole ring, indole ring, carbazole ring, pyrroloimidazolium ring, pyrrolopyrazole ring, pyrrolopyrrole ring, thienopyrrole ring, thienothiophene ring, furanolopyrrole ring, furanolofuran ring, thienofuran ring, thienothiazole ring, benzoisoxazole ring, benzoisothiazole ring, benzoimidazolium ring, pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, borazine ring, quinoxaline ring, phenanthridine ring, quinazoline ring, quinazoline ketone ring, azulene ring, etc.

[0274] The connecting aromatic heterocyclic group is a divalent group consisting of multiple monocyclic or fused aromatic heterocycles bonded by single bonds, with connecting bonds on the atoms constituting the rings. For the reason that molecular orientation is good due to a suitable-sized nucleus, the number of carbon atoms in the monocyclic or fused rings is preferably 4 to 20. The number of carbon atoms connecting the aromatic heterocyclic group is more preferably 4 to 15.

[0275] As a linking aromatic heterocyclic group, examples include a monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms in the first ring bonded to a monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms in the second ring bond, having a first linking bond on the atom of the ring constituting the monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms, and a divalent group having a second linking bond on the atom of the ring constituting the monocyclic or fused aromatic heterocycle with 4 to 20 carbon atoms.

[0276] Non-aromatic heterocyclic groups include unlinked non-aromatic heterocyclic groups and linked non-aromatic heterocyclic groups.

[0277] The non-linked non-aromatic heterocyclic group is a monocyclic or fused non-aromatic heterocyclic divalent group, and its carbon number is preferably 4 to 20 for the reason that molecular orientation is good due to a suitable-sized nucleus. The carbon number of the non-linked non-aromatic heterocyclic group is more preferably 4 to 15.

[0278] Examples of non-aromatic heterocycles that are monocyclic or fused non-aromatic heterocycles with 4 to 20 carbon atoms include: tetrahydrofuran ring, tetrahydropyran ring, dioxane ring, tetrahydrothiophene ring, tetrahydrothioran ring, pyrrolidine ring, piperidine ring, dihydropyridine ring, piperazine ring, tetrahydrothiazole ring, tetrahydrooxazole ring, octahydroquinoline ring, tetrahydroquinoline ring, octahydroquinazoline ring, tetrahydroquinazoline ring, tetrahydroimidazolium ring, tetrahydrobenzimidazole ring, quinacrine ring, etc.

[0279] The non-aromatic heterocyclic group is a divalent group consisting of multiple monocyclic or fused non-aromatic heterocycles bonded by single bonds, forming a linking bond on the atoms constituting the ring. For the reason that molecular orientation is good due to a suitable-sized nucleus, the number of carbon atoms in the monocyclic or fused ring is preferably 4 to 20. The number of carbon atoms in the non-aromatic heterocyclic group is more preferably 4 to 15.

[0280] As a linking aromatic heterocyclic group, examples include monocyclic or fused non-aromatic heterocycles having 4 to 20 carbon atoms in the first ring and monocyclic or fused non-aromatic heterocycles having 4 to 20 carbon atoms in the second ring, which are bonded by a single bond, have a first linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms in the first ring and a second linking bond on the atom of the ring constituting the monocyclic or fused non-aromatic heterocycle having 4 to 20 carbon atoms in the second ring.

[0281] -Q 3 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - can also be selected from -R. n -OH, -OR n -OC(=O)-R n -NH2, -NH-R n -N(R) n ')-R n -C(=O)-R n -C(=O)-OR n , -C(=O)-NH2, -C(=O)-NH-R n -C(=O)-N(R) n ')-R n -SH, -SR n It is substituted with one or more groups from the group consisting of trifluoromethyl, aminosulfonyl, carboxyl, sulfonyl, cyano, nitro, and halogen. Here, -R n and -R n Each can be used independently to represent a straight-chain or branched alkyl group having 1 to 6 carbon atoms.

[0282] In terms of the high linearity of the molecular structure, the ease with which polymerizable liquid crystal compounds (2) associate with each other, and the tendency to exhibit a liquid crystal state, -Q 3 The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - are each preferably unsubstituted or substituted with methyl, methoxy, fluorine, chlorine, or bromine atoms, and more preferably unsubstituted.

[0283] -Q 3The aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group in - can have the same or different substituents. In addition, the aromatic hydrocarbon cyclic group, non-aromatic hydrocarbon cyclic group, aromatic heterocyclic group, and non-aromatic heterocyclic group can be completely substituted, completely unsubstituted, or partially substituted and partially unsubstituted.

[0284] -A 11 -、-A 12 -and-A 13 - The divalent organic groups in - can have the same or different substituents, -A 11 -、-A 12 -and-A 13 The divalent organic groups in - can be completely substituted, completely unsubstituted, or partially substituted and partially unsubstituted.

[0285] As -Q 3 -, preferably a hydrocarbon cyclic group, more preferably a phenylene or cyclohexane dimethyl group. In terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), as -Q 3 -, more preferably 1,4-phenylene, cyclohexane-1,4-diyl.

[0286] As -A 11 -、-A 12 -and-A 13 - a divalent organic group, preferably -Q 3 - is a hydrocarbon cyclic group, that is, as a divalent organic group, it is a hydrocarbon cyclic group. As a divalent organic group, it is more preferably phenylene or cyclohexane-1,4-dimethyl, and in terms of improving the linearity of the molecular structure of the polymerizable liquid crystal compound (2), it is even more preferably 1,4-phenylene or cyclohexane-1,4-dimethyl.

[0287] As the polymerizable liquid crystal compound (2), -A is preferred. 11 -、-A 12 -and-A 13 One of them is a partial structure represented by formula (3), and the other two are independently divalent organic groups, preferably -A. 11 -、-A 12 -and-A 13 - In formula (3), the -Cy- group of the partial structure is a hydrocarbon cyclic group, and it is particularly preferred that the divalent organic group is a hydrocarbon cyclic group. Further preferred is that the hydrocarbon cyclic group is 1,4-phenylene or cyclohexane-1,4-diyl. In addition, -A is preferred. 11 -and-A 13 One of them is cyclohexane-1,4-diyl.

[0288] Better - A 11 -and-A13 One of them is a partial structure represented by equation (3), and the other is -A 12 - is a divalent organic group. In this case, -A is preferred. 11 -and-A 13 The divalent organic group in - is cyclohexane-1,4-diyl, with -A being particularly preferred. 12 - is 1,4-phenylene.

[0289] -Y 1 -and-Y 2 - Represents, independently, a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-. Regarding the linearity of the polymerizable liquid crystal compound (2) and its tendency to easily rotate around its short molecular axis, -Y 1 -and-Y 2 - Each is preferably a single bond with a small π bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O)-, -CH2O-, -OCH2-, -CH2S- or -SCH2-, more preferably a single bond, -C(=O)O-, -OC(=O)-, -CH2CH2-, -CH2O- or -OCH2-.

[0290] In the case of equations (2A), (2C), (2D), and (2F) above, -X 1 -and-Y 1 -or-X 1 -and-Y 2 In the case of -bonding, with -X 1 -bonded-Y 1 -or with -X 1 -bonded-Y 2 - Preferably a single bond. -X 1 -and-Y 1 -and-Y 2 The other option is preferably -C(=O)O- or -OC(=O)-.

[0291] In the case of -X as described in equations (2B) and (2E) above 1 -Not with-Y 1 -and-Y 2 In the case of any of the - bonds, -X1 - Preferably -CH2CH2-, -CH2O-, or -OCH2-, -Y 1 -and-Y 2 - Preferably, both are -C(=O)O- or -OC(=O)-.

[0292] k is either 1 or 2. As one option, k is preferably 1. As another option, k is preferably 2.

[0293] When k is 2, each -Y 2 - Choose any two that are the same or different from each other, each -A 13 - You can choose to be the same as or different from each other.

[0294] As for the polymerizable liquid crystal compound (2), the preferred compound is one represented by the above formula (2A), (2B), (2E) or (2F) for the reason that the intermolecular interactions between the liquid crystal compounds are optimal and the molecular orientation becomes good as a core of suitable size.

[0295] (Specific examples of polymeric liquid crystal compounds)

[0296] As polymerizable liquid crystal compounds included in the anisotropic pigment film of the present invention, the following polymerizable liquid crystal compounds are specifically listed, but not limited to these. In the following exemplary formulas, C6H 13 It refers to the orthohexyl group. C5H 11 It refers to n-pentyl.

[0297]

[0298]

[0299]

[0300]

[0301]

[0302]

[0303]

[0304]

[0305]

[0306]

[0307]

[0308]

[0309]

[0310] The liquid crystal compound contained in the anisotropic pigment film of the present invention preferably includes a polymeric liquid crystal compound (2). The anisotropic pigment film of the present invention may contain only one polymeric liquid crystal compound, or may contain two or more in any combination and ratio.

[0311] The content of liquid crystal compounds in the anisotropic pigment film of the present invention (the sum of the contents of each compound when two or more liquid crystal compounds are used in combination) is preferably 50 parts by mass or more, more preferably 55 parts by mass or more, more preferably 99 parts by mass or less, and more preferably 98 parts by mass or less, relative to the anisotropic pigment film (100 parts by mass). If the content of liquid crystal compounds in the anisotropic pigment film is within the above range, there is a tendency to improve the orientation of liquid crystal molecules.

[0312] The anisotropic pigment film of the present invention may also contain one or more polymeric or non-polymeric liquid crystal compounds other than the polymeric liquid crystal compound (2). From the viewpoint of more effectively obtaining the effects of the present invention achieved by using the polymeric liquid crystal compound (2), the ratio of polymeric liquid crystal compound (2) in 100% by mass of the total amount of liquid crystal compounds contained in the anisotropic pigment 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.

[0313] From a process point of view, the isotropic phase of the polymerizable liquid crystal compound contained in the anisotropic pigment film of the present invention preferably appears at a temperature of 160°C or less, more preferably at 140°C or less, even more preferably at 115°C or less, and even more preferably at 110°C or less, and particularly preferably at 105°C or less.

[0314] Here, the isotropic phase emergence temperature refers to the phase transition temperature from liquid crystal to liquid and the phase transition temperature from liquid to liquid crystal. In this invention, it is preferable that at least one of these phase transition temperatures is below the aforementioned upper limit, and more preferably that both of these phase transition temperatures are below the aforementioned upper limit.

