Optical film, optical laminate, and image display device

Abstract

The objective of this invention is to provide an optical film, an optical laminate, and an image display device that, when used in self-emissive image display devices employing inorganic EL elements and organic EL elements, can achieve both anti-reflective properties against external light and improved utilization efficiency of light emitted by the light-emitting element. The optical film of this invention is an anisotropic light-absorbing film formed from a cured liquid crystal composition comprising a polymeric liquid crystal compound and a dichroic pigment compound. The anisotropic light-absorbing film has a region A with an inclination of θA relative to the absorption axis of the film surface and a region B with an inclination of θB relative to the absorption axis of the film surface within the same film surface, and θA and θB satisfy the following relationships: |θA-θB|≥10° (Equation (1)) and 0°≤θB≤5° (Equation (2)).

Description

Technical Field

[0001] This invention relates to an optical film, an optical laminate, and an image display device. Background Technology

[0002] In recent years, as a replacement for liquid crystal display devices, display devices using self-emissive light-emitting elements such as organic electroluminescence (organic EL) and inorganic EL (inorganic LED) are being developed.

[0003] Image display devices, especially in bright environments, reflect external light, which degrades contrast.

[0004] Therefore, self-emissive display devices that use light-emitting elements such as organic EL display devices and inorganic EL display devices have a circular polarizer consisting of a polarizer and a λ / 4 plate on the surface as an anti-reflective film.

[0005] For example, Patent Document 1 describes an organic EL display device that includes an organic EL element composed of a reflective electrode, an organic EL light-emitting layer, and a transparent electrode, and a circular polarizer composed of a phase difference plate and a polarizer. An anti-reflective layer with high reflectivity in the complementary wavelength region of the light reflected from the surface of the circular polarizer is provided at the air interface of a component that is positioned closer to the observer than the circular polarizer.

[0006] Furthermore, Patent Document 2 describes a circular polarizer for an organic EL display device, comprising a polarizer, a phase difference layer that functions as a λ / 4 plate, a blocking layer, and an adhesive layer that has a blocking function, wherein the blocking layer is a thin glass with a thickness of 5 to 100 μm, and an organic EL display device comprising the circular polarizer.

[0007] Previous technical documents

[0008] Patent documents

[0009] Patent Document 1: Japanese Patent Application Publication No. 2009-259721

[0010] Patent Document 2: Japanese Patent Application Publication No. 2017-022016 Summary of the Invention

[0011] The technical problem to be solved by the invention

[0012] Such inorganic EL display devices and organic EL display devices, which are self-emissive display devices, have an anti-reflective film (circular polarizer) composed of a polarizer and a λ / 4 plate, which can prevent the reflection of external light and thus achieve high-contrast image display.

[0013] However, on the other hand, the anti-reflective film composed of polarizers and λ / 4 plates also absorbs the light emitted by the light-emitting elements. Therefore, in conventional self-emissive display devices, the light utilization efficiency is low, and the performance of light-emitting elements such as LEDs cannot be fully utilized.

[0014] The purpose of this invention is to solve the problems of the prior art and to provide an optical film that, when used in self-emissive image display devices such as inorganic EL elements and organic EL elements, can achieve both anti-reflective effects against external light and improved utilization efficiency of light emitted by the light-emitting elements.

[0015] Furthermore, the present invention also aims to provide an optical laminate and an image display device.

[0016] means for solving technical problems

[0017] As a result of in-depth research in order to solve the above-mentioned problems, the inventors discovered that the above-mentioned problems can be achieved through the following structure.

[0018] [1] An optical film having a light-absorbing anisotropic film formed from a cured liquid crystal composition comprising a polymeric liquid crystal compound and a dichroic pigment compound, wherein the light-absorbing anisotropic film has a region A with an inclination of θA relative to the absorption axis of the film surface and a region B with an inclination of θB relative to the absorption axis of the film surface in the same film surface, and θA and θB satisfy the following relationship (1) and (2).

[0019] |θA-θB|≥10° Formula (1)

[0020] 0°≤θB≤5° Equation (2)

[0021] [2] According to the optical film described in [1], wherein,

[0022] The inclination θA of the absorption axis is 45–90°.

[0023] [3] The optical film according to [1] or [2], wherein,

[0024] The inclination θA of the absorption axis is 80–90°.

[0025] [4] The optical film according to any one of [1] to [3], wherein,

[0026] The transmittance of region A in the direction of the absorption axis is over 65%.

[0027] [5] The optical film according to any one of [1] to [4], wherein,

[0028] The orientation degree of region B in the in-plane direction is greater than 0.950.

[0029] [6] The optical film according to any one of [1] to [5], wherein,

[0030] The content of dichroic pigment compounds is more than 15% by mass relative to the total mass of the light-absorbing anisotropic membrane.

[0031] [7] An optical laminate having an optical film and a λ / 4 plate as described in any one of [1] to [6] laminated thereon.

[0032] [8] An image display device having an optical film as described in any one of [1] to [6] or an optical laminate as described in [7].

[0033] [9] The image display device according to [8], wherein,

[0034] The position of region A of the light-absorbing anisotropic film corresponds to the position of the light-emitting element of the image display device.

[0035]

[10] The image display device according to [8] or [9], wherein,

[0036] The image display device is an electroluminescent display device.

[0037]

[11] The image display apparatus according to any one of [8] to

[10] , wherein,

[0038] The combined thickness of the optical film and the λ / 4 plate is less than 20 μm.

[0039] Invention Effects

[0040] According to the present invention, an optical film is provided that, when applied to a self-emissive image display device using inorganic EL elements and organic EL elements, can achieve both anti-reflective properties against external light and improved utilization efficiency of light emitted by the light-emitting element.

[0041] Furthermore, according to the present invention, an optical laminate and an image display device can be provided. Attached Figure Description

[0042] Figure 1 This is a diagram that conceptually illustrates an example of the image display device of the present invention.

[0043] Figure 2 This is a schematic diagram illustrating the definition of the angle θ of the absorption axis of the anisotropic light-absorbing film used in this invention.

[0044] Figure 3 This is a cross-sectional view that conceptually represents an example of the optical film of the present invention.

[0045] Figure 4This is a diagram that conceptually illustrates an example of an EL substrate used in the image display device of the present invention.

[0046] Figure 5 This is a diagram that conceptually illustrates an example of an EL substrate used in the image display device of the present invention.

[0047] Figure 6 This is a diagram that conceptually illustrates an example of an EL substrate used in the image display device of the present invention.

[0048] Figure 7 This is a diagram that conceptually illustrates an example of an EL substrate used in the image display device of the present invention.

[0049] Figure 8 This is a diagram that conceptually illustrates an example of an EL substrate used in the image display device of the present invention.

[0050] Figure 9 This is a conceptual diagram illustrating an example of a method for forming anisotropic light-absorbing films used in this invention.

[0051] Figure 10 This is a diagram that conceptually illustrates an example of an embodiment of the light-absorbing anisotropic film used in this invention.

[0052] Figure 11 It means Figure 10 An example of a photograph of an implementation method.

[0053] Figure 12 This is a diagram that conceptually illustrates an example of an embodiment of the light-absorbing anisotropic film used in this invention.

[0054] Figure 13 It means Figure 12 An example of a photograph of an implementation method. Detailed Implementation

[0055] Hereinafter, the optical film, optical laminate, and image display device of the present invention will be described in detail with reference to the preferred embodiments shown in the accompanying drawings.

[0056] The following description of the constituent elements is based on a representative embodiment of the present invention, but the present invention is not limited to this embodiment.

[0057] In addition, in this specification, the numerical range indicated by “~” refers to the range including the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0058] Furthermore, in this specification, parallel, orthogonal, horizontal, and vertical refer to the ranges of parallel ±10°, orthogonal ±10°, horizontal ±10°, and vertical ±10°, respectively, rather than referring to parallel, orthogonal, horizontal, and vertical in the strict sense.

[0059] Furthermore, in this specification, the concept of liquid crystal composition and liquid crystal compound also includes liquid crystal compositions and liquid crystal compounds that no longer exhibit liquid crystal properties due to curing or the like.

[0060] Furthermore, in this specification, each component may be used alone with one corresponding substance, or with two or more substances used in combination. Here, regarding each component, when two or more substances are used in combination, unless otherwise specified, the content of that component refers to the total content of the substances used in combination.

[0061] Furthermore, in this specification, "(meth)acrylate" is the expression for "acrylate" or "methacrylate", "(meth)acrylic acid" is the expression for "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" is the expression for "acryloyl" or "methacryloyl".

[0062] In this invention, visible light refers to light of electromagnetic waves with wavelengths observable by the human eye, specifically light in the wavelength range of 380–780 nm. Invisible light refers to light in the wavelength range below 380 nm and above 780 nm.

[0063] Furthermore, although not limited to this, in visible light, light in the wavelength region of 420–490 nm is blue light, light in the wavelength region of 495–570 nm is green light, and light in the wavelength region of 620–750 nm is red light.

[0064] <Optical film>

[0065] The optical film of the present invention is an optical film having a light absorption anisotropic film formed from a cured liquid crystal composition comprising a polymeric liquid crystal compound and a dichroic pigment compound, wherein the light absorption anisotropic film has a region A with an inclination of θA relative to the absorption axis of the film surface and a region B with an inclination of θB relative to the absorption axis of the film surface in the same film surface, and θA and θB satisfy the relationship of the following equations (1) and (2).

[0066] |θA-θB|≥10° Formula (1)

[0067] 0°≤θB≤5° Equation (2)

[0068] Here, the absorption axis refers to the direction in which the transmittance is highest at a wavelength of 550 nm when the tilt angle and tilt direction relative to the normal direction of the thin film are changed to measure transmittance. For example, it refers to the average value (average direction) of the molecules of the oriented dichroic pigment compound along its long axis. The transmittance measurement with changes in the tilt angle and tilt direction can be performed, for example, using an AxoScan OPMF-1 (manufactured by Opto Sciernce, Inc.).

[0069] Here, as Figure 2 As shown, the angle between the direction 30, which is parallel to the surface of the optical film of the present invention, and the absorption axis 31 in a certain region of the light absorption anisotropic film used in the present invention is defined as θ. θA refers to the angle between the surface of the optical film of the present invention and the absorption axis in region A, and θB refers to the angle between the surface of the optical film of the present invention and the absorption axis in region B.

[0070] Figure 3 This is a cross-sectional view that conceptually represents an example of the optical film of the present invention.

[0071] Figure 3 The optical film 20 shown has a transparent support 16 and a light-absorbing anisotropic film 18, which is formed from a cured liquid crystal composition comprising a polymeric liquid crystal compound and a dichroic pigment compound. Furthermore, within the same film surface, there are 18A with an inclination of θA relative to the absorption axis of the film surface and 18B with an inclination of θB relative to the absorption axis of the film surface, and θA and θB satisfy the relationships of equations (1) and (2) below.

[0072] |θA-θB|≥10° Formula (1)

[0073] 0°≤θB≤5° Equation (2)

[0074] By having two regions with different absorption axes within the same film surface, the anti-reflective properties of external light and the transmission properties of the light-emitting element can be adjusted for each region. Furthermore, in self-emissive display devices using inorganic EL elements and organic EL elements, a display device that can simultaneously achieve anti-reflective effects of external light and improve the utilization efficiency of light emitted by the light-emitting element can be provided.

[0075] Specifically, in region B, where the absorption axis is nearly parallel to the film surface, the polarization performance of external light relative to the perpendicular incident direction is higher and the anti-reflection effect is better compared to region A. In region A, the absorption axis is closer to the perpendicular to the film surface than in region B, resulting in higher transmittance of visible light in the perpendicular incident direction and improving the luminous efficiency of the self-emissive element.

[0076] In this invention, from the viewpoint of achieving superior effects, |θA-θB| is preferably 10° or more, more preferably 45° or more, and even more preferably 80° or more. There is no particular limitation on the upper limit; 90° is an example.

[0077] By setting |θA-θB| to a value within the above range, it is possible to achieve both the anti-reflection effect of external light absorption in anisotropic films and the improved utilization efficiency of light emitted by light-emitting elements.

[0078] In this invention, from the viewpoint of achieving superior effects, θA is preferably 45–90°, more preferably 80–90°. By setting θA to a value within the above range, the absorption of light emitted from the light-emitting element in the light-absorbing anisotropic film is reduced, thereby improving light utilization efficiency.

[0079] In this invention, from the viewpoint of achieving superior effects, the transmittance of region A in the absorption axis direction is preferably 65% ​​or more, more preferably 75% or more. By setting the transmittance to a value within the above range, the absorption of light emitted from the light-emitting element in the light-absorbing anisotropic film is reduced, thereby improving light utilization efficiency. There is no particular upper limit to the transmittance; values ​​less than 100% are common.

[0080] In this invention, there is no particular limitation on the orientation degree of region B in the in-plane direction; values ​​of 0.930 and above are common. From the viewpoint of achieving superior performance, the orientation degree of region B in the in-plane direction is preferably 0.950 or above, and more preferably 0.955 or above. By setting the orientation degree to a value within the above range, the antireflective performance when using anisotropic light-absorbing films can be improved. There is no particular limitation on the upper limit of the orientation degree; 1.000 is an example.

[0081] The degree of orientation in the in-plane direction can be determined by the following method.

[0082] With a linear polarizer inserted on the light source side of an optical microscope (Nikon Corporation, product name "ECLIPSE E600 POL"), the sample was set up, and the absorbance of the anisotropic film in the wavelength region of 380–780 nm was measured using a multi-channel spectrometer (Ocean Optics, Inc., product name "QE65000") at 1 nm intervals. The orientation degree at wavelengths of 400–700 nm was calculated using the following formula.

[0083] Orientation degree: S=((Az0 / Ay0)-1) / ((Az0 / Ay0)+2)

[0084] In the above formula, "Az0" represents the absorbance of polarized light in the absorption axis direction in region B of the optically anisotropic film, and "Ay0" represents the absorbance of polarized light in the transmission axis direction in region B of the optically anisotropic layer. The orientation degree of the wavelength 560nm in the above measurement is set as the orientation degree in the in-plane direction of region B.

[0085] (Anisotropic light absorption film)

[0086] As described above, the light-absorbing anisotropic film used in this invention is formed from a cured liquid crystal composition comprising a polymeric liquid crystal compound and a dichroic pigment compound.

[0087] [Polymerizable liquid crystal compounds]

[0088] As the polymerizable liquid crystal compound included in the liquid crystal composition, either a high molecular weight polymerizable liquid crystal compound or a low molecular weight polymerizable liquid crystal compound can be used. From the perspective of improving the degree of orientation, a high molecular weight polymerizable liquid crystal compound is preferred.

[0089] Here, "polymeric liquid crystal compound" refers to a polymeric liquid crystal compound having repeating units in its chemical structure.

