Light-absorbing anisotropic film, laminate, and image display device

Abstract

The objective of this invention is to provide a light-absorbing anisotropic film capable of producing an image display device with excellent display performance and durability, as well as a laminate using the light-absorbing anisotropic film and an image display device. The light-absorbing anisotropic film of this invention is a light-absorbing anisotropic film used in an image display device, formed using a liquid crystal composition containing a liquid crystal compound and a dichroic substance. The relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface of the light-absorbing anisotropic film corresponding to the visual recognition side of the image display device, for a signal originating from the dichroic substance detected by time-of-flight secondary ion mass spectrometry, satisfies the following equation (I-1): 2.0 ≤ Imax / Isur1 … (I-1).

Description

Technical Field

[0001] This invention relates to a light-absorbing anisotropic film, a laminate, and an image display device. Background Technology

[0002] Previously, when functions such as attenuation, polarization, scattering, or light blocking of laser or natural light were required, devices were used that operated on different principles for each function. Therefore, products corresponding to these functions were manufactured through different processes for each function.

[0003] For example, in image display devices (e.g., liquid crystal displays), linear polarizers or circular polarizers are used to control optical rotation or birefringence in the display. Furthermore, in organic light-emitting diodes (OLEDs), circular polarizers are also used to prevent reflection of external light.

[0004] In the past, iodine has been widely used as a dichroic material in these polarizers, but research is also underway on polarizers that use organic pigments as dichroic materials instead of iodine.

[0005] For example, Patent Document 1 describes a light-absorbing anisotropic film formed using a composition containing a dichroic substance having a defined structure ([Claim 1][Claim 14]).

[0006] Previous technical documents

[0007] Patent documents

[0008] Patent Document 1: International Publication No. 2017 / 195833 Summary of the Invention

[0009] The technical problem to be solved by the invention

[0010] The inventors studied the light-absorbing anisotropic film and image display device described in Patent Document 1 and found that, depending on the type and amount of dichroic substances contained in the light-absorbing anisotropic film, and the layer structure in the image display device other than the light-absorbing anisotropic film, the display performance and durability of the image display device may sometimes be reduced.

[0011] Therefore, the objective of this invention is to provide a light-absorbing anisotropic film capable of producing an image display device with excellent display performance and durability, as well as a laminate using the light-absorbing anisotropic film and an image display device.

[0012] means for solving technical problems

[0013] As a result of in-depth research conducted by the inventors in order to achieve the above-mentioned problem, they discovered that by reducing the amount of dichroic material present on the surface of the light-absorbing anisotropic film corresponding to the visual recognition side of the image display device, it is possible to produce an image display device with excellent display performance and durability, thereby completing the present invention.

[0014] That is, it was discovered that the above-mentioned task can be achieved through the following structure.

[0015] [1] A light-absorbing anisotropic film, which is a light-absorbing anisotropic film used in an image display device, formed using a liquid crystal composition containing a liquid crystal compound and a dichroic substance, wherein,

[0016] For signals originating from dichroic substances detected by time-of-flight secondary ion mass spectrometry, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface corresponding to the visual recognition side of the image display device satisfies the following equation (I-1).

[0017] 2.0≤Imax / Isur1……(I-1).

[0018] [2] According to the light absorption anisotropic film described in [1], wherein,

[0019] The thickness of the light-absorbing anisotropic film from the surface corresponding to the visual recognition side of the image display device to the position where the maximum intensity Imax is displayed exceeds 50 nm.

[0020] [3] According to the light absorption anisotropic film described in [1], wherein,

[0021] The thickness of the light-absorbing anisotropic film from the surface corresponding to the visual recognition side of the image display device to the position where the maximum intensity Imax is displayed exceeds 60 nm.

[0022] [4] The light-absorbing anisotropic film according to any one of [1] to [3], wherein,

[0023] The liquid crystal composition also contains surfactants.

[0024] The difference between the logP value of the surfactant and the logP value of the liquid crystal compound is less than 3.1.

[0025] [5] The light-absorbing anisotropic film according to any one of [1] to [3], wherein,

[0026] The liquid crystal composition also contains surfactants.

[0027] The difference between the logP value of the surfactant and the logP value of the liquid crystal compound is less than 1.4.

[0028] [6] The light-absorbing anisotropic film according to any one of [1] to [3], wherein,

[0029] The liquid crystal composition also contains a surfactant whose logP value differs from that of the liquid crystal compound by less than 1.4, and a surfactant whose logP value differs from that of the liquid crystal compound by more than 1.4.

[0030] [7] A laminate, comprising a substrate, an alignment film, and a light-absorbing anisotropic film sequentially, for use in an image display device, wherein,

[0031] The light-absorbing anisotropic film is any one of [1] to [6],

[0032] For signals originating from dichroic substances detected by time-of-flight secondary ion mass spectrometry, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface corresponding to the visual recognition side of the image display device satisfies the following equation (I-1).

[0033] 2.0≤Imax / Isur1……(I-1).

[0034] [8] The laminate according to [7] further comprises a phase retardation plate disposed on the light-absorbing anisotropic film.

[0035] The retardation plate has multiple optically anisotropic layers containing liquid crystal compounds.

[0036] At least one of the multiple optically anisotropic layers is an optically anisotropic layer containing a liquid crystal compound with a twisted orientation about the thickness direction as the helical axis.

[0037] [9] The laminate according to [7] further comprises a surface protective material disposed on the light-absorbing anisotropic film.

[0038] The substrate is a glass substrate with a thickness of less than 100μm.

[0039]

[10] The laminate according to [7] further comprises a λ / 4 plate disposed on the light-absorbing anisotropic film.

[0040]

[11] An image display device having a light-absorbing anisotropic film as described in any one of [1] to [6] or a laminate as described in any one of [7] to

[10] .

[0041] Invention Effects

[0042] According to the present invention, a light-absorbing anisotropic film capable of producing an image display device with excellent display performance and durability, as well as a laminate using the light-absorbing anisotropic film and an image display device, are provided. Detailed Implementation

[0043] The present invention will now be described in detail.

[0044] The following description of the constituent elements is sometimes made in accordance with representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0045] In addition, the numerical range indicated by “~” in this specification refers to the range included by the values ​​recorded before and after “~” as the lower limit and upper limit values.

[0046] Furthermore, in this specification, for each component, one substance corresponding to that component may be used alone, or two or more substances may be used together. Here, regarding each component, when two or more substances are used together, the content of that component, unless otherwise specified, refers to the total content of the substances used together.

[0047] Furthermore, in this specification, "(meth)acrylate" is a designation for "acrylate" or "methacrylate", "(meth)acrylic acid" is a designation for "acrylic acid" or "methacrylic acid", and "(meth)acryloyl" is a designation for "acryloyl" or "methacryloyl".

[0048] Furthermore, in this specification, the substituent W represents the following groups.

[0049] As substituent W, examples include alkyl groups (preferably alkyl groups with 1 to 20 carbon atoms, more preferably alkyl groups with 1 to 12 carbon atoms, and especially preferably alkyl groups with 1 to 8 carbon atoms, such as methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, and cyclohexyl), alkenyl groups (preferably alkenyl groups with 2 to 20 carbon atoms, more preferably alkenyl groups with 2 to 12 carbon atoms, and especially preferably alkenyl groups with 2 to 8 carbon atoms, such as vinyl, aryl, 2-butenyl, and 3-pentenyl), alkynyl groups (preferably alkenyl groups with 2 to 20 carbon atoms, more preferably alkenyl groups with 2 to 12 carbon atoms, and especially preferably alynyl groups with 2 to 8 carbon atoms, such as propynyl and 3-pentynyl), aryl groups (preferably... The aryl group has 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and especially preferably 6 to 12 carbon atoms. Examples include phenyl, 2,6-diethylphenyl, 3,5-ditrifluoromethylphenyl, styryl, naphthyl, and biphenyl, etc.); substituted or unsubstituted amino groups (preferably 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, and especially preferably 0 to 6 carbon atoms, examples include unsubstituted amino, methylamino, dimethylamino, diethylamino, and aniline, etc.); alkoxy groups (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, examples include methoxy, ethoxy, and butoxy, etc.); and oxycarbonyl groups (preferably 2 to 20 carbon atoms, more preferably carbon...). The number of carbon atoms is 2 to 15, particularly preferably 2 to 10, for example, methoxycarbonyl, ethoxycarbonyl and phenoxycarbonyl, etc.); acyloxy (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6, for example, acetoxy, benzoyloxy, acryloyl and methacryloyl, etc.); amide (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, amide and benzoylamide, etc.); alkoxycarbonylamino (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, especially preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino, etc.); aryloxycarbonylamino. (Preferably 7-20 carbon atoms, more preferably 7-16 carbon atoms, especially preferably 7-12 carbon atoms, for example, phenoxycarbonylamino, etc.), sulfonylamino (preferably 1-20 carbon atoms, more preferably 1-10 carbon atoms, especially preferably 1-6 carbon atoms, for example, methanesulfonylamino and benzenesulfonylamino, etc.), aminosulfonyl (preferably 0-20 carbon atoms, more preferably 0-10 carbon atoms, especially preferably 0-6 carbon atoms, for example, aminosulfonyl, methylaminosulfonyl, dimethylaminosulfonyl and phenylaminosulfonyl, etc.), carbamoyl (preferably 1-20 carbon atoms, more preferably 1-10 carbon atoms, especially preferably 1-6 carbon atoms, for example,Examples of suitable carbonyl groups include unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl, and phenylcarbamoyl, etc.; alkylthio (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, and especially preferably with 1 to 6 carbon atoms, for example, methylthio and ethylthio, etc.); arylthio (preferably with 6 to 20 carbon atoms, more preferably with 6 to 16 carbon atoms, and especially preferably with 6 to 12 carbon atoms, for example, phenylthio, etc.); and sulfonyl (preferably with 1 to 20 carbon atoms). More preferably, the carbon number is 1 to 10, especially preferably 1 to 6, for example, methanesulfonyl and toluenesulfonyl, etc.); thionyl (preferably 1 to 20 carbon atoms, more preferably 1 to 10, especially preferably 1 to 6, for example, methanethionyl and phenylthionyl, etc.); urea (preferably 1 to 20 carbon atoms, more preferably 1 to 10, especially preferably 1 to 6, for example, unsubstituted urea, methylurea, and Phosphamide group (preferably with 1 to 20 carbon atoms, more preferably with 1 to 10 carbon atoms, especially preferably with 1 to 6 carbon atoms, for example, diethylphosphamide group and phenylphosphamide group, etc.), hydroxyl group, mercapto group, halogen atom (e.g., fluorine atom, chlorine atom, bromine atom and iodine atom), cyano group, nitro group, hydroxamic acid group, sulfinyl group, hydrazyl group, imino group, azo group, heterocyclic group (preferably heterocyclic group with 1 to 30 carbon atoms, more preferably heterocyclic group with 1 to 12 carbon atoms, for example, a group having a nitrogen atom). Heterocyclic groups containing heteroatoms such as oxygen, sulfur, etc., including, for example, epoxy, oxacyclobutyl, imidazolyl, pyridinyl, quinolinyl, furanyl, piperidinyl, morpholinyl, maleimide, benzoxazolyl, benzimidazolyl, and benzothiazolyl. Silicyl groups (preferably silyl groups with 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, and especially preferably silyl groups with 3 to 24 carbon atoms, for example, trimethylsilyl, triphenylsilyl, etc.), carboxyl groups, sulfonic acid groups, phosphate groups, etc.

[0050] [Anisotropic light absorption film]

[0051] The light-absorbing anisotropic film of the present invention is a light-absorbing anisotropic film used in image display devices, formed using a liquid crystal composition containing a liquid crystal compound and a dichroic substance.

[0052] In the light absorption anisotropic film of the present invention, for the signal derived from the dichroic substance detected by Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS), the relationship between the maximum intensity Imax in the thickness direction of the light absorption anisotropic film and the intensity Isur1 on the surface of the light absorption anisotropic film corresponding to the visual recognition side of the image display device (hereinafter, also simply referred to as "visual recognition side surface") satisfies the following formula (I-1).

[0053] 2.0 ≤ Imax / Isur1……(I-1)

[0054] <Measurement method of TOF-SIMS>

[0055] The measurement based on TOF-SIMS in the present invention is carried out as follows.

[0056] (1) Apparatus and conditions

[0057] · Apparatus: TOF-SIMS 5 (manufactured by ION-TOF Co., Ltd.)

[0058] · Depth direction analysis: combined with Ar ion sputtering

[0059] · Measurement range: 128-point raster scans are performed along one direction and its orthogonal direction respectively

[0060] · Polarity: positive, negative

[0061] (2) Intensity Isur1 and maximum intensity Imax

[0062] For the light absorption anisotropic film to be measured, the intensity in each of the following regions is measured while measuring at a constant speed in the thickness direction from the visual recognition side surface of the light absorption anisotropic film to the surface on the side opposite to the visual recognition side surface.

[0063] (Intensity Isur1)

[0064] The average value of the intensity of the mass spectrometry analysis of the fragments derived from the dichroic substance (the average value of the intensity from the baseline) in the region 1% away from the visual recognition side surface of the light absorption anisotropic film is set as the intensity Isur1 on the visual recognition side surface.

[0065] (Maximum intensity Imax)

[0066] The maximum value of the intensity of the mass spectrometry analysis of the fragments derived from the dichroic substance (the intensity from the baseline) in the region of 98% of the overall thickness obtained by removing 1% of the total thickness from each surface is set as the maximum intensity Imax in the thickness direction.

[0067] (3) Regarding the test subjects

[0068] When the light absorption anisotropic film, which is the object of measurement, exists as a stack with adjacent layers, the visual recognition side surface (i.e. the interface with the adjacent layer) of the light absorption anisotropic film can be determined as the point where the intensity of the simple analysis of the fragment originating from the liquid crystal compound detected from the light absorption anisotropic film intersects with the intensity of the simple analysis of the fragment originating from the most abundant compound among the fragments detected from the adjacent layer.

