WO2021124803A1

WO2021124803A1 - Organic electroluminescent display device

Info

Publication number: WO2021124803A1
Application number: PCT/JP2020/043544
Authority: WO
Inventors: 柴田　直也; 慶介吉政
Original assignee: 富士フイルム株式会社
Priority date: 2019-12-17
Filing date: 2020-11-24
Publication date: 2021-06-24
Also published as: JP7271721B2; JPWO2021124803A1

Abstract

The present invention addresses the problem of providing an organic electroluminescent display device which has excellent wet heat durability. An organic electroluminescent display device according to the present invention sequentially comprises, in the following order from the viewing side, at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer and an organic electroluminescent display element that comprises a pair of electrodes and an organic light emitting layer that is sandwiched between the electrodes. With respect to this organic electroluminescent display device, the circularly polarizing plate comprises a polarizer and an optically anisotropic layer; the polarizer comprises a dichroic organic dye; the optically anisotropic layer is formed using a composition that contains a polymerizable liquid crystal compound; and a layer that is present between the circularly polarizing plate and the silicon nitride layer has a thickness of 35 μm or less.

Description

Organic electroluminescence display device

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

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 and the like.
In recent years, due to the demand for thinning of the apparatus to which the polarizing plate is applied, the optically anisotropic layer contained in the polarizing plate is also required to be thinned.
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.

International Publication No. 2014/010325 Japanese Unexamined Patent Publication No. 2011-207765

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

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

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

[1] From the visual side, an organic electro that includes at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer, a pair of electrodes, and an organic electroluminescence display device having an organic light emitting layer sandwiched between them in this order. Luminescence display device
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 by using a composition containing a polymerizable liquid crystal compound.
An organic electroluminescence display device in which the thickness of the layer existing 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 by using a composition containing a dichroic organic dye and a polymerizable liquid crystal compound.
[3] circularly polarized moisture permeability layers present between the light plate and the silicon nitride layer is the 100 g / m 2 · ^day or more, [1] or an organic electroluminescent display device according to [2].
[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 the formula (II) described later. Organic electroluminescence display device.
[5] Re (450), which is an in-plane retardation value measured at a wavelength of 450 nm of the optically anisotropic layer, and Re (550), which is an in-plane retardation value measured at a wavelength of 550 nm of the optically anisotropic layer. Re (650), which is the value of the in-plane retardation measured at a wavelength of 650 nm of the optically anisotropic layer, satisfies the relationship of Re (450) ≤ Re (550) ≤ Re (650), [1] to 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 formed by 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 is 60% by mass or more of the solid content mass of the composition, [1] to [8]. ] The organic electroluminescence display device according to any one of.
[10] yen has a surface protective layer on the viewer side of the polarizing plate, the moisture permeability of the surface protective layer is is 1g / m 2 · ^day or more, [1] The organic electroluminescence according to any one of to [9] Display device.

According to the present invention, it is possible to provide an organic electroluminescence display device having excellent wet and heat durability.

It is a schematic cross-sectional view which shows an example of embodiment of the organic electroluminescence display device of this invention. It is a schematic cross-sectional view which shows an example of embodiment of the organic electroluminescence display device of this invention. It is a schematic cross-sectional view which shows an example of embodiment of the organic electroluminescence display device of this invention. It is a schematic cross-sectional view which shows an example of embodiment of the organic electroluminescence display device of this invention.

Hereinafter, the present invention will be described in detail.
The description of the constituent elements described below may be based on typical embodiments of the present invention, but the present invention is not limited to such embodiments.
In the present specification, the numerical range represented by using "-" means a range including the numerical values before and after "-" as the lower limit value and the upper limit value.
Further, in the present specification, as each component, a substance corresponding to each component may be used alone or in combination of two or more. Here, when two or more kinds of substances are used in combination for each component, the content of the component means the total content of the substances used in combination unless otherwise specified.
Further, in the present specification, the bonding direction of the divalent group (for example, -O-CO-) described is not particularly limited unless the bonding position is specified. When D ^{1 in} III) is -CO-O-, assuming ^{that the position bonded to the G 1} side is * 1 and the position bonded to the Ar side is * 2, D ¹ is * 1-. It may be CO-O- * 2 or * 1-O-CO- * 2.
Further, in the present specification, "(meth) acrylate" is a general term for "acrylate" and "methacrylate", and "(meth) acrylic" is a general term for "acrylic" and "methacrylic", and "(meth) acrylic" is a general term for "(meth) acrylic". ) "Acryloyl" is a general term for "acryloyl" and "methacrylic".
Further, in the present specification, "orthogonal" and "parallel" with respect to an angle mean a range of a strict angle of ± 10 °, and "same" and "different" with respect to an angle have a difference of less than 5 °. It can be judged based on whether or not it is.
Further, in the present specification, "visible light" means 380 to 780 nm.
Further, in the present specification, unless otherwise specified, the measurement wavelength is 550 nm.

In the present specification, the "moisture content" means the initial mass of the cut-out 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.

In the present specification, the "slow phase axis" means the direction in which the refractive index becomes maximum in the plane. The slow axis of the optically anisotropic layer is intended to be the slow axis of the entire optically anisotropic layer.

In the present specification, "Re (λ)" and "Rth (λ)" represent in-plane retardation at wavelength λ and retardation in the thickness direction, 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 the film thickness (d (μm)) in AxoScan OPMF-1.
Slow phase axial direction (°)
Re (λ) = R0 (λ)
Rth (λ) = ((nx + ny) /2-nz) × d
Is calculated.
Although R0 (λ) is displayed as a numerical value calculated by AxoScan OPMF-1, it means Re (λ).

The organic electroluminescence display device of the present invention comprises, from the visual side, a circular polarizing plate, an adhesive layer, a silicon nitride layer, a pair of electrodes, and an organic electroluminescence display element having an organic light emitting layer sandwiched between them. 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 is a polarizing element having a polarizing element and an optically anisotropic layer, the polarizer is a polarizer having a bicolor organic dye, and the optically anisotropic layer is , A layer formed using a composition containing a polymerizable liquid crystal compound.
Further, 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 a plurality of layers are present, it means the total of the plurality of layers; the same applies hereinafter). It is 35 μm or less.

The organic electroluminescence display device of the present invention having a predetermined optically anisotropic layer and a predetermined polarizer has excellent moist heat durability.
This is not clear in detail, but the present inventors speculate as follows.

It is known that a silicon nitride layer, which is usually used as a barrier layer of an organic light emitting device in an organic electroluminescence display device, reacts with water to generate ammonia depending on the production method.
Further, as the polarizer, a polyvinyl alcohol-based resin and iodine are often used, and the polarizer using such iodine retains the PVA-iodine complex by cross-linking the polyvinyl alcohol-based resin with boric acid. And dichroism is expressed.
As a factor of inferior wet heat durability, the present inventors retain the PVA-iodine complex by hydrolyzing the boric acid cross-linked site of the polarizer using iodine in the presence of ammonia generated in the silicon nitride layer. It seems that the factors are that the dichroism is lost and the dichroism is deteriorated, and that the swelling rate of the polyvinyl alcohol-based resin is increased, and that the water supply to the silicon nitride layer is increased as the main water supply source in the organic electroluminescence display device. I'm estimating.

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 moist heat durability of the organic electroluminescence display device is improved. It is thought that it was.

1, FIG. 2, FIG. 3 and FIG. 4 show a schematic cross-sectional view 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 layered organic EL 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 a layered organic EL display device.
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, and silicon nitride. This is a layered organic EL display device having layers 17 and an organic EL display element 18 in this order.
In FIGS. 1 to 4, the positive A plate 15 corresponds to the optically anisotropic layer included in the organic EL display device of the present 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.
Hereinafter, each layer and component of the organic EL display device of the present invention will be described in detail.

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

[Optically anisotropic layer]
The optically anisotropic layer included in the circularly polarizing plate is a layer formed by using a composition containing a polymerizable liquid crystal compound.
Generally, liquid crystal compounds can be classified into rod-shaped type and disk-shaped type according to their shape. Furthermore, there are low molecular weight and high molecular weight types, respectively. A polymer generally refers to a polymer having a degree of polymerization of 100 or more (Polymer Physics / Phase Transition Dynamics, Masao Doi, p. 2, Iwanami Shoten, 1992).
In the present invention, any liquid crystal compound can be used, but it is preferable to use a rod-shaped liquid crystal compound or a discotic liquid crystal compound, and it is more preferable to use a rod-shaped 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 above-mentioned liquid crystal compound, but the liquid crystal compound further has two or more polymerizable groups in one molecule. preferable. When the liquid crystal compound is a mixture of two or more kinds, it is preferable that at least one kind of liquid crystal compound 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.

The type of the polymerizable group is not particularly limited, and a functional group capable of an 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 preferably mentioned, and a (meth) acryloyl group is more preferable.