[0315] (Method for manufacturing polymeric liquid crystal compounds)

[0316] The polymerizable liquid crystal compound contained in the anisotropic pigment film of the present invention can be manufactured by combining known chemical reactions such as alkylation, esterification, amidation, etherification, IPSO substitution, and coupling reaction using a metal catalyst.

[0317] For example, the polymeric liquid crystal compound contained in the anisotropic pigment film of the present invention can be synthesized according to the methods described in the examples mentioned below or the methods described on pages 449 to 468 of the "Liquid Crystal Handbook" (Maruzen Co., Ltd., issued on October 30, 2000).

[0318] (The relationship between polymeric liquid crystal compounds and pigments)

[0319] The number (r) of ring structures of the polymeric liquid crystal compound contained in the anisotropic pigment film of the present invention n1 The number of ring structures possessed by the pigment (r) n2 The ratio of (r) n1 / r n2 There is no particular limitation, but 0.7 to 1.5 is preferred. The reason is that, from the viewpoint of easily improving the orientation of the anisotropic pigment film, in order to make the intermolecular interaction between liquid crystal molecules and pigment molecules stronger and to make it less likely for pigment molecules to hinder the association between liquid crystal molecules, it is preferable that the difference between the molecular length of the polymerizable liquid crystal compound and the molecular length of the pigment is small.

[0320] It should be noted that a fused ring consisting of two or more rings is referred to as a single ring structure.

[0321] Here, taking the compound represented by the above formula (A) as an example, the number of ring structures (r) is discussed. n2 The number of ring structures is D in equation (A). 1 D 2 and D 3 The sum, specifically, when p is 0, r n2 The value is 2; when p is 1, r n2 The value is 3; when p is 4, r n2 It is 6.

[0322] It should be noted that even with -R 11 and -R 12 The cyclic functional group is such as pyrrolidinyl or piperidinyl, -R 11 and -R 12 The ring structures included are not included in the number (r) of ring structures possessed by the compound represented by formula (A). n2 )middle.

[0323] The number of ring structures (r) of polymerizable liquid crystal compounds contained in anisotropic pigment films n1 The compound does not contain the ring structures (such as ethylene oxide rings or oxobutane rings) contained in the polymerizable groups of polymerizable liquid crystal compounds.

[0324] (Other additives)

[0325] The anisotropic pigment films of the present invention may further include, as needed, non-polymerizable liquid crystal compounds, thermal polymerization initiators, polymerization inhibitors, polymerization aids, polymerizable non-liquid crystal compounds, non-polymerizable non-liquid crystal compounds, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, organic and inorganic fillers, organic and inorganic nanosheets, organic and inorganic nanofibers, metal oxides, etc.

[0326] (Composition for anisotropic pigment films)

[0327] The anisotropic pigment film of the present invention can be formed using anisotropic pigment film composition (hereinafter, sometimes referred to as "anisotropic pigment film composition of the present invention").

[0328] The anisotropic pigment film composition of the present invention contains the pigments, polymerizable liquid crystal compounds, and photopolymerizable initiators listed in the anisotropic pigment films described above, and may also contain other additives mentioned above.

[0329] The anisotropic pigment film composition of the present invention may also contain solvents as needed.

[0330] There are no particular limitations on the solvents that can be used, as long as they can adequately disperse or dissolve the polymerizable liquid crystal compound, pigments, and other additives in the anisotropic pigment film composition. Examples include: alcohol solvents such as methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, and propylene glycol monomethyl ether; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, and ethyl lactate; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, and methyl isobutyl ketone; aliphatic hydrocarbon solvents such as pentane, hexane, and heptane; aromatic hydrocarbon solvents such as toluene and xylene; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; fluorinated solvents such as perfluorobenzene, perfluorotoluene, perfluorodehydronaphthalene, perfluoromethylcyclohexane, and hexafluoro-2-propanol; and chlorinated solvents such as chloroform, dichloromethane, chlorobenzene, and dichlorobenzene.

[0331] These solvents can be used in single or combined in combination.

[0332] The solvent is preferably a solvent that can dissolve the polymerizable liquid crystal compound and the pigment, and more preferably a solvent that can completely dissolve the polymerizable liquid crystal compound and the pigment. Furthermore, the solvent is preferably a solvent that is inert to the polymerization reaction of the polymerizable liquid crystal compound. Moreover, from the viewpoint of coating the anisotropic pigment film composition of the present invention described below, a solvent with a boiling point in the range of 50 to 200°C is preferred.

[0333] When the anisotropic pigment film composition of the present invention contains a solvent, the proportion of the solvent in the anisotropic pigment film composition relative to the total amount (100% by mass) of the anisotropic pigment film composition of the present invention is preferably 50 to 98% by mass. In other words, the content of solid components in the anisotropic pigment film composition of the present invention is preferably 2 to 50% by mass.

[0334] If the solid content in the anisotropic pigment film composition is below the above-mentioned upper limit, the viscosity of the anisotropic pigment film composition will not become too high, the thickness of the obtained anisotropic pigment film will become uniform, and the anisotropic pigment film will not easily become uneven.

[0335] The solid content of the composition for anisotropic pigment films can be determined by taking into account the thickness of the anisotropic pigment film to be manufactured.

[0336] The viscosity of the anisotropic pigment film composition of the present invention is not particularly limited, as long as a uniform film without thickness unevenness can be produced by the coating method described below. From the viewpoint of obtaining large-area thickness uniformity, coating speed and other productivity, and in-plane uniformity of optical properties, it is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0337] The method for manufacturing the anisotropic pigment film composition of the present invention is not particularly limited. For example, pigments, polymerizable liquid crystal compounds, photopolymerization initiators, solvents as needed, and other additives are mixed and stirred and shaken at 0 to 80°C to dissolve the pigments. In the case of poor solubility, homogenizers, bead mills, dispersers, etc., may also be used.

[0338] As a method for manufacturing the anisotropic pigment film composition of the present invention, a filtration step may also be included in order to remove foreign matter from the composition.

[0339] Regarding the anisotropic pigment film composition of the present invention, the composition obtained by removing the solvent from the anisotropic pigment film composition may or may not be a liquid crystal at any temperature, but preferably exhibits liquid crystal properties at any temperature.

[0340] Regarding the composition obtained by removing the solvent from the composition for anisotropic pigment films, from the viewpoint of the coating process described below, the temperature at which the isotropic phase appears is generally less than 200°C, preferably less than 160°C, more preferably less than 140°C, even more preferably less than 115°C, and even more preferably less than 110°C, and particularly preferably less than 105°C.

[0341] (Method for manufacturing anisotropic pigment films)

[0342] The anisotropic pigment film of the present invention is preferably manufactured using the anisotropic pigment film composition of the present invention and by a wet film-forming method.

[0343] The wet film-forming method mentioned in this invention refers to a method of coating anisotropic pigment film composition onto a substrate and orienting it using a certain method. Therefore, the anisotropic pigment film composition only needs to have fluidity and may or may not contain a solvent. From the viewpoint of viscosity during coating or film uniformity, it is preferable to include a solvent.

[0344] The orientation of liquid crystal compounds and pigments in anisotropic pigment films can be achieved during coating by shearing or during solvent drying. Alternatively, the liquid crystal compounds and pigments can be re-oriented by heating after coating and drying, allowing them to be oriented and stacked on the substrate. In wet film deposition methods, when anisotropic pigment film compositions are applied to the substrate, the pigments and liquid crystal compounds undergo self-association (molecular association states such as liquid crystal states) within the anisotropic pigment film composition, either during solvent drying or after the solvent is completely removed, resulting in a small area of ​​orientation. By applying an external field to this state, orientation can be achieved over a large area along a fixed direction, obtaining anisotropic pigment films with desired properties. This differs from methods that use a solution containing pigment to dye polyvinyl alcohol (PVA) films and then stretch them, where pigment orientation is achieved solely through a stretching process. Here, the term "external field" can include the effects of the alignment treatment layer applied to the substrate beforehand, such as shear force, magnetic field, electric field, and heat. These can be used individually or in combination. A heating process may also be applied as needed.

[0345] The process of applying the anisotropic pigment film composition to the substrate and forming the film, the process of applying an external field for orientation, and the process of drying the solvent can be performed sequentially or simultaneously.

[0346] Methods for applying anisotropic pigment films to a substrate using a composition in wet film deposition include, for example, coating methods, dip coating methods, LB film formation methods, and known printing methods. Furthermore, there are methods for transferring anisotropic pigment films obtained in the above manner to other substrates.

[0347] Among these, it is preferable to use a coating method to apply the anisotropic pigment film composition onto a substrate.

[0348] The orientation direction of anisotropic pigment films may also differ from the coating direction. In this invention, the orientation direction of anisotropic pigment films, for example, is the transmission axis (polarization axis) or absorption axis of polarized light if it is a polarizing film, and the fast axis or slow axis if it is a phase difference film.

[0349] There are no particular limitations on the method for obtaining anisotropic pigment films using the composition for coating anisotropic pigment films. Examples include: the method described on pages 253-277 of "Coating Engineering" by Yuji Harasaki (Asakura Shoten Co., Ltd., published March 20, 1971); the method described on pages 118-149 of "Creation and Application of Molecular Coordination Materials" edited by Kunihiro Ichimura (CMC Co., Ltd., published March 3, 1998); and methods for coating substrates with a high-low structure (which may also be pre-oriented) using methods such as slit coating, spin coating, spray coating, rod coating, roller coating, doctor blade coating, curtain coating, injection coating, and dip coating. Among these, slit coating or rod coating is preferred because it yields anisotropic pigment films with higher uniformity.

[0350] The slit-die coating method typically uses a slit-die coating machine that sprays out the coating liquid. Slit dies are disclosed, for example, in Japanese Patent Application Publication No. 2-164480, Japanese Patent Application Publication No. 6-154687, Japanese Patent Application Publication No. 9-131559, "Basic and Application of Dispersion, Coating and Drying" (2014, TECHNOSYSTEMS Co., Ltd., ISBN 9784924728707C 305), "Wet Coating Technology in Displays and Optical Components" (2007, Information Agency, ISBN 9784901677752), and "Precision Coating and Drying Technology in the Electronics Field" (2007, Technical Information Association, ISBN 9784861041389), etc. These well-known slit molds can be used to coat even flexible components such as films or tapes, and harder components such as glass substrates.

