CN118202811A - Organic EL display device - Google Patents

Organic EL display device Download PDF

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Publication number
CN118202811A
CN118202811A CN202280074060.0A CN202280074060A CN118202811A CN 118202811 A CN118202811 A CN 118202811A CN 202280074060 A CN202280074060 A CN 202280074060A CN 118202811 A CN118202811 A CN 118202811A
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group
organic
anisotropic layer
light
absorbing anisotropic
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三户部史岳
志贺溪伍
网中英一郎
吉成伸一
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Fujifilm Corp
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Fujifilm Corp
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Priority claimed from PCT/JP2022/041514 external-priority patent/WO2023085255A1/en
Publication of CN118202811A publication Critical patent/CN118202811A/en
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Abstract

The invention provides an organic EL display device capable of suppressing color tone change when white display is visually recognized from an oblique direction. An organic EL display device comprises an organic EL display element and a light-absorbing anisotropic layer, wherein the light-absorbing anisotropic layer is formed using a composition containing a liquid crystalline compound and a dichroic material, the angle between the central axis of transmittance of the light-absorbing anisotropic layer and the normal to the layer plane of the light-absorbing anisotropic layer is 0 DEG to 45 DEG, A (lambda) of the light-absorbing anisotropic layer represented by the following formula (1) is 15 to 225nm at the maximum absorption wavelength of the light-absorbing anisotropic layer, and the formula (1) A (lambda) = { kz (lambda) - (kx (lambda) +ky (lambda))/2 } x d.

Description

Organic EL display device
Technical Field
The present invention relates to an organic EL display device.
Background
In recent years, attention has been paid to a self-luminous display element typified by an organic electroluminescent element (organic EL element) as a display element constituting a flat display device.
Among them, the self-luminous display element having a microcavity structure is excellent in brightness and color purity. The microcavity structure is configured to resonate only light of a predetermined wavelength and attenuate light of other wavelengths by matching the optical path length between the upper and lower electrodes (i.e., the anode electrode and the cathode electrode) of the organic material with the peak wavelength of the spectrum to be output.
On the other hand, conventionally, in order to suppress adverse effects caused by reflection of external light, a circularly polarizing plate has been used for an organic EL display device.
For example, patent document 1 describes that a circularly polarizing plate (elliptical polarizing plate) to which a vertically oriented liquid crystal cured film and a horizontally oriented phase difference film are applied is applied to an organic EL display device.
Technical literature of the prior art
Patent literature
Patent document 1: international publication No. 2020/095831
Disclosure of Invention
Technical problem to be solved by the invention
However, the present inventors have studied an organic EL display device using a conventional polarizing plate (for example, a circular polarizing plate described in patent document 1), and as a result, have found the following problems: in the case of using the conventional polarizing plate, although adverse effects due to external light reflection are suppressed when viewing from the oblique direction, the color tone is changed when viewing the white display from the oblique direction, as compared with the case of viewing the white display from the front direction.
Accordingly, an object of the present invention is to provide an organic EL display device capable of suppressing a change in color tone when white display is visually recognized from an oblique direction.
Means for solving the technical problems
As a result of intensive studies, the present inventors have found that by using a light absorbing anisotropic layer in which the angle between the central axis of transmittance and the normal to the layer plane is 0 ° or more and 45 ° or less and the absorbing anisotropy in the thickness direction is controlled, the change in color tone upon white display can be improved in visual observation from the oblique direction.
That is, the present inventors have found that the above-described problems can be achieved by the following configuration.
An organic EL display device comprising an organic EL display element and a light absorbing anisotropic layer, wherein in the organic EL display device,
The light-absorbing anisotropic layer is formed using a composition containing a liquid crystalline compound and a dichroic material,
The angle between the central transmittance axis of the light-absorbing anisotropic layer and the normal line of the layer plane of the light-absorbing anisotropic layer is 0 DEG to 45 DEG, and A (lambda) of the light-absorbing anisotropic layer represented by the following formula (1) is 15 to 225nm at the maximum absorption wavelength of the light-absorbing anisotropic layer.
The organic EL display device according to [ 2], wherein,
At the maximum absorption wavelength of the light absorbing anisotropic layer, B (λ) represented by the following formula (2) is 30 or more.
The organic EL display device according to [ 1] or [2 ], further comprising a polarizer, wherein the light absorbing anisotropic layer is disposed on the viewing side of the polarizer.
The organic EL display device according to [ 4 ], further comprising a polarization control layer disposed on the viewing side of the polarizer.
The organic EL display device according to [ 5 ], wherein,
The polarization control layer is a lambda/4 film, and the retardation Rth of the light absorbing anisotropic layer in the thickness direction of the light absorbing anisotropic layer at the maximum absorption wavelength is-200 to-20 nm.
The organic EL display device as described in [ 6 ], wherein,
The polarization control layer is a depolarization film.
The organic EL display device as described in any one of [1] to [ 6], wherein,
The liquid crystal compound has positive wavelength dispersion, and the composition contains a homeotropic alignment agent.
The organic EL display device as described in any one of [1] to [ 7 ], wherein,
The ratio of the value of A (lambda) at the minimum of the light absorbing anisotropic layer at a wavelength of 400 to 650nm to the value of A (lambda) at the maximum of the light absorbing anisotropic layer is 0.35 or less.
The organic EL display device as described in any one of [1] to [ 8 ], wherein,
In the organic EL light-emitting element, deltau 'v' (60 DEG) represented by the following formula (3A) on a CIE1976 u 'v' chromaticity diagram is larger than 0.005 in white display,
In at least 1 layer of the light absorbing anisotropic layers, an angle formed between a transmittance central axis of the light absorbing anisotropic layer and a normal line of a layer plane of the light absorbing anisotropic layer is 15 DEG or more and 45 DEG or less,
The organic EL display device according to [ 10 ], which further comprises a polarizer and a polarization control layer,
The polarization control layer, the light absorbing anisotropic layer, and the polarizer are laminated in this order from the viewing side.
The organic EL display device as described in any one of [ 1 ] to [ 8 ], wherein,
The organic EL light emitting element satisfies the relationship of u ' (0 °) > u ' (30 °) > u ' (60 °) and the relationship of v ' (0 °) > v ' (30 °) and v ' (0 °) > v ' (60 °) in white display,
The maximum absorption wavelength of the light absorption anisotropic layer is within a range of 460 to 500 nm.
Here, u '(c°) is an average value of u' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram, and v '(c°) is an average value of v' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram.
The organic EL display device as described in any one of [ 1 ] to [ 8 ], wherein,
The organic EL light-emitting element satisfies the relationship of u '(0) > u' (30 DEG) and u '(0 DEG) > u' (60 DEG) and satisfies the relationship of v '(0 DEG) > v' (30 DEG) and v '(30 DEG) < v' (60 DEG) in white display,
The maximum absorption wavelength of the light absorption anisotropic layer is in the range of 510 to 570 nm.
Here, u '(c°) is an average value of u' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram, and v '(c°) is an average value of v' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram.
Effects of the invention
According to the present invention, an organic EL display device capable of suppressing a change in color tone when white display is visually recognized from an oblique direction can be provided.
Detailed Description
The present invention will be described in detail below.
The following description of the constituent elements is made in accordance with the representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range indicated by "to" refers to a range in which numerical values described before and after "to" are included as a lower limit value and an upper limit value.
In the present specification, the term "parallel" and "orthogonal" do not mean exactly parallel and orthogonal, but mean a range of ±5° from parallel or orthogonal.
In the present specification, the term "liquid crystalline composition" and "liquid crystalline compound" include concepts that liquid crystallinity is no longer exhibited by curing or the like.
In the present specification, 1 type of substance corresponding to each component may be used alone, or 2 or more types may be used in combination. In the case where 2 or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
In the present specification, "(meth) acrylate" means "acrylate" or "methacrylate", "(meth) acrylic" means "acrylic" or "methacrylic", and "(meth) acryl" means "acryl" or "methacryl".
In the present invention, refractive indices nx and ny are refractive indices in the in-plane direction of the optical member, respectively, and typically nx is a refractive index in a slow axis direction, and ny is a refractive index in a fast axis direction (i.e., a direction orthogonal to the slow axis). And nz is the refractive index in the thickness direction. nx, ny and nz can be measured by using, for example, an Abbe refractometer (NAR-4T, ATAGO CO., LTD. Manufactured), and a sodium lamp (λ=589 nm) as a light source. In the case of measuring the wavelength dependence, the measurement can be performed by using a combination of a multi-wavelength Abbe refractometer DR-M2 (manufactured by ATAGOCO., LTD.) and an interference filter. Further, a polymer manual (JOHN WILEY & SONS, INC) and a value of a product catalog of various optical films can be used.
In the present specification, re (λ) and Rth (λ) represent the in-plane phase difference and the thickness-direction phase difference at the wavelength λ, respectively, and refractive indices nx, ny, nz and a film thickness d (μm) are used and expressed by the following formulas (7) and (8).
Formula (7): re (lambda) = (nx-ny) x d x 1000 (nm)
Formula (8): rth (λ) = ((nx+ny)/2-nz) ×d×1000 (nm)
Unless otherwise specified, the wavelength λ is 550nm.
The slow axis orientation, re (λ), and Rth (λ) can be measured using AxoScan OPMF-1 (manufactured by Opto Science, inc.), for example.
The organic EL display device of the present invention includes an organic EL display element and a light absorbing anisotropic layer. The light absorbing anisotropic layer is formed using a composition containing a liquid crystalline compound and a dichroic material.
Here, the angle between the transmittance central axis of the light-absorbing anisotropic layer and the normal line of the layer plane of the light-absorbing anisotropic layer is 0 ° or more and 45 ° or less, and a (λ) of the light-absorbing anisotropic layer represented by formula (1) shown in the subsequent stage is 15 to 225nm at the maximum absorption wavelength of the light-absorbing anisotropic layer.
When the light-absorbing anisotropic layer is used as described above, it is considered that the color tone change when white display is visually recognized from an oblique direction can be adjusted on the light-absorbing anisotropic layer, and therefore the color tone change can be suppressed.
The structure of the organic EL display device of the present invention will be described below.
< Light absorbing Anisotropic layer >)
In the light absorbing anisotropic layer used in the organic EL display device of the present invention, an angle formed between a transmittance central axis of the light absorbing anisotropic layer and a normal line of a layer plane of the light absorbing anisotropic layer is 0 ° or more and 45 ° or less. Here, the transmittance central axis means an angle and a direction indicating the highest transmittance when the transmittance is measured by changing the inclination angle and the inclination direction with respect to the normal direction of the film.
The angle formed by the transmittance central axis of the light absorbing anisotropic layer and the normal line of the layer plane of the light absorbing anisotropic layer can be adjusted according to the organic EL display element.
In order to control the central axis of the transmission axis of the light absorbing anisotropic layer, a method of aligning a dichroic substance (preferably an organic dichroic dye) is preferable, and a method of aligning a dichroic substance (preferably an organic dichroic dye) by alignment of a liquid crystalline compound is further preferable.
And, a composition containing the liquid crystal compound and the dichroic material used in the organic EL display device of the present invention is used.
As an example, a light absorbing anisotropic layer in which at least one organic dichroic dye is aligned vertically in plane can be given.
As a technique for aligning the organic dichroic dye to a desired orientation, a technique for producing a polarizer using the organic dichroic dye, a technique for producing a guest-host liquid crystal cell, or the like can be referred to. For example, the technique used in the method for producing a dichroic polarizing element described in JP-A11-305036 or JP-A2002-90526 or the method for producing a guest-host liquid crystal display device described in JP-A2002-99388 or JP-A2016-27387 can be used in the production of a light absorbing anisotropic layer used in the present invention.
For example, the molecules of the organic dichroic dye can be aligned as desired as described above by using a guest host liquid crystal cell technology, along with alignment of the host liquid crystal. Specifically, the light absorbing anisotropic layer used in the present invention can be produced by mixing an organic dichroic dye serving as a guest and a rod-like liquid crystal compound serving as a host liquid crystal, aligning the molecules of the organic dichroic dye according to the alignment of the liquid crystal molecules, and fixing the aligned state.
In order to prevent the light absorption characteristics of the light absorption anisotropic layer used in the present invention from varying depending on the use environment, it is preferable to fix the orientation of the organic dichroic dye by forming chemical bonds. For example, the alignment can be fixed by polymerizing a host liquid crystal, an organic dichroic dye, or a polymerizable component added as needed.
In addition, a guest host liquid crystal cell having a liquid crystal layer containing at least an organic dichroic dye and a host liquid crystal on a pair of substrates may be used as the light absorbing anisotropic layer used in the present invention. The alignment of the host liquid crystal (and the alignment of the organic dichroic dye molecules accompanying it) can be controlled by the alignment film formed on the inner surface of the substrate, and the alignment state thereof can be maintained as long as no external stimulus such as an electric field is applied, so that the light absorption characteristics of the light absorbing anisotropic layer used in the present invention can be maintained constant.
In the present invention, the retardation Rth of the light absorbing anisotropic layer in the thickness direction of the light absorbing anisotropic layer at the maximum absorption wavelength is preferably-200 to-20 nm, more preferably-150 to-20 nm, further preferably-20 to-60 nm. By controlling Rth within the above range, it is possible to compensate for the retardation in the thickness direction of the λ/4 retardation layer that the organic EL display device of the present invention can have, and to reduce the reflectance of light incident from an oblique direction.
In the present invention, the maximum absorption wavelength of the light absorbing anisotropic layer is preferably between 380 to 780nm in wavelength of the visible region.
In the present invention, the above light absorbing anisotropic layer is used. The degree of absorption anisotropy can be expressed by various parameters, and as an example thereof, a (λ) defined by the following formula (1) is given.
Formula (1) a (λ) = { kz (λ) - (kx (λ) +ky (λ))/2 } ×d
Where d is the thickness of the light absorbing anisotropic layer, and the unit of the thickness of the light absorbing anisotropic layer denoted by d is nm. Kx (λ) and ky (λ) are absorption coefficients of light with respect to the wavelength λ in directions of the orthogonal x-axis and y-axis in the plane of the light absorbing anisotropic layer, respectively. kz (λ) is a light absorption coefficient of light with respect to wavelength λ in a z-axis direction orthogonal to a plane including the x-axis and the y-axis. Here, the absorption coefficient k is also referred to as an extinction coefficient (attenuation index), and is a value related to how much light energy is absorbed in a substance. In general, the real component n of the complex refractive index is a so-called refractive index, and the imaginary component k is an absorption coefficient. In the present invention, k is a physical property value different from that of attenuation coefficient α. For attenuation index and attenuation coefficient, details are described in pages 218 to 219 of 4.11.2"Beam propagation in an absorbing mediun of" PRINCIPLES OF OPTICS,7th (expanded) edition "of Max Born and Emil Wolf, for example.
In the present invention, the value of A (lambda) of the light absorbing anisotropic layer at the maximum absorption wavelength is 15 to 225nm, preferably 20 to 200nm, more preferably 20 to 100nm. By controlling the value of a (λ) within this range, a change in color tone in white display of the display can be suppressed.
In the present invention, the light absorbing anisotropic layer may have a laminated structure of 2 or more layers. In the laminated structure, the values of a (λ) and Rth (λ) can be obtained by adding the values of a (λ) and Rth (λ) of the respective layers.
When the light absorbing anisotropic layer includes 2 or more layers and the maximum absorption wavelengths of the light absorbing anisotropic layers are different, a (λ) is obtained by adding the values of the layers for the respective maximum absorption wavelengths, and a (λ) at least 1 of the obtained a (λ) is within the above range. In the case where the light absorbing anisotropic layer includes 2 or more layers and the maximum absorption wavelengths of the light absorbing anisotropic layers are different, a (λ) obtained at any of the maximum absorption wavelengths is preferably within the above range.
In the present invention, the above light absorbing anisotropic layer is used. The degree of absorption anisotropy can be expressed by various parameters, and as an example thereof, B (λ) defined by the following formula (2) can be given.
Formula (2) B (λ) =kz (λ)/{ (kx (λ) +ky (λ))/2 }
Where kx (λ) and ky (λ) are extinction coefficients of light with respect to wavelength λ in respective directions of orthogonal x-axis and y-axis within a plane of the light absorbing anisotropic layer, and kz (λ) is an extinction coefficient of light with respect to wavelength λ in a z-axis direction orthogonal to a plane including the x-axis and the y-axis. The meaning of each parameter is the same as that in the above formula (1).
In the present invention, the value of B (λ) of the light absorbing anisotropic layer at the maximum absorption wavelength is preferably 30 or more, more preferably 50 or more, and still more preferably 100 or more. By controlling the value of B (λ) within this range, it is possible to further suppress the absorption of light emitted from the display and suppress the color tone variation in white display.
The upper limit of the value of B (λ) is not particularly limited, but is preferably 250 or less.