As the rod-shaped 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 discotics can be used. 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. However, it is not limited to these.

In the present invention, the optically anisotropic layer is a composition containing a polymerizable liquid crystal compound (hereinafter, also referred to as “specific liquid crystal compound”) exhibiting anti-wavelength dispersibility from the viewpoint of excellent optical characteristics (hereinafter, “specific liquid crystal compound”). It is preferably a layer formed by using "a polymerizable liquid crystal composition").
The specific liquid crystal compound is a polymerizable liquid crystal compound, and is a compound exhibiting "reverse wavelength dispersibility".
Here, the compound exhibiting "reverse wavelength dispersibility" in the present specification refers to an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer produced using the compound. When measured, the Re value becomes equal or higher as the measurement wavelength becomes larger, and as will be described later, it means that the relationship of Re (450) ≤ Re (550) ≤ Re (650) is satisfied.

The reverse wavelength dispersible polymerizable liquid crystal compound is not particularly limited as long as it can form a reverse wavelength dispersible film as described above. For example, the general formula (I) described in JP-A-2008-297210 (In particular, the compounds described in paragraphs [0034] to [0039]), and the compounds represented by the general formula (1) described in JP-A-2010-084032 (particularly, paragraphs [0067] to [0067] to paragraphs [0067] to [0039]. [0073], the compound represented by the general formula (1) described in JP-A-2019-73496 (particularly, the compound described in paragraphs [0117] to [0124]), and JP-A-2016. Examples thereof include compounds represented by the general formula (1) described in -081035A (particularly, compounds described in paragraphs [0043] to [0055]).

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 effect of the present invention is more excellent.
* -D ¹ -Ar-D ^2- * ... (II)

In the above formula (II), D ¹ and D ² are independently single-bonded, -O-, -CO-, -CO-O-, -C (= S) O-, and -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 -, - NR}}} 1 -CR 2 R 3 -, or -CO-NR ¹ - represents a.
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. When each of R ¹ , R ² , R ³ and R ⁴ exists, the plurality of R ¹ , 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 the groups represented by the 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 the description of the reference numerals in the following formulas (Ar-1) to (Ar-7). Is the same as that described by Ar in the formula (III) described later.

As the polymerizable liquid crystal compound having a partial structure represented by the above formula (II), the polymerizable liquid crystal compound represented by the following formula (III) is preferable.
The 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 independently single-bonded, -O-, -CO-, -CO-O-, -C (= S) O-, and -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 -, - NR}}} 1 -CR 2 R 3 -, or -CO-NR ¹ - represents a.
R ¹ , R ² , R ³ and R ⁴ independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. When each of R ¹ , R ² , R ³ and R ⁴ exists, the plurality of R ¹ , 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 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- may be substituted.
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 the groups represented by the 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 Representing 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. Represent.
Examples of the alkyl group having 1 to 6 carbon atoms indicated by R ⁷ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group and an n-pentyl group. Groups and n-hexyl groups can be mentioned.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms indicated by Y ¹ include a phenyl group, a 2,6-diethylphenyl group, and an aryl group of a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms indicated by Y ¹ include a thienyl group, a thiazolyl group, a frill group, and a heteroaryl group of a pyridyl group.
Further ^{, 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 (for example, methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group). Groups, t-butyl groups, and cyclohexyl groups) are more preferred, alkyl groups having 1 to 4 carbon atoms are even more preferred, and methyl or ethyl groups are particularly preferred. The alkyl group 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 (for example, a methoxy group, an ethoxy group, an n-butoxy group, and a methoxyethoxy group) is more preferable, and carbon. Alkoxy groups of numbers 1 to 4 are more preferable, and methoxy groups or ethoxy groups are particularly preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and among them, a fluorine atom or a chlorine atom is preferable.

Further, in the above formulas (Ar-1) to (Ar-7), Z ¹ , Z ² and Z ³ are independently hydrogen atoms, monovalent aliphatic hydrocarbon groups having 1 to 20 carbon atoms, and carbons. A monovalent alicyclic hydrocarbon group having a number of 3 to 20, 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 and 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 be bonded to each other to form an aromatic ring. Good.
As the monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, an alkyl group having 1 to 15 carbon atoms is preferable, an alkyl group having 1 to 8 carbon atoms is more preferable, and a methyl group, an ethyl group, an isopropyl group, and tert are preferable. -Pentyl group (1,1-dimethylpropyl group), tert-butyl group, or 1,1-dimethyl-3,3-dimethyl-butyl group is more preferable, and methyl group, ethyl group, or tert-butyl group is particularly preferable. preferable.
Examples of the monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecyl group, a methylcyclohexyl group, and the like. Monocyclic saturated hydrocarbon groups such as ethylcyclohexyl group; cyclobutenyl group, cyclopentenyl group, cyclohexenyl group, cycloheptenyl group, cyclooctenyl group, cyclodecenyl group, cyclopentadienyl group, cyclohexadienyl group, cyclooctadienyl group, And monocyclic unsaturated hydrocarbon groups such as cyclodecadien; 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, polycyclic saturated hydrocarbon group such as adamantyl group; and the like.
Examples of the monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms include a phenyl group, a 2,6-diethylphenyl group, a naphthyl group, and a biphenyl group, and an aryl group having 6 to 12 carbon atoms (an aryl group having 6 to 12 carbon atoms). Especially phenyl group) is preferable.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom, and among them, a fluorine atom, a chlorine atom or a bromine atom is preferable.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁸ to R ¹¹ include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a tert-butyl group. Examples thereof include an n-pentyl group and an n-hexyl group.

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

Further, in the above formula (Ar-2), X represents a non-metal atom of Groups 14 to 16 to which a hydrogen atom or a substituent may be bonded.
Further, as the non-metal atom of Group 14 to 16 indicated by X, for example, an oxygen atom, a sulfur atom, a hydrogen atom or a nitrogen atom to which a substituent is bonded [= N- ^RN1 , ^RN1 is a hydrogen atom or a substituent. Represents. ], A carbon atom to which a hydrogen atom or a substituent is bonded [= C- ( ^RC1 ) ₂ , ^RC1 represents a hydrogen atom or a substituent. ] Can be mentioned.

Further, in the above formula (Ar-3), D ⁴ and D ⁵ are independently single-bonded 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 of these, and R ^1a to R ^5a are independent hydrogen atoms, respectively. Represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Here, examples of the divalent linking group, 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} - Can be mentioned. R ^1b , R ^2b and R ^3b independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

Further, in the above formula (Ar-3), SP ¹ and SP ² are independently single-bonded, linear or branched alkylene groups having 1 to 12 carbon atoms, or 1 to 12 carbon atoms. _{One or more of -CH 2-} constituting the linear or branched alkylene group was replaced with -O-, -S-, -NH-, -N (Q)-, or -CO-. It 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, examples of the linear or branched alkylene group having 1 to 12 carbon atoms include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, a methylhexylene group, and the like. A petitene group is preferred.

Further, in the above formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group.
Examples of the monovalent organic group include an alkyl group, an aryl group, and a heteroaryl group. The alkyl group may be linear, branched or cyclic, but linear is preferred. The number of carbon atoms of the alkyl group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 10. The aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The aryl group preferably has 6 to 25 carbon atoms, more preferably 6 to 10 carbon atoms. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The hetero atom 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. Further, the alkyl group, the aryl group and the heteroaryl group may be unsubstituted or 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 an aromatic hydrocarbon ring and an aromatic heterocycle, and has 2 to 30 carbon atoms. Represents an organic group.
Further, in the above formulas (Ar-4) to (Ar-7), Ay is an alkyl group having 1 to 12 carbon atoms which may have a hydrogen atom and a substituent, 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 group heterocycles.
Here, the aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Further, Q ³ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Examples of Ax and Ay include those described in paragraphs [0039] to [0995] of Patent Document 1 (International Publication No. 2014/010325).
The alkyl group having 1 to 6 carbon atoms represented by ^{Q 3,} specifically, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, n- butyl group, isobutyl group, sec- butyl group, tert -Butyl group, n-pentyl group, n-hexyl group and the like can be mentioned, and examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have. Can be mentioned.

Regarding the definition and preferable range of each substituent of the liquid crystal compound represented by the formula (III), D ¹ , D ² , G ¹ , G ² , L relating to the compound (A) described in JP2012-021068 ¹ , L ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , Y ¹ , Q ¹ , Q ² are described as D ₁ , D ₂ , G ₁ , G ₂ , L ₁ , L ₂ , respectively. R ¹ , R ² , R ³ , R ⁴ , Q ₁ , Y ₁ , Z ₁ , and Z ₂ can be referred to, and the compound represented by the general formula (I) described in JP-A-2008-107767 can be referred to. a _1, _{a 2,} and _a 1 a description of X respectively, _{a 2,} and can refer to the X, Ax of the compound represented by the general formula described in WO 2013/018526 (I), Ay, The ^{description regarding Q 1} can be referred to for Ax, Ay, and Q _{2, respectively.} For Z ₃ can refer to the description for ^{Q 1} relates to compounds (A) described in JP-A-2012-21068.