[0069] Furthermore, when two or more dichroic substances are present in the light absorption anisotropic film, the intensity of the simple analysis of a fragment originating from a dichroic substance with a maximum absorption wavelength in the wavelength range of 500–650 nm (hereinafter, in this paragraph, it is also referred to as the "target dichroic substance") is measured. When two or more target dichroic substances are included, the intensity of the simple analysis of a fragment originating from the dichroic substance with the highest absorbance among the target dichroic substances is measured.

[0070] In this invention, as described above, by reducing the amount of dichroic material present on the visual recognition side surface of the light-absorbing anisotropic film, that is, for the signal originating from the dichroic material detected by TOF-SIMS, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the visual recognition side surface satisfies the above formula (I-1), an image display device with excellent display performance and durability can be manufactured.

[0071] While the details of the cause are unclear, the inventors speculate that it is based on the following reasons.

[0072] First, as a reason for the poor display performance in the prior art, the inventors speculate that the reason is as follows: because the refractive index of the dichroic material present on the visual recognition side surface of the light-absorbing anisotropic film is high, internal reflection occurs at the interface with the adjacent layer on the visual recognition side.

[0073] Furthermore, as a reason for the poor durability in the prior art, the inventors speculate that the reason is as follows: the dichroic material present on the visual recognition side surface of the light-absorbing anisotropic film will transfer to the adjacent layer depending on the type of the adjacent layer on the visual recognition side.

[0074] Therefore, in this invention, it is believed that by satisfying the above formula (I-1), the amount of dichroic material present on the visual recognition side surface of the light-absorbing anisotropic film is reduced, internal reflection at the interface with the adjacent layer is suppressed, and the transfer of dichroic material to the adjacent layer is suppressed, thus enabling the manufacture of an image display device with excellent display performance and durability.

[0075] Furthermore, in this invention, for signals originating from dichroic substances detected by TOF-SIMS, the relationship between the maximum intensity Imax in the thickness direction of the light absorption anisotropic film and the intensity Isur1 on the visual recognition side surface satisfies the above formula (I-1). Even without additional refractive index adjustment layer or blocking layer (oxygen barrier layer), the display performance and durability will be good, thus enabling the thinning of the image display device.

[0076] In this invention, the above formula (I-1) does not specify an upper limit for the ratio (Imax / Isur1) of the maximum strength Imax to the strength Isur1. This clarifies that it also includes the method in which the maximum strength Imax is effectively measured and the strength Isur1 is below the measurement limit.

[0077] Furthermore, considering the reason that the display performance and durability of the image display device are further improved, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the visual recognition side surface of the light-absorbing anisotropic film preferably satisfies the following formula (I-2), and more preferably satisfies the following formula (I-3).

[0078] 5≤Imax / Isur1……(I-2)

[0079] 20 <Imax / Isur1≤100……(I-3)

[0080] Furthermore, in this invention, considering the need to further improve the display performance and durability of the image display device, the thickness (hereinafter referred to as "gradient thickness") from the visual recognition side surface of the light absorption anisotropic film to the position where the maximum intensity Imax is displayed is preferably more than 50 nm, more preferably 60 nm, and even more preferably more than 60 nm and less than 300 nm.

[0081] Here, "gradient thickness" refers to the value calculated by measuring the maximum intensity Imax using the TOF-SIMS measurement method described above, and in the following order.

[0082] (1) Measure the overall scanning time X of the film thickness direction from the visual recognition side surface of the light-absorbing anisotropic film to the surface on the opposite side of the visual recognition side surface.

[0083] (2) Measure the scanning time Y from the visual recognition side surface of the light-absorbing anisotropic film to the position where the maximum intensity Imax is displayed.

[0084] (3) The overall thickness Z (nm) of the light-absorbing anisotropic film was determined using scanning electron microscopy (SEM).

[0085] (4) Calculate the gradient thickness (nm) according to the following formula.

[0086] Gradient thickness (nm) = Z (nm) × (Y / X)

[0087] [Liquid Crystal Composition]

[0088] The components contained in the liquid crystal composition used in the formation of the light-absorbing anisotropic film of the present invention will be described in detail below.

[0089] <Liquid Crystal Compounds>

[0090] As the liquid crystal compound contained in the liquid crystal composition, either a high molecular weight liquid crystal compound or a low molecular weight liquid crystal compound can be used. From the perspective of improving the degree of orientation, a high molecular weight liquid crystal compound is preferred.

[0091] Here, "polymeric liquid crystal compound" refers to a liquid crystal compound that has repeating units in its chemical structure.

[0092] Here, "low molecular weight liquid crystal compound" refers to a liquid crystal compound that does not have repeating units in its chemical structure.

[0093] Examples of polymeric liquid crystal compounds include, for example, the thermotropic liquid crystal polymer described in Japanese Patent Application Publication No. 2011-237513 and the polymeric liquid crystal compounds described in paragraphs

[0012] to

[0042] of International Publication No. 2018 / 199096.

[0094] As a low-molecular-weight liquid crystal compound, examples include the liquid crystal compounds described in paragraphs

[0072] to

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

[0095] Furthermore, as a liquid crystal compound, it can be used in combination with both high-molecular-weight liquid crystal compounds and low-molecular-weight liquid crystal compounds.

[0096] Considering that the orientation degree of the obtained light absorption anisotropic film is higher, the liquid crystal compound is preferably a polymeric liquid crystal compound containing the repeating unit (hereinafter referred to as "repeating unit (1)") represented by the following formula (1).

[0097] 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".

[0098] [Chemical Formula 1]

[0099]

[0100] 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.

[0101] 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, wherein, from the viewpoint of the diversity of monomers as raw materials and ease of handling, the group represented by the following formula (P1-A) is preferred.

[0102] [Chemical Formula 2]

[0103]

[0104] In the above formulas (P1-A) to (P1-D), "*" indicates the bonding position with L1 in the above formula (1).

[0105] In the above formulas (P1-A) to (P1-D), R 1 R 2 R 3 and R 4 Each of the above-mentioned alkyl groups independently represents a hydrogen atom, a halogen atom, a cyano group, or 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 number of carbon atoms in the alkyl group is preferably 1 to 5.

[0106] 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.

[0107] 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.

[0108] 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.

[0109] 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 The meaning of R in (P1-D) 14 The meanings are the same, multiple R15 Alkyl groups, which can be independently represented by 1 to 10 hydrogen or carbon atoms respectively.

[0110] In the above formula (1), L1 is a single bond or a divalent linking group.

[0111] 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 4 - etc. In the formula, R 3 and R 4 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.

[0112] 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.

[0113] 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.

[0114] 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.

[0115] Here, the ethylene oxide 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 most preferably 3.

[0116] Furthermore, considering the superior effects of the present invention, the propylene oxide 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.

[0117] 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.

[0118] 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.

[0119] 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 in an intermediate state (intermediate phase) between the crystalline state and the isotropic liquid state. There are no particular limitations on 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 Editorial Committee, Liquid Crystal Handbook" (Maruzen, 2000), especially Chapter 3.

[0120] 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.

[0121] 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.

[0122] 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).

[0123] [Chemical Formula 3]

[0124]

[0125] 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.

[0126] 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.

[0127] * indicates the bonding position with SP1 or T1.

[0128] Examples of divalent aromatic hydrocarbon groups represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and tetraphenyl-diyl. From the perspective of the diversity of mesocrystalline framework design or the availability of raw materials, phenylene or naphthylene is preferred, and phenylene is more preferred.

[0129] 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.

[0130] 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 that form the ring besides carbon, these atoms may be the same or different.

[0131] 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.

[0132] Specific examples of the divalent alicyclic group represented by A1 include cyclopentylene and cyclohexylene.

[0133] In the above 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.

[0134] 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.

[0135] 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.

[0136] 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 LA1s is independently a single bond or a divalent linking group, and at least one of the plurality of LA1s 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 LA1s is a divalent linking group and the other is a single bond.

[0137] 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-, -OC(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 a hydrogen atom, C1-C4 alkyl, cycloalkyl, aryl, cyano, or halogen atom.), -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 these, -C(O)O- is preferred for reasons of superior performance of the present invention. LA1 can also be a group formed by combining two or more of these groups.

[0138] Specific examples of M1 include the following structures. Additionally, in the following examples, "Ac" represents an acetyl group.

[0139] [Chemical Formula 4]

[0140]

[0141] [Chemical Formula 5]

[0142]

[0143] [Chemical Formula 6]

[0144]

[0145] [Chemical Formula 7]

[0146]

[0147] [Chemical Formula 8]

[0148]

[0149] [Chemical Formula 9]

[0150]

[0151] [Chemical Formula 10]

[0152]

[0153] In the above formula (1), the terminal group represented by T1 can be a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group with 1 to 10 carbon atoms, an alkoxy group with 1 to 10 carbon atoms, an alkylthio group with 1 to 10 carbon atoms, an alkoxycarbonyloxy group with 1 to 10 carbon atoms, an alkoxycarbonyl group with 1 to 10 carbon atoms (ROC(O)-: R is an alkyl group), an acyloxy group with 1 to 10 carbon atoms, an amide group with 1 to 10 carbon atoms, an alkoxycarbonylamino group with 1 to 10 carbon atoms, a sulfonylamino group with 1 to 10 carbon atoms, an aminosulfonyl group with 1 to 10 carbon atoms, an carbamoyl group with 1 to 10 carbon atoms, a sulfinyl group with 1 to 10 carbon atoms, a urea group with 1 to 10 carbon atoms, and a group containing a (meth)acryloyloxy group, etc. Examples of groups containing (meth)acryloyloxy groups include, for instance, the group represented by -LA (L represents a single bond or a linking group. Specific examples of linking groups are the same as those for L1 and SP1 above. A represents (meth)acryloyloxy).

[0154] From the perspective of the superior effect of the present invention, T1 is preferably an alkoxy group with 1 to 10 carbon atoms, more preferably an alkoxy group with 1 to 5 carbon atoms, and even more preferably a methoxy group.

[0155] These terminal groups can be further replaced by these groups or by the polymerizable groups described in Japanese Patent Application Publication No. 2010-244038.

[0156] Considering the reasons that it improves adhesion to adjacent layers and enhances the cohesiveness of the membrane, T1 is preferably a polymerizable group.

[0157] There are no particular limitations on the polymerizable groups, but preferably polymerizable groups that can undergo free radical polymerization or cationic polymerization.

[0158] As a free radical polymerizable group, commonly known free radical polymerizable groups can be used. Acryloyl or methacryloyl are examples of preferred free radical polymerizable groups. In this case, acryloyl is known to generally have a fast polymerization rate, and from the viewpoint of improving productivity, acryloyl is preferred, but methacryloyl can also be used as a polymerizable group.

[0159] As the cationic polymerizable group, commonly known cationic polymerizable groups can be used, specifically including 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 particularly preferred.

[0160] For the sake of superior performance 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 1,000 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.

[0161] In particular, from the viewpoint of suppressing cracks 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.

[0162] 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.

[0163] In this invention, the weight-average molecular weight and number-average molecular weight are values ​​determined by gel permeation chromatography (GPC).

[0164] • Solvent (eluent): N-methylpyrrolidone

[0165] • Device Name: TOSOH HLC-8220GPC

[0166] • String: Connect 3 TOSOH TSKgelSuperAWM-H (6mm×15cm) tubes for use.

[0167] • Column temperature: 25℃

[0168] • Sample concentration: 0.1% by mass

[0169] • Flow rate: 0.35 mL / min

[0170] • Calibration curve: The calibration curve was obtained using seven samples of TSK standard polystyrene prepared by TOSOH CORPORATION with Mw = 2,800,000 to 1,050 (Mw / Mn = 1.03 to 1.06).

[0171] In this invention, for the sake of ease of adjustment of the compatibility with the dichroic substances described later, the logP value of the liquid crystal compound is preferably 0.0 to 10, more preferably 1.0 to 7.0, and even more preferably 2.0 to 5.0.

[0172] Here, the logP value is an indicator of the hydrophilicity and hydrophobicity of a chemical structure, sometimes referred to as the hydrophilic / hydrophobic parameter. The logP value can be calculated using software such as ChemBioDraw Ultra or HSPiP (Ver. 4.1.07). It can also be experimentally determined using methods such as those outlined in OECD Guidelines for the Testing of Chemicals, Section 1, Test No. 117. In this invention, unless otherwise specified, the logP value is the value calculated by inputting the compound's structural formula into HSPiP (Ver. 4.1.07).

[0173] In this invention, the content of the liquid crystal compound is preferably 8 to 99% by mass of the solid components in the liquid crystal composition, more preferably 8 to 96% by mass.

[0174] Here, "solid components in the liquid crystal composition" refers to components other than solvents. Specific examples of solid components include the liquid crystal compounds mentioned above, as well as dichroic substances, polymerization initiators, surfactants, etc., which will be described later.

[0175] <Dichromatic substances>

[0176] There are no particular limitations on the dichroic substances 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 substances (dichroic pigments) can be used.

[0177] 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. 2013-14883, 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 2013-37353, paragraphs

[0051] to

[0065] of the Japanese JP 2012-63387, paragraphs

[0049] to

[0073] of the Japanese JP 2012-63387, 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, are also mentioned. Paragraphs

[0021] to

[0075] of Japanese Announcement No. 42, paragraphs

[0011] to

[0025] of Japanese Announcement No. 2010-215846, paragraphs

[0017] to

[0069] of Japanese Announcement No. 2011-048311, paragraphs

[0013] to

[0133] of Japanese Announcement No. 2011-213610, paragraphs

[0074] to

[0246] of Japanese Announcement No. 2011-237513, paragraphs

[0005] to

[0051] of Japanese Announcement No. 2016-006502, WO2016 / The dichroic substances described in paragraphs

[0005] to

[0041] of Published No. 060173, 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.

[0178] In this invention, two or more dichroic materials 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 material with a maximum absorption wavelength in the range of 370 nm or more and less than 550 nm and at least one dichroic material with a maximum absorption wavelength in the range of 500 nm or more and less than 700 nm.

[0179] The aforementioned dichroic substances may have cross-linking groups.

[0180] Specifically, examples of the crosslinking groups mentioned above include (meth)acryloyl, epoxy, oxocyclobutyl, styryl, etc., with (meth)acryloyl being preferred.