[0090] Furthermore, "low molecular weight polymeric liquid crystal compounds" refers to polymeric liquid crystal compounds that do not have repeating units in their chemical structure.

[0091] Furthermore, as a polymerizable liquid crystal compound, both high-molecular-weight polymerizable liquid crystal compounds and low-molecular-weight polymerizable liquid crystal compounds can be used together. As a low-molecular-weight polymerizable liquid crystal compound, for example, reference can be made to paragraphs

[0042] to

[0053] of International Publication No. 2019 / 235355.

[0092] Considering that the resulting anisotropic light absorption film has a higher degree of orientation, the polymeric liquid crystal compound is preferably a polymeric liquid crystal compound containing the repeating unit (hereinafter also simply referred to as "repeating unit (1)") represented by the following formula (1).

[0093] Furthermore, in the following description, "the orientation degree of the obtained light absorption anisotropic film becomes higher" is also referred to as "the effect of the present invention is more superior".

[0094] [Chemical Formula 1]

[0095]

[0096] In the above formula (1), P1 represents the main chain of the repeating unit, L1 represents the single bond or divalent linking group, SP1 represents the spacer group, M1 represents the mesocrystalline group, and T1 represents the terminal group.

[0097] As the main chain of the repeating unit represented by P1, specifically, for example, the groups represented by the following formulas (P1-A) to (P1-D) can be cited, of which, from the viewpoint of the diversity of monomers as raw materials and ease of operation, the group represented by the following formula (P1-A) is preferred.

[0098] [Chemical Formula 2]

[0099]

[0100] In the above formulas (P1-A) to (P1-D), "*" indicates the bonding position with L1 in the above formula (1).

[0101] In the above equations (P1-A) to (P1-D), R 1 R 2 R 3 and R 4 Each of the following can be independently represented: a hydrogen atom, a halogen atom, a cyano group, an alkyl group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms. The alkyl group can be a straight-chain or branched alkyl group, or an alkyl group having a cyclic structure (cycloalkyl). Furthermore, the alkyl group preferably has 1 to 5 carbon atoms.

[0102] The group represented by the above formula (P1-A) is preferably a unit of a partial structure of poly(meth)acrylate obtained by polymerization of (meth)acrylate.

[0103] The group represented by the above formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of the epoxy group of a compound having an epoxy group.

[0104] The group represented by the above formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetane compound having an oxetane.

[0105] The group represented by the above formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one of alkoxysilyl and silanol groups. Here, as a compound having at least one of alkoxysilyl and silanol groups, an example can be a compound having the formula SiR. 14 (OR 15 Compounds containing the group represented by )2-. Where R 14 R in (P1-D) 4 Multiple Rs with the same meaning 15 Alkyl groups, which can be independently represented by 1 to 10 hydrogen or carbon atoms respectively.

[0106] In the above formula (1), L1 is a single bond or a divalent linking group.

[0107] Examples of divalent linking groups represented by L1 include -C(O)O-, -OC(O)-, -O-, -S-, and -C(O)NR. 3 -、-NR 3 C(O)-, -SO2- and -NR 3 R 3 - etc. In the formula, R 3 and R 3 Each of the following can be independently represented: a hydrogen atom and an alkyl group having 1 to 6 carbon atoms that may have substituents.

[0108] When P1 is a group represented by formula (P1-A), L1 is preferably a group represented by -C(O)O- for the sake of better performance of the present invention.

[0109] When P1 is a group represented by formulas (P1-B) to (P1-D), L1 is preferably a single bond for the sake of better performance of the present invention.

[0110] In the above formula (1), considering reasons such as easy liquid crystal properties or availability of raw materials, the spacer group represented by SP1 preferably includes at least one structure selected from the group consisting of ethylene oxide structure, propylene oxide structure, polysiloxane structure and fluorinated alkylene structure.

[0111] Here, the oxyethylene structure represented by SP1 is preferably *-(CH2-CH2O). n1 -* represents the group. In the formula, n1 represents an integer from 1 to 20, and * represents the bonding position with L1 or M1 in the above formula (1). For the sake of better effects of the present invention, n1 is preferably an integer from 2 to 10, more preferably an integer from 2 to 4, and even more preferably 3.

[0112] Furthermore, considering the superior effects of the present invention, the oxypropylene structure represented by SP1 is preferably *-(CH(CH3)-CH2O). n2 -* represents the group. In the formula, n2 represents an integer from 1 to 3, and * represents the bonding position with L1 or M1.

[0113] Furthermore, considering the superior effects of the present invention, the polysiloxane structure represented by SP1 is preferably *-(Si(CH3)2-O). n3 -* represents the group. In the formula, n3 represents an integer from 6 to 10, and * represents the bonding position with L1 or M1.

[0114] Furthermore, considering the superior effects of the present invention, the fluorinated alkylene structure represented by SP1 is preferably *-(CF2-CF2). n4-* represents the group. In the formula, n4 represents an integer from 6 to 10, and * represents the bonding position with L1 or M1.

[0115] In the above formula (1), the mesocrystalline group represented by M1 is a group that represents the main framework of liquid crystal molecules that contribute to the formation of liquid crystals. Liquid crystal molecules exhibit liquid crystal properties as an intermediate state (intermediate phase) between the crystalline state and the isotropic liquid state. There are no particular limitations regarding the mesocrystalline group. For example, one can refer to the description in "Flussige Kristalle in Tabellen II" (VEB Deutsche Verlag fur Grundstoff Industrie, Leipzig, 1984), especially pages 7 to 16, and the description in "Liquid Crystal Handbook" (Maruzen, 2000), edited by the Liquid Crystal Handbook Editorial Committee, especially Chapter 3.

[0116] As a mesocrystalline group, it is preferably a group having at least one cyclic structure selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups and alicyclic groups.

[0117] From the perspective of the superior effect of the present invention, the mesocrystalline group preferably has aromatic hydrocarbon groups, more preferably has 2 to 4 aromatic hydrocarbon groups, and even more preferably has 3 aromatic hydrocarbon groups.

[0118] From the viewpoints of liquid crystal properties, liquid crystal phase transition temperature adjustment, raw material availability and synthetic applicability, and superior effects of the present invention, the group represented by the following formula (M1-A) or the following formula (M1-B) is preferred as the mesocrystalline group, and more preferably the group represented by formula (M1-B).

[0119] [Chemical Formula 3]

[0120]

[0121] In formula (M1-A), A1 is a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. These groups may be substituted with alkyl, fluorinated alkyl, alkoxy, or substituents.

[0122] The divalent group represented by A1 is preferably a 4- to 6-membered ring. Furthermore, the divalent group represented by A1 can be a monocyclic ring or a fused ring.

[0123] * indicates the bonding position with SP1 or T1.

[0124] Examples of divalent aromatic hydrocarbon groups represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetraphenyl-diyl. From the viewpoint of the diversity of mesocrystalline framework design or the availability of raw materials, phenylene or naphthylene is preferred, and phenylene is more preferred.

[0125] The divalent heterocyclic group represented by A1 can be either aromatic or non-aromatic, but from the viewpoint of further improving the degree of orientation, a divalent aromatic heterocyclic group is preferred.

[0126] Examples of atoms other than carbon that constitute a divalent aromatic heterocyclic group include nitrogen, sulfur, and oxygen atoms. When an aromatic heterocyclic group has multiple atoms forming rings other than carbon, these atoms may be the same or different.

[0127] Specific examples of divalent aromatic heterocyclic groups include, for example, pyridinyl (pyridin-diyl), pyridazin-diyl, imidazole-diyl, thiophenyl (thiophen-diyl), quinolineyl (quinoline-diyl), isoquinolineyl (isoquinoline-diyl), oxazole-diyl, thiazole-diyl, oxadiazole-diyl, benzothiazole-diyl, benzothiadiazole-diyl, phthalimide-diyl, thienothiazole-diyl, thiazonothiazole-diyl, thienothiphene-diyl, and thienooxazole-diyl.

[0128] Specific examples of the divalent alicyclic group represented by A1 include cyclopentylene and cyclohexylene.

[0129] In formula (M1-A), a1 represents an integer from 1 to 10. When a1 is 2 or higher, multiple A1 values ​​can be the same or different.

[0130] In formula (M1-B), A2 and A3 are each independently a divalent group selected from the group consisting of aromatic hydrocarbon groups, heterocyclic groups, and alicyclic groups. Specific examples and preferred embodiments of A2 and A3 are the same as A1 in formula (M1-A), therefore their description is omitted.

[0131] In formula (M1-B), a2 represents an integer from 1 to 10. When a2 is 2 or more, multiple A2s can be the same or different, multiple A3s can be the same or different, and multiple LA1s can be the same or different. For the sake of superior performance of the present invention, a2 is preferably an integer of 2 or more, and more preferably 2.

[0132] In formula (M1-B), when a2 is 1, LA1 is a divalent linking group. When a2 is 2 or more, each of the plurality of LA1 is independently a single bond or a divalent linking group, and at least one of the plurality of LA1 is a divalent linking group. When a2 is 2, for the sake of better effects of the present invention, it is preferable that one of the two LA1 is a divalent linking group and the other is a single bond.

[0133] In formula (M1-B), examples of divalent linking groups represented by LA1 include -O- and -(CH2).g -、-(CF2) g -、-Si(CH3)2-、-(Si(CH3)2O) g -、-(OSi(CH3)2) g -(g represents an integer from 1 to 10.), -N(Z)-, -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)2-C(Z')2-, -C(O)-, -OC(O)-, -C(O)O-, -OC(O)O-, -N(Z)C(O)-, -C( O)N(Z)-, -C(Z)=C(Z')-C(O)O-, -0-C(O)-C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z')-C(O)N(Z”)-, -N(Z”)-C(O)-C(Z)=C(Z’)-, -C (Z)=C(Z')-C(O)-S-, -SC(O)-C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (Z, Z', Z” independently represent hydrogen, C1~C4 (1~4 carbon atoms) alkyl, cycloalkyl, aryl, cyano or halogen atom, respectively), -C≡C-, -N=N-, -S-, -S(O)-, -S(O)(O)-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)- and -C(O)S-, etc. Among them, -C(O)O- is preferred for the sake of superior effect of the present invention. LA1 can also be a group formed by combining two or more of these groups.

[0134] Specific examples of M1 include the following structures. Additionally, in the following examples, "Ac" represents an acetyl group.

[0135] [Chemical Formula 4]

[0136]

[0137] [Chemical Formula 5]

[0138]

[0139] [Chemical Formula 6]

[0140]

[0141] [Chemical Formula 7]

[0142]

[0143] [Chemical Formula 8]

[0144]

[0145] [Chemical Formula 9]

[0146]

[0147] [Chemical Formula 10]

[0148]

[0149] Considering the reasons that it improves adhesion to adjacent layers and enhances the cohesiveness of the membrane, T1 is preferably a polymerizable group.

[0150] There are no particular limitations on the polymerizable groups, but preferably polymerizable groups that can undergo free radical polymerization or cationic polymerization.

[0151] As a free radical polymerizable group, commonly known free radical polymerizable groups can be used. Examples of preferred free radical polymerizable groups include acryloyl and methacryloyl. In this case, it is known that acryloyl generally polymerizes quickly, and from the viewpoint of improving productivity, acryloyl is preferred, but methacryloyl can also be used as a polymerizable group.

[0152] As a cationic polymerizable group, commonly known cationic polymerizable groups can be used. Specifically, examples include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spirocyclic orthoester groups, and ethyleneoxy groups. Among these, alicyclic ether groups or ethyleneoxy groups are preferred, and epoxy groups, oxetyl groups, or ethyleneoxy groups are more preferred.

[0153] From the perspective of achieving superior effects of the present invention, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound containing the repeating unit represented by formula (1) above is preferably 100 to 500,000, more preferably 2,000 to 300,000. If the Mw of the polymeric liquid crystal compound is within the above range, the processing of the polymeric liquid crystal compound becomes easier.

[0154] In particular, from the viewpoint of crack suppression during coating, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably 10,000 or more, and more preferably 10,000 to 300,000.

[0155] Furthermore, from the viewpoint of temperature tolerance of orientation, the weight-average molecular weight (Mw) of the polymeric liquid crystal compound is preferably less than 10,000, and more preferably 2,000 or more but less than 10,000.

[0156] In this invention, the weight-average molecular weight and number-average molecular weight are values ​​determined by gel permeation chromatography (GPC).

[0157] • Solvent (eluent): N-methylpyrrolidone

[0158] • Device Name: TOSOH HLC-8220GPC

[0159] • String: Connect 3 TOSOH TSKgelSuperAWM-H (6mm×15cm) tubes for use.

[0160] • Column temperature: 25℃

[0161] • Sample concentration: 0.1% by mass

[0162] • Flow rate: 0.35 mL / min

[0163] • Calibration curves: Calibration curves based on 7 samples were used, using TOSOH CORPORATION's TSK standard polystyrene Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06).

[0164] In this invention, the content of the polymerizable liquid crystal compound is preferably 8 to 99% by mass of the solid component in the liquid crystal composition, more preferably 8 to 96% by mass.

[0165] Here, "solid components in the liquid crystal composition" refers to components other than solvents. Specific examples of solid components include the aforementioned polymerizable liquid crystal compounds and dichroic pigment compounds, polymerization initiators, surfactants, etc., which will be described later.

[0166] [Dichroic pigment compound]

[0167] There are no particular limitations on the dichroic pigment compounds contained in the liquid crystal composition. Examples include visible light absorbing substances (dichroic pigments), luminescent substances (fluorescent substances, phosphorescent substances), ultraviolet light absorbing substances, infrared light absorbing substances, nonlinear optical substances, carbon nanotubes, inorganic substances (such as quantum rods), etc., and conventionally known dichroic pigment compounds (dichroic pigments) can be used.

[0168] Specifically, examples include paragraphs

[0067] to

[0071] of Japanese Patent Application Publication No. 2013-228706, paragraphs

[0008] to

[0026] of Japanese Patent Application Publication No. 2013-227532, paragraphs

[0008] to

[0015] of Japanese Patent Application Publication No. 2013-209367, paragraphs

[0045] to

[0058] of Japanese Patent Application Publication No. 2013-014883, paragraphs

[0012] to

[0029] of Japanese Patent Application Publication No. 2013-101328, and Japanese Patent Application Publication No. 2013-101328. Paragraphs

[0009] to

[0017] of the Japanese JP 2013-037353, paragraphs

[0051] to

[0065] of the Japanese JP 2012-063387, paragraphs

[0049] to

[0073] of the Japanese JP 2012-063387, paragraphs

[0016] to

[0018] of the Japanese JP 2001-133630, paragraphs

[0009] to

[0011] of the Japanese JP 2011-215337, paragraphs

[0030] to

[0169] of the Japanese JP 2010-1062, and the Japanese JP 2010-1062, etc. Paragraphs

[0021] to

[0075] of Japanese Patent Application Publication No. 42, paragraphs

[0011] to

[0025] of Japanese Patent Application Publication No. 2010-215846, paragraphs

[0017] to

[0069] of Japanese Patent Application Publication No. 2011-048311, paragraphs

[0013] to

[0133] of Japanese Patent Application Publication No. 2011-213610, paragraphs

[0074] to

[0246] of Japanese Patent Application Publication No. 2011-237513, paragraphs

[0005] to

[0051] of Japanese Patent Application Publication No. 2016-006502, WO2016 / 0 The dichroic substances described in paragraphs

[0005] to

[0041] of Published No. 60173, paragraphs

[0008] to

[0062] of Published No. WO2016 / 136561, paragraphs

[0014] to

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

[0014] to

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

[0013] to

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

[0014] to

[0034] of International Publication No. 2018 / 164252.