[0351] Examples of substrates for forming the anisotropic pigment film of the present invention include glass or triacetate, acrylic, polyester, polyimide, polyetherimide, polyetheretherketone, polycarbonate, cyclic olefin polymers, polyolefins, polyvinyl chloride, cellulose triacetate or carbamate films.

[0352] To control the orientation direction of the pigment, the substrate surface can be aligned using known methods described on pages 226-239 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., October 30, 2000), such as the rubbing method, the method of forming grooves (fine groove structures) on the surface of the alignment film, the method of using polarized ultraviolet light or polarized laser (photoalignment method), the alignment method based on LB film formation, and the alignment method based on tilted evaporation of inorganic materials. The rubbing method and the photoalignment method are particularly preferred. Materials used in the rubbing method include polyvinyl alcohol (PVA), polyimide (PI), epoxy resin, and acrylic resin. Materials used in the photoalignment method include polycinnamate, polyamic acid / polyimide, and azobenzene. When an alignment treatment layer is provided, it is believed that the liquid crystal compound and pigment are aligned due to the influence of the alignment treatment layer and the shear force applied to the anisotropic pigment film composition during coating.

[0353] There are no particular limitations on the method or interval for supplying the anisotropic pigment film composition when coating anisotropic pigment films. However, since the supply operation of the coating liquid becomes complicated and the coating film thickness varies at the start and stop of the coating liquid supply, it is ideal to continuously supply the anisotropic pigment film composition while coating when the thickness of the anisotropic pigment film is relatively thin.

[0354] The coating speed of the composition for coating anisotropic pigment films is typically 0.001 m / min or more, preferably 0.01 m / min or more, more preferably 0.1 m / min or more, further preferably 1.0 m / min or more, and particularly preferably 5.0 m / min or more. The coating speed of the composition for coating anisotropic pigment films is typically 400 m / min or less, preferably 200 m / min or less, more preferably 100 m / min or less, and further preferably 50 m / min or less. By setting the coating speed within the above range, there is a tendency to obtain anisotropy of the anisotropic pigment film and to achieve uniform coating.

[0355] The coating temperature of the anisotropic pigment film composition is generally above 0°C and below 100°C, preferably below 80°C, and more preferably below 60°C.

[0356] The humidity during coating of the anisotropic pigment film composition is preferably 10% RH or higher, and preferably 80% RH or lower.

[0357] Anisotropic pigment films can also be treated to prevent dissolution. Insolution refers to the process of controlling the dissolution of compounds from the anisotropic pigment film by reducing the solubility of the compounds in the film, thereby improving the stability of the film.

[0358] Specifically, in terms of ease of subsequent processes and durability of anisotropic pigment films, polymerization and external coating of the film are preferred.

[0359] In the case of film polymerization, light and / or radiation are used to polymerize the film in which liquid crystal molecules and pigment molecules have been oriented.

[0360] When using light or radiation for polymerization, it is preferable to irradiate with active energy rays in the wavelength range of 190 to 450 nm.

[0361] There are no particular limitations on the light source for active energy rays with wavelengths of 190–450 nm. Examples include: 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 arc lamps, fluorescent lamps, etc.; and laser sources such as argon ion lasers, YAG lasers, excimer lasers, nitrogen lasers, helium-cadmium lasers, semiconductor lasers, etc. Optical filters can also be used when irradiating with light of a specific wavelength. The preferred exposure dose for active energy rays is 1–100,000 J / m². 2 More preferably, it is 10 to 10,000 J / m 2 .

[0362] Although polymerization can be carried out using light and / or radiation, photopolymerization or a combination of photopolymerization and thermal polymerization is preferred in terms of shorter film formation time and simpler equipment. In the case of thermal polymerization, it is preferred to carry out the process in the range of 50 to 200°C, and more preferably in the range of 60 to 150°C.

[0363] [Photocurable film]

[0364] The photocurable film mentioned in this invention is a functional film with photopolymerization properties. Examples of functional films include coating films with protective functions (e.g., abrasion resistance, scratch resistance, stress mitigation, chemical resistance, gas resistance, water resistance, corrosion resistance), anti-leakage, planarization, easy adhesion, and easy demolding; adhesive films with adhesive and / or bonding properties; anti-reflective films; phase reversal films; light control films that absorb light or reflect or scatter light; low-refractive-index films; high-refractive-index films; electrically insulating films; electrically conductive films; and alignment films. From the viewpoint that a photocurable film laminated on an anisotropic pigment film can serve as a protective film for the anisotropic pigment film, a coating film is preferred; and from the viewpoint that it is easy to form optical elements using anisotropic optical laminates, an adhesive film is preferred.

[0365] The optical anisotropic laminate of the present invention has at least one photocurable film laminated on anisotropic pigment film. The photocurable film may be selected appropriately according to the application, and may be a single layer or multiple layers.

[0366] For example, as a photocurable film, an adhesive film and an outer coating film can be formed. In this case, a laminated structure of anisotropic pigment film / outer coating film / adhesive film is preferred. Other layers may also be laminated between the anisotropic pigment film, the outer coating film, and the adhesive film. When the outer coating film has the function of protecting the anisotropic pigment film, from the viewpoint of effective protection, it is preferable to have the outer coating film laminated on the anisotropic pigment film.

[0367] (Photopolymerization initiator)

[0368] The photocurable film of the present invention contains a photopolymerization initiator.

[0369] 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), preferably 300 nm or more, more preferably 320 nm or more, and even more preferably 340 nm or more. Furthermore, it is preferably 450 nm or less, more preferably 430 nm or less, and even more preferably 410 nm or less. By being within this range, a photocurable film with good curing degree is obtained, allowing the photopolymerization reaction to proceed sufficiently.

[0370] As a photopolymerization initiator for photocurable films, the photopolymerization initiators listed in the above anisotropic pigment films can be used.

[0371] From the viewpoint of obtaining a photocurable film with good curing degree, the content of photopolymerization initiator in 100% by mass of the photocurable film is preferably 0.1% by mass or more, more preferably 0.5% by mass or more. Furthermore, it is preferably 30% by mass or less, more preferably 10% by mass or less, and even more preferably 8% by mass or less, particularly preferably 3% by mass or less.

[0372] Therefore, from the viewpoint of obtaining a photocurable film with good curability, the content of the photopolymerization initiator in the following photocurable film-forming composition 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 components of the photocurable film composition. Furthermore, it is preferably 30 parts by mass or less, more preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less, particularly preferably 3 parts by mass or less.

[0373] (Curing resin)

[0374] The photocurable film of the present invention contains a curable resin as a polymeric component that is cured by photopolymerization.

[0375] As the curing resin, various conventionally known resins can be used, such as acrylic resins, polyester resins, urethane resins, polyethylene resins, epoxy resins, silicone resins, vinyl acetate resins, nitrile rubbers, chloroprene rubbers, and styrene-butadiene rubbers. Among these, acrylic resins are preferred, especially in terms of their excellent ease of introducing curable carbon-carbon double bonds such as (meth)acryloyl groups.

[0376] 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 exudation of low-molecular-weight components. Consequently, this type of curable resin also exhibits excellent bending properties. It is speculated that this is because by including an appropriate amount of crosslinking groups in the resin components, both flexibility and curability can be achieved simultaneously.

[0377] As curable functional groups contained in curable resins, examples include carbon-carbon double bonds and other functional groups that are curable by active energy rays, such as (meth)acryloyl groups or vinyl ether compounds. Among these, (meth)acryloyl groups are preferred, and acryloyl groups are particularly preferred, considering ease of introduction or reactivity.

[0378] As for acrylic resins with active energy-curable functional groups such as carbon-carbon double bonds, the following methods (1 to 6) can be used as examples of methods for introducing such double bonds.

[0379] Method 1: A method for reacting compounds with double bonds and carboxyl groups with acrylic resins containing epoxy groups.

[0380] Method 2: A method for reacting compounds with double bonds and epoxy groups with acrylic resins containing carboxyl groups.

[0381] Method 3: A method of reacting compounds with double bonds and carboxyl groups with acrylic resins containing hydroxyl groups.

[0382] Method 4: A method for reacting compounds with double bonds and hydroxyl groups with acrylic resins containing carboxyl groups.

[0383] Method 5: A method for reacting compounds with double bonds and hydroxyl groups with acrylic resins containing isocyanate groups.

[0384] Method 6: A method for reacting compounds containing double bonds and isocyanate groups with acrylic resins containing hydroxyl groups.

[0385] The above methods can also be used in combination.

[0386] Hereinafter, monomers with carbon-carbon double bonds that are capable of free radical polymerization are sometimes referred to as vinyl monomers.

[0387] In Method 1, examples of epoxy-containing vinyl monomers used to obtain epoxy-containing acrylic resins include glycidyl methacrylate, cyclohexyl methacrylate (3,4-epoxycyclohexyl methacrylate), and methyl 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate is preferred, and particularly preferred, considering its good reactivity and ease of use. Only one of these monomers may be used, or two or more may be combined.

[0388] Examples of compounds having double bonds and carboxyl groups in Method 1 include: (meth)acrylic acid, carboxyethyl (meth)acrylate, adducts of glycerol di(meth)acrylate and succinic anhydride, adducts of pentaerythritol tri(meth)acrylate and succinic anhydride, and adducts of pentaerythritol tri(meth)acrylate and phthalic anhydride. Among these, adducts of (meth)acrylic acid, pentaerythritol tri(meth)acrylate and succinic anhydride are preferred, (meth)acrylic acid is more preferred, and acrylic acid is even more preferred. Only one compound having double bonds and carboxyl groups may be used, or two or more may be combined.

[0389] In method 2, the vinyl monomers with carboxyl groups used to obtain the acrylic resin having carboxyl groups can be, for example, (meth)acrylic acid, carboxyethyl (meth)acrylate, and polyacid-modified (meth)acrylate. Among these, (meth)acrylic acid is preferred, and acrylic acid is more preferred. Only one of these may be used, or two or more may be combined.

[0390] In method 2, compounds having double bonds and epoxy groups can be listed as, for example, glycidyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate glycidyl ether, etc. Among these, glycidyl (meth)acrylate is preferred. Only one of these can be used, or two or more can be combined.

[0391] In method 3, examples of hydroxyl-containing vinyl monomers used to obtain hydroxyl-containing acrylic resins include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and hydroxypropyl (meth)acrylate. Only one of these monomers may be used, or two or more may be combined.

[0392] In method 3, the same compound as that in method 1 can be used as the compound having double bonds and carboxyl groups.