[0181] In this invention, considering the improved display performance and durability of the image display device, the difference between the logP value of the dichroic substance and the logP value of the liquid crystal compound is preferably 5.0 or more, more preferably 7.0 or more, and even more preferably 7.0 or more and less than 10.0.

[0182] Here, the difference (absolute value) between the logP value of a dichroic substance and the logP value of a liquid crystal compound, when using multiple dichroic substances or liquid crystal compounds, refers to the largest difference among the differences calculated from the logP values ​​of each compound.

[0183] From the viewpoint of achieving better results with respect to the present invention, the content of the dichroic substance relative to 100 parts by mass of the above-mentioned liquid crystal compound is preferably 1 to 400 parts by mass, more preferably 2 to 100 parts by mass, and even more preferably 5 to 30 parts by mass.

[0184] Furthermore, the content of the dichroic substance is preferably 1 to 50% by mass of the solid components in the liquid crystal composition, more preferably 2 to 40% by mass.

[0185] <Polymerization initiator>

[0186] The liquid crystal composition preferably contains a polymerization initiator.

[0187] There are no particular restrictions on the type of polymerization initiator, but it is preferred to use a photosensitive compound, i.e., a photopolymerization initiator.

[0188] 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), azobinyl ethers (as described in U.S. Patent No. 2,448,828), α-hydrocarbon-substituted aromatic azobinyl 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 oxime compounds (paragraph

[0065] of Japanese Patent Application Publication No. 2016-27384), and acylphosphine oxide compounds (Japanese Patent Application Publication No. 63-40799, Japanese Patent Application Publication No. 5-29234, Japanese Patent Application Publication No. 10-95788, and Japanese Patent Application Publication No. 10-29997), etc.

[0189] 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.

[0190] 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 100 parts by mass of the dichroic substance 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 better; when it is 30 parts by mass or less, the orientation degree of the light-absorbing anisotropic film becomes better.

[0191] 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.

[0192] <surfactants>

[0193] The liquid crystal composition preferably contains a surfactant.

[0194] 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.

[0195] As a surfactant, a surface modifier that makes the dichroic substance and the liquid crystal compound horizontal on the coating surface side is preferred. For example, compounds described in paragraphs

[0155] to

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

[0253] to

[0293] of Japanese Patent Application Publication No. 2011-237513 (horizontal alignment agent) can be used.

[0196] The surfactant contained in the liquid crystal composition of the present invention may be a fluoropolymer having a repeating structure B1 represented by formula (B-1) described later and a repeating structure B2 containing fluorine atoms.

[0197] (Repeating structure B1)

[0198] The repeating structure B1 of the above-mentioned fluoropolymer is the repeating structure represented by the following formula (B-1).

[0199] [Chemical Formula 11]

[0200]

[0201] In the above formula (B-1), R 1 It represents hydrogen atoms, alkyl groups or halogen atoms with 1 to 5 carbon atoms.

[0202] Furthermore, L 1 Indicates a single bond or -CO-.

[0203] 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.

[0204] L 2 and L 3 Each can be used independently to represent a single bond or a divalent linker.

[0205] 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.

[0206] As L in the above formula (B-1) 1 Preferably -CO-.

[0207] 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.

[0208] 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.

[0209] Furthermore, as described above, one or more non-adjacent -CH2- groups constituting a 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.

[0210] 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 L2 - 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.

[0211] 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 replaced by 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.

[0212] [Chemical Formula 12]

[0213]

[0214]

[0215] 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.

[0216] Considering the reason that the orientation degree of the formed light absorption 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).

[0217] Furthermore, in the above formula (B-1), D represents a hydrogen-bonded group composed of a hydrogen atom and a nonmetallic atom from groups 14 to 16. The nonmetallic atom may have substituents.

[0218] Here, nonmetallic atoms from groups 14 to 16 can be exemplified by, for example, oxygen, sulfur, nitrogen, and carbon atoms.

[0219] 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.

[0220] Examples of such hydrogen-bonding groups include hydrogen bond donor groups and hydrogen bond acceptor groups.

[0221] Specifically, examples of hydrogen bond-donating groups include 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 groups are preferred.

[0222] Specifically, examples of hydrogen bond accepting groups include heteroatoms with non-shared electron pairs on heterocycles, 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 polymeric structures with oxygen atoms included in polyether structures), aliphatic amine groups, aromatic amine groups, etc., among which carboxyl groups and amide groups are preferred.

[0223] (Repeating structure B2)

[0224] The repeating structure B2 of the aforementioned fluoropolymer is a repeating structure containing fluorine atoms.

[0225] 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.

[0226] 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.

[0227] (Repeated structure B3)

[0228] In this invention, considering the reason that the coating properties of the formed anisotropic light absorption film are improved, it is preferable that the fluoropolymer contains, in addition to the repeating structures B1 and B2 described above, a repeating structure B3 derived from a monomer with a molecular weight of 300 or less.

[0229] 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.

[0230] [Chemical Formula 13]

[0231]

[0232] In equation (N-1), R B11 and RB12 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.

[0233] 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.

[0234] R B11 molecular weight and R B12 The lower limit of the total molecular weight is preferably 2 or more.

[0235] As R B11 and R B12 The substituents indicated 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.

[0236] Examples of organic groups mentioned above include straight-chain, branched, or cyclic alkyl groups, aromatic hydrocarbon groups, and heterocyclic groups.

[0237] The alkyl group preferably has 1 to 15 carbon atoms, more preferably 1 to 12, and even more preferably 1 to 8.

[0238] The carbon atom of an alkyl group can be replaced 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(O)-C(Z)=C(Z’)-, -C(Z)=C(Z’)-C(O)-S-, -SC(O The groups -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, are preferred. From the viewpoint of further enhancing the effects of the present invention, -O-, -C(O)-, -N(Z)-, -OC(O)-, or -C(O)O- are preferred among the groups that can replace the carbon atoms of the alkyl group.

[0239] The hydrogen atom of an alkyl group can be a halogen atom, cyano group, aryl group, nitro group, or -OZ group. H -C(O)Z H -C(O)OZ H -OC(O)Z H -OC(O)OZ H -NZ H Z H '、-NZ H C(O)Z H '、-NZ H C(O)OZ H '、-C(O)NZ H Z H '、-OC(O)NZ H Z H '、-NZ H C(O)NZ H 'OZ H "、-SZ H -C(S)Z H -C(O)SZ H or -SC(O)Z H Replace. Z H Z H 'and Z H"Each of the following groups independently represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms, a cyano group, or a nitro group. Among the groups that can replace the hydrogen atoms of the alkyl group, from the viewpoint of better performance of the present invention, -OH, -COOH, or aryl (phenyl) are preferred."

[0240] The hydrogen atoms of aromatic hydrocarbon groups and heterocyclic groups can be halogen atoms, cyano groups, alkyl groups with 1 to 10 carbon atoms, cyano groups, nitro groups, and -OZ groups. H -C(O)Z H -C(O)OZ H -OC(O)Z H -OC(O)OZ H -NZ H Z H '、-NZ H C(O)Z H '、-NZ H C(O)OZ H '、-C(O)NZ H Z H '、-OC(O)NZ H Z H '、-NZ H C(O)NZ H 'OZ H "、-SZ H -C(S)Z H -C(O)SZ H -SC(O)Z H -B(OH)2 substitution. Z H Z H 'and Z H "Each group independently represents a hydrogen atom, a halogen atom, an alkyl group with 1 to 10 carbon atoms, a cyano group, or a nitro group. From the viewpoint of better performance of the present invention, -OH and -B(OH)2 are preferred among groups that can replace hydrogen atoms of aromatic hydrocarbon groups and hydrogen atoms of heterocyclic groups."

[0241] From the viewpoint that the present invention has superior effects, 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.

[0242] From the viewpoint that the present invention has superior effects, 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.

[0243] R B11 and R B12The 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.

[0244] From the viewpoint that the present invention has superior effects, 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.

[0245] From the viewpoint that the present invention has 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.

[0246] R B11 and R B12 The rings formed by the connections 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.

[0247] As R B11 and R B12 Specific examples of rings formed by linkages include the following groups.

[0248] [Chemical Formula 14]

[0249]

[0250] R B13 It represents a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, a halogen atom, or a cyano group, wherein a hydrogen atom or an alkyl group having 1 to 5 carbon atoms is preferred, and a hydrogen atom is more preferred.

[0251] The alkyl group has 1 to 5 carbon atoms, preferably 1 to 3, and more preferably 1. The alkyl group can be any structure, whether straight-chain, branched, or cyclic.

[0252] The following shows a specific example of the repeating structure B3, but the repeating structure B3 is not limited to the following structures.

[0253] [Chemical Formula 15]

[0254]

[0255] The content of repeating structure B3 relative to the total mass of all repeating structures of the fluoropolymer 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.

[0256] 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.

[0257] (Other repeating structures (1 of them))

[0258] The fluoropolymers mentioned above may also have repeating structures represented by the following general formula (M-3).

[0259] [Chemical Formula 16]

[0260]

[0261] 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.

[0262] As a linking group for L3, the same group as SP21 in the above formula (F-2) can be cited.

[0263] Examples of aromatic cyclic groups for T3 include aromatic hydrocarbon cyclic groups such as benzyl, naphthyl, anthracene, and phenanthroline groups; and aromatic heterocyclic groups such as furanyl, pyrroleyl, thiophene, pyridine, thiazole, and benzothiazole groups. Among these, benzyl groups (e.g., 1,4-phenyl) are preferred. Including these groups in the polymer improves compatibility.

[0264] As a single entity forming the repeating structure represented by the above formula (M-3), specifically, for example, the structures represented by the following formulas (M3-1) to (M3-5) can be cited, but the present invention is not limited thereto.

[0265] [Chemical Formula 17]

[0266]

[0267] (Other repeating structures (2))

[0268] The fluoropolymers mentioned above may also have repeating structures represented by the following general formula (M-4).

[0269] [Chemical Formula 18]

[0270]

[0271] 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 the crosslinking group represented by the above formulas (P1) to (P30).

[0272] As the linking group of L4, the same group as SPW in the above formula (W1) can be mentioned. Examples 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, the groups are straight-chain, branched, or cyclic alkylene groups with 1 to 20 carbon atoms, and aromatic hydrocarbon groups with 4 to 20 carbon atoms. Preferably, the groups have -O-, -CO-O-, -CO-NH-, or -O-CO-.

[0273] When Q4 represents a group containing a cationic polymerizable group, there are no particular limitations 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.

[0274] As a cationic polymerizable group, an alicyclic ether or ethoxy group is preferred, more preferably an epoxy group, oxetyl or ethoxy group, further preferably an epoxy group or oxetyl, 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.

[0275] 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, the interlayer adhesion can be improved, for example, when the liquid crystal film is configured as a stack of multiple liquid crystal composition layers as described later.

[0276] 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.

[0277] [Chemical Formula 19]

[0278]

[0279] The aforementioned fluoropolymers 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.

[0280] Furthermore, in copolymers with random structures and fluorinated alkyl chain lengths of 1 to 4, the fluorine groups are relatively small, exhibiting excellent solubility in common solvents but low transferability to the coating surface. On the other hand, in the aforementioned polymers, 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.

[0281] In this invention, when the liquid crystal composition contains a surfactant, from the perspective of improving the display performance and durability of the image display device, the difference between the logP value of the surfactant and the logP value of the liquid crystal compound is preferably less than 3.1, more preferably less than 1.4, and even more preferably 0 or more and less than 1.4.

[0282] Here, the difference (absolute value) between the logP value of the surfactant and the logP value of the liquid crystal compound, when using multiple surfactants or liquid crystal compounds, refers to the smallest difference among the differences calculated from the logP values ​​of each compound.

[0283] Furthermore, the present invention may contain two or more surfactants. From the viewpoint of further improving the display performance and durability of the image display device, it is preferable to contain a surfactant whose logP value differs from that of the liquid crystal compound by less than 1.4. From the viewpoint of improving the smoothness of the coated surface and thus further improving the orientation, or suppressing depressions and unevenness and thus improving the in-plane uniformity, it is preferable to further contain a surfactant whose logP value differs from that of the liquid crystal compound by 1.4 or more.

[0284] 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 substance and the liquid crystal compound in the liquid crystal composition.

[0285] A single surfactant may be used, or two or more surfactants may be used simultaneously. When two or more surfactants are used, it is preferable that their total amount is within the range described above.

[0286] <Sealing Modifier>

[0287] From the viewpoint of adhesion to the barrier layer described later, the liquid crystal composition may 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.

[0288] As a compound containing a boric acid group, for example, a compound represented by the following formula can be preferably cited.

[0289] [Chemical Formula 20]

[0290]

[0291] (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 heterocyclic group. R 3 This indicates a substituent containing a functional group that can bond with a (meth)acrylate group.

[0292] Solvent

[0293] From an operability point of view, the liquid crystal composition preferably contains a solvent.

[0294] 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., ethyl acetate). Organic solvents such as methyl 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 heterocyclic compounds (e.g., pyridine, etc.) and water are permitted. One of these solvents may be used alone, or two or more may be used simultaneously.

[0295] Among these solvents, from the viewpoint of achieving excellent solubility for liquid crystal compositions, ketones (especially cyclopentanone and cyclohexanone), ethers (especially tetrahydrofuran, cyclopentyl methyl ether, tetrahydropyran, and dioxolane), and amides (especially dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and N-ethylpyrrolidone) are preferred.

[0296] 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 particularly preferably 85 to 95% by mass.

[0297] 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.

[0298] [Production Method]

[0299] Regarding the method for manufacturing the light-absorbing anisotropic film of the present invention, there are no particular limitations as long as the proportion of dichroic substances can be adjusted to satisfy the above formula (I-1). For example, the following methods can be cited: a step of coating a composition from which the dichroic substances are removed from the liquid crystal composition onto an adjacent layer (e.g., an alignment film) to form a first coated film (hereinafter also referred to as the "first coated film forming step"); a step of coating the liquid crystal composition onto the first coated film to form a second coated film (hereinafter also referred to as the "second coated film forming step"); a step of aligning the liquid crystal components contained in the first coated film and the second coated film (hereinafter also referred to as the "alignment step"); a method of adjusting the compatibility of the liquid crystal compound and the dichroic substances contained in the liquid crystal composition by controlling their hydrophilicity / hydrophobicity; a method of adjusting the flowability of the liquid crystal composition by adjusting the heating temperature in the alignment step described later; etc.