In the present invention, the light absorbing anisotropic layer may have a laminated structure of 2 or more layers, and in the laminated structure, the value of B (λ) can be obtained by averaging the value of B (λ) in each layer with a (λ) in each layer. For example, the light absorbing anisotropic layer is composed of the light absorbing anisotropic layer X1 and the light absorbing anisotropic layer X2, the value of B (λ) in the laminated structure is obtained by the following formula, assuming that a (λ) at each maximum absorption wavelength is a 1 and a 2, and the value of B (λ) at each maximum absorption wavelength is B 1 and B 2.
(In a laminated structure) B(λ))=B1×(A1/(A1+A2))+B2×(A2/(A1+A2))
When the light-absorbing anisotropic layer includes 2 or more layers and the maximum absorption wavelengths of the light-absorbing anisotropic layers are different, B (λ) is obtained by the above method for each maximum absorption wavelength, and B (λ) at least 1 maximum absorption wavelength among the obtained B (λ) is preferably within the above range. In the case where the light absorbing anisotropic layer includes 2 or more layers and the maximum absorption wavelengths of the light absorbing anisotropic layers are different, B (λ) obtained at any of the maximum absorption wavelengths is more preferably within the above range.
The absorption coefficients kx (λ), ky (λ) and kz (λ) can be related by the values of the absorption anisotropy (Diattenuation) of the sample measured using AxoScan from Axometrics. The degree a (λ) of the absorption anisotropy can be obtained by measuring a mueller matrix at a plurality of wavelengths λ at predetermined intervals (for example, every 5 °) in the in-plane slow axis direction (for example, -70 to 70 °) using the measuring device and fitting the polar angle.
The ratio of the value of a (λ) at which the light absorbing anisotropic layer is smallest at a wavelength of 400 to 650nm with respect to the value of a (λ) at which the light absorbing anisotropic layer is at the maximum absorption wavelength is also preferably 0.35 or less. The minimum value of a (λ) may be 0, and thus the lower limit of the ratio may be 0.00 or more.
The value of the minimum A (lambda) of the light absorption anisotropic layer at the wavelength of 400 to 650nm was measured at each wavelength lambda by the above-mentioned method.
In the case where the light absorbing anisotropic layer includes 2 or more layers, the ratio is obtained for each light absorbing anisotropic layer, and in any light absorbing anisotropic layer, the ratio is preferably within the above range, and in all light absorbing anisotropic layers, the ratio is more preferably within the above range.
In the light absorbing anisotropic layer used in the present invention, the transmittance of the central axis of the transmission axis is preferably 80% or more, more preferably 90% or more, and still more preferably 95% or more. When the transmittance of the transmittance central axis is adjusted within the above-described preferable range, the illuminance of the field center of view of the organic EL display device can be improved and the visibility can be improved.
[ Liquid Crystal Compound ]
The light absorbing anisotropic layer of the present invention is formed using a composition containing a liquid crystalline compound and a dichroic substance (hereinafter also referred to as a "liquid crystal composition"). Therefore, the light absorbing anisotropic layer of the present invention contains a liquid crystalline compound. The light-absorbing anisotropic layer of the present invention contains a liquid-crystalline compound, whereby the precipitation of a dichroic substance can be suppressed, and the dichroic substance can be aligned with a high degree of alignment.
The liquid crystalline compound is a liquid crystalline compound that does not exhibit dichroism.
As the liquid crystalline compound, either a low molecular liquid crystalline compound or a high molecular liquid crystalline compound may be used, and it is preferable to use both. The "low-molecular liquid crystalline compound" herein refers to a liquid crystalline compound having no repeating unit in its chemical structure. The term "polymer liquid crystalline compound" refers to a liquid crystalline compound having a repeating unit in its chemical structure.
Examples of the low-molecular liquid crystalline compound include liquid crystalline compounds described in JP-A2013-228706.
Examples of the polymer liquid crystalline compound include thermotropic liquid crystalline polymers described in JP 2011-237513A. Further, from the viewpoint of excellent strength (in particular, bending resistance) of the light absorbing anisotropic film, the polymer liquid crystalline compound preferably has a repeating unit having a crosslinkable group at the terminal. Examples of the crosslinkable group include polymerizable groups described in paragraphs [0040] to [0050] of JP-A2010-244038. Among them, from the viewpoint of improving reactivity and synthesis suitability, acryl, methacryl, epoxy, oxetanyl and styryl groups are preferable, and acryl and methacryl groups are more preferable.
When the light absorbing anisotropic layer in the present invention includes a high molecular liquid crystalline compound, the high molecular liquid crystalline compound preferably forms a nematic liquid crystal phase.
The temperature range showing the nematic liquid crystal phase is preferably room temperature (23 ℃) to 450 ℃, and from the viewpoint of handling or manufacturing applicability, 50℃to 400℃is preferable.
The content of the liquid crystalline compound is preferably 25 to 2000 parts by mass, more preferably 100 to 1300 parts by mass, and even more preferably 200 to 900 parts by mass, relative to 100 parts by mass of the content of the dichroic substance in the liquid crystal composition. The content of the liquid crystalline compound in the above range further improves the degree of alignment of the dichroic material.
The liquid crystalline compound may be contained in 1 kind alone or in 2 or more kinds. When the liquid crystalline compound contains 2 or more kinds, the content of the liquid crystalline compound refers to the total content of the liquid crystalline compounds.
For reasons of more excellent alignment, the liquid crystalline compound preferably contains a polymer liquid crystalline compound containing a repeating unit represented by the following formula (1L) (hereinafter, also referred to as "repeating unit (1L)").
[ Chemical formula 1]
In the above formula (1L), P1 represents a main chain of a repeating unit, L1 represents a single bond or a 2-valent linking group, SP1 represents a spacer group, M1 represents a mesogenic group, and T1 represents an end group.
Specifically, examples of the main chain of the repeating unit represented by P1 include groups represented by the following formulas (P1-A) to (P1-D), and among them, the group represented by the following formula (P1-A) is preferable from the viewpoints of diversity of monomers to be used as a raw material and easiness of handling.
[ Chemical formula 2]
In the formulae (P1-a) to (P1-D), "×" indicates a bonding position to L1 in the formula (1L). In the formulae (P1-A) to (P1-D), R 1、R2、R3 and R 4 each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 10 carbon atoms or an alkoxy group having 1 to 10 carbon atoms. The alkyl group may be a linear or branched alkyl group, or may be an alkyl group (cycloalkyl group) having a cyclic structure. The number of carbon atoms of the alkyl group is preferably 1 to 5.
The group represented by the formula (P1-A) is preferably a unit of a partial structure of a poly (meth) acrylate obtained by polymerization of a (meth) acrylate.
The group represented by the formula (P1-B) is preferably an ethylene glycol unit formed by ring-opening polymerization of an epoxy group of a compound having an epoxy group.
The group represented by the formula (P1-C) is preferably a propylene glycol unit formed by ring-opening polymerization of an oxetanyl group of a compound having an oxetanyl group.
The group represented by the formula (P1-D) is preferably a siloxane unit of a polysiloxane obtained by polycondensation of a compound having at least one group of an alkoxysilyl group and a silanol group. Here, as the compound having at least one group of an alkoxysilyl group and a silanol group, a compound having a group represented by the formula SiR 4(OR5)2 -is exemplified. Wherein R 4 has the same meaning as R 4 in (P1-D), and each of R 5 independently represents a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
L1 represents a single bond or a 2-valent linking group.
As the 2-valent linking group represented by L1, examples include-C (O) O-; -OC (O) -, -O-; -S-, -C (O) NR 3-、-NR3C(O)-、-SO2 -and-NR 3R4 -, etc. Wherein R 3 and R 4 each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent W (described later).
When P1 is a group represented by the formula (P1-A), L1 is preferably a group represented by-C (O) O-for reasons of more excellent degree of orientation.
When P1 is a group represented by the formulae (P1-B) to (P1-D), L1 is preferably a single bond for reasons of more excellent degree of orientation.
The spacer group represented by SP1 preferably contains at least 1 structure selected from the group consisting of an oxyethylene structure, an oxypropylene structure, a polysiloxane structure and a fluorinated alkylene structure, from the viewpoint of easy development of liquid crystallinity, availability of raw materials, and the like.
In the formula, n1 represents an integer of 1 to 20, and represents a bonding position to L1 or M1 in the formula (1L), n1 is preferably an integer of 2 to 10, more preferably an integer of 2 to 4, and most preferably 3, from the viewpoint of more excellent degree of orientation.
The oxypropylene structure represented by SP1 is preferably a group represented by- (CH (CH 3)-CH2O)n2 -) in the formula, n2 represents an integer of 1 to 3, and represents a bonding position to L1 or M1, for reasons of more excellent alignment.
In the formula, n3 represents an integer of 6 to 10, and represents a bonding position to L1 or M1.
The fluorinated alkylene structure represented by SP1 is preferably a group represented by- (CF 2-CF2)n4 -) in the formula, n4 represents an integer of 6 to 10, and represents a bonding position to L1 or M1, for reasons of more excellent alignment.
The mesogenic group represented by M1 means a group representing a main skeleton of liquid crystal molecules contributing to formation of liquid crystal. The liquid crystal molecules exhibit liquid crystallinity in an intermediate state (mesophase) between a crystalline state and an isotropic liquid state. The mesogenic group is not particularly limited, and for example, reference may be made to "Flussige KRISTALLE IN tabellin II" (VEB Deutsche Verlag fur Grundstoff Industrie, leipzig, journal of 1984), especially the records on pages 7 to 16, and the records on liquid crystal stool and view edit committee, liquid crystal stool and view (wan, journal of 2000), especially chapter 3.
The mesogenic group is preferably a group having at least 1 cyclic structure selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group, and an alicyclic group.
For reasons of more excellent degree of orientation, the mesogenic group preferably has an aromatic hydrocarbon group, more preferably 2 to 4 aromatic hydrocarbon groups, and still more preferably 3 aromatic hydrocarbon groups.
The mesogenic group is preferably a group represented by the following formula (M1-A) or the following formula (M1-B), more preferably a group represented by the following formula (M1-B), from the viewpoints of the appearance of liquid crystal properties, adjustment of the phase transition temperature of liquid crystal, availability of raw materials, and synthesis suitability, and further from the viewpoint of more excellent alignment.
[ Chemical formula 3]
In the formula (M1-A), A1 is a 2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. These groups may be substituted with an alkyl group, a fluorinated alkyl group, an alkoxy group, or a substituent W described later.
The 2-valent group represented by A1 is preferably a 4-to 6-membered ring. The group having a valence 2 represented by A1 may be a single ring or a condensed ring.
* Represents the bonding position with SP1 or T1.
Examples of the 2-valent aromatic hydrocarbon group represented by A1 include phenylene, naphthylene, fluorene-diyl, anthracene-diyl, and naphthacene-diyl, and from the viewpoints of diversity in the design of the mesogenic skeleton, availability of raw materials, and the like, phenylene or naphthylene is preferable, and phenylene is more preferable.
The heterocyclic group having a valence of 2 represented by A1 may be any of aromatic and non-aromatic, but is preferably an aromatic heterocyclic group having a valence of 2 from the viewpoint of further improving the degree of orientation.
Examples of the atom other than carbon constituting the 2-valent aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. In the case where the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
Specific examples of the 2-valent aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene group (thiophene-diyl group), a quinolinylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), an oxazol-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiazole-diyl group, and a thienothiazole-diyl group.
Specific examples of the alicyclic group having 2 valence represented by A1 include cyclopentylene group and cyclohexylene group.
In the formula (M1-A), a1 represents an integer of 1 to 10. When A1 is 2 or more, a plurality of A1 may be the same or different.
In the formula (M1-B), A2 and A3 are each independently A2-valent group selected from the group consisting of an aromatic hydrocarbon group, a heterocyclic group and an alicyclic group. Specific examples and preferred modes of A2 and A3 are the same as those of A1 of the formula (M1-A), and therefore, the description thereof will be omitted.
In the formula (M1-B), A2 represents an integer of 1 to 10, and when A2 is 2 or more, a plurality of A2's may be the same or different, a plurality of A3's may be the same or different, and a plurality of LA 1's may be the same or different. For reasons of more excellent degree of orientation, a2 is preferably an integer of 2 or more, and more preferably 2.
In the formula (M1-B), when a2 is 1, LA1 is a 2-valent linking group. When a2 is 2 or more, each of the plurality of LA1 s is independently a single bond or a 2-valent linking group, and at least 1 of the plurality of LA1 s is a 2-valent linking group. When a2 is 2, one of 2 LA1 is a 2-valent linking group and the other is a single bond, which is preferable from the viewpoint of more excellent degree of orientation.
In the formula (M1-B), as the 2-valent linking group represented by LA1, there may be mentioned an integer .)、-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-、-O-C(O)O-、-N(Z)C(O)-、-C(O)N(Z)-、-C(Z)=C(Z')-C(O)O-、-O-C(O)-C(Z)=C(Z')-、-C(Z)=N-、-N=C(Z)-、-C(Z)=C(Z')-C(O)N(Z")-、-N(Z")-C(O)-C(Z)=C(Z')-、-C(Z)=C(Z')-C(O)-S-、-S-C(O)-C(Z)=C(Z')-、-C(Z)=N-N=C(Z')-(Z、Z'、Z" in which -O-、-(CH2)g-、-(CF2)g-、-Si(CH3)2-、-(Si(CH3)2O)g-、-(OSi(CH3)2)g-(g represents 1 to 10, each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a cycloalkyl group, an aryl group, a cyano group or a halogen atom. ) -c≡c-, -n=n-, -S (O) -, - (O) S (O) O-, -O (O) S (O) O-, -SC (O) -and-C (O) S-, etc. Among them, from the reason that the degree of orientation is more excellent, C (O) O-is preferable. LA1 may be a group formed by combining 2 or more of these groups.
Specific examples of M1 include the following structures. In the following specific examples, "Ac" represents an acetyl group.
[ Chemical formula 4]
[ Chemical formula 5]
Examples of the terminal group represented by T1 include a hydrogen atom, a halogen atom, a cyano group, a nitro group, a hydroxyl group, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkylthio group having 1 to 10 carbon atoms, an alkoxycarbonyloxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms (ROC (O) -: R is an alkyl group), an acyloxy group having 1 to 10 carbon atoms, an amido group having 1 to 10 carbon atoms, an alkoxycarbonylamino group having 1 to 10 carbon atoms, a sulfonylamino group having 1 to 10 carbon atoms, a sulfamoyl group having 1 to 10 carbon atoms, a carbamoyl group having 1 to 10 carbon atoms, a sulfinyl group having 1 to 10 carbon atoms, an ureido group having 1 to 10 carbon atoms, and a group containing a (meth) acryloyloxy group. Examples of the (meth) acryloyloxy group-containing group include a group represented by-L-A (L represents a single bond or a linking group, and a specific example of the linking group is the same as that of the above-mentioned L1 and SP 1. A represents a (meth) acryloyloxy group).
For reasons of more excellent degree of orientation, T1 is preferably an alkoxy group having 1 to 10 carbon atoms, more preferably an alkoxy group having 1 to 5 carbon atoms, and still more preferably a methoxy group. These terminal groups may be further substituted with these groups or the crosslinkable groups described above.
For reasons of more excellent degree of orientation, the number of atoms of the main chain of T1 is preferably 1 to 20, more preferably 1 to 15, still more preferably 1 to 10, and particularly preferably 1 to 7. The degree of orientation is further improved by the number of atoms of the main chain of T1 being 20 or less. Here, the "main chain" in T1 means the longest molecular chain bonded to M1, and the number of atoms of the main chain of T1 is not counted as hydrogen atoms. For example, when T1 is n-butyl, the number of atoms of the main chain is 4, and when T1 is sec-butyl, the number of atoms of the main chain is 3.
For reasons of more excellent alignment, the content is preferably 20 to 100 mass% with respect to 100 mass% of all the repeating units of the polymer liquid crystalline compound.
In the present invention, the content of each repeating unit contained in the polymer liquid crystalline compound is calculated from the amount (mass) of each monomer to be charged for obtaining each repeating unit.
The polymer liquid crystalline compound may contain 1 kind of repeating unit (1L) alone or 2 or more kinds of repeating units. Among them, 2 kinds of repeating units (1L) may be contained in the polymer liquid crystalline compound for reasons of more excellent alignment.
When the polymer liquid crystalline compound contains 2 kinds of repeating units (1L), it is preferable that one (repeating unit a) of the terminal groups represented by T1 is an alkoxy group and the other (repeating unit B) of the terminal groups represented by T1 is a group other than an alkoxy group, from the viewpoint of more excellent degree of alignment.
For reasons of more excellent degree of orientation, the terminal group represented by T1 in the repeating unit B is preferably an alkoxycarbonyl group, a cyano group or a group containing a (meth) acryloyloxy group, and more preferably an alkoxycarbonyl group or a cyano group.