In particular, the organic group _{represented by L 1} and L ₂ is preferably a group represented by _{-D 3-} G _3- Sp-P _{3, respectively.}
D ₃ is synonymous with _{D 1.}
G ₃ represents a single bond, a divalent aromatic ring group 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₎ 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. Further, -CH 2 in the above group _- hydrogen atoms may be substituted with a methyl group.
P ₃ represents a polymerizable group.

The polymerizable group is not particularly limited, but a polymerizable group capable of radical polymerization or cationic polymerization is preferable.
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 the acryloyl group is generally faster in terms of polymerization rate, and the acryloyl group is preferable from the viewpoint of improving productivity, but the methacryloyl group can also be used as the polymerizable group of the highly birefringent liquid crystal.
Examples of the cationically polymerizable group include known cationically polymerizable groups, and examples thereof include an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiroorthoester group, and a vinyloxy group. Of these, 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 preferable polymerizable groups include the following.

In the present specification, the "alkyl group" may be linear, branched or cyclic, and may be, for example, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group or an isobutyl group. , Se-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 Cyclohexyl group can be mentioned.

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

In the above formula, "*" represents the connection 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 replaced with an ethylene group), and the positions of the methyl groups are different. Represents a mixture of bodies.

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

Further, as another preferable embodiment of the specific liquid crystal compound, a compound represented by the following formula (V) can also be mentioned.
L ^1- [D ^1- G ¹ ] _m- E ^1- A-E ^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 independently single-bonded or divalent linking groups;
L ¹ and L ² are independently of -H, -F, -Cl, -Br, -I, -CN, -NC, -NCO, -OCN, -SCN, -C (= O) NR ¹ R. ² , -C (= O) R ¹ , -OC (= 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 carbil group or hydrocarbyl group having 1 to 40 carbon atoms, or -Sp-P, which is of L ¹ and L ² . At least one of is -Sp-P, P is a polymerizable group, Sp is a spacer group or a single bond, and R ¹ and R ² are independently -H or 1 carbon atoms, respectively. ~ 12 alkyls;
m and n are independently integers from 1 to 5; if m or n is 2 or more, they are repeated 2 or more-(D ^1- G ¹ )-or-(G ^2- D ² ). -Each repeating unit may be the same or different from each other;
G ¹ and G ² are independently non-aromatic carbocyclic groups or heterocyclic groups having 5 to 8 carbon atoms, or aromatic groups or heteroaromatic groups having 6 to 20 carbon atoms. , G ¹ and G ² are at least one carbocyclic group or heterocyclic group, and any one hydrogen atom contained in the carbocyclic group or heterocyclic group is described below. Substituted with a group represented by the 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 2 or more may be the same as or different from each other.
Q ¹ was independently selected from the group consisting of -C≡C-, -CY ¹ = CY ^2- , and a substituted or unsubstituted aromatic group or heteroaromatic group having 6 to 20 carbon atoms. The divalent groups, Y ¹ and Y ² , are independently -H, -F, -Cl, -CN, or -R ¹ , respectively.
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, 2 to 6 carbon atoms Alkoxy group, alkynyl group having 2 to 6 carbon atoms, acyl group having 2 to 4 carbon atoms, alkynylene group having 2 to 6 carbon atoms with an acyl group having 2 to 4 carbon atoms bonded to the end, and alkynylene group having 1 to 5 carbon atoms. It is an alcohol group or an alkoxy group having 1 to 12 carbon atoms.
R ¹ and R ² are independently alkyls having −H or 1 to 12 carbon atoms.

A preferable specific example of the above formula (V) is shown below.

The content of the specific liquid crystal compound in the polymerizable liquid crystal composition is not particularly limited, but 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 compound may be used alone or in combination of two or more.
The solid content means other components in the polymerizable liquid crystal composition excluding the solvent, and is calculated as a solid content even if the property is liquid.

The polymerizable liquid crystal composition may contain a polymerizable rod-like compound in addition to the above-mentioned specific liquid crystal compound from the viewpoint of controlling the liquid crystal orientation.
The polymerizable rod-like compound may or may not be liquid crystal.

The above-mentioned polymerizable rod-shaped compound is a compound having a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group (hereinafter, "alkylcyclohexane ring") from the viewpoint of compatibility with the above-mentioned specific liquid crystal compound. It is also abbreviated as "containing compound").
Here, the "cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group" is, for example, as shown in the following formula (2), when it has two cyclohexane rings, it is on the molecular terminal side. A cyclohexane ring in which one hydrogen atom of the cyclohexane ring present in is substituted with a linear alkyl group.

Examples of the alkylcyclohexane ring-containing compound include compounds having a group represented by the following formula (2). Among them, a (meth) acryloyl group is used from the viewpoint of imparting moist heat durability to the optically anisotropic layer. It is preferably a compound represented by the following formula (3).

Here, in the above equation (2), * represents a coupling position.
Further, in the above formulas (2) and (3), R ² represents an alkyl group having 1 to 10 carbon atoms, n represents 1 or 2, and W ¹ and W ² independently represent an alkyl group and an alkoxy. It represents a group or halogen atom, and W ¹ and W ² may be bonded to 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 an alkylcyclohexane ring-containing compound include compounds represented by the following formulas A-1 to A-5. Incidentally, in the following formula A-3, ^{R 4} represents an ethyl group or a butyl group.

When the polymerizable liquid crystal composition contains the above-mentioned polymerizable rod-like compound, the content of the above-mentioned polymerizable rod-like compound is preferably 1 to 30% by mass with respect to the total mass of the above-mentioned specific liquid crystal compound and the above-mentioned polymerizable rod-like compound. More preferably, 1 to 20% by mass.

The polymerizable liquid crystal composition may contain a polymerizable liquid crystal compound (hereinafter, also abbreviated as “another polymerizable liquid crystal compound”) other than the above-mentioned specific liquid crystal compound and the polymerizable rod-shaped compound.
Here, the polymerizable group contained in the other polymerizable liquid crystal compound is not particularly limited, and examples thereof include a (meth) acryloyl group, a vinyl group, a styryl group, and an allyl group. Of these, the (meth) acryloyl group is preferable.

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, and more preferably a polymerizable compound having 2 polymerizable groups. preferable.

Examples of such other polymerizable liquid crystal compounds include compounds represented by the formulas (M1), (M2), and (M3) described in paragraphs 0030 to 0033 of JP-A-2014-0770668. More specifically, specific examples described in paragraphs 0046 to 0055 of the same publication can be mentioned.
Other polymerizable liquid crystal compounds may be used alone 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 described above. 1 to 40% by mass is preferable, and 1 to 10% by mass is more preferable.

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 to be formed.
This is because the increase in the cross-linking point density suppresses the movement of the compound that catalyzes the hydrolysis reaction (presumed to be a liquid crystal decomposition product), and as a result, the rate of the hydrolysis reaction slows down, and in the meantime, to the edge of water It is presumed that this is due to the progress of diffusion.

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, with a (meth) acrylic equivalent of 100 g / eq. The following compounds are more preferred, with a (meth) acrylic equivalent of 90 g / eq. The following compounds are more preferred.

Non-liquid polyfunctional polymerizable compounds include esters of polyhydric alcohols and (meth) acrylic acid (eg, ethylene glycol di (meth) acrylate, 1,4-cyclohexanediacrylate, pentaerythritol tetra (meth) acrylate. , Pentaerythritol tri (meth) acrylate, trimethylolpropantri (meth) acrylate, trimethylol ethanetri (meth) acrylate, dipentaerythritol tetra (meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa ( Meta) acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, and polyester polyacrylate), vinylbenzene and derivatives thereof (eg, 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl). Examples include esters and 1,4-divinylcyclohexanone), vinylsulfone (eg, divinylsulfone), acrylamide (eg, methylenebisacrylamide), and methacrylicamide.

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 determined from the viewpoint of expressing the phase difference of the formed optically anisotropic layer. It is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, still 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 irradiation with ultraviolet rays is preferable.
Examples of the photopolymerization initiator include α-carbonyl compounds (described in the US Pat. Group acidoine compounds (described in US Pat. No. 2722512), polynuclear quinone compounds (described in US Pat. Nos. 3,043127 and 2951758), combinations of triarylimidazole dimers and p-aminophenyl ketone (US patents). 3549367 (described in US Pat. No. 3,549,67), aclysine and phenazine compounds (Japanese Patent Laid-Open No. 60-105667, US Pat. No. 4,239,850), oxadiazole compounds (described in US Pat. No. 4,212,970), acylphosphine. Examples thereof include oxide compounds (described in JP-A-63-40799, JP-A-5-29234, JP-A-10-95788, and JP-A-10-29997).

