JP7271721B2 - organic electroluminescence display - Google Patents

Description

The present invention relates to an organic electroluminescence (hereinafter also abbreviated as "EL") display device.

BACKGROUND ART Conventionally, a polarizing plate having an optically anisotropic layer and a polarizer has been used in an organic electroluminescence display device for the purpose of antireflection or the like.
In recent years, there has been a demand for thinner optically anisotropic layers included in polarizing plates due to the demand for thinner devices to which polarizing plates are applied.
In response to such demands, for example, Patent Documents 1 and 2 propose the use of a polymerizable liquid crystal compound having a predetermined structure as a compound used for forming an optically anisotropic layer.

WO2014/010325 JP 2011-207765 A

In an organic electroluminescence display device, an organic light-emitting element is vulnerable to oxygen and moisture, and a silicon nitride layer is often provided to block them.
Therefore, the present inventors prepared a circularly polarizing plate having an optically anisotropic layer formed using a polymerizable liquid crystal compound described in Patent Documents 1 and 2, and attached this circularly polarizing plate to an adhesive layer. It was clarified that the deterioration of the antireflection performance occurs when the obtained laminate is placed on the silicon nitride layer through the intermediary and exposed to the conditions of high temperature and high humidity for a long time.
In addition, the present inventors have clarified as a result of analysis that changes in the degree of polarization and changes in the in-plane retardation (Re) occur in the failure region.
Henceforth, the fact that the change in in-plane retardation is suppressed when the laminate is exposed to high humidity and high temperature is expressed as excellent wet heat durability.

An object of the present invention is to provide an organic electroluminescence display device having excellent wet heat durability.

The inventors have found that the above problems can be solved by the following configuration.

[1] An organic electroluminescence display element having at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer, a pair of electrodes and an organic light-emitting layer sandwiched therebetween, in this order from the viewing side. A luminescence display device,
A circularly polarizing plate has a polarizer and an optically anisotropic layer,
the polarizer is a polarizer having a dichroic organic dye,
The optically anisotropic layer is a layer formed using a composition containing a polymerizable liquid crystal compound,
An organic electroluminescence display device, wherein the thickness of the layer present between the circularly polarizing plate and the silicon nitride layer is 35 μm or less.
[2] The organic electroluminescence display device according to [1], wherein the polarizer is formed using a composition containing a dichroic organic dye and a polymerizable liquid crystal compound.
[3] The organic electroluminescence display device according to [1] or [2], wherein the layer present between the circularly polarizing plate and the silicon nitride layer has a moisture permeability of 100 g/m ² ·day or more.
[4] The composition according to any one of [1] to [3], wherein the composition used for forming the optically anisotropic layer contains a polymerizable liquid crystal compound having a partial structure represented by formula (II) described later. Organic electroluminescence display device.
[5] Re(450), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 450 nm, and Re(550), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 550 nm. , Re(650), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 650 nm, satisfies the relationship Re(450)≦Re(550)≦Re(650), [1]- The organic electroluminescence display device according to any one of [4].
[6] The organic electroluminescence display device according to any one of [1] to [5], wherein the optically anisotropic layer is a positive A plate.
[7] The organic electroluminescence display device according to any one of [1] to [6], wherein the optically anisotropic layer is a λ/4 plate.
[8] The organic electroluminescence display device according to any one of [1] to [7], wherein the angle between the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45°±10°.
[9] The polarizer is formed from a composition containing a dichroic organic dye and a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound accounts for 60% by mass or more of the solid content of the composition, [1] to [8 ] The organic electroluminescence display device according to any one of the above.
[10] The organic electroluminescence according to any one of [1] to [9], which has a surface protective layer on the viewing side of the circularly polarizing plate, and the surface protective layer has a moisture permeability of 1 g/m ² ·day or more. display device.

ADVANTAGE OF THE INVENTION According to this invention, the organic electroluminescent display device excellent in wet heat durability can be provided.

BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of embodiment of the organic electroluminescent display apparatus of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of embodiment of the organic electroluminescent display apparatus of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of embodiment of the organic electroluminescent display apparatus of this invention. BRIEF DESCRIPTION OF THE DRAWINGS It is typical sectional drawing which shows an example of embodiment of the organic electroluminescent display apparatus of this invention.

The present invention will be described in detail below.
The description of the constituent elements described below may be made based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.
In this specification, a numerical range represented by "-" means a range including the numerical values before and after "-" as lower and upper limits.
In addition, in the present specification, each component may be a substance corresponding to each component either singly or in combination of two or more. Here, when two or more substances are used in combination for each component, the content of the component refers to the total content of the substances used in combination unless otherwise specified.
Further, in this specification, the bonding direction of the divalent group (e.g., —O—CO—) indicated is not particularly limited unless the bonding position is specified. When D ¹ in III) is —CO—O—, if the position bonded to the G ¹ side is *1 and the position bonded to the Ar side is *2, then D ¹ is *1- It may be CO-O-*2 or *1-O-CO-*2.
In the present specification, "(meth)acrylate" is a generic term for "acrylate" and "methacrylate", "(meth)acrylic" is a generic term for "acrylic" and "methacrylic", and "(meth) ) acryloyl” is a generic term for “acryloyl” and “methacryloyl”.
In addition, in this specification, the terms “perpendicular” and “parallel” with respect to angles shall mean a strict angle range of ±10°, and the terms “identical” and “different” with respect to angles shall have a difference of less than 5°. It can be determined based on whether or not
Further, in this specification, "visible light" means 380 to 780 nm.
In this specification, the measurement wavelength is 550 nm unless otherwise specified.

As used herein, the term "moisture content" means the initial mass of the cut sample and the mass obtained by converting the amount of change in the dry mass after drying at 120°C for 2 hours per unit area.

As used herein, the term “slow axis” means the direction in which the refractive index is maximized within the plane. The slow axis of the optically anisotropic layer means the slow axis of the entire optically anisotropic layer.

In this specification, "Re(λ)" and "Rth(λ)" represent in-plane retardation and thickness direction retardation at wavelength λ, respectively.
Here, the values of in-plane retardation and retardation in the thickness direction refer to values measured using light of a measurement wavelength using AxoScan OPMF-1 (manufactured by Optoscience).
Specifically, by inputting the average refractive index ((nx+ny+nz)/3) and film thickness (d (μm)) into AxoScan OPMF-1,
Slow axis direction (°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2−nz)×d
is calculated.
Note that R0(λ), which is displayed as a numerical value calculated by AxoScan OPMF-1, means Re(λ).

The organic electroluminescence display device of the present invention comprises, from the viewing side, a circularly polarizing plate, an adhesive layer, a silicon nitride layer, and an organic electroluminescence display element having a pair of electrodes and an organic light-emitting layer sandwiched therebetween. It is an organic electroluminescence display device including at least in this order.
Further, in the organic EL display device of the present invention, the circularly polarizing plate has a polarizer and an optically anisotropic layer, the polarizer is a polarizer having a dichroic organic dye, and the optically anisotropic layer is , which is a layer formed using a composition containing a polymerizable liquid crystal compound.
In addition, in the organic EL display device of the present invention, the thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer (when there are multiple layers, the total of the multiple layers. The same shall apply hereinafter.) is 35 μm or less.

The organic electroluminescence display device of the present invention having a given optically anisotropic layer and a given polarizer is excellent in wet heat durability.
Although this is not clear in detail, the present inventors presume as follows.

It is known that a silicon nitride layer, which is usually used as a barrier layer of an organic light-emitting element in an organic electroluminescence display device, reacts with water to generate ammonia depending on the manufacturing method.
Polyvinyl alcohol-based resin and iodine are often used as polarizers. In polarizers using such iodine, the polyvinyl alcohol-based resin is crosslinked with boric acid to hold the PVA-iodine complex. and dichroism is expressed.
The present inventors have found that the reason for the poor wet heat durability is that the boric acid cross-linking site of the polarizer using iodine is hydrolyzed in the presence of ammonia generated in the silicon nitride layer, so that the PVA-iodine complex is retained. The reason is that the dichroism deteriorates, and the swelling rate of the polyvinyl alcohol resin increases, increasing the water supply to the silicon nitride layer as the main water supply source in the organic electroluminescence display device. I'm guessing.

Therefore, in the present invention, by introducing a dichroic organic dye that is not affected by boric acid cross-linking, deterioration of the polarizer is suppressed, and as a result, the wet heat durability of the organic electroluminescence display device is improved. It is thought that

1, 2, 3 and 4 are schematic cross-sectional views showing an example of the organic EL display device of the present invention.
Here, the organic EL display device 10 shown in FIG. 1 is a layered organic EL display device having a polarizer 13, a positive A plate 15, an adhesive layer 20, a silicon nitride layer 17 and an organic EL display element 18 in this order. .
Further, the organic EL display device 20 shown in FIG. 2 has a layer structure having a surface protective layer 11, a polarizer 13, a positive A plate 15, an adhesive layer 20, a silicon nitride layer 17 and an organic EL display element 18 in this order. It is a display device.
Further, the organic EL display device 30 shown in FIG. 3 has a surface protective layer 11, a polarizer 13, a positive A plate 15, a positive C plate 16, an adhesive layer 20, a silicon nitride layer 17 and an organic EL display element 18 in this order. It is an organic EL display device having a layer structure.
Further, the organic EL display device 40 shown in FIG. 4 includes a surface protective layer 11, a polarizer protective film 12, a polarizer 13, a polarizer protective film 14, a positive A plate 15, a positive C plate 16, an adhesive layer 20, silicon nitride The organic EL display device has a layer structure having a layer 17 and an organic EL display element 18 in this order.
1 to 4, the positive A plate 15 corresponds to the optically anisotropic layer included in the organic EL display device of the invention.
The present invention includes at least a polarizer, an optically anisotropic layer, an adhesive layer, a silicon nitride layer, and an organic EL display element.
Each layer and component of the organic EL display device of the present invention will be described in detail below.

[Circularly polarizing plate]
The organic electroluminescence display device of the present invention has a circularly polarizing plate having an optically anisotropic layer and a polarizer.

[Optically anisotropic layer]
The optically anisotropic layer included in the circularly polarizing plate is a layer formed using a composition containing a polymerizable liquid crystal compound.
In general, liquid crystal compounds can be classified into a rod-like type and a disk-like type according to their shape. Furthermore, there are low-molecular-weight and high-molecular-weight types, respectively. Polymers generally refer to those having a degree of polymerization of 100 or more (Polymer Physics: Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
Although any liquid crystal compound can be used in the present invention, it is preferable to use a rod-like liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-like liquid crystal compound.

In the present invention, a liquid crystal compound having a polymerizable group (polymerizable liquid crystal compound) is used for immobilization of the liquid crystal compound described above, and it is further preferred that the liquid crystal compound has two or more polymerizable groups in one molecule. preferable. In the case of a mixture of two or more liquid crystal compounds, at least one liquid crystal compound preferably has two or more polymerizable groups in one molecule. After the liquid crystal compound is fixed by polymerization, it is no longer necessary to exhibit liquid crystallinity.

Moreover, the type of the polymerizable group is not particularly limited, and a functional group capable of addition polymerization reaction is preferable, and a polymerizable ethylenically unsaturated group or a ring-polymerizable group is preferable. More specifically, a (meth)acryloyl group, a vinyl group, a styryl group, an allyl group and the like are preferred, and a (meth)acryloyl group is more preferred.

As the rod-like liquid crystal compound, for example, those described in claim 1 of JP-A-11-513019 and paragraphs [0026] to [0098] of JP-A-2005-289980 can be preferably used, and discotic As the liquid crystal compound, for example, those described in paragraphs [0020] to [0067] of JP-A-2007-108732 and paragraphs [0013] to [0108] of JP-A-2010-244038 can be preferably used. but not limited to these.

In the present invention, the optically anisotropic layer is a composition (hereinafter referred to as " Also referred to as "polymerizable liquid crystal composition").
The specific liquid crystal compound is a polymerizable liquid crystal compound and is a compound exhibiting "reverse wavelength dispersion".
Here, in the present specification, a compound exhibiting "reverse wavelength dispersion" means an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer produced using the compound. It means that the Re value becomes equal or higher as the measurement wavelength becomes larger when measured, and as described later, it means that Re(450)≤Re(550)≤Re(650).

The reverse wavelength dispersion polymerizable liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersion film as described above. Compounds represented by (especially the compounds described in paragraphs [0034] to [0039]), compounds represented by the general formula (1) described in JP-A-2010-084032 (especially paragraphs [0067] to [0073] compound), the compound represented by the general formula (1) described in JP-A-2019-73496 (especially the compound described in paragraphs [0117] to [0124]), and JP-A-2016 -081035 (especially the compounds described in paragraphs [0043] to [0055]) represented by the general formula (1).

As the polymerizable liquid crystal compound, a polymerizable liquid crystal compound having a partial structure represented by the following formula (II) is preferable because the effects of the present invention are more excellent.
*-D ¹ -Ar-D ² -* (II)

In the above formula (II), D ¹ and D ² are each independently a single bond, -O-, -CO-, -CO-O-, -C(=S)O-, -CR ¹ R ² - , -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O- CO-CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -O-CO-, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O- represents CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, or -CO-NR ¹ -;
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. When there are a plurality of each of R ¹ , R ² , R ³ and R ⁴ , the plurality of R ¹ s, the plurality of R ² , the plurality of R ³ and the plurality of R ⁴ may be the same or different from each other. good.
Ar represents any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D ¹ or D ² , and explanation of the symbols in the following formulas (Ar-1) to (Ar-7). is the same as that described for Ar in formula (III) described later.

As the polymerizable liquid crystal compound having the partial structure represented by the above formula (II), a polymerizable liquid crystal compound represented by the following formula (III) is preferable.
A polymerizable liquid crystal compound represented by the following formula (III) is a compound exhibiting liquid crystallinity.
L ¹ -G ¹ -D ¹ -Ar-D ² -G ² -L ² (III)

In the above formula (III), D ¹ and D ² are each independently a single bond, -O-, -CO-, -CO-O-, -C(=S)O-, -CR ¹ R ² - , -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O- CO-CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -O-CO-, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O- represents CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, or -CO-NR ¹ -;
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. When there are a plurality of each of R ¹ , R ² , R ³ and R ⁴ , the plurality of R ¹ s, the plurality of R ² , the plurality of R ³ and the plurality of R ⁴ may be the same or different from each other. good.
G ₁ and G ₂ each independently represent a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms or an aromatic hydrocarbon group, and the methylene group contained in the alicyclic hydrocarbon group is , —O—, —S—, or —NH—.
L ₁ and L ₂ each independently represent a monovalent organic group, and at least one selected from the group consisting of L ₁ and L ₂ represents a monovalent group having a polymerizable group.
Ar represents any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7). In the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D ¹ or D ² .

In the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ is a hydrogen atom or represents an alkyl group having 1 to 6 carbon atoms, and Y ¹ represents an optionally substituted aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms; show.
Examples of alkyl groups having 1 to 6 carbon atoms represented by R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group and n-pentyl. and n-hexyl groups.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include aryl groups such as phenyl group, 2,6-diethylphenyl group and naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include a thienyl group, a thiazolyl group, a furyl group, and a heteroaryl group such as a pyridyl group.
Examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.
The alkyl group is preferably an alkyl group having 1 to 18 carbon atoms, and an alkyl group having 1 to 8 carbon atoms (e.g., methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, and cyclohexyl group), more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. Alkyl groups may be linear, branched, or cyclic.
As the alkoxy group, for example, an alkoxy group having 1 to 18 carbon atoms is preferable, and an alkoxy group having 1 to 8 carbon atoms (eg, methoxy group, ethoxy group, n-butoxy group, and methoxyethoxy group) is more preferable, and carbon An alkoxy group of numbers 1 to 4 is more preferred, and a methoxy group or an ethoxy group is particularly preferred.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms, with fluorine or chlorine atoms being preferred.