[0300] In addition, the liquid crystal component is as follows: it not only includes the liquid crystal compound mentioned above, but also, in the case that the dichroic substance mentioned above has liquid crystal properties, it includes a dichroic substance that has liquid crystal properties.

[0301] <First Coating Film Formation Process>

[0302] The first coating film forming step is a step of coating a composition from which dichroic substances are removed from a liquid crystal composition onto an adjacent layer (e.g., an alignment film) to form a first coating film.

[0303] As a coating method for the composition, examples include known methods such as roller coating, gravure printing, spin coating, wire rod coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.

[0304] <Second Coating Film Forming Process>

[0305] The second coating film formation process is a process of coating a liquid crystal composition onto a first coating film to form a second coating film.

[0306] By using a liquid crystal composition containing the aforementioned solvent, or by using a substance that melts the liquid crystal composition through heating, the liquid crystal composition can be easily coated onto the first coating film.

[0307] As a coating method for the liquid crystal composition, a method identical to the first coating film formation step can be cited.

[0308] <Orientation Process>

[0309] The alignment process is a process of aligning the liquid crystal components contained in the first and second coated films. This yields a light-absorbing anisotropic film that satisfies the above formula (I-1).

[0310] The orientation process may 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.

[0311] Here, the liquid crystal components contained in the liquid crystal composition are sometimes oriented through the above-described coating formation process or drying process. For example, in the case where the liquid crystal composition is prepared as a coating liquid containing a solvent, the solvent is removed from the coating film by drying the coating film, and a coating film with light absorption anisotropy (i.e., a light absorption anisotropy film) can be obtained.

[0312] If the drying process is performed at a temperature above the transition temperature at which the liquid crystal components contained in the coated film transform into the liquid crystal phase, the heating process described later may not be necessary.

[0313] From the perspective of manufacturing applicability, the transition temperature of the liquid crystal component 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, high temperatures are not required when setting the isotropic liquid state to a temperature higher than the temporary liquid crystal phase temperature range, thereby reducing heat waste, substrate deformation, and deterioration, which is also preferable.

[0314] The alignment process preferably includes a heat treatment. This allows the liquid crystal components contained in the coated film to be aligned, thus enabling the heat-treated coated film to be preferably used as a light-absorbing anisotropic film.

[0315] From the perspective of manufacturing applicability, the heat treatment is preferably 10–250°C, more preferably 25–190°C. Furthermore, the heating time is preferably 1–300 seconds, more preferably 1–60 seconds.

[0316] The alignment process can include a cooling process performed after the heat treatment. The cooling process involves cooling the heated coating film to approximately room temperature (20–25°C). This helps to fix the alignment of the liquid crystal components contained in the coating film. There are no particular limitations on the cooling method; known methods can be used.

[0317] Through the above processes, an anisotropic light-absorbing film can be obtained.

[0318] Furthermore, in this method, drying treatment and heat treatment are cited as methods for aligning the liquid crystal components contained in the coating film, but it is not limited to these, and can be implemented by known alignment treatments.

[0319] (Other processes)

[0320] The method for manufacturing anisotropic light-absorbing films may include a step of curing the anisotropic light-absorbing film after the above-mentioned orientation step (hereinafter also referred to as the "curing step").

[0321] For example, when the light-absorbing anisotropic film has crosslinking groups (polymeric groups), the curing process is carried out by heating and / or light irradiation (exposure). Preferably, the curing process is carried out by light irradiation.

[0322] The light source used for curing can be various light sources such as infrared, visible light, or ultraviolet light, but ultraviolet light is preferred. Furthermore, during curing, ultraviolet light can be irradiated while heating is being performed, or ultraviolet light can be irradiated through a filter that transmits only a specific wavelength.

[0323] When heating is performed while exposure is being performed, although the heating temperature during exposure also depends on the transition temperature of the liquid crystal components contained in the light-absorbing anisotropic film to the liquid crystal phase, it is preferably 25 to 140°C.

[0324] Furthermore, exposure can also be performed in a nitrogen atmosphere. In the case of curing light-absorbing anisotropic films via free radical polymerization, the polymerization hindrance caused by oxygen can be reduced, therefore exposure in a nitrogen atmosphere is preferred.

[0325] There is no particular limitation on the thickness of the light-absorbing anisotropic film, but from the viewpoint of flexibility when using the laminate of the present invention described later in a polarizing element, it is preferably 100 to 8000 nm, more preferably 300 to 5000 nm.

[0326] [Layered Body]

[0327] The laminate of the present invention is a laminate used in an image display device having a substrate, an alignment film, and a light-absorbing anisotropic film in sequence.

[0328] The light absorption anisotropic film of the laminate of the present invention is the light absorption anisotropic film of the present invention described above. For the signal originating from the dichroic substance detected by TOF-SIMS, the relationship between the maximum intensity Imax in the thickness direction of the light absorption anisotropic film and the intensity Isur1 on the visual recognition side surface of the light absorption anisotropic film satisfies the following formula (I-1).

[0329] 2.0 ≤ Imax / Isur1……(I-1)

[0330] The layers constituting the laminate of the present invention will be described below.

[0331] [Substrate]

[0332] The substrate used in the laminate of the present invention can be appropriately selected according to the application of the anisotropic light absorption film; for example, glass and polymer films can be used. The light transmittance of the substrate is preferably 80% or more.

[0333] When using a polymer film as a substrate, an optically isotropic polymer film is preferred. Specific examples and preferred embodiments of the polymer are described in paragraph

[0013] of Japanese Patent Application Publication No. 2002-22942. Furthermore, polymers that are conventionally known to exhibit birefringence, such as polycarbonate or polysulfone, can also be used, but whose birefringence is reduced by modifying the molecules described in International Publication No. 2000 / 26705.

[0334] [Orientation film]

[0335] Regarding the alignment film of the laminate of the present invention, it can be any layer as long as the dichroic material contained in the liquid crystal composition can be aligned to the desired state on the alignment film.

[0336] Methods for forming alignment films include, for example, rubbing treatment of the film surface of an organic compound (preferably a polymer), tilting evaporation of an inorganic compound, formation of a layer with microgrooves, and accumulation of organic compounds (e.g., ω-trisanoic acid, dioctadecylmethylammonium chloride, methyl stearate, etc.) based on the Langmuir-Blodgett process (LB film). Furthermore, alignment films that generate alignment functions by applying an electric field, a magnetic field, or irradiating with light are also known.

[0337] In this invention, from the viewpoint of ease of control of the pretilt angle of the alignment film, an alignment film formed by friction treatment is preferred, and from the viewpoint of alignment uniformity, a photo-alignment film formed by light irradiation is even more preferred.

[0338] <Friction-treated Orientation Film>

[0339] Polymer materials used for alignment films formed by friction processing are described in numerous documents, and many commercially available products are readily available. In this invention, polyvinyl alcohol or polyimide and its derivatives are preferably used. Regarding the alignment film, refer to the description on page 43, line 24 to page 49, line 8 of International Publication No. 2001 / 88574A1. The thickness of the alignment film is preferably 0.01 to 10 μm, more preferably 0.01 to 2 μm.

[0340] <Optical alignment film>

[0341] Photoalignment compounds used in alignment films formed by light irradiation are described in numerous documents. In this invention, preferred examples include, for instance, the azo compounds described in Japanese Patent Application Publication Nos. 2006-285197, 2007-76839, 2007-138138, 2007-94071, 2007-121721, 2007-140465, 2007-156439, 2007-133184, 2009-109831, Japanese Patent No. 3883848, and Japanese Patent No. 4151746. Compounds; aromatic ester compounds disclosed in Japanese Patent Application Publication No. 2002-229039; maleimides and / or alkenyl-substituted naphthalene diimides having photo-orientation units disclosed in Japanese Patent Application Publication No. 2002-265541 and Japanese Patent Application Publication No. 2002-317013; photocrosslinkable silane derivatives disclosed in Japanese Patent No. 4205195 and Japanese Patent No. 4205198; and photocrosslinkable polyimides, polyamides, or esters disclosed in Japanese Patent Publication No. 2003-520878, Japanese Patent Publication No. 2004-529220, or Japanese Patent No. 4162850. More preferably, azo compounds, photocrosslinkable polyimides, polyamides, or esters.

[0342] Among these, as a photooriented compound, a photosensitive compound having a photoreactive group that produces at least one of dimerization and isomerization through the action of light is preferred.

[0343] Furthermore, examples of photoreactive groups include groups having a cinnamic acid (cinnamoyl) structure (skeleton), a coumarin structure (skeleton), a chalcone structure (skeleton), a benzophenone structure (skeleton), and an anthracene structure (skeleton). Among these groups, groups having a cinnamoyl structure and groups having a coumarin structure are preferred, and groups having a cinnamoyl structure are more preferred.

[0344] Furthermore, photosensitive compounds having the aforementioned photo-orientation groups may also have cross-linking groups.

[0345] As the aforementioned crosslinking group, the preferred crosslinking groups are thermal crosslinking groups that cause curing reactions through the action of heat and photocrosslinking groups that cause curing reactions through the action of light. Alternatively, the crosslinking group may possess both thermal and photocrosslinking groups.

[0346] Examples of crosslinking groups include at least one group selected from the group consisting of epoxy groups, oxetyl groups, -NH-CH2-OR groups (where R represents an alkyl group with 1 to 20 carbon atoms), groups having olefinic unsaturated double bonds, and terminal isocyanate groups. Among these, epoxy groups, oxetyl groups, and groups having olefinic unsaturated double bonds are preferred.

[0347] In addition, the cyclic ether group of a 3-membered ring is also called an epoxy group, and the cyclic ether group of a 4-membered ring is also called an oxobutyl group.

[0348] Furthermore, as a group having an olefinic unsaturated double bond, examples include vinyl, allyl, styryl, acryloyl, and methacryloyl, with acryloyl or methacryloyl being preferred.

[0349] A photo-alignment film is manufactured by irradiating a photo-alignment film formed from the above materials with linearly polarized light or unpolarized light.

[0350] In this specification, "linearly polarized light irradiation" and "unpolarized light irradiation" are operations used to induce a photoreaction in a photoalignment material. The wavelength of the light used varies depending on the photoalignment material used, and is not particularly limited as long as it is the wavelength required for the photoreaction. The peak wavelength of the light used in the irradiation is preferably 200 nm to 700 nm, and more preferably ultraviolet light with a peak wavelength of 400 nm or less.

[0351] The light sources used in illumination can be categorized into commonly used light sources, such as tungsten lamps, halogen lamps, xenon lamps, xenon flash lamps, mercury lamps, mercury-xenon lamps, and carbon arc lamps, various lasers [e.g., semiconductor lasers, helium-neon lasers, argon-ion lasers, helium-cadmium lasers, and YAG (yttrium aluminum garnet) lasers], light-emitting diodes, and cathode ray tubes.

[0352] As a method for obtaining linearly polarized light, one can use methods such as using polarizers (e.g., iodine polarizers, dichroic pigment polarizers, and metal wire grid polarizers), using prism elements (e.g., Glan-Thomson prisms), or using reflective polarizers utilizing Brewster's angle, or using light emitted from a laser source with polarized light. Furthermore, filters or wavelength conversion elements can be used to selectively illuminate only the desired wavelength of light.

[0353] When the irradiated light is linearly polarized, a method is employed where light is irradiated onto the alignment film from its upper or back surface in a direction perpendicular or oblique to the surface of the alignment film. The incident angle of the light varies depending on the photoalignment material, but is preferably 0–90° (perpendicular), and more preferably 40–90°.

[0354] In the case of unpolarized light, the alignment film is irradiated with unpolarized light from an oblique direction. The incident angle is preferably 10 to 80°, more preferably 20 to 60°, and even more preferably 30 to 50°.

[0355] The irradiation time is preferably 1 minute to 60 minutes, more preferably 1 minute to 10 minutes.

[0356] When patterning is required, one can use a method that applies light through a photomask to the pattern as many times as needed, or write the pattern by laser scanning.

[0357] [Anisotropic light absorption film]

[0358] Regarding the light-absorbing anisotropic film of the laminate of the present invention, as described above, its description is omitted.

[0359] [Optical anisotropic films]

[0360] The laminate of the present invention preferably has an optically anisotropic film.

[0361] Here, an optical anisotropic film refers to a thin film that generates a phase difference. Examples include stretched polymer films and phase difference films in which an optical anisotropic layer of an oriented liquid crystal compound is disposed on a support.

[0362] Here, there are no particular restrictions on the orientation of the liquid crystal compound contained in the optical anisotropic layer; examples include horizontal, vertical, and twisted orientations relative to the film surface.

[0363] Furthermore, specific functions of optical anisotropic films include, for example, λ / 4 plates and λ / 2 plates.

[0364] Furthermore, the optical anisotropic layer can be composed of multiple layers. For example, regarding an optical anisotropic layer composed of multiple optical anisotropic layers, one can refer to paragraphs

[0008] to

[0053] of Japanese Patent Application Publication No. 2014-209219.

[0365] Furthermore, this optical anisotropic film can be disposed in contact with the aforementioned light-absorbing anisotropic film, or other layers can be disposed between them. Examples of such layers include adhesive layers or bonding layers used to ensure a tight seal.

[0366] The laminate of the present invention preferably uses a λ / 4 plate as the above-mentioned optical anisotropic film, and more preferably has a λ / 4 plate on the light absorption anisotropic film.

[0367] Here, the so-called "λ / 4 plate" is a plate with λ / 4 function, specifically, a plate with the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).

[0368] For example, as a single-layer structure, the λ / 4 plate can be a stretched polymer film or a phase difference film with an optical anisotropy layer having λ / 4 function on a support. As a multi-layer structure, the λ / 4 plate can be a broadband λ / 4 plate formed by stacking λ / 4 plates and λ / 2 plates.