[0393] In method 4, the same acrylic resin as in method 2 can be used as the one with carboxyl groups.

[0394] In method 4, compounds having double bonds and hydroxyl groups can be listed as, for example, 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, hydroxypropyl (meth)acrylate, etc. Only one of these can be used, or two or more can be combined.

[0395] In method 5, vinyl monomers with isocyanate groups used to obtain acrylic resins with isocyanate groups include, for example, ethyl isocyanate (meth)acrylate. Only one of these may be used, or two or more may be combined.

[0396] In method 5, the compound having double bonds and hydroxyl groups can be, for example, the same compound listed in method 4.

[0397] In method 6, the same compound as that in method 3 can be used as the acrylic resin having hydroxyl groups.

[0398] In method 6, compounds having double bonds and isocyanate groups can be used, for example, ethyl isocyanate of (meth)acrylate. Only one of these can be used, or two or more can be combined.

[0399] Of the above methods, method 1 is preferred because the reaction is easy to control. In method 1, the double bond is introduced through 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 both a double bond and a carboxyl group.

[0400] In Method 1, the epoxy-containing monomers in the epoxy-containing acrylic resin preferably comprise 5% by mass or more, more preferably 10% by mass or more, and even more preferably 15% by mass or more in the total amount of monomers constituting the epoxy-containing acrylic resin. Furthermore, 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 outer coating film with excellent impermeability and bending properties is obtained.

[0401] In method 1, the compound having double bonds and carboxyl groups is preferably 10 to 150 mol%, more preferably 30 to 130 mol%, and even more preferably 50 to 110 mol%, based on the ratio of the compound having double bonds and carboxyl groups to the epoxy groups in the acrylic resin having epoxy groups. Using it within this range is preferred from the viewpoint of ensuring proper reaction and reducing residues of the raw materials.

[0402] The aforementioned acrylic resins with epoxy groups, such as acrylic resins, may also be copolymers of (meth)acrylates or other vinyl monomers other than those mentioned above.

[0403] The polymerization of these raw materials is usually a free radical polymerization, which can be carried out under previously known conditions.

[0404] Monomers that can be used in combination as raw materials include: methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate, phenyl methacrylate, methoxy (poly)ethylene glycol (meth)acrylate, methoxy (poly)propylene glycol (meth)acrylate, methoxy (poly)ethylene glycol (poly)propylene glycol (meth)acrylate, octyloxy (poly)ethylene glycol (meth)acrylate, and octyloxy (poly)propylene glycol (meth)acrylate. Acrylates include esters such as octyl tetramethylene glycol (meth)acrylate, dodecyloxy polyethylene glycol (meth)acrylate, and stearoyloxy polyethylene glycol (meth)acrylate; acrylamides such as ethyl (meth)acrylamide, n-butyl (meth)acrylamide, isobutyl (meth)acrylamide, tert-butyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, N-hydroxypropyl (meth)acrylamide, and N,N-dihydroxyethyl (meth)acrylamide; and styrene monomers such as styrene, p-chlorostyrene, and p-bromostyrene. Only one of these monomers may be used, or two or more may be combined.

[0405] Acrylic resins can be manufactured using the aforementioned vinyl monomers via free radical polymerization. The free radical polymerization reaction is preferably carried out in an organic solvent and in the presence of a free radical polymerization initiator.

[0406] Examples of organic solvents used in free radical polymerization include: ketone solvents such as acetone and methyl ethyl ketone (MEK); alcohol solvents such as ethanol, methanol, isopropanol (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. Only one of these organic solvents may be used, or two or more may be used in combination.

[0407] Examples of free radical polymerization initiators for free radical polymerization include: organic peroxides such as benzoyl peroxide and di-tert-butyl peroxide; and azo compounds such as 2,2'-azobisbutyronitrile, 2,2'-azobis(2,4-dimethylpentanonitrile), and 2,2'-azobis(4-methoxy-2,4-dimethylpentanonitrile). Only one of these free radical polymerization initiators may be used, or two or more may be used in combination. The free radical polymerization initiator is preferably used in the range of 0.01 to 5 parts by mass relative to 100 parts by mass of the total vinyl monomers in the starting material.

[0408] In free radical polymerization, chain transfer agents can be used to control the weight-average molecular weight and other properties of acrylic resins. Examples of chain transfer agents include: butanethiol, octylthiol, decanethiol, dodecylthiol, hexadecylthiol, octadecylthiol, cyclohexanethiol, benzenethiophenol, octyl thioglycolate, octyl 2-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl mercaptopropionate, 2-ethylhexyl thioglycolate, butyl-3-mercaptopropionate, mercaptopropyltrimethoxysilane, methyl-3-mercaptopropionate, and 2,2-(ethylenedioxy)silane. Thiol compounds include diethylthiol, ethanethiol, 4-methylbenzylthiol, 2-mercaptoethyl octanoate, 1,8-dimercapto-3,6-dioxooctane, decantrithiol, dodecylthiol, diphenyl sulfoxide, dibenzyl sulfide, 2,3-dimercapto-1-propanol, mercaptoethanol, thiosalicylic acid, thioglycerol, thioglycolic acid, 3-mercaptopropionic acid, thiomalic acid, mercaptoacetic acid, mercaptosuccinic acid, and 2-mercaptoethanesulfonic acid.

[0409] These can be used in single-use or in combination of two or more types.

[0410] The amount of chain transfer agent used is preferably 0.1 to 25 parts by mass relative to 100 parts by mass of the total vinyl monomers of the raw material, more preferably 0.5 to 20 parts by mass, and even more preferably 1.0 to 15 parts by mass.

[0411] The reaction time for free radical polymerization is preferably 1 to 20 hours, more preferably 3 to 12 hours.

[0412] The reaction temperature is preferably 40–120°C, and more preferably 50–100°C.

[0413] When reacting compounds having double bonds and carboxyl groups with acrylic resins, the compounds having double bonds and carboxyl groups are added to the acrylic resin obtained as described above. The reaction is carried out in the presence of one or more catalysts such as triphenylphosphine, tetrabutylammonium bromide, tetramethylammonium chloride, and triethylamine, at a temperature typically of 90–140°C, preferably 100–120°C, for approximately 3–9 hours. Here, the catalyst is preferably used at a ratio of approximately 0.5–3 parts by mass relative to the total 100 parts by mass of the (meth)acrylate polymer and the compounds having double bonds and carboxyl groups. This reaction can be carried out immediately after the acrylic resin is produced by polymerization, or it can be carried out after temporarily separating the acrylic resin from the reaction system and then adding the compounds having double bonds and carboxyl groups.

[0414] The double bond equivalent in the acrylic resin is preferably 0.1–10 mmol / g, more preferably 0.2–7.0 mmol / g, further preferably 0.5–6.0 mmol / g, particularly preferably 1.0–5.5 mmol / g, and most preferably in the range of 2.0–5.0 mmol / g. By setting it within this range, it is easy to balance impermeability and flexural properties. It should be noted that 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.

[0415] The curable resin contained in the photocurable film of the present invention typically has a weight-average molecular weight (Mw) of 5,000 or more, preferably 7,000 or more, more preferably 9,000 or more, typically 200,000 or less, preferably 100,000 or less, more preferably 70,000 or less, and even more preferably 50,000 or less. When the Mw falls within the above range, surface irregularities are easily formed.

[0416] 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 more than 12,000, even more preferably more than 14,000, and particularly preferably more than 15,000. If it is above the lower limit mentioned above, curing shrinkage can be reduced and the optical performance of the optically anisotropic laminate can be improved.

[0417] The weight-average molecular weight (Mw) of the resin can be determined using gel permeation chromatography (GPC) as a conversion value based on polystyrene standards. Specific determination conditions are shown in the examples below.

[0418] From the viewpoint of exhibiting the function of a photocurable film or obtaining a smooth photocurable film, the content of 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, out of 100% by mass. Furthermore, it is preferably 99.99% by mass or less, more preferably 99.9% by mass or less.

[0419] Therefore, from the viewpoint of exhibiting the function of a photocurable film or obtaining a smooth photocurable film, the content of the curable resin in the following photocurable film-forming composition 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. Furthermore, it is preferably 99.99 parts by mass or less, more preferably 99.9 parts by mass or less.

[0420] (Other constituent components)

[0421] In addition to having a curable resin as a polymeric component that is cured by photopolymerization, the photocurable film of the present invention may also have a polymeric liquid crystal compound, etc.

[0422] As the polymerizable liquid crystal compound, various polymerizable liquid crystal compounds known in the past can be used. For example, the polymerizable liquid crystal compounds listed in the above-mentioned anisotropic pigment films, and the descriptions on pages 408-410, 521-524, and 562-563 of "Liquid Crystal Handbook" (Maruzen Co., Ltd., published on October 30, 2000) can be cited.

[0423] The photocurable film of the present invention may further include nonpolymerizable resins, nonpolymerizable liquid crystal compounds, thermal polymerization initiators, polymerization inhibitors, polymerization aids, surfactants, leveling agents, coupling agents, pH adjusters, dispersants, antioxidants, antistatic agents, ultraviolet absorbers, light stabilizers, thickeners, defoamers, pigments, organic and inorganic fillers, organic and inorganic nanosheets, organic and inorganic nanofibers, metal oxides, etc.

[0424] (Thickness of the photocurable film)

[0425] From the viewpoint of enhancing mechanical strength and exhibiting functionality, the thickness of the photocurable film of the present invention is preferably 0.1 μm or more, more preferably 0.3 μm or more, further preferably 0.5 μm or more, and even more preferably 1 μm or more. Furthermore, from the viewpoint of enabling a thinner optically anisotropic laminate, it is preferably 175 μm or less, more preferably 120 μm or less, further preferably 80 μm or less, even more preferably 60 μm or less, particularly preferably 20 μm or less, and even more preferably 10 μm or less.

[0426] (Composition for photocurable films)

[0427] The photocurable film of the present invention can be formed using a photocurable film composition (hereinafter, sometimes referred to as "the photocurable film composition of the present invention").

[0428] The composition for photocurable films contains the photopolymerization initiator and curing resin listed in the above-mentioned photocurable films, and may also contain other components.

[0429] The compositions for photocurable films may also contain solvents as needed.