The ratio (A/B) of the content of the repeating unit A in the polymer liquid crystalline compound to the content of the repeating unit B in the polymer liquid crystalline compound is preferably 50/50 to 95/5, more preferably 60/40 to 93/7, and even more preferably 70/30 to 90/10, from the viewpoint of further excellent degree of alignment.
The polymer liquid crystalline compound may have a repeating unit having no mesogenic group together with the repeating unit (1L). Examples of the repeating unit having no mesogenic group include repeating units in which M1 in formula (1L) is a single bond.
When the polymer liquid crystalline compound has a repeating unit having no mesogenic group, it is preferable that the content of the repeating unit is more than 0% by mass and 30% by mass or less, and more preferably more than 10% by mass and 20% by mass or less, relative to 100% by mass of the total repeating unit of the polymer liquid crystalline compound, for the reason that the degree of alignment is more excellent.
(Weight average molecular weight)
The weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 1000 to 500000, more preferably 2000 to 300000, from the viewpoint of more excellent alignment degree. If the Mw of the polymer liquid crystalline compound is within the above range, the polymer liquid crystalline compound can be easily handled.
In particular, from the viewpoint of suppressing cracks at the time of coating, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably 10000 or more, more preferably 10000 to 300000.
In addition, from the viewpoint of temperature latitude in the degree of orientation, the weight average molecular weight (Mw) of the polymer liquid crystalline compound is preferably less than 10000, preferably 2000 or more and less than 10000.
The weight average molecular weight and the number average molecular weight in the present invention are values measured by Gel Permeation Chromatography (GPC).
Solvent (eluent): n-methylpyrrolidone
Device name: TOSOH HLC-8220GPC
Column: 3 TOSOH TSKgelSuperAWM-H (6 mm. Times.15 cm) were used in a ligation
Column temperature: 25 DEG C
Sample concentration: 0.1 mass%
Flow rate: 0.35 mL/min
Calibration curve: calibration curves obtained using 7 samples of TSK standard polystyrene mw=2800000-1050 (Mw/mn=1.03-1.06) made by TOSOH were used
The substituent W in the present specification will be described.
Examples of the substituent W include an alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms), an alkyl group (preferably an alkyl group having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, and more preferably 2 to 12 carbon atoms), an alkynyl group (preferably 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms), particularly preferred are alkynyl groups having 2 to 8 carbon atoms such as propargyl and 3-pentynyl groups, aryl groups (preferably aryl groups having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferred aryl groups having 6 to 12 carbon atoms such as phenyl, 2, 6-diethylphenyl, 3, 5-bistrifluoromethylphenyl, styryl, naphthyl and biphenyl groups), substituted or unsubstituted amino groups (preferably amino groups having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferred amino groups having 0 to 6 carbon atoms such as unsubstituted amino groups, methylamino groups, dimethylamino groups, diethylamino, anilino, and the like), alkoxy (preferably 1 to 20 carbon atoms, more preferably 1 to 15 carbon atoms, for example, methoxy, ethoxy, butoxy, and the like), oxycarbonyl (preferably 2 to 20 carbon atoms, more preferably 2 to 15 carbon atoms, and particularly preferably 2 to 10 carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, phenoxycarbonyl, and the like), acyloxy (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, acetoxy, benzoyloxy, acryl, methacryl, and the like), acylamino (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, acetamido group, benzoylamino group and the like), alkoxycarbonylamino group (preferably 2 to 20 carbon atoms, more preferably 2 to 10 carbon atoms, particularly preferably 2 to 6 carbon atoms, for example, methoxycarbonylamino group and the like), aryloxycarbonylamino group (preferably 7 to 20 carbon atoms, more preferably 7 to 16 carbon atoms, particularly preferably 7 to 12 carbon atoms, for example, phenoxycarbonylamino group and the like), sulfonylamino group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, examples thereof include methanesulfonylamino and benzenesulfonylamino, etc.), sulfamoyl (preferably having 0 to 20 carbon atoms, more preferably having 0 to 10 carbon atoms, particularly preferably having 0 to 6 carbon atoms, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl and phenylsulfamoyl, etc.), carbamoyl (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl and phenylcarbamoyl, etc.), alkylthio (preferably having 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methylthio group, ethylthio group and the like), arylthio group (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenylthio group and the like), sulfonyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methanesulfonyl group, toluenesulfonyl group and the like), sulfinyl group (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, examples thereof include a methane sulfinyl group and a phenylsulfinyl group), a urea group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, an unsubstituted urea group, a methylurea group, a phenylurea group, etc.), a phosphoric acid amide group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, a diethyl phosphoric acid amide group, a phenylphosphoramide group, etc.), a hydroxyl group, a mercapto group, a halogen atom (for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), a cyano group, a nitro group, a hydroxamic acid group, a sulfinyl group, a, A hydrazino group, an imino group, an azo group, a heterocyclic group (preferably a heterocyclic group having 1 to 30 carbon atoms, more preferably 1 to 12 carbon atoms, for example, a heterocyclic group having a hetero atom such as a nitrogen atom, an oxygen atom, a sulfur atom, etc., for example, an epoxy group, an oxetanyl group, an imidazolyl group, a pyridyl group, a quinolyl group, a furyl group, a piperidyl group, a morpholino group, a maleimide group, a benzoxazolyl group, a benzimidazolyl group, a benzothiazolyl group, etc.), a silyl group (preferably a silyl group having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, for example, a trimethylsilyl group, a triphenylsilyl group, etc.), a, Carboxyl, sulfonic acid, phosphoric acid, and the like.
The wavelength dispersion of the liquid crystalline compound used to form the light absorbing anisotropic layer of the present invention is preferably positive wavelength dispersion. The positive wavelength dispersion of the liquid crystalline compound means that the phase difference layer obtained by uniformly aligning the liquid crystalline compound exhibits positive wavelength dispersion.
[ Solvent ]
From the viewpoint of handleability and the like, the liquid crystal composition for forming the light absorbing anisotropic layer of the present invention preferably contains a solvent.
Examples of the solvent include ketones (e.g., acetone, 2-butanone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, etc.), ethers (e.g., dioxane, tetrahydrofuran, 2-methyltetrahydrofuran, cyclopentylmethyl 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 hydrocarbons (e.g., methylene chloride, chloroform, dichloroethane, dichlorobenzene, chlorotoluene, etc.), esters (e.g., methyl acetate, ethyl acetate, butyl acetate, ethyl lactate, etc.), alcohols (e.g., ethanol, isopropanol, butanol, cyclohexanol, isoamyl alcohol, N-amyl alcohol, diacetone alcohol, benzyl alcohol, etc.), cellosolves (e.g., methylcellosolve, ethylcellosolve, 1, 2-dimethoxyethane, etc.), cellosolve acetate esters, sulfoxides (e.g., dimethyl sulfoxide, etc.), amides (e.g., dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethyl pyrrolidone, etc.), and heterocyclic compounds (e.g., pyridine, etc.), and the like. These solvents may be used singly or in combination of 1 or more than 2.
Among these solvents, ketones (particularly cyclopentanone, cyclohexanone), ethers (particularly tetrahydrofuran, cyclopentylmethyl ether, tetrahydropyran, dioxolane) and amides (particularly dimethylformamide, dimethylacetamide, N-methylpyrrolidone, N-ethylpyrrolidone) are preferable.
When the liquid crystal composition contains a solvent, the content of the solvent is preferably 80 to 99 mass%, more preferably 83 to 98 mass%, and even more preferably 85 to 96 mass% relative to the total mass of the liquid crystal composition.
When the solvent is contained in an amount of 2 or more, the content of the solvent means the total content of the solvents.
[ Dichromatic substance ]
The light absorbing anisotropic layer of the present invention is formed using a composition (liquid crystal composition) containing a liquid crystalline compound and a dichroic substance. Therefore, the light absorbing anisotropic layer of the present invention contains a dichroic substance. The dichroic material used for forming the light absorbing anisotropic layer of the present invention is not particularly limited, and examples thereof include visible light absorbing materials (dichroic dyes and dichroic azo compounds), luminescent materials (fluorescent materials and phosphorescent materials), ultraviolet light absorbing materials, infrared light absorbing materials, nonlinear optical materials, carbon nanotubes, inorganic materials (for example, quantum rods), and the like, and conventionally known dichroic materials (dichroic dyes) can be used.
Particularly preferably used dichroic materials are dichroic azo dye compounds.
The dichroic azo dye compound is not particularly limited, and a conventionally known dichroic azo dye can be used, but a compound described below is preferably used.
In the present invention, the dichroic azo dye compound means an azo dye compound in which absorbance varies depending on the direction.
The dichroic azo dye compound may or may not exhibit liquid crystallinity.
When the dichroic azo dye compound exhibits liquid crystallinity, either nematic property or smectic property may be exhibited. The temperature range showing the liquid crystal phase is preferably room temperature (about 20 ℃ C. To 28 ℃ C.) and 300 ℃ C. And more preferably 50 ℃ C. To 200 ℃ C. From the viewpoints of handleability and manufacturing applicability.
In the present invention, 2 or more kinds of dichroic azo dye compounds may be used in combination.
In the present invention, it is preferable that the dichroic azo dye compound has a crosslinkable group from the viewpoint of better compression resistance.
Specific examples of the crosslinkable group include a (meth) acryloyl group, an epoxy group, an oxetanyl group, and a styryl group, and among them, (meth) acryloyl groups are preferable.
Examples of the preferable dichroic azo dye compound used in the present invention include a 1 st dichroic azo dye compound, a2 nd dichroic azo dye compound, and a 3 rd dichroic azo dye compound.
(1 St dichromatic azo dye Compound)
In the present invention, the 1 st dichroic azo dye compound having the maximum absorption wavelength in the range of 560nm to 700nm can be preferably used.
The 1 st dichroic azo dye compound is preferably a compound having a chromophore (chromophore) as a core and a side chain bonded to the end of the chromophore.
Specific examples of the chromophore include an aromatic ring group (for example, an aromatic hydrocarbon group, an aromatic heterocyclic group) and an azo group, and a structure having both an aromatic ring group and an azo group is preferable, and a disazo structure having an aromatic heterocyclic group (preferably a thienothiazole group) and 2 azo groups is more preferable.
The side chain is not particularly limited, and examples thereof include a group represented by L3, R2 or L4 of the following formula (3).
The maximum absorption wavelength (nm) of the dichroic azo dye compound in the present specification is determined from an ultraviolet-visible spectrum having a wavelength in the range of 380 to 800nm measured by a spectrophotometer using a solution in which the dichroic azo dye compound is dissolved in a good solvent.
In the present invention, the 1 st dichroic azo dye compound is preferably a compound represented by the following formula (4) from the viewpoint of further improving the degree of orientation of the formed light absorbing anisotropic layer.
(4)
[ Chemical formula 6]
In the formula (4), ar1 and Ar2 each independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent, preferably a phenylene group.
In the formula (4), R1 represents a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms and optionally having a substituent, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkoxycarbonyl group, an acyloxy group, an alkylcarbonate group, an alkylamino group, an acylamino group, an alkylcarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylcarbamoyl group, an alkylsulfinyl group, an alkylureyl group, an alkylphosphoramido group, an alkylimino group or an alkylsilyl group.
-CH 2 -which constitutes an alkyl group as described above may is substituted by -O-、-CO-、-C(O)-O-、-O-C(O)-、-Si(CH3)2-O-Si(CH3)2-、-N(R1')-、-N(R1')-CO-、-CO-N(R1')-、-N(R1')-C(O)-O-、-O-C(O)-N(R1')-、-N(R1')-C(O)-N(R1')-、-CH=CH-、-C≡C-、-N=N-、-C(R1')=CH-C(O)- or-O-C (O) -O-.
When R1 is a group other than a hydrogen atom, the hydrogen atom of each group may be substituted with a halogen atom, a nitro group, a cyano group, -N (R1 ') 2, an amino group, -C (R1')=c (R1 ') -NO 2, -C (R1')=c (R1 ') -CN, or-C (R1')=c (CN) 2.
R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When a plurality of R1's are present in each group, they may be the same or different from each other.
In the formula (4), R2 and R3 each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 20 carbon atoms and optionally having a substituent, an alkoxy group, an acyl group, an alkoxycarbonyl group, an alkylamido group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group or an arylamido group.
-CH 2 -which constitutes an alkyl group as described above may is substituted by -O-、-S-、-C(O)-、-C(O)-O-、-O-C(O)-、-C(O)-S-、-S-C(O)-、-Si(CH3)2-O-Si(CH3)2-、-NR2'-、-NR2'-CO-、-CO-NR2'-、-NR2'-C(O)-O-、-O-C(O)-NR2'-、-NR2'-C(O)-NR2'-、-CH=CH-、-C≡C-、-N=N-、-C(R2')=CH-C(O)- or-O-C (O) -O-.
When R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms of each group may be substituted with a halogen atom, a nitro group, a cyano group, -OH group, -N (R2 ') 2, an amino group, -C (R2')=c (R2 ') -NO 2, -C (R2')=c (R2 ') -CN, or-C (R2')=c (CN) 2.
R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When a plurality of R2's are present in each group, they may be the same or different from each other.
R2 and R3 may be bonded to each other to form a ring, or R2 or R3 may be bonded to Ar2 to form a ring.
From the viewpoint of light resistance, R1 is preferably an electron withdrawing group, and R2 and R3 are preferably groups having low electron donating properties.
Specific examples of such groups include alkylsulfonyl, alkylcarbonyl, alkoxycarbonyl, acyloxy, alkylsulfonylamino, alkylsulfamoyl, alkylsulfinyl and alkylureyl, as R1. Examples of R2 and R3 include those having the following structures. The group having the following structure is represented by the formula (4) above, and includes a nitrogen atom to which R2 and R3 are bonded.
[ Chemical formula 7]
Specific examples of the 1 st dichroic azo dye compound are shown below, but are not limited thereto.
[ Chemical formula 8]
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(2 Nd dichromatic azo dye Compound)
In the present invention, a 2 nd dichroic azo dye compound having a maximum absorption wavelength in a range of a wavelength of 455nm or more and less than 560nm can be preferably used.
The 2 nd dichroic azo dye compound is a compound different from the 1 st dichroic azo dye compound, specifically, a chemical structure thereof is different.
The 2 nd dichroic azo dye compound is preferably a compound having a chromophore as a nucleus of the dichroic azo dye compound and a side chain bonded to the end of the chromophore.
Specific examples of the chromophore include an aromatic ring group (for example, an aromatic hydrocarbon group, an aromatic heterocyclic group) and an azo group, and the structure preferably has two of an aromatic hydrocarbon group and an azo group, and more preferably has a disazo or trisazo structure having an aromatic hydrocarbon group and 2 or 3 azo groups.
The side chain is not particularly limited, and examples thereof include groups represented by R4, R5 or R6 in the formula (5) described below.
The 2 nd dichroic azo dye compound is preferably a compound represented by the formula (5) from the viewpoint of further improvement in the degree of orientation.
(5)
[ Chemical formula 9]
In the formula (5), n represents 1 or 2.
In the formula (5), ar3, ar4 and Ar5 each independently represent a phenylene group which may have a substituent, a naphthylene group which may have a substituent or a heterocyclic group which may have a substituent.
The heterocyclic group may be either aromatic or non-aromatic.
Examples of the atom other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. In the case where the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
Specific examples of the aromatic heterocyclic group include a pyridylene group (pyridine-diyl group), a pyridazine-diyl group, an imidazole-diyl group, a thienylene group (thiophene-diyl group), a quinolinylene group (quinoline-diyl group), an isoquinolylene group (isoquinoline-diyl group), an oxazol-diyl group, a thiazole-diyl group, an oxadiazole-diyl group, a benzothiazole-diyl group, a benzothiadiazole-diyl group, a phthalimide-diyl group, a thienothiazole-diyl group, a thiazolothiazole-diyl group, a thienothiothiophene-diyl group, and a thienooxazole-diyl group.
In formula (5), R4 is as defined for R1 in formula (4).
In the formula (5), R5 and R6 are as defined for R2 and R3 in the formula (4), respectively.
From the viewpoint of light resistance, R4 is preferably an electron withdrawing group, and R5 and R6 are preferably groups having low electron donating properties.
Among such groups, the specific example when R4 is an electron withdrawing group is the same as the specific example when R1 is an electron withdrawing group, and the specific example when R5 and R6 are groups having low electron donating properties is the same as the specific example when R2 and R3 are groups having low electron donating properties.
Specific examples of the 2 nd dichroic azo dye compound are shown below, but are not limited thereto.
[ Chemical formula 10]
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(Difference in logP values)
The logP value is an index of the properties of hydrophilicity and hydrophobicity of the chemical structure.