From the viewpoint of improving the durability of the optically anisotropic layer, an oxime-type polymerization initiator is preferable as the polymerization initiator, and a polymerization initiator represented by the following formula (III) is more preferable.

In the above formula (III), X represents a hydrogen atom or a halogen atom, and Y represents a monovalent organic group.
Further, 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), examples of the halogen atom represented by X include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and a chlorine atom is preferable.
Further, in the above formula (III) ^{, examples of the divalent aromatic group represented by Ar 3} include aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring. Examples thereof include a divalent group having an aromatic heterocycle such as a pyrrole ring, a thiophene ring, a pyridine ring, a thiazole ring, and a benzothiazole ring.
Further, in the above formula (III) ^{, examples of the divalent organic group having 1 to 12 carbon atoms represented by L 6} include a linear or branched alkylene group having 1 to 12 carbon atoms, and specific examples thereof. Examples include a methylene group, an ethylene group, and a propylene group.
Further, 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.
Further, in the above formula (III), examples of the monovalent organic group represented by Y include a functional group containing _{a benzophenone skeleton ((C 6} H ₅ ) _{2 CO).} Specifically, a functional group containing a benzophenone skeleton in which the terminal benzene ring is unsubstituted or monosubstituted, such as the groups represented by the following formulas (3a) and (3b), is preferable.

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

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

The content of the polymerization initiator is not particularly limited, but the content of the polymerization initiator is preferably 0.5 to 10 parts by mass with respect to 100 parts by mass of the specific liquid crystal compound contained in the polymerizable liquid crystal composition. Up to 5 parts by mass is more preferable.

The polymerizable liquid crystal composition may contain an orientation control agent, if necessary.
Examples of the orientation control agent include a low molecular weight orientation control agent and a polymer orientation control agent. Examples of the low-molecular-weight orientation control agent include paragraphs 0009 to 0083 of JP-A-2002-020363, paragraphs 0111 to 0120 of JP-A-2006-106662, and paragraphs 0021- of JP-2012-2011306A. The description of 0029 can be taken into consideration and this content is incorporated herein by reference. Further, as the polymer orientation control agent, for example, paragraphs 0021 to 0057 of JP-A-2004-198511 and paragraphs 0121 to 0167 of JP-A-2006-106662 can be referred to. Incorporated into the specification.
The amount of the orientation 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 the orientation control agent, for example, a homogeneous orientation state oriented 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 the organic solvent include ketones (for example, acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (for example, dioxane and tetrahydrofuran), and aliphatic hydrocarbons. (Eg, hexane), alicyclic hydrocarbons (eg, cyclohexane), aromatic hydrocarbons (eg, toluene, xylene, and trimethylbenzene), carbon halides (eg, dichloromethane, dichloroethane, dichlorobenzene, etc.) And chlorotoluene), esters (eg, methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (eg, ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (eg, methyl cellosolves, etc.) And ethyl cellosolve), cellosolve acetates, sulfoxides (eg, dimethylsulfoxide), amides (eg, dimethylformamide, and dimethylacetamide), and these may be used alone or in combination of two or more. May be used together.

The polymerizable liquid crystal composition may contain components other than the above-mentioned components, for example, liquid crystal compounds other than the above-mentioned specific liquid crystal compounds, surfactants, tilt angle control agents, orientation aids, plasticizers, and Examples include cross-linking agents.

The optically anisotropic layer is formed by using the above-mentioned polymerizable liquid crystal composition.
The method for producing the optically anisotropic layer is not particularly limited, but for example, the polymerizable liquid crystal composition is applied to a predetermined substrate (for example, a polarizer described later, a support described later, or a support having an orientation layer). Then, a coating film is formed, the coating film is subjected to an orientation treatment to bring the specific liquid crystal compound into a predetermined orientation state, and then the coating film is subjected to a curing treatment.

The above coating can be carried out by known methods (for example, wire bar coating method, extrusion coating method, direct gravure coating method, reverse gravure coating method, and die coating method).

The orientation treatment can be carried out by drying or heating at room temperature (for example, 20 to 25 ° C.). In the case of a thermotropic liquid crystal compound, the liquid crystal phase formed by the orientation treatment can generally be transferred by a change in temperature or pressure. In the case of a liquid crystal compound having a lyotropic property, the transfer can also be carried out by the composition ratio of the amount of the solvent.
When the orientation treatment is a heating temperature, the heating time (heat aging time) is preferably 10 seconds to 5 minutes, more preferably 10 seconds to 3 minutes, still more preferably 10 seconds to 2 minutes.

The curing treatment (irradiation of active energy rays (light irradiation treatment) and / or heat treatment) on the coating film can also be said to be an immobilization treatment for fixing the orientation of the specific liquid crystal compound.
Above all, it is preferable to carry out the light irradiation treatment. In the polymerization by light irradiation, it is preferable to use ultraviolet rays.
Irradiation dose is preferably ^{10mJ / cm 2 ~ 50J / cm} 2, more preferably ^{20mJ / cm 2 ~ 5J / cm} 2, more preferably ^{30mJ / cm 2 ~ 3J / cm} 2, particularly 50 ~ 1000mJ / cm ² preferable.
Further, in order to promote the polymerization reaction, the light irradiation treatment may be carried out under heating conditions.
As described above, the optically anisotropic layer can be formed on the support described later and on the polarizer 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, and 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 lettering of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents the in-plane letter of the optically anisotropic film at a wavelength of 550 nm. Re (650) represents the in-plane retardation of the optically anisotropic film at a wavelength of 650 nm.

The optically anisotropic layer is preferably a positive A plate.
In this specification, the positive A plate is defined as follows. The positive A plate (positive A plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane 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 the formula (A1) is satisfied. The positive A plate shows a positive value for Rth.
Equation (A1) nx> ny≈nz
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, “ny ≈ nz” when (ny-nz) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include.

A positive A plate can be obtained by horizontally orienting a rod-shaped polymerizable liquid crystal compound. For details of the method for producing a positive A plate, for example, Japanese Patent Application Laid-Open No. 2008-225281 and Japanese Patent Application Laid-Open No. 2008-026730 can be referred to.

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

Further, the optically anisotropic layer may have a positive C plate in addition to the positive A plate.
In this specification, the positive C plate is defined as follows. The positive C plate (positive C plate) has a refractive index of nx in the slow axis direction in the film plane (the direction in which the refractive index in the plane is maximized), and is orthogonal to the slow axis in the plane 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 the formula (A2) is satisfied. The positive C plate shows a negative value for Rth.
Equation (A2) nx≈ny <nz
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, “nx≈ny” when (nx−ny) × d (where d is the thickness of the film) is -10 to 10 nm, preferably -5 to 5 nm. include.
Further, in the positive C plate, Re ≈ 0 according to the above definition.

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

[Polarizer]
The polarizer provided by the circularly polarizing plate is an absorption-type polarizing element (light absorption anisotropic layer) having a dichroic organic dye, and is a so-called linear polarized light having a function of converting light into specific linearly polarized light. ..
The type of the polarizer is not particularly limited as long as it has a dichroic organic dye. Unlike iodine, a polarizer using a dichroic organic dye can easily adjust the tint, and it is possible to perform an optimum design according to the wavelength of the light emitting element.

<Dichroic organic dye>
The bicolor 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 usually used for a so-called coating type 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, the 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 either nematic property or smectic property. The temperature range indicating the liquid crystal phase is preferably room temperature (about 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, at least one dye compound in which the polarizer has 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 the formula (1) described later and a dichroic azo dye compound represented by the formula (2) described later. More preferred.

In the present invention, three or more kinds of dichroic azo dye compounds may be used in combination. For example, from the viewpoint of bringing the polarizer closer to black, the first dichroic azo dye compound and the second dichroic azo dye compound are used. Also referred to as 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, “third dichroic azo dye compound”). It is preferable to use abbreviated) together.

In the present invention, it is preferable that the dichroic azo dye compound has a crosslinkable group for the reason that the pressing resistance is improved.
Specific examples of the crosslinkable group include (meth) acryloyl group, epoxy group, oxetanyl group, styryl group and the like, and among them, (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 attached to the end of the chromophore.
Specific examples of the color-developing group include an aromatic ring group (for example, an aromatic hydrocarbon group and an aromatic heterocyclic group), an azo group, and the like, and a structure having both an aromatic ring group and an azo group is preferable. A bisazo structure having an aromatic heterocyclic group (preferably a thienothiazole group) and two azo groups is more preferable.
The side chain is not particularly limited, and examples thereof include groups represented by L3, R2, or L4 of the formula (1) described later.