[0369] [Blocking layer]

[0370] The laminate of the present invention may have a blocking layer on a light-absorbing anisotropic film (in the case of having the above-described λ / 4 plate).

[0371] Here, the barrier layer is also referred to as the gas barrier layer (oxygen barrier layer), which has the function of protecting the polarization element of the present invention from the influence of gases such as oxygen in the atmosphere, moisture, or compounds contained in adjacent layers.

[0372] Regarding the barrier layer, for example, reference can be made to paragraphs

[0014] to

[0054] of Japanese Patent Application Publication No. 2014-159124, paragraphs

[0042] to

[0075] of Japanese Patent Application Publication No. 2017-121721, paragraphs

[0045] to

[0054] of Japanese Patent Application Publication No. 2017-115076, paragraphs

[0010] to

[0061] of Japanese Patent Application Publication No. 2012-213938, and paragraphs

[0021] to

[0031] of Japanese Patent Application Publication No. 2005-169994.

[0373] [Adhesive layer]

[0374] From the viewpoint of adhering to the aforementioned λ / 4 plate, the laminate of the present invention can have an adhesive layer on the surface adhering to the λ / 4 plate.

[0375] 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.

[0376] Among these, acrylic adhesives (pressure-sensitive adhesives) are preferred from the perspectives of transparency, weather resistance, and heat resistance.

[0377] The adhesive layer can be formed, for example, by methods such as: 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.

[0378] The adhesive solution is prepared, for example, as a solution of about 10 to 40% by mass by dissolving or dispersing the adhesive in a solvent such as toluene or ethyl acetate.

[0379] Coating methods can include reverse coating, gravure coating, roller coating, spin coating, screen coating, spray coating, dip coating, and spray coating.

[0380] 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; nonwoven fabric; wire mesh; foam sheets; metal foil, etc.

[0381] In this invention, the thickness of any adhesive layer is not particularly limited, but it is preferably 3μm to 50μm, more preferably 4μm to 40μm, and even more preferably 5μm to 30μm.

[0382] 〔use〕

[0383] The laminate of the present invention can be used as a polarizing element (polarizer), specifically, for example, as a linear polarizer or a circular polarizer.

[0384] In the absence of an optically anisotropic layer such as the λ / 4 plate described above, the laminate of the present invention can be used as a linear polarizer.

[0385] On the other hand, when the laminate of the present invention has the above-mentioned λ / 4 plate, the laminate can be used as a circular polarizer.

[0386] [Image display device]

[0387] The image display device of the present invention has the light absorption anisotropic film or laminate of the present invention as described above.

[0388] There is no particular limitation on the display element used in the image display device of the present invention. Examples include liquid crystal cells, organic electroluminescent (hereinafter referred to as "EL") display panels, and plasma display panels.

[0389] Among these, liquid crystal cells or organic EL display panels are preferred, and liquid crystal cells are more preferred. That is, as the image display device of the present invention, a liquid crystal display device that uses a liquid crystal cell as a display element, an organic EL display device that uses an organic EL display panel as a display element, and a liquid crystal display device are more preferred.

[0390] [Field of view control layer]

[0391] The image display device of the present invention may have a field of view control layer.

[0392] Here, the field-of-view control layer is a layer used to prevent peeping at the display device or to control the transmittance when viewing the image display device from the front and tilt directions. Examples include light-control films manufactured by 3M Company or laminates utilizing anisotropic light-absorbing layers having an absorption axis in the thickness direction. Regarding laminates utilizing anisotropic light-absorbing layers having an absorption axis in the thickness direction, for example, reference can be made to paragraphs

[0006] to

[0043] of International Publication No. 2018 / 079854.

[0393] Furthermore, as an example of the image display device of the present invention, an organic EL display device may preferably be provided, for example, in a manner in which the above-mentioned field of view control layer, the above-mentioned light absorption anisotropic film, the above-mentioned arbitrary optical anisotropic film, and organic EL display panel are sequentially arranged from the visual recognition side.

[0394] [Surface protective materials]

[0395] The image display device of the present invention preferably has a surface protective material on the side closest to visual recognition.

[0396] Here, there are no particular limitations on the materials constituting the surface protective material; it can be either inorganic or organic. Examples of inorganic materials include glass substrates. Examples of organic materials include supports made of polymer films such as polyimide or cellulose acylates. The surface of each surface protective material may include one or more layers selected from surface-cured layers (hard coatings) or low-reflection layers that suppress surface reflections generated at air interfaces.

[0397] There is no particular limitation on the thickness of the surface protective material, but from the viewpoint of thinness, it is preferably 800 μm or less, more preferably 100 μm or less. There is no particular limitation on the lower limit, but it is preferably 0.1 μm or more.

[0398] For example, a glass substrate with a thickness of less than 100 μm that can be bent is preferred as it can give full play to the flexibility of organic EL display devices.

[0399] Furthermore, regarding glass substrates with a thickness of 100 μm or less, from the viewpoint of impact resistance, as a protective film, it is preferable to adhere a resin film of polyester resins such as (meth)acrylic acid resins, polyethylene terephthalate (PET), cellulose resins such as triacetyl cellulose (TAC), or cyclic olefin resins such as norbornene resins to the glass substrate using an adhesive or the like. In particular, from the viewpoint of flexibility, it is preferable to adhere polyethylene terephthalate (PET), and further from the viewpoint of visual legibility, it is preferable to adhere polyethylene terephthalate (PET) having a Re value of 3000 nm or more and 10000 nm or less.

[0400] [Liquid Crystal Display Device]

[0401] As an example of the display device of the present invention, the liquid crystal display device is a liquid crystal display device having the above-described laminate (excluding the λ / 4 plate) and liquid crystal cells of the present invention.

[0402] Furthermore, in this invention, among the stacked bodies disposed on both sides of the liquid crystal cell, it is preferable to use the stacked body of this invention as a front polarizing element, and more preferably, to use the stacked body of this invention as both front and rear polarizing elements.

[0403] The liquid crystal unit that constitutes a liquid crystal display device will be described in detail below.

[0404] <Liquid Crystal Unit>

[0405] The liquid crystal cells used in the liquid crystal display device are preferably in VA (Vertical Alignment) mode, OCB (Optically Compensated Bend) mode, IPS (In-Plane-Switching) mode, or TN (Twisted Nematic) mode, but are not limited to these.

[0406] In TN mode liquid crystal cells, bar-shaped liquid crystal molecules (bar-shaped liquid crystal compounds) are substantially horizontally aligned when no voltage is applied, and then twisted at 60–120°. TN mode liquid crystal cells are the most widely used as color TFT liquid crystal display devices and are described in numerous documents.

[0407] In a VA mode liquid crystal cell, the rod-shaped liquid crystal molecules are substantially vertically oriented when no voltage is applied. In VA mode liquid crystal cells, besides (1) the narrow definition of VA mode liquid crystal cells in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied and substantially horizontally aligned when a voltage is applied (described in Japanese Patent Application Publication No. 2-176625), there are also (2) liquid crystal cells in which the VA mode is multi-domained to expand the field of view (MVA mode (Multi-domain Vertical Alignment)) (described in SID97, Digest of Tech. Papers (Draft Collection) 28 (1997) 845), (3) liquid crystal cells in which rod-shaped liquid crystal molecules are substantially vertically aligned when no voltage is applied and twisted multi-domain alignment when a voltage is applied (n-ASM (Axially Symmetric Aligned Microcell) mode) (described in the Japanese Liquid Crystal Conference Draft Collection 58-59 (1998)), and (4) SURVIVAL mode liquid crystal cells (in LCD (liquid crystal)). (Display: Liquid Crystal Display) International Publication No. 98. Furthermore, it can be any of PVA (Patterned Vertical Alignment), Optical Alignment, or PSA (Polymer-Sustained Alignment). Detailed information regarding these modes is available in Japanese Patent Application Publication Nos. 2006-215326 and 2008-538819.

[0408] In IPS-mode liquid crystal cells, rod-shaped liquid crystal molecules are substantially parallel to the substrate. By applying an electric field parallel to the substrate surface, the liquid crystal molecules exhibit planar response. In IPS mode, the display becomes black when no electric field is applied, and the absorption axes of the upper and lower polarizers are orthogonal. Methods for improving the field of view by using optical compensation sheets to reduce light leakage during black display in the tilt direction are disclosed in Japanese Patent Application Publications Nos. 10-54982, 11-202323, 9-292522, 11-133408, 11-305217, and 10-307291.

[0409] [Organic EL display device]

[0410] As an example of the image display device of the present invention, an organic EL display device may be provided, for example, in which the above-described laminate (excluding the adhesive layer and the λ / 4 plate) and the organic EL display panel are sequentially arranged from the visual recognition side. In this case, in the laminate, a transparent support, an alignment film provided as needed, a light-absorbing anisotropic film, a transparent resin layer, an adhesive layer, and a λ / 4 plate are sequentially arranged from the visual recognition side.

[0411] Furthermore, the organic EL display panel is a display panel constructed using organic EL elements formed by sandwiching an organic light-emitting layer (organic electroluminescent layer) between electrodes (between the cathode and the anode). There are no particular limitations on the structure of the organic EL display panel; known structures can be used.

[0412] Example

[0413] The present invention will now be described in more detail with reference to embodiments. The materials, amounts, proportions, processing contents, and processing steps shown in the following embodiments can be appropriately modified without departing from the spirit of the invention. Therefore, the scope of the present invention should not be interpreted as limited by the embodiments shown below.

[0414] [Example 1]

[0415] [Fabrication of the transparent support]

[0416] <Preparation of Core Cellulose Acid Compound Concentrate>

[0417] The following composition is 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.

[0418]

[0419]

[0420] Compound F

[0421] [Chemical Formula 21]

[0422]

[0423] <Preparation of concentrated outer cellulose acylate>

[0424] A cellulose acetate solution for use as an outer layer cellulose acylate concentration was prepared by adding 10 parts by mass of the following matting agent solution to 90 parts by mass of the above core layer cellulose acylate concentrate.

[0425]

[0426] <Preparation of Cellulose Acid Film 1>

[0427] 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).

[0428] Next, the film was peeled off with a solvent content of approximately 20% by mass, and the two ends of the film in the width direction were fixed with a tenter frame clamp. The film was then dried while being stretched laterally at a stretch ratio of 1.1.

[0429] The film is then further dried by conveying it between rollers in a heat treatment apparatus, thereby producing an optical film (transparent support) with a thickness of 40 μm, which is used as cellulose acylated film 1. The resulting cellulose acylated film 1 has an in-plane retardation of 0 nm.

[0430] [Formation of photoalignment film PA1]

[0431] The photo-alignment film forming coating solution PA1 (described later) was continuously coated onto the cellulose acylated film 1 using a winding bar. The support with the coating was dried with warm air at 140°C for 120 seconds, followed by polarized ultraviolet irradiation (10 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a photo-aligned film PA1 was formed, resulting in a TAC (triacetyl cellulose) film with a photo-aligned film. The thickness of the photo-aligned film PA1 was 0.5 μm.

[0432]

[0433] Polymer PA-1

[0434] [Chemical Formula 22]

[0435]

[0436] Acid-producing agent PAG-1

[0437] [Chemical Formula 23]

[0438]

[0439] stabilizer DIPEA

[0440] [Chemical Formula 24]

[0441]

[0442] [Fabrication of the light-absorbing anisotropic film P1]

[0443] A coating layer P1 is formed by continuously coating the obtained photo-aligned film PA1 with a light-absorbing anisotropic film forming composition P1, which consists of the following composition, using a winding bar.

[0444] Next, the coating layer P1 was heated at 140°C for 15 seconds and then cooled to room temperature (23°C).

[0445] Next, heat at the heating temperature described in Table 1 below for 60 seconds, and then cool to room temperature again.

[0446] Then, using an LED light (center wavelength 365nm) at an illuminance of 200mW / cm² 2 Irradiation was performed for 2 seconds under the specified irradiation conditions, thereby fabricating an anisotropic light-absorbing film P1 on the light-aligned film PA1. The thickness of the anisotropic light-absorbing film P1 is 0.5 μm.

[0447]

[0448]

[0449] Dichroic substance C-1 (maximum absorption wavelength: 570nm)

[0450] [Chemical Formula 25]

[0451]

[0452] Dichroic substance M-1 (maximum absorption wavelength: 466nm)

[0453] [Chemical Formula 26]

[0454]

[0455] Dichroic substance Y-1 (maximum absorption wavelength: 417nm)

[0456] [Chemical Formula 27]

[0457]

[0458] Liquid crystal compound L-1

[0459] [Chemical Formula 28]

[0460]

[0461] Surfactant F-1

[0462] [Chemical Formula 29]

[0463]

[0464] [Formation of oxygen barrier layer B1]

[0465] A coating solution B1 with the following composition was continuously coated onto the light-absorbing anisotropic film P1 using a winding rod. Then, by drying with warm air at 80°C for 5 minutes, a laminate A was obtained, which has an oxygen barrier layer B1 composed of polyvinyl alcohol (PVA) with a thickness of 1.0 μm. That is, a laminate A having a cellulose acylated film 1 (transparent support), a light-aligning film PA1, a light-absorbing anisotropic film P1, and an oxygen barrier layer B1 sequentially adjacent to each other.

[0466]

[0467] Modified polyvinyl alcohol

[0468] [Chemical Formula 30]

[0469]

[0470] [Fabrication of TAC film A1 with positive plate A1]

[0471] The photo-alignment film forming coating solution PA2, with the following composition, was continuously coated onto the cellulose acylated film 1 using a winding bar. The support with the coating was dried with warm air at 140°C for 120 seconds, followed by polarized ultraviolet irradiation (10 mJ / cm²). 2 Using an ultra-high pressure mercury lamp, a photo-aligned film PA2 with a thickness of 0.2 μm was formed, thus obtaining a TAC thin film with a photo-aligned film.

[0472]

[0473]

[0474] Polymer PA-2

[0475] [Chemical Formula 31]

[0476]

[0477] Composition A-1, comprising the following components, was applied onto the photoalignment film PA2 using a bar coater. The coating formed on the photoalignment film PA2 was heated to 120°C using warm air, then cooled to 60°C, and then subjected to a high-pressure mercury lamp at a wavelength of 365 nm in 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 Ultraviolet light is 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.