In the above formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a carbon a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -OR ⁸ , -NR ⁹ R ¹⁰ , or , —SR ¹¹ , R ⁸ to R ¹¹ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring. good.
The monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms is preferably an alkyl group having 1 to 15 carbon atoms, more preferably an alkyl group having 1 to 8 carbon atoms, methyl group, ethyl group, isopropyl group, tert -pentyl group (1,1-dimethylpropyl group), tert-butyl group or 1,1-dimethyl-3,3-dimethyl-butyl group is more preferred, and methyl group, ethyl group or tert-butyl group is particularly preferred. preferable.
Examples of monovalent alicyclic hydrocarbon groups having 3 to 20 carbon atoms include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclodecyl, methylcyclohexyl, and monocyclic saturated hydrocarbon groups such as ethylcyclohexyl; cyclobutenyl, cyclopentenyl, cyclohexenyl, cycloheptenyl, cyclooctenyl, cyclodecenyl, cyclopentadienyl, cyclohexadienyl, cyclooctadienyl, and monocyclic unsaturated hydrocarbon groups such as cyclodecadiene; bicyclo[2.2.1]heptyl group, bicyclo[2.2.2]octyl group, tricyclo[5.2.1.0 ^2,6 ]decyl group, tricyclo[3.3.1.1 ^3,7 ]decyl group, tetracyclo[6.2.1.1 ^3,6 . 0 ^2,7 ]dodecyl group and polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
Examples of monovalent aromatic hydrocarbon groups having 6 to 20 carbon atoms include phenyl group, 2,6-diethylphenyl group, naphthyl group, and biphenyl group, and aryl groups having 6 to 12 carbon atoms ( phenyl group) is particularly preferred.
Halogen atoms include, for example, fluorine, chlorine, bromine, and iodine atoms, with fluorine, chlorine, and bromine atoms being preferred.
Examples of alkyl groups having 1 to 6 carbon atoms represented by R ⁸ to R ¹¹ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, Examples include n-pentyl and n-hexyl groups.

In the above formulas (Ar-2) and (Ar-3), A ¹ and A ² are each independently from -O-, -N(R ¹² )-, -S-, and -CO- represents a group selected from the group consisting of R ¹² represents a hydrogen atom or a substituent;
Examples of the substituent represented by R ¹² include the same substituents that Y ¹ in the above formula (Ar-1) may have.

In the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be attached.
In addition, the nonmetallic atom of Groups 14 to 16 represented by X includes, for example, an oxygen atom, a sulfur atom, a hydrogen atom, or a nitrogen atom to which a substituent is bonded [=NR ^N1 , R ^N1 is a hydrogen atom or a substituent represents ], a hydrogen atom or a carbon atom to which a substituent is bonded [=C-(R ^C1 ) ₂ , R ^C1 represents a hydrogen atom or a substituent. ] is mentioned.

Further, in the above formula (Ar-3), D ⁴ and D ⁵ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ^1a R ^2a —, —CR ^3a ═CR ^4a —, —NR ^5a —, or a divalent linking group consisting of a combination of two or more thereof, wherein R ^1a to R ^5a each independently represent a hydrogen atom, represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Here, the divalent linking group includes, for example, -CO-, -O-, -CO-O-, -C(=S)O-, -CR ^1b R ^2b -, -CR ^1b R ^2b -CR ^1b R ^2b -, -O-CR ^1b R ^2b -, -CR ^1b R ^2b -O-CR ^1b R ^2b -, -CO-O-CR ^1b R ^2b -, -O-CO-CR ^1b R ^2b -, -CR ^1b R ^2b -O-CO-CR ^1b R ^2b -, -CR ^1b R ^2b -CO-O-CR ^1b R ^2b -, -NR ^3b -CR ^1b R ^2b -, and -CO-NR ^3b - is mentioned. R ^1b , R ^2b and R ^3b each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the above formula (Ar-3), SP ¹ and SP ² are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a one or more —CH ₂ — constituting a linear or branched alkylene group is substituted with —O—, —S—, —NH—, —N(Q)—, or —CO— represents a divalent linking group, and Q represents a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.
Here, the linear or branched alkylene group having 1 to 12 carbon atoms includes, for example, methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, and A butylene group is preferred.

In the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
Monovalent organic groups include, for example, alkyl groups, aryl groups, and heteroaryl groups. The alkyl group may be linear, branched or cyclic, preferably linear. The number of carbon atoms in the alkyl group is preferably 1-30, more preferably 1-20, even more preferably 1-10. Also, the aryl group may be monocyclic or polycyclic, but is preferably monocyclic. The number of carbon atoms in the aryl group is preferably 6-25, more preferably 6-10. Also, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1-3. A heteroatom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. In addition, the alkyl group, aryl group and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Further, in the above formulas (Ar-4) to (Ar-7), Ax has at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings, and has 2 to 30 carbon atoms. represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-7), Ay is a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and aromatic represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of heterocyclic rings.
Here, the aromatic rings in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms.
Examples of Ax and Ay include those described in paragraphs [0039] to [0095] of Patent Document 1 (International Publication No. 2014/010325).
Specific examples of the alkyl group having 1 to 6 carbon atoms represented by Q ³ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert -butyl group, n-pentyl group, n-hexyl group and the like, and the substituents are the same as the substituents that Y ¹ in the above formula (Ar-1) may have. mentioned.

For the definition and preferred range of each substituent of the liquid crystal compound represented by formula (III), D ¹ , D ² , G ¹ , G ² , L ¹ , L ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , Y ¹ , Q 1 , and Q ² are respectively described as D ₁ , D ₂ , G ₁ , _{G 2} ^, L ₁ , L ₂ , Reference can be made to R ¹ , R ² , R ³ , R ⁴ , Q ₁ , Y ₁ , Z ₁ , and Z ₂ , and the compound represented by the general formula (I) described in JP-A-2008-107767. The descriptions of A ₁ , A ₂ and X can be referred to for A ₁ , A ₂ and X respectively, Ax, Ay, The description for ^Q1 can be referred to for Ax, Ay and _Q2 respectively. For Z ₃ , the description of Q ¹ regarding compound (A) described in JP-A-2012-21068 can be referred to.

In particular, the organic groups represented by L ₁ and L ₂ are preferably groups represented by -D ₃ -G ₃ -Sp-P ₃ .
_D3 is synonymous with _D1 .
G ₃ represents a single bond, a divalent aromatic or heterocyclic group having 6 to 12 carbon atoms, or a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, and the above alicyclic hydrocarbon group The methylene group contained in may be substituted with —O—, —S— or —NR ⁷ —, where R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Sp is a single bond, -(CH ₂ ) _n -, -(CH ₂ ) _n -O-, -(CH ₂ -O-) _n -, -(CH ₂ CH ₂ -O-) _m , -O- (CH ₂ ) _n —, —O—(CH ₂ ) _n —O—, —O—(CH ₂ —O—) _n —, —O—(CH ₂ CH ₂ —O—) _m , —C(= O)-O-(CH ₂ ) _n -, -C(=O)-O-(CH ₂ ) _n -O-, -C(=O)-O-(CH ₂ -O-) _n -,- C(=O)-O-(CH ₂ CH ₂ -O-) _m , -C(=O)-N(R ⁸ )-(CH ₂ ) _n -, -C(=O)-N(R ⁸ )-(CH ₂ ) _n -O-, -C(=O)-N(R ⁸ )-(CH ₂ -O-) _n -, -C(=O)-N(R ⁸ )-(CH ₂ a spacer group represented by CH ₂ -O-) _m or -(CH ₂ ) _n -O-(C=O)-(CH ₂ ) _n -C(=O)-O-(CH ₂ ) _{n -} represents Here, n represents an integer of 2 to 12, m represents an integer of 2 to 6, and R ⁸ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. Also, the hydrogen atom of —CH ₂ — in each of the above groups may be substituted with a methyl group.
_P3 represents a polymerizable group.

Although the polymerizable group is not particularly limited, a polymerizable group capable of radical polymerization or cationic polymerization is preferred.
Examples of the radically polymerizable group include known radically polymerizable groups, and an acryloyl group or a methacryloyl group is preferable. It is known that acryloyl groups generally have a high polymerization rate, and acryloyl groups are preferred from the viewpoint of productivity improvement, but methacryloyl groups can also be used as polymerizable groups for high birefringence liquid crystals.
Examples of cationic polymerizable groups include known cationic polymerizable groups such as alicyclic ether groups, cyclic acetal groups, cyclic lactone groups, cyclic thioether groups, spiroorthoester groups, and vinyloxy groups. Among them, an alicyclic ether group or a vinyloxy group is preferable, and an epoxy group, an oxetanyl group or a vinyloxy group is more preferable.
Examples of particularly preferred polymerizable groups include the following.

In the present specification, the "alkyl group" may be linear, branched or cyclic, for example, methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group , sec-butyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, 1,1-dimethylpropyl group, n-hexyl group, isohexyl group, cyclopropyl group, cyclobutyl group, cyclopentyl group, and, A cyclohexyl group is mentioned.

Preferred examples of the polymerizable liquid crystal compound represented by formula (II) are shown below, but the liquid crystal compound is not limited to these.

In addition, in the above formula, "*" represents a bonding position.

II-2-8

II-2-9

The group adjacent to the acryloyloxy group in the above formulas II-2-8 and II-2-9 represents a propylene group (a group in which a methyl group is substituted with an ethylene group), and positional isomerism in which the position of the methyl group is different. Represents a mixture of bodies.

In addition to the above preferred examples, other preferred examples of side chain structures are shown below.

Further, as another preferred embodiment of the specific liquid crystal compound, a compound represented by the following formula (V) is also included.
L ¹ -[D ¹ -G ¹ ] _m -E ¹ -AE ² -[G ² -D ² ] _n -L ² (V)
In the above formula (V),
A is a non-aromatic carbocyclic or heterocyclic group having 5 to 8 carbon atoms, or an aromatic or heteroaromatic group having 6 to 20 carbon atoms;
E ¹ , E ² , D ¹ and D ² are each independently a single bond or a divalent linking group;
L ¹ and L ² are each independently -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C(=O)NR ¹ R ² , —C(=O)R ¹ , —O—C(=O)R ¹ , —NH ₂ , —SH, —SR ¹ , —SO ₃ H, —SO ₂ R ¹ , —OH, —NO ₂ , —CF ₃ , —SF ₃ , substituted or unsubstituted silyl, substituted or unsubstituted carbyl or hydrocarbyl group having 1 to 40 carbon atoms, or —Sp—P, wherein L ¹ and L ² is -Sp-P, P is a polymerizable group, Sp is a spacer group or a single bond, and R ¹ and R ² are each independently -H or 1 carbon is an alkyl of -12;
m and n are each independently an integer of 1 to 5; if m or n is 2 or more, repeat 2 or more -(D ¹ -G ¹ )- or -(G ² -D ² ) - each repeating unit may be the same or different;
G ¹ and G ² are each independently a non-aromatic carbocyclic or heterocyclic group having 5 to 8 carbon atoms, or an aromatic or heteroaromatic group having 6 to 20 carbon atoms, , G ¹ and G ² is the above carbocyclic group or heterocyclic group, and any one hydrogen atom contained in the above carbocyclic or heterocyclic group is the following substituted with a group of formula (VI):
*-[Q ¹ ] _p -B ¹ (VI)
In the above formula (VI),
p is an integer of 1 to 10, and if p is 2 or more, each repeating unit of -(Q ¹ )- repeated two or more times may be the same or different;
Q ¹ is independently selected from the group consisting of -C≡C-, -CY ¹ =CY ² -, and a substituted or unsubstituted aromatic or heteroaromatic group having 6 to 20 carbon atoms a divalent group, wherein Y ¹ and Y ² are each independently —H, —F, —Cl, —CN, or —R ¹ ;
B ¹ is -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C(=O)NR ¹ R ² , -C(=O ) R ¹ , —NH ₂ , —SH, —SR ¹ , —SO ₃ H, —SO ₂ R ¹ , —OH, —NO ₂ , —CF ₃ , —SF ₃ , polymerizable group, carbon number 2-6 an alkenyl group having 2 to 6 carbon atoms, an acyl group having 2 to 4 carbon atoms, an alkynylene group having 2 to 6 carbon atoms with an acyl group having 2 to 4 carbon atoms attached to the end, an alkynylene group having 1 to 5 carbon atoms, an alcohol group or an alkoxy group having 1 to 12 carbon atoms,
R ¹ and R ² are each independently —H or alkyl having 1 to 12 carbon atoms.

Preferred specific examples of the above formula (V) are shown below.

Although the content of the specific liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, it is preferably 50 to 100% by mass, more preferably 70 to 99% by mass, based on the total solid content in the polymerizable liquid crystal composition.
The specific liquid crystal compounds may be used singly or in combination of two or more.
The solid content means the components other than the solvent in the polymerizable liquid crystal composition, and even if the composition is liquid, it is calculated as the solid content.

In order to control liquid crystal orientation, the polymerizable liquid crystal composition may contain a polymerizable rod-like compound in addition to the specific liquid crystal compound described above.
The polymerizable rod-shaped compound may or may not have liquid crystallinity.

From the viewpoint of compatibility with the above-described specific liquid crystal compound, the polymerizable rod-shaped compound is a compound partially having a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group (hereinafter referred to as "alkylcyclohexane ring Also abbreviated as "containing compound").
Here, "a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group" means, for example, as shown in the following formula (2), in the case of having two cyclohexane rings, A cyclohexane ring in which one hydrogen atom of the cyclohexane ring present in is substituted with a linear alkyl group.

The alkylcyclohexane ring-containing compound includes, for example, a compound having a group represented by the following formula (2). It is preferably a compound represented by the following formula (3) having

Here, * represents a bonding position in the above formula (2).
In the above formulas (2) and (3), R ² represents an alkyl group having 1 to 10 carbon atoms, n represents 1 or 2, W ¹ and W ² each independently represent an alkyl group, an alkoxy represents a group or a halogen atom, and W ¹ and W ² may combine with each other to form a ring structure which may have a substituent.
Further, in the above formula (3), Z represents -COO-, L represents an alkylene group having 1 to 6 carbon atoms, and R ³ represents a hydrogen atom or a methyl group.

Specific examples of such alkylcyclohexane ring-containing compounds include compounds represented by the following formulas A-1 to A-5. In formula A-3 below, R ⁴ represents an ethyl group or a butyl group.

When the polymerizable liquid crystal composition contains the polymerizable rod-shaped compound, the content of the polymerizable rod-shaped compound is preferably 1 to 30% by mass with respect to the total weight of the specific liquid crystal compound and the polymerizable rod-shaped compound. , 1 to 20 mass % is more preferred.

The polymerizable liquid crystal composition may contain a polymerizable liquid crystal compound (hereinafter also abbreviated as “another polymerizable liquid crystal compound”) other than the specific liquid crystal compound and the polymerizable rod-like compound described above.
Here, the polymerizable group possessed by the other polymerizable liquid crystal compound is not particularly limited, and examples thereof include (meth)acryloyl group, vinyl group, styryl group, and allyl group. Among them, a (meth)acryloyl group is preferred.