In the present invention, when the 1 st dichroic azo dye compound and the 2 nd dichroic azo dye compound are used in combination, the absolute value of the difference between the log p value of the side chain of the 1 st dichroic azo dye compound and the log p value of the side chain of the 2 nd dichroic azo dye compound (hereinafter also referred to as "log p difference") is preferably 2.30 or less, more preferably 2.0 or less, still more preferably 1.5 or less, and particularly preferably 1.0 or less. When the log p difference is 2.30 or less, the affinity between the 1 st dichroic azo dye compound and the 2 nd dichroic azo dye compound increases, and the alignment structure is more easily formed, so that the degree of orientation of the light absorbing anisotropic layer is further increased.
In the case where there are a plurality of side chains of the 1 st dichroic azo dye compound or the 2 nd dichroic azo dye compound, it is preferable that at least 1 log p difference satisfies the above-mentioned value.
Here, the side chain of the 1 st dichroic azo dye compound and the 2 nd dichroic azo dye compound means a group bonded to the end of the chromophore. For example, when the 1 st dichroic azo dye compound is a compound represented by formula (4), R1, R2, and R3 in formula (4) are side chains, and when the 2 nd dichroic azo dye compound is a compound represented by formula (5), R4, R5, and R6 in formula (5) are side chains. In particular, in the case where the 1 st dichroic azo dye compound is a compound represented by the formula (4) and the 2 nd dichroic azo dye compound is a compound represented by the formula (5), it is preferable that at least 1 log p difference among the difference between log p values of R1 and R4, the difference between log p values of R1 and R5, the difference between log p values of R2 and R4, and the difference between log p values of R2 and R5 satisfies the above values.
The log p value is an index of the properties of hydrophilicity and hydrophobicity of the chemical structure, and is sometimes referred to as a hydrophilic-hydrophobic parameter. The log p value can be calculated using software such as ChemBioDraw Ultra or hsPIP (Ver.4.1.07). Further, the measurement can be experimentally obtained by a method of OECD Guidelines for THE TESTING of Chemicals, sections, test No.117, or the like. In the present invention, unless otherwise specified, a value calculated by inputting a structural formula of a compound in hsppi (ver.4.1.07) is used as a log p value.
(3. Th dichromatic azo dye Compound)
In the present invention, a 3 rd dichroic azo dye compound having a maximum absorption wavelength in a range of 380nm to 455nm inclusive can be preferably used.
The 3 rd dichroic azo dye compound is a dichroic azo dye compound other than the 1 st dichroic azo dye compound and the 2 nd dichroic azo dye compound, and specifically, has a chemical structure different from that of the 1 st dichroic azo dye compound and the 2 nd dichroic azo dye compound.
The 3 rd dichroic azo dye compound preferably contains a dichroic azo dye represented by the following formula (6).
[ Chemical formula 11]
In the formula (6), A and B each independently represent a crosslinkable group.
In the formula (6), a and b each independently represent 0 or 1. In view of excellent degree of orientation at 420nm, a and b are preferably 0.
In formula (6), L 1 represents a 1-valent substituent in the case of a=0, and L 1 represents a single bond or a 2-valent linking group in the case of a=1. In the case of b=0, L 2 represents a 1-valent substituent, and in the case of b=1, L 2 represents a single bond or a 2-valent linking group.
In the formula (6), ar 1 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n1+2), ar 2 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n2+2), and Ar 3 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n3+2).
In formula (6), R 1、R2 and R 3 each independently represent a substituent having a valence of 1. In the case where n1 is not less than 2, a plurality of R 1 may be the same as or different from each other, in the case where n2 is not less than 2, a plurality of R 2 may be the same as or different from each other, and in the case where n3 is not less than 2, a plurality of R 3 may be the same as or different from each other.
In the formula (6), k represents an integer of 1 to 4. When k is not less than 2, a plurality of Ar 2 may be the same as or different from each other, and a plurality of R 2 may be the same as or different from each other.
In the formula (6), n1, n2 and n3 each independently represent an integer of 0 to 4. But n1+n2+n3.gtoreq.0 in the case of k=1 and n1+n2+n3.gtoreq.1 in the case of k.gtoreq.2.
Examples of the crosslinkable groups represented by A and B in the formula (6) include polymerizable groups described in paragraphs [0040] to [0050] of JP-A2010-244038. Among them, from the viewpoint of improving reactivity and synthesis suitability, acryl, methacryl, epoxy, oxetanyl and styryl groups are preferable, and from the viewpoint of further improving solubility, acryl and methacryl groups are more preferable.
In formula (6), L 1 represents a 1-valent substituent in the case of a=0, and L 1 represents a single bond or a 2-valent linking group in the case of a=1. In the case of b=0, L 2 represents a 1-valent substituent, and in the case of b=1, L 2 represents a single bond or a 2-valent linking group.
The 1-valent substituent represented by L 1 and L 2 is preferably a group introduced to enhance the solubility of the dichroic material or a group having electron donating or electron withdrawing properties introduced to adjust the color tone of the dye.
For example, as the substituent, it is possible to use
An alkyl group (preferably an alkyl group having 1 to 20 carbon atoms, more preferably 1 to 12 carbon atoms, particularly preferably 1 to 8 carbon atoms, and examples thereof include methyl, ethyl, isopropyl, tert-butyl, n-octyl, n-decyl, n-hexadecyl, cyclopropyl, cyclopentyl, cyclohexyl, etc.)
Alkenyl (preferably alkenyl having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, vinyl, allyl, 2-butenyl, 3-pentenyl, etc.)
Alkynyl (preferably alkynyl having 2 to 20 carbon atoms, more preferably 2 to 12 carbon atoms, particularly preferably 2 to 8 carbon atoms, for example, propargyl, 3-pentynyl and the like),
Aryl (preferably an aryl group having 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, particularly preferably 6 to 12 carbon atoms, and examples thereof include phenyl, 2, 6-diethylphenyl, 3, 5-bistrifluoromethylphenyl, naphthyl and biphenyl),
Substituted or unsubstituted amino group (preferably an amino group having 0 to 20 carbon atoms, more preferably 0 to 10 carbon atoms, particularly preferably 0 to 6 carbon atoms, and examples thereof include unsubstituted amino group, methylamino group, dimethylamino group, diethylamino group, anilino group and the like),
Alkoxy (preferably having 1 to 20 carbon atoms, more preferably having 1 to 15 carbon atoms, for example, methoxy, ethoxy, butoxy and the like),
An oxycarbonyl group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 15, particularly preferably a carbon number of 2 to 10, for example, methoxycarbonyl group, ethoxycarbonyl group, phenoxycarbonyl group or the like), an acyloxy group (preferably a carbon number of 2 to 20, more preferably a carbon number of 2 to 10, particularly preferably a carbon number of 2 to 6, for example, an acetoxy group, benzoyloxy group or the like), an acetoxy group or the like,
An amido group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, an acetamido group, a benzoylamino group and the like),
An alkoxycarbonylamino group (preferably having 2 to 20 carbon atoms, more preferably having 2 to 10 carbon atoms, particularly preferably having 2 to 6 carbon atoms, for example, methoxycarbonylamino group and the like),
An aryloxycarbonylamino group (preferably having 7 to 20 carbon atoms, more preferably having 7 to 16 carbon atoms, particularly preferably having 7 to 12 carbon atoms, for example, phenoxycarbonylamino group),
A sulfonylamino group (preferably having 1 to 20 carbon atoms, more preferably having 1 to 10 carbon atoms, particularly preferably having 1 to 6 carbon atoms, for example, a methanesulfonylamino group, a benzenesulfonylamino group and the like),
Sulfamoyl (preferably, a C0-20, more preferably, a C0-10, and particularly preferably, a C0-6) group, for example, sulfamoyl, methylsulfamoyl, dimethylsulfamoyl, phenylsulfamoyl, etc.),
Carbamoyl (preferably a C1-20, more preferably a C1-10, particularly preferably a C1-6, for example, unsubstituted carbamoyl, methylcarbamoyl, diethylcarbamoyl, phenylcarbamoyl and the like) group,
Alkylthio (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methylthio, ethylthio and the like),
Arylthio (preferably 6 to 20 carbon atoms, more preferably 6 to 16 carbon atoms, particularly preferably 6 to 12 carbon atoms, for example, phenylthio and the like),
Sulfonyl (preferably a C1-20, more preferably a C1-10, particularly preferably a C1-6, for example, methanesulfonyl, toluenesulfonyl, etc.), a functional group,
Sulfinyl (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, methane sulfinyl, benzene sulfinyl and the like), ureido (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, unsubstituted ureido, methyl ureido, phenylureido and the like), phosphoric acid amido (preferably 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, particularly preferably 1 to 6 carbon atoms, for example, diethyl phosphoric acid amido, phenyl phosphoric acid amido and the like), heterocyclic group (preferably 1 to 30 carbon atoms, more preferably 1 to 12 heterocyclic groups having a hetero atom, for example, nitrogen atom, oxygen atom, sulfur atom and the like, for example, imidazolyl, pyridyl, quinolyl, furyl, piperidyl, morpholinyl, benzoxazolyl, benzimidazolyl, benzothiazolyl and the like) and the like,
Silyl groups (preferably silyl groups having 3 to 40 carbon atoms, more preferably 3 to 30 carbon atoms, particularly preferably 3 to 24 carbon atoms, and examples thereof include trimethylsilyl groups and triphenylsilyl groups),
Halogen atoms (for example, fluorine atom, chlorine atom, bromine atom, iodine atom),
Hydroxy, mercapto, cyano, nitro, hydroxamic acid, sulfenate, hydrazino, imino, azo, and the like.
These substituents may also be substituted by these substituents. In the case of having 2 or more substituents, they may be the same or different. And, where possible, may be bonded to each other to form a ring.
Examples of the substituent further substituted with the substituent include an R B-(O-RA)na -group which is a group in which an alkoxy group is substituted with an alkyl group. In the formula, R A represents an alkylene group having 1 to 5 carbon atoms, R B represents an alkyl group having 1 to 5 carbon atoms, and na represents an integer of 1 to 10 (preferably 1 to 5, more preferably 1 to 3).
Among them, as the 1-valent substituent represented by L 1 and L 2, an alkyl group, an alkenyl group, an alkoxy group, and a group in which these groups are further substituted with these groups (for example, the above-mentioned R B-(O-RA)na -group), and more preferably an alkyl group, an alkoxy group, and a group in which these groups are further substituted with these groups (for example, the above-mentioned R B-(O-RA)na -group) are preferable.
Examples of the 2-valent linking group represented by L 1 and L 2 include -O-、-S-、-CO-、-COO-、-OCO-、-O-CO-O-、-CO-NRN-、-O-CO-NRN-、-NRN-CO-NRN-、-SO2-、-SO-、 alkylene, cycloalkylene, alkenylene, and a group formed by combining 2 or more of these groups.
Among them, the group of the organic compounds is, preferably, the alkylene is combined with a member selected from the group consisting of-O-, -COO-, -OCO-and-O-CO-O-and a group comprising at least 1 group.
Here, R N represents a hydrogen atom or an alkyl group. In the case where a plurality of R N are present, a plurality of R N may be the same as or different from each other.
From the viewpoint of further improving the solubility of the dichroic material, the number of atoms of at least one main chain of L 1 and L 2 is preferably 3 or more, more preferably 5 or more, still more preferably 7 or more, and particularly preferably 10 or more. The upper limit of the number of atoms in the main chain is preferably 20 or less, more preferably 12 or less.
On the other hand, from the viewpoint of further improving the degree of orientation of the light absorbing anisotropic layer, the number of atoms of at least one main chain of L 1 and L 2 is preferably 1 to 5.
In the case where a in the formula (6) is present, the "main chain" in L 1 means a moiety required for directly connecting the "O" atom and the "a" which are connected to L 1, and the "number of atoms of the main chain" means the number of atoms constituting the moiety. Similarly, in the case where B in the formula (6) is present, the "main chain" in L 2 means a moiety required for directly connecting the "O" atom and the "B" which are connected to L 2, and the "number of atoms of the main chain" means the number of atoms constituting the moiety. The "number of atoms in the main chain" does not include the number of atoms in a branched chain described later.
In the case where a is not present, the "number of atoms of the main chain" in L 1 means the number of atoms of L 1 containing no branch. In the case where B is not present, the "number of atoms of the main chain" in L 2 means the number of atoms of L 2 containing no branch.
Specifically, in the following formula (D1), the number of atoms of the main chain of L 1 is 5 (the number of atoms in the left dotted frame of the following formula (D1)), and the number of atoms of the main chain of L 2 is 5 (the number of atoms in the right dotted frame of the following formula (D1)). In the following formula (D10), the number of atoms of the main chain of L 1 is 7 (the number of atoms in the left dot frame of the following formula (D10)), and the number of atoms of the main chain of L 2 is 5 (the number of atoms in the right dot frame of the following formula (D10)).
[ Chemical formula 12]
L 1 and L 2 may have a branched chain.
Here, when a is present in formula (6), the "branched chain" in L 1 means a moiety other than that required for directly connecting the "O" atom and the "a" that are connected to L 1 in formula (6). Similarly, in the case where B is present in formula (6), the "branch" in L 2 means a moiety other than that required for directly connecting the "O" atom and "B" connected to L 2 in formula (6).
In the case where a is not present in the formula (6), the "branch" in L 1 means a portion other than the longest atom chain (i.e., main chain) extending from the "O" atom connected to L 1 in the formula (6). Similarly, in the case where B is not present in formula (6), the "branch" in L 2 means a portion other than the longest atom chain (i.e., main chain) extending from the "O" atom linked to L 2 in formula (6).
The number of atoms of the branched chain is preferably 3 or less. The branched chain has 3 or less atoms, which has an advantage of further improving the degree of orientation of the light absorbing anisotropic layer. The number of hydrogen atoms is not included in the number of atoms of the branched chain.
In formula (6), ar 1 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n1+2) (for example, 3 when n1 is 1), ar 2 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n2+2) (for example, 3 when n2 is 1), and Ar 3 represents an aromatic hydrocarbon group or a heterocyclic group having a valence of (n3+2) (for example, 3 when n3 is 1). Here, in other words, ar 1~Ar3 may be a 2-valent aromatic hydrocarbon group or a 2-valent heterocyclic group substituted with n1 to n3 substituents (R 1~R3 described below), respectively.
The 2-valent aromatic hydrocarbon group represented by Ar 1~Ar3 may be a single ring or may have a condensed ring structure of 2 or more rings. The number of rings of the 2-valent aromatic hydrocarbon group is preferably 1 to 4, more preferably 1 to 2, and still more preferably 1 (i.e., phenylene) from the viewpoint of further improving the solubility.
Specific examples of the 2-valent aromatic hydrocarbon group include phenylene, azulenyl-diyl, naphthylene, fluorene-diyl, anthracene-diyl, and naphthacene-diyl, and from the viewpoint of further improving solubility, phenylene and naphthylene are preferable, and phenylene is more preferable.
Specific examples of the 3 rd dichroic dye compound are shown below, but the present invention is not limited thereto. In the following specific examples, n represents an integer of 1 to 10.
[ Chemical formula 13]
In view of excellent degree of orientation at 420nm, the 3 rd pigment preferably has a structure having no radical polymerizable group. For example, the following structure is given.
[ Chemical formula 14]
In view of the particularly excellent degree of alignment at 420nm, it is more preferable that the 3 rd dichroic azo dye compound is a dichroic substance having a structure represented by the following formula (1-1).
[ Chemical formula 15]
In the formula (1-1), R 1、R3、R4、R5、n1、n3、L1 and L 2 are as defined for R 1、R3、R4、R5、n1、n3、L1 and L 2, respectively, in the formula (4).
In the formula (1-1), R 21 and R 22 are each independently the same as R 2 in the formula (4).
In the formula (1-1), n21 and n22 are each independently defined as n2 in the formula (4).
N1+n21+n22+n3.gtoreq.1, n1+n21+n22+n3 is preferably 1 to 9, more preferably 1 to 5.
Specific examples of the 3 rd dichroic azo dye compound (a dichroic substance having a structure represented by the formula (1-1)) are shown below, but the present invention is not limited to these.
[ Chemical formula 16]
[ Chemical formula 17]
[ Chemical formula 18]
(Content of dichromatic substance)
The content of the dichroic material is preferably 1 to 30% by mass, more preferably 1 to 20% by mass, and even more preferably 2 to 10% by mass, based on the total solid content mass of the light absorbing anisotropic layer. When the content of the dichroic material is within the above range, a light absorbing anisotropic layer having a high degree of orientation can be easily obtained even when the light absorbing anisotropic layer is a thin film. Therefore, a light absorbing anisotropic layer excellent in flexibility is easily obtained. When the content of the dichroic material is 30 mass% or less, precipitation of the dichroic material is less likely to occur, and a light absorbing anisotropic layer having a high degree of orientation is easily obtained.
The liquid crystal composition may contain components other than the liquid crystal compound and the dichroic dye compound, and examples thereof include solvents, vertical aligning agents, surface modifiers, polymerizable components, polymerization initiators (for example, radical polymerization initiators), and the like. In this case, the light absorbing anisotropic layer in the present invention contains a solid component other than a liquid component (a solvent or the like).