[0478] The thickness of plate A1 is 2.5 μm, and the Re(550) is 144 nm. Furthermore, plate A1 satisfies the relationship Re(450) ≤ Re(550) ≤ Re(650). The Re(450) / Re(550) ratio is 0.82.

[0479]

[0480]

[0481] Polymerizable liquid crystal compound LA-1 (tBu represents tert-butyl)

[0482] [Chemical Formula 32]

[0483]

[0484] Polymerizable liquid crystal compound LA-2

[0485] [Chemical Formula 33]

[0486]

[0487] Polymerizable liquid crystal compound LA-3

[0488] [Chemical Formula 34]

[0489]

[0490] Polymerizable liquid crystal compound LA-4 (Me represents methyl)

[0491] [Chemical Formula 35]

[0492]

[0493] Polymerization initiator PI-1

[0494] [Chemical Formula 36]

[0495]

[0496] Leveling agent T-1

[0497] [Chemical Formula 37]

[0498]

[0499] [Fabrication of TAC film C1 with positive C plate C1]

[0500] The aforementioned cellulose acylated film 1 was used as a pseudo-support.

[0501] 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 and heated to 110°C, and then conveyed for 10 seconds under a steam-type far-infrared heater manufactured by Noritake Co., Ltd.

[0502] Next, using a bar coater, 3 ml / m of pure water was coated onto the film. 2 .

[0503] Next, after repeated water washing based on a spray coating machine and dehydration based on an air knife three times, the film is dried by conveying it in a drying zone at 70°C for 10 seconds, thereby producing an alkali-saponified cellulose acylated film 1.

[0504]

[0505] Using a #8 winding bar, the following oriented film forming coating solution PA3 was continuously coated onto the alkali-saponified cellulose acylated film 1. 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 PA3.

[0506]

[0507] The following coating solution C1, used for forming positive C-plates, is applied onto the alignment film PA3. The resulting coating is cured at 60°C for 60 seconds and then subjected to air treatment at 70 mW / cm². 2 Irradiation with a gas-cooled metal halide lamp (manufactured by EYE GRAPHICS Co., Ltd.) at 1000 mJ / cm 2 The orientation state of the liquid crystal compound is fixed by ultraviolet light, thereby making the liquid crystal compound vertically oriented, thus producing a TAC film C1 with a positive C plate C1 with a thickness of 0.5 μm.

[0508] The obtained Rth(550) of the positive C plate is -60nm.

[0509]

[0510]

[0511] Liquid crystal compound LC-1

[0512] [Chemical Formula 38]

[0513]

[0514] Liquid crystal compound LC-2

[0515] [Chemical Formula 39]

[0516]

[0517] Vertically aligned liquid crystalline compound S01

[0518] [Chemical Formula 40]

[0519]

[0520] Compound B03

[0521] [Chemical Formula 41]

[0522]

[0523] [Preparation of adhesives N1 and N2]

[0524] Next, an acrylate polymer was prepared according to the following steps.

[0525] In a reaction vessel equipped with a condenser, a nitrogen inlet tube, 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) having an average molecular weight of 2 million and a molecular weight distribution (Mw / Mn) of 3.0.

[0526] Next, the obtained acrylate polymer (A1) was used to prepare an acrylate adhesive with the following composition. These compositions were coated on a release film surface-treated with a silicone-based release agent using a die coater, dried for 1 minute in an environment of 90 °C, and irradiated with ultraviolet light (UV) under the following conditions to obtain the following acrylate adhesives N1 and N2 (adhesive layers). The composition and film thickness of the acrylate adhesive are shown below.

[0527] <UV irradiation conditions>[ <\

[0528] ·Electrodeless lamp H bulb of Fusion Co.

[0529] ·Illuminance 600 mW / cm 2 , light quantity 150 mJ / cm 2

[0530] ·The UV illuminance and light quantity were measured using "UVPF-36" manufactured by EYE GRAPHICS Co., Ltd.

[0531]

[0532] (A) Multifunctional acrylate monomer: Tris(acryloyloxyethyl)isocyanurate, molecular weight = 423, trifunctional (manufactured by TOAGOSEI CO., LTD., trade name "ARONIX M-315")

[0533] (B) Photopolymerization initiator: a 1:1 mass ratio mixture of benzophenone and 1-hydroxycyclohexylphenyl ketone, manufactured by CibaSpecialty Chemicals Co., Ltd. as "IRGACURE500".

[0534] (C) Isocyanate-based crosslinking agent: Trimethylolpropane-modified toluene diisocyanate ("CORONATE L" manufactured by Nippon Polyurethane Industry Co., Ltd.)

[0535] (D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd. as “KBM-403”)

[0536] [Preparation of UV adhesive]

[0537] A UV adhesive composition with the following composition was prepared.

[0538]

[0539] CPI-100P

[0540] [Chemical Formula 42]

[0541]

[0542] [Fabrication of Layer A-1]

[0543] Using the above UV adhesive composition, at 600mJ / cm 2 UV irradiation was used to bond the phase retardation side of the TAC film A1 having the aforementioned positive A plate A1 and the phase retardation side of the TAC film C1 having the aforementioned positive C plate C1. The thickness of the UV adhesive layer was 3 μm. In addition, the surfaces bonded with the UV adhesive were subjected to corona treatment. Next, the photoalignment film PA2 and the cellulose acylated film 1 on the positive A plate A1 side were removed, and this was used as the phase retardation plate 1. In addition, the layer structure of the phase retardation plate 1 is positive A plate A1, UV adhesive layer, positive C plate C1, photoalignment film PA3 and cellulose acylated film 1.

[0544] Using the adhesive N1 described above, the oxygen barrier layer side B1 of the laminate A was bonded to the support side of the low-reflectivity surface film CV-LC5 (manufactured by Fujifilm Corporation). Next, only the cellulose acylated film 1 included in the laminate A was removed, and the removed surface and the positive A-plate A1 side of the phase retardation plate 1 were bonded together using the adhesive N1. Then, the light alignment film PA3 and the cellulose acylated film 1 on the positive C-plate C1 side of the phase retardation plate 1 were removed, thereby fabricating the laminate A-1. At this time, the angle between the absorption axis of the light absorption anisotropic film P1 included in the laminate A and the slow axis of the positive A-plate A1 is 45°. Furthermore, the layer structure of the laminate A-1 is: low-reflectivity surface film CV-LC5, adhesive layer N1, oxygen barrier layer B1, light absorption anisotropic film P1, light alignment film PA1, adhesive layer N1, positive A-plate A1, UV adhesive layer, and positive C-plate C1.

[0545] A Samsung Co., Ltd.-manufactured Galaxy S5 equipped with an organic EL panel (organic EL display element) was disassembled. The touch panel with a circular polarizer was peeled off from the organic EL display device, and then the circular polarizer was peeled off from the touch panel, thus separating the organic EL display element, touch panel, and circular polarizer individually. Next, the separated touch panel was re-bonded to the organic EL display element, and then the laminate A-1 prepared above was bonded to the touch panel using the adhesive N2 in an airtight manner, thereby fabricating the organic EL display device.

[0546] [Examples 2-4 and Comparative Examples 2-3]

[0547] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P2 with the following composition, and the heating temperature was changed to the temperatures shown in Tables 1 and 2 below. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0548]

[0549]

[0550] Liquid crystal compound L-2

[0551] [Chemical Formula 43]

[0552]

[0553] [Example 5]

[0554] For the composition of the light absorption anisotropic film forming composition P2, a composition was used in which the composition was changed to replace surfactant F-1 with the following surfactant F-2. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 4.

[0555] (Surfactant F-2)

[0556] [Chemical Formula 44]

[0557]

[0558] [Example 6]

[0559] For the composition of the light absorption anisotropic film forming composition P2, a composition was used in which the composition was changed to replace surfactant F-1 with the following surfactant F-3. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 4.

[0560] (Surfactant F-3)

[0561] [Chemical Formula 45]

[0562]

[0563] [Example 7]

[0564] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P3 with the following composition, and the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0565]

[0566]

[0567] Liquid crystal compound L-4 (in the following formulas, the numerical values ​​represent the mass ratio)

[0568] [Chemical Formula 46]

[0569]

[0570] [Example 8]

[0571] The thickness of the light-absorbing anisotropic film P1 was changed to 1.2 μm (Example 8). Otherwise, the laminate and organic EL display device were fabricated using the same method as in Example 7.

[0572] [Example 9]

[0573] The thickness of the light-absorbing anisotropic film P1 was changed to 0.8 μm (Example 9). Otherwise, the laminate and organic EL display device were fabricated using the same method as in Example 7.

[0574] [Example 10]

[0575] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P4 with the following composition, and the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0576]

[0577]

[0578] [Example 11]

[0579] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P5 with the following composition, and the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0580]

[0581]

[0582] [Example 12]

[0583] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P6 with the following composition, and the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0584]

[0585] [Example 13]

[0586] Replace the composition of oxygen barrier layer B1 with the composition of oxygen barrier layer B2 described below, and change the process to: after drying the oxygen barrier layer, use an LED lamp (center wavelength 365nm) at an illuminance of 200mW / cm². 2 Irradiated for 2 seconds under the same irradiation conditions as in Example 12, otherwise, a laminate and an organic EL display device were fabricated using the same method.

[0587]

[0588]

[0589] Surfactant F-5

[0590] [Chemical Formula 47]

[0591]

[0592] [Example 14]

[0593] In the composition of oxygen barrier layer B2, ACRIT 8KX-078 was changed to ACRIT 8KX-212. Otherwise, the laminate and organic EL display device were fabricated using the same method as in Example 13.

[0594] [Example 15]

[0595] The acrylic adhesive N1 was replaced with the acrylic adhesive N3 described below. Furthermore, in the fabrication of laminate A-1, the low-reflection surface film CV-LC5 (manufactured by FUJIFILM Corporation) was replaced with alkali-free glass EAGLEX G1.1 mm thick (manufactured by Coming Incorporated). Using the aforementioned adhesive N3, the oxygen barrier layer B1 side of laminate A was bonded without air bubbles. At this time, the adhesive N3 was pre-placed in a low-humidity environment (25°C, 10% RH) for 24 hours to dehydrate before bonding. The moisture content of the dehydrated adhesive N3 was 0.2% (Karl Fischer process).

[0596] In addition to the above, a laminate and an organic EL display device were fabricated using the same method as in Example 7.

[0597]

[0598]

[0599] [Example 16]

[0600] In the fabrication of laminate A-1, the oxygen barrier layer B1 side of laminate A was bonded to a commercially available cyclic olefin film (ZEONOR ZB12, 50 μm thick, manufactured by Zeon Corporation) using adhesive N1. Then, the cyclic olefin film side of the laminate was bonded to alkali-free glass EAGLEX G1.1 mm thick (manufactured by Corning Incorporated) using adhesive N3 to prevent air bubbles from entering. At this time, the low-humidity environment of adhesive N3 was not applied. The moisture content of adhesive N3 was 1.1% (Karl Fischer process).

[0601] In addition to the above, a laminate and an organic EL display device were fabricated using the same method as in Example 15.

[0602] [Example 17]

[0603] In the fabrication of laminate A-1, the cyclic olefin film was replaced with a commercially available polyethylene terephthalate film (Cosmo Shine SRF, 80 μm thick). Otherwise, the laminate and organic EL display device were fabricated using the same method as in Example 16.

[0604] [Example 18]

[0605] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P7 with the following composition. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 7.

[0606]

[0607]

[0608] Sealing Modifier A-1

[0609] [Chemical Formula 48]

[0610]

[0611] [Example 19]

[0612] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P8 with the following composition. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 7.

[0613]

[0614]

[0615] Surfactant F-6

[0616] [Chemical Formula 49]

[0617]

[0618] [Example 20]

[0619] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P9 with the following composition. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 7.

[0620]

[0621] Surfactant F-7

[0622] [Chemical Formula 50]

[0623]

[0624] [Example 21]

[0625] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P10 with the following composition. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 7.

[0626]

[0627] Surfactant F-8

[0628] [Chemical Formula 51]

[0629]

[0630] [Example 22]

[0631] <Preparation of Cellulose Acid Film 2>

[0632] The following composition was added to a mixing vessel, stirred, and then heated at 90°C for 10 minutes. The resulting composition was then filtered through filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm to prepare a concentrate. The concentrate had a solids content of 23.5% by mass, the amount of plasticizer added was relative to the cellulose acylate, and the solvent for the concentrate was dichloromethane / methanol / butanol = 81 / 18 / 1 (mass ratio).

[0633]

[0634] Glycolipid compound 1

[0635] [Chemical Formula 52]

[0636]

[0637] Glycolipid compound 2

[0638] [Chemical Formula 53]

[0639]

[0640] The concentrated liquid prepared above was cast using a roller film casting machine. The concentrated liquid was cast from a mold in contact with a metal support cooled to 0°C, and then the resulting sheet (film) was peeled off. The roller was made of SUS steel.

[0641] After the film is peeled off from the roller, it is dried for 20 minutes in a tenter frame at 30–40°C using clamps that hold both ends of the film. Subsequently, the film is further dried by zone heating while being conveyed by rollers. The resulting film is then knurled and rolled up.

[0642] The obtained cellulose acylated film 2 has a thickness of 40 μm, an in-plane retardation Re(550) of 1 nm at a wavelength of 550 nm, and a thickness direction retardation Rth(550) of 26 nm at a wavelength of 550 nm.

[0643] The prepared cellulose acylated film 2 was continuously subjected to friction treatment. At this time, the length direction of the elongated film was parallel to the conveying direction, and the angle between the film's length direction (conveying direction) and the rotation axis of the friction roller was set to 80°. If the film's length direction (conveying direction) is set to 90°, and viewed from the film side with the film width direction as a reference (0°) and clockwise as the reference, the rotation axis of the friction roller is at 10°. In other words, the position of the friction roller's rotation axis is based on the film's length direction and rotated 80° counterclockwise.

[0644] Using the cellulose acylated film 2 that has undergone the above-mentioned friction treatment as a substrate, a composition Q1 for forming an optical anisotropic layer, comprising a liquid crystal compound with the following composition, is coated using a die coater, thereby forming a composition layer.