[0169] In this invention, two or more dichroic pigment compounds may be used together. For example, from the viewpoint of making the obtained light absorption anisotropic film close to black, it is preferable to use at least one dichroic pigment compound having a maximum absorption wavelength in the range of wavelengths above 370 nm and below 500 nm, and at least one dichroic pigment compound having a maximum absorption wavelength in the range of wavelengths above 500 nm and below 700 nm.

[0170] The aforementioned dichroic pigment compounds may also have cross-linking groups.

[0171] Specifically, examples of the crosslinking groups mentioned above include (meth)acryloyl, epoxy, oxocyclobutyl and styryl, among which (meth)acryloyl is preferred.

[0172] From the viewpoint of achieving excellent results of the present invention, the content of the dichroic pigment compound is preferably 1 to 400 parts by mass relative to 100 parts by mass of the polymeric liquid crystal compound, more preferably 2 to 100 parts by mass, and even more preferably 5 to 30 parts by mass.

[0173] Furthermore, from the viewpoint of enabling the light-absorbing anisotropic film to be thinner and improving the orientation degree, the content of the dichroic pigment compound is preferably 10% by mass or more of the solid components in the liquid crystal composition, more preferably 15% by mass or more. Furthermore, from the viewpoint of having cohesiveness as a layer and maintaining flexibility, it is preferably 40% by mass or less of the solid components in the liquid crystal composition, more preferably 30% by mass or less.

[0174] Furthermore, the content of the dichroic pigment compound in the light-absorbing anisotropic film is preferably 15% by mass or more relative to the total mass of the light-absorbing anisotropic film. There is no particular upper limit, but it is preferably 40% by mass or less.

[0175] From the viewpoint of superior performance of the present invention, the dichroic pigment compound is preferably oriented in a predetermined direction in the light absorption anisotropic film. The method for orienting the dichroic pigment compound is not particularly limited; techniques for achieving the desired orientation of the dichroic pigment compound can be referenced from techniques for fabricating polarizers using the dichroic pigment compound, or techniques for fabricating guest-host type liquid crystal cells, etc. For example, techniques used in the fabrication methods of dichroic polarizing elements described in Japanese Patent Application Publication No. 11-305036 or Japanese Patent Application Publication No. 2002-090526, and in the fabrication methods of guest-host type liquid crystal display devices described in Japanese Patent Application Publication No. 2002-99388 or Japanese Patent Application Publication No. 2016-27387, can also be used in the fabrication of the light absorption anisotropic film used in the present invention.

[0176] In addition, the liquid crystal composition may also contain components such as polymerization initiators, surfactants, and adhesion modifiers.

[0177] [Polymerization initiator]

[0178] There are no particular restrictions on the polymerization initiator used, but photosensitive compounds, i.e., photopolymerization initiators, are preferred.

[0179] As photopolymerization initiators, a wide variety of compounds can be used without particular limitations. Examples of photopolymerization initiators include α-carbonyl compounds (as described in U.S. Patent Nos. 2,367,661 and 2,367,670), azobin ethers (as described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic azobin compounds (as described in U.S. Patent No. 2,722,512), polynuclear quinone compounds (as described in U.S. Patent Nos. 3,046,127 and 2,951,758), and combinations of triarylimidazolium dimers and p-aminophenyl ketones (as described in U.S. Patent No. 3,549,367). ), acridine and phenazine compounds (Japanese Patent Application Publication No. 60-105667 and US Patent No. 4239850), oxadiazole compounds (US Patent No. 4212970), o-acyl compounds (Japanese Patent Application Publication No. 2016-027384

[0065] paragraph) and acylphosphine oxide compounds (Japanese Patent Application Publication No. 63-040799, Japanese Patent Application Publication No. 5-29234, Japanese Patent Application Publication No. 10-095788 and Japanese Patent Application Publication No. 10-029997), etc.

[0180] Commercially available products can also be used as photopolymerization initiators, such as Irgacure-184, Irgacure-907, Irgacure-369, Irgacure-651, Irgacure-819, Irgacure-OXE-01, and Irgacure-OXE-02 manufactured by BASF.

[0181] When the liquid crystal composition contains a polymerization initiator, the content of the polymerization initiator is preferably 0.01 to 30 parts by mass, more preferably 0.1 to 15 parts by mass, relative to the total of 100 parts by mass of the dichroic pigment compound and the liquid crystal compound in the liquid crystal composition. When the content of the polymerization initiator is 0.01 parts by mass or more, the durability of the light-absorbing anisotropic film becomes good; when the content of the polymerization initiator is 30 parts by mass or less, the orientation degree of the light-absorbing anisotropic film becomes good.

[0182] A polymerization initiator can be used alone or in combination with two or more. When two or more polymerization initiators are used, it is preferable that their total amount is within the range described above.

[0183] [surfactant]

[0184] The liquid crystal composition preferably contains a surfactant.

[0185] By including surfactants, it is expected that the smoothness of the coated surface will be improved and the orientation degree will be further improved, or the in-plane uniformity will be improved by suppressing depressions and unevenness.

[0186] As surfactants, surfactants that make the dichroic pigment compound and the liquid crystal compound horizontal on the coating surface side can be used, or surfactants that make them vertical can be used. For example, compounds described in paragraphs

[0155] to

[0170] of International Publication No. 2016 / 009648, compounds described in paragraphs

[0253] to

[0293] of Japanese Patent Application Publication No. 2011-237513 (horizontal alignment agent), or compounds described in paragraphs

[0071] to

[0097] of International Publication No. 2019 / 235355 (vertical alignment agent) can also be used. Furthermore, polyacrylate-based surfactants or surfactants containing fluorine atoms are preferred as surfactants.

[0187] The surfactant contained in the liquid crystal composition may be a fluoropolymer having a repeating structure B1 represented by formula (B-1) described later and a repeating structure B2 containing fluorine atoms.

[0188] (Repeating structure B1)

[0189] The repeating structure B1 of the above-mentioned fluoropolymer is the repeating structure represented by the following formula (B-1).

[0190] [Chemical Formula 11]

[0191]

[0192] In the above formula (B-1), R 1 It represents hydrogen atoms, alkyl groups or halogen atoms with 1 to 5 carbon atoms.

[0193] Furthermore, L 1 Indicates a single bond or -CO-.

[0194] Furthermore, Sp represents a divalent hydrocarbon group with 1 to 20 carbon atoms, either straight-chain or branched. One or more non-adjacent -CH2- atoms that constitute part of the hydrocarbon group can be independently replaced by -O-, -S-, -NH-, or -N(Q)-, where Q represents a substituent.

[0195] L 2 and L 3 Each can be used independently to represent a single bond or a divalent linker.

[0196] R in the above equation (B-1) 1 Preferably, it is an alkyl group having 1 to 5 carbon atoms, and more preferably a hydrogen atom or a methyl group.

[0197] As L in the above formula (B-1) 1 Preferably -CO-.

[0198] As the divalent hydrocarbon group with 1 to 20 carbon atoms represented by Sp in the above formula (B-1), examples include divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms, divalent alicyclic hydrocarbon groups with 3 to 20 carbon atoms, divalent aromatic hydrocarbon groups with 6 to 20 carbon atoms, and divalent aromatic heterocyclic groups with 6 to 20 carbon atoms. Among these, divalent aliphatic hydrocarbon groups with 1 to 20 carbon atoms are preferred.

[0199] Here, the preferred divalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is an alkylene group having 1 to 15 carbon atoms or an alkylene group having 1 to 8 carbon atoms. Specifically, preferred examples include methylene, ethylene, propylene, butylene, pentylene, hexylene, methylhexylene, and heptylene.

[0200] Furthermore, as described above, one or more non-adjacent -CH2- groups constituting part of a straight-chain or branched divalent hydrocarbon group having 1 to 20 carbon atoms can be independently substituted by -O-, -S-, -NH-, or -N(Q)-. Additionally, as the substituent represented by Q, the aforementioned substituent W can be cited, preferably an alkyl, alkoxy, or halogen atom.

[0201] As L in the above formula (B-1) 2 and L 3 The divalent linking group represented in one manner can be exemplified by, for example, -C(O)O-, -OC(O)-, -O-, -S-, -C(O)NR. L1 -、-NR L1 C(O)-, -SO2- and -NR L1 R 12 - etc. In the formula, R L1 and R L2 Each of the above-mentioned substituents W can be independently represented by a hydrogen atom and an alkyl group having 1 to 6 carbon atoms, which may have substituents.

[0202] Furthermore, in the above formula (B-1), A represents any of the divalent linking groups represented by formulas (A-1) to (A-15) below. Wherein, * in formulas (A-1) to (A-15) below indicates a linking group with L. 2 or L 3 At the bonding positions, the carbon atoms constituting the ring structure in the following formulas (A-1) to (A-15) can be substituted with heteroatoms or have substituents. Furthermore, examples of substituents that can be present on the carbon atoms constituting the ring structure include the aforementioned substituent W, wherein alkyl, alkoxy, or halogen atoms are preferred.

[0203] [Chemical Formula 12]

[0204]

[0205] As the divalent linking group represented by any one of the above formulas (A-1) to (A-15), specifically, examples include 1,4-phenylene, 1,4-cyclohexene, 1,4-cyclohexenyl, tetrahydropyran-2,5-diyl, 1,4-piperazinyl, 1,4-piperidinyl, 1,3-dioxane-2,5-diyl, tetrahydrothiaran-2,5-diyl, 1,4-bicyclo(2,2,2)octylene, decahydronaphthalene-2,6-diyl, pyridine-2, 5-Diyl, pyrimidine-2,5-diyl, pyrazin-2,5-diyl, 1,2,3,4-tetrahydronaphthyl-2,6-diyl, 2,6-naphthylene, phenanthrene-2,7-diyl, 9,10-dihydrophenanthrene-2,7-diyl, 1,2,3,4,4a,9,10a-octahydrophenanthrene-2,7-diyl, 9-fluorenone-2,7-diyl, fluorene-2,7-diyl, thienothiophene-3,6-diyl, carbazole-3,6-diyl, and carbazole-2,7-diyl, etc.

[0206] Considering the reason that the orientation degree of the formed light-absorbing anisotropic film becomes higher, A in the above formula (B-1) is preferably a divalent linking group represented by any one of the above formulas (A-1), (A-4), (A-7), (A-10) and (A-13), and more preferably a divalent linking group represented by any one of the above formulas (A-7) and (A-13).

[0207] Furthermore, in the above formula (B-1), D represents a hydrogen-bonded group composed of hydrogen atoms and non-metallic atoms from groups 14 to 16. The non-metallic atoms may have substituents.

[0208] Here, nonmetallic atoms from groups 14 to 16 can be exemplified by, for example, oxygen, sulfur, nitrogen, and carbon atoms.

[0209] Furthermore, the substituents that can be present as non-metallic atoms (especially nitrogen and carbon atoms) include, for example, halogen atoms, alkyl groups, alkoxy groups, alkyl-substituted alkoxy groups, cyclic alkyl groups, aryl groups (e.g., phenyl, naphthyl, etc.), cyano groups, amino groups, nitro groups, alkyl carbonyl groups, sulfonyl groups, and hydroxyl groups.

[0210] Examples of such hydrogen-bonding groups include hydrogen bond donor groups and hydrogen bond acceptor groups.

[0211] Specifically, examples of hydrogen bond-donating groups include, for example, amino, amide, urea, carbamate, sulfonamide, sulfonyl, phosphate group, hydroxyl, mercapto, carboxyl, methylene substituted with an electron-withdrawing group, and methine substituted with an electron-withdrawing group, among which carboxyl and amide are preferred.

[0212] Specifically, examples of hydrogen bond accepting groups include heteroatoms with non-shared electron pairs on heteroatom rings, hydroxyl groups, aldehyde groups, ketone groups, carboxyl groups, carboxylic acid ester groups, carboxylic acid amide groups, lactone groups, lactam groups, sulfonamide groups, sulfonyl groups, phosphoric acid groups, phosphoroamide groups, urethane groups, urea groups, ether structures (especially polymer structures containing oxygen atoms in polyether structures), aliphatic amine groups, and aromatic amine groups, among which carboxyl or amide groups are preferred.

[0213] (Repeating structure B2)

[0214] The repeating structure B2 of the aforementioned fluorine-containing polymer is a repeating structure with fluorine atoms.

[0215] In this invention, considering the reason that the orientation degree of the formed light-absorbing anisotropic film becomes higher, the content of repeating structure B2 relative to the total mass of the surfactant is preferably 15 to 90% by mass, more preferably 20 to 80% by mass, and even more preferably 30 to 70% by mass.

[0216] Furthermore, in surfactants, the repeating structure B2 can consist of one type or two or more types. When two or more repeating structures B2 are present, the aforementioned content of repeating structure B2 refers to the total content of all repeating structures B2.

[0217] (Repeated structure B3)

[0218] In this invention, considering the reason that the coating properties of the formed light-absorbing anisotropic film are improved, it is preferable that the fluorinated polymer, in addition to the repeating structures B1 and B2 described above, also includes a repeating structure B3 derived from a monomer with a molecular weight of 300 or less.

[0219] As for the repeating structure B3, considering the improved coatability of the resulting anisotropic light-absorbing film, the repeating structure represented by the following formula (N-1) is preferred. The repeating structure B3 has a different structure from the repeating structure B2 described above, and preferably does not contain fluorine atoms.

[0220] [Chemical Formula 13]

[0221]

[0222] In equation (N-1), R B11and R B12 Each can be used independently to represent a hydrogen atom or a substituent. Specifically, in R... B11 and R B12 In the case of substituents, R B11 and R B12 They can be connected to form a ring.

[0223] R B11 molecular weight and R B12 The total molecular weight is preferably 200 or less, more preferably 100 or less, and even more preferably 70 or less. If the total molecular weight is 100 or less, the interaction between the repeating structures B3 is further enhanced, thereby further reducing the compatibility between the surfactant and the liquid crystal molecules. As a result, a light-absorbing anisotropic film with few orientation defects and excellent orientation degree can be obtained.