From the viewpoint of adjusting the tint of the polarizer, the first dichroic azo dye compound has a maximum absorption wavelength in the range of 560 nm or more and 700 nm or less (more preferably 560 to 650 nm, particularly preferably 560 to 640 nm). It is preferably a dichroic azo dye compound having.
The maximum absorption wavelength (nm) of the dichroic azo dye compound in the present specification is a wavelength of 380 to 800 nm measured by a spectrophotometer using a solution of the dichroic azo dye compound in a good solvent. Obtained from the ultraviolet visible light spectrum in the range.

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

In the formula (1), Ar1 and Ar2 each independently represent a phenylene group which may have a substituent or a naphthylene group which may have a substituent, and a phenylene group is preferable.

In formula (1), R1 is a linear or branched alkyl group, alkoxy group, alkylthio group, alkylsulfonyl group, alkylcarbonyl group, which may have a hydrogen atom and a substituent having 1 to 20 carbon atoms. Alkyloxycarbonyl group, acyloxy group, alkyl carbonate group, alkylamino group, acylamino group, alkylcarbonylamino group, alkoxycarbonylamino group, alkylsulfonylamino group, alkylsulfamoyl group, alkylcarbamoyl group, alkylsulfinyl group, alkylureid Represents a group, an alkylphosphate amide group, an alkylimino group, or an alkylsilyl group.
_{-CH 2-} constituting the above alkyl group is -O-, -CO-, -C (O) -O-, -OC (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 -OC (O) -O-.
When R1 is a group other than a hydrogen atom, the hydrogen atom of 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. When a plurality of R1'are present in each group, they may be the same or different from each other.

In formula (1), R2 and R3 independently have a hydrogen atom and a linear or branched alkyl group which may have a substituent having 1 to 20 carbon atoms, an alkoxy group, an acyl group, and an alkyloxycarbonyl. Represents a group, an alkylamide group, an alkylsulfonyl group, an aryl group, an arylcarbonyl group, an arylsulfonyl group, an aryloxycarbonyl group, or an arylamide group.
_{-CH 2-} constituting the above alkyl group is -O-, -S-, -C (O)-, -C (O) -O-, -OC (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-,- It may be replaced by N = N-, -C (R2') = CH-C (O)-, or -OC (O) -O-.
When R2 and R3 are groups other than hydrogen atoms, the hydrogen atoms of each group are halogen atom, nitro group, cyano group, -OH group, -N (R2') ₂ , amino group, -C (R2'). ) = C (R2')-NO ₂ , -C (R2') = C (R2')-CN, or -C (R2') = C (CN) ₂ .
R2'represents a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms. When a plurality of R2'are present in each group, they may be the same or different from each other.
R2 and R3 may combine with each other to form a ring, and 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.
As a specific example of such a group, R1 includes 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. Examples of R2 and R3 include groups having the following structures. The group having the following structure 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 the present invention is not limited to this.

(Second dichroic azo dye compound)
The second dichroic azo dye compound is a compound different from the first dichroic azo dye compound, and specifically, the chemical structure thereof is different.
The second dichroic azo dye compound is preferably a compound having a chromophore, which is the core of the dichroic azo dye compound, and a side chain attached to the end of the chromophore.
Specific examples of the color-developing group include an aromatic ring group (for example, an aromatic hydrocarbon group and an aromatic heterocyclic group), an azo group, and the like, and a structure having both an aromatic hydrocarbon group and an azo group is preferable. , 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 examples thereof include groups represented by R4, R5, or R6 of the formula (2) described later.

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 has a wavelength in the range of 455 to 555 nm from the viewpoint of adjusting the tint of the polarizer. 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, if 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 are used, the color of the polarizer is used. 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 the formula (2), Ar3, Ar4 and Ar5 independently have a phenylene group which may have a substituent, a naphthylene group which may have a substituent or a hetero which may have a substituent. Represents a ring group.
The heterocyclic group may be either aromatic or non-aromatic.
Examples of atoms other than carbon constituting the aromatic heterocyclic group include nitrogen atom, sulfur atom and oxygen atom. When the aromatic heterocyclic group has a plurality of atoms constituting a ring other than carbon, they may be the same or different.
Specific examples of the aromatic heterocyclic group include pyridylene group (pyridine-diyl group), pyridazine-diyl group, imidazole-diyl group, thienylene (thiophene-diyl group), quinolylene group (quinolin-diyl group), and isoquinolylene. Group (isoquinoline-diyl group), oxazole-diyl group, thiazole-diyl group, oxazole-diyl group, benzothiazole-diyl group, benzothiaziazole-diyl group, phthalimide-diyl group, thienothiazole-diyl group, thiazolo Examples thereof include a thiazole-diyl group, a thienothiophene-diyl group, and a thienooxazole-diyl group.

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

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, a specific example when R4 is an electron-withdrawing group is the same as a specific example when R1 is an electron-withdrawing group, and R5 and R6 are groups with low electron-donating properties. The specific example of the case is the same as the specific example when R2 and R3 are groups having a low electron donating property.

Specific examples of the second dichroic azo dye compound are shown below, but the present invention is not limited to this.

(Third dichroic azo dye compound)
The third bicolor azo dye compound is a bicolor azo dye compound other than the first bicolor azo dye compound and the second bicolor azo dye compound, and specifically, the first two. The chemical structure is different from that of the chromatic azo dye compound and the second dichromatic azo dye compound. If the polarizer contains a third dichroic azo dye compound, there is an advantage that the tint 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.
As a specific example of the third dichroic azo dye compound, among the compounds including the compound represented by the formula (1) described in International Publication No. 2017/195833, the above-mentioned first bicolor azo dye compound. Examples thereof include compounds and compounds other than the above-mentioned second dichroic azo dye compound.

Specific examples of the third dichroic dye compound are shown below, but the present invention is not limited thereto. In the following specific example, n represents an integer of 1 to 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, and even more preferably 20 to 26% by mass with respect to the total solid content mass of the polarizer. When the content of the dichroic azo dye compound is within the above range, it is possible to obtain a polarizer having a high degree of orientation even when the polarizer is made into a thin film. Therefore, it is easy to obtain a polarizer having excellent flexibility. On the other hand, if it exceeds 30% by mass, it becomes difficult for the refractive index adjusting layer to suppress internal reflection.
The content of the first dichroic azo dye compound is 100 parts by mass of the total content of the dichroic azo dye compound in the polarizing element forming composition (composition for forming a light absorption anisotropic layer). , 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, preferably 8 to 35 parts by mass, based on 100 mass by mass of the total content of the dichroic azo dye compound in the composition for forming a polarizer. Part is more preferable.
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 by mass of the content of the dichroic azo dye compound in the composition for forming a polarizer. Is more preferable.
The content ratio of the first dichroic azo dye compound, the second dichroic azo dye compound, and the third dichroic azo dye compound used as needed is the tint of the polarizer. It can be set arbitrarily to adjust. 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 molars. , 0.1 to 10, more preferably 0.2 to 5, and particularly preferably 0.3 to 0.8.

<PVA polarizer with dichroic organic dye>
As the polarizer having a dichroic organic dye, for example, a polarizer formed by adsorbing a dichroic organic dye on a polyvinyl alcohol (PVA) -based resin and stretching it (hereinafter, abbreviated as “PVA polarizer”). .) Can be mentioned.
Polyvinyl alcohol resin is a resin containing a repeating unit of -CH ₂ -CHOH-, e.g., polyvinyl alcohol, and an ethylene - vinyl alcohol copolymer.
In this embodiment, the dichroic organic dye is preferably a highly hydrophilic dye, and it is preferable to use the azo dye having a sulfo group described in paragraphs [0027] to [0030] of JP-A-2019-86622.

On the other hand, the polyvinyl alcohol-based resin is very hydrophilic and has high water absorption, and contributes very much to the water content of the entire polarizing plate. The water content can be adjusted by reducing the film thickness of the polarizer. Further, as described in Japanese Patent Application Laid-Open No. 2015-129286, a laminate having a 9 μm-thick polyvinyl alcohol layer formed on a non-liquid crystal PET (polyethylene terephthalate) base material is dyed and stretched to obtain a thickness of 4 μm. It is disclosed that a polyvinyl alcohol layer can be obtained, and it is also preferable to use such a method.
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, not only can the display device be made thinner, but also the water content can be further reduced, and the moist heat durability of the display device can be improved. Further, in order to obtain the absorbance required as a polarizer, the thickness of the polyvinyl alcohol-based resin layer is preferably 1 μm or more.

<Polarizer with dichroic organic dye and polymerizable liquid crystal compound>
As another example of a polarizing element having a dichroic organic dye, as described in WO2019 / 131943 and 2017-83843, a polymerizable liquid crystal compound without using polyvinyl alcohol as a binder. And by application using a composition (composition for forming a polarizer) containing a dichroic organic dye (for example, a dichroic azo dye used for a light-absorbing anisotropic film described in WO2017 / 195833). Preferred examples thereof include a polarizer to be formed (hereinafter, abbreviated as "coating type polarizer").
Since the coating type polarizer does not require a polyvinyl alcohol-based resin layer, it is possible to further reduce the water content of the polarizing plate with respect to the PVA polarizer, and it is possible to further improve the moist heat durability of the display device. It will be possible.