[0430] There are no particular limitations on the solvents that can be used, as long as they can adequately disperse or dissolve the photopolymerization initiator, curing resin, and other components contained in the photocurable film composition. Examples of solvents include: water, methanol, ethanol, ethylene glycol, isopropanol, propylene glycol, ethylene glycol methyl ether, ethylene glycol butyl ether, propylene glycol monomethyl ether, etc.; ester solvents such as ethyl acetate, butyl acetate, ethylene glycol methyl ether acetate, γ-butyrolactone, propylene glycol methyl ether acetate, ethyl lactate, etc.; ketone solvents such as acetone, methyl ethyl ketone, cyclopentanone, cyclohexanone, 2-heptanone, methyl isobutyl ketone, etc.; aliphatic hydrocarbon solvents such as pentane, hexane, heptane, etc.; aromatic hydrocarbon solvents such as toluene, xylene, etc.; nitrile solvents such as acetonitrile; ether solvents such as tetrahydrofuran, dimethoxyethane, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc.; fluorinated solvents such as perfluorobenzene, perfluorotoluene, perfluorodehydronaphthalene, perfluoromethylcyclohexane, hexafluoro-2-propanol, etc.; and chlorinated solvents such as chloroform, dichloromethane, chlorobenzene, dichlorobenzene, etc.

[0431] These solvents can be used in single or combined in combination.

[0432] From the viewpoint of compositions for coating photocurable films, solvents with a boiling point in the range of 50 to 200°C are preferred.

[0433] When the photocurable film composition of the present invention contains a solvent, the percentage of solvent in the photocurable film composition relative to the total amount (100% by mass) of the photocurable film composition of the present invention is preferably 50 to 98% by mass. In other words, the content of solid components in the photocurable film composition of the present invention is preferably 2 to 50% by mass.

[0434] If the solid content in the composition for photocurable film is below the above-mentioned upper limit, the viscosity of the composition for photocurable film will not become too high, the thickness of the obtained photocurable film will become uniform, and the photocurable film will not easily become uneven.

[0435] The content of this solid component can be determined with reference to the thickness of the photocurable film to be manufactured.

[0436] The viscosity of the composition for photocurable film is not particularly limited, as long as it can produce a uniform film without thickness unevenness. From the viewpoint of obtaining large-area thickness uniformity, coating speed and other productivity through the coating method described below, it is preferably 0.1 mPa·s or more, preferably 500 mPa·s or less, more preferably 100 mPa·s or less, and even more preferably 50 mPa·s or less.

[0437] The method for manufacturing the photocurable film composition of the present invention is not particularly limited. For example, a curable resin, a photopolymerization initiator, a solvent as needed, and other constituent components are mixed. A filtration step may also be included to remove foreign matter from the composition.

[0438] (Manufacturing method of photocurable film)

[0439] The method for manufacturing the photocurable film of the present invention is not particularly limited. Examples include a method of using the photocurable film composition of the present invention to form a sheet and a method of manufacturing by wet film formation.

[0440] The method for forming a sheet mentioned in this invention is a method of curing the photocurable film composition by forming it into a shape, such as a sheet, by a certain method, and then curing it by irradiating it with heat and / or active energy rays.

[0441] As a method for forming sheets, known methods can be used, such as wet lamination, dry lamination, extrusion casting using a T-die, extrusion lamination, calendering or blow molding, injection molding, and liquid injection curing. Among these, wet lamination, extrusion casting, and extrusion lamination are preferred.

[0442] The wet film-forming method mentioned in this invention refers to a method in which a photocurable film composition is coated onto a substrate by a certain method, and then the photocurable film composition is cured by polymerization using active energy rays. Thermal polymerization may also be used in combination with the polymerization using active energy rays.

[0443] The substrate described above can be either a substrate containing an anisotropic pigment film or a substrate not containing anisotropic pigment film. In the case of a substrate not containing anisotropic pigment film, a photocurable film can be manufactured by transferring a photocurable film composition coated on the substrate to a substrate containing anisotropic pigment film, or by transferring anisotropic pigment film coated on the substrate to a substrate containing a photocurable film composition, and then curing it by irradiating it with active energy rays.

[0444] Examples of methods for coating a photocurable film composition onto a substrate include: reverse coating, gravure coating, bar coating, rod coating, Mayer bar coating, die coating, and spray coating.

[0445] The compositions for photocurable films may also be dried at a temperature above 40°C and below 130°C, as needed, before polymerization by irradiation with active energy rays.

[0446] Examples of such active energy rays include light and radiation. Among these, from the viewpoint of easy control of polymerization, ultraviolet light and visible light are preferred.

[0447] When curing is performed by ultraviolet (UV) irradiation, xenon lamps, high-pressure mercury lamps, metal halide lamps, LED-UV lamps, etc., can be used as the light source for the UV irradiation device. The UV irradiation dose is appropriately determined based on the composition of the photocurable film, and is typically 10 mJ / cm². 2 Above and 10000 mJ / cm 2 From the viewpoint of degree of cure, 15 mJ / cm is preferred. 2 Above 5000mJ / cm 2 The following is more preferably 20 mJ / cm 2 Above and 3000mJ / cm 2 the following.

[0448] (Outer coating)

[0449] An outer coating film can also be provided as a photocurable film. There are no particular limitations on the outer coating film; it can be manufactured using an outer coating film composition with the same composition as the photocurable film composition of the present invention.

[0450] Similar to the photocurable film composition, by including a curable resin in the outer coating film composition, anisotropic pigment films can be protected and low-molecular-weight components can be prevented from leaching out from each layer. The preferred curable resin for the outer coating film composition is also the same as the curable resin in the photocurable film composition described above.

[0451] To exhibit functions such as protection, prevention of exudation, planarization, easy adhesion, and easy demolding, the thickness of the outer coating 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. On the other hand, from the viewpoint of making the optically anisotropic laminate thinner, 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.

[0452] The outer coating contains a photopolymerization initiator. The photopolymerization initiator for the outer coating may be any of the photopolymerization initiators listed in the above-described photocurable films.

[0453] (Adhesive film)

[0454] An adhesive film with adhesive and / or bonding properties can also be provided as a photocurable film. The adhesive film can be manufactured using an adhesive film composition equivalent to the photocurable film composition used to form the adhesive film.

[0455] The transmittance of the adhesive film at wavelengths below 400 nm is preferably less than 30%, more preferably less than 25%, even more preferably less than 22%, and particularly preferably less than 20%. By ensuring that the transmittance of light at wavelengths below 400 nm does not reach the above-mentioned upper limit, the degradation of coated optical elements due to light can be suppressed.

[0456] Furthermore, from the viewpoint of visual recognition when used in image display devices, the light transmittance of the adhesive film at a wavelength of 430 nm is preferably 60% or more, more preferably 70% or more, even more preferably 75% or more, and particularly preferably 80% or more.

[0457] From the viewpoint of ensuring adhesive adhesion, 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. On the other hand, from the viewpoint of contributing to the thinning of optically anisotropic laminates, 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 especially preferably 60 μm or less.

[0458] The adhesive film comprises a curable resin and a photopolymerization initiator. The photopolymerization initiator for the adhesive film may be any of the photopolymerization initiators listed above for photocurable films.

[0459] There is no particular limitation on the content of the photopolymerization initiator in the adhesive film. From the viewpoint of fully carrying out 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, further 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 adhesion, the upper limit of the content of the photopolymerization initiator in the adhesive film relative to 100 parts by mass of the curable resin is preferably 15 parts by mass or less, more preferably 10 parts by mass or less, further preferably 6 parts by mass or less, and particularly preferably 4 parts by mass or less.

[0460] The curable resin contained in the adhesive film has adhesive and / or bonding properties. Various conventionally known resins can be used as the curable resin, such as acrylic resins, epoxy resins, urethane resins, silicone resins, vinyl acetate resins, nitrile rubbers, chloroprene rubbers, and styrene-butadiene rubbers. Among these, acrylic resins are preferred in terms of superior adhesive properties.

[0461] The aforementioned acrylic resin is not particularly limited. As a (meth)acrylic polymer (A), in addition to homopolymers of alkyl (meth)acrylic esters, copolymers obtained by polymerizing alkyl (meth)acrylic esters with monomer components capable of copolymerizing therewith are also examples. As a copolymer, a preferred example is a (meth)acrylic resin (A) copolymerized from an alkyl (meth)acrylic ester (a1) with 4 to 18 carbon atoms in its side chains as the main component and monomer components capable of copolymerizing therewith.

[0462] The aforementioned main component refers to the component that has a significant impact on the properties of the (meth)acrylic polymer (A). The content of this component is usually 30% or more by mass of the total (meth)acrylic polymer (A), preferably 35% or more by mass.

[0463] Furthermore, from the viewpoints of processability, adhesion, stress relief, heat resistance reliability, and resistance to damp heat haze, (meth)acrylic polymer (A) may also contain two or more (meth)acrylic polymers with different glass transition temperatures.

[0464] Alkyl methacrylates (a1) with 4 to 18 carbon atoms as side chains include, for example: n-butyl methacrylate, pentyl methacrylate, hexyl methacrylate, heptyl methacrylate, n-octyl methacrylate, nonyl methacrylate, decyl methacrylate, undecyl methacrylate, lauryl methacrylate, tridecyl methacrylate, tetradecyl methacrylate, cetyl methacrylate, stearyl methacrylate, etc. (a1) linear alkyl methacrylates; isobutyl methacrylate, sec-butyl methacrylate, etc. Branched alkyl esters of methacrylates include tert-butyl acrylate, isoamyl acrylate, neopentyl acrylate, 2-ethylhexyl acrylate, isooctyl acrylate, isononyl acrylate, isodecanyl acrylate, isostearyl acrylate, and other branched alkyl esters of methacrylates; cyclohexyl acrylate, tert-butylcyclohexyl acrylate, 3,5,5-trimethylcyclohexane(meth)acrylate, dicyclopentyl acrylate, dicyclopentenyl acrylate, dicyclopentenoxyethyl acrylate, isobornyl acrylate, and other alicyclic methacrylates. These can be used alone or in combination of two or more.

[0465] From the viewpoint of improving the stress relief and heat resistance reliability of the adhesive film, the content of alkyl methacrylate (a1) relative to the overall composition of the (meth)acrylic polymer (A) is preferably 3% by mass or more, more preferably 5% by mass or more, further preferably 8% by mass or more, particularly preferably 10% by mass or more, and most preferably 12% by mass or more. Furthermore, from the viewpoint of suppressing the reduction of adhesive strength, the content of the aforementioned alkyl methacrylate (a1) relative to the overall composition of the (meth)acrylic polymer (A) is preferably 80% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, particularly preferably 40% by mass or less, and most preferably 30% by mass or less.