From the viewpoint of improving the durability of the optically anisotropic layer, the other polymerizable liquid crystal compound is preferably a polymerizable compound having 2 to 4 polymerizable groups, more preferably a polymerizable compound having 2 polymerizable groups. preferable.

Examples of such other polymerizable liquid crystal compounds include compounds represented by formulas (M1), (M2), and (M3) described in paragraphs 0030 to 0033 of JP-A-2014-077068. and, more specifically, specific examples described in paragraphs 0046 to 0055 of the same publication.
Other polymerizable liquid crystal compounds may be used singly or in combination of two or more.

When the polymerizable liquid crystal composition contains another polymerizable liquid crystal compound, the content of the other polymerizable liquid crystal compound is based on the total mass of the specific liquid crystal compound, the polymerizable rod-shaped compound and the other polymerizable liquid crystal compound. , preferably 1 to 40% by mass, more preferably 1 to 10% by mass.

The polymerizable liquid crystal composition preferably contains a non-liquid crystal polyfunctional polymerizable compound from the viewpoint of further improving the durability of the polarizing plate having the optically anisotropic layer formed thereon.
This is because the movement of the hydrolysis catalyst compound (presumed to be a liquid crystal decomposition product) is suppressed by increasing the cross-linking point density, and as a result, the speed of the hydrolysis reaction slows down. It is presumed that this is because the diffusion of

The non-liquid crystal polyfunctional polymerizable compound is preferably a compound having a low acrylic equivalent from the viewpoint of the orientation of the specific liquid crystal compound described above.
Specifically, the (meth)acrylic equivalent is 120 g/eq. The following compounds are preferred and have a (meth)acrylic equivalent of 100 g/eq. A compound having the following is more preferable, and has a (meth)acrylic equivalent of 90 g/eq. Further preferred compounds are:

Examples of non-liquid crystalline polyfunctional polymerizable compounds include esters of polyhydric alcohols and (meth)acrylic acid (e.g. ethylene glycol di(meth)acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra(meth)acrylate , pentaerythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa( meth)acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, and polyester polyacrylate), vinylbenzene and its derivatives (e.g. 1,4-divinylbenzene, 4-vinylbenzoate-2-acryloylethyl esters and 1,4-divinylcyclohexanone), vinyl sulfones (eg divinyl sulfone), acrylamides (eg methylenebisacrylamide), and methacrylamide.

When the polymerizable liquid crystal composition contains a non-liquid crystal polyfunctional polymerizable compound, the content of the non-liquid crystal polyfunctional polymerizable compound is It is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, and even more preferably 1 to 6% by mass, based on the total solid content in the polymerizable liquid crystal composition.

The polymerizable liquid crystal composition preferably contains a polymerization initiator.
As the polymerization initiator, a photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation is preferred.
Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), and α-hydrocarbon-substituted aromatic compounds. group acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. No. 3549367), acridine and phenazine compounds (Japanese Patent Application Laid-Open No. 60-105667, US Pat. No. 4,239,850) and oxadiazole compounds (US Pat. No. 4,212,970), acylphosphine Oxide compounds (described in JP-B-63-40799, JP-B-5-29234, JP-A-10-95788, and JP-A-10-29997).

As the polymerization initiator, an oxime-type polymerization initiator is preferable, and a polymerization initiator represented by the following formula (III) is more preferable, since the durability of the optically anisotropic layer is improved.

In formula (III) above, X represents a hydrogen atom or a halogen atom, and Y represents a monovalent organic group.
Ar ³ represents a divalent aromatic group, L ⁶ represents a divalent organic group having 1 to 12 carbon atoms, and R ¹⁰ represents an alkyl group having 1 to 12 carbon atoms.

In the above formula (III), the halogen atom represented by X includes, for example, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, with a chlorine atom being preferred.
In the above formula (III), the divalent aromatic group represented by Ar ³ includes, for example, aromatic hydrocarbon rings such as benzene ring, naphthalene ring, anthracene ring, and phenanthroline ring; furan ring; A divalent group having an aromatic heterocyclic ring such as a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.
In the above formula (III), the divalent organic group having 1 to 12 carbon atoms represented by L ⁶ includes, for example, a linear or branched alkylene group having 1 to 12 carbon atoms. includes methylene, ethylene, and propylene groups.
In the above formula (III), examples of the alkyl group having 1 to 12 carbon atoms represented by R ¹⁰ include a methyl group, an ethyl group and a propyl group.
In the above formula (III), the monovalent organic group represented by Y includes, for example, a functional group containing a benzophenone skeleton ((C ₆ H ₅ ) ₂ CO). Specifically, a functional group containing a benzophenone skeleton having an unsubstituted or monosubstituted terminal benzene ring, such as groups represented by the following formulas (3a) and (3b), is preferred.

Here, in the above formulas (3a) and (3b), * represents the bonding position, that is, the bonding position with the carbon atom of the carbonyl group in the above formula (III).

Examples of the oxime-type polymerization initiator represented by the above formula (III) include compounds represented by the following formula S-1 and compounds represented by the following formula S-2.

The content of the polymerization initiator is not particularly limited. ~5 parts by mass is more preferred.

The polymerizable liquid crystal composition may contain an alignment control agent, if necessary.
Alignment control agents include, for example, low-molecular alignment control agents and high-molecular alignment control agents. Low-molecular alignment control agents include, for example, paragraphs 0009 to 0083 of JP-A-2002-020363, paragraphs 0111-0120 of JP-A-2006-106662, and paragraph 0021- of JP-A-2012-211306. 0029, the contents of which are incorporated herein. Further, as the polymer alignment control agent, for example, paragraphs 0021 to 0057 of JP-A-2004-198511 and paragraphs 0121-0167 of JP-A-2006-106662 can be referred to, and the contents thereof are the present invention. incorporated into the specification.
The amount of the alignment control agent used is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the polymerizable liquid crystal composition. By using an alignment control agent, for example, a homogeneous alignment state in which the layers are aligned parallel to the surface of the optically anisotropic layer can be formed.

The polymerizable liquid crystal composition preferably contains an organic solvent from the viewpoint of workability for forming an optically anisotropic layer.
Examples of organic solvents include ketones (eg, acetone, 2-butanone, methylethylketone, methylisobutylketone, cyclohexanone, and cyclopentanone), ethers (eg, dioxane, and tetrahydrofuran), and aliphatic hydrocarbons. (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, and ethyl cellosolve), cellosolve acetates, sulfoxides (e.g., dimethylsulfoxide), amides (e.g., dimethylformamide and dimethylacetamide), and these may be used singly or two or more may be used together.

The polymerizable liquid crystal composition may contain components other than the components described above, for example, liquid crystal compounds other than the specific liquid crystal compounds described above, surfactants, tilt angle control agents, alignment aids, plasticizers, and A cross-linking agent may be mentioned.

The optically anisotropic layer is formed using the polymerizable liquid crystal composition described above.
The method for producing the optically anisotropic layer is not particularly limited, but for example, a predetermined substrate (for example, a polarizer described later, a support described later, or a support having an alignment layer) is coated with a polymerizable liquid crystal composition. to form a coating film, subjecting the coating film to alignment treatment to bring the specific liquid crystal compound into a predetermined alignment state, and then subjecting the coating film to curing treatment.

The coating can be performed by known methods (eg, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method).

Alignment treatment can be performed by drying at room temperature (eg, 20 to 25° C.) or by heating. In the case of a thermotropic liquid crystal compound, the liquid crystal phase formed by alignment treatment can generally be caused to transition by a change in temperature or pressure. In the case of a liquid crystal compound having lyotropic properties, transition can also be achieved by changing the composition ratio of the amount of solvent.
When the orientation treatment is at a heating temperature, the heating time (heat aging time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, even more preferably 10 seconds to 2 minutes.

The curing treatment (activation energy ray irradiation (light irradiation treatment) and/or heat treatment) on the coating film can also be said to be a fixing treatment for fixing the orientation of the specific liquid crystal compound.
Among them, it is preferable to carry out light irradiation treatment. In polymerization by light irradiation, it is preferable to use ultraviolet rays.
The irradiation dose is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , still more preferably 30 mJ/cm ² to 3 J/cm ² , particularly 50 to 1000 mJ/cm ² . preferable.
Moreover, in order to accelerate the polymerization reaction, light irradiation treatment may be performed under heating conditions.
In addition, as described above, the optically anisotropic layer can be formed on a support to be described later and on a polarizer to be described later.

The thickness of the optically anisotropic layer is not particularly limited, and is preferably 1 to 5 μm, more preferably 1 to 4 μm, even more preferably 1 to 3 μm.

The optically anisotropic layer preferably satisfies the following formula (IV).
Re(450)≦Re(550)≦Re(650) (IV)
Here, in the above formula (IV), Re(450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re(550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. Re(650) represents the in-plane retardation of an optically anisotropic film at a wavelength of 650 nm.

The optically anisotropic layer is preferably a positive A plate.
In addition, in this specification, a positive A plate is defined as follows. The positive A plate (positive A plate) has a refractive index nx in the slow axis direction in the plane of the film (the direction in which the refractive index is maximized in the plane), and is orthogonal to the in-plane slow axis in the plane. When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relationship of formula (A1) is satisfied. Note that the positive A plate has a positive Rth value.
Formula (A1) nx>ny≈nz
Note that the above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, that (ny−nz)×d (where d is the thickness of the film) is −10 to 10 nm, preferably −5 to 5 nm, and “ny≈nz”. include.

A positive A plate can be obtained by horizontally aligning a rod-shaped polymerizable liquid crystal compound. Details of the method for manufacturing the positive A plate can be referred to, for example, JP-A-2008-225281 and JP-A-2008-026730.

The optically anisotropic layer (positive A plate) preferably functions as a λ/4 plate.
A λ/4 plate is a plate that has the function of converting linearly polarized light of a specific wavelength into circularly polarized light (or circularly polarized light into linearly polarized light), and the in-plane retardation Re(λ) at a specific wavelength λnm is A plate that satisfies Re(λ)=λ/4.
This formula may be achieved at any wavelength in the visible light range (for example, 550 nm), but the in-plane retardation Re (550) at a wavelength of 550 nm satisfies the relationship of 110 nm ≤ Re (550) ≤ 160 nm. preferably 110 nm≦Re(550)≦150 nm.

Also, the optically anisotropic layer may have a positive C plate in addition to the positive A plate.
In addition, in this specification, a positive C plate is defined as follows. A positive C plate (positive C plate) has a refractive index of nx in the film in-plane slow axis direction (the direction in which the in-plane refractive index is maximum), and the in-plane slow axis is perpendicular to the in-plane When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relation of formula (A2) is satisfied. A positive C plate has a negative Rth value.
Formula (A2) nx≈ny<nz
Note that the above "≈" includes not only the case where both are completely the same, but also the case where both are substantially the same. “Substantially the same” means, for example, that (nx−ny)×d (where d is the thickness of the film) is −10 to 10 nm, preferably −5 to 5 nm, and “nx≈ny” include.
Also, in the positive C plate, Re≈0 from the above definition.

A positive C plate can be obtained by vertically aligning a rod-shaped polymerizable liquid crystal compound. For details of the method for manufacturing the positive C plate, for example, the descriptions in JP-A-2017-187732, JP-A-2016-53709, and JP-A-2015-200861 can be referred to.

[Polarizer]
The polarizer included in the circularly polarizing plate is an absorptive polarizer (optical absorption anisotropic layer) having a dichroic organic dye, and is a so-called linear polarizer having the function of converting light into specific linearly polarized light. .
The type of polarizer is not particularly limited as long as it contains a dichroic organic dye. Unlike iodine, a polarizer using a dichroic organic dye can be easily adjusted in color and can be optimally designed according to the wavelength of the light emitting element.

<Dichroic organic dye>
The dichroic organic dye used in the present invention is not particularly limited.
As the dichroic organic dye, a dichroic azo dye compound is preferable, and a dichroic azo dye compound that is usually used for a so-called coated polarizer can be used. The dichroic azo dye compound is not particularly limited, and conventionally known dichroic azo dyes can be used, but the compounds described below are preferably used.

In the present invention, a dichroic azo dye compound means a dye having different absorbance 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, it may exhibit nematicity or smecticity. The temperature range showing the liquid crystal phase is preferably room temperature (approximately 20° C. to 28° C.) to 300° C., and more preferably 50° C. to 200° C. from the viewpoint of handleability and production suitability.

In the present invention, from the viewpoint of color adjustment, the polarizer contains at least one dye compound having a maximum absorption wavelength in the wavelength range of 560 to 700 nm (hereinafter, also abbreviated as "first dichroic azo dye compound" ) and at least one dye compound having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm (hereinafter also abbreviated as “second dichroic azo dye compound”). Preferably, specifically, it has at least a dichroic azo dye compound represented by formula (1) described later and a dichroic azo dye compound represented by formula (2) described later. more preferred.

In the present invention, three or more dichroic azo dye compounds may be used in combination. For example, from the viewpoint of making the polarizer closer to black, the first dichroic azo dye compound and the second dichroic azo dye compound an azo dye compound and at least one dye compound having a maximum absorption wavelength in the wavelength range of 380 nm or more and less than 455 nm (preferably in the wavelength range of 380 to 454 nm) (hereinafter also referred to as "third dichroic azo dye compound") abbreviated.) is preferably used in combination.

In the present invention, the dichroic azo dye compound preferably has a crosslinkable group for the reason that the pressure resistance is better.
Specific examples of the crosslinkable group include a (meth)acryloyl group, an epoxy group, an oxetanyl group, a styryl group, etc. Among them, a (meth)acryloyl group is preferable.

(First dichroic azo dye compound)
The first dichroic azo dye compound is preferably a compound having a chromophore as a nucleus and a side chain bonded to the terminal of the chromophore.
Specific examples of the chromophore include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups, etc., and structures having both aromatic ring groups and azo groups are preferred. A bisazo structure having an aromatic heterocyclic group (preferably a thienothiazole group) and two azo groups is more preferred.
The side chain is not particularly limited, and includes groups represented by L3, R2 or L4 in formula (1) described below.

The first dichroic azo dye compound has a maximum absorption wavelength of 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, particularly preferably 560 to 640 nm) from the viewpoint of color adjustment of the polarizer. It is preferably a dichroic azo dye compound having
The maximum absorption wavelength (nm) of the dichroic azo dye compound in this specification is a solution of the dichroic azo dye compound dissolved in a good solvent, and is measured with a spectrophotometer at a wavelength of 380 to 800 nm. It is determined from the UV-visible spectrum in the range.

In the present invention, the first dichroic azo dye compound is preferably a compound represented by the following formula (1) because the degree of orientation of the formed polarizer is further improved.

In formula (1), Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group, preferably a phenylene group.

In formula (1), R1 is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, alkyloxycarbonyl group, acyloxy group, alkylcarbonate group, alkylamino group, acylamino group, alkylcarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, alkylsulfamoyl group, alkylcarbamoyl group, alkylsulfinyl group, alkylureido group, an alkylphosphoamide group, an alkylimino group, or an alkylsilyl group.
—CH ₂ — constituting the alkyl group is —O—, —CO—, —C(O)—O—, —O—C(O)—, —Si(CH ₃ ) ₂ —O—Si( CH ₃ ) 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 possessed by each group is 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. In each group, when a plurality of R1' are present, they may be the same or different.