[0645] Next, the resulting composition layer was heated at 80°C for 60 seconds. This heating caused the liquid crystal compound in the composition layer to align in a predetermined direction.

[0646] Then, the composite layer was irradiated with ultraviolet light (irradiation dose: 35 mJ / cm²) at 30°C in oxygen-containing air (oxygen concentration: approximately 20% by volume) using a 365 nm LED lamp (manufactured by AcroEdge Corporation). 2 ).

[0647] Next, the resulting composition layer was heated at 80°C for 10 seconds.

[0648] Then, nitrogen purging was performed, the oxygen concentration was set to 100 ppm by volume, and the composite layer was irradiated with ultraviolet light (irradiation dose: 500 mJ / cm²) at 80°C using a metal halide lamp (manufactured by EYEGRAPHICS Co., Ltd.). 2 This process forms an optically anisotropic layer that fixes the orientation state of the liquid crystal compound. Thus, an optical film A with an optically anisotropic layer formed on a cellulose acylate film 2 was fabricated.

[0649] Furthermore, the left-handed twisted chiral reagent (CL1) in the optical anisotropic layer forming composition Q1 has a molar absorptivity of 40 L / (mol·cm) at 365 nm, even when irradiated with 365 nm light (35 mJ / cm). 2 The helical torsional force (HTP) of the chiral reagent did not change compared to before irradiation. Furthermore, the HTP was determined using the method described in paragraph

[0064] of Japanese Patent Application Publication No. 2013-129819.

[0650] The molar absorptivity of the right-hand twisted chiral reagent (CR1) at 365 nm is 38,450 L / (mol·cm). If it is irradiated with light at 365 nm (35 mJ / cm²),... 2 The HTP of the chiral reagent decreased by 35 μm compared to before irradiation. -1 .

[0651] In the photopolymerization initiator (Irgacure819), the absorption at 365 nm is relatively small (molar absorptivity 860 L / (mol·cm)), and the molar absorptivity at the absorption peak wavelength of 290 nm is 7,700 L / (mol·cm).

[0652]

[0653]

[0654] Liquid crystal compound LQ-1 (in the following formulas, the numerical values ​​represent the mass ratio)

[0655] [Chemical Formula 54]

[0656]

[0657] Liquid crystal compound LQ-2

[0658] [Chemical Formula 55]

[0659]

[0660] Polymer compound (A)

[0661] [Chemical Formula 56]

[0662]

[0663] Left-handed tortuous chiral reagent (CL1)

[0664] [Chemical Formula 57]

[0665]

[0666] Right-handed tortuous chiral reagent (CR1)

[0667] [Chemical Formula 58]

[0668]

[0669] Polymer (A) (where the value recorded for each repeating unit represents the content (mass%) of each repeating unit relative to all repeating units.)

[0670] [Chemical Formula 59]

[0671]

[0672] Polymer (B) (where the value recorded for each repeating unit represents the content (mass%) of each repeating unit relative to all repeating units.)

[0673] [Chemical Formula 60]

[0674]

[0675] The optical film A fabricated above was cut parallel to the rubbing direction, and the optical anisotropic layer was observed in cross-section under a polarizing microscope. The thickness of the optical anisotropic layer is 2.7 μm. The region (second region) with a thickness (d2) of 1.3 μm on the substrate side of the optical anisotropic layer has a uniform orientation without twist angle, while the liquid crystal compound in the region (first region) with a thickness (d1) of 1.4 μm on the air side (opposite to the substrate) of the optical anisotropic layer has a twisted orientation.

[0676] Furthermore, the optical properties of optical film A were determined using Axometrics' Axoscan and Axometrics' Multi-Layer Analysis software. The product of Δn2 and thickness d2 (Δn2d2) at a wavelength of 550 nm in the second region is 173 nm. The twist angle of the liquid crystal compound is 0°. The orientation axis angle of the liquid crystal compound relative to the strip length direction is -10° on the side in contact with the substrate and -10° on the side in contact with the first region.

[0677] Furthermore, the product of Δn1 and thickness d1 at a wavelength of 550nm in the first region (Δn1d1) is 184nm, the twist angle of the liquid crystal compound is 75°, and the orientation axis angle of the liquid crystal compound relative to the strip length direction is -10° on the side in contact with the second region and -85° on the air side.

[0678] In addition, regarding the orientation axis angle of the liquid crystal compound contained in the optical anisotropic layer, with the width direction of the substrate as the reference, i.e., 0°, when observing the substrate from the surface side of the optical anisotropic layer, clockwise (right turn) is represented as negative and counterclockwise (left turn) is represented as positive.

[0679] Furthermore, regarding the twist angle of the liquid crystal compound, when observing the substrate from the surface side of the optical anisotropic layer, with the orientation axis direction of the liquid crystal compound on the surface side (near the front side) as a reference, the orientation axis direction of the liquid crystal compound on the substrate side (inner side) is indicated as negative when it is clockwise (right turn) and positive when it is counterclockwise (left turn).

[0680] (Fabrication of a circular polarizer)

[0681] Using adhesive N1, a substrate surface included in the optical film A prepared above and the surface of the aforementioned laminate A (with the cellulose acylated film 1 removed), prepared in the same manner as in Example 20, are bonded together to form a laminate A-2. That is, the laminate A-2 sequentially comprises a low-reflection surface film, an adhesive layer, an oxygen barrier layer, a light-absorbing anisotropic film, a light-aligning film, an adhesive layer, a cellulose acylated film, and an optical anisotropic layer.

[0682] In addition, the absorption axis of the light-absorbing anisotropic film is aligned with the length direction of the laminate A-2. The in-plane slow axis of the second region of the optical anisotropic layer rotates at an angle of 10° relative to the absorption axis of the light-absorbing anisotropic film. The in-plane slow axis of the surface on the side opposite to the second region of the first region of the optical anisotropic layer rotates at an angle of 85° relative to the absorption axis of the light-absorbing anisotropic film.

[0683] The laminate A-2 prepared above was replaced with laminate A-1. Otherwise, an organic EL display device was prepared using the same method as in Example 1.

[0684] [Example 23]

[0685] The cellulose acylated film 2, prepared in the same manner as in Example 22, was passed through a dielectric heating roller at a temperature of 60°C and subjected to alkaline saponification treatment in the same manner as in Example 1.

[0686] (Formation of the orientation film)

[0687] On the surface of the cellulose acylated film 2 that has undergone alkali saponification treatment, a coating solution for forming an orientation film with the following composition was continuously applied using a #14 winding bar. It was dried in warm air at 60°C for 60 seconds, and then dried in warm air at 100°C for 120 seconds.

[0688]

[0689]

[0690] Polyvinyl alcohol

[0691] [Chemical Formula 61]

[0692]

[0693] (Formation of an anisotropic optical layer)

[0694] The alignment film prepared above was continuously subjected to friction treatment. At this time, the length direction of the elongated film was parallel to the conveying direction, and the angle between the length direction of the film (conveying direction) and the rotation axis of the friction roller was set to 76°. If the length direction of the film (conveying direction) is set to 90°, and viewed from the film side with the film width direction as the reference (0°) and clockwise as the reference, the rotation axis of the friction roller is at 14°. In other words, the position of the rotation axis of the friction roller is 76° counterclockwise from the length direction of the film.

[0695] On the alignment film that has undergone the above-described friction treatment, an optically anisotropic layer coating liquid (1a) containing a disk-shaped liquid crystal compound with the following composition is coated using a die coater, thereby forming a composite layer. Then, the resulting composite layer is heated at 110°C under warm air for 2 minutes to dry the solvent and ripen the alignment of the disk-shaped liquid crystal compound. Next, the resulting composite layer is subjected to UV irradiation at 80°C (500 mJ / cm²). 2 This process is used to fix the orientation of the liquid crystal compound, thereby forming an optically anisotropic layer (1a).

[0696] The thickness of the optical anisotropic layer (1a) is 1.1 μm. Furthermore, the retardation at 550 nm is 168 nm. The average tilt angle of the disk surface of the disk-shaped liquid crystal compound relative to the film surface is 90°, confirming its perpendicular orientation relative to the film surface. Moreover, if the slow axis angle of the optical anisotropic layer (1a) is parallel to the rotation axis of the friction roller, and the width direction of the film is set to 0° (the length direction is set to 90° counterclockwise and -90° clockwise), then when viewed from the optical anisotropic layer (1a) side, the slow axis is 14°.

[0697]

[0698] Disk-shaped liquid crystal compound LQ-3

[0699] [Chemical Formula 62]

[0700]

[0701] Disk-shaped liquid crystal compound LQ-4

[0702] [Chemical Formula 63]

[0703]

[0704] Orientation agent 1 for orientation film surface

[0705] [Chemical Formula 64]

[0706]

[0707] Fluorine-containing compound A (where 'a' and 'b' in each repeating unit represent the content (mass%) of each repeating unit relative to all repeating units, with 'a' representing 90% by mass and 'b' representing 10% by mass).

[0708] [Chemical Formula 65]

[0709]

[0710] Fluorine compound B (the values ​​in each repeating unit represent the content (mass%) relative to all repeating units; the content of the repeating unit on the left is 32.5% by mass, and the content of the repeating unit on the right is 67.5% by mass).

[0711] [Chemical Formula 66]

[0712]

[0713] Fluorine compound C (the values ​​in each repeating unit represent the content (mass%) relative to all repeating units; the content of the repeating unit on the left is 25% by mass, the content of the repeating unit in the middle is 25% by mass, and the content of the repeating unit on the right is 50% by mass).

[0714] [Chemical Formula 67]

[0715]

[0716] On the cellulose acylated film 2 prepared above, an optically anisotropic layer coating liquid (1c) containing a rod-shaped liquid crystal compound with the following composition was coated using a die coater, thereby forming a composition layer. Then, holding both ends of the film, a cooling plate (9°C) was placed at a distance of 5 mm from the film on the side where the coating was formed, and a heater (75°C) was placed at a distance of 5 mm from the film on the side of the film opposite to the side where the coating was formed, and the film was dried for 2 minutes.

[0717] Next, the mixture was heated to 60°C with warm air for 1 minute, while nitrogen purging was performed simultaneously, and irradiated with a 365nm UV-LED at an irradiation dose of 100mJ / cm². 2The environment is exposed to ultraviolet light to create an oxygen concentration below 100 ppm. Then, it is annealed with warm air at 120°C for 1 minute to form the precursor layer.

[0718] The obtained precursor layer was irradiated at room temperature with 7.9 mJ / cm2 (wavelength: 313 nm) UV light (ultra-high pressure mercury lamp; UL750; manufactured by HOYA) passing through a metal wire grid polarizer, thereby forming a composite layer with orientation control capability on the surface.

[0719] Furthermore, the thickness of the formed composite layer is 0.5 μm. The in-plane retardation Re at 550 nm is 0 nm, and the thickness retardation Rth at 550 nm is -68 nm. The average tilt angle of the long axis of the rod-shaped liquid crystal compound relative to the film surface is 90°, confirming its perpendicular orientation relative to the film surface.

[0720] Thus, an optically anisotropic layer (1c) is formed on the cellulose acylated film 2.

[0721]

[0722] Polymerization initiator S-1

[0723] [Chemical Formula 68]

[0724]

[0725] Photoacid generator D-1

[0726] [Chemical Formula 69]

[0727]

[0728] Polymer M-1

[0729] [Chemical Formula 70]

[0730]

[0731] Vertical Orientation Agent S01

[0732] [Chemical Formula 71]

[0733]

[0734] Photooriented polymer A-1 (The values ​​listed in each repeating unit represent the content (mass%) of each repeating unit relative to all repeating units, which are 43% mass, 27% mass, and 30% mass from the left-hand repeating units. The weight-average molecular weight is 69,800.)

[0735] [Chemical Formula 72]

[0736]

[0737] Fluorine compound D (weight average molecular weight: 2200)

[0738] [Chemical Formula 73]

[0739]

[0740] Next, on the optically anisotropic layer (1c) prepared above, an optically anisotropic layer coating liquid (1b) containing a rod-shaped liquid crystal compound with the following composition was coated using a die coater, and heated with warm air at 80°C for 60 seconds. Then, the resulting composite layer was subjected to UV irradiation (500 mJ / cm²) at 80°C. 2 This fixes the orientation of the liquid crystal compound, thereby forming an optically anisotropic layer (1b).

[0741] The thickness of the optical anisotropic layer (1b) is 1.2 μm, the Δnd at a wavelength of 550 nm is 164 nm, and the twist angle of the liquid crystal compound is 81°. If the width direction of the film is set to 0° (and the length direction is set to 90°), then when viewed from the optical anisotropic layer (1b) side, the orientation axis angle of the liquid crystal compound is -14° on the air side and -95° on the side in contact with the optical anisotropic layer (1c).

[0742]

[0743] Left-handed tortuous chiral reagent (CL2)

[0744] [Chemical Formula 74]

[0745]

[0746] Following the steps described above, a laminate (1c-1b) consisting of an optically anisotropic layer (1c) and an optically anisotropic layer (1b) directly stacked on a cellulose acylated film 2 was fabricated. Furthermore, when examining the surface of the optically anisotropic layer (1c) that contacts the optically anisotropic layer (1b) using the method described above, the presence of a photo-oriented polymer was confirmed.

[0747] The surface side of the optically anisotropic layer (1a) formed on the cellulose acylated film 2 and the surface side of the optically anisotropic layer (1b) of the laminate (1c-1b) formed on the cellulose acylated film 2 were bonded together using an ultraviolet-curable adhesive.

[0748] Next, the cellulose acylate film on the optical anisotropic layer (1a) side is peeled off, exposing the surface of the optical anisotropic layer (1a) that is in contact with the cellulose acylate film. Thus, an optical film (1c-1b-1a) is obtained, in which an optical anisotropic layer (1c), an optical anisotropic layer (1b), and an optical anisotropic layer (1a) are sequentially stacked on a strip-shaped cellulose acylate film.