[0224] R B11 molecular weight and R B12 The lower limit of the total molecular weight is preferably 2 or more.

[0225] As R B11 and R B12 From the viewpoint of better effects of the present invention, the substituents represented are preferably organic groups, more preferably organic groups with 1 to 15 carbon atoms, even more preferably organic groups with 1 to 12 carbon atoms, and especially preferably organic groups with 1 to 8 carbon atoms.

[0226] Examples of organic groups mentioned above include straight-chain, branched, or cyclic alkyl groups, aromatic hydrocarbon groups, and heterocyclic groups.

[0227] The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 8.

[0228] The carbon atom of an alkyl group can be represented by -O-, -Si(CH3)2-, or -(Si(CH3)2O). g -、-(OSi(CH3)2) g-(g represents an integer from 1 to 10.), -N(Z)-, -C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(O)-, -OC(O)-, -C(O)O-, -OC(O)O-, -N(Z)C(O)-, -C(O)N(Z)-, -C(Z)=C(Z') -C(O)O-, -OC(O)-C(Z)=C(Z')-, -C(Z)=N-, -N=C(Z)-, -C(Z)=C(Z')-C( O)N(Z”)-, -N(Z”)-C(0)-C(Z)=C(Z’)-, -C(Z)=C(Z’)-C(0)-S-, -SC(O)- C(Z)=C(Z')-, -C(Z)=NN=C(Z')- (Z, Z', and Z” independently represent hydrogen, alkyl, cycloalkyl, aryl, cyano, or halogen atoms having 1 to 4 carbon atoms, respectively), -C≡C-, -N=N-, -S-, -C(S)-, -S(O)-, -SO2-, -(O)S(O)O-, -O(O)S(O)O-, -SC(O)-, and -C(O)S-, as well as groups formed by combining two or more of these groups. Among the groups in which the carbon atoms of the alkyl group can be substituted, from the viewpoint of better effect of the present invention, -O-, -C(O)-, -N(Z)-, -OC(O)-, or -C(O)O- are preferred.

[0229] The hydrogen atom of the alkyl group can be substituted with a halogen atom, cyano, aryl, nitro, -0ZH, -C(O)ZH, -C(O)OZH, -OC(O)ZH, -OC(O)OZH, -NZHZH', -NZHC(O)ZH', -NZHC(O)OZH', -C(O)NZHZH', -OC(O)NZHZH', -NZHC(O)NZH'OZH", -SZH, -C(S)ZH, -C(O)SZH, or -SC(O)ZH. ZH, ZH', and ZH" independently represent a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, or a nitro group, respectively. Among the groups in which the hydrogen atom of the alkyl group can be substituted, from the viewpoint of better effect of the present invention, -OH, -COOH, or aryl (preferably phenyl) are preferred.

[0230] The hydrogen atoms of aromatic hydrocarbon groups and heterocyclic groups can be substituted by halogen atoms, cyano groups, alkyl groups with 1 to 10 carbon atoms, cyano groups, nitro groups, -OZH, -C(O)ZH, -C(O)OZH, -OC(O)ZH, -OC(O)OZH, -NZHZH', -NZHC(O)ZH', -NZHC(O)OZH', -C(O)NZHZH', -OC(O)NZHZH', -NZHC(O)NZH'OZH", -SZH, -C(S)ZH, -C(O)SZH, -SC(O)ZH, and -B(OH)2. ZH, ZH', and ZH” independently represent hydrogen atoms, halogen atoms, alkyl groups with 1 to 10 carbon atoms, cyano groups, or nitro groups, respectively. From the viewpoint of better performance of the present invention, -OH and -B(OH)2 are preferred among the groups in which the hydrogen atoms of the aromatic hydrocarbon group and the hydrogen atoms of the heterocyclic group can be substituted.

[0231] From the viewpoint that the present invention offers superior performance, R B11 and R B12 Each organic group is preferably composed of 1 to 15 hydrogen atoms or carbon atoms. The preferred method for the organic group is as described above.

[0232] From the viewpoint that the present invention offers superior performance, R B11 and R B12 In the presence of the present invention, at least one of the present inventions is preferably a substituent, and more preferably at least one of the present inventions is an organic group having 1 to 15 carbon atoms.

[0233] R B11 and R B12 The resulting ring is a heterocycle containing nitrogen atoms from formula (N-1), and may further contain heteroatoms such as oxygen atoms, sulfur atoms, and nitrogen atoms.

[0234] From the viewpoint that the present invention offers superior performance, R B11 and R B12 The ring formed by the connection is preferably a 4- to 8-membered ring, more preferably a 5- to 7-membered ring, and even more preferably a 5- to 6-membered ring.

[0235] From the viewpoint that the present invention offers superior effects, constituting R B11 and R B12 The number of carbon atoms in the linked ring is preferably 3 to 7, more preferably 3 to 6.

[0236] R B11 and R B12 The rings formed by the links may or may not be aromatic, but from the viewpoint of better performance of the present invention, it is preferable that they are not aromatic.

[0237] As R B11 and RB12 Specific examples of rings formed by linkages include the following groups.

[0238] [Chemical Formula 14]

[0239]

[0240] R B13 It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a cyano group, wherein, preferably, it is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and more preferably, it is a hydrogen atom.

[0241] The alkyl group has 1 to 5 carbon atoms, preferably 1 to 3, and more preferably 1. The alkyl group can be any of the following structures: straight-chain, branched, or cyclic.

[0242] The following shows a specific example of the repeating structure B3, but the repeating structure B3 is not limited to the following structures.

[0243] [Chemical Formula 15]

[0244]

[0245] The content of repeating structure B3 relative to the total mass of all repeating structures of the fluorinated polymer is preferably 3 to 75% by mass, more preferably 15 to 70% by mass, and even more preferably 20 to 65% by mass. The effect of the present invention is even better if the content of repeating structure B3 is within the above range.

[0246] In surfactants, repeating structure B3 can be contained as a single type or as two or more types. When two or more repeating structures B3 are contained, the aforementioned content of repeating structure B3 refers to the total content of all repeating structures B3.

[0247] (Other repeating structures (1 of them))

[0248] The fluorinated polymers mentioned above may also have repeating structures represented by the following general formula (M-3).

[0249] [Chemical Formula 16]

[0250]

[0251] In the above formula (M-3), R3 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group with 1 to 20 carbon atoms, L3 represents a single bond or a divalent linking group, and T3 represents an aromatic ring.

[0252] The linking group of L3 is preferably a single bond or a straight-chain, branched, or cyclic alkylene group having 1 to 10 carbon atoms. Here, the carbon atom of the alkylene group can be substituted with -O-, -S-, -N(Z)-, -C(Z)=C(Z')-, -C(O)-, -C(S)-, -OC(O)-, -OC(S)-, -SC(O)-, -C(O)O-, -C(S)O-, -C(O)S-, -OC(O)O-, -N(Z)C(O)-, or -C(O)N(Z)- (where Z and Z' independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group, or a halogen atom, respectively.). Furthermore, the hydrogen atom of the alkylene group can be substituted with a fluorine atom or a fluoroalkyl group.

[0253] Examples of aromatic cyclic groups for T3 include aromatic hydrocarbon cyclic groups such as benzene, naphthyl, anthracene, and phenanthroline; and aromatic heterocyclic groups such as furanyl, pyrroleyl, thiophene, pyridine, thiazole, and benzothiazole. Among these, benzene cyclic groups (e.g., 1,4-phenyl) are preferred. Including these groups in the polymer improves compatibility.

[0254] As a monomer forming the repeating structure represented by the above formula (M-3), specifically, for example, monomers represented by the following formulas (M3-1) to (M3-5) can be cited, but the present invention is not limited thereto.

[0255] [Chemical Formula 17]

[0256]

[0257] (Other repeating structures (2))

[0258] The fluorinated polymers mentioned above may also have repeating structures represented by the following general formula (M-4).

[0259] [Chemical Formula 18]

[0260]

[0261] In the above formula (M-4), R4 represents a hydrogen atom, a fluorine atom, a chlorine atom, or an alkyl group with 1 to 20 carbon atoms, L4 represents a single bond or a divalent linking group, and Q4 represents any one of the crosslinking groups represented by the following formulas (P1) to (P30).

[0262] R in equations (P1) to (P30) PThis refers to hydrogen atoms, halogen atoms, straight-chain, branched, or cyclic alkylene groups with 1 to 10 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, alkoxy groups with 1 to 20 carbon atoms, alkenyl groups with 1 to 20 carbon atoms, alkynyl groups with 1 to 20 carbon atoms, aryl groups with 1 to 20 carbon atoms, heterocyclic groups (also called heteroatom-containing cyclic groups), cyano, hydroxyl, nitro, carboxyl, aryloxy, silyloxy, heterocyclic, acyloxy, carbamoyloxy, alkoxycarbonyloxy, aryloxycarbonyloxy, amino (including aniline), ammonium, amide, and aminocarbonylamine. alkyl, alkoxycarbonylamino, aryloxycarbonylamino, aminosulfonylamino, alkyl or arylsulfonylamino, mercapto, alkylthio, arylthio, heterocyclic thio, aminosulfonyl, sulfonyl, alkyl or arylsulfinyl, alkyl or arylsulfonyl, acyl, aryloxycarbonyl, alkoxycarbonyl, carbamoyl, aryl or heterocyclic azo, imide, phosphinyl, oxophosphinyl, oxophosphinyloxy, oxophosphinylamino, phosphonyl, silyl, hydrazyl, urea, borate (-B(OH)2), phosphate (-OPO(OH)2) or sulfate (-OSO3H), multiple R P They can be the same or different.

[0263] [Chemical Formula 19]

[0264]

[0265] Examples of linking groups for L4 include aromatic hydrocarbon groups with 4 to 20 carbon atoms, cyclic alkylene groups with 4 to 20 carbon atoms, and heterocyclic groups with 1 to 20 carbon atoms. Preferably, they are straight-chain, branched, or cyclic alkylene groups with 1 to 20 carbon atoms or aromatic hydrocarbon groups with 4 to 20 carbon atoms, and preferably have -O-, -CO-P-, -CO-NH-, or -P-CP-.

[0266] In the case where Q4 represents a group containing a cationic polymerizable group, there is no particular limitation on what constitutes a cationic polymerizable group. Examples include alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spirocyclic orthoester groups, and ethyleneoxy groups.

[0267] As a cationic polymerizable group, an alicyclic ether group or an ethyleneoxy group is preferred, more preferably an epoxy group, an oxetyl group, or an ethyleneoxy group, further preferably an epoxy group or an oxetyl group, and especially preferably an epoxy group. As an epoxy group, an alicyclic epoxy group is particularly preferred. Furthermore, each of the above-mentioned groups may have substituents.

[0268] When Q4 represents a group containing a free radical polymerizable group, there is no particular limitation on what constitutes a free radical polymerizable group. Examples include groups containing polymerizable carbon-carbon double bonds, specifically (meth)acryloyl, (meth)acryloyloxy, (meth)acrylamido, vinyl, styrene, allyl, etc., with (meth)acryloyloxy being preferred. Furthermore, each of the above-mentioned groups may have substituents. By including these groups, for example, the interlayer adhesion can be improved when multiple layers are stacked in the optical film described later.

[0269] As a monomer forming the repeating structure represented by the above formula (M-4), specifically, for example, the monomers represented by the following formulas (M4-1) to (M4-17) can be cited, but the present invention is not limited thereto.

[0270] [Chemical Formula 20]

[0271]

[0272] The aforementioned fluorinated polymers can be polymers with end-capped structures, grafted structures, branched structures, or star-shaped structures. By having such end-capped, grafted, branched, or star-shaped structures, the fluorine groups exist in bulk, thus offering advantages in improving the transferability of the polymer to the coating surface.

[0273] Furthermore, in copolymers with random structures where the fluorinated alkyl chain length is 1 to 4, the fluorine groups are relatively small, resulting in excellent solubility in common solvents, but low transferability to the coating surface. On the other hand, in the polymers described above, since the fluorine groups exist as bulk groups, even with fluorinated alkyl chain lengths of 1 to 4, the transferability to the coating surface is high. By adding such copolymers to the composition, the surface tension of the coating can be reduced, resulting in good wettability (homogeneous coating) of the composition to the substrate and good surface finish of the coating during coating, which is therefore preferred.

[0274] When the liquid crystal composition contains a surfactant, the surfactant content is preferably 0.001 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, relative to the total of 100 parts by mass of the dichroic pigment compound and the liquid crystal compound in the liquid crystal composition.

[0275] A single surfactant may be used alone, or two or more may be used in combination. When two or more surfactants are used, it is preferable that their total amount is within the range described above.

[0276] [Sealing Improver]

[0277] From the viewpoint of adhesion to the protective layer described later, the liquid crystal composition may also contain an adhesion modifier. Examples of adhesion modifiers include compounds containing hydroxyl, carboxyl, or boric acid groups, with compounds containing boric acid groups being preferred.

[0278] As a compound containing a boric acid group, for example, a compound represented by the following formula can be preferably cited.

[0279] [Chemical Formula 21]

[0280]

[0281] (where R is in the formula) 1 and R 2 Each can independently represent a hydrogen atom, or a substituted or unsubstituted aliphatic hydrocarbon group, aryl group, or heteroatom-containing cyclic group. R 2 This indicates a substituent containing a functional group that can bond with a (meth)acrylate group.

[0282] [solvent]

[0283] From the point of view of operability, the liquid crystal composition preferably contains a solvent.

[0284] Examples of solvents include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane, etc.), aliphatic hydrocarbons (e.g., hexane, etc.), alicyclic hydrocarbons (e.g., cyclohexane, etc.), aromatic hydrocarbons (e.g., benzene, toluene, xylene, trimethylbenzene, etc.), halogenated carbons (e.g., dichloromethane, trichloromethane, dichloroethane, dichlorobenzene, chlorotoluene, etc.), and esters (e.g., methyl acetate). Organic solvents including esters, ethyl acetate, butyl acetate, ethyl lactate, etc.; alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, isoamyl alcohol, neopentyl alcohol, diacetone alcohol, benzyl alcohol, etc.); cellosols (e.g., methyl cellosol, ethyl cellosol, 1,2-dimethoxyethane, etc.); cellosol acetates; sulfoxides (e.g., dimethyl sulfoxide, etc.); amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone, etc.); and heteroatom-containing cyclic compounds (e.g., pyridine, etc.) as well as water. These solvents may be used alone or in combination of two or more.

[0285] From the viewpoint of achieving excellent solubility of the liquid crystal composition, ketones (especially cyclopentanone, cyclohexanone), ethers (especially tetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, dioxolane), and amides (especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone) are preferred among these solvents.