In formula (1), R2 and R3 are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamido group.
—CH ₂ — constituting the alkyl group is —O—, —S—, —C(O)—, —C(O)—O—, —O—C(O)—, —C(O) -S-, -S-C(O)-, -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C(O)-O-, -O-C(O)-NR2'-, -NR2'-C(O)-NR2'-, -CH=CH-, -C≡C-, - optionally substituted by 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 possessed by each group are halogen atoms, nitro groups, cyano groups, —OH groups, —N(R2′) ₂ , amino groups, —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. In each group, when there are multiple R2's, they may be the same or different.
R2 and R3 may combine with each other to form a ring, or R2 or R3 may combine with 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 with low electron-donating properties.
Specific examples of such groups for R1 include an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, an alkylsulfonylamino group, an alkylsulfamoyl group, an alkylsulfinyl group, an alkylureido group, and the like. and R2 and R3 include groups having the following structures. The group having the structure below is shown in the above formula (1) in a form containing a nitrogen atom to which R2 and R3 are bonded.

Specific examples of the first dichroic azo dye compound are shown below, but are not limited thereto.

(Second dichroic azo dye compound)
The second dichroic azo dye compound is a different compound from the first dichroic azo dye compound, specifically in its chemical structure.
The second dichroic azo dye compound is preferably a compound having a chromophore that is the nucleus of the dichroic azo dye compound and a side chain that binds to the terminal of the chromophore.
Specific examples of the chromophore include aromatic ring groups (e.g., aromatic hydrocarbon groups, aromatic heterocyclic groups), azo groups and the like, and structures having both aromatic hydrocarbon groups and azo groups are preferred. , a bisazo or trisazo structure having an aromatic hydrocarbon group and two or three azo groups is more preferred.
The side chain is not particularly limited, and includes groups represented by R4, R5 or R6 in formula (2) described below.

The second dichroic azo dye compound is a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 455 nm or more and less than 560 nm, and from the viewpoint of adjusting the color of the polarizer, the wavelength is in the range of 455 to 555 nm. A dichroic azo dye compound having a maximum absorption wavelength is preferable, and a dichroic azo dye compound having a maximum absorption wavelength in the wavelength range of 455 to 550 nm is more preferable.
In particular, by using a first dichroic azo dye compound having a maximum absorption wavelength of 560 to 700 nm and a second dichroic azo dye compound having a maximum absorption wavelength of 455 nm or more and less than 560 nm, the color of the polarizer Taste adjustment becomes easier.

The second dichroic azo dye compound is preferably a compound represented by the formula (2) from the viewpoint of further improving the degree of orientation of the polarizer.

In formula (2), n represents 1 or 2.
In formula (2), Ar3, Ar4 and Ar5 are each independently a phenylene group optionally having substituent(s), a naphthylene group optionally having substituent(s) or a heterocyclic group optionally having substituent(s) represents a cyclic group.
Heterocyclic groups can be either aromatic or non-aromatic.
Atoms other than carbon constituting the aromatic heterocyclic group include a nitrogen atom, a sulfur atom and an oxygen atom. When the aromatic heterocyclic group has a plurality of non-carbon ring-constituting atoms, these may be the same or different.
Specific examples of aromatic heterocyclic groups include, for example, pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinoline-diyl group), and isoquinolylene. group (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxadiazole-diyl group, benzothiazole-diyl group, benzothiadiazole-diyl group, phthalimido-diyl group, thienothiazole-diyl group, thiazolo A thiazole-diyl group, a thienothiophene-diyl group, a thienooxazole-diyl group, and the like can be mentioned.

In formula (2), the definition of R4 is the same as that of R1 in formula (1).
In formula (2), definitions of R5 and R6 are the same as those of R2 and R3 in formula (1).

From the viewpoint of light resistance, R4 is preferably an electron-withdrawing group, and R5 and R6 are preferably groups with low electron-donating properties.
Among such groups, specific examples in which R4 is an electron-withdrawing group are the same as specific examples in which R1 is an electron-withdrawing group, and R5 and R6 are groups with low electron-donating properties. When R2 and R3 are low electron-donating groups, specific examples are the same as those for R2 and R3.

Specific examples of the second dichroic azo dye compound are shown below, but are not limited thereto.

(Third dichroic azo dye compound)
The third dichroic azo dye compound is a dichroic azo dye compound other than the first dichroic azo dye compound and the second dichroic azo dye compound, specifically, the first dichroic azo dye compound The chemical structure is different from that of the chromatic azo dye compound and the second dichroic azo dye compound. If the polarizer contains the third dichroic azo dye compound, there is an advantage that the color of the polarizer can be easily adjusted.
The maximum absorption wavelength of the third dichroic azo dye compound is 380 nm or more and less than 455 nm, preferably 385 to 454 nm.
Specific examples of the third dichroic azo dye compound include compounds represented by the formula (1) described in WO 2017/195833, among the compounds, the first dichroic azo dye compounds and compounds other than the second dichroic azo dye compound.

Specific examples of the third dichroic dye compound are shown below, but the present invention is not limited to these. In the following specific examples, n represents an integer of 1-10.

(Content of dichroic azo dye compound)
The content of the dichroic azo dye compound is preferably 15 to 30% by mass, more preferably 18 to 28% by mass, still more preferably 20 to 26% by mass, relative to the total solid mass of the polarizer. If the content of the dichroic azo dye compound is within the above range, a polarizer with a high degree of orientation can be obtained even when the polarizer is made into a thin film. Therefore, it is easy to obtain a polarizer having excellent flexibility. Moreover, when it exceeds 30% by mass, it becomes difficult to suppress internal reflection by the refractive index adjusting layer.
The content of the first dichroic azo dye compound is based on 100 parts by mass of the total content of the dichroic azo dye compound in the polarizer-forming composition (composition for forming the light absorption anisotropic layer). , preferably 40 to 90 parts by mass, more preferably 45 to 75 parts by mass.
The content of the second dichroic azo dye compound is preferably 6 to 50 parts by mass with respect to 100 mass of the total content of the dichroic azo dye compound in the polarizer-forming composition, and 8 to 35 parts by mass. part is more preferred.
The content of the third dichroic azo dye compound is preferably 3 to 35 parts by mass, and 5 to 30 parts by mass, with respect to 100 mass parts of the dichroic azo dye compound in the polarizer-forming composition. is more preferred.
The content ratio of the first dichroic azo dye compound, the second dichroic azo dye compound, and the optionally used third dichroic azo dye compound is the color of the polarizer. It can be set arbitrarily for adjustment. However, the content ratio of the second dichroic azo dye compound to the first dichroic azo dye compound (second dichroic azo dye compound / first dichroic azo dye compound) is in terms of moles , is preferably 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8.

<PVA Polarizer Having Dichroic Organic Dye>
As a polarizer having a dichroic organic dye, for example, a polarizer formed by adsorbing a dichroic organic dye to a polyvinyl alcohol (PVA) resin and stretching it (hereinafter, abbreviated as "PVA polarizer" ).
A polyvinyl alcohol-based resin is a resin containing a repeating unit of —CH ₂ —CHOH—, and examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymers.
In this embodiment, the dichroic organic dye is preferably a highly hydrophilic dye, and it is preferable to use an azo dye having a sulfo group described in paragraphs [0027] to [0030] of JP-A-2019-86622.

On the other hand, polyvinyl alcohol-based resins are very hydrophilic and highly water absorbent, and contribute significantly to the water content of the entire polarizing plate. It becomes possible to adjust the water content by reducing the film thickness of the polarizer. Further, as described in JP-A-2015-129826, by dyeing and stretching a laminate in which a 9 μm-thick polyvinyl alcohol layer is formed on a non-liquid crystal PET (polyethylene terephthalate) base material, a 4 μm-thick It is disclosed that a polyvinyl alcohol layer can be obtained, and the use of such a method is also preferred.
The thickness of the polyvinyl alcohol-based resin layer is preferably 15 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. By reducing the thickness of the polarizer, it is possible not only to make the display device thinner, but also to further reduce the water content, thereby improving the wet heat durability of the display device. Moreover, in order to obtain the absorbance necessary for a polarizer, the thickness of the polyvinyl alcohol-based resin layer is preferably 1 μm or more.

<Polarizer Containing Dichroic Organic Dye and Polymerizable Liquid Crystal Compound>
Another example of a polarizer having a dichroic organic dye is a polymerizable liquid crystal compound without using polyvinyl alcohol as a binder, as described in WO2019/131943 and JP-A-2017-83843. And a composition (polarizer-forming composition) containing a dichroic organic dye (for example, a dichroic azo dye used in a light-absorbing anisotropic film described in WO2017/195833), by coating A formed polarizer (hereinafter abbreviated as "coating type polarizer") is preferred.
Since the coated polarizer does not require a polyvinyl alcohol-based resin layer, it is possible to further reduce the water content of the polarizing plate compared to the PVA polarizer, and further improve the wet heat durability of the display device. It becomes possible.

The polymerizable liquid crystal compound contained in the polarizer-forming composition is not particularly limited, and examples thereof include the same polymerizable liquid crystal compounds contained in the composition used for forming the optically anisotropic layer described above.
Moreover, the polymerizable liquid crystal compound preferably has a polymerizable group from the viewpoint of film strength, and the solid content ratio to the coating composition is preferably 60% by mass or more.
More preferably, the polymerizable liquid crystal compound or the dichroic organic dye contained in the polarizer-forming composition has a radically polymerizable group.
The molar content of the radically polymerizable group is preferably 0.6 mmol/g or more, more preferably 1.0 mmol/g or more, relative to the solid weight of the polarizer-forming composition. It is more preferable if it is 5 mmol/g or more.
This coated polarizer is a technique for orienting a dichroic organic dye by utilizing the orientation of a liquid crystal compound. As described in JP-A-2012-83734, when the polymerizable liquid crystal compound exhibits smectic properties, it is preferable from the viewpoint of increasing the degree of orientation. Alternatively, as described in WO2018/186503, it is preferable to crystallize the dye from the viewpoint of increasing the degree of orientation. WO2019/131943 describes a preferred polymer liquid crystal structure for increasing the degree of alignment.
In order to orient the coated polarizer, it is preferable to have an orientation layer. Details of the orientation layer will be described later.

A polarizer in which a dichroic organic dye is oriented by utilizing the orientation of liquid crystal without stretching has the following characteristics. It can be made very thin with a thickness of about 0.1 μm to 5 μm, and as described in JP-A-2019-194685, it is difficult for cracks to occur when bent and thermal deformation is small. As described in 1., even a polarizing plate with a high transmittance exceeding 50% has many advantages such as excellent durability.
By taking advantage of these advantages, it can be used for applications requiring high brightness, small size and light weight, applications for fine optical systems, applications for molding parts having curved surfaces, and applications for flexible parts. Of course, it is also possible to peel off the support and transfer the polarizer for use.

The thickness of the coated polarizer is preferably 0.1 to 5 μm, more preferably 0.3 to 3 μm, even more preferably 0.3 to 2 μm. By reducing the thickness of the polarizer, the thickness of the display device can be reduced. Lamination coating of an optically anisotropic layer and a coating-type polarizer and coating them on both sides of the same support can also omit the adhesive layer, thereby reducing the thickness of the circularly polarizing plate and increasing production efficiency. It is preferable from the viewpoint of conversion.
Since the coating-type polarizer has excellent durability even at a high transmittance compared to the PVA polarizer, it is preferable that the luminosity correction single transmittance of the polarizer is 40% or more from the viewpoint of power saving. It is more preferably 45% or more, and even more preferably 50% or more.

The relationship between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer in the polarizing plate is not particularly limited.
When the polarizing plate is used for antireflection purposes, the optically anisotropic layer is a λ/4 plate, and the angle formed by the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45±10°. A range (35-55°) is preferred.

[Adhesive layer]
The organic electroluminescence display device of the present invention has an adhesive layer between the circularly polarizing plate described above and the silicon nitride layer described later.

Examples of adhesives contained in the adhesive layer include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, and polyvinylpyrrolidone-based adhesives. , polyacrylamide-based adhesives, cellulose-based adhesives, and the like.
Among these, acrylic adhesives (pressure-sensitive adhesives) are preferable from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The adhesive layer is formed, for example, by applying an adhesive solution onto a release sheet, drying it, and then transferring it to the surface of the transparent resin layer; applying the adhesive solution directly to the surface of the transparent resin layer and drying it. method;
The adhesive solution is prepared as a solution of about 10 to 40% by mass by dissolving or dispersing the adhesive in a solvent such as toluene or ethyl acetate.
As the coating method, a roll coating method such as reverse coating or gravure coating, a spin coating method, a screen coating method, a fountain coating method, a dipping method, a spray method, or the like can be employed.

Materials constituting the release sheet include, for example, synthetic resin films such as polyethylene, polypropylene, and polyethylene terephthalate; rubber sheets; paper; cloth; mentioned.

In the present invention, the thickness of the adhesive layer is not particularly limited, but is preferably 3 μm to 50 μm, more preferably 4 μm to 40 μm, even more preferably 5 μm to 30 μm.

[Silicon nitride layer]
The organic electroluminescence display device of the present invention has a silicon nitride layer between the above adhesive layer and the organic electroluminescence element.
Since organic electroluminescence elements are sensitive to moisture and oxygen, a silicon nitride layer is used as a barrier layer (low-moisture-permeable substrate) that blocks moisture and oxygen.
The moisture permeability of the silicon nitride layer is desirably 1 g/m ² ·day or less, preferably 10 ⁻³ g/m ² ·day or less. Above all, it is more preferably 10 ⁻⁴ g/m ² ·day or less, and even more preferably 10 ⁻⁵ g/m ² ·day or less, from the viewpoint of durability of the organic electroluminescence display element. Although the lower limit is not particularly limited, it is often 10 ⁻¹⁰ g/m ² ·day or more.
Here, the moisture permeability refers to the method described in JIS Z 0208: 1976 "Moisture-proof packaging material moisture permeability test method (cup method)", at a temperature of 40 ° C. and a relative humidity of 90% for 24 hours. It refers to the amount of water vapor that has passed (g/m ² ·day).
A method for measuring the moisture permeability of the substrate is as follows. Measurement is performed using a water vapor transmission rate measuring device (AQUATRAN2 (registered trademark) manufactured by MOCON, INC.) under conditions of a measurement temperature of 40°C and a relative humidity of 90%.
From the viewpoint of gas barrier performance, the thickness of the silicon nitride layer is preferably 10 nm, more preferably 20 nm or more. From the viewpoint of preventing film cracking, the thickness is preferably 150 nm or less, more preferably 80 nm or less.

The silicon nitride layer preferably contains silicon atoms, nitrogen atoms and hydrogen atoms, and specifically SiNH (element ratio Si:N:H=1:1:1). more preferred.