The components will be described below.
(Surface modifier)
As the surface modifier, the surface modifiers described in the examples section below can be used.
When the liquid crystal composition contains a surface modifier, the content of the surface modifier is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total of the dichroic dye compound and the liquid crystalline compound in the liquid crystal composition.
(Polymerizable component)
Examples of the polymerizable component include a compound containing an acrylate (for example, an acrylate monomer). In this case, the light absorbing anisotropic layer in the present invention contains a polyacrylate obtained by polymerizing a compound containing the above-mentioned acrylate.
Examples of the polymerizable component include a compound described in paragraph 0058 of JP-A2017-122776.
When the liquid crystal composition contains a polymerizable component, the content of the polymerizable component is preferably 3 to 20 parts by mass based on 100 parts by mass of the total of the dichroic dye compound and the liquid crystal compound in the liquid crystal composition.
(Vertical alignment agent)
Examples of the vertical alignment agent include boric acid compounds and onium salts.
As the boric acid compound, a compound represented by the formula (30) is preferable.
(30)
[ Chemical formula 19]
In the formula (30), R 1 and R 2 each independently represent a hydrogen atom, a substituted or unsubstituted aliphatic hydrocarbon group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group.
R 3 represents a substituent containing a (meth) acryloyl group.
Specific examples of the boric acid compound include boric acid compounds represented by the general formula (I) described in paragraphs 0023 to 0032 of japanese patent application laid-open publication No. 2008-225281.
As the boric acid compound, the following exemplified compounds are also preferable.
[ Chemical formula 20]
I-34)
I-35)
I-36)
As the onium salt, a compound represented by the formula (31) is preferable.
(31)
[ Chemical formula 21]
In the formula (31), the ring A represents a quaternary ammonium ion composed of a nitrogen-containing heterocyclic ring. X represents an anion. L 1 represents a 2-valent linking group. L 2 represents a single bond or a 2-valent linking group. Y 1 represents a 2-valent linking group having a 5-or 6-membered ring as a partial structure. Z represents a 2-valent linking group having an alkylene group of 2 to 20 as a partial structure. P 1 and P 2 each independently represent a monovalent substituent having a polymerizable ethylenically unsaturated bond.
Specific examples of the onium salts include the onium salts described in paragraphs 0052 to 0058 of JP 2012-208397, the onium salts described in paragraphs 0024 to 0055 of JP 2008-026730, and the onium salts described in JP 2002-37777.
The content of the vertical alignment agent in the liquid crystal composition is preferably 0.1 to 400% by mass, more preferably 0.5 to 350% by mass, based on the total mass of the liquid crystal compound.
The vertical alignment agent may be used alone or in combination of 2 or more. When 2 or more vertical aligning agents are used, the total amount thereof is preferably within the above range.
(Leveling agent for vertical alignment)
In the case of vertical orientation, the following leveling agent is preferably contained. When the liquid crystal composition contains the leveling agent, it is possible to suppress surface roughness due to dry wind applied to the surface of the light absorbing anisotropic layer, and the dichroic material is further uniformly aligned.
The leveling agent is not particularly limited, but is preferably a fluorine atom-containing leveling agent (fluorine-based leveling agent) or a silicon atom-containing leveling agent (silicon-based leveling agent), and more preferably a fluorine-based leveling agent.
Examples of the fluorine-based leveling agent include fatty acid esters of polycarboxylic acids in which a part of the fatty acid is substituted with a fluoroalkyl group, and polyacrylates having a fluorine substituent. In particular, when a rod-shaped compound is used as the dichroic material and the liquid crystalline compound, a leveling agent containing a repeating unit derived from the compound represented by formula (40) is preferable from the viewpoint of promoting the vertical alignment of the dichroic material and the liquid crystalline compound.
(40)
[ Chemical formula 22]
R 0 represents a hydrogen atom, a halogen atom or a methyl group.
L represents a 2-valent linking group. L is preferably an alkylene group having 2 to 16 carbon atoms, any of the above-mentioned alkylene groups which are not adjacent to each other may be substituted by-O-; -COO-, -CO-or-CONH-substitution.
N represents an integer of 1 to 18.
The leveling agent having a repeating unit derived from the compound represented by the formula (40) may further contain other repeating units.
Examples of the other repeating unit include repeating units derived from the compound represented by formula (41).
(41)
[ Chemical formula 23]
R 11 represents a hydrogen atom, a halogen atom or a methyl group.
X represents an oxygen atom, a sulfur atom or-N (R 13)-.R13 represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms).
R 12 represents a hydrogen atom, an alkyl group which may have a substituent or an aromatic group which may have a substituent. The number of carbon atoms of the alkyl group is preferably 1 to 20. The alkyl group may be any of linear, branched, and cyclic.
Further, examples of the substituent which may have the above alkyl group include a poly (alkyleneoxy) group and a polymerizable group. The definition of the polymerizable groups is as described above.
In the case where the leveling agent contains a repeating unit derived from the compound represented by formula (40) and a repeating unit derived from the compound represented by formula (41), the content of the repeating unit derived from the compound represented by formula (40) is preferably 10 to 90 mol%, more preferably 15 to 95 mol% with respect to the total repeating units contained in the leveling agent.
In the case where the leveling agent contains a repeating unit derived from the compound represented by formula (40) and a repeating unit derived from the compound represented by formula (41), the content of the repeating unit derived from the compound represented by formula (41) is preferably 10 to 90 mol%, more preferably 5 to 85 mol% with respect to the total repeating units contained in the leveling agent.
Further, as the leveling agent, there may be mentioned a leveling agent containing a repeating unit derived from the compound represented by the formula (42) instead of the repeating unit derived from the compound represented by the formula (40).
(42)
[ Chemical formula 24]
R 2 represents a hydrogen atom, a halogen atom or a methyl group.
L 2 represents a 2-valent linking group.
N represents an integer of 1 to 18.
Specific examples of the leveling agent include the compounds exemplified in paragraphs 0046 to 0052 of JP-A2004-331812 and the compounds described in paragraphs 0038 to 0052 of JP-A2008-257205.
The content of the leveling agent in the liquid crystal composition is preferably 0.001 to 10 mass%, more preferably 0.01 to 5 mass%, based on the total mass of the liquid crystal compound.
The leveling agent may be used alone or in combination of 2 or more. When 2 or more leveling agents are used, the total amount thereof is preferably within the above range.
< Polymerization initiator >)
The liquid crystal composition preferably contains a polymerization initiator.
The polymerization initiator is not particularly limited, and is preferably a compound having photosensitivity, that is, a photopolymerization initiator.
As the photopolymerization initiator, various compounds can be used without particular limitation. Examples of the photopolymerization initiator include an α -carbonyl compound (U.S. Pat. No. 2367661, 2367670, the respective specifications of U.S. Pat. No. 2448828), an acyloin ether (U.S. Pat. No. 2448828), an α -hydrocarbon-substituted aromatic acyloin compound (U.S. Pat. No. 2722512), a polynuclear quinone compound (U.S. Pat. No. 3046127 and the respective specifications of U.S. Pat. No. 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (U.S. Pat. No. 3549367), an acridine phenazine compound (Japanese patent application publication No. 60-105667, japanese patent application publication No. 4239850), an oxadiazole compound (Japanese patent application publication No. 4212970), an orthoacyl oxime compound (Japanese patent application publication No. 2016-27384 [0065 ]), an acylphosphine oxide compound (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), and the like.
As such photopolymerization initiators, commercially available ones can be used, and examples thereof include IRGACURE184, IRGACURE907, IRGACURE369, IRGACURE651, IRGACURE819, IRGACUREOXE-01, IRGACUREOXE-02, etc. manufactured by BASF corporation.
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, based on 100 parts by mass of the total of the dichroic material and the liquid crystalline compound in the liquid crystal composition. When the content of the polymerization initiator is 0.01 parts by mass or more, durability of the light absorbing anisotropic layer becomes good, and when it is 30 parts by mass or less, the degree of orientation of the light absorbing anisotropic layer becomes more good.
The polymerization initiator may be used alone or in combination of 2 or more. When the polymerization initiator is contained in an amount of 2 or more, the total amount thereof is preferably within the above range.
Transparent substrate film
The organic EL display device of the present invention may have a transparent substrate film.
The transparent base film is preferably disposed on the viewing side of the light absorbing anisotropic layer in the organic EL display device.
As the transparent base film, a known transparent resin film, a transparent resin plate, a transparent resin sheet, or the like can be used, and is not particularly limited. As the transparent resin film, a cellulose acylate film (for example, a cellulose triacetate film (refractive index 1.48), a cellulose diacetate film, a cellulose acetate butyrate film, a cellulose acetate propionate film), a cyclic olefin resin film, a polyethylene terephthalate film, a polyether sulfone film, a polyacrylic resin film, a polyurethane resin film, a polyester film, a polycarbonate film, a polysulfone film, a polyether film, a polymethylpentene film, a polyetherketone film, a (meth) acrylonitrile film, or the like can be used.
Among them, cellulose acylate films which have high transparency, little optical birefringence and are easy to manufacture and are generally used as protective films for polarizing plates are preferable, and cellulose triacetate films are particularly preferable.
The thickness of the transparent base film is usually 20 μm to 100. Mu.m.
< Alignment film >
In the organic EL display device of the present invention, an alignment film may be provided between the transparent base film and the light absorbing anisotropic layer.
The alignment film may be any layer as long as the dichroic dye compound can be placed in a desired alignment state on the alignment film.
For example, a film formed of a polyfunctional acrylate compound or polyvinyl alcohol may be used.
Method for forming light-absorbing anisotropic layer
The method for forming the light absorbing anisotropic layer is not particularly limited, and examples thereof include the following steps in order: a step of forming a coating film by applying the liquid crystal composition (hereinafter, also referred to as a "composition for forming a light-absorbing anisotropic layer"); and a step of aligning the liquid crystalline component or the dichroic material contained in the coating film (hereinafter, also referred to as an "alignment step").
The liquid crystalline component is a component that contains not only the liquid crystalline compound but also a dichroic substance having liquid crystallinity when the dichroic substance has liquid crystallinity.
[ Coating film Forming Process ]
The coating film forming step is a step of forming a coating film by applying the composition for forming a light absorbing anisotropic layer.
The composition for forming a light-absorbing anisotropic layer can be easily applied by using a composition for forming a light-absorbing anisotropic layer containing the above-mentioned solvent or by using a substance in which the composition for forming a light-absorbing anisotropic layer is prepared as a liquid such as a solution by heating or the like.
Specific examples of the method for applying the composition for forming the light-absorbing anisotropic layer include known methods such as roll coating, gravure printing, spin coating, bar coating, extrusion coating, direct gravure coating, reverse gravure coating, die coating, spray coating, and inkjet coating.
[ Alignment procedure ]
The alignment step is a step of aligning the liquid crystal component contained in the coating film. Thus, a light absorbing anisotropic layer can be obtained.
The orientation process may have a drying process. The drying treatment can remove components such as a solvent from the coating film. The drying treatment may be performed by a method (for example, natural drying) of leaving the coating film at room temperature for a predetermined time, or may be performed by a method of heating and/or blowing.
Here, the liquid crystalline component contained in the composition for forming a light absorbing anisotropic layer may be oriented by the coating film forming step or the drying treatment. For example, in the manner in which the composition for forming a light absorbing anisotropic layer is prepared as a coating liquid containing a solvent, a coating film having light absorbing anisotropy (i.e., a light absorbing anisotropic film) can be obtained by drying the coating film to remove the solvent from the coating film.
In the case where the liquid crystalline component contained in the coating film is subjected to the drying treatment at a temperature equal to or higher than the transition temperature to the liquid crystal phase, the heating treatment to be described later may not be performed.
The transition temperature of the liquid crystalline component contained in the coating film to the liquid crystal phase is preferably 10 to 250 ℃, more preferably 25 to 190 ℃, from the viewpoint of manufacturing applicability and the like. If the transition temperature is 10 ℃ or higher, it is not necessary to perform a cooling treatment or the like for reducing the temperature to a temperature range in which the liquid crystal phase is present, and thus it is preferable. Further, when the above-mentioned transition temperature is 250 ℃ or lower, even when the liquid crystalline component is brought into an isotropic liquid state at a temperature higher than the temperature range in which the liquid crystalline phase is temporarily present, a high temperature is not required, and waste of heat energy, deformation and deterioration of the substrate, and the like can be reduced, which is preferable.
The orientation step preferably includes a heat treatment. In this way, the liquid crystalline component contained in the coating film can be oriented, and therefore, the coating film after the heat treatment can be preferably used as a light absorbing anisotropic film.
The heat treatment is preferably 10 to 250℃and more preferably 25 to 190℃in view of the production suitability and the like. The heating time is preferably 1 to 300 seconds, more preferably 1 to 60 seconds.
The orientation process may have a cooling process performed after the heating process. The cooling treatment is a treatment of cooling the heated coating film to about room temperature (20 to 25 ℃). This fixes the orientation of the liquid crystal component contained in the coating film. The cooling method is not particularly limited, and can be performed by a known method.
Through the above steps, a light absorbing anisotropic film can be obtained.
In the present embodiment, the method of aligning the liquid crystalline component contained in the coating film includes, but is not limited to, a drying process, a heating process, and the like, and can be performed by a known alignment process.
[ Other procedures ]
The method for forming the light absorbing anisotropic layer may include a step of curing the light absorbing anisotropic layer after the alignment step (hereinafter, also referred to as a "curing step").
For example, in the case where the light absorbing anisotropic layer has a crosslinkable group (polymerizable group), the curing step is performed by heating and/or light irradiation (exposure). Among them, the curing step is preferably performed by light irradiation.
The light source used for curing may be any of various light sources such as infrared light, visible light and ultraviolet light, but ultraviolet light is preferable. The ultraviolet rays may be irradiated while heating at the time of curing, or may be irradiated through a filter that transmits only a specific wavelength.
In the case of performing exposure while heating, the heating temperature at the time of exposure is also dependent on the transition temperature of the liquid crystalline component contained in the liquid crystal film to the liquid crystal phase, but is preferably 25 to 140 ℃.
Also, the exposure may be performed under a nitrogen atmosphere. In the case of curing the liquid crystal film by radical polymerization, inhibition of polymerization by oxygen can be reduced, and therefore, exposure under a nitrogen atmosphere is preferable.
The thickness of the light absorbing anisotropic layer is not particularly limited, but is preferably 100 to 8000nm, more preferably 100 to 1000nm, from the viewpoint of flexibility.
In the organic EL display device of the present invention, the light absorbing anisotropic layer may include only 1 layer, or may include 2 or more light absorbing anisotropic layers.
In the case where the organic EL display device of the present invention includes 2 or more light-absorbing anisotropic layers, each light-absorbing anisotropic layer may have the same structure or may have a different structure. The different structures may be different from each other in terms of the angle formed by the transmittance central axis of the light absorbing anisotropic layer and the normal line of the layer plane of the light absorbing anisotropic layer, or may be different from each other in terms of the dichroic material contained in the light absorbing anisotropic layer. By using light absorbing anisotropic layers of different structures in combination, it is possible to suppress color tone variations in a plurality of directions and/or a plurality of wavelength regions.
< Polarizer >)
The organic EL display device of the present invention may further have a polarizer. The polarizer is not particularly limited, and a known polarizer can be used. For example, the polarizer may be a polarizer in which a dichroic material is dyed with polyvinyl alcohol or other polymer resin and stretched to be oriented horizontally, or a polarizer in which a dichroic material is oriented horizontally by using the orientation of a liquid crystal compound as in the light absorbing anisotropic layer of the present invention, and particularly, a polarizer in which a dichroic material is oriented by using the orientation of liquid crystal without stretching is preferable.
Polarizers that use the orientation of liquid crystals to orient dichroic materials have several advantages: the thickness is about 0.1 μm to 5 μm, and the film can be made very thin; as described in japanese patent application laid-open No. 2019-194685, cracking or thermal deformation is less likely to occur at the time of bending; as described in japanese patent No. 6483486, even a polarizing plate having a high transmittance of more than 50% is excellent in durability and the like.
These advantages can be used for applications requiring high brightness, small size, and light weight, for applications of a fine optical system, for molding applications in a portion having a curved surface, and for applications in a flexible portion. In addition, when a polarizing plate having a high transmittance, for example, more than 50% is used in an organic EL display device having a reflectance of a screen display panel of less than 30%, both high brightness and suppression of a decrease in visibility due to reflection of external light can be achieved.
In the organic EL display device of the present invention, the polarizer is preferably disposed on the side of the organic EL display element with respect to the light absorbing anisotropic layer. That is, in the case where the organic EL display device of the present invention includes a polarizer, the light absorbing anisotropic layer is preferably disposed on the viewing side of the polarizer. With this configuration, the change in color tone in the oblique direction in white display can be suppressed.