[0466] Examples of monomer components that can copolymerize with alkyl methacrylates (a1) having 4 to 18 carbon atoms in their side chains include: hydroxyl-containing methacrylate monomers (a2), methacrylate monomers or vinyl ester monomers having 1 to 3 carbon atoms in their side chains (a3), olefinically unsaturated monomers containing functional groups (a4), and other copolymerizable monomers (a5).

[0467] Examples of hydroxyl-containing monomers (a2) include: hydroxy(meth)acrylates such as 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 5-hydroxypentyl methacrylate, 6-hydroxyhexyl methacrylate, and 8-hydroxyoctyl methacrylate; caprolactone-modified monomers such as caprolactone-modified 2-hydroxyethyl methacrylate; alkylene oxide-modified monomers such as diethylene glycol methacrylate and polyethylene glycol methacrylate; monomers containing primary hydroxyl groups such as 2-acryloyloxyethyl-2-hydroxyethyl phthalate; monomers containing secondary hydroxyl groups such as 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, and 3-chloro-2-hydroxypropyl methacrylate; and monomers containing tertiary hydroxyl groups such as 2,2-dimethyl-2-hydroxyethyl methacrylate. These can be used alone or in combination of two or more.

[0468] Among the hydroxyl-containing monomers (a2), monomers containing primary hydroxyl groups are preferred in terms of the excellent balance between resistance to damp heat and heat resistance, especially 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate, 2-hydroxypropyl methacrylate, and especially 2-hydroxyethyl methacrylate and 4-hydroxybutyl methacrylate.

[0469] From the viewpoint of improving resistance to damp heat, the lower limit of the content of hydroxyl monomer (a2) relative to the overall composition of (meth)acrylic polymer (A) is generally 3% by mass or more, preferably 5% by mass or more, more preferably 8% by mass or more, further preferably 10% by mass or more, and particularly preferably 12% by mass or more.

[0470] From the viewpoint of suppressing the self-crosslinking reaction of (meth)acrylic polymer (A), improving processability and heat resistance reliability, the upper limit of the content of hydroxyl-containing monomer (a2) is generally 60% by mass or less, preferably 45% by mass or less, more preferably 35% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0471] (a3) monomers with 1 to 3 carbon atoms in their side chains include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, vinyl propionate, vinyl acetate, etc. These monomers (a3) ​​can be used alone or in combination of two or more.

[0472] Of the components mentioned above (a3), from the viewpoint of improving cohesive strength when used as an adhesive, methyl methacrylate and ethyl methacrylate are preferred.

[0473] From the viewpoint of improving cohesive strength when used as an adhesive film, the lower limit of the content of the above-mentioned component (a3) ​​relative to the total composition of the (meth)acrylic polymer (A) is preferably 5% by mass or more, more preferably 7% by mass or more, and even more preferably 10% by mass or more. Furthermore, from the viewpoint of improving processability, the upper limit of the content of the above-mentioned component (a3) ​​relative to the total composition of the (meth)acrylic polymer (A) is preferably 40% by mass or less, more preferably 30% by mass or less, and even more preferably 20% by mass or less.

[0474] Examples of functionalized olefinic unsaturated monomers (a4) include: monomers containing carboxyl groups, monomers containing functional groups with nitrogen atoms, monomers containing acetoacetyl groups, monomers containing isocyanate groups, monomers containing glycidyl groups, etc.

[0475] Among these, in terms of imparting cohesive force and promoting cross-linking, monomers containing functional groups having nitrogen atoms are preferred, more preferably amino-containing monomers or amide-containing monomers, and even more preferably amino-containing monomers.

[0476] Examples of carboxyl-containing monomers include: (meth)acrylic acid, (meth)acrylic acid carboxyethyl ester, 2-(meth)acryloyloxyethyl hexahydrophthalic acid ester, 2-(meth)acryloyloxypropyl hexahydrophthalic acid ester, 2-(meth)acryloyloxyethyl phthalic acid ester, 2-(meth)acryloyloxypropyl phthalic acid ester, 2-(meth)acryloyloxyethyl maleate, 2-(meth)acryloyloxypropyl maleate, 2-(meth)acryloyloxyethyl succinate, 2-(meth)acryloyloxypropyl succinate, crotonic acid, fumaric acid, maleic acid, itaconic acid, monomethyl maleate, monomethyl itaconic acid, etc.

[0477] Examples of amino-containing monomers include: methyl methacrylate, amino ethyl methacrylate, and other (meth)acrylates containing primary amino groups; tert-butylaminoethyl methacrylate, tert-butylaminopropyl methacrylate, and other (meth)acrylates containing secondary amino groups; ethylaminoethyl methacrylate, dimethylaminoethyl methacrylate, diethylaminoethyl methacrylate, dimethylaminopropyl methacrylate, diethylaminopropyl methacrylate, dimethylaminopropyl acrylamide, and other (meth)acrylates containing tertiary amino groups.

[0478] Examples of monomers containing amide groups include: (meth)acrylamide; N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl (meth)acrylamide, diacetone (meth)acrylamide, N,N'-methylenebis(meth)acrylamide, and other N-alkyl (meth)acrylamides; N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N,N-dipropyl (meth)acrylamide, N,N-ethylmethylacrylamide, N,N-diallyl (meth)acrylamide, and other N,N-dialkyl (meth)acrylamides; N-hydroxymethyl (meth)acrylamide, N-hydroxyethyl (meth)acrylamide, and other hydroxyalkyl (meth)acrylamides; N-methoxymethyl (meth)acrylamide, N-(n-butoxymethyl)(meth)acrylamide, and other alkoxyalkyl (meth)acrylamides, etc.

[0479] Examples of monomers containing acetoacetyl groups include 2-(acetoacetoxy)ethyl methacrylate and allyl acetoacetate.

[0480] Examples of isocyanate-containing monomers include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and their alkyl oxide adducts. The isocyanate group can also be protected by end-capping agents such as methyl ethyl ketone oxime, 3,5-dimethylpyrazole, 1,2,4-triazole, and diethyl malonate.

[0481] Examples of monomers containing glycidyl groups include glycidyl (meth)acrylate and allyl (meth)acrylate.

[0482] These functionalized olefinic unsaturated monomers (a4) can be used alone or in combination of two or more.

[0483] From the viewpoint of improving the heat resistance and light resistance of adhesive films, the upper limit of the content of functional group-containing olefinic unsaturated monomer (a4) is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 10% by mass or less, and particularly preferably 5% by mass or less, relative to the overall composition of (meth)acrylic polymer (A).

[0484] Other comonomers (a5) that may be used as needed include, for example: phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, diethylene glycol methacrylate, phenoxy polyethylene glycol methacrylate, phenoxy polyethylene glycol-polypropylene glycol-methacrylate, nonylphenol ethylene oxide adduct methacrylate, and other aromatic (meth)acrylate monomers; 4-acryloyloxybenzophenone, 4-acryloyloxyethoxybenzophenone, 4-acryloyloxy-4'-methoxybenzophenone, 4-acryloyloxyethoxy-4'-methoxybenzophenone, 4-acryloyloxy-4'-bromobenzophenone, 4-acryloyloxyethoxy-4'- (Meth)acrylate monomers with a benzophenone structure, including 4-methylacryloyloxybenzophenone, 4-methylacryloyloxyethoxybenzophenone, 4-methylacryloyloxy-4'-methoxybenzophenone, 4-methylacryloyloxyethoxy-4'-methoxybenzophenone, 4-methylacryloyloxy-4'-bromobenzophenone, 4-methylacryloyloxyethoxy-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 itaconic acid, dialkyl fumarate, allyl alcohol, acryl chloride, methyl vinyl ketone, N-acrylamidomethyltrimethylammonium chloride, allyltrimethylammonium chloride, and dimethylallyl vinyl ketone. These can be used alone or in combination of two or more.

[0485] (Meth)acrylic polymers (A) can also have polymerizable carbon double bond groups introduced into their side chains. This improves the crosslinking sensitivity of (meth)acrylic polymers (A), allowing them to be crosslinked by irradiation with lower-energy active radiation to impart cohesion and heat resistance.

[0486] As a method for introducing polymeric carbon double bond groups into the side chain of (meth)acrylic polymer (A), for example, the following method can be used: a copolymer comprising the above-mentioned hydroxyl-containing monomer (a2) and an olefinic unsaturated monomer (a4) containing functional groups is prepared, and then a compound (a6) having functional groups that can react with these functional groups and polymeric carbon double bond groups is subjected to a condensation or addition reaction while maintaining the activity of the polymeric carbon double bond groups.

[0487] Examples of combinations of these functional groups include: epoxy (glycidyl) and carboxyl, amino and carboxyl, amino and isocyanate, epoxy (glycidyl) and amino, hydroxyl and epoxy, hydroxyl and isocyanate, etc. Among these combinations of functional groups, the combination of hydroxyl and isocyanate is preferred in terms of ease of reaction control. Of these, a combination in which the copolymer has hydroxyl groups and the compound (a6) has isocyanate groups is particularly preferred.

[0488] Examples of isocyanate compounds with polymerizable carbon double bonds include 2-acryloyloxyethyl isocyanate, 2-methacryloyloxyethyl isocyanate, and their alkyl oxide adducts.

[0489] From the viewpoint of improving adhesion and stress relief, the amount of compound (a6) added relative to 100 parts by weight of (meth)acrylic polymer (A) is preferably 10 parts by weight or less, more preferably 8 parts by weight or less, further preferably 5 parts by weight or less, and particularly preferably 3 parts by weight or less.

[0490] From the viewpoint of obtaining an adhesive film with high cohesive strength, 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.

[0491] Furthermore, from the viewpoint of obtaining an adhesive film with high fluidity and stress relief, the upper limit of the weight-average molecular weight (Mw) of the (meth)acrylic polymer (A) is preferably 2 million or less, more preferably 1.5 million or less, and even more preferably 1 million or less.

[0492] The adhesive film may contain polyfunctional (meth)acrylates. Examples of polyfunctional (meth)acrylates include (meth)acrylate monomers and (meth)acrylate oligomers having two or more functional groups.

[0493] By incorporating polyfunctional (meth)acrylates into the adhesive film, a cross-linked structure can be formed in the adhesive film, thereby imparting cohesion and durability.