Any conventionally known method can be used to form the silicon nitride layer. For example, a sputtering method, a vacuum deposition method, an ion plating method, and a plasma CVD (Chemical Vapor Deposition) method are suitable. The formation method described in each publication of No. 361774 can be employed.
A silicon nitride layer may generate ammonia gas by hydrolysis reaction, but the hydrolysis reaction is accelerated in the following cases, and the effect of the present invention becomes remarkable.
The silicon nitride layer has a Si—N bond peak (absorption peak (peak intensity) due to stretching vibration of Si—N) located at 800 to 900 cm ⁻¹ in FT-IR (Fourier transform infrared absorption spectrum) measurement, Si—H bond peak located at 2100 to 2200 cm ⁻¹ (absorption peak due to Si—H stretching vibration), and N—H bond peak located at 3300 to 3400 cm ⁻¹ (due to N—H stretching vibration absorption peak). From the point that the effect of the present invention appears more remarkably, N—H/Si—N, which is the intensity ratio between the Si—N bond peak and the N—H bond peak, is preferably 0.04 or more, and 0.06. It is more preferably 0.08 or more, and most preferably 0.10 or more. From the viewpoint of the barrier performance of the film, N—H/Si—N is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.15 or less.
As for the film density of the silicon nitride layer, the film density [g/cm ³ ] can be measured by an X-ray reflectance measurement method using a thin-film X-ray diffractometer (ATX-E manufactured by Rigaku Corporation). The film density is preferably 2.4 g/cm ³ or less, more preferably 2.3 g/cm ³ or less, from the viewpoint that the effects of the present invention appear more remarkably. From the viewpoint of the barrier performance of the film, it is preferably 1.8 g/cm ³ or more, more preferably 2.0 g/cm ³ or more, and even more preferably 2.2 g/cm ³ or more.

[Organic EL display element]
The organic EL display element of the organic electroluminescence display device of the present invention is a display element having a pair of electrodes and an organic light-emitting layer sandwiched therebetween.
Between the electrodes of the organic EL display element, in addition to the organic light-emitting layer, a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, a protective layer, and the like may be provided. It may have other functions. Various materials can be used to form each layer.

[Other layers]
The organic electroluminescence display device of the present invention may have the above-mentioned circularly polarizing plate (optically anisotropic layer and polarizer), adhesive layer, silicon nitride layer, and other members other than the organic EL element. good.

[Support]
The organic electroluminescent display device of the present invention may have a support for supporting the optically anisotropic layer and the coating-type polarizer, but the support may be peeled off for thinning. preferable.
The support is preferably transparent, and specifically preferably has a light transmittance of 80% or more.

Supports include, for example, polymer films.
Materials for the polymer film include cellulose-based polymers; (meth)acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; , polyester-based polymers such as polyethylene naphthalate; styrene-based polymers such as polystyrene and acrylonitrile-styrene copolymers (AS resins); polyolefin-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl-based polymer; nylon and amide-based polymer such as aromatic polyamide; imide-based polymer; sulfone-based polymer; polyethersulfone-based polymer; polyetheretherketone-based polymer; polyphenylene sulfide-based polymer; vinyl butyral-based polymer; arylate-based polymer; polyoxymethylene-based polymer; epoxy-based polymer;
Moreover, the above-described polarizer may also serve as such a support.

The thickness of the support is not particularly limited, but is preferably 5 to 80 μm, more preferably 10 to 40 μm, even more preferably 10 to 25 μm.

[Orientation layer]
The organic electroluminescence display device of the present invention preferably has an alignment layer in order to promote the alignment of the optically anisotropic layer and the coating-type polarizer, but the alignment layer may be peeled off for thinning. preferable. In addition, the above-described support may also serve as an orientation layer.

In order to form a positive A plate, which is one aspect of an optically anisotropic layer, a technique is used to bring molecules of a specific liquid crystal compound into a desired alignment state. Techniques for orienting a compound in a desired direction are common.
As the alignment layer, a rubbed film of a layer containing an organic compound such as a polymer, an oblique deposition film of an inorganic compound, a film having microgrooves, or ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearate. A film obtained by accumulating LB (Langmuir-Blodgett) films by the Langmuir-Blodgett method of organic compounds such as .
Furthermore, as the alignment layer, a photo-alignment layer in which an alignment function is produced by irradiation with light is also preferable.

As the alignment layer, one formed by rubbing the surface of a layer (polymer layer) containing an organic compound such as a polymer can be preferably used. The rubbing treatment is carried out by rubbing the surface of the polymer layer with paper or cloth several times in a given direction (preferably in the longitudinal direction of the support). Polymers used to form the alignment layer include polyimide, polyvinyl alcohol, modified polyvinyl alcohol described in paragraphs 0071 to 0095 of Japanese Patent No. 3907735, and polymerizable groups described in JP-A-9-152509. Polymers with
The thickness of the alignment layer is not particularly limited as long as the alignment function can be exhibited, but is preferably 0.01 to 5 μm, more preferably 0.05 to 2 μm.

As the alignment layer, it is more preferable to use a so-called photo-alignment layer (photo-alignment layer) obtained by irradiating a photo-alignment material with polarized or non-polarized light to form an alignment layer.
It is preferable to impart an alignment regulating force to the photo-alignment layer by a step of irradiating polarized light from a vertical direction or an oblique direction, or a step of irradiating non-polarized light from an oblique direction.
By using the photo-alignment layer, it is possible to horizontally align the specific liquid crystal compound with excellent symmetry. Therefore, the positive A plate formed using the photo-alignment layer is particularly useful for optical compensation in liquid crystal display devices such as IPS (In-Place-Switching) mode liquid crystal display devices that do not require a pre-tilt angle of the driving liquid crystal. is.

As the photo-alignment material used in the photo-alignment layer, for example, JP-A-2006-285197, JP-A-2007-076839, JP-A-2007-138138, JP-A-2007-094071, JP-A-2007- 121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, JP 3883848, the azo compound described in JP 4151746 , Aromatic ester compounds described in JP-A-2002-229039, JP-A-2002-265541, maleimide and / or alkenyl-substituted nadimide compound having a photo-orientation unit described in JP-A-2002-317013, patent No. 4205195, a photocrosslinkable silane derivative described in Patent No. 4205198, a photocrosslinkable polyimide, a polyamide, or an ester described in JP 2003-520878, JP 2004-529220, JP 4162850, Described in JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, International Publication No. 2010/150748, JP-A-2013-177561, JP-A-2014-12823 of photodimerizable compounds, particularly cinnamate compounds, chalcone compounds, and coumarin compounds.
Particularly preferred examples include cinnamate compounds.

Although the thickness of the alignment layer is not particularly limited, it is preferably 0.01 to 10 μm, and 0.01 to 10 μm, from the viewpoint of alleviating surface irregularities that may exist on the support and forming an optically anisotropic layer of uniform thickness. 01 to 1 μm is more preferable, and 0.01 to 0.5 μm is even more preferable.

[Trap layer]
The organic electroluminescence display device of the present invention may have a base trapping layer containing a compound having a carboxylic acid group for the purpose of trapping ammonia.
It is also possible to incorporate a compound having a carboxylic acid group into an adhesive layer, a barrier layer, or a layer such as a positive C plate to form a base trap layer.

[Polarizer protective film]
The organic electroluminescence display device of the present invention may have a polarizer protective film on the surface of the polarizer.
The polarizer protective film may be arranged only on one surface of the polarizer (on the surface opposite to the optically anisotropic layer), or may be arranged on both surfaces of the polarizer. The structure of the polarizer protective film is not particularly limited, and may be, for example, a so-called transparent support, a hard coat layer, or a laminate of a transparent support and a hard coat layer. The visible side of the polarizer protective film can be used together with the surface protective layer described below.
As the transparent support, a known transparent support can be used. For example, the material for forming the transparent support is a cellulose-based polymer (hereinafter referred to as "cellulose acylate" typified by triacetyl cellulose). ), norbornene-based resins (ZEONEX and ZEONOR manufactured by Zeon Corporation, ARTON manufactured by JSR Corporation), acrylic resins, polyester-based resins, and polystyrene-based resins. Resins that hardly absorb water, such as acrylic resins, thermoplastic norbornene resins, and polystyrene resins, are preferred for suppressing the total water content of the polarizing plate, and norbornene resins are particularly preferred.
The resin preferably has an equilibrium moisture content of 80% at 25° C. of 2% or less, more preferably 0.5% or less, and more preferably 0.2% or less.
Although the thickness of the polarizer protective film is not particularly limited, it is preferably 40 µm or less, more preferably 25 µm or less, even more preferably 10 µm or less, and particularly preferably 5 µm or less, in order to reduce the thickness of the polarizing plate. Although the lower limit is not particularly limited, it is often 1 μm or more.

An adhesive layer or adhesive layer may be arranged between the layers to ensure the adhesion between the layers. Furthermore, a transparent support may be placed between each layer.
The polarizing plate may have an optically anisotropic layer other than the optically anisotropic layer formed using the polymerizable liquid crystal composition containing the specific liquid crystal compound described above.
Other optically anisotropic layers may be A-plates or C-plates.

The water content of the polarizing plate is not particularly limited, but is preferably 5.0 g/m ² or less, more preferably 3.0 g/m ² or less, still more preferably 1.5 g/m ² or less, and 0.8 g/m ² or less. is particularly preferred.

[Surface protective layer]
As one preferred embodiment of the organic electroluminescence display device of the present invention, it is preferable to have a surface protective layer on the visible side of the circularly polarizing plate, that is, on the most visible side when used as a part of the display device. Here, the surface protective layer is selected from a support made of a polymer film such as polyimide or cellulose acylate, a hardened surface layer, a low-reflection layer that suppresses surface reflection occurring at an air interface, and the like. include. As the hard coat layer, a known layer can be used, and for example, a layer obtained by polymerizing and curing a polyfunctional monomer may be used.

The moisture permeability of the surface protective layer is preferably 1 g/m ² ·day or more, preferably more than 1 g/m ² ·day, and 2 to 500 g/m ² ·day, since the effect of the present invention appears more remarkably. more preferred.

〔Touch sensor〕
The touch sensor has an on-cell type that forms a metal mesh electrode directly on the silicon nitride layer that barriers the organic electroluminescence element, and an out-cell type that externally attaches a film sensor with electrodes formed on the film. , the on-cell type is preferable from the viewpoint of thinning and the effect of the present invention is remarkably exhibited.

[Adhesive layer]
The organic electroluminescence display device of the present invention may have an adhesive layer.
The adhesive is not particularly limited as long as it develops adhesiveness through drying or reaction after bonding.
Polyvinyl alcohol-based adhesive (PVA-based adhesive) develops adhesiveness when dried, making it possible to bond materials together.
Specific examples of curable adhesives that exhibit adhesiveness through reaction include active energy ray curable adhesives such as (meth)acrylate adhesives and cationic polymerization curable adhesives. The curable component in the (meth)acrylate adhesive includes, for example, a compound having a (meth)acryloyl group and a compound having a vinyl group.
Compounds having an epoxy group or an oxetanyl group can also be used as cationic polymerization curing adhesives. The compound having an epoxy group is not particularly limited as long as it has at least two epoxy groups in the molecule, and various commonly known curable epoxy compounds can be used. Preferred epoxy compounds include compounds having at least two epoxy groups and at least one aromatic ring in the molecule (aromatic epoxy compounds), and compounds having at least two epoxy groups in the molecule, at least one of which Examples include compounds (alicyclic epoxy compounds) formed between two adjacent carbon atoms constituting an alicyclic ring.

[Function layer]
It is preferable to have a functional layer having a function of reducing short-wave light on the viewing side of the optically anisotropic layer. By reducing short-wave light, it is possible to suppress photodecomposition of the dye compound and provide an organic electroluminescence display device having excellent light resistance.
As one aspect, it is preferable that the adhesive layer, the support, the polarizer protective film, and the like described above have a function of reducing short-wave light.
As another aspect, it is also preferable to newly provide a layer having a function of reducing short-wave light on the viewing side of the optically anisotropic layer.

A method for reducing short-wave light is not particularly limited, and examples thereof include a method using light absorption by an absorbent or the like and a method using wavelength selective reflection by a multilayer film.

The aforementioned short-wave light refers to light with a wavelength of 430 nm or less. By reducing light with a wavelength of 430 nm or less, it is possible to suppress photodecomposition of the liquid crystal compound due to sunlight or the light source used in the light resistance test of JIS B 7751 and JIS B 7754.
In order not to affect the performance of the polarizer in visible light, it is preferably transparent in the wavelength region of 450 nm or more.
The transmittance is preferably 0.1% or less in the wavelength range of 350 to 390 nm, 20 to 70% in the wavelength range of 410 nm, and 90% or more in the wavelength range of 450 nm or more.
More preferably, the transmittance at a wavelength of 410 nm is 40-50%.

As the compound that absorbs short-wave light, merocyanine compounds described in JP-A-2017-119700 and WO2018/123267 are preferably used.
Moreover, it is also preferable to use a conventionally well-known ultraviolet absorber together. Examples include organic UV absorbers such as oxybenzophenone UV absorbers, benzotriazole UV absorbers, salicylic acid ester UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. be done.

〔Layer structure〕
Since the effect of the present invention appears remarkably, it is preferable that the layer present between the circularly polarizing plate and the silicon nitride layer has a moisture permeability of 100 g/m ² ·day or more. In other words, it is preferable that there is no layer between the circularly polarizing plate and the silicon nitride layer having a moisture permeability of less than 100 g/m ² ·day.
In the present invention, from the viewpoint of thinning, the thickness of the layer present between the circularly polarizing plate and the silicon nitride layer must be 35 μm or less, preferably 1 to 30 μm.

The present invention will be described in more detail below based on examples. Materials, usage amounts, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limited by the examples shown below.

<Preparation of surface protective layer H1>
(Manufacturing of polyimide powder)
832 g of N,N-dimethylacetamide (DMAc) was added to a 1 L reactor equipped with a stirrer, a nitrogen injector, a dropping funnel, a temperature controller and a condenser under a nitrogen stream, and then the temperature of the reactor was reduced to 25. °C. 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added thereto and dissolved. While maintaining the resulting solution at 25° C., 31.09 g (0.07 mol) of 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride (6FDA) and biphenyltetracarboxylic dianhydride were added. 8.83 g (0.03 mol) of product (BPDA) was added and stirred for a certain period of time to react. After that, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution with a solid concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to the polyamic acid solution, stirred for 30 minutes, further stirred at 70° C. for 1 hour, and then cooled to room temperature. 20 L of methanol was added thereto, and the precipitated solid matter was filtered and pulverized. Then, it was dried under vacuum at 100° C. for 6 hours to obtain 111 g of polyimide powder.

(Preparation of support S1)
100 g of polyimide powder was dissolved in 670 g of N,N-dimethylacetamide (DMAc) to obtain a 13 wt% solution. The resulting solution was cast on a stainless plate and dried with hot air at 130° C. for 30 minutes. After that, the film was peeled off from the stainless steel plate and fixed to the frame with pins. The frame with the film fixed was placed in a vacuum oven and heated for 2 hours while gradually increasing the heating temperature from 100°C to 300°C, and then gradually. cooled to After the cooled film was separated from the frame, it was further heat-treated at 300° C. for 30 minutes as a final heat treatment step to obtain a support S1 made of a polyimide film and having a thickness of 30 μm.

<Synthesis of polymerizable polyorganosilsesquioxane>
(Synthesis of compound (A))
A 1000 mL flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen inlet was charged with 297 mmol of 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane (73.0 mmol) under a stream of nitrogen. 2 g), 3 millimoles (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methyl isobutyl ketone) were mixed, and 73.9 g of pure water was added dropwise over 30 minutes using a dropping funnel. This reaction solution was heated to 80° C., and the polycondensation reaction was carried out for 10 hours under a nitrogen stream.
After that, the reaction solution was cooled, 300 g of 5% by mass saline was added, and the organic layer was extracted. The organic layer was washed with 300 g of 5% by weight saline solution and 300 g of pure water twice in sequence, and then concentrated under conditions of 1 mmHg and 50° C. to produce a colorless transparent liquid MIBK solution with a solid content concentration of 59.8% by weight. (Rb in (1) below: 2-(3,4-epoxycyclohexyl)ethyl group, Rc: methyl group, q= A methyl isobutyl ketone (MIBK) solution containing 59.0% by mass of solid content concentration of 99, r=1) was obtained.