The polymerizable liquid crystal compound contained in the composition for forming a polarizer 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.
Further, the polymerizable liquid crystal compound preferably has a polymerizable group from the viewpoint of film strength, and the solid content ratio with respect to the coating composition is preferably 60% by mass or more.
It is more preferable that the polymerizable liquid crystal compound or the dichroic organic dye contained in the composition for forming a polarizer has a radically polymerizable group.
It is preferable that the molar content of the radically polymerizable group is 0.6 mmol / g or more, and more preferably 1.0 mmol / g or more, based on the solid content weight of the composition for forming a polarizer. More preferably, it is 5 mmol / g or more.
This coating type 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, it is preferable that the polymerizable liquid crystal compound exhibits smectic properties from the viewpoint of increasing the degree of orientation. Alternatively, as described in WO2018 / 186503, crystallization of the dye is also preferable from the viewpoint of increasing the degree of orientation. WO2019 / 131943 describes a structure of a polymer liquid crystal preferable for increasing the degree of orientation.
In order to orient the coated polarizer, it is preferable to have an alignment layer. Details of the oriented layer will be described later.

The polarizer in which the dichroic organic dye is oriented by utilizing the orientation of the liquid crystal without stretching has the following characteristics. The thickness can be made very thin, about 0.1 μm to 5 μm, cracks are less likely to occur when bent as described in JP-A-2019-194685, and thermal deformation is small. Patent No. 6483486 As described in the above, even a polarizing plate having a high transmittance exceeding 50% has many advantages such as excellent durability.
Taking advantage of these advantages, it can be used for applications requiring high brightness, small size and light weight, fine optical system applications, molding applications for curved surfaces, and flexible regions. 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, and even more preferably 0.3 to 2 μm. By reducing the thickness of the polarizer, the display device can be made thinner. Further, by laminating and coating the optically anisotropic layer and the coating type polarizing element on both sides of the same support, the adhesive layer can be omitted, and the circular polarizing plate can be thinned and the manufacturing efficiency can be increased. It is preferable from the viewpoint of conversion.
Since the coating type polarizer has excellent durability with respect to the PVA polarizer even with a high transmittance, from the viewpoint of power saving, the visibility correction simple substance transmittance of the polarizer is preferably 40% or more. It is more preferably 45% or more, and further 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 applied to antireflection applications, the optically anisotropic layer is a λ / 4 plate, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ± 10 °. The range (35-55 °) is preferred.

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

Examples of the adhesive 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.
Of these, an acrylic pressure-sensitive adhesive (pressure-sensitive pressure-sensitive adhesive) is preferable from the viewpoint of transparency, weather resistance, heat resistance, and the like.

The pressure-sensitive adhesive layer is, for example, a method in which a solution of a pressure-sensitive adhesive is applied onto a release sheet, dried, and then transferred to the surface of the transparent resin layer; the solution of the pressure-sensitive adhesive is directly applied to the surface of the transparent resin layer and dried. It can be formed by a method of making it; etc.
The pressure-sensitive adhesive solution is prepared as a solution of about 10 to 40% by mass in which the pressure-sensitive adhesive is dissolved or dispersed 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 and the like can be adopted.

Further, as the constituent material of the release sheet, for example, an appropriate thin leaf body such as a synthetic resin film such as polyethylene, polypropylene, polyethylene terephthalate; rubber sheet; paper; cloth; non-woven fabric; net; foam sheet; metal leaf; Can be 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, and further 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-mentioned adhesive layer and the organic electroluminescence element.
Since the organic electroluminescence element is sensitive to the influence of moisture and oxygen, a silicon nitride layer is used as a barrier layer (low moisture permeability substrate) that blocks moisture and oxygen.
The moisture permeability of the silicon nitride layer ^{is preferably 1 g / m 2} · day or less, and preferably 10 ^-3 g / m ² · day or less. ^{Among them, 10-4} g / m ² · day or less is more preferable, and ^10-5 g / m ² · day or less is further preferable, from the viewpoint of durability of the organic electroluminescence display element. The lower limit is not particularly limited, but ^{it is often 10-10} g / m ² · day or more.
Here, the humidity permeation is defined as 24 hours under the conditions of a temperature of 40 ° C. and a relative humidity of 90% according to the method described in "Humidity Permeability Test Method for Moisture-Proof Packaging Material (Cup Method)" of JIS Z 0208: 1976. The amount of water vapor that has passed (g / m ² · day).
The method for measuring the moisture permeability of the substrate is as follows. The measurement is performed using a water vapor transmittance measuring device (AQUATRAN2 (registered trademark) manufactured by MOCON, INC.) Under the conditions of a measuring temperature of 40 ° C. and a relative humidity of 90%.
The thickness of the silicon nitride layer is preferably 10 nm, more preferably 20 nm or more, from the viewpoint of gas barrier ability. From the viewpoint of preventing cracking of the film, it is preferably 150 nm or less, and more preferably 80 nm or less.

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

As a method for forming the silicon nitride layer, any conventionally known method can be used. For example, a sputtering method, a vacuum deposition method, an ion plating method, a plasma CVD (Chemical Vapor Deposition) method, and the like are suitable. Specifically, Japanese Patent No. 3400324, Japanese Patent Application Laid-Open No. 2002-322561, Japanese Patent Application Laid-Open No. 2002- The forming method described in each of the publications of No. 361774 can be adopted.
Ammonia gas may be generated in the silicon nitride layer by the hydrolysis reaction, but the hydrolysis reaction is promoted in the following cases, and the effect of the present invention becomes remarkable.
The silicon nitride layer has a Si—N bond peak (peak of absorption due to expansion and contraction vibration of Si—N (peak intensity)) located at ^{800 to 900 cm -1} as measured by FT-IR (Fourier transform infrared absorption spectrum). The peak of the Si—H bond located at 2100 to 2200 cm ^-1 (the peak of absorption due to the expansion and contraction vibration of Si—H) and ^{the peak of the NH bond located at 3300 to 3400 cm -1} (due to the expansion and contraction vibration of NH). Has a peak of absorption). From the viewpoint that the effect of the present invention appears more prominently, the strength ratio of the peak of Si—N bond to the peak of NH bond, NH / Si—N, is preferably 0.04 or more, preferably 0.06. The above is more preferable, 0.08 or more is further preferable, and 0.10 or more is most preferable. From the viewpoint of the barrier ability of the film, NH / Si—N is preferably 0.3 or less, more preferably 0.2 or less, and even more preferably 0.15 or less.
^{Regarding the film density of the silicon nitride layer, the film density [g / cm 3} ] can be measured by the X-ray reflectance measurement method using a thin film X-ray diffractometer (ATX-E manufactured by Rigaku Co., Ltd.). From the viewpoint of effect appears more remarkably in the present invention, the film density is preferably 2.4 g / cm ³ or less, 2.3 g / cm ³ or less is more preferable. From the viewpoint of the barrier ability of the membrane, 1.8 g / cm ³ or more is preferable, 2.0 g / cm ³ or more is more preferable, and 2.2 g / cm ³ or more is further preferable.

[Organic EL display element]
The organic EL display element included in 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 between them.
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 between the electrodes of the organic EL display element, and each of these layers may be provided. It may have other functions. Various materials can be used to form each layer.

[Other layers]
Even if the organic electroluminescence display device of the present invention has 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 electroluminescence display device of the present invention may have a support for supporting the optically anisotropic layer or the coated polarizer, but the support may be peeled off for thinning. preferable.
The support is preferably transparent, and specifically, the light transmittance is preferably 80% or more.

Examples of the support include a polymer film.
Materials for the polymer film include cellulose-based polymers; (meth) acrylic polymers having acrylic acid ester polymers such as polymethylmethacrylate and lactone ring-containing polymers; thermoplastic norbornene-based polymers; polycarbonate-based polymers; polyethylene terephthalates, and , Polyester-based polymers such as polyethylene naphthalate; Polystyrene and styrene-based polymers such as acrylonitrile-styrene copolymer (AS resin); Polyethylene-based polymers such as polyethylene, polypropylene, and ethylene-propylene copolymers; Vinyl-based polymers; Nylon and amide-based polymers such as aromatic polyamides; Imid-based polymers; Sulfon-based polymers; Polyether sulfone-based polymers; Polyether ether ketone-based polymers; Polyphenylene sulfide-based polymers; Examples include polymer; vinyl butyral polymer; allylate polymer; polyoxymethylene polymer; epoxy polymer; or a polymer in which these polymers are mixed.
Further, the above-mentioned 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, and 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 orientation of the optically anisotropic layer and the coating type polarizer, but the alignment layer may be peeled off for thinning. preferable. The support described above may also serve as an orientation layer.