[0286] When the liquid crystal composition contains a solvent, the solvent content relative to the total mass of the liquid crystal composition is preferably 80 to 99% by mass, more preferably 83 to 97% by mass, and even more preferably 85 to 95% by mass.

[0287] One solvent may be used alone, or two or more solvents may be used in combination. When two or more solvents are used, it is preferable that their total amount is within the range described above.

[0288] There is no limit to the thickness of the light-absorbing anisotropic film; as long as the thickness is appropriately set according to the forming material and other factors to obtain the desired polarization characteristics, it is acceptable.

[0289] The thickness of the light-absorbing anisotropic film is preferably 0.1 to 5 μm, more preferably 0.3 to 2.5 μm. Furthermore, as described later, when the light-absorbing anisotropic film has a stepped difference (thickness distribution), the above-mentioned thickness refers to the thickness at the thickest position.

[0290] <Methods for forming anisotropic light-absorbing films>

[0291] There are no limitations on the method for forming the light absorption anisotropic film using the above-described liquid crystal composition, and various known film-forming methods using the composition can be employed.

[0292] As an example of a method for forming a light-absorbing anisotropic film, a method comprising the following steps in sequence is described: coating the aforementioned liquid crystal composition onto a support to form a coating film; and aligning the liquid crystal compound contained in the coating film. In the following description, the step of coating the liquid crystal composition onto the support to form a coating film is also referred to as the "coating film forming step." The step of aligning the liquid crystal compound contained in the coating film is also referred to as the "alignment step."

[0293] In addition, liquid crystal compound refers to a component that not only includes the liquid crystal compound mentioned above, but also, in the case that the dichroic pigment compound mentioned above has liquid crystal properties, includes a dichroic pigment compound that also has liquid crystal properties.

[0294] Here, in the display device of the present invention, the light absorption anisotropic film of the optical film has a region A with an inclination of θA relative to the absorption axis of the film surface and a region B with an inclination of θB relative to the absorption axis of the film surface within the same film surface, and θA and θB satisfy the following relationship (1) and (2).

[0295] |θA-θB|≥10° Formula (1)

[0296] 0°≤θB≤5° Equation (2)

[0297] Therefore, in anisotropic light absorption films, regions A and B are formed within the same film surface along with pattern formation. This pattern formation will be described later.

[0298] [Coating film formation process]

[0299] The coating film formation process is the process of coating a liquid crystal composition onto a support to form a coating film.

[0300] By using a liquid crystal composition containing the above-mentioned solvent, or by using a substance that forms a liquid liquid such as a molten liquid by heating, the liquid crystal composition can be easily coated onto a support.

[0301] Specifically, known methods for coating liquid crystal compositions include roller coating, gravure printing, spin coating, wire-wound coating, extrusion coating, direct gravure coating, reverse gravure coating, mold coating, spray coating, and inkjet coating.

[0302] In addition, this example shows an example of a liquid crystal composition coated on a support, but it is not limited to this. For example, the liquid crystal composition can also be coated on an alignment film disposed on a support.

[0303] Orientation films will be discussed later.

[0304] (Orientation process)

[0305] The alignment process is the process of orienting the liquid crystal compounds contained in the coated film.

[0306] The orientation process can also include a drying process. This drying process removes components such as solvents from the coated film. The drying process can be performed by placing the coated film at room temperature for a specified time (e.g., natural drying), or by heating and / or air supply.

[0307] Here, the liquid crystal compound contained in the liquid crystal composition is sometimes oriented according to the above-described coating film formation process or drying process. In this case, for example, in a method where the liquid crystal composition is prepared as a coating liquid containing a solvent, a polarizing layer can be obtained by drying the coating film to remove the solvent from the coating film.

[0308] If the drying process is performed at a temperature above the transition temperature at which the liquid crystal compound contained in the coated film transforms into the liquid crystal phase, the heating process described later may not be necessary.

[0309] From the perspective of manufacturing applicability, the transition temperature of the liquid crystal compound contained in the coating film to the liquid crystal phase is preferably 10 to 250°C, more preferably 25 to 190°C. If the transition temperature is 10°C or higher, cooling treatment to lower the temperature to the liquid crystal phase temperature range is not required, which is therefore preferable. Furthermore, if the transition temperature is 250°C or lower, even if the liquid is in an isotropic liquid state at a temperature higher than the temporary liquid crystal phase temperature range, high temperature is not required, and heat waste, substrate deformation, and deterioration can be reduced, which is also preferable.

[0310] The alignment process preferably includes a heat treatment. By performing a heat treatment, the liquid crystal compound contained in the coated film can be aligned, and therefore the heat-treated coated film can preferably be used as a light-absorbing anisotropic film.

[0311] There are no restrictions on the temperature and time of the heat treatment. The temperature and time should be appropriately set based on the liquid crystal compound and dichroic pigment present in the coated film to ensure proper orientation of the liquid crystal compound. From a manufacturing applicability perspective, the heat treatment temperature is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds.

[0312] The alignment process can also include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coating film to approximately room temperature (around 20–25°C). This helps to fix the alignment of the liquid crystal compound contained in the coating film.

[0313] There are no restrictions on the cooling method; various known cooling methods for sheet-like materials can be used.

[0314] By combining the above processes with the pattern formation method described later, it is possible to form an anisotropic light absorption film with regions A and B having different absorption axes in the plane.

[0315] Furthermore, in the examples described above, methods for aligning the liquid crystal compound contained in the coating film include drying and heating treatments. However, in this invention, the method for aligning the liquid crystal compound is not limited to these methods and can be implemented using known alignment treatments.

[0316] [Curing process]

[0317] In the formation of the light-absorbing anisotropic film, a curing process for the light-absorbing anisotropic film can be performed after the above-mentioned orientation process.

[0318] The curing process is carried out, for example, by heating and / or light irradiation (exposure). Preferably, the curing process is carried out by light irradiation.

[0319] The light source used in the curing process can be various light sources such as infrared, visible light, and ultraviolet light, but ultraviolet light is preferred. Furthermore, ultraviolet light can be irradiated while heating is being performed during curing, or ultraviolet light can be irradiated through a filter that transmits only a specific wavelength.

[0320] When heating is accompanied by ultraviolet light irradiation, there is no limitation on the heating temperature; it can be appropriately set according to factors such as the transition temperature of the liquid crystal compound contained in the light-absorbing anisotropic film to the liquid crystal phase. The preferred heating temperature is 25–140°C.

[0321] Furthermore, light irradiation during the curing process can also be carried out in a nitrogen environment. In the case of curing anisotropic films with light absorption via free radical polymerization, light irradiation in a nitrogen environment is preferred because it reduces the hindrance of oxygen to polymerization.

[0322] As described above, the optical film of the present invention includes the aforementioned light-absorbing anisotropic film, but in addition to the light-absorbing anisotropic film, it may also have other layers such as a transparent support, an alignment film, an oxygen barrier layer, and a surface protective layer. For example, it is preferable to have at least one alignment film and at least one light-absorbing anisotropic film, and it is even more preferable to include at least one oxygen barrier layer in addition to the alignment film and the light-absorbing anisotropic film.

[0323] The following is a description of the layers of an optical film.

[0324] [Transparent support]

[0325] There are no particular limitations on the transparent support; commonly used polymer films (e.g., polarizer protective films) or glass substrates can be used. For applications requiring flexibility, polymer films or glass substrates with a thickness of 100 μm or less are preferred.

[0326] Specifically, examples of polymers constituting polymer films include, for example, cellulose-based polymers; acrylic polymers containing acrylate polymers such as polymethyl methacrylate and polymers containing lactone rings; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyester-based polymers such as polyethylene terephthalate and polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; vinyl chloride-based polymers; amide-based polymers such as nylon and aromatic polyamides; imide-based polymers; sulfone-based polymers; polyethersulfone-based polymers; polyetheretherketone-based polymers; polyphenylene sulfide-based polymers; vinylidene chloride-based polymers; vinyl alcohol-based polymers; vinyl butyral-based polymers; aromatic ester-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; or polymers formed by mixing these polymers.

[0327] Among these, cellulose polymers, represented by triacetylcellulose (hereinafter also referred to as "cellulose acylates"), are preferred.

[0328] Furthermore, from the viewpoint of processability and optical properties, acrylic polymers are preferred.

[0329] Examples of acrylic polymers include polymethyl methacrylate or polymers containing lactone rings as described in paragraphs

[0017] to

[0107] of Japanese Patent Application Publication No. 2009-098605.

[0330] In this invention, from the viewpoint of thinning, it is also preferable to peel the transparent support off from the optical film. When using a peelable polymer film, cellulose-based polymers or polyester-based polymers are preferred.

[0331] Furthermore, in this invention, the aforementioned transparent support is preferably transparent.

[0332] In this invention, "transparent" means that the transmittance of visible light is 60% or more, preferably 80% or more, and especially preferably 90% or more.

[0333] There is no particular limitation on the thickness of the transparent support, but considering reasons such as enabling thinner optical laminates, it is preferably 40 μm or less. There is no particular limitation on the lower limit, but it is typically 5 μm or more.

[0334] [Orientation film]

[0335] Examples of alignment films include photoalignment layers and rubbing-treated alignment layers. Among these, a photoalignment layer is preferred for the sake of superior performance of the present invention. Examples of photoalignment layers can be described in paragraphs

[0018] to

[0078] of International Publication No. 2020 / 179864.

[0336] [Oxygen Barrier Layer]

[0337] To improve durability, the optical film may also have an oxygen barrier layer. Preferably, the oxygen barrier layer is located on the side opposite to the orientation of the light-absorbing anisotropic film.

[0338] Here, the oxygen barrier layer refers to an oxygen barrier membrane with oxygen barrier function. As a specific example, a layer containing organic compounds such as polyvinyl alcohol, polyvinyl alcohol, polyvinyl ether, polyvinylpyrrolidone, polyacrylamide, polyacrylic acid, cellulose ether, polyamide, polyimide, styrene / maleic acid copolymer, gelatin, vinylidene chloride and cellulose nanofibers can be cited.

[0339] Furthermore, in this specification, the oxygen barrier function is not limited to a state that completely prevents oxygen from passing through, but also includes a state that allows a small amount of oxygen to pass through, depending on the target performance.

[0340] When an oxygen barrier layer is provided on a transparent polymer film and the aforementioned photo-alignment layer is provided thereon, from the viewpoint of improving orientation, polyvinyl alcohol with a saponification degree of 95 mol% or more or modified polyvinyl alcohol with a saponification degree of 95 mol% or more is preferably used in the oxygen barrier layer.

[0341] Furthermore, thin layers composed of metal compounds (metal compound thin layers) can also be cited as examples. Regarding the method for forming metal compound thin layers, any method capable of forming the target thin layer can be used. For example, sputtering, vacuum evaporation, ion plating, and plasma CVD (Chemical Vapor Deposition) are suitable. Specifically, the formation methods described in Japanese Patent No. 3400324, Japanese Unexamined Patent Application Publication No. 2002-322561, and Japanese Unexamined Patent Application Publication No. 2002-361774 can be employed.

[0342] The components contained in the metal compound thin layer are not particularly limited as long as they can perform oxygen barrier functions. For example, oxides, nitrides, or oxynitrides containing one or more metals selected from Si, Al, In, Sn, Zn, Ti, Cu, Ce, or Ta can be used. Among these, oxides, nitrides, or oxynitrides containing metals selected from Si, Al, In, Sn, Zn, and Ti are preferred, and metal oxides, nitrides, or oxynitrides containing metals selected from Si, Al, Sn, and Ti are particularly preferred. They may contain other elements as minor components.

[0343] Furthermore, as described in, for example, U.S. Patent No. 6,413,645, Japanese Patent Application Publication No. 2015-226,995, 2013-202,971, 2003-335,880, 53-012,953, and 58-217,344, the oxygen barrier layer can be a stack of layers containing the aforementioned organic materials and thin layers of metal compounds, as described in International Patent Publication No. 2011 / 11836, 2013-248,832, and 3,855,004, or it can be a layer composed of a mixture of organic and inorganic compounds.

[0344] In the case where the optical laminate of the present invention has a λ / 4 plate (described later), and the λ / 4 plate is a phase retardation film having an optical anisotropic layer with λ / 4 function disposed on a support, the aforementioned oxygen barrier layer can also serve as an orientation layer of the optical anisotropic layer having λ / 4 function. In this case, an oxygen barrier layer comprising polyvinyl alcohol, polyamide, or polyimide is preferred.

[0345] [Thickness of the oxygen barrier layer]

[0346] There is no particular limitation on the thickness of the oxygen barrier layer, but in the case of a layer containing organic compounds, for the sake of better performance of the present invention, a thickness of 0.1 to 10 μm is preferred, and more preferably 0.5 to 5.5 μm is preferred. In the case of a thin layer of metal compounds, for the sake of better performance of the present invention, the thickness of the oxygen barrier layer is preferably 5 to 500 nm, and more preferably 10 to 200 nm.

[0347] (protective layer)

[0348] The optical film of the present invention may have a surface protective layer on the side most accessible to visual perception. The surface protective layer is not limited as long as it functions to protect the surface. It may be a single layer, but multiple layers are preferred. High hardness is preferred, as is high resilience. A low-reflection layer that suppresses surface reflections generated on the air surface is also preferred.

[0349] As one preferred embodiment, a structure of transparent support and surface coating is assumed. Regarding the transparent support, the transparent support described in the section on transparent support described above can also be used.

[0350] The surface coating is described below.

[0351] [Surface Coating]

[0352] As a surface coating, at least one can be selected from the group consisting of anti-reflective layers, anti-glare layers, and hard coatings. They use known layer materials. In addition, multiple layers can be stacked.

[0353] Unlike circular polarizers, antireflective layers reduce reflection by utilizing the interference of light. The simplest structure is a low-refractive-index layer. To further reduce reflectivity, a combination of a high-refractive-index layer and a low-refractive-index layer is preferred. Examples of structures include a double-layer structure consisting of a high-refractive-index layer and a low-refractive-index layer, or a structure consisting of three layers with different refractive indices stacked in the order of a medium-refractive-index layer (a layer with a higher refractive index than the layer below and a lower refractive index than the high-refractive-index layer) / a high-refractive-index layer / a low-refractive-index layer. Structures with even more layers have also been proposed. From the perspectives of durability, optical properties, cost, or productivity, it is preferable to have a medium refractive index layer, a high refractive index layer, and a low refractive index layer sequentially on the hard coating. Examples include structures described in Japanese Patent Application Publication Nos. 8-122504, 8-110401, 10-300902, 2002-243906, and 2000-111706. Furthermore, Japanese Patent Application Publication No. 2008-262187 describes a three-layer antireflective film with excellent durability against variations in film thickness. When this three-layer antireflective film is applied to the surface of an image display device, the average reflectivity can be set to 0.5% or less, significantly reducing reflection and resulting in an image with excellent stereoscopic effect. Furthermore, other functions can be assigned to each layer. For example, layers can be configured as anti-fouling low-refractive-index layers, anti-static high-refractive-index layers, anti-static hard coatings, and anti-glare hard coatings (e.g., Japanese Patent Application Publication No. 10-206603, Japanese Patent Application Publication No. 2002-243906, Japanese Patent Application Publication No. 2007-264113, etc.).