Also, a polarizer may be used in combination with the lambda/4 film so as to function as a circular polarizer. That is, the organic EL display device of the present invention may include a circularly polarizing plate. In the case where the organic EL display device of the present invention includes a circularly polarizing plate, it is preferable that the organic EL display device includes a polarizer, a λ/4 thin film, and an organic EL display element in this order from the viewing side.
The λ/4 thin film is a plate (thin film) having a function of generating a phase difference of λ/4 corresponding to a wavelength λ, specifically, a plate (thin film) having a function of converting linearly polarized light of a certain specific wavelength into circularly polarized light (or converting circularly polarized light into linearly polarized light).
The lambda/4 film may be composed of a single optically anisotropic layer or may be composed of a plurality of optically anisotropic layers. For a λ/4 thin film composed of a plurality of optically anisotropic layers, for example, refer to paragraphs [0008] to [0053] of JP-A2014-209219.
For example, the λ/4 thin film has a single-layer structure, and specifically, a stretched polymer film, a retardation film having an optically anisotropic layer having a λ/4 function provided on a support, and the like are exemplified. The λ/4 plate has a multilayer structure, and specifically, a wide-band λ/4 plate formed by laminating a λ/4 plate and a λ/2 plate is exemplified.
The lambda/4 film may be in contact with a light absorbing anisotropic layer described later, or another layer may be provided therebetween. Examples of such a layer include an adhesive layer or an adhesive layer for ensuring adhesion.
< Polarization control layer >)
The organic EL display device of the present invention may further have a polarization control layer.
The polarization control layer refers to a layer that changes the state of polarized light of light incident on its layer.
As the polarization control layer, a retardation layer and a depolarization layer can be mentioned. Examples of the retardation layer include a λ/4 thin film.
In the case where the organic EL display device of the present invention includes the polarizer, the polarization control layer is preferably disposed on the viewing side of the polarizer.
[ Lambda/4 film ]
The λ/4 thin film of the organic EL display device of the present invention may be a plate having a function of generating a phase difference of λ/4 corresponding to the wavelength λ, and specifically, may be the same as the λ/4 thin film used in the circular polarizer. The lambda/4 film as the polarization control layer is a layer different from the lambda/4 film contained in the circular polarizing plate.
In the case where the organic EL display device of the present invention includes the λ/4 thin film as the polarization control layer and includes the polarizer, the λ/4 thin film is preferably disposed on the viewing side of the polarizer. With this configuration, the change in color tone in the oblique direction in white display can be suppressed.
In the case of using a lambda/4 film, rth of the light absorbing anisotropic layer at the maximum absorption wavelength is also preferably in the above preferred range (for example, -200 to-20 nm).
[ Depolarizing layer ]
The depolarizing layer that the organic EL display device of the present invention may have may be any type as long as it has the ability to convert part or all of the linearly polarized light into natural light (randomly polarized light). Among them, a random alignment liquid crystal layer or a layer containing fine particles is preferable in the present invention. In view of easy obtaining of depolarization ability, avoidance of whitening originating from regions within the layer, and easy obtaining of a transparent layer, a random-aligned liquid crystal layer is given as a particularly preferred embodiment.
(Randomly oriented liquid Crystal layer)
The randomly oriented liquid crystal layer refers to a layer in which the orientation direction of liquid crystal is randomly oriented in various directions in a liquid crystal state such as a nematic phase or a smectic phase. More preferably a randomly oriented liquid crystal layer as nematic phase. The randomly oriented liquid crystal layer can be produced by: a liquid crystal layer having a photopolymerizable group and a liquid crystal layer having a photopolymerization initiator are provided on a support which has not been subjected to an alignment treatment such as rubbing treatment, and the layer is heated as necessary to prepare a liquid crystal state (nematic phase, smectic phase, etc.), and the alignment state is immobilized by exposure to ultraviolet light.
[ Microparticle-containing layer ]
The depolarization layer may be formed using a layer that generates light scattering to some extent inside the layer, in addition to the above-described random alignment liquid crystal layer. Depolarization occurs when light is scattered within the layer. The fine particles may be inorganic particles such as silica, alumina, zirconium, and zirconia, or organic fine particles such as an acrylic resin, a melamine resin, and a polyamide resin. Various sizes having diameters of about 0.1 to 3 μm can be used. The shape may be spherical, rod-like, fibrous, or the like. The degree of depolarization can also be adjusted by using these.
As the depolarizing film, japanese patent application laid-open publication 2012-027259 and japanese patent application laid-open publication 2011-257479 are described in detail, and reference is also made thereto.
Barrier layer >, barrier layer
The organic EL display device of the present invention preferably has a barrier layer.
The barrier layer is also referred to as a gas barrier layer (oxygen barrier layer), and has a function of protecting the polarizing element of the present invention from a gas such as oxygen in the atmosphere, moisture, or a compound contained in an adjacent layer.
For the barrier layer, for example, references can be made to paragraphs [0014] to [0054] of JP-A2014-159724, paragraphs [0042] to [0075] of JP-A2017-121721, paragraphs [0045] to [0054] of JP-A2017-115076, paragraphs [0010] to [0061] of JP-A2012-213938, and paragraphs [0021] to [0031] of JP-A2005-169994.
< Refractive index adjusting layer >)
In the organic EL display device of the present invention, the light absorbing anisotropic layer has a dichroic material, and internal reflection due to the high refractive index of the light absorbing anisotropic layer may be a problem. In this case, the refractive index adjustment layer is preferably present. The refractive index adjustment layer is a layer disposed so as to contact the light absorbing anisotropic layer, and preferably has an in-plane average refractive index of 1.55 to 1.70 at a wavelength of 550 nm. The refractive index adjusting layer is also preferably used for so-called refractive index matching.
< Tone adjustment layer >)
The organic EL display device of the present invention may include a color tone adjustment layer having at least 1 pigment compound. The pigment compound contained in the color tone adjustment layer is preferably in a non-oriented state.
In the case of adjusting the pigment amount of the light absorbing anisotropic layer, there is a case where a change in color tone viewed from the oblique direction with respect to the central axis of transmittance becomes large, but in this case, by adjusting the color tone using the color tone adjusting layer, a change in color tone viewed from the oblique direction with respect to the central axis of transmittance can be suppressed.
The tone adjustment layer may have only a function of the tone adjustment layer alone or may be combined with other layers.
The absorption peak wavelength of the pigment compound contained in the color tone adjustment layer used in the present invention is preferably 500nm to 650nm, more preferably 550nm to 600 nm. By setting the absorption of the pigment compound within this range, the color tone of the organic EL display device of the present invention can be adjusted to be more neutral.
Examples of the dye compound contained in the color tone adjustment layer include azo, methine, anthraquinone, triarylmethane, oxazine, azomethine, phthalocyanine, porphyrin, perylene, pyrrolopyrrole, squaraine, and the like, and azo, phthalocyanine, and anthraquinone are preferable, and anthraquinone is particularly preferable from the viewpoint of excellent absorption waveform, heat resistance, and light resistance. Examples thereof include pigment compounds described in Dachuan original, songgangxian, ping Daoheng Liang, bei-tikou Kong, functional pigments, kodansha Ltd., 1992, time Tian Chengnan, electronic materials, CMC Publishing Co., ltd., 1998, and the like.
Specific examples of the pigment compound used in the color tone adjustment layer of the present invention are described below, but the pigment compound is not limited to these.
Anthraquinone
[ Chemical formula 25]
Azo
[ Chemical formula 26]
Triarylmethane
[ Chemical formula 27]
Oxazines
[ Chemical formula 28]
Phthalocyanine
[ Chemical formula 29]
/>
< Adhesive layer >)
The organic EL display device of the present invention may have an adhesive layer.
The adhesive layer in the present invention is preferably a transparent and optically isotropic adhesive similar to the adhesive layer used in a general liquid crystal display device, and a pressure sensitive adhesive is generally used.
In the adhesive layer of the present invention, in addition to the base material (adhesive), the conductive particles, and the thermally expandable particles used as needed, a crosslinking agent (for example, an isocyanate-based crosslinking agent, an epoxy-based crosslinking agent, or the like), a tackifier (for example, a rosin derivative resin, a polyterpene resin, a petroleum resin, an oil-soluble phenol resin, or the like), a plasticizer, a filler, an aging inhibitor, a surfactant, an ultraviolet absorber, a light stabilizer, an antioxidant, or the like may be blended.
The thickness of the adhesive layer is usually 3 to 200. Mu.m, preferably 5 to 30. Mu.m. If the thickness is less than 3 μm, the desired adhesion or reworkability may not be obtained, and if the thickness exceeds 200 μm, the adhesive may protrude or ooze from the peripheral edge of the image display device.
The formation of the adhesive layer can be performed by an appropriate method such as the following method: a method of directly coating a base material, conductive particles, and a coating liquid containing thermally expandable particles, additives, solvents, and the like as needed on the support 110 for a protective member and pressure-bonding via a release liner, a method of coating a coating liquid on an appropriate release liner (release paper, and the like) to form a thermally expandable adhesive layer and pressure-bonding and transferring (transferring) the layer to the support 110 for a protective member, and the like.
On the other hand, as the protective member, for example, a structure in which conductive particles are added to a structure of a heat peelable adhesive sheet described in japanese unexamined patent publication No. 2003-29292916 or the like is applicable.
As the protective member, a member obtained by dispersing conductive particles on the surface of an adhesive layer in a commercially available product such as "revapha" manufactured by Nitto Denko Corporation can be used.
< Adhesive layer >)
In the present invention, an adhesive may be used in the case of bonding the above-described members. That is, the organic EL display device of the present invention may have an adhesive layer.
The adhesive exhibits adhesion by drying or reaction after bonding.
Polyvinyl alcohol adhesives (PVA adhesives) exhibit adhesiveness by drying, and can bond materials to each other.
Specific examples of the curable adhesive exhibiting adhesiveness by the reaction include an active energy ray curable adhesive such as a (meth) acrylate adhesive and a cationic polymerization curable adhesive. In addition, (meth) acrylate means acrylate and/or methacrylate. Examples of the curable component in the (meth) acrylate adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group. As the cationic polymerization curable adhesive, a compound having an epoxy group or an oxetane group can be used. The compound having an epoxy group is not particularly limited as long as it has at least 2 epoxy groups in the molecule, and various conventionally known curable epoxy compounds can be used. Examples of the preferable epoxy compound include a compound having at least 2 epoxy groups and at least 1 aromatic ring in the molecule (aromatic epoxy compound), a compound having at least 2 epoxy groups in the molecule and at least 1 of them being formed between adjacent 2 carbon atoms constituting an alicyclic ring (alicyclic epoxy compound), and the like.
Among them, an ultraviolet-curable adhesive cured by ultraviolet irradiation is preferably used from the viewpoint of heat deformation resistance.
The adhesive layer or each layer of the adhesive layer may be a layer or the like having ultraviolet absorption ability by: and a method of treating with an ultraviolet absorber such as a salicylate compound, a benzophenol compound, a benzotriazole compound, a cyanoacrylate compound, or a nickel complex salt compound.
The adhesive layer on the object can be attached by an appropriate method. Examples thereof include a method of preparing a binder solution of about 10 to 40% by weight in which a base polymer or a composition thereof is dissolved or dispersed in a solvent composed of a single or a mixture of an appropriate solvent such as toluene or ethyl acetate, and directly attaching the binder solution to an object by an appropriate development method such as a casting method or a coating method, a method of forming an adhesive layer on a separator, and the like.
The adhesive layer or the adhesive layer may be provided on one side or both sides of the film as a stacked layer of layers having different compositions, types, or the like. In addition, when the adhesive layer or the adhesive layer is provided on both surfaces of the object, the adhesive layer or the adhesive layer having different compositions, types, thicknesses, and the like can be provided on the front surface and the rear surface of the object.
< Organic EL display element >)
The organic EL display device of the present invention includes an organic EL display element.
The organic EL display device can use a known device. For example, an organic EL display element includes a display element in which a light-emitting layer or a plurality of organic compound films including a light-emitting layer are formed between a pair of electrodes of an anode and a cathode. The organic compound film may have a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like in addition to the light-emitting layer, and each of these layers may have other functions. The layers such as the electrode and the organic compound film of the organic EL display element can be formed by a known material and method.
Among them, an organic EL display element having a red organic EL element, a green organic EL element, and a blue organic EL element is preferable. The red organic EL element, the green organic EL element, and the blue organic EL element preferably have microcavity structures.
As an example of the organic EL display element described above, an organic EL display element (hereinafter, also referred to as "organic EL display element X") having a Δu 'v' (60 °) of more than 0.005 represented by the following formula (3A) on the CIE1976u 'v' chromaticity diagram in white display is given.
And (3A)Δu'v'(60°)=√{(u'(0°,60°)-u'(180°,60°))2+(v'(0°,60°)-v'(180°,60°))2}+√{(u'(90°,60°)-u'(270°,60°))2+(v'(90°,60°)-v'(270°,60°))2}
In the formula (3A), u '(a°, b°) is a u' value in an azimuth angle a° and a polar angle b° on the CIE1976 u 'v' chromaticity diagram, and v '(a°, b°) is a v' value in an azimuth angle a° and a polar angle b° on the CIE1976 u 'v' chromaticity diagram. The azimuth angle is an angle that increases counterclockwise with respect to the azimuth from the lower direction toward the upper direction in the plane of the display region when the display region of the organic EL display device is viewed from the vertical direction.
In addition, a known colorimeter (for example, EZ-Contrast XL88 manufactured by ELDIM COMPANY and SR-UL1R manufactured by TOPCON CORPORATION TECHNOHOUSE CORPORATION) can be used for the measurement of the chromaticity.
The above Δu 'v' (60 °) of more than 0.005 means that the color tone of the white display is different depending on the azimuth angle when the organic EL display element is viewed from a direction inclined from the front direction.
In the case where the organic EL display element X is used in the organic EL display device of the present invention, in at least 1 or more light absorbing anisotropic layers, an angle formed between a transmittance central axis of the light absorbing anisotropic layer and a normal line of a layer plane of the light absorbing anisotropic layer is preferably 15 ° or more and 45 ° or less. By setting the range in the above preferred range, when the organic EL display element X is used, it is easier to suppress the change in color tone when white display is visually recognized from an oblique direction.
In the case of using the organic EL display element X, it is also preferable to use a combination of a light absorbing anisotropic layer having an angle of 10 ° or more and 45 ° or less (more preferably 15 ° or more and 45 ° or less) with a light absorbing anisotropic layer having an angle of 0 ° or more and 10 ° or less (more preferably 0 °).
The maximum absorption wavelength of the light absorbing anisotropic layer can be adjusted according to the organic EL display element X.
In the above embodiments, the polarizer and the polarization control layer are preferably further included. In this case, in the organic EL display device, it is preferable to stack the polarization control layer, the light absorbing anisotropic layer, and the polarizer in this order from the viewing side.
As an example of the organic EL display element described above, an organic EL display element (hereinafter, also referred to as "organic EL display element Y") satisfying the relationship of u ' (0 °) > u ' (30 °) > u ' (60 °) and satisfying the relationship of v ' (0 °) > v ' (30 °) and v ' (0 °) > v ' (60 °) in white display is given.
Here, u '(c°) is an average value of u' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram, and v '(c°) is an average value of v' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram.
The average value of u ' values in the polar angle c° in the all azimuth angle means an arithmetic average value of u ' values measured at the polar angle c° and u ' values measured at the all azimuth angle while changing the azimuth angle every 5 °.
The average value of v ' values in the polar angle c ° in the all azimuth angle means an arithmetic average value of v ' values measured at the polar angle b ° and v ' values measured at the all azimuth angle while changing the azimuth angle every 5 °.
The colorimeter described above can be used for the measurement of the chromaticity.
In the case where the relationship between u '(c) and v' (c) is satisfied, it is indicated that the polar angle increases from 0 ° to 30 ° and from 30 ° to 60 ° in the CIE1976 u 'v' chromaticity diagram to be displaced in the substantially lower left direction. That is, it means that as the polar angle of visual recognition increases from 0 ° to 30 °, from 30 ° to 60 °, the tone of white display changes from a substantially neutral tone to a blue tone.
In the case where the organic EL display element Y is used in the organic EL display device of the present invention, in at least 1 or more light absorbing anisotropic layers, an angle formed by a transmittance central axis of the light absorbing anisotropic layer and a normal line of a layer plane of the light absorbing anisotropic layer is preferably 0 ° or more and 10 ° or less (more preferably 0 °). Further, the maximum absorption wavelength of the light absorbing anisotropic layer is preferably in the range of 460 to 500 nm. By setting the ranges in the above-described preferred ranges, when the organic EL display element Y is used, it is easier to suppress the change in color tone when white display is visually recognized from an oblique direction.
In the above embodiments, the polarizer and the polarization control layer are preferably further included. In this case, in the organic EL display device, it is preferable to stack the light absorbing anisotropic layer, the polarization control layer, and the polarizer in this order from the viewing side.