In order to form the positive A plate, which is one aspect of the optically anisotropic layer, a technique for aligning the molecules of the specific liquid crystal compound in a desired orientation state is used. For example, the orientation layer is used to form the specific liquid crystal. A technique for orienting a compound in a desired direction is common.
The orientation layer includes a rubbing-treated film of a layer containing an organic compound such as a polymer, an oblique vapor deposition film of an inorganic compound, a film having microgrooves, or ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearylate. Examples thereof include a membrane obtained by accumulating LB (Langmuir-Blodgett) membranes obtained by the Langmuir-Blodget method of organic compounds such as.
Further, as the alignment layer, a photo-alignment layer in which an alignment function is generated by irradiation with light is also preferable.

As the orientation layer, a layer 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 certain direction (preferably in the longitudinal direction of the support). Examples of the polymer used for forming the alignment layer include polyimide, polyvinyl alcohol, the modified polyvinyl alcohol described in paragraphs 0071 to 0905 of Japanese Patent No. 3907735, and the polymerizable group described in JP-A-9-152509. The polymer having is preferable.
The thickness of the alignment layer is not particularly limited as long as it can exhibit the alignment function, 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) in which a photo-alignment material is irradiated with polarized light or non-polarized light to form an alignment layer.
It is preferable to impart an orientation regulating force to the photoalignment layer by a step of irradiating the photoalignment layer with polarized light from a vertical direction or an oblique direction, or a step of irradiating unpolarized light from an oblique direction.
By using the photo-alignment layer, it is possible to horizontally orient the specific liquid crystal compound with excellent symmetry. Therefore, the positive A plate formed by using the photoalignment layer is particularly useful for optical compensation in a liquid crystal display device that does not require a pre-tilt angle of the driving liquid crystal, such as an IPS (In-Place-Switching) mode liquid crystal display device. Is.

Examples of the photo-alignment material used for the photo-alignment layer include JP-A-2006-285197, JP-A-2007-076839, JP-A-2007-138138, JP-A-2007-094071, and JP-A-2007-. The azo compounds described in JP-A-121721, JP-A-2007-140465, JP-A-2007-156439, JP-A-2007-133184, JP-A-2009-109831, Patent No. 3883848, and Patent No. 4151746. , Aromatic ester compounds described in JP-A-2002-229039, maleimide and / or alkenyl-substituted nadiimide compounds having photo-orientation units described in JP-A-2002-265541 and JP-A-2002-317013, patents. Photocrossable silane derivatives described in No. 4205195, Patent No. 4205198, Photocrossable polyimides, polyamides, or esters described in JP-A-2003-520878, JP-A-2004-522220, and Patent No. 4162850. Described in JP-A-9-118717, JP-A-10-506420, JP-A-2003-505561, International Publication No. 2010/150748, JP-A-2013-177561, and JP-A-2014-12823. Examples of photodimerizable compounds, particularly synchromate compounds, chalcone compounds, and coumarin compounds.
Particularly preferred examples include synnamate compounds.

The thickness of the oriented layer is not particularly limited, but is preferably 0.01 to 10 μm from the viewpoint of alleviating the surface irregularities that may exist on the support and forming an optically anisotropic layer having a uniform film 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 trap layer containing a compound having a carboxylic acid group for the purpose of trapping ammonia.
It is also possible to include a compound having a carboxylic acid group in a layer such as an adhesive layer and a barrier layer or 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 side of the polarizer (on the surface opposite to the optically anisotropic layer side), or may be arranged on both sides of the polarizer. The structure of the polarizer protective film is not particularly limited, and may be, for example, a so-called transparent support or 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 in combination with the surface protective layer described later.
A known transparent support can be used as the transparent support. For example, the material for forming the transparent support is a cellulosic polymer represented by triacetyl cellulose (hereinafter, referred to as "cellulose acylate". ), Norbornen-based resin (Zeonex and Zeonoa manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Co., Ltd.), acrylic resin, polyester resin, and polystyrene resin. Resins that are difficult to contain water, such as acrylic resins, thermoplastic norbornene-based resins, and polystyrene-based resins, are preferable for suppressing the total water content of the polarizing plate, and norbornene-based resins are particularly preferable.
The resin has an equilibrium water content of 80% at 25 ° C., preferably 2% or less, more preferably 0.5% or less, and even more preferably 0.2% or less.
The thickness of the polarizer protective film is not particularly limited, but is preferably 40 μm or less, more preferably 25 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less, from the viewpoint that the thickness of the polarizing plate can be reduced. The lower limit is not particularly limited, but is often 1 μm or more.

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

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, further preferably 1.5 g / m 2} or less, and 0.8 g / m ² or less. Is particularly preferable.

[Surface protective layer]
As one of the preferred embodiments 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 one or a plurality of layers selected from a support made of a polymer film such as polyimide or cellulose acylate, a surface hardening layer, and a low reflection layer that suppresses surface reflection generated at the air interface. Including. 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 because the effect of the present invention appears more remarkably. More preferred.

〔Touch sensor〕
There are two types of touch sensors: an on-cell type in which a metal mesh electrode is formed directly on the silicon nitride layer that barriers the organic electroluminescence element, and an out-cell type in which a film sensor with electrodes formed on a film is externally attached. , 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 exhibits adhesiveness by drying or reaction after bonding.
The polyvinyl alcohol-based adhesive (PVA-based adhesive) develops adhesiveness when dried, and makes it possible to bond the materials together.
Specific examples of the curable adhesive that develops adhesiveness by reaction include an active energy ray-curable adhesive such as a (meth) acrylate-based adhesive and a cationic polymerization curable adhesive. Examples of the curable component in the (meth) acrylate-based adhesive include a compound having a (meth) acryloyl group and a compound having a vinyl group.
Further, as the cationic polymerization curable adhesive, a compound having an epoxy group or an oxetanyl group can also be used. 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 generally 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 at least one of them having at least two epoxy groups in the molecule. Examples thereof include a compound (alicyclic epoxy compound) formed between two adjacent carbon atoms constituting an alicyclic ring.

[Functional layer]
It is preferable to have a functional layer having a function of reducing short wave light on the visual side of the optically anisotropic layer. By reducing short-wave light, it is possible to provide an organic electroluminescence display device which suppresses photodecomposition of a dye compound and has excellent light resistance.
In one aspect, it is preferable that the above-mentioned adhesive layer, support, polarizer protective film and the like 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 visual side of the optically anisotropic layer.

The method for reducing shortwave light is not particularly limited, and a method using light absorption by an absorber or the like and a method using wavelength selective reflection by a multilayer film are exemplified.

The above-mentioned shortwave light refers to light having a wavelength of 430 nm or less. By reducing the light having a wavelength of 430 nm or less, it is possible to suppress the photodecomposition of the liquid crystal compound by sunlight or the light source light used in the light resistance test of JIS B 7751 and JIS B 7754.
Further, it is preferable to be transparent in the wavelength range of 450 nm or more so as not to affect the performance of the polarizer in visible light.
The transmittance is preferably 0.1% or less in the wavelength range of 350 to 390 nm, 20 to 70% in the range of 410 nm, and 90% or more in the range of 450 nm or more.
The transmittance at a wavelength of 410 nm is more preferably 40 to 50%.

As the compound that absorbs shortwave light, the merocyanine compound described in JP-A-2017-119700 and WO2018 / 123267 is preferably used.
It is also preferable to use a conventionally known ultraviolet absorber in combination. Examples include organic UV absorbers such as oxybenzophenone UV absorbers, benzotriazole UV absorbers, salicylate ester UV absorbers, benzophenone UV absorbers, cyanoacrylate UV absorbers, and triazine UV absorbers. Be done.

〔Layer structure〕
Since the effect of the present invention is remarkably exhibited, it is preferable that the moisture permeability of the layer existing between the circularly polarizing plate and the silicon nitride layer is 100 g / m ^{2 · day or more.} In other words, it is preferable not to have a layer having a ^{moisture permeability of less than 100 g / m 2} · day between the circularly polarizing plate and the silicon nitride layer.
Further, in the present invention, from the viewpoint of thinning, the thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer needs to be 35 μm or less, and preferably 1 to 30 μm.

The present invention will be described in more detail below based on examples. The materials, amounts used, ratios, treatment contents, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present invention. Therefore, the scope of the present invention should not be construed as limiting by the examples shown below.