[0354] As one aspect of the present invention, for a foldable organic EL display device, in addition to the polarizer, reference can also be made to the description in Japanese Patent Application Publication No. 2018-56069. Since a cover glass cannot be used, a surface film is required. For example, in sections

[0030] to

[0040] , it is described that: as a substrate having a bending capacity of preferably 200,000 bends, more preferably 300,000 bends, and even more preferably 500,000 bends with a radius of curvature of 3 mm or less (e.g., 3 mm, 2 mm, 1 mm), a polyimide-based resin is preferred; as a hard coating, an organic-inorganic mixture of materials, such as silica particles or cage-like silsesquioxane compounds, is preferred, which is incorporated into an ultraviolet-curable acrylic resin.

[0355] In the surface protective layer of the present invention, a hard coating of a silsesquioxane compound with the structure described in Japanese Patent Application Publication No. 2015-212353 or Japanese Patent Application Publication No. 2017-008148 is preferred.

[0356] <Optical laminate>

[0357] like Figure 1 As shown, the optical laminate of the present invention comprises an optical film 20 having a light-absorbing anisotropic film 18 and at least a λ / 4 plate 14. Through this combination, an anti-reflective effect against external light can be effectively achieved.

[0358] [λ / 4 board]

[0359] The “λ / 4 plate” in this invention is a plate with λ / 4 function (λ / 4 wavelength plate), specifically, a plate with the function of converting linear polarization of a specific wavelength into circular polarization (or converting circular polarization into linear polarization).

[0360] As a specific example of a λ / 4 plate, U.S. Patent Application Publication No. 2015 / 0277006 can be cited.

[0361] For example, as a single-layer structure of the λ / 4 plate, examples include stretched polymer films and phase difference films with an optical anisotropy layer having λ / 4 function disposed on a support. As a multi-layer structure of the λ / 4 plate, examples include broadband λ / 4 plates formed by stacking λ / 4 plates and λ / 2 plates.

[0362] The phase retardation film having an optical anisotropy layer with λ / 4 function is more preferably a phase retardation film having one or more layers containing at least one liquid crystal compound (disc-shaped liquid crystal, rod-shaped liquid crystal compound, etc.), which is formed by polymerizing liquid crystal monomers that exhibit a nematic liquid crystal layer or a smectic liquid crystal layer.

[0363] Furthermore, as a λ / 4 plate with excellent optical performance, a liquid crystal compound with reverse wavelength dispersion is even more preferred. Specifically, a liquid crystal compound of general formula (II) described in International Publication No. WO2017 / 043438 is preferred. Regarding the method for manufacturing the λ / 4 plate using a liquid crystal compound with reverse wavelength dispersion, reference can be made to Examples 1 to 10 of Publication No. WO2017 / 043438 or Example 1 of Japanese Patent Application Publication No. 2016-91022.

[0364] (Other phase difference layers)

[0365] The optical stack of the present invention can also have phase retardation layers other than the λ / 4 plate. For example, a C-plate can be considered as another phase retardation layer. There are two types of C-plates: positive C-plates and negative C-plates. Positive C-plates satisfy the relationship in equation (C1), and negative C-plates satisfy the relationship in equation (C2). Furthermore, a positive C-plate indicates that Rth has a negative value, and a negative C-plate indicates that Rth has a positive value.

[0366] Equation (C1) nz>nx≈ny

[0367] Equation (C2) nz<nx≈ny

[0368] Furthermore, the “≈” above includes not only cases where the two are exactly the same, but also cases where they are substantially the same. “Substantially the same” means, for example, that the case where (nx-ny)×d (where d is the thickness of the film) is 0 to 10 nm, preferably 0 to 5 nm, is also included in “nx≈ny”.

[0369] [Adhesive layer]

[0370] The optical laminate of the present invention may also have an adhesive layer between the optical film and the λ / 4 plate.

[0371] Examples of adhesives included in the adhesive layer include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives.

[0372] Among these, acrylic adhesives (pressure-sensitive adhesives) are preferred from the viewpoints of transparency, weather resistance, and heat resistance.

[0373] The adhesive layer can be formed, for example, by applying an adhesive solution to a release sheet, drying it, and then transferring it to the surface of a transparent resin layer; or by applying an adhesive solution directly to the surface of a transparent resin layer and drying it.

[0374] The adhesive solution is prepared, for example, into a solution of about 10 to 40% by mass, which dissolves or disperses the adhesive in a solvent such as toluene or ethyl acetate.

[0375] Coating methods can include reverse coating, gravure coating, roller coating, spin coating, screen coating, spray coating, dip coating, and spray coating.

[0376] Furthermore, suitable sheet materials that can be used as the constituent materials of the release sheet include, for example, synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate; rubber sheets; paper; cloth; non-woven fabric; wire mesh; foam sheets; metal foil, etc.

[0377] In this invention, the thickness of any adhesive layer is not particularly limited, but it is preferably 3 to 50 μm, more preferably 4 to 40 μm, and even more preferably 5 to 30 μm.

[0378] In the display device 10 of the present invention, the thickness of the optical film 20 is not limited, and can be appropriately set according to the structure of the optical film and the forming material of the optical film. Regarding the thickness of the optical film 20, it is preferably 1 to 100 μm, more preferably 1 to 30 μm, and even more preferably 1 to 10 μm.

[0379] In the display device 10 of the present invention, the combined thickness of the λ / 4 plate 14 and the optical film 20 is preferably 20 μm or less.

[0380] By setting the combined thickness of the λ / 4 plate 14 and the optical film 20 to 20 μm or less, the EL substrate 12 can be brought closer to the light-absorbing anisotropic film 18, thereby increasing the viewing angle from the light-emitting element to region A and improving the utilization efficiency of the light emitted by the light-emitting element.

[0381] Furthermore, the thickness of the optical film can be measured using existing contact film thickness gauges. It can also be measured directly by observing the cross-section of the optical film using a microscope or scanning electron microscope (SEM). When determining the film thickness from cross-sectional observation, for example, a Leica RM2265 rotary slicer can be used to cut the cross-section along the film thickness direction, and observation can be performed using a Nikon Corporation LV100-POL polarizing microscope.

[0382] The optical film 20 shown in the figure has a structure in which an anisotropic light-absorbing film 18 is formed on the surface of the support 16, but the present invention is not limited thereto.

[0383] As an example, the optical film 20 can be a structure in which the light-absorbing anisotropic film 18 is formed directly on the λ / 4 plate 14 without a support 16. That is, the display device of the present invention can also be a structure in which the optical film 20 is formed solely of the light-absorbing anisotropic film 18. Alternatively, an alignment film can be formed on the λ / 4 plate 14, and the light-absorbing anisotropic film 18 can be formed on its surface.

[0384] With this structure, it is preferable to set the total thickness of the λ / 4 plate 14 and the optical film 20 to be 20 μm or less.

[0385] <Image display device>

[0386] Figure 1A conceptual diagram illustrating an example of the image display device of the present invention is shown below. Furthermore, in the following description, the image display device of the present invention will also be simply referred to as a display device.

[0387] As mentioned above, Figure 1 The display device 10 shown is a self-emissive display device that utilizes inorganic EL light-emitting elements, etc., and has an EL substrate 12, a λ / 4 plate 14, and an optical film 20.

[0388] The optical film 20 has a support 16 and a light-absorbing anisotropic film 18. The light-absorbing anisotropic film 18 has two regions A and B with different inclinations relative to the absorption axis of the film surface within the same film surface. That is, in the light-absorbing anisotropic film 18, region 18A is region A in this invention, and region 18B is region B in this invention.

[0389] [EL substrate]

[0390] The EL substrate 12 is a known EL substrate with EL light-emitting elements used in inorganic EL display devices and organic EL display devices.

[0391] The display device 10 shown in the figure corresponds to the display of a full-color image. The EL substrate 12 has an R light-emitting element 12R that emits red light, a G light-emitting element 12G that emits green light, and a B light-emitting element 12B that emits blue light. In the following description, without needing to distinguish between the R light-emitting element 12R, the G light-emitting element 12G, and the B light-emitting element 12B, the R light-emitting element 12R, the G light-emitting element 12G, and the B light-emitting element 12B are collectively referred to as "light-emitting elements".

[0392] The EL substrate 12, like the known EL substrate, has a plurality of such R light-emitting elements 12R, G light-emitting elements 12G and B light-emitting elements 12B arranged in two dimensions.

[0393] In this invention, the EL substrate 12 can utilize known EL substrates used in various self-emissive display devices that employ inorganic EL light-emitting elements and organic EL light-emitting elements.

[0394] Therefore, the EL substrate 12 can be as follows: Figure 4 The conceptual illustration shows an EL substrate 12a, which has arranged R light-emitting elements 12R, G light-emitting elements 12G and B light-emitting elements 12B based on organic EL (Organic Light Emitting Diode).

[0395] Furthermore, the EL substrate 12 can also be as follows: Figure 5The conceptual illustration shows an EL substrate 12b, which is an array of R light-emitting elements 12R, G light-emitting elements 12G, and B light-emitting elements 12B based on inorganic EL. Inorganic EL refers to what is called an LED (Light Emitting Diode).

[0396] In addition, the EL substrate 12 can also be as follows: Figure 6 The EL substrate shown in the conceptual diagram is an EL substrate 12c, which is a two-dimensional arrangement of light-emitting portions 24 having fine inorganic EL light-emitting elements, namely R light-emitting element 12R, G light-emitting element 12G and B light-emitting element 12B.

[0397] In the display device 10 of the present invention, the area ratio of the light-emitting elements in the EL substrate 12 is not limited. The area ratio of the light-emitting elements in the EL substrate 12 is preferably 30% or less, more preferably 10% or less, even more preferably 3% or less, and even more preferably 1% or less.

[0398] As described later, in the display device 10 of the present invention, the light-absorbing anisotropic film 18 is preferably positioned such that the position of region 18A in the light-absorbing anisotropic film 18 corresponds to the position of the light-emitting element in the EL substrate 12. Therefore, by setting the area ratio of the light-emitting element in the EL substrate 12 to 30% or less, the area of ​​region B, which helps to prevent external light reflection, can be increased, and the utilization efficiency of the light emitted by the light-emitting element can be more appropriately and sufficiently ensured, thereby improving the anti-reflection effect of external light.

[0399] When visual recognition is performed from a typical visual recognition distance corresponding to the display device, the external light reflection in the display device 10 of the present invention depends on the external light reflectivity and its area ratio at various locations within the screen. That is, the screen resolution of the display device 10 does not contribute to the anti-reflection of external light. On the other hand, from the viewpoint of providing a display device with excellent display quality, a high screen resolution of the display device 10 is preferred.

[0400] In order to reduce the area ratio of the light-emitting element in the display device 10, it is necessary to increase the output of the light-emitting element to obtain sufficient brightness. In this regard, the light-emitting element in the EL substrate 12 is preferably an inorganic EL light-emitting element (so-called LED). By using an inorganic EL light-emitting element, even if the area ratio of the light-emitting element is set to a preferred range of 30% or less, more preferably 10% or less, further preferably 3% or less, and even more preferably 1% or less, sufficient brightness can be obtained.

[0401] In order to obtain a display device 10 that achieves high resolution and sufficient brightness while reducing the area ratio of the light-emitting element, it is preferable to use a fine inorganic EL light-emitting element. As a fine inorganic EL light-emitting element, it is preferable to have an inorganic EL light-emitting element with a diameter of 360 μm or less for the circle inscribed in the inorganic EL light-emitting element, more preferably an inorganic EL light-emitting element with a diameter of 200 μm or less, even more preferably an inorganic EL light-emitting element with a diameter of 100 μm or less, and even more preferably an inorganic EL light-emitting element with a diameter of 50 μm or less.

[0402] In one embodiment, the EL substrate 12 can be a transparent substrate. Furthermore, it is preferable that inorganic EL light-emitting elements are arranged on the transparent substrate. By using a transparent substrate, a highly customizable display device can be achieved by allowing the background of the display device to be seen through it while suppressing the reflection of external light from the substrate surface.

[0403] Furthermore, in the display device 10 shown in the figure, the EL substrate 12 corresponds to the display of a full-color image having R light-emitting element 12R, G light-emitting element 12G and B light-emitting element 12B, etc., but the present invention is not limited thereto.

[0404] For example, the organic EL substrate can also be used for displaying monochrome images (monochrome images) that have only R light-emitting elements 12R, only G light-emitting elements 12G, or only B light-emitting elements 12B. Alternatively, the organic EL substrate can also be used for displaying two-color images that have R light-emitting elements 12R and G light-emitting elements 12G, R light-emitting elements 12R and B light-emitting elements 12B, or G light-emitting elements 12G and B light-emitting elements 12B.

[0405] Furthermore, in the display device of the present invention, as long as a circular polarizer with an optical film (polarizer) and a λ / 4 plate is not provided as an anti-reflection layer, a commercially available self-emissive display device (display) using inorganic EL light-emitting elements and organic EL light-emitting elements can be used as the EL substrate 12. Moreover, commercially available display devices can also have a touch panel, etc.

[0406] Furthermore, from the viewpoint of superior performance of the present invention, it is preferable that the position of region 18A of the light-absorbing anisotropic film 18 used in the present invention corresponds to the position of the light-emitting element of the EL substrate 12. "Position correspondence" means that when the position of region A of the light-absorbing anisotropic film is viewed from the normal direction of the display surface and the position of the light-emitting element of the image display device corresponds to that of the display device 10, at least a portion of region 18A of the light-absorbing anisotropic film 18 overlaps with the light-emitting element of the EL substrate 12. Preferably, it means that region 18A of the light-absorbing anisotropic film 18 includes the light-emitting element of the EL substrate 12.

[0407] Furthermore, when viewing the display device 10 from the normal direction of the display surface, it is preferable that the region 18A of the light-absorbing anisotropic film 18 is aligned with the center of the light-emitting element of the EL substrate 12 (the light-emitting element is the optical axis). In addition, it is particularly preferable that the center of the region 18A of the light-absorbing anisotropic film 18 is aligned with the center of the light-emitting element of the EL substrate 12, and that the region 18A of the light-absorbing anisotropic film 18 includes the light-emitting element of the EL substrate 12.