[0494] Examples of (meth)acrylic acid monomers with two or more functional groups include: 1,4-butanediol di(meth)acrylate, glycerol di(meth)acrylate, neopentyl glycol di(meth)acrylate, glycerol glycidyl ether di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethacrylate, tricyclodecanediethanol di(meth)acrylate, bisphenol A polyethoxydi(meth)acrylate, bisphenol A polypropoxydi(meth)acrylate, bisphenol F polyethoxydi(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, and propoxylated pentaerythritol tri(meth)acrylate. Ester, ethoxylated pentaerythritol tri(meth)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, poly(1,4-butanediol di(meth)acrylate, (tris(acryloyloxyethyl)isocyanurate, dipentaerythritol hexa(meth)acrylate The following are examples of methacrylates: pentaerythritol pentamethacrylate, pentaerythritol hexamethacrylate, pentaerythritol pentamethacrylate, neopentyl glycol dimethacrylate, ε-caprolactone adduct of neopentyl glycol hydroxypivalate, trimethylolpropane trimethacrylate, trimethylolpropane polyethoxytrimethacrylate, and di-trimethylolpropane tetramethacrylate.

[0495] From the viewpoint of imparting appropriate toughness to the cured material, (meth)acrylic monomers are preferred, and more preferably are polyfunctional (meth)acrylic monomers with an alkylene glycol backbone, such as polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, and poly1,4-butanediol di(meth)acrylate.

[0496] From the viewpoint of imparting appropriate flexibility to the cured material, the molecular weight of the polyfunctional (meth)acrylic acid monomer is preferably 200 or more, more preferably 300 or more, even more preferably 400 or more, and particularly preferably 500 or more.

[0497] Examples of (meth)acrylic oligomers with two or more functional groups include: polyester (meth)acrylates, epoxy (meth)acrylates, urethane (meth)acrylates, polyether (meth)acrylates, and other multifunctional (meth)acrylic oligomers.

[0498] From the viewpoint of imparting appropriate toughness to the cured material, urethane (meth)acrylate oligomers are preferred.

[0499] From the viewpoint of imparting appropriate flexibility to the cured material, the molecular weight of the polyfunctional (meth)acrylic acid oligomer is preferably 300 or more, more preferably 400 or more, even more preferably 600 or more, and particularly preferably 800 or more.

[0500] From the viewpoint of the shape stability of the adhesive film and its ability to impart durability when forming laminates, the lower limit of the content of the polyfunctional (meth)acrylate in the adhesive film is preferably 1 part by weight or more, more preferably 2 parts by weight or more, further preferably 4 parts by weight or more, and particularly preferably 10 parts by weight or more, relative to 100 parts by weight of the (meth)acrylate polymer (A). From the viewpoint of ensuring adhesion, the upper limit of the content of the polyfunctional (meth)acrylate is preferably 100 parts by weight or less, more preferably 60 parts by weight or less, further preferably 40 parts by weight or less, and particularly preferably 30 parts by weight or less, relative to 100 parts by weight of the (meth)acrylate polymer (A).

[0501] Adhesive films may also contain UV absorbers. By including UV absorbers, the degradation of optically anisotropic laminates caused by light can be reduced.

[0502] Examples of UV absorbers include benzophenone-based, benzotriazole-based, triazine-based, salicylic acid-based, and cyanoacrylate-based UV absorbers. Among these, benzophenone-based, benzotriazole-based, and triazine-based UV absorbers are preferred for their ability to readily achieve UV absorption. Benzophenone-based UV absorbers are more preferred for their superior resistance to yellowing. These UV absorbers can be used individually or in combination of two or more.

[0503] [Manufacturing method of optical anisotropic laminates]

[0504] The method for manufacturing the optical anisotropic laminate of the present invention is not particularly limited, and the following methods (1) to (4) can be listed.

[0505] (1) A method for manufacturing an optically anisotropic laminate by coating a photocurable film composition onto a substrate having an anisotropic pigment film and polymerizing it using active energy rays.

[0506] (2) A method for manufacturing an optically anisotropic laminate by forming a photocurable film into a sheet shape on a substrate having an anisotropic pigment film, and polymerizing it using active energy rays.

[0507] (3) A method for manufacturing an optically anisotropic laminate by transferring a photocurable film coated or formed in sheet form on a substrate without an anisotropic pigment film onto a substrate with an anisotropic pigment film, and then curing it using active energy rays to form a photocurable film.

[0508] (4) A method for manufacturing an optically anisotropic laminate by transferring an anisotropic pigment film from a substrate having an anisotropic pigment film to a photocurable film composition coated or formed in sheet form on a substrate without an anisotropic pigment film, and then curing it using active energy rays to form a photocurable film.

[0509] From the viewpoint of shortening the process, it is preferable to coat the photocurable film with a composition or form it in sheet form on a substrate on which an anisotropic pigment film is manufactured, and polymerize it using active energy rays to form a photocurable film to manufacture an optically anisotropic laminate.

[0510] [Optical Components]

[0511] The optical element of the present invention comprises the optical anisotropic laminate of the present invention.

[0512] The optical elements in this invention refer to polarizing elements, phase difference elements, optical compensation elements, and elements that utilize the anisotropy of light absorption to obtain linearly polarized light, circularly polarized light, elliptical polarized light, etc., as well as elements with functions such as reflection, brightness enhancement, refractive anisotropy, or conduction anisotropy. The optical element may have a single function or multiple functions. These functions can be appropriately adjusted through the anisotropic pigment film formation process and the selection of the substrate or composition containing organic compounds (pigments, transparent materials).

[0513] The optical element of the present invention is preferably used as a polarizing element, or as a polarizing element combined with other functions, and more preferably as a polarizing element.

[0514] The optical element of the present invention can be used to obtain a polarizing element by coating an anisotropic pigment film formed on a substrate, and is also preferably used for applications such as flexible displays.

[0515] [Polarizing element]

[0516] When the optical element of the present invention is used as a polarizing element, the polarizing element may also have other arbitrary layers, as long as it has the optical anisotropic laminate of the present invention.

[0517] The layers that can be used in combination for the polarizing element can be appropriately set according to the manufacturing process, characteristics, and functions, and there are no special limitations on the stacking position, order, etc.

[0518] The layers having optical functions can be formed by the following various methods.

[0519] The layer having the function as a retardation film can be formed by coating or laminating a retardation film on other layers constituting the polarizing element, etc. The retardation film can be formed, for example, by performing a stretching treatment described in Japanese Patent Laid-Open No. 2-59703, Japanese Patent Laid-Open No. 4-230704, etc. or by performing a treatment described in Japanese Patent Laid-Open No. 7-230007, etc.

[0520] The layer having the function as a brightness enhancement film can be formed by coating or laminating a brightness enhancement film on other layers constituting the polarizing element, etc. The brightness enhancement film can be formed, for example, by forming micropores by the methods described in Japanese Patent Laid-Open No. 2002-169025 and Japanese Patent Laid-Open No. 2003-29030 or by laminating two or more cholesteric liquid crystal layers having different center wavelengths of selective reflection.

[0521] The layer having the function as a reflective film or a semi-transmissive reflective film can be formed, for example, by coating or laminating a metal thin film obtained by vapor deposition or sputtering, etc. on other layers constituting the polarizing element.

[0522] The layer having the function as a diffusion film can be formed, for example, by coating a resin solution containing fine particles on other layers constituting the polarizing element.

[0523] When the optical element of the present invention is used for various display elements such as LCD or OLED, etc., the optical element of the present invention can be directly formed on the surface of the electrode substrate, etc. constituting these display elements, or the optical element of the present invention can be used as a constituent member of these display elements.

[0524] Examples

[0525] Hereinafter, the present invention will be specifically described by way of examples. The present invention is not limited to the following examples as long as it does not depart from its gist.

[0526] In the following description, "parts" means "parts by mass".

[0527] [Measurement of Transmittance]

[0528] Transmittance was measured using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., product name "NDH-5000SP"). The transmittance before and after lamination of the photocurable film was compared. If the transmittance did not decrease after lamination, the optical performance of the optically anisotropic laminate was maintained and it was judged as "○ (Good)". If the transmittance decreased after lamination, the optical performance of the optically anisotropic laminate was not adequately maintained and it was judged as "× (Poor)".

[0529] [Determination of weight-average molecular weight (Mw)]

[0530] The converted value of standard polystyrene obtained by gel permeation chromatography (GPC) is set as the weight-average molecular weight (Mw).

[0531] The details of the polymeric liquid crystal compounds and pigments contained in the anisotropic pigment films used in the examples and comparative examples are as follows.

[0532] [Polymerizable liquid crystal compounds]

[0533] <Polymerizable liquid crystal compound (I-1)>

[0534] According to Japanese Patent Application Publication No. 2020-042305, a polymeric liquid crystal compound (I-1) with the following structural formula was synthesized. In the following structural formula, C... 11 H 22 It refers to a straight chain composed of 11 methylene bonds.

[0535]

[0536] <Polymerizable liquid crystal compound (I-2)>

[0537] The polymeric liquid crystal compound (I-2) with the following structural formula was synthesized using the method described in Lub et al., Recl. Trav. Chim. Pays-Bas, 115, 321-328 (1996). In the following structural formula, C... 11 H 22 It refers to a straight chain composed of 11 methylene bonds.

[0538]

[0539] [pigment]

[0540] The chemical structures of the pigments (II-1) and (II-2) used in the examples and comparative examples are shown below.

[0541]

[0542]

[0543] [Example 1]

[0544] <Preparation of Compositions for Anisotropic Pigment Films>

[0545] 28.57 parts of polymerizable liquid crystal compound (I-1), 0.34 parts of pigment (II-1) (manufactured by Hayashibara Co., Ltd.), 0.84 parts of pigment (II-2) (manufactured by Showa Chemical Co., Ltd.), 0.29 parts of IRGACURE (registered trademark) 369 (manufactured by BASF Corporation), and 0.34 parts of BYK-361N (manufactured by BYK-Chemie Corporation) were added to 69.31 parts of cyclopentanone. After heating and stirring at 80°C, the mixture was filtered using a syringe equipped with an injection filter (manufactured by Membrane Solutions Corporation, PTFE13045, 0.45 μm diameter) to obtain an anisotropic pigment film composition 1.

[0546] <Fabrication of Anisotropic Pigment Membranes>

[0547] An anisotropic pigment film was formed using composition 1 on a glass substrate on which a polyimide alignment film (LX1400, manufactured by Hitachi Chemical DuPont MicroSystems, alignment film formed by friction) was formed. The film was then heated and dried at 120°C for 2 minutes, followed by cooling until the liquid crystal phase was reached. The exposure was then performed at 500 mJ / cm². 2 Polymerization was performed at a 365nm reference to obtain an anisotropic pigment film 1 with a thickness of 3μm.