The obtained compound (A) had a number average molecular weight (Mn) of 2310 and a polydispersity (Mw/Mn) of 2.1.
Note that 1 mmHg is approximately 133.322 Pa.

(Synthesis of polymer (1-1))
25.0 g of t-amyl alcohol was placed in a 200 ml three-necked flask equipped with a stirrer, thermometer, reflux condenser and nitrogen gas inlet tube, and the temperature was raised to 120°C. Then, 2-(perfluorohexyl)ethyl acrylate {corresponding to monomer (K2)} 3.25 g (7.8 mmol), compound (I-1) having the following structure {corresponding to monomer (K1)} 2.26 g (4.7 mmol), 25.0 g of cyclohexanone and 4.7 g of "V-601" (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise at a constant rate so that the dropwise addition was completed in 120 minutes. After the dropwise addition was completed, stirring was continued for an additional 3.5 hours to obtain 5.5 g of polymer (1-1) (solid content conversion value). The weight average molecular weight (Mw) of this polymer was 1,1001,600.

<Preparation of composition for forming hard coat layer>
(Composition HC-1 for hard coat layer formation)
CPI-100P, polymer (1-1) and MIBK (methyl isobutyl ketone) were added to the MIBK solution containing the above compound (A), and the concentrations of each component were adjusted to the following concentrations, It was put into a mixing tank and stirred. The resulting composition was filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a hard coat layer forming composition HC-1.

Compound (A) 98.6 parts by mass CPI-100P 1.3 parts by mass Polymer (1-1) 0.1 parts by mass Methyl isobutyl ketone 100.0 parts by mass

The compounds used in the composition for forming the hard coat layer are as follows.
CPI-100P: cationic photopolymerization initiator, manufactured by San-Apro Co., Ltd.

<Preparation of Mixed Layer Forming Composition>
(Mixed layer forming composition M-1)
The MIBK solution containing the above compound (A) is subjected to solvent substitution with a MEK (methyl ethyl ketone) solution, DPHA, CPI-100P, Irgacure 127, leveling agent-1 and MEK are added, and the concentrations of each component are as follows. It was adjusted so that The resulting composition was filtered through a polypropylene filter having a pore size of 0.4 μm to obtain mixed layer forming composition M-1. The mixing ratio of the compound (A) and DPHA in the mixed layer-forming composition M-1 was compound (A)/DPHA=50% by mass/50% by mass.

Compound (A) 42.85 parts by mass DPHA 42.85 parts by mass CPI-100P 1.3 parts by mass Irgacure 127 5.0 parts by mass Leveling agent-1 8.0 parts by mass Methyl ethyl ketone 500.0 parts by mass

The compounds used in the mixed layer-forming composition are as follows.
DPHA: a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, manufactured by Nippon Kayaku Co., Ltd. Irgacure 127: radical photopolymerization initiator, manufactured by BASF Leveling agent-1: a polymer having the following structure (Mw = 20000, the following The composition ratio of repeating units is the mass ratio)

<Preparation of composition for forming scratch-resistant layer>
(Scratch-resistant layer-forming composition SR-1)
Each component having the composition described below was charged into a mixing tank, stirred, and filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a scratch-resistant layer-forming composition SR-1.

DPHA 96.2 parts by mass Irgacure 127 2.8 parts by mass RS-90 1.0 parts by mass Methyl ethyl ketone 300.0 parts by mass

The compounds used in the scratch-resistant layer-forming composition are as follows.
RS-90: Lubricant, manufactured by DIC Corporation

(Production of surface protective layer H1)
The composition HC-1 for forming a hard coat layer was applied onto the substrate S-1 using a die coater. After drying at 120° C. for 1 minute, the hard coat layer was semi-cured by irradiating ultraviolet rays with an illumination intensity of 18 mW/cm ² and an irradiation dose of 10 mJ/cm ² using an air-cooled mercury lamp at 25° C. The refractive index of this layer was 1.53.
A mixed layer-forming composition was prepared by adding MEK to the mixed layer-forming composition M-1 to dilute the solid content concentration to 1/10, and applied onto the semi-cured hard coat layer using a die coater. . After drying at 120°C for 1 minute, the mixed layer is semi-cured by irradiating ultraviolet rays with an illumination intensity of 18 mW/cm ² and an irradiation dose of 10 mJ/cm ² using an air-cooled mercury lamp at 25°C and an oxygen concentration of 1%. A mixed layer was provided on the hard coat layer.
A scratch-resistant layer-forming composition SR-1 was applied onto the semi-cured mixed layer using a die coater. After drying at 120°C for 1 minute, using an air-cooled mercury lamp under the conditions of 25°C and an oxygen concentration of 100 ppm, an illuminance of 60 mW/cm ² and an irradiation dose of 800 mJ/cm ² were applied. The hard coat layer, the mixed layer, and the scratch resistant layer were completely cured by irradiating ultraviolet rays with an illuminance of 60 mW/cm ² and an irradiation amount of 800 mJ/cm ² using an air-cooled mercury lamp at a concentration of 100 ppm. The resulting film was then heat-treated at 120° C. for 1 hour to form a surface protective layer having a 0.1 μm-thick mixed layer and a 1.0 μm-thick anti-scratch layer on a 11.0 μm-thick hard coat layer. H1 was obtained. The moisture permeability of the surface protective layer H1 was more than 1 g/m ² ·day.

<Preparation of PVA adhesive>
Polyvinyl alcohol resin containing acetoacetyl groups (average degree of polymerization: 1200, degree of saponification: 98.5 mol%, degree of acetoacetylation: 5 mol%) was added with 20 parts of methylolmelamine at 30°C. It was dissolved in pure water under temperature conditions to prepare an aqueous solution adjusted to a solid concentration of 3.7%.

<Production of Adhesive Layers N1 and N2>
Next, an acrylate-based polymer was prepared according to the following procedure.
95 parts by weight of butyl acrylate and 5 parts by weight of acrylic acid are polymerized by a solution polymerization method in a reaction vessel equipped with a cooling tube, a nitrogen inlet tube, a thermometer and a stirring device, and the average molecular weight is 2,000,000 and the molecular weight distribution (Mw/ An acrylate polymer A1 having Mn) of 3.0 was obtained.

Next, using the obtained acrylate-based polymer A1, an acrylate-based pressure-sensitive adhesive having the composition shown in Table 3 below was prepared.
These compositions are applied to a separate film surface-treated with a silicone-based release agent using a die coater, dried in an environment of 90 ° C. for 1 minute, and irradiated with ultraviolet rays (UV) under the following conditions to form an adhesive layer. N1 and N2 were obtained. Table 3 below shows the composition, film thickness and storage modulus of the acrylate adhesive.
(UV irradiation conditions (only N1 irradiation))
・Electrodeless lamp H bulb from Fusion ・Illuminance 600 mW/cm ² , Light quantity 150 mJ/cm ²
・The UV illuminance/light quantity was measured using “UVPF-36” manufactured by Eye Graphics.

(A) Polyfunctional acrylate-based monomer: tris (acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional (manufactured by Toagosei Co., Ltd., trade name "Aronix M-315") (B) Photopolymerization initiator: benzophenone and 1-hydroxycyclohexyl phenyl ketone at a mass ratio of 1: 1, Ciba Specialty Chemicals Co., Ltd. "Irgacure 500"
(C) Isocyanate-based cross-linking agent: trimethylolpropane-modified tolylene diisocyanate ("Coronate L" manufactured by Nippon Polyurethane Co., Ltd.)
(D) Silane coupling agent: 3-glycidoxypropyltrimethoxysilane ("KBM-403" manufactured by Shin-Etsu Chemical Co., Ltd.)

[Preparation of Polarizer 1 with Surface Protective Layer H1]
The surface of the support of a cellulose triacetate film TJ25 (manufactured by Fujifilm; thickness 25 μm) was saponified with an alkali. Specifically, the support was immersed in a 1.5 N sodium hydroxide aqueous solution at 55° C. for 2 minutes, washed in a water washing bath at room temperature, and further treated with 0.1 N sulfuric acid at 30° C. neutralized using After neutralization, the support was washed in a water washing bath at room temperature and dried with warm air at 100° C. to obtain a polarizer protective film 1 .
After swelling a polyvinyl alcohol-based film (VF-XS manufactured by Kuraray Co., Ltd.) with a thickness of 75 μm, a degree of polymerization of 2400, and a degree of saponification of 99% or more with hot water at 40 ° C., an aqueous solution containing iodine, potassium iodide and boric acid. dyed. The dyed film was stretched in a solution containing 3% by weight of boric acid and, after stretching, immersed in an aqueous solution containing 5% by weight of potassium iodide. The film immersed in an aqueous potassium iodide solution for 15 seconds was dried in a drier at 70° C. for 10 minutes to obtain a polarizer 1 having a thickness of 15 μm.
The polarizer protective film 1 was adhered to one surface of the polarizer 1 using the PVA adhesive to prepare a polarizer 1 with a single-sided protective film.
Furthermore, using the adhesive layer N1, the protective film 1 side of the polarizer 1 with a single-sided protective film and the support S1 side of the surface protective layer H1 were bonded together to prepare the polarizer 1 with the surface protective layer H1.

[Preparation of PVA polarizer 2 using dichroic organic dye]
A polarizing plate SHC-215U manufactured by Polatechno Co., Ltd. was prepared by dyeing a polyvinyl alcohol film with a dichroic organic dye.
Next, the support S1 side of the surface protective layer H1 and the polarizing plate SHC-215U were adhered using the adhesive layer N1 to prepare a polarizer 2 with the surface protective layer H1.

[Preparation of Polarizer 3 Using Dichroic Organic Dye and Polymerizable Liquid Crystal Compound]
A composition E1 for forming a photo-alignment layer was prepared with the following composition, dissolved with stirring for 1 hour, and filtered through a 0.45 μm filter.
―――――――――――――――――――――――――――――――――
Photo-alignment layer-forming composition E1
―――――――――――――――――――――――――――――――――
・The following photoactive compound E-4 5.0 parts by mass ・Cyclopentanone 95.0 parts by mass ―――――――――――――――――――――――――――― ―――――

Photoactive compound E-4 (weight average molecular weight; 51000)

A composition P1 for forming a light absorption anisotropic layer was prepared according to the following composition, heated and dissolved at 80° C. for 2 hours with stirring, and filtered through a 0.45 μm filter. The molar content of radically polymerizable groups is 1.98 mmol/g.
―――――――――――――――――――――――――――――――――
Composition P1 for forming light absorption anisotropic layer
―――――――――――――――――――――――――――――――――
・2.6 parts by mass of the following dichroic dye D1 ・2.6 parts by mass of the following dichroic dye D2 ・2.2 parts by mass of the following dichroic dye D3 ・100.0 parts by mass of the following liquid crystal compound M1 ・Polymerization initiator IRGACURE369 (manufactured by BASF) 5.0 parts by mass BYK361N (manufactured by BYK-Chemie Japan) 0.9 parts by mass Cyclopentanone 925.0 parts by mass ―――――――――――――――― ―――――――――――――――――

Dichroic dye D1

Dichroic Dye D2

dichroic dye D3

Liquid crystal compound M1 (compound A/compound B = 75/25 mixed)

(Compound A)

(Compound B)

<Formation of light absorption anisotropic layer P1>
The composition E1 for forming a photo-alignment layer was applied onto a cellulose triacetate film TJ40 (manufactured by Fuji Film; thickness 40 μm) and dried at 60° C. for 2 minutes. After that, the obtained coating film was irradiated with linearly polarized ultraviolet rays (100 mJ/cm ² ) using a polarized ultraviolet exposure device to prepare a photo-alignment layer E1.
On the obtained photo-alignment layer E1, the composition P1 for forming an anisotropic light absorption layer was applied with a wire bar. Next, the resulting coating film was heated at 120° C. for 60 seconds and cooled to room temperature.
After that, a light absorption anisotropic layer P1 having a thickness of 1.7 μm was formed by irradiating ultraviolet light with an exposure amount of 2000 mJ/cm ² using a high-pressure mercury lamp.
It was confirmed that the liquid crystal of the light absorption anisotropic layer was smectic B phase.

<Formation of protective layer B1>
On the formed light absorption anisotropic layer P1, dipentaerythritol hexaacrylate (Aronix M-403, manufactured by Toagosei Co., Ltd.) (50 parts by mass), acrylate resin (Ebecryl 4858, manufactured by Daicel UCB Co., Ltd.) (50 mass part), and 2-[4-(methylthio)benzoyl]-2-(4-morpholinyl)propane (IRGACURE 907, manufactured by BASF) (3 parts by weight) in isopropanol (250 parts by weight). (Protective layer-forming composition) was applied by a bar coating method and dried by heating in a drying oven at 50°C for 1 minute.
The resulting coating film was irradiated with ultraviolet rays at an exposure amount of 400 mJ/cm ² (365 nm standard) using an ultraviolet (UV) irradiation device (SPOT CURE SP-7, manufactured by Ushio Inc.). A protective layer B1 (3 μm) was formed on the anisotropic absorption layer P1 to prepare a polarizing film 3B including the anisotropic light absorption layer P1.

The TJ40 side of the polarizing film 3B and the support S1 side of the surface protective layer H1 were adhered using the adhesive sheet N1 to prepare the polarizer 3 with the surface protective layer H1.

[Preparation of Polarizer 4 Using Dichroic Organic Dye and Polymerizable Liquid Crystal]
<Formation of photo-alignment layer PA1>
A coating solution PA1 for forming an orientation layer, which will be described later, was continuously applied on a cellulose triacetate film TJ40 (manufactured by Fujifilm, thickness 40 μm) with a wire bar. The support on which the coating film was formed was dried with hot air at 140° C. 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) to form a photo-alignment layer. PA1 was formed to obtain a TAC film with a photo-alignment layer PA1.
The film thickness of the photo-alignment layer PA1 was 0.3 μm.

―――――――――――――――――――――――――――――――――
Orientation layer forming coating solution PA1
―――――――――――――――――――――――――――――――――
Polymer PA-1 below 100.00 parts by mass Acid generator PAG-1 below 5.00 parts by mass Acid generator CPI-110TF below 0.005 parts by mass Xylene 1220.00 parts by mass Methyl isobutyl ketone 122.00 parts by mass - ――――――――――――――――――――――――――――――――

Polymer PA-1

Acid generator PAG-1

Acid generator CPI-110F

<Formation of light absorption anisotropic layer P2>
On the obtained photo-alignment layer PA1, the following composition P2 for forming a light absorption anisotropic layer was continuously applied with a wire bar to form a coating film P2.
Next, the coating film P2 was heated at 140° C. for 30 seconds, and then the coating film P2 was cooled to room temperature (23° C.).
Next, the obtained coating film P2 was heated at 90° C. for 60 seconds and cooled again to room temperature.
Thereafter, an LED (light emitting diode) lamp (center wavelength 365 nm) was used to irradiate for 2 seconds under irradiation conditions of an illuminance of 200 mW/cm ² to form a light absorption anisotropic layer P2 on the photo-alignment layer PA1. The molar content of radically polymerizable groups is 1.17 mmol/g.
The film thickness of the light absorption anisotropic layer P2 was 1.5 μm.