[0408] In addition, such as Figure 6 As shown in the EL substrate 12c, in the case of an EL substrate formed by arranging light-emitting portions 24 having R light-emitting elements 12R, G light-emitting elements 12G, and B light-emitting elements 12B, the center of the light-emitting element is defined as the center of the circle inscribed within the three light-emitting elements (or multiple light-emitting elements) constituting the light-emitting portion 24. This also applies to the spacing of the light-emitting elements, for example, in the following description.

[0409] Figure 7 In the optical film 20 shown, the region 18A of the light-absorbing anisotropic film 18 is square, but the present invention is not limited thereto. That is, the shape of the region 18A in the top view of the display device 10 can utilize various shapes corresponding to the emission characteristics of the light-emitting elements, the arrangement of the light-emitting elements, etc. The emission characteristics of the light-emitting elements are, for example, the divergence angle of the emitted light.

[0410] For example, as in Figure 8 As conceptually shown in the planar diagram, the region 18A of the light-absorbing anisotropic film 18 can also be circular. Alternatively, the region 18A can be an ellipse, a triangle, or a polygon of pentagon or higher.

[0411] In addition, regardless of the shape, the center of region A is the center of the circle inscribed in region A.

[0412] exist Figure 7 In the optical film 20 shown, the sizes of regions 18A and 18B of the light absorption anisotropic film 18 are not limited to these, but it is preferable that 18A is at the same level as the light-emitting element. That is, as with the size of the light-emitting element described above, the diameter of the inscribed circle of region A is preferably 360 μm or less, more preferably 200 μm or less, even more preferably 100 μm or less, and particularly preferably 50 μm or less.

[0413] The proportion of region A in the entire region of the light-absorbing anisotropic film 18 is preferably 1 to 50%, more preferably 5 to 30%.

[0414] The proportion of region B in the entire region of the light-absorbing anisotropic film 18 is preferably 50-99%, more preferably 70-95%.

[0415] <Pattern Formation Methods>

[0416] As described above, in the display device 10 of the present invention, the light-absorbing anisotropic film 18 is formed by patterning regions 18A and 18B with different inclinations relative to the absorption axis of the film surface within the same film surface.

[0417] Therefore, there are no limitations on the method for forming the light absorption anisotropic film 18, which has two or more regions with different inclinations of absorption axes within the plane, and various known methods can be used. As examples, methods such as controlling the thickness of the light absorption anisotropic film 18 within the plane, using magnetic force to orient the dichroic pigment compound in the light absorption anisotropic film 18, and using a light-aligning film adjacent to the light absorption anisotropic film 18 for control can be cited.

[0418] Methods for controlling the thickness of the anisotropic light-absorbing film 18 in-plane include imprinting and forming the film on a substrate with an uneven structure. Methods for orienting the dichroic pigment compound in the anisotropic light-absorbing film 18 using magnetic force include applying a magnetic field to orient the liquid crystal compound in any direction. Furthermore, methods for controlling the orientation using an alignment film adjacent to the anisotropic light-absorbing film 18 include photolithography.

[0419] In order to form a pattern of tens of μm to several mm corresponding to the arrangement of light-emitting elements on the EL substrate 12, it is preferable to use an alignment film adjacent to the light-absorbing anisotropic film 18 for control, and in particular, it is preferable to use a photolithography method.

[0420] <Formation of anisotropic light-absorbing films using photolithography>

[0421] Figure 9 This illustrates an example of a method for forming a light-absorbing anisotropic film 18 using photolithography.

[0422] When forming the light-absorbing anisotropic film 18 using photolithography, firstly, a coating film 26 of the aforementioned photo-alignment film is formed on the surface of the support 16. Next, the resulting coating film C is subjected to first light irradiation. As the first light irradiation, the coating film 26 is linearly polarized from the top surface or back surface, and from a direction perpendicular to the film surface, thus obtaining a photo-alignment film thin film with orientation-restricting force in the horizontal direction. Figure 9 (Figure 1).

[0423] Next, the obtained photoalignment film is subjected to a second light irradiation. As the second light irradiation, unpolarized light is irradiated onto the surface of the photoalignment film from any direction. Here, as... Figure 9As shown in Figure 2, a patterned photoalignment film is obtained by exposing a mask 28 with a pattern of light-transmitting portions 28a and light-shielding portions 28b to light. Furthermore, the light-transmitting portions 28a and light-shielding portions 28b of the mask 28 are arranged in a pattern where the light-transmitting portions 28a correspond to region 18A of the light-absorbing anisotropic film 18, and the light-shielding portions 28b correspond to region 18B of the light-absorbing anisotropic film 18.

[0424] Next, on the obtained patterned photoalignment film, as described above, a coating film 18 of the liquid crystal composition is formed by a coating film forming process. Figure 9 (Figure 3). Next, through an alignment process, the liquid crystal composition in the coated film 18 is aligned to form a light absorption anisotropic film 18 having regions 18A and 18B with different tilts relative to the absorption axis of the film surface. Figure 9 (Figure 4).

[0425] In this example, a first light irradiation and a second light irradiation of the light-aligned film corresponding to the two regions 18A and 18B are shown. However, in this invention, multiple irradiations can be performed to obtain a light-absorbing anisotropic film with three or more different absorption axes.

[0426] Furthermore, the irradiation amount in each light irradiation can be appropriately set according to the forming material of the light absorption anisotropic film 18, so that the absorption axes of regions 18A and 18B become the target values. The same applies to other examples.

[0427] Example

[0428] The present invention will now be specifically described based on embodiments. Regarding the materials, reagents, quantities, proportions, and operations shown in the following embodiments, appropriate modifications can be made without departing from the spirit of the invention. Therefore, the present invention is not limited to the following embodiments.

[0429] [Example 1]

[0430] Fabrication of Optical Films

[0431] <Fabrication of the Support Structure>

[0432] A polymer coating liquid with the following composition was continuously coated onto a 40 μm thick TAC substrate (manufactured by FUJIFILM Corporation, TG40) using a #8 winding bar. Then, it was dried with warm air at 100°C for 2 minutes to obtain a support having a 0.8 μm thick polyvinyl alcohol (PVA) polymer film formed on the TAC substrate.

[0433] In addition, modified polyvinyl alcohol was added to the polymer coating solution at a solid component concentration of 4% by mass.

[0434]

[0435] Modified polyvinyl alcohol

[0436] [Chemical Formula 22]

[0437]

[0438] <Formation of Orientation Film>

[0439] To 1 part by mass of photo-alignment material E-1 with the following structure, 41.6 parts by mass of butoxyethanol, 41.6 parts by mass of dipropylene glycol monomethyl and 15.8 parts by mass of pure water were added, and the resulting solution was filtered under pressure using a 0.45 μm membrane filter to prepare a coating solution for photo-alignment film.

[0440] Next, the obtained photo-aligned film was coated onto the fabricated support using a coating solution and dried at 60°C for 1 minute. Then, the coated film was irradiated with linearly polarized ultraviolet light (illuminance 4.5 mW / cm²) using a polarized ultraviolet exposure device. 2 Cumulative radiation dose 300 mJ / cm 2 (Irradiation with first light) was used to prepare a photoalignment film with orientation constraint force in the horizontal direction. The thickness of the photoalignment film was 50 nm.

[0441] Next, the obtained photo-aligned film is irradiated with unpolarized ultraviolet light (illuminance 4.5 mW / cm²) through a photomask from a direction perpendicular to the film surface. 2 Cumulative radiation dose 2000 mJ / cm 2 (Second light irradiation) thus prepares a patterned photo-aligned film.

[0442] In addition, the mask pattern of the mask is set as a mask pattern having a light-shielding part and a light-transmitting part, wherein the light-shielding part has a light-shielding part corresponding to the position of the light-emitting element (area ratio 25%) of the EL substrate 1 described later.

[0443] [Chemical Formula 23]

[0444] E-1

[0445]

[0446] Fabrication of anisotropic light-absorbing films

[0447] On the obtained patterned photo-aligned film, a light-absorbing anisotropic film forming composition F1 with the following composition is continuously coated by a winding bar, thereby forming a coating layer F.

[0448] Next, the coating layer F is heated at 140°C for 15 seconds and then cooled to room temperature (23°C).

[0449] Next, heat at 75°C for 60 seconds and then cool to room temperature again.

[0450] Then, by using LED lights (center wavelength 365nm) at an illuminance of 200mW / cm², 2 Anisotropic light absorption films were prepared on a patterned oriented film by irradiating for 2 seconds under specific irradiation conditions, resulting in regions A and B with different inclinations relative to the absorption axis of the film surface. When the absorption axes of regions A and B were measured using the aforementioned method, the absorption axis angle θA of region A was 78°, and the absorption axis angle θB of region B was 0°. Furthermore, the transmittance along the absorption axis direction in region A was 64%, and the in-plane orientation degree in region B was 0.962. The thickness of the anisotropic light absorption film was 2.0 μm.

[0451] In addition, region A accounts for 25% of the entire region of the light absorption anisotropic film, while region B accounts for 75%.

[0452]

[0453] Dichroic substance C-1 (maximum absorption wavelength: 570nm)

[0454] [Chemical Formula 24]

[0455]

[0456] Dichroic substance M-1 (maximum absorption wavelength: 466nm)

[0457] [Chemical Formula 25]

[0458]

[0459] Dichroic substance Y-1 (maximum absorption wavelength: 417nm)

[0460] [Chemical Formula 26]

[0461]

[0462] Liquid crystal compound L-1

[0463] [Chemical Formula 27]

[0464]

[0465] Liquid crystal compound L-2 (in the following formulas, the numerical values ​​represent the mass ratio)

[0466] [Chemical Formula 28]

[0467]

[0468] Surfactant S-1

[0469] [Chemical Formula 29]

[0470]

[0471] <Preparation of the Oxygen Barrier Layer>

[0472] On the obtained light-absorbing anisotropic film, a coating liquid B1 with the following composition was continuously coated using a wire-wound bar. Then, it was dried with warm air at 80°C for 5 minutes, thereby obtaining an optical film with an oxygen barrier layer composed of polyvinyl alcohol (PVA) with a thickness of 1.0 μm, that is, an optical film 1 having a TAC substrate (transparent support), a light-aligning film and an oxygen barrier layer sequentially adjacent to each other.

[0473]

[0474]

[0475] [Examples 2-10, Comparative Examples 1-4]

[0476] The conditions for second light irradiation during the formation of the alignment film and the composition for forming the light absorption anisotropic film were replaced as shown in Table 1. Otherwise, the optical films 2 to 9 described in the examples having light absorption anisotropic films and the optical films 10 to 14 described in the comparative examples were obtained by the same method as in Example 1.

[0477] The absorption axis angles θA and θB, as well as the transmittance and orientation degree in each embodiment, are shown in Table 1.

[0478]

[0479] Surfactant S-2

[0480] [Chemical Formula 30]

[0481]

[0482]

[0483]

[0484]

[0485]

[0486]

[0487]

[0488]

[0489] Dichroic substance D1

[0490] [Chemical Formula 31]

[0491]

[0492] Dichroic substance D2

[0493] [Chemical Formula 32]

[0494]

[0495] Dichroic substance D3

[0496] [Chemical Formula 33]

[0497]

[0498] Dichroic substance D4

[0499] [Chemical Formula 34]

[0500]

[0501] Liquid crystal compound M1 (mixed with compound A / compound B in a ratio of 75 / 25) (compound A)

[0502] [Chemical Formula 35]

[0503]

[0504] (Compound B)

[0505] [Chemical Formula 36]

[0506]

[0507]

[0508]

[0509] Dichroic substance C-2 (maximum absorption wavelength: 570nm)

[0510] [Chemical Formula 37]

[0511]

[0512]

[0513] Fabrication of Optical Laminates

[0514] <Fabrication of λ / 4 board>

[0515] [Fabrication of the transparent support]

[0516] (Preparation of concentrated cellulose acylate from the core layer)

[0517] The following composition was added to a mixing tank and stirred to dissolve the components, thereby preparing a cellulose acetate solution for use as a core layer cellulose acylate concentrate.

[0518]

[0519]

[0520] Compound F

[0521] [Chemical Formula 38]

[0522]

[0523] (Preparation of concentrated outer cellulose acylate)

[0524] A cellulose acetate solution for use as an outer layer cellulose acylate was prepared by adding 10 parts by mass of the following matting agent solution to 90 parts by mass of the above-mentioned core layer cellulose acylate concentrate.

[0525]

[0526] (Preparation of cellulose acylated film 1)

[0527] After filtering the above-mentioned core layer cellulose acylate concentrate and the above-mentioned outer layer cellulose acylate concentrate with filter paper with an average pore size of 34 μm and sintered metal filter with an average pore size of 10 μm, the above-mentioned core layer cellulose acylate concentrate and the outer layer cellulose acylate concentrate on both sides are simultaneously cast from the casting port onto a roller at 20°C (belt casting machine).

[0528] Next, the film is peeled off with a solvent content of approximately 20% by mass, and the two ends of the film in the width direction are fixed with a tenter frame clamp. The film is then dried while being stretched laterally at a stretch ratio of 1.1.

[0529] The film is then further dried by conveying it between rollers in a heat treatment apparatus to produce an optical film (transparent support) with a thickness of 40 μm, which is then designated as cellulose acylated film 1. The resulting cellulose acylated film 1 has an in-plane retardation of 0 nm.

[0530] [Fabrication of TAC film A1 with positive plate A1]

[0531] The photo-alignment film forming coating solution PA1, with the following composition, was continuously coated onto the cellulose acylated film 1 described above using a winding rod. The support with the coated film was dried with warm air at 140°C for 120 seconds, and then the coating was irradiated with polarized ultraviolet light (10 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a photo-aligned film PA1 with a thickness of 0.2 μm was formed, thus obtaining a TAC thin film with a photo-aligned film.

[0532]

[0533] Acid-producing agent PAG-1

[0534] [Chemical Formula 39]

[0535]

[0536] Polymer PA-1

[0537] [Chemical Formula 40]

[0538]

[0539] The composition A-1 with the following composition was coated onto the photoalignment film PA1 using a rod coater. The coating formed on the photoalignment film PA1 was heated to 120°C with warm air, then cooled to 60°C, and then subjected to a high-pressure mercury lamp at a wavelength of 365 nm under a nitrogen atmosphere at a concentration of 100 mJ / cm². 2 The coating was irradiated with ultraviolet light, and then heated to 120°C while applying 500 mJ / cm² of UV radiation. 2 The ultraviolet light was irradiated onto the coating, thereby fixing the orientation of the liquid crystal compound and producing a TAC thin film A1 with a positive A plate A1.

[0540] The thickness of the positive A plate A1 is 2.5 μm, and the resulting positive A plate A1 is equivalent to a λ / 4 plate with a Re(550) of 144 nm. Furthermore, the positive A plate A1 satisfies the relationship Re(450) ≤ Re(550) ≤ Re(650). The Re(450) / Re(550) ratio is 0.82.