As an example of the organic EL display element described above, an organic EL display element (hereinafter, also referred to as "organic EL display element Z") satisfying the relationship of u '(0) > u' (30 °) and u '(0 °) > u' (60 °) and satisfying the relationship of v '(0 °) > v' (30 °) and v '(30 °) < v' (60 °) in white display is given.
The definition of u '(c) and v' (c) is the same as the definition described above.
When the relationship between u '(c) and v' (c) is satisfied, the CIE1976 u 'v' chromaticity diagram shows a displacement in the substantially lower left direction when the visually recognized polar angle is changed from 0 ° to 30 °. Further, when the angle is changed from 30 ° to 60 °, the displacement is substantially in the upward direction on the CIE1976 u 'v' chromaticity diagram. That is, when the viewing angle is changed from 0 ° to 30 °, the color tone of the white display is changed from the substantially blue color to the green color tone, and when the viewing angle is changed from 30 ° to 60 °, the color tone of the white display is changed to the substantially green color tone.
In the case where the organic EL display element Z is used in the organic EL display device of the present invention, in at least 1 or more light absorbing anisotropic layers, an angle formed by a transmittance central axis of the light absorbing anisotropic layer and a normal line of a layer plane of the light absorbing anisotropic layer is preferably 0 ° or more and 10 ° or less (more preferably 0 °). Further, the maximum absorption wavelength of the light absorbing anisotropic layer is preferably in the range of 510 to 570 nm. By setting the ranges in the above-described preferred ranges, when the organic EL display element Z is used, it is easier to suppress the change in color tone when white display is visually recognized from an oblique direction.
In the above embodiments, the polarizer and the polarization control layer are preferably further included. In this case, in the organic EL display device, it is preferable to stack the light absorbing anisotropic layer, the polarization control layer, and the polarizer in this order from the viewing side.
Examples
Hereinafter, the present invention will be specifically described with reference to examples. The materials, reagents, mass, proportion thereof, operations and the like shown in the following examples can be appropriately changed without departing from the gist of the present invention. Accordingly, the present invention is not limited to the following examples.
Example 1 >
[ Formation of oriented film ]
The surface of a cellulose acylate film (TAC substrate having a thickness of 40 μm; TG40 FUJIFILM Corporation) was saponified in an alkaline solution, and the following composition 1 for forming an alignment film was applied thereon with a wire bar. The support having the coating film formed thereon was dried under warm air at 60℃for 60 seconds, and further dried under warm air at 100℃for 120 seconds to form an alignment film AL1, thereby obtaining a cellulose acylate film 1 with an alignment film. The thickness of the alignment film AL1 was 1. Mu.m.
Modified polyvinyl alcohol PVA-1
[ Chemical formula 30]
[ Formation of light absorbing Anisotropic layer P1 ]
The following composition P1 for forming a light-absorbing anisotropic layer was continuously applied onto the obtained alignment film AL1 with a wire bar, heated at 125 ℃ for 60 seconds, and cooled to room temperature (23 ℃).
Then, an LED lamp (center wavelength 365 nm) was used to irradiate ultraviolet light under irradiation conditions of illuminance 200mW/cm 2 for 2 seconds, thereby producing a light absorption anisotropic layer P1 on the alignment film AL 1. The film thickness of the light absorbing anisotropic layer P1 was 0.18. Mu.m.
In addition, it was confirmed that the high-molecular liquid crystalline compound P-1 and the low-molecular liquid crystalline compound M-1 were each positive wavelength dispersive liquid crystalline compounds.
Dichromatic substance D-1
[ Chemical formula 31]
Polymer liquid Crystal Compound P-1
[ Chemical formula 32]
Low molecular liquid crystalline compound M-1
[ Chemical formula 33]
Compound E-1
[ Chemical formula 34]
Compound E-2
[ Chemical formula 35]
Surfactant F-1
[ Chemical formula 36]
[ Formation of oxygen Barrier layer B1 ]
A coating liquid (oxygen barrier layer-forming composition B1) having the following composition was continuously applied onto the formed light-absorbing anisotropic layer P1 with a wire bar. Then, it was dried under warm air at 100℃for 2 minutes, thereby forming a polyvinyl alcohol (PVA) alignment layer (oxygen barrier layer B1) having a thickness of 0.5 μm on the light absorbing anisotropic layer P1.
Thus, an optical film 1 including a cellulose acylate film, a photoalignment layer AL1, a light absorbing anisotropic layer P1, and an oxygen barrier layer B1 in this order was obtained.
Modified polyvinyl alcohol
[ Chemical formula 37]
/>
[ Production of lambda/4 film ]
The coating liquid PA1 for forming a photo-alignment film having the following composition was continuously applied to the cellulose acylate film with a bar, thereby forming a coating film. The support on which the coating film was formed was dried under warm air at 140℃for 120 seconds, and then, the coating film was irradiated with polarized ultraviolet rays (10 mJ/cm 2, using an ultra-high pressure mercury lamp), thereby forming a photo-alignment film PA1 having a thickness of 0.2. Mu.m, to obtain a cellulose acylate film with a photo-alignment film.
Polymer PA-1
[ Chemical formula 38]
Acid generator PAG-1
[ Chemical formula 39]
Acid generator CPI-110TF
[ Chemical formula 40]
Composition A-1 having the following composition was applied to the above photo-alignment film PA1 by a bar coater. The coating film formed on the photo-alignment film PA1 was heated to 120 ℃ by warm air, then cooled to 60 ℃, and then irradiated with ultraviolet light of 100mJ/cm 2 at a wavelength of 365nm using a high-pressure mercury lamp under a nitrogen atmosphere, and then irradiated with ultraviolet light of 500mJ/cm 2 while heating to 120 ℃, whereby the alignment of the liquid crystalline compound was immobilized, and a cellulose acylate film A1 having a λ/4 retardation layer A1 was produced.
The thickness of the lambda/4 retardation layer A1 was 2.5. Mu.m, and Re (550) was 144nm. And, the positive A plate A1 satisfies the relationship of Re (450) to Re (550) to Re (650). Re (450)/Re (550) was 0.82.
Polymerizable liquid crystalline compound LA-1 (tBu represents t-butyl)
[ Chemical formula 41]
Polymerizable liquid crystalline compound LA-2
[ Chemical formula 42]
Polymerizable liquid crystalline compound LA-3
[ Chemical formula 43]
Polymerizable liquid crystalline compound LA-4 (Me represents a methyl group)
[ Chemical formula 44]
Polymerization initiator PI-1
[ Chemical formula 45]
Leveling agent T-1
[ Chemical formula 46]
[ Production of polarizer C1 ]
A polarizer 1 having a polarizer thickness of 8 μm and one side surface of the polarizer exposed and the other side surface protected by the protective film was produced by the same method as the polarizer 02 with the one side surface protective film described in international publication No. 2015/166991.
The optical film A1 was bonded to both surfaces of the polarizer-exposed surface and the protective film-side surface of the polarizer 1 with a commercially available adhesive (Soken Chemical & Engineering co., ltd., ltd.) so that the retardation sides of the optical film A1 including the λ/4 retardation layer were opposed to each other. The optical film 1 was bonded to the optical film A1 bonded to the surface exposed to the polarizer by a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057) so that the oxygen barrier layer B1 side of the optical film 1 including the optically anisotropic absorbing layer produced in the above-described step was the optical film A1 side, thereby obtaining a polarizing plate C1.
[ Production of organic EL display device 1]
The Apple inc APPLE WATCH SERIES (r) product having an organic EL panel (organic EL display device) mounted thereon was decomposed, and the organic EL display device was taken out. Then, the circularly polarizing plate was peeled off from the organic EL display device, and the organic EL display element was taken out. The polarizing plate C1 produced in the above-described step was bonded to the organic EL display element using a commercially available adhesive (Soken Chemical & engineering co., ltd., SK 2057) instead of the peeled circular polarizing plate so that the optically anisotropic absorbing layer became the viewing side. Through the above steps, the organic EL display device 1 used in example 1 was produced.
Example 2 >
[ Formation of light absorbing Anisotropic layer P2-1 ]
In the production of the light absorbing anisotropic layer P1, the optical film 2-1 was produced in the same manner as in the light absorbing anisotropic layer P1, except that the coating amount was adjusted so that the film thickness of the light absorbing anisotropic layer became 0.2 μm, and after coating, the coating was heated at 125 ℃ for 60 seconds, cooled to room temperature (23 ℃) and then heated at 85 ℃ for 60 seconds, cooled again to room temperature.
[ Formation of light absorbing Anisotropic layer P2-2 ]
The light absorbing anisotropic layer with pigment obliquely oriented was produced as follows.
(Production of transparent support 1 with second alignment layer)
The surface of a cellulose acylate film (TAC substrate having a thickness of 40 μm; TG40 fujifilco., ltd.) was saponified with an alkaline solution, and the following composition for forming an alignment film was coated thereon with a wire bar. The support having the coating film formed thereon was dried under warm air at 60 ℃ for 60 seconds, and further dried under warm air at 100 ℃ for 120 seconds to form the second alignment layer 1, thereby obtaining a cellulose acylate film with an alignment layer. The film thickness of the second alignment layer 1 was 0.5. Mu.m.
Further, the surface of the orientation film layer of the produced cellulose acylate film having the second orientation layer was subjected to a rubbing treatment.
(Fabrication of first alignment layer)
The first alignment layer forming composition 1 having the following composition was applied onto the second alignment film of the cellulose acylate film with the second alignment layer thus produced using a bar, to produce a first coating layer T1.
Next, the first coating layer T1 was heated at 120 ℃ for 30 seconds, and the coating layer T1 was cooled to become room temperature (23 ℃). Further, the mixture was heated at 80℃for 60 seconds and cooled again to room temperature.
Then, an LED lamp (center wavelength 365 nm) was used to irradiate ultraviolet light under irradiation conditions of an illuminance of 200mW/cm 2 for 1 second, thereby producing a first alignment layer T1 on the second alignment layer 1.
The film thickness of the first alignment layer T1 was 0.64. Mu.m.
[ Formation of light absorbing Anisotropic layer P2-2 ]
The following composition P2 for forming a light-absorbing anisotropic layer was continuously applied onto the obtained alignment film T1 by a wire bar, heated at 150 ℃ for 60 seconds, cooled to room temperature (23 ℃) and then heated at 75 ℃ for 60 seconds, and cooled again to room temperature.
Then, an LED lamp (center wavelength 365 nm) was used to irradiate ultraviolet light under irradiation conditions of an illuminance of 200mW/cm 2 for 2 seconds, thereby producing a light absorption anisotropic layer P2-2 on the alignment layer T1.
The film thickness of the light absorbing anisotropic layer P2-2 was 0.4. Mu.m. Next, in the same manner as in example 1, an oxygen barrier layer B1 was formed on the light absorbing anisotropic layer P2-2, and an optical film 2-2 was produced.
Dichromatic substance D-2
[ Chemical formula 47]
< Production of polarizer C2 >
First, the polarizing plate 1 used in example 1 was produced in the same manner as in example 1.
Next, the optical film A1 was bonded with a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057) so that the protective film side surface of the polarizing plate 1 faced the retardation side surface of the optical film A1 including the λ/4 retardation layer. The optical film 2-1 was bonded to the exposed surface of the polarizer with a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057) so that the oxygen barrier layer B1 side of the optical film 2-1 including the optically anisotropic absorbing layer produced in the above-described step was the optical film A1 side. Next, the optical film 2-2 and the optical film 2-1 were bonded with a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057) so that the oxygen barrier layer B1 side of the optical film 2-2 including the optically anisotropic absorption layer produced as described above was the optical film A1 side, thereby obtaining a polarizing plate C2.
< Fabrication of organic EL display device 2>
An organic EL display device 2 used in example 2 was produced in the same manner as in example 1 except that the polarizing plate C1 was changed to the polarizing plate C2 in the production of the organic EL display device 1. However, the polarizing plate C2 was attached to the organic EL display device so that the azimuth direction of the central axis of the transmission axis of the optical film 2-2 became 0 ° with respect to the azimuth from the lower direction to the upper direction in the plane of the organic EL display device.
Example 3 >
[ Production of optical film 3 ]
In the production of the optical film 1 of example 1, an optical film 3 including the light absorbing anisotropic layer P3 was produced in the same manner except that the light absorbing anisotropic layer-forming composition P1 was changed to the light absorbing anisotropic layer-forming composition P3, the coating amount was adjusted so that the film thickness of the light absorbing anisotropic layer became 0.5 μm, and after coating, the film was heated at 150 ℃ for 60 seconds, cooled to room temperature (23 ℃) and then heated at 75 ℃ for 60 seconds, and cooled again to room temperature.
Dichromatic substance D-3
[ Chemical formula 48]
[ Production of organic EL display device 3 ]
An organic EL display device 3 was produced in the same manner as in example 1 except that the optical film 3 was used in the production of the organic EL display device 1 by changing Apple inc. APPLE WATCH SERIES to Apple inc. IPhone (registered trademark) 12 Pro.
Example 4 >
An organic EL display device 4 was produced in the same manner as in example 3 except that the composition P3 for forming a light-absorbing anisotropic layer was changed to the composition P4 for forming a light-absorbing anisotropic layer in the production of the optical film 3 of example 3. The light absorbing anisotropic layer contained in the optical film 4 produced in example 4 is also referred to as a light absorbing anisotropic layer P4.
Dichromatic substance D-4
[ Chemical formula 49]
Example 5 >
[ Production of optical film 5 ]
In the production of the optical film 3 of example 3, an optical film 5 including the light absorbing anisotropic layer P5 was produced in the same manner as in example 3 except that the light absorbing anisotropic layer forming composition P3 was changed to the light absorbing anisotropic layer forming composition P5 and the coating amount was adjusted so that the film thickness of the light absorbing anisotropic layer became 0.3 μm.
[ Production of organic EL display device 5 ]
An organic EL display device 5 was produced in the same manner as in example 1 except that the optical film 5 was used in the production of the organic EL display device 1 by changing Apple inc. APPLE WATCH SERIES to Apple inc. IPhone (registered trademark) 12.
Example 6 >
In the production of the optical film 1 of example 1, an optical film 6 including the light absorbing anisotropic layer P6 was produced in the same manner as in example 1, except that the optical film was heated at 125 ℃ for 60 seconds, then cooled to room temperature (23 ℃) and then heated at 85 ℃ for 60 seconds, and then cooled again to room temperature. An organic EL display device 6 was produced in the same manner as in example 1 except that the produced optical film 6 was used instead of the optical film 1.
Example 7 >
An organic EL display device 7 was produced in the same manner as in example 4 except that the composition P4 for forming a light-absorbing anisotropic layer was changed to the composition P7 for forming a light-absorbing anisotropic layer in the formation of a light-absorbing anisotropic layer in example 4. The light absorbing anisotropic layer contained in the optical film 7 produced in example 7 is also referred to as a light absorbing anisotropic layer P7.
Dichromatic substance D-5
[ Chemical formula 50]
Example 8 >
An optical film 8 including a light-absorbing anisotropic layer P8 was produced in the same manner as in example 5, except that the light-absorbing anisotropic layer-forming composition P5 was changed to the light-absorbing anisotropic layer-forming composition P8 in the production of the optical film 5 of example 5. An organic EL display device 8 was produced in the same manner as in example 5 except that the produced optical film 8 was used instead of the optical film 5.
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Example 9 >
[ Production of optical film 9 ]
In the production of the optical film 6 of example 6, an optical film 9 including the light absorbing anisotropic layer P9 was produced in the same manner except that the coating amount was adjusted so that the film thickness of the light absorbing anisotropic film became 0.35 μm.
[ Production of organic EL display device 9 ]
An organic EL display device 9 was produced in the same manner as in example 8 except that the optical film 8 was changed to the optical film 9 in the production of the organic EL display device 8.
Example 10 >
An organic EL display device 10 was produced in the same manner as in example 7 except that the optical film A1 (λ/4 film) attached to the viewing side was changed to COSMOSHINE super-birefringent type (SRF, toyobo co., ltd.) (polarizing film) in example 7.
Example 11 >
[ Formation of light absorbing Anisotropic layer P11 ]
In the production of the light-absorbing anisotropic layer P2-2, the first alignment film was coated by changing the light-absorbing anisotropic layer-forming composition P2 to the light-absorbing anisotropic layer-forming composition P11 and adjusting the coating amount so that the film thickness of the light-absorbing anisotropic layer became 0.2 μm. At this time, the thickness of the first alignment film was adjusted to be thicker so that the central axis of transmittance of the light absorbing anisotropic film became 10 °. An optical film 11 including the light absorbing anisotropic layer P11 was produced in the same manner as the light absorbing anisotropic layer P2-2 except that after the application, the film was heated at 125 ℃ for 60 seconds, then cooled to room temperature (23 ℃) and then heated at 85 ℃ for 60 seconds, and cooled again to room temperature.