[0749] (Fabrication of a circular polarizer)

[0750] The surface of the optical anisotropic layer (1a) of the optical film (1c-1b-1a) prepared above and the surface of the aforementioned laminate A with the cellulose acylated film 1 removed, prepared in the same manner as in Example 20, were bonded together with adhesive N1. Next, the cellulose acylated film on the optical anisotropic layer (1c) side was peeled off, exposing the surface of the optical anisotropic layer (1c) in contact with the cellulose acylated film.

[0751] Thus, a laminate A-3 was fabricated, consisting of an optical film (1c-1b-1a) and a laminate A. Specifically, in laminate A-3, a low-reflection surface film, an adhesive layer, an oxygen barrier layer, a light-absorbing anisotropic film, a light-aligning film, an adhesive layer, an optically anisotropic layer (1a), an optically anisotropic layer (1b), and an optically anisotropic layer (1c) are sequentially stacked. The angle between the absorption axis of the light-absorbing anisotropic film and the slow axis of the optically anisotropic layer (1a) is 76°. Furthermore, with the width direction as a reference (0°), the alignment axis angle of the liquid crystal compound on the optically anisotropic layer (1b) side (1a) is 14°, which is consistent with the slow axis direction of the optically anisotropic layer (1a).

[0752] The laminate A-3 prepared above was replaced with laminate A-1. Otherwise, an organic EL display device was prepared using the same method as in Example 1.

[0753] [Example 24]

[0754] In Example 16, the composition for forming the light-absorbing anisotropic film was changed to P9, and the alkali-free glass EAGLEXG 1.1 mm thick (made by Coming Incorporated) was changed to a 50 μm thick glass substrate (SHOTT Corporation, D263). Otherwise, an organic EL display device was fabricated using the same method as in Example 16.

[0755] [Example 25]

[0756] In Example 17, the composition for forming the light-absorbing anisotropic film was changed to P9, and the alkali-free glass EAGLEXG 1.1 mm thick (made by Coming Incorporated) was changed to a 50 μm thick glass substrate (SCHOTT AG, D263). Otherwise, an organic EL display device was fabricated using the same method as in Example 17.

[0757] [Example 26]

[0758] In Example 25, the AR thin film (Dexerials Corporation, AR100; 91 μm) with multilayer sputtered metal oxide film and the 50 μm thick glass substrate (SCHOTT AG, D263) were replaced with glass with the AR thin film bonded together using the UV adhesive. Otherwise, an organic EL display device was fabricated using the same method as in Example 25. Furthermore, when bonding with the UV adhesive, at 600 mJ / cm²... 2 The bonding was performed under UV irradiation. The thickness of the UV adhesive layer was 3 μm. In addition, the surfaces bonded with the UV adhesive were subjected to corona treatment.

[0759] [Example 27]

[0760] In Example 26, the AR film (Dexerials Corporation, AR100; 91 μm) and the 50 μm thick glass substrate (SHOTT Corporation, D263) were replaced with glass with the AR film bonded to it using the adhesive N1. Otherwise, an organic EL display device was fabricated using the same method as in Example 26.

[0761] [Example 28]

[0762] As a thin film for field-of-view control, a light-absorbing anisotropic layer P11 with dichroic material oriented perpendicularly to the film thickness direction was fabricated as follows.

[0763] <Creation of Transparent Support 1>

[0764] The surface of cellulose acylated film 3 (40 μm thick TAC substrate; TG40 FUJIFILM Corporation) was saponified with an alkaline solution, and the following coating solution PA5 for forming an alignment film was applied to it using a winding rod. The support with the coating film was dried with warm air at 60°C for 60 seconds, and then dried with warm air at 100°C for 120 seconds to form an alignment layer, thereby obtaining a TAC film with an alignment layer.

[0765] The thickness of the orientation layer is 1 μm.

[0766]

[0767] Modified polyvinyl alcohol

[0768] [Chemical Formula 75]

[0769]

[0770] <Formation of the light-absorbing anisotropic layer P11>

[0771] The following light-absorbing anisotropic layer forming composition P11 was continuously coated onto the obtained orientation layer using a winding bar to form a coating layer P11.

[0772] Next, the coating layer P11 was heated at 140°C for 30 seconds and then cooled to room temperature (23°C).

[0773] Next, heat at 80°C for 60 seconds and then cool to room temperature again.

[0774] Then, by using an LED light (center wavelength 365nm) at an illuminance of 200mW / cm² 2 An anisotropic light-absorbing layer P11, in which a dichroic material is perpendicularly oriented to the film surface, was fabricated by irradiating the film for 2 seconds under the specified irradiation conditions. The coating layer P11 has a thickness of 3 μm and an orientation degree of 0.96. It is designated as film 1 for field-view angle control.

[0775]

[0776]

[0777] Compound E-1

[0778] [Chemical Formula 76]

[0779]

[0780] Compound E-2

[0781] [Chemical Formula 77]

[0782]

[0783] Fluorine compound E

[0784] [Chemical Formula 78]

[0785]

[0786] Fluorine compound F

[0787] [Chemical Formula 79]

[0788]

[0789] In Example 16, the cyclic olefin film was replaced with the aforementioned field-of-view control film 1, and the surface of the cellulose acylated film side of the field-of-view control film was bonded to the oxygen barrier layer B1 side of the aforementioned laminate A using adhesive N1. Otherwise, an organic EL display device was fabricated using the same method as in Example 16. The resulting organic EL display device exhibits high transmittance from the front and low transmittance from the tilt direction.

[0790] [Comparative Example 1]

[0791] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P12 with the following composition, and the heating temperature was changed to the temperature shown in Table 2 below. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0792]

[0793] Dichroic substance M-2 (maximum absorption wavelength: 475nm)

[0794] [Chemical Formula 80]

[0795]

[0796] Dichroic substance Y-2 (maximum absorption wavelength: 416nm)

[0797] [Chemical Formula 81]

[0798]

[0799] Liquid crystal compound L-3

[0800] [Chemical Formula 82]

[0801]

[0802] Surfactant F-4

[0803] [Chemical Formula 83]

[0804]

[0805] [Example 29]

[0806] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P13 with the following composition, the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm, and the heating temperature was set as described in Table 1 below. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0807]

[0808]

[0809] Surfactant F-9

[0810] [Chemical Formula 84]

[0811]

[0812] [Example 30]

[0813] The light absorption anisotropic film forming composition P1 was replaced with the light absorption anisotropic film forming composition P14 with the following composition, the film thickness of the light absorption anisotropic film P1 was changed to 2.0 μm, and the heating temperature was set as described in Table 1 below. Otherwise, the laminate and organic EL display device were fabricated in the same manner as in Example 1.

[0814]

[0815]

[0816] [Display Performance]

[0817] The visual legibility and display quality of the fabricated organic EL display device were evaluated under bright light. The display screen was set to black, and the reflected light from fluorescent lamps projected from the front and at a 45-degree angle was observed. The display performance was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2 below.

[0818] <Evaluation Criteria>

[0819] A: It is black, and the color is completely undetectable by visual inspection.

[0820] B: Coloration is slightly discernible visually, but reflectivity is very low.

[0821] C: Coloration can be slightly visually discerned, but reflectivity is low.

[0822] D: Colors can be slightly visually discerned, and the reflectivity is high.

[0823] E: Clearly recognizable coloration and high reflectivity

[0824] [Durability]

[0825] The fabricated organic EL display device was subjected to an environment of 80°C and relative humidity less than 10% for 500 hours. The visual legibility and display quality of the resulting display device were then evaluated under bright light. The display screen was set to black, and the reflected light from fluorescent lamps projected from the front and at a 45-degree angle was observed. The display performance was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2 below.

[0826] <Evaluation Criteria>

[0827] A: It is black, and the color is completely undetectable by visual inspection.

[0828] B: Coloration is slightly discernible visually, but reflectivity is very low.

[0829] C: Coloration can be slightly visually discerned, but reflectivity is low.

[0830] D: Colors can be slightly visually discerned, and the reflectivity is high.

[0831] E: Clearly recognizable coloration and high reflectivity

[0832] [95℃ Durability]

[0833] The fabricated organic EL display device was subjected to an environment of 95°C and relative humidity less than 5% for 600 hours. The visual legibility and display quality of the resulting display device were then evaluated under bright light. The display screen was set to black, and the reflected light from fluorescent lamps projected from the front and at a 45-degree angle was observed. The display performance was evaluated according to the following criteria. The evaluation results are shown in Tables 1 and 2 below.

[0834] <Evaluation Criteria>

[0835] A: It is black, and the color is completely undetectable by visual inspection.

[0836] B: Coloration is slightly discernible visually, but reflectivity is very low.

[0837] C: Coloration can be slightly visually discerned, but reflectivity is low.

[0838] D: Colors can be slightly visually discerned, and the reflectivity is high.

[0839] E: Clearly recognizable coloration and high reflectivity

[0840]

[0841]

[0842] Based on the results shown in Tables 1 and 2 above, it can be seen that for signals originating from dichroic materials detected by TOF-SIMS, when the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface of the light-absorbing anisotropic film corresponding to the visual recognition side of the image display device does not satisfy the above formula (I-1), the display performance and durability are both poor (Comparative Examples 1 to 3).

[0843] In contrast, it can be seen that when the relationship between the maximum strength Imax and the strength Isur1 satisfies the above formula (I-1), the display performance and durability are both good (Examples 1-30).

[0844] In particular, a comparison of the examples shows that if the gradient thickness exceeds 50 nm, the display performance and durability become good; if it exceeds 60 nm, the display performance and durability become even better. Similarly, if the difference between the logP value of the surfactant and the logP value of the liquid crystal compound is less than 3.1, the display performance and durability become good; if it is less than 1.4, the display performance and durability become even better.

[0845] Furthermore, a comparison between the examples and comparative examples shows that the relationship between the maximum intensity Imax and the intensity Isur1 can be adjusted by the type of dichroic material or the heating temperature when forming anisotropic light absorption film.

[0846] Furthermore, in the cases of surfactants containing a difference of less than 1.4 from the logP value of the liquid crystal compound and surfactants containing a difference of 1.4 or more from the logP value of the liquid crystal compound, in addition to good display performance and durability, the surface smoothness is high and depressions and unevenness are suppressed, resulting in excellent in-plane uniformity.

Claims

1. A light-absorbing anisotropic film, which is a light-absorbing anisotropic film used in an image display device, formed using a liquid crystal composition containing a liquid crystal compound and a dichroic substance, wherein, For the signal originating from the dichroic substance detected by time-of-flight secondary ion mass spectrometry, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface of the light-absorbing anisotropic film corresponding to the visual recognition side of the image display device satisfies the following equation (I-1). 2.0 ≤ Imax / Isur1 (I-1) The maximum intensity Imax is the maximum intensity obtained by mass spectrometry analysis of a fragment originating from the dichroic material in a region comprising 98% of the total thickness of both the visually recognizable side surface and the side opposite to the visually recognizable side surface of the light-absorbing anisotropic film, excluding 1% of the total thickness. The intensity Isur1 is the average intensity of a fragment derived from the dichroic material in a region representing 1% of the total thickness of the visually recognizable side surface of the light-absorbing anisotropic film, obtained by mass spectrometry analysis.

2. The light-absorbing anisotropic film according to claim 1, wherein, The thickness of the light-absorbing anisotropic film from the surface corresponding to the visual recognition side of the image display device to the position where the maximum intensity Imax is displayed exceeds 50 nm.

3. The light-absorbing anisotropic film according to claim 1, wherein, The thickness of the light-absorbing anisotropic film from the surface corresponding to the visual recognition side of the image display device to the position where the maximum intensity Imax is displayed exceeds 60 nm.

4. The light-absorbing anisotropic film according to any one of claims 1 to 3, wherein, The liquid crystal composition also contains a surfactant. The difference between the logP value of the surfactant and the logP value of the liquid crystal compound is less than 3.

1.

5. The light-absorbing anisotropic film according to any one of claims 1 to 3, wherein, The liquid crystal composition also contains a surfactant. The difference between the logP value of the surfactant and the logP value of the liquid crystal compound is less than 1.

4.

6. The light-absorbing anisotropic film according to any one of claims 1 to 3, wherein, The liquid crystal composition further comprises a surfactant having a logP value difference of less than 1.4 from that of the liquid crystal compound, and a surfactant having a logP value difference of 1.4 or more from that of the liquid crystal compound.

7. A laminate, comprising a substrate, an alignment film, and a light-absorbing anisotropic film sequentially thereof, for use in an image display device, wherein, The light-absorbing anisotropic film is the light-absorbing anisotropic film according to any one of claims 1 to 6. For signals originating from dichroic substances detected by time-of-flight secondary ion mass spectrometry, the relationship between the maximum intensity Imax in the thickness direction of the light-absorbing anisotropic film and the intensity Isur1 on the surface of the light-absorbing anisotropic film corresponding to the visual recognition side of the image display device satisfies the following equation (I-1). 2.0 ≤ Imax / Isur1 (I-1) The maximum intensity Imax is the maximum intensity obtained by mass spectrometry analysis of a fragment originating from the dichroic material in a region comprising 98% of the total thickness of both the visually recognizable side surface and the side opposite to the visually recognizable side surface of the light-absorbing anisotropic film, excluding 1% of the total thickness. The intensity Isur1 is the average intensity of a fragment derived from the dichroic material in a region representing 1% of the total thickness of the visually recognizable side surface of the light-absorbing anisotropic film, obtained by mass spectrometry analysis.

8. The laminate according to claim 7, wherein, The laminate also includes a phase retardation plate disposed on the light-absorbing anisotropic film. The retardation plate has multiple optically anisotropic layers containing liquid crystal compounds. At least one of the plurality of optically anisotropic layers is an optically anisotropic layer containing a liquid crystal compound with a twisted orientation along the thickness direction as the helical axis.

9. The laminate according to claim 7, wherein, The laminate also has a surface protective material disposed on the light-absorbing anisotropic film. The substrate is a glass substrate with a thickness of less than 100 μm.

10. The laminate according to claim 7, wherein, The laminate also has a λ / 4 plate disposed on the light-absorbing anisotropic film.

11. An image display device having a light-absorbing anisotropic film according to any one of claims 1 to 6 or a laminate according to any one of claims 7 to 10.

Images