―――――――――――――――――――――――――――――――――
Light absorption anisotropic layer forming composition P2
―――――――――――――――――――――――――――――――――
・ 0.25 parts by mass of the following dichroic dye D-4 ・ 0.36 parts by mass of the following dichroic dye D-5 ・ 0.59 parts by mass of the following dichroic dye D-6 ・ The following polymer liquid crystal compound P- 1 2.21 parts by mass 1.36 parts by mass of the following low-molecular liquid crystalline compound M-1 Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.150 parts by mass 0.026 parts by mass of the following surfactant F-1 parts Cyclopentanone 46.00 parts by mass Tetrahydrofuran 46.00 parts by mass Benzyl alcohol 3.00 parts by mass―――――――――――――――――――――――――― ――――――――

Dichroic dye D-4

Dichroic dye D-5

Dichroic dye D-6

Polymer liquid crystal compound P-1

Low-molecular-weight liquid crystalline compound M-1

Surfactant F-1

<Formation of hardened layer K1>
On the obtained light absorption anisotropic layer P2, the following cured layer forming composition K1 was continuously applied with a wire bar to form a coating film.
Next, the coating film was dried at room temperature and then irradiated with a high-pressure mercury lamp at an illuminance of 28 mW/cm ² for 15 seconds to form a cured layer K1 on the light absorption anisotropic layer P2.
The film thickness of the hardened layer K1 was 0.05 μm.
―――――――――――――――――――――――――――――――――
Cured layer forming composition K1
―――――――――――――――――――――――――――――――――
2.61 parts by mass of the following rod-like liquid crystal compound mixture L1 0.11 parts by mass of the modified trimethylolpropane triacrylate below 0.05 parts by mass of the photopolymerization initiator I-1 below 0.05 parts by mass of the following surfactant F-3 21 parts by mass, methyl isobutyl ketone 297 parts by mass ――――――――――――――――――――――――――――――――――

Mixture L1 of rod-like liquid crystal compounds (values in the following formula represent % by mass, and R represents a group that bonds with an oxygen atom.)

Modified trimethylolpropane triacrylate

Photoinitiator I-1

Surfactant F-3

<Formation of oxygen blocking layer B2>
On the cured layer K1, the following composition B2 for forming an oxygen barrier layer was continuously applied with a wire bar. After that, by drying with hot air at 100° C. for 2 minutes, an oxygen blocking layer B2 having a thickness of 1.0 μm was formed on the cured layer K1, and a polarizing film 4B including the light absorption anisotropic layer P2 was produced.
The luminous efficiency correction single transmittance of the polarizer was 43%.
―――――――――――――――――――――――――――――――――
Oxygen barrier layer-forming composition B2
―――――――――――――――――――――――――――――――――
・The following modified polyvinyl alcohol 3.80 parts by mass ・Initiator Irg2959 0.20 parts by mass ・Water 70 parts by mass ・Methanol 30 parts by mass ―――――――――――――――――――― ―――――――――――――

Modified polyvinyl alcohol

The oxygen blocking layer B2 side of the polarizing film 4B and the support S1 side of the surface protective layer H1 were attached using the adhesive sheet N1. After that, only TJ40 was peeled off to produce a polarizer 4 with a surface protective layer H1.

<Preparation of UV adhesive>
The following UV adhesive composition was prepared.
──────────────────────────────────
UV adhesive composition ──────────────────────────────────
・CEL2021P (manufactured by Daicel) 70 parts by mass ・1,4-Butanediol diglycidyl ether 20 parts by mass ・2-Ethylhexyl glycidyl ether 10 parts by mass ・CPI-100P 2.25 parts by mass ────────── ────────────────────────

CPI-100P

[Production example 1]
[Preparation of Cellulose Acylate Film 1]
The following composition was put into a mixing tank and stirred to prepare a cellulose acetate solution used as a core layer cellulose acylate dope.
──────────────────────────────────
Core layer cellulose acylate dope────────────────────────────────────
- 100 parts by weight of cellulose acetate having a degree of acetyl substitution of 2.88 - 12 parts by weight of polyester compound B described in Examples of JP-A-2015-227955 - 2 parts by weight of compound G below - methylene chloride (first solvent) 430 Parts by mass Methanol (second solvent) 64 parts by mass────────────────────────────────────

Compound G

To 90 parts by mass of the core layer cellulose acylate dope was added 10 parts by mass of the following matting agent solution to prepare a cellulose acetate solution used as the outer layer cellulose acylate dope.
──────────────────────────────────
Matting agent solution ──────────────────────────────────
・Silica particles with an average particle size of 20 nm (AEROSIL R972, manufactured by Nippon Aerosil Co., Ltd.) 2 parts by mass ・Methylene chloride (first solvent) 76 parts by mass ・Methanol (second solvent) 11 parts by mass ・The above core layer cellulose acetate Rate dope 1 part by mass──────────────────────────────────

After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope through a filter paper having an average pore size of 34 μm and a sintered metal filter having an average pore size of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope were formed on both sides thereof. 3 layers were simultaneously cast on a drum at 20° C. from a casting port (band casting machine). The film was peeled off from the drum with a solvent content of approximately 20% by mass, fixed at both ends in the width direction of the film with tenter clips, and dried while being stretched in the transverse direction at a draw ratio of 1.1. After that, the obtained film was further dried by conveying it between rolls of a heat treatment apparatus, and a cellulose acylate film 1 having a thickness of 20 μm was produced. The Re(550) of the obtained cellulose acylate film 1 was 0 nm.

[Formation of photo-alignment layer 1]
Next, with reference to the description of Example 3 of JP-A-2012-155308, Coating Liquid 1 for Photo-Alignment Layer was prepared and coated on Cellulose Acylate Film 1 with a wire bar. Thereafter, the resulting cellulose acylate film 1 was dried with hot air at 60° C. for 60 seconds to prepare a coating film 1 having a thickness of 300 nm.

Subsequently, a composition A1 for forming a positive A plate having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Composition of Composition A1 for Forming Positive A Plate――――――――――――――――――――――――――――――――
16.00 parts by mass of polymerizable liquid crystal compound X-1 below 42.00 parts by mass of specific liquid crystal compound L-1 below 42.00 parts by mass of specific liquid crystal compound L-2 below 0.00 part by mass of polymerization initiator S-1 below 50 parts by mass Polymerizable compound B-1 below 2.00 parts by mass Leveling agent (Compound T-1 below) 0.20 parts by mass Methyl ethyl ketone (solvent) 230.00 parts by mass Cyclopentanone (solvent) 70. 00 parts by mass――――――――――――――――――――――――――――――――――

The prepared coating film 1 was irradiated with ultraviolet rays using an ultra-high pressure mercury lamp in the atmosphere. At this time, a wire grid polarizer (manufactured by Moxtek, ProFlux PPL02) was set parallel to the surface of the coating film 1 for exposure, and photo-alignment treatment was performed to obtain a photo-alignment layer 1 .
At this time, the illuminance of the ultraviolet rays was 10 mJ/cm ² in the UV-A region (ultraviolet A waves, integrated wavelength of 320 to 380 nm).

[Preparation of optical film 1 including positive A plate A1]
Next, the composition A1 for forming a positive A plate was applied onto the photo-alignment layer 1 using a bar coater. The resulting coating film was heat-aged at a film surface temperature of 100° C. for 20 seconds, cooled to 90° C., and exposed to ultraviolet rays of 300 mJ/cm ² under air using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.). was irradiated to fix the nematic orientation state to form a positive A plate A1 (corresponding to an optically anisotropic layer), and an optical film 1 including the positive A plate A1 was produced.

The formed positive A plate A1 had a film thickness of 2.5 μm. Positive A plate A1 has Re(550) of 145 nm, Rth(550) of 73 nm, Re(550)/Re(450) of 1.13, Re(650)/Re(550) of 1.01, and optical axis The tilt angle was 0°, and the liquid crystal compound was homogeneously aligned.

[Preparation of Optically Anisotropic Film 1 Laminated with Positive C Plate Film]
Next, the surface of the optical film 1 on the positive A plate A1 side was subjected to corona treatment, and then the following composition C-1 was applied. The coating film formed on the temporary support for formation is heated to 60° C. in a heating atmosphere, and is irradiated with ultraviolet rays (300 mJ/cm ² ) at 70° C. with an oxygen concentration of 100 ppm under a nitrogen purge to align the liquid crystalline compound. A fixed optically anisotropic film 1 was formed. The thickness of the positive C plate was 0.4 μm.

―――――――――――――――――――――――――――――――――
(Composition C-1)
―――――――――――――――――――――――――――――――――
・The following rod-shaped liquid crystalline compound (M-1) 83 parts by mass ・The following rod-shaped liquid crystalline compound (M-2) 15 parts by mass ・The following rod-shaped liquid crystalline compound (M-3) 2 parts by mass ・The following urethane monomers (EBECRYL1290,
Daicel Allnex Co., Ltd.) 3.3 parts by mass The following polymerization initiator (IrgacureOXE01,
BASF Corporation) 4 parts by mass, the following fluorine-based polymer (M-4) 3 parts by mass, the following fluorine-based polymer (M-5) 0.3 parts by mass, the following onium compound S01 1.5 parts by mass, toluene 552 parts by mass・Methyl ethyl ketone (MEK) 138 parts by mass――――――――――――――――――――――――――――――――――

Rod-shaped liquid crystalline compound (M-1)

Rod-shaped liquid crystalline compound (M-2)

Rod-shaped liquid crystalline compound (M-3)

Urethane monomer

polymerization initiator

Fluorinated polymer (M-4)

Fluorinated polymer (M-5)

Onium salt compound S01

[Production of laminate 1]
After the cellulose acylate film 1 side of the optically anisotropic film 1 prepared above was subjected to corona treatment, it was attached to the PVA polarizer side of the polarizer 1 with the surface protective layer H1 prepared above with the above PVA adhesive. Thus, the laminate 1 of Production Example 1 was obtained. At this time, the film was attached so that the angle formed by the absorption axis of the polarizer included in the polarizer 1 with the surface protective layer H1 and the slow axis of the positive A plate A1 included in the optically anisotropic film 1 was 45°. combined (same below).

[Production example 2]
In the same manner as in Preparation Example 1, the cellulose acylate film 1 side of the optically anisotropic film 1 and the polarizer protective film side of the polarizer 2 with the surface protective layer H1 prepared above were each subjected to corona treatment. was attached with a PVA adhesive of No. 2 to obtain a laminate 2 of Production Example 2.

[Production example 3]
In the same manner as in Production Example 1 above, the cellulose acylate film 1 side of the optically anisotropic film 1 and the polarizer protective layer B1 side of the polarizer 3 with the surface protective layer H1 prepared above were each subjected to corona treatment. , and pasted with the above UV adhesive to obtain a laminate 2 of Production Example 3.

[Production example 4]
In the same manner as in Production Example 1 above, the cellulose acylate film 1 side of the optically anisotropic film 1 and the polarizer alignment layer PA1 side of the polarizer 4 with the surface protective layer H1 prepared above were each subjected to corona treatment. , and pasted with the above UV adhesive to obtain a laminate 4 of Production Example 4.

[Production example 5]
As the surface protective layer H2, a low-reflection surface film CV-LC5 (manufactured by Fuji Film Co., Ltd., moisture permeability of 1 g/m ² ·day or more) was prepared. The oxygen blocking layer B2 side of the polarizing film 4B and the support side of the surface protective layer H2 were attached using the adhesive sheet. After that, only TJ40 was peeled off to produce a polarizer 4 with a surface protective layer H2.
In the same manner as in Preparation Example 1, the cellulose acylate film 1 side of the optically anisotropic film 1 and the polarizer orientation layer PA1 side of the polarizer 4 with the surface protective layer H2 prepared above were each subjected to corona treatment. After that, they were attached with the UV adhesive described above to obtain a laminate 5 of Production Example 5.

[Production Examples 6 to 29]
Production Examples 1 to 4, except that the composition for forming a positive A plate shown in Table 4 below was used instead of the composition for forming a positive A plate A1, and the polarizer shown in Table 4 below was used instead of the polarizer 1. Laminates 6 to 29 were produced according to the same procedure.
Compositions A2 to A12 for forming an optically anisotropic layer (positive A plate) shown in Table 4 below are shown below.

(Preparation of composition A2 for forming positive A plate)
In the composition A1 for forming a positive A plate, 100 parts by mass of the following specific liquid crystal compound L-6 was used instead of the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2. A positive A plate forming composition A2 was prepared in the same manner as the positive A plate forming composition A1, except for the above.

(Preparation of composition A3 for forming positive A plate)
In the composition A1 for forming a positive A plate, 100 parts by mass of the following specific liquid crystal compound L-9 was used instead of the polymerizable liquid crystal compound X-1, the specific liquid crystal compound L-1, and the specific liquid crystal compound L-2. A positive A plate forming composition A3 was prepared in the same manner as the positive A plate forming composition A1, except for the above.

Specific liquid crystal compound L-9

(Preparation of composition A4 for forming positive A plate)
A composition A4 for forming a positive A plate having the following composition was prepared.
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Composition of Composition A4 for Forming Positive A Plate――――――――――――――――――――――――――――――――
・The following specific liquid crystal compound L-17 70.00 parts by mass ・The following specific liquid crystal compound L-5 30.00 parts by mass ・Polymerization initiator OXE-03 (manufactured by BASF Japan) 4.00 parts by mass ・Adeka Arcles NCI- 831 (manufactured by Adeka) 5.00 parts by mass Leveling agent (above compound T-1) 0.10 parts by mass Antioxidant BHT (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.90 parts by mass Methyl ethyl ketone (solvent) 60. 00 parts by mass Cyclopentanone (solvent) 240.00 parts by mass ――――――――――――――――――――――――――――――――――

Liquid crystalline compound L-17

(Preparation of composition A5 for forming positive A plate)
In the positive A plate forming composition A4, the same as the positive A plate forming composition A4, except that 100 parts by mass of the following specific liquid crystal compound L-7 was used instead of the specific liquid crystal compounds L-17 and L-5. A positive A plate-forming composition A5 was prepared by the method.

(Preparation of composition A6 for forming positive A plate)
In the positive A plate forming composition A4, the same as the positive A plate forming composition A4, except that 100 parts by mass of the following specific liquid crystal compound L-8 was used instead of the specific liquid crystal compounds L-17 and L-5. A composition A6 for forming a positive A plate was prepared by the method.

(Preparation of composition A7 for forming positive A plate)
In the positive A plate forming composition A4, the same as the positive A plate forming composition A4, except that 100 parts by mass of the following specific liquid crystal compound L-10 was used instead of the specific liquid crystal compounds L-17 and L-5. A composition A7 for forming a positive A plate was prepared by the method.

Specific liquid crystal compound L-10

(Preparation of composition A8 for forming positive A plate)
The same as composition A4 for forming a positive A plate, except that 100 parts by mass of the following specific liquid crystal compound L-11 was used in place of the specific liquid crystal compounds L-17 and L-5 in the composition A4 for forming a positive A plate. A positive A plate-forming composition A8 was prepared by the method.

Specific liquid crystal compound L-11

(Preparation of composition A9 for forming positive A plate)
In the positive A plate forming composition A4, the same as the positive A plate forming composition A4, except that 100 parts by mass of the following specific liquid crystal compound L-12 was used instead of the specific liquid crystal compounds L-17 and L-5. A positive A plate-forming composition A9 was prepared by the method.