[0548] When the anisotropic pigment film 1 is observed by placing a polarizing plate over the anisotropic pigment film, brightness and darkness appear whenever the polarizing plate is rotated 90 degrees, thus demonstrating polarization properties.

[0549] The maximum absorption wavelength λ0 of the photopolymerization initiator (IRGACURE (registered trademark) 369) contained in the anisotropic pigment film 1 is 319 nm.

[0550] <Preparation of the outer coating>

[0551] An outer coating film is formed on an anisotropic pigment film 1 using an outer coating film composition. The curable resin (R-1) included in the outer coating film composition is synthesized using the method described below.

[0552] Add 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-dimethylpentanonitrile) (1.0 part), and γ-trimethoxysilylpropanethiol (manufactured by Shin-Etsu Chemical Industry Co., Ltd. KBM-803) (1.9 parts) to a flask equipped with a thermometer, stirrer, and reflux condenser, and allow it to react at 65°C for 3 hours.

[0553] Subsequently, 0.5 parts of 2,2'-azobis(2,4-dimethylpentanonitrile) were added and allowed to react for 3 hours. Then, 138 parts of propylene glycol monomethyl ether and 0.45 parts of p-methoxyphenol were added and heated to 100°C.

[0554] Next, acrylic acid (51 parts) and triphenylphosphine (3.1 parts) were added, and the mixture was reacted at 110°C for 6 hours to obtain a cured resin (R-1) of a (meth)acryloyl copolymer with a carbon-carbon double bond content (acryloyl equivalent (acryloyl group introduction amount)) of 4.6 mmol / g. The weight-average molecular weight (Mw) of the cured resin (R-1) was 17700.

[0555] 23.08 parts of a 65% by weight solution of propylene glycol monomethyl ether of curable resin (R-1), 0.13 parts of photopolymerization initiator (PI-1) with 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 then filtered using a syringe equipped with an injection filter (manufactured by Membrane Solutions, PTFE13045, 0.45 μm diameter) to obtain a composition for external coating film.

[0556]

[0557] The composition for external coating was formed on an anisotropic pigment film by spin coating, and then dried at 50°C for 2 minutes with an exposure dose of 5000 mJ / cm. 2 (Based on 365nm) Polymerization is carried out to form an outer coating film, thereby obtaining an optically anisotropic laminate 1.

[0558] The maximum absorption wavelength λ1 of the photopolymerization initiator (PI-1) contained in the outer coating of the photocurable film is 356 nm.

[0559] The change in transmittance of the optical anisotropic laminate 1 before and after the photocurable film was stacked was evaluated, and the result was ○ (good), indicating that even with the stacked photocurable film, the optical performance is good.

[0560] [Comparative Example 1]

[0561] The photopolymerization initiator contained in the outer coating film of Example 1 was set to IRGACURE (registered trademark) 369. Otherwise, the optically anisotropic laminate 2 was obtained in the same manner as in Example 1.

[0562] The change in transmittance of the optical anisotropic laminate 2 before and after the photocurable film was laminated was evaluated, and the result was × (poor), indicating that the optical performance was reduced due to the laminated photocurable film.

[0563] The results of evaluating the changes in transmittance of λ0, λ1, and the optically anisotropic laminates before and after lamination in Example 1 and Comparative Example 1 are shown in Table 1. According to these results, the optically anisotropic laminate satisfying Equation (1) exhibits higher optical performance.

[0564] [Table 1]

[0565] Example 1 Comparative Example 1 λ0 319nm 319nm λ1 356nm 319nm Changes in transmittance ○ ×

[0566] [Example 2]

[0567] The polymeric liquid crystal compound (I-1) contained in the anisotropic pigment film composition of Example 1 was designated as polymeric liquid crystal compound (I-2), and otherwise, an optically anisotropic laminate 3 was obtained in the same manner as in Example 1.

[0568] The change in transmittance of the optical anisotropic laminate 3 before and after the photocurable film was stacked was evaluated, and the result was ○ (good), indicating that even with the stacked photocurable film, the optical performance is good.

[0569] [Comparative Example 2]

[0570] The polymeric liquid crystal compound (I-1) contained in the anisotropic pigment film composition of Comparative Example 1 was set as polymeric liquid crystal compound (I-2), and otherwise, the optically anisotropic laminate 4 was obtained in the same manner as in Comparative Example 1.

[0571] The change in transmittance of the optical anisotropic laminate 4 before and after the photocurable film was laminated was evaluated, and the result was × (poor), indicating that the optical performance was reduced due to the laminated photocurable film.

[0572] The results of evaluating the changes in transmittance of λ0, λ1, and the optically anisotropic laminates before and after lamination in Example 2 and Comparative Example 2 are shown in Table 2. According to these results, the optically anisotropic laminate satisfying Equation (1) exhibits higher optical performance.

[0573] [Table 2]

[0574] Example 2 Comparative Example 2 λ0 319nm 319nm λ1 356nm 319nm Changes in transmittance ○ ×

[0575] [Comparative Example 3]

[0576] The curable resin (R-1) contained in the composition of Example 1 was replaced with UV-curable urethane acrylate UV-7750B (manufactured by Mitsubishi Chemical Corporation, weight average molecular weight Mw = 2400), otherwise, an optically anisotropic laminate 5 was obtained in the same manner as in Example 1.

[0577] The change in transmittance of the optical anisotropic laminate 5 before and after the photocurable film was laminated was evaluated, and the result was × (poor), indicating that the optical performance was reduced due to the laminated photocurable film.

[0578] The results of evaluating the changes in λ0, λ1, weight-average molecular weight (Mw) of the curable resin, and the transmittance of the optically anisotropic laminate before and after lamination in Examples 1 and Comparative Example 3 are shown in Table 3. According to these results, optically anisotropic laminates with a weight-average molecular weight (Mw) of the curable resin exceeding 10,000 exhibit higher optical performance.

[0579] [Table 3]

[0580]

[0581] The invention has been described in detail using specific methods, but those skilled in the art will understand that various modifications can be made without departing from the intent and scope of the invention.

[0582] This application is based on Japanese Patent Application 2020-197232, filed on November 27, 2020, and its entire contents are incorporated herein by reference.

Claims

1. An optically anisotropic laminate, wherein at least one photocurable film is laminated on an anisotropic pigment film. The anisotropic pigment film is a film obtained by irradiating an anisotropic pigment film composition containing pigment, polymerizable liquid crystal compound, and photopolymerization initiator with active energy rays. The photocurable film is a film obtained by irradiating 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 anisotropic pigment film composition and the maximum absorption wavelength λ1 of the photopolymerization initiator contained in the photocurable film composition satisfy the following formula (1). The curable resin contained in the photocurable film composition has a weight-average molecular weight (Mw) exceeding 10,000. λ0<λ1…(1) λ0 and λ1 are wavelengths above 250 nm that show an upward convex inflection point in the absorption spectrum. In the case of multiple maximum absorption wavelengths, λ0 and λ1 are the maximum absorption wavelengths on the long wavelength side.

2. An optically anisotropic laminate, wherein at least one adhesive film is laminated on anisotropic pigment films. The anisotropic pigment film is a film obtained by irradiating an anisotropic pigment film composition containing pigment, polymerizable liquid crystal compound, and photopolymerization initiator with active energy rays. The adhesive film is obtained by irradiating an adhesive 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 anisotropic pigment film composition and the maximum absorption wavelength λ1 of the photopolymerization initiator in the adhesive film composition satisfy the following formula (1). λ0<λ1…(1) λ0 and λ1 are wavelengths above 250 nm that show an upward convex inflection point in the absorption spectrum. In the case of multiple maximum absorption wavelengths, λ0 and λ1 are the maximum absorption wavelengths on the long wavelength side.

3. The optically anisotropic laminate according to claim 1, wherein, At least one layer of the photocurable film is an adhesive film.

4. The optically anisotropic laminate according to claim 1, wherein, At least one layer of the photocurable film is an outer coating.

5. The optically anisotropic laminate according to claim 2, wherein, At least one outer coating film is then stacked on the anisotropic pigment film.

6. The optically anisotropic laminate according to any one of claims 1 to 5, wherein, The difference between λ1 and λ0 is greater than 5 nm.

7. The optically anisotropic laminate according to claim 1, wherein, The curable resin is an acrylic resin having (meth)acryloyl groups.

8. The optically anisotropic laminate according to claim 7, wherein, The double bond equivalent of the acrylic resin is 0.1~10 mmol / g.

9. The optically anisotropic laminate according to claim 1, 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 equation (2), -Q 1 Represents a hydrogen atom or a polymeric group; -Q 2 Indicates a polymerizable group; -R 1 -and-R 2 - Each represents a chain-like organic group independently; -A 11 -and-A 13 - Represent independently the partial structures, divalent organic groups, or single bonds represented by the following formula (3); -A 12 - represents a portion of the structure or a divalent organic group represented by the following formula (3); -Y 1 -and-Y 2 - can represent single bonds, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C≡C-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-, respectively. -A 11 -and-A 13 - One of them is a partial structure or a divalent organic group represented by the following formula (3); k is 1 or 2; When k is 2, there are 2 -Y 2 -A 13 - Choose either the same or different -Cy-X 2 -C≡C-X 1 -…(3) In equation (3), -Cy- indicates a hydrocarbon cyclic group or a heterocyclic group; -X 1 - indicates -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S)-, -C(=O)S-, -SC(=O-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-; -X 2 - indicates a single bond, -C(=O)O-, -OC(=O)-, -C(=S)O-, -OC(=S-, -C(=O)S-, -SC(=O)-, -CH2CH2-, -CH=CH-, -C(=O)NH-, -NHC(=O-, -CH2O-, -OCH2-, -CH2S-, or -SCH2-.

10. The optically anisotropic laminate according to claim 1, wherein, The pigment is an azo dichromatic pigment.

11. The optically anisotropic laminate according to claim 1, wherein, The polymeric liquid crystal compound has a number (r) of ring structures n1 The number of ring structures (r) of the pigment n2 The ratio of r to r n1 / r n2 It ranges from 0.7 to 1.

5.

12. An optical element having an optically anisotropic laminate as described in any one of claims 1 to 11.

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