[ Production of organic EL display device 11 ]
An organic EL display device 11 was produced in the same manner as in example 6 except that the optical film 6 was changed to the optical film 9 and the optical film 11 was bonded to the optical film 9 with a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057). But is attached to the organic EL display device such that the azimuth direction of the central axis of the transmission axis of the optical film 11 is 180 ° with respect to the azimuth from the lower direction to the upper direction in the plane of the organic EL display device.
Example 12 >
An organic EL display device 12 was produced in the same manner as in example 11 except that the optical film 9 was changed to the optical film 2-1 and the optical film 11 was changed to the optical film 2-2 in the production of the organic EL display device 11 of example 11. But is bonded to the organic EL display device such that the azimuth direction of the transmission axis center axis of the optical film 2-2 becomes 0 ° with respect to the azimuth from the lower direction to the upper direction in the plane of the organic EL display device.
Example 13 >
An organic EL display device 13 was produced in the same manner as in example 2 except that the optical film A1 was bonded to the optical film P2-2 in the production of the organic EL display device 2 of example 2.
Example 14 >
[ Formation of light absorbing Anisotropic layer P14 ]
An optical film 14 having a light-absorbing anisotropic layer P14 was produced in the same manner as in example 1, except that in the production of the optical film 1 of example 1, the light-absorbing anisotropic layer-forming composition P1 was changed to the light-absorbing anisotropic layer-forming composition P14, the coating amount was adjusted so that the film thickness of the light-absorbing anisotropic film became 1 μm, and after coating, the film was heated at 150 ℃ for 60 seconds, cooled to room temperature (23 ℃) and then heated at 70 ℃ for 60 seconds, and cooled again to room temperature.
[ Production of organic EL display device 14 ]
The optical film 14 produced in the above was bonded to a display screen of a Galaxy Z fold3 5G (a commercially available organic EL display device without a polarizing plate) produced by Samsung corporation on which an organic EL panel (organic EL display element) was mounted, using a commercially available adhesive (Soken Chemical & Engineering co., ltd., SK 2057), and the organic EL display device 14 was produced.
Example 15 >
An organic EL display device 15 was produced in the same manner as in example 14 except that the composition P14 for forming a light-absorbing anisotropic layer was changed to the composition P15 for forming a light-absorbing anisotropic layer in example 14.
Example 16 >
An organic EL display device 16 was produced in the same manner as in example 7 except that the composition P7 for forming a light-absorbing anisotropic layer was changed to the composition P16 for forming a light-absorbing anisotropic layer in example 7.
Example 17 >
An organic EL display device 17 was produced in the same manner as in example 6 except that the composition P1 for forming a light-absorbing anisotropic layer was changed to the composition P17 for forming a light-absorbing anisotropic layer in example 6.
In addition, it was confirmed that the low-molecular liquid crystalline compound M-2 and the low-molecular liquid crystalline compound M-3 were each a positive wavelength dispersive liquid crystalline compound.
Dichromatic substance D-6
[ Chemical formula 51]
Low molecular liquid crystalline compound M-2
[ Chemical formula 52]
Low molecular liquid crystalline compound M-3
[ Chemical formula 53]
Example 18 >
An organic EL display device 18 was produced in the same manner as in example 3 except that the composition P3 for forming a light-absorbing anisotropic layer was changed to the composition P18 for forming a light-absorbing anisotropic layer in example 3.
Dichromatic substance D-7
[ Chemical formula 54]
Comparative example 1 >
An organic EL display device B1 was produced in the same manner as in example 1 except that the optical film 1 was not bonded in the production of the organic EL display device 1 of example 1.
Comparative example 2 >
An organic EL display device B2 was produced in the same manner as in comparative example 1 except that in comparative example 1, apple inc. APPLE WATCH SERIES was changed to Apple inc. IPhone (registered trademark) 12.
Comparative example 3 >
An organic EL display device B3 was produced in the same manner as in comparative example 1 except that in comparative example 1, apple inc. APPLE WATCH SERIES was changed to Apple inc. IPhone (registered trademark) 12 Pro.
Comparative example 4 >
An organic EL display device B4 was produced in the same manner as in example 1 except that the coating amount was adjusted so that the film thickness of the light absorbing anisotropic layer became 0.03 μm in the production of the optical film 1 of example 1. The light absorbing anisotropic layer contained in the optical film B4 produced in comparative example 4 is also referred to as a light absorbing anisotropic layer PB4.
Comparative example 5 >
An organic EL display device B5 was produced in the same manner as in example 1 except that the coating amount was adjusted so that the film thickness of the light absorbing anisotropic layer became 0.8 μm in the production of the optical film 1 of example 1. The light absorbing anisotropic layer contained in the optical film B5 produced in comparative example 5 is also referred to as a light absorbing anisotropic layer PB5.
Comparative example 6 >
An organic EL display device B6 was produced in the same manner as in comparative example 6 except that the light-absorbing anisotropic layer-forming composition P1 was changed to the light-absorbing anisotropic layer-forming composition PB6 so that the film thickness of the light-absorbing anisotropic film was 1.6 μm. The light absorbing anisotropic layer contained in the optical film B6 produced in comparative example 6 is also referred to as a light absorbing anisotropic layer PB6.
< Measurement and evaluation >)
The results of measurement and evaluation of the optical films and the organic EL display devices produced in examples and comparative examples are shown in the following table.
[ Measurement of optical Properties ]
(1) Determination of the absorption wavelength
Using the obtained light absorbing anisotropic layer and AxoScan OPMF-1 (manufactured by Opto Science, inc.) the muller matrix was measured every 10nm in the wavelength range of 400 to 750nm in the polar angle 30 ° direction among 4 azimuth directions of 0 °, 90 °, 180 ° and 270 °, and the maximum absorption wavelength was obtained from the average value of 4 azimuth directions.
(2) Transmittance center axis and Rth
Using the obtained light absorbing anisotropic layer, and using AxoScan OPMF-1 (manufactured by Opto Science, inc.), the polar angle was measured every 5 ° in the range of 70 ° to 70 ° for the muller matrix of the light absorbing anisotropic layer in the maximum absorption wavelength λ. From the measurement results, the transmittance central axis angles θ and Rth at which the transmittance became extremely large were obtained. Further, the assumed value of the average refractive index of 1.60 and the film thickness were inputted in the calculation of Rth. When there are a plurality of maximum absorption wavelengths, the average value of the transmittance central axis angles at the respective maximum absorption wavelengths is set as the transmittance central axis angle θ.
(3) Absorption anisotropy A (lambda), B (lambda)
In order to determine the absorption anisotropy of the light absorption anisotropic layer, the polar angle direction in the in-plane slow axis direction of the optical film was changed to measure, and the polarized light characteristics of each obtained optical film were obtained.
Specifically, axoscan of the measuring device was used to measure the muller matrix at each 5 of the maximum absorption wavelength λ in the in-plane slow axis direction within the range of-70 ° to 70 °, and the polar angles were obtained by fitting kx (λ), ky (λ), and kz (λ). Next, absorption anisotropies a (λ) and B (λ) were obtained from the above-described formulas (1) and (2).
The value (A min) of the minimum A (lambda) of the light absorption anisotropic layer at the wavelength of 400 to 650nm was obtained by the same method, and the wavelength lambda min was also obtained.
[ Evaluation of display Performance ]
The manufactured organic EL display device was evaluated for visibility and display quality of white display in bright light according to the following criteria. In practice, the evaluation of A+ to E is preferable. The evaluation results are shown in tables 1 to 3 below.
(Evaluation criteria for white display Performance)
A +: in the state of naked eyes and wearing polarized sunglasses, the change of the tone is small when the azimuth angle and the polar angle are changed, and the change of the tone is not obvious.
A: the change in hue is small and hardly noticeable when the azimuth angle and the polar angle are changed in a state where the polarized sunglasses are worn by the naked eye.
B: in the state of the naked eye and the polarized sunglasses, the change of the color tone when the azimuth angle is changed is small, but the change of the color tone when the polar angle is changed is small, and the change of the color tone is hardly obvious.
C: the change in hue when the azimuth angle is changed is small, but the change in hue when the polar angle is changed is hardly noticeable even though the change in hue is the same in hue when the polarized sunglasses are worn with the naked eye.
D: the change in color tone was hardly noticeable with the naked eye and with the polarized sunglasses, but the overall feeling was somewhat dark regardless of the angle from which it was observed.
E: the change in hue is not noticeable with the naked eye, but in the state of wearing polarized sunglasses, the change in hue or darkness is noticeable depending on the direction of observation.
F: the change in hue at the time of change in azimuth is not obvious even in the state of naked eyes or wearing polarized sunglasses, but the change in hue at the time of change in polar angle is large and the change in hue is obvious.
G: in the state of naked eyes and wearing polarized sunglasses, the change of the color tone is large and obvious when the azimuth angle and the polar angle are changed.
< Result >
The measurement results and evaluation results are shown in tables 1 to 4 below.
In the table, when Apple inc. APPLE WATCH SERIES is used as the organic EL display element, "OLED1" is described. In the table, when Apple inc. IPhone (registered trademark) 12Pro is used as the organic EL display element, it is described as "OLED2". In the table, when Apple inc. IPhone (registered trademark) 12 is used as the organic EL display element, it is described as "OLED3". In the table, when Galaxy Z fold3 5G manufactured by Samsung is used as the organic EL display element, it is referred to as "OLED4".
In the table, "OLED1" corresponds to the organic EL display element X, "OLED2" corresponds to the organic EL display element Y, and "OLED3" corresponds to the organic EL display element Z.
In the table, the lambda/4 retardation film is described as "lambda/4 plate".
In the table, each light absorbing anisotropic layer contained in each optical film is described by the symbol of each light absorbing anisotropic layer. For example, the light absorbing anisotropic layer P1 is described as "P1".
In the table, the column A min indicates the value of A (lambda) which is the smallest at wavelengths of 400 to 650nm for the light absorbing anisotropic layer. And, the column of λ min indicates the wavelength showing the value of the smallest a (λ).
In the table, the column of a (λ min)/A(λmax) represents the ratio of the values of a (λ) that are the smallest at a wavelength of 400 to 650nm with respect to the values of a (λ) of the light absorbing anisotropic layer at the maximum absorption wavelength.
TABLE 1
TABLE 2
TABLE 3
TABLE 4
From the results of tables 1 to 4, it was confirmed that the organic EL display device of the present invention having a predetermined structure and a (λ) represented by the above formula (1) of 15 to 225nm at the maximum absorption wavelength of the light absorbing anisotropic layer can suppress the change in color tone when white display is visually recognized from an oblique direction.
On the other hand, the organic EL display device of the comparative example having no light-absorbing anisotropic layer or having a (λ) of not 15 to 225nm at the maximum absorption wavelength cannot suppress the change in color tone when white display is visually recognized from the oblique direction.
From a comparison between example 2 and examples 12 and 13, it was confirmed that when the polarizing plate further includes a polarizing plate, the polarizing plate is disposed on the viewing side of the polarizer, the polarizing plate is a λ/4 thin film, and the retardation Rth in the thickness direction of the light absorbing anisotropic layer at the maximum absorption wavelength is-200 to-20 nm, the change in color tone at the time of white display can be further suppressed from being viewed from the oblique direction.

Claims (12)

1. An organic EL display device comprising an organic EL display element and a light absorbing anisotropic layer,
The light absorbing anisotropic layer is formed by using a composition containing a liquid crystalline compound and a dichroic substance,
The angle between the transmittance central axis of the light-absorbing anisotropic layer and the normal line of the layer plane of the light-absorbing anisotropic layer is 0 DEG to 45 DEG, A (lambda) of the light-absorbing anisotropic layer represented by formula (1) is 15 to 225nm at the maximum absorption wavelength of the light-absorbing anisotropic layer,
The formula (1) A (λ) = { kz (λ) - (kx (λ) +ky (λ))/2 } ×d,
In the formula (1), d is the thickness of the light absorbing anisotropic layer, kx (λ) and ky (λ) are the extinction coefficients of light with respect to the wavelength λ in the directions of the orthogonal x-axis and y-axis, respectively, in the plane of the light absorbing anisotropic layer, kz (λ) is the extinction coefficient of light with respect to the wavelength λ in the direction of the z-axis orthogonal to the plane including the x-axis and y-axis,
Wherein the thickness of the light absorbing anisotropic layer denoted by d is in nm.
2. The organic EL display device according to claim 1, wherein,
At the maximum absorption wavelength of the light absorbing anisotropic layer, B (lambda) represented by formula (2) is 30 or more,
Formula (2) B (λ) =kz (λ)/{ (kx (λ) +ky (λ))/2 }
In the formula (2), kx (λ) and ky (λ) are extinction coefficients of light with respect to the wavelength λ in directions of respective orthogonal x-axis and y-axis within the plane of the light absorbing anisotropic layer, and kz (λ) is an extinction coefficient of light with respect to the wavelength λ in a z-axis direction orthogonal to the plane including the x-axis and the y-axis.
3. The organic EL display device according to claim 1 or 2, wherein the organic EL display device further comprises a polarizer, and the light absorbing anisotropic layer is arranged on a viewing side of the polarizer.
4. The organic EL display device according to claim 3, further comprising a polarization control layer disposed on a viewing side of the polarizer.
5. The organic EL display device according to claim 4, wherein,
The polarization control layer is a lambda/4 film, and the retardation Rth of the light absorbing anisotropic layer in the thickness direction of the light absorbing anisotropic layer at the maximum absorption wavelength is-200 to-20 nm.
6. The organic EL display device according to claim 4, wherein,
The polarization control layer is a depolarization film.
7. The organic EL display device according to claim 1 or 2, wherein,
The liquid crystalline compound has positive wavelength dispersion, and the composition contains a vertical alignment agent.
8. The organic EL display device according to claim 1 or 2, wherein,
The ratio of the value of A (lambda) at the minimum of the light absorbing anisotropic layer at a wavelength of 400-650 nm relative to the value of A (lambda) at the maximum absorbing wavelength of the light absorbing anisotropic layer is 0.35 or less.
9. The organic EL display device according to claim 1 or 2, wherein,
The organic EL light-emitting element has a delta u 'v' (60 DEG) represented by the following formula (3A) on a CIE1976 u 'v' chromaticity diagram of greater than 0.005 in white display,
In at least 1 layer of the light absorbing anisotropic layers, an angle formed by a transmittance central axis of the light absorbing anisotropic layers and a normal line of a layer plane of the light absorbing anisotropic layers is 15 DEG or more and 45 DEG or less,
And (3A)Δu'v'(60°)=√{(u'(0°,60°)-u'(180°,60°))2+(v'(0°,60°)-v'(180°,60°))2}+√{(u'(90°,60°)-u'(270°,60°))2+(v'(90°,60°)-v'(270°,60°))2}
In the formula (3A), u '(a°, b°) is a u' value in an azimuth angle a ° polar angle b° on a CIE1976 u 'v' chromaticity diagram, and v '(a°, b°) is a v' value in an azimuth angle a° and a polar angle b° on the CIE1976 u 'v' chromaticity diagram, wherein the azimuth angle is an angle in which an in-plane direction of a display area of the organic EL display device is set to 0 ° from a lower direction to an upper direction and becomes larger counterclockwise when the display area is viewed from a vertical direction.
10. The organic EL display device according to claim 9, wherein the organic EL display device further comprises a polarizer and a polarization control layer,
The polarization control layer, the light absorbing anisotropic layer, and the polarizer are laminated in this order from the viewing side.
11. The organic EL display device according to claim 1 or 2, wherein,
The organic EL light emitting element satisfies a relationship of u ' (0 DEG) > u ' (30 DEG) > u ' (60 DEG) and satisfies a relationship of v ' (0 DEG) > v ' (30 DEG) and v ' (0 DEG) > v ' (60 DEG) in white display,
The maximum absorption wavelength of the light absorption anisotropic layer is in the range of 460-500 nm,
Here, u '(c°) is an average value of u' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram, and v '(c°) is an average value of v' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram.
12. The organic EL display device according to claim 1 or 2, wherein,
The organic EL light emitting element satisfies the relationship of u '(0) > u' (30 DEG) and u '(0 DEG) > u' (60 DEG) in white display, and satisfies the relationship of v '(0 DEG) > v' (30 DEG) and v '(30 DEG) < v' (60 DEG),
The maximum absorption wavelength of the light absorption anisotropic layer is in the range of 510-570 nm,
Here, u '(c°) is an average value of u' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram, and v '(c°) is an average value of v' values in a polar angle c° in an all-azimuth angle on the CIE1976 u 'v' chromaticity diagram.
CN202280074060.0A 2021-11-09 2022-11-08 Organic EL display device Pending CN118202811A (en)

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JP2021-182514 2021-11-09
JP2022-177929 2022-11-07
JP2022177929 2022-11-07
PCT/JP2022/041514 WO2023085255A1 (en) 2021-11-09 2022-11-08 Organic el display device

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