Specific liquid crystal compound L-12

(Preparation of composition A10 for forming positive A plate)
The same as composition A4 for forming a positive A plate, except that 100 parts by mass of the following specific liquid crystal compound L-13 was used in place of the specific liquid crystal compounds L-17 and L-5 in the composition A4 for forming a positive A plate. A positive A plate-forming composition A10 was prepared by the method.

Specific liquid crystal compound L-13

(Preparation of composition A11 for forming positive A plate)
A composition A11 for forming a positive A plate having the following composition was prepared.
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Composition of Composition A11 for Forming Positive A Plate――――――――――――――――――――――――――――――――
・ 35.00 parts by mass of the following specific liquid crystal compound L-14 ・ 15.00 parts by mass of the above polymerizable liquid crystal compound X-1 ・ 35.00 parts by mass of the following polymerizable liquid crystal compound X-2 ・ The following polymerizable liquid crystal compound X-3 15.00 parts by mass Polymerization initiator OXE-03 (manufactured by BASF Japan) 5.00 parts by mass Adeka Arcles NCI-831 (manufactured by Adeka) 4.00 parts by mass Acid anhydride K-1 above 4. 00 parts by mass Leveling agent (the above compound T-1) 0.10 parts by mass Antioxidant BHT (manufactured by Tokyo Chemical Industry Co., Ltd.) 0.90 parts by mass Methyl ethyl ketone (solvent) 60.00 parts by mass Cyclopentanone ( Solvent) 240.00 parts by mass ――――――――――――――――――――――――――――――――

Specific liquid crystal compound L-14

Polymerizable liquid crystal compound X-2

Polymerizable liquid crystal compound X-3

(Preparation of composition A12 for forming positive A plate)
A composition A12 for forming a positive A plate having the following composition was prepared.
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Composition of Composition A12 for Forming Positive A Plate――――――――――――――――――――――――――――――――
・The following specific liquid crystal compound L-15 42.00 parts by mass ・The following specific liquid crystal compound L-16 42.00 parts by mass ・The above polymerizable liquid crystal compound X-1 5.00 parts by mass ・The following polymerizable liquid crystal compound X-5 11 .00 parts by mass 0.50 parts by mass of the polymerization initiator S-1 4.00 parts by mass of the acid anhydride K-1 2.00 parts by mass of the polymerizable compound B-1 Leveling agent (the above compound T -1) 0.23 parts by mass Methyl ethyl ketone (solvent) 50.00 parts by mass Cyclopentanone (solvent) 250.00 parts by mass ―――――――――――――――――――― ―――――――――――――

Specific liquid crystal compound L-15

Specific liquid crystal compound L-16

Polymerizable liquid crystal compound X-5

<Production of Silicon Nitride Layer>
Corning Glass EAGLE-XG was used as a glass substrate A (thickness: 1.1 mm). The glass substrate A was set on a substrate holder in a vacuum chamber of a CVD apparatus, and the vacuum chamber was closed. Next, the inside of the vacuum chamber was evacuated, and when the pressure reached 0.1 Pa, the raw material gas was introduced. The silane gas flow rate was 100 cc/min, the ammonia gas flow rate was 300 cc/min, and the hydrogen gas flow rate was 1000 cc/min.
When the pressure in the vacuum chamber stabilizes at 100 Pa, a plasma excitation power of 2000 W is supplied from a 13.5 MHz high-frequency power supply to the electrodes to form a gas barrier film mainly composed of silicon nitride on the surface of the glass substrate, A glass substrate with a silicon nitride layer was used.
Note that the film thickness of the gas barrier film was set to 50 nm. The film thickness was controlled in previous experiments. During film formation, the temperature of the substrate was adjusted to 70° C. or less by the temperature adjusting means built in the substrate holder.
For the prepared gas barrier film, using an infrared spectrometer (a device in which ATR-PRO410-S is attached to FT-IR6100 manufactured by JASCO Corporation), 800 in FT-IR ATR (total reflection infrared absorption method) mode. The peak intensity of the Si—N bond located at ~900 cm ⁻¹ and the peak intensity of the N—H bond located at 3300-3400 cm ⁻¹ were measured. From this measurement result, NH/SiN, which is the intensity ratio of the peak intensity of the Si—N bond and the peak intensity of the N—H bond, was calculated and found to be 0.11.
Under the same conditions, a silicon nitride layer was formed on a 100 μPET film (water vapor permeability: 3 g/m ² ·day), and a water vapor transmission rate measuring device (AQUATRAN2 (registered trademark) manufactured by MOCON, INC.) was used to measure 40%. C., 90% RH atmosphere was measured and found to be less than 0.9×10 ⁻¹ g/m ² ·day. That is, the moisture permeability of the silicon nitride layer alone in an atmosphere of 40° C. and 90% RH was less than 1×10 ⁻¹ g/m ² ·day.

[evaluation]
<Reflectance evaluation>
In order to exclude the influence of surface reflection, the surface reflectance was obtained by applying black glue (containing carbon black) which has a high absorptivity and does not reflect at all on the support side of the surface protective layers H1 and H2.
Instead of the organic EL display device, a reflective substrate was produced by attaching an aluminum foil to a PET film having a thickness of 100 μm using an adhesive sheet N1. Laminates 1 to 29 were adhered onto this reflective substrate using adhesive sheet N2, reflectance (total reflection) was measured, and the value obtained by subtracting the surface reflectance was taken as effective reflectance. This effective reflectance is an index of the antireflection function of the circularly polarizing plate composed of the polarizer layer and the optically anisotropic layer.
As for the total reflectance, a spectrophotometer (Konica Minolta Co., Ltd.) was used, and the Y value of the display system under observation conditions of 10° field of view and observation light source D65 was taken as the total reflectance.

<Wet heat durability evaluation>
The positive C plate side of the laminates 1 to 29 is attached to the silicon nitride layer on the glass substrate with the silicon nitride layer using the adhesive layer N2, and 85 ° C., 85% relative humidity, wet heat durability for 60 hours. did the test.
The adhesive layer was the only layer present between the circularly polarizing plate and the silicon nitride layer, had a thickness of 35 μm or less, and had a moisture permeability of 100 g/m ² ·day or more.
After durability evaluation, the laminates 1 to 29 were evaluated for effective reflectance in the same manner as described above, and the difference in effective reflectance before and after wet heat durability was evaluated according to the following criteria. The results are shown in Table 4 below.
AA: reflectance difference is 0.2% or less A: reflectance difference is greater than 0.2% and is 0.5% or less B: reflectance difference is greater than 0.5% and 2 .0% or less C: Reflectance difference is greater than 2.0%

[Production example 30]
Instead of the glass substrate with the silicon nitride layer, the glass substrate A was used, and the laminate 1 of Production Example 1 was bonded together using the adhesive layer N2. In the same manner as described above, the difference in effective reflectance before and after the wet heat durability test was evaluated according to the above criteria and used as reference data.

In Table 4 below, the column of "type" in the column of "optically anisotropic layer" represents the type of composition used for forming a positive A plate.
In addition, the "Laminate type" column indicates the type of the laminate used.

From the results shown in Table 4, it was found that all of the production examples of the present invention had good wet heat durability.

<Production of organic EL display device>
A Royole FlexPai equipped with an organic EL display panel (organic EL display element) was disassembled, and the circularly polarizing plate was peeled off from the organic EL display device.
Next, the laminates 1 to 29 prepared above are attached to the isolated organic EL display panel (the outermost surface is a silicon nitride layer) so that the positive C plate 1 side is on the panel side, and the organic EL display device is manufactured. made.

It was confirmed that the produced organic EL display device exhibited an antireflection effect.

REFERENCE SIGNS LIST 10, 20, 30, 40 organic EL display device 11 surface protective layer 12 polarizer protective film 13 polarizer 14 polarizer protective film 15 positive A plate 16 positive C plate 17 silicon nitride layer 18 organic EL display element 20 adhesive layer

Claims (11)

An organic electroluminescence display device comprising at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer, and an organic electroluminescence display element having a pair of electrodes and an organic light-emitting layer sandwiched therebetween in this order from the viewing side. and
The nitrogen silicon layer has a Si—N bond peak located at 800 to 900 cm ⁻¹ and an N—H bond peak located at 3300 to 3400 cm ⁻¹ observed by Fourier transform infrared absorption spectrometry. A layer in which the intensity ratio NH/Si-N is 0.04 or more,
The circularly polarizing plate has a polarizer and an optically anisotropic layer,
The polarizer is a polarizer having a dichroic organic dye,
The optically anisotropic layer is a layer formed using a composition containing a polymerizable liquid crystal compound,
An organic electroluminescence display device, wherein a layer existing between the circularly polarizing plate and the silicon nitride layer has a thickness of 35 μm or less. An organic electroluminescence display device comprising at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer, and an organic electroluminescence display element having a pair of electrodes and an organic light-emitting layer sandwiched therebetween in this order from the viewing side. and
The circularly polarizing plate has a polarizer and an optically anisotropic layer,
The polarizer has a dichroic organic dye containing at least a dichroic azo dye compound represented by the following formula (1) and a dichroic azo dye compound represented by the following formula (2): and
The optically anisotropic layer is a layer formed using a composition containing a polymerizable liquid crystal compound,
An organic electroluminescence display device, wherein a layer existing between the circularly polarizing plate and the silicon nitride layer has a thickness of 35 μm or less.

In formula (1),
Ar1 and Ar2 each independently represent an optionally substituted phenylene group or an optionally substituted naphthylene group.
R1 is a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an alkylthio group, an alkylsulfonyl group, an alkylcarbonyl group, an alkyloxycarbonyl group, an acyloxy group, alkyl carbonate group, alkylamino group, acylamino group, alkylcarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, alkylsulfamoyl group, alkylcarbamoyl group, alkylsulfinyl group, alkylureido group, alkylphosphoric acid amide group, an alkylimino group, or an alkylsilyl group. However, —CH constituting the alkyl group ₂ - is -O-, -CO-, -C(O)-O-, -O-C(O)-, -Si(CH ₃ ) ₂ -O-Si(CH ₃ ) ₂ -, -N(R1')-, -N(R1')-CO-, -CO-N(R1')-, -N(R1')-C(O)-O-, -OC( 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—. Further, when R1 is a group other than a hydrogen atom, the hydrogen atom possessed by each group is 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 , may be replaced by R1' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When there are multiple R1's, the multiple R1's may be the same or different.
R2 and R3 are each independently a hydrogen atom, an optionally substituted linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group, an acyl group, an alkyloxycarbonyl group, an alkylamide group; , an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamide group. However, —CH constituting the alkyl group ₂ - is -O-, -S-, -C (O) -, -C (O) -O-, -O-C (O) -, -C (O) -S-, -S-C ( O)-, -Si(CH ₃ ) ₂ —O—Si(CH ₃ ) ₂ -, -NR2'-, -NR2'-CO-, -CO-NR2'-, -NR2'-C (O) -O-, -OC (O) -NR2'-, -NR2'-C (O)-NR2'-, -CH=CH-, -C≡C-, -N=N-, -C(R2')=CH-C(O)-, or -O-C(O) —O—, may be substituted. Further, when R2 and R3 are a group other than a hydrogen atom, the hydrogen atom possessed by each group is 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 , may be replaced by R2' represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When multiple R2' are present, the multiple R2' may be the same or different. In addition, R2 and R3 may combine with each other to form a ring, or R2 or R3 may combine with Ar2 to form a ring.

In formula (2),
n represents 1 or 2;
Ar3, Ar4 and Ar5 each independently represent an optionally substituted phenylene group, an optionally substituted naphthylene group or an optionally substituted heterocyclic group.
The definition of R4 is the same as that of R1 in the formula (1).
The definitions of R5 and R6 are the same as those of R2 and R3 in formula (1) above. 3. The organic electroluminescence display device according to claim 1 , wherein said polarizer is formed using a composition containing said dichroic organic dye and a polymerizable liquid crystal compound. 4. The organic electroluminescence display device according to claim 1, wherein a layer present between said circularly polarizing plate and said silicon nitride layer has a moisture permeability of 100 g/m ² ·day or more . The organic electroluminescent material according to any one of claims 1 to 4 , wherein the composition used for forming the optically anisotropic layer contains a polymerizable liquid crystal compound having a partial structure represented by the following formula (II). Luminescent display device.
*-D ¹ -Ar-D ² -* (II)
In the formula (II),
D ¹ and D ² are each independently a single bond, -O-, -CO-, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² - CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² - , -CR ¹ R ² -CR ³ R ⁴ -O-CO-, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -,- represents NR ¹ -CR ² R ³ - or -CO-NR ¹ -;
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Ar represents any aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-7).

In the formulas (Ar-1) to (Ar-7),
* represents the binding position with ^D1 or ^D2 .
Q ¹ represents N or CH.
Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms, a carbon number represents a 6-20 monovalent aromatic hydrocarbon group, a halogen atom, a cyano group, a nitro group, —OR ⁸ , —NR ⁹ R ¹⁰ , or —SR ¹¹ , wherein R ⁸ to R ¹¹ each independently , represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form an aromatic ring.
A ¹ and A ² each independently represent a group selected from the group consisting of -O-, -N(R ¹² )-, -S- and -CO-, and R ¹² is a hydrogen atom or represents a substituent.
X represents a hydrogen atom or a nonmetallic atom of Groups 14-16 to which a substituent may be attached.
D ⁴ and D ⁵ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ^1a R ^2a -, -CR ^3a =CR ^4a - , —NR ^5a —, or a divalent linking group consisting of a combination of two or more thereof, wherein R ^1a to R ^5a each independently represent a hydrogen atom, a fluorine atom, or represents an alkyl group.
SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of the constituent —CH ₂ — represents a divalent linking group substituted with —O—, —S—, —NH—, —N(Q)—, or —CO—, and Q is represents a substituent.
L ³ and L ⁴ each independently represent a monovalent organic group.
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocyclic rings.
Ay has at least one aromatic ring selected from the group consisting of a hydrogen atom, an optionally substituted alkyl group having 1 to 12 carbon atoms, or an aromatic hydrocarbon ring and an aromatic heterocyclic ring , represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, and Ax and Ay may combine to form a ring.
Q ³ represents a hydrogen atom or an optionally substituted alkyl group having 1 to 6 carbon atoms. Re (450), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 450 nm; Re (550), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 550 nm; Claims 1 to 3, wherein Re(650), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 650 nm, satisfies the relationship Re(450) ≤ Re(550) ≤ Re(650) 6. The organic electroluminescence display device according to any one of 5 . 7. The organic electroluminescence display device according to claim 1, wherein said optically anisotropic layer is a positive A plate. 8. The organic electroluminescence display device according to claim 1, wherein said optically anisotropic layer is a λ/4 plate. 9. The organic electroluminescence display device according to claim 1 , wherein the angle between the slow axis of said optically anisotropic layer and the absorption axis of said polarizer is 45°±10°. Claims 1 to 9 , wherein the polarizer is formed from a composition containing the dichroic organic dye and a polymerizable liquid crystal compound, and the polymerizable liquid crystal compound is 60% by mass or more of the solid content of the composition. The organic electroluminescence display device according to any one of . The organic electroluminescence display according to any one of claims 1 to 10 , wherein a surface protective layer is provided on the viewing side of the circularly polarizing plate, and the moisture permeability of the surface protective layer is 1 g/m ² ·day or more. Device.

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