[0541]

[0542] Polymerizable liquid crystal compound LA-1 (tBu represents tert-butyl)

[0543] [Chemical Formula 41]

[0544]

[0545] Polymerized liquid crystal compound LA-2

[0546] [Chemical Formula 42]

[0547]

[0548] Polymerized liquid crystal compound LA-3

[0549] [Chemical Formula 43]

[0550]

[0551] Polymerizable liquid crystal compound LA-4 (Me represents methyl)

[0552] [Chemical Formula 44]

[0553]

[0554] Polymerization initiator PI-1

[0555] [Chemical Formula 45]

[0556]

[0557] Leveling agent T-1

[0558] [Chemical Formula 46]

[0559]

[0560] (Fabrication of TAC film C1 with positive C plate C1)

[0561] The aforementioned cellulose acylated film 1 was used as a pseudo-support.

[0562] After the cellulose acylated film 1 is passed through a dielectric heating roller at a temperature of 60°C to raise the surface temperature of the film to 40°C, a bar coater is used to coat one side of the film at a coating amount of 14 ml / m. 2 The alkaline solution with the composition shown below was coated, heated to 110°C, and conveyed for 10 seconds under a vapor-type far-infrared heater manufactured by Noritake Co., Ltd.

[0563] Next, a 3ml / m film was coated onto the film using a bar coater. 2 Pure water.

[0564] Next, after repeated water washing based on a spray coating machine and dehydration based on an air knife three times, the film was transported to a drying area at 70°C and dried for 10 seconds, thereby producing an alkali-saponified cellulose acylated film 1.

[0565]

[0566] The following oriented film forming coating solution PA2 was continuously coated onto the alkali-saponified cellulose acylated film 1 using a #8 winding bar. The resulting film was dried with warm air at 60°C for 60 seconds, and then further dried with warm air at 100°C for 120 seconds to form the oriented film PA2.

[0567]

[0568]

[0569] The following coating solution C1, used for forming a positive C-plate, is applied onto the alignment film PA2. The resulting coating is then cured at 60°C for 60 seconds and subjected to air treatment with 70 mW / cm² solution. 2 Irradiation with a gas-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) at 1000 mJ / cm 2 By immobilizing the orientation state of the liquid crystal compound with ultraviolet light, a TAC thin film C1 with a positive C plate C1 and a thickness of 0.5 μm was produced.

[0570] The obtained Rth(550) of the positive C plate is -60nm.

[0571]

[0572] Liquid crystal compound LC-1

[0573] [Chemical Formula 47]

[0574]

[0575] Liquid crystal compound LC-2

[0576] [Chemical Formula 48]

[0577]

[0578] Vertically oriented liquid crystal compound S01

[0579] [Chemical Formula 49]

[0580]

[0581] Compound B03

[0582] [Chemical Formula 50]

[0583]

[0584] [Preparation of Adhesive N1]

[0585] Next, acrylate polymers were prepared according to the following steps.

[0586] In a reaction vessel equipped with a cooling pipe, a nitrogen inlet pipe, a thermometer, and a stirring device, 95 parts by mass of butyl acrylate and 5 parts by mass of acrylic acid were polymerized by solution polymerization to obtain an acrylate polymer (A1) with an average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0.

[0587] Next, using the obtained acrylate polymer (A1), an acrylate adhesive was prepared according to the following composition. These compositions were coated onto a release membrane that had been surface-treated with a silicone-based release agent using a die coater, dried at 90°C for 1 minute, and then irradiated with ultraviolet light (UV) under the following conditions to obtain the following acrylate adhesive N1. The composition and film thickness of the acrylate adhesive are shown below.

[0588] (UV irradiation conditions)

[0589] Fusion's induction lamp H-bulb

[0590] Illuminance 600mW / cm 2 Light intensity 150 mJ / cm 2

[0591] • UV illuminance and light intensity were measured using “UVPF-36” manufactured by EYE GRAPHICS Co., Ltd.

[0592]

[0593]

[0594] (A) Multifunctional acrylate monomer: Tris(acryloyloxyethyl)isocyanurate, molecular weight = 423, trifunctional (manufactured by TOAGOSEI CO., LTD., trade name "ARONIX M-315")

[0595] (B) Photopolymerization initiator: a 1:1 mass ratio mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone, manufactured by CibaSpecialty Chemicals Co., Ltd. as "IRGACURE500".

[0596] (C) Isocyanate-based crosslinking agent: Trimethylolpropane-modified toluene diisocyanate (produced by Nippon Polyurethane Industry Co., Ltd. as "CORONATE L")

[0597] (D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. as “KBM-403”)

[0598] [Preparation of UV adhesive]

[0599] A UV adhesive composition with the following composition was prepared.

[0600]

[0601] CPI-100P

[0602] [Chemical Formula 51]

[0603]

[0604] (Fabrication of Optical Laminate 1)

[0605] Using the above-mentioned UV adhesive composition, at 600 mJ / cm 2 UV irradiation was used to bond the phase retardation layer side of the TAC film A1 having the positive A plate A1 and the phase retardation layer side of the TAC film C1 having the positive C plate C1. The thickness of the UV adhesive layer was 2 μm. In addition, the surfaces bonded with the UV adhesive were subjected to corona treatment. Next, the photoalignment film PA1 and the cellulose acylated film 1 on the positive A plate A1 side were removed, and this was set as the phase retardation sheet 1. In addition, the layer structure of the phase retardation sheet 1 is positive A plate A1, UV adhesive layer, positive C plate C1, photoalignment film PA2 and cellulose acylated film 1.

[0606] Using the aforementioned adhesive N1, the oxygen barrier layer side of the optical film 1 was bonded to the support side of the low-reflectivity surface film CV-LC5 (manufactured by Fujifilm Corporation). Next, after standing for 24 hours at 25°C and 90% relative humidity, the TAC substrate and photoalignment film contained in the optical film 1 were removed, and the removed surface was bonded to the positive A-plate A1 side of the retardation film 1 using the aforementioned UV adhesive. The thickness of the UV adhesive layer was 4.45 μm. Next, the photoalignment film PA2 and cellulose acylate film 1 on the positive C-plate C1 side of the retardation film 1 were removed, thereby fabricating the optical laminate 1. At this time, bonding was performed such that the azimuth angle of the absorption axis of region B of the light-absorbing anisotropic film contained in the laminate 1 formed a 45° angle with the slow axis of the positive A-plate A1.

[0607] In addition, the layer structure of the optical laminate 1 is a low-reflection surface film CV-LC5, an adhesive layer N1, an oxygen barrier layer, a light-absorbing anisotropic film, a UV adhesive layer, a positive A plate A1, a UV adhesive layer and a positive C plate C1, and the total thickness of the optical film 1 (oxygen barrier layer to light-absorbing anisotropic film) and the λ / 4 plate (positive A plate A1) is 10 μm.

[0608] [Fabrication of optical laminates 2-14]

[0609] The optical films used were replaced with optical films 2 to 14. Otherwise, optical laminates 2 to 14 were fabricated in the same way as optical laminate 1.

[0610] "evaluate"

[0611] The results of measurement and evaluation of each optical laminate produced in the examples and comparative examples are shown in Table 1 below.

[0612] Light utilization efficiency

[0613] [Production example 1]

[0614] On a printed circuit board, three-color LEDs (manufactured by ROHMCo., Ltd., PICOLED, model: SMLP34RGB) are arranged in a two-dimensional lattice pattern with an LED (light-emitting element) area ratio of 30%. In the areas where no LEDs are arranged, a black layer composed of a black matrix material used in liquid crystal displays is formed using photolithography. Thus, EL substrate 1 (reference) is fabricated. Figure 6 ).

[0615] Relative to the EL substrate 1, the optical laminate 1 having the optical film 1 is arranged with the C-plate side becoming the EL substrate 1 side, and is bonded together with adhesive N1, thereby manufacturing the (EL) display device 1 of Manufacturing Example 1. During bonding, the positions are aligned such that the region A of the light-absorbing anisotropic film included in the manufactured optical laminate corresponds to the light-emitting element of the EL substrate 1.

[0616] [Production Examples 2 to 14]

[0617] The optical laminate 1 was replaced with optical laminates 2 to 14. Otherwise, the display devices 2 to 14 were manufactured in the same manner as in Example 1.

[0618] The light utilization efficiency (light utilization efficiency) of the light-emitting element was measured by using a spectrophotometer (TOPCON TECHNOHOUSE CORPORATION, SR3) at a distance of 700 mm from the display surface of the manufactured display device.

[0619] In order to measure the light utilization efficiency of the light-emitting element, a display device 0 was fabricated using an optical laminate without a light-absorbing anisotropic film instead of the optical laminates of the embodiments and comparative examples.

[0620] The light utilization efficiency of the light-emitting elements of each display device manufactured in Examples 1 to 14 was measured relative to the brightness of display device 0, using the brightness of each display device in the embodiments and comparative examples as a reference.

[0621] Regarding the brightness relative to display device 0, the evaluation is as follows:

[0622] In over 80% of cases, the answer is A.

[0623] In cases where the percentage is above 70% but below 80%, the answer is B.

[0624] In cases where the percentage is above 60% but below 70%, the answer is C.

[0625] The answer is D if the percentage is less than 60%.

[0626] The evaluation results are shown in Table 1 below.

[0627] [Measurement of reflectivity]

[0628] Using a spectrochromometer (manufactured by Konica Minolta, Inc., CM2022), the Y value was measured 10 times in the SCI measurement method by changing the in-plane position, and the average value was used as the reflectance.

[0629] Regarding reflectivity, the evaluation is as follows:

[0630] In cases where it is less than 2%, it is A.

[0631] In cases where the percentage is above 2% but less than 3%, the answer is B.

[0632] In cases where the percentage is above 3% but less than 4%, the answer is C.

[0633] In cases where the percentage is above 4%, the answer is D.

[0634] The evaluation results are shown in Table 1 below.

[0635] In Table 1, the "Irradiation Angle" column indicates the incident angle of light when irradiating the thin film surface with various lights.

[0636] In Table 1, the "Transmittance" column indicates the transmittance along the absorption axis.

[0637] In Table 1, the "Orientation Degree" column indicates the orientation degree of region B in the in-plane direction.

[0638]

[0639] As shown in Table 1, the display device of the present invention can combine the light utilization efficiency (light utilization efficiency) of the light-emitting element with the function of preventing external light reflection.

[0640] Furthermore, as shown in Examples 1, 2, and 8, it can be seen that by setting the absorption axis angle θA of region A to 45–90°, it is possible to appropriately combine utilization efficiency and anti-reflection function of external light, and by setting it to 80–90°, it is possible to more appropriately combine utilization efficiency and anti-reflection function of external light.

[0641] Furthermore, through a comparison of Examples 5 and 6, it can be seen that the orientation degree in the in-plane direction of region B is 0.950 or higher, which can more appropriately combine utilization efficiency and anti-reflection function of external light.

[0642] And, as Figure 10 As shown, the optical film 4 used in Example 4 was placed on an observation window equipped with the linear polarizer P with the absorption axis of region 18B orthogonal to the absorption axis of the linear polarizer P. When the test pattern in the optical film was observed from the vertical direction, it was confirmed that 18A, corresponding to region A, was bright, and 18B, corresponding to region B, was dark. Figure 11 ).

[0643] Next, as Figure 12 As shown, when the same optical film 4 is placed in a configuration where the absorption axis of region 18B and the absorption axis of the linear polarizer P are in an open nicol configuration, and observed from a horizontal plane at an angle of 30°, it is confirmed that region 18A, corresponding to region A, is darker, while region 18B, corresponding to region B, is brighter. Figure 13 This is believed to be because the absorption axis of region 18A is close to the orthogonal Nicol configuration of the linear polarizer P.

[0644] Based on the above observations, it can be inferred that the light-absorbing anisotropic film used in this invention has a region A with an inclination of θA relative to the absorption axis of the film surface and a region B with an inclination of θB relative to the absorption axis of the film surface within the same film surface, and θB is horizontal while θA is close to vertical.

[0645] Furthermore, although the effect differs from that of the present invention, in the light-absorbing anisotropic film used in the present invention, by appropriately adjusting the film thickness, the dimensions of region A and region B, an optical film with high transmittance in the vertical direction and low transmittance from the tilt direction can be formed on the film surface. Such an optical film, as a viewing angle control film, can be expected to provide privacy mode for image display devices or prevent light emitted by image display devices such as automotive displays from reflecting onto the glass.

[0646] Industrial availability

[0647] It can be preferentially used in various display devices.

[0648] Symbol Explanation

[0649] 10-EL (electroluminescent) display device, 12-EL substrate, 12R-R light-emitting element, 12G-G light-emitting element, 12B-B light-emitting element, 14-λ / 4 plate, 16-support, 18-light absorption anisotropic film, 18A, 18B-regions, 20-optical film, 24-light-emitting part, 26-light-aligning film, 28-mask, 28a-light-transmitting part, 28b-light-shielding part, 30-optical film surface, 31-absorption axis.

Claims

1. An optical film having a light-absorbing anisotropic film formed of a cured product of a liquid crystal composition containing a polymerizable liquid crystal compound and a dichroic pigment compound, in the optical film, the light-absorbing anisotropic film has a region A in which the tilt of the absorption axis with respect to the film surface is θA and a region B in which the tilt of the absorption axis with respect to the film surface is θB within the same film surface, θA and θB satisfy the following relationships of formula (1) and formula (2), |θA - θB| ≥ 10° formula (1), 0° ≤ θB ≤ 5° formula (2).

2. The optical film according to claim 1, wherein the tilt θA of the absorption axis is 45 to 90°.

3. The optical film according to claim 1 or 2, wherein the tilt θA of the absorption axis is 80 to 90°.

4. The optical film according to claim 1 or 2, wherein the transmittance of the region A in the absorption axis direction is 65% or more.

5. The optical film according to claim 1 or 2, wherein the degree of orientation of the region B in the in-plane direction is 0.950 or more.

6. The optical film according to claim 1 or 2, wherein the content of the dichroic pigment compound is 15% by mass or more with respect to the total mass of the light-absorbing anisotropic film.

7. An optical laminate in which the optical film according to any one of claims 1 to 6 and a λ / 4 plate are laminated.

8. An image display device having the optical film according to any one of claims 1 to 6 or the optical laminate according to claim 7.

9. An image display device having the optical laminate according to claim 7, the total of the thickness of the optical film and the thickness of the λ / 4 plate is 20 μm or less.

10. The image display device according to claim 8 or 9, wherein the position of the region A of the light-absorbing anisotropic film corresponds to the position of a light-emitting element of the image display device.

11. The image display device according to claim 8 or 9, wherein the image display device is an electroluminescent display device.

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