<Creation of surface protective layer H1>
(Manufacturing of polyimide powder)
After adding 832 g of N, N-dimethylacetamide (DMAc) to a 1 L reactor equipped with a stirrer, a nitrogen injection device, a dropping funnel, a temperature controller and a cooler under a nitrogen stream, the temperature of the reactor was changed to 25. It was set to ℃. To this, 64.046 g (0.2 mol) of bistrifluoromethylbenzidine (TFDB) was added and dissolved. While maintaining the obtained 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 a substance (BPDA) was added, and the mixture was stirred for a certain period of time to react. Then, 20.302 g (0.1 mol) of terephthaloyl chloride (TPC) was added to obtain a polyamic acid solution having a solid content concentration of 13% by mass. Next, 25.6 g of pyridine and 33.1 g of acetic anhydride were added to this polyamic acid solution and 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 content was filtered and pulverized. Then, it was dried in a vacuum at 100 degreeC 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 mass% solution. The obtained solution was cast on a stainless steel plate and dried with hot air at 130 ° C. for 30 minutes. After that, the film is peeled off from the stainless steel plate, fixed to the frame with a pin, the frame to which the film is fixed is placed in a vacuum oven, heated for 2 hours while gradually increasing the heating temperature from 100 ° C to 300 ° C, and then gradually. Cooled to. After separating the cooled film from the frame, as a final heat treatment step, the film was further heat-treated at 300 ° C. for 30 minutes to obtain a support S1 having a thickness of 30 μm and made of a polyimide film.

<Synthesis of polymerizable polyorganosylsesquioxane>
(Synthesis of compound (A))
2- (3,4-Epoxycyclohexyl) ethyltrimethoxysilane 297 mmol (73.) in a 1000 ml flask (reaction vessel) equipped with a thermometer, stirrer, reflux condenser, and nitrogen introduction tube under a nitrogen stream. 2 g), 3 mmol (409 mg) of methyltrimethoxysilane, 7.39 g of triethylamine, and 370 g of MIBK (methylisobutylketone) 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 under a nitrogen stream for 10 hours.
Then, the reaction solution was cooled, 300 g of 5 mass% saline was added, and the organic layer was extracted. The organic layer was washed twice with 300 g of 5 mass% saline and 300 g of pure water, and then concentrated under the conditions of 1 mmHg and 50 ° C. to form a colorless and transparent liquid as a MIBK solution having a solid content concentration of 59.8 mass%. Object {Compound (A) which is a polyorganosyl sesquioxane having an alicyclic epoxy group (Rb: 2- (3,4-epoxycyclohexyl) ethyl group, Rc: methyl group, q = in the following (1)) A methyl isobutyl ketone (MIBK) solution containing 59.0% by mass as a solid content concentration (99, a compound having r = 1) was obtained.

The obtained compound (A) had a number average molecular weight (Mn) of 2310 and a dispersity (Mw / Mn) of 2.1.
In addition, 1 mmHg is about 133.322 Pa.

(Synthesis of polymer (1-1))
25.0 g of t-amyl alcohol was charged into a 200 ml three-necked flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen gas introduction tube, and the temperature was raised to 120 ° C. Next, 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 A mixed solution consisting of (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 velocity so that the addition was completed in 120 minutes. After the dropping was completed, stirring was continued for another 3.5 hours to obtain 5.5 g (solid content conversion value) of the polymer (1-1). The weight average molecular weight (Mw) of this polymer was 1,1001,600.

<Preparation of composition for forming hard coat layer>
(Composition for forming a hard coat layer HC-1)
CPI-100P, the polymer (1-1) and MIBK (methyl isobutyl ketone) are added to the MIBK solution containing the compound (A), and the concentration of each component is adjusted to the following concentration. It was put into a mixing tank and stirred. The obtained 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 Sun Appro Co., Ltd.

<Preparation of composition for forming mixed layer>
(Composition for forming a mixed layer M-1)
The MIBK solution containing the compound (A) was replaced with a MEK (methyl ethyl ketone) solution, and DPHA, CPI-100P, Irgacure 127, leveling agent-1 and MEK were added, and the concentration of each component was as follows. The mixture was adjusted so as to be, put into a mixing tank, and stirred. The obtained composition was filtered through a polypropylene filter having a pore size of 0.4 μm to obtain a mixed layer forming composition M-1. The mixing ratio of the compound (A) and DPHA in the mixed layer forming composition M-1 is 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: Mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, Irgacure 127: Radical photopolymerization initiator, BASF leveling agent-1: Polymer with the following structure (Mw = 20000, below The composition ratio of the repeating unit is the mass ratio)

<Preparation of composition for forming scratch resistant layer>
(Composition SR-1 for forming a scratch-resistant layer)
Each component was charged into a mixing tank with the composition described below, 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: Slipper, manufactured by DIC Corporation

(Preparation of surface protective layer H1)
The composition for forming a hard coat layer HC-1 was applied onto the base material 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 illuminance of 18 mW / cm 2} and an irradiation amount 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 prepared by adding MEK to the mixed layer forming composition M-1 and diluting the solid content concentration to 1/10 was prepared and applied on a 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 illuminance of 18 mW / cm 2} and an irradiation amount of 10 mJ / cm ² using an air-cooled mercury lamp at 25 ° C. and an oxygen concentration of 1%. Then, a mixed layer was provided on the hard coat layer.
The 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, it is irradiated with ultraviolet rays having an illuminance of 60 mW / cm 2} and an irradiation amount of 800 mJ / cm ² using an air-cooled mercury lamp under the conditions of 25 ° C. and an oxygen concentration of 100 ppm, and then further 80 ° C. and oxygen. 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 obtained film is then heat-treated at 120 ° C. for 1 hour to provide a surface protective layer having a 0.1 μm-thick mixed layer and a 1.0 μm-thick scratch-resistant layer on a 11.0 μm-thick hard coat layer. I got H1. Moisture permeability of the surface protective layer H1 is was 1g ^/ m 2 · day than.

<Preparation of PVA adhesive>
20 parts of methylol melamine at 30 ° C. with respect to 100 parts of a polyvinyl alcohol-based resin containing an acetoacetyl group (average degree of polymerization: 1200, saponification degree: 98.5 mol%, acetoacetylation degree: 5 mol%). An aqueous solution was prepared by dissolving it in pure water under temperature conditions and adjusting the solid content concentration to 3.7%.

<Preparation 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 introduction tube, a thermometer and a stirrer to achieve an average molecular weight of 2 million and a molecular weight distribution (Mw /). An acrylate-based polymer A1 of Mn) 3.0 was obtained.

Next, using the obtained acrylate-based polymer A1, an acrylate-based pressure-sensitive adhesive was prepared with the compositions shown in Table 3 below.
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 obtain an adhesive layer. N1 and N2 were obtained. The composition, film thickness, and storage elastic modulus of the acrylate-based pressure-sensitive adhesive are shown in Table 3 below.
(UV irradiation conditions (irradiation only for N1))
Fusion Co. electrodeless lamp H Valve illuminance 600 mW / cm ^2, light quantity 150 mJ / cm ²
-UV illuminance and light intensity were measured using "UVPF-36" manufactured by Eye Graphics.

(A) Polyfunctional acrylate-based monomer: Tris (acryloyloxyethyl) isocyanurate, molecular weight = 423, trifunctional type (manufactured by Toa Synthetic Co., Ltd., trade name "Aronix M-315") (B) Photopolymerization initiator: Benzophenone A mixture of 1-hydroxycyclohexylphenyl ketone and 1-hydroxycyclohexylphenyl ketone in a mass ratio of 1: 1, "Irgacure 500" manufactured by Ciba Specialty Chemicals, Inc.
(C) Isocyanate-based cross-linking agent: Trimethylolpropane-modified tolylene diisocyanate (“Coronate L” manufactured by Nippon Polyurethane Industry 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 the cellulose triacetate film TJ25 (manufactured by Fujifilm: thickness 25 μm) was subjected to alkali saponification treatment. Specifically, after immersing the support in a 1.5-standard sodium hydroxide aqueous solution at 55 ° C. for 2 minutes, the support is washed in a water-washing bath at room temperature, and then 0.1-standard sulfuric acid at 30 ° C. is added. Neutralized using. After neutralization, the support was washed in a water washing bath at room temperature and further dried with warm air at 100 ° C. to obtain a polarizer protective film 1.
A polyvinyl alcohol-based film (VF-XS manufactured by Kuraray Co., Ltd.) having a thickness of 75 μm, a degree of polymerization of 2400, and a saponification degree of 99% or more is swollen with warm water at 40 ° C. Staining was performed. The dyed film was stretched in a solution containing 3% by weight of boric acid, stretched, and then immersed in an aqueous solution containing 5% by weight of potassium iodide. The film immersed in the potassium iodide aqueous solution for 15 seconds was dried in a dryer at 70 ° C. for 10 minutes to obtain a polarizer 1 having a thickness of 15 μm.
The polarizer protective film 1 was attached to one surface of the polarizer 1 using the PVA adhesive to prepare a polarizer 1 with a single-sided protective film.
Further, using the adhesive layer N1, the protective film 1 side of the polarizing element 1 with a single-sided protective film and the support S1 side of the surface protective layer H1 were bonded to each other to prepare a polarizing element 1 with a surface protective layer H1.

[Preparation of PVA Polarizer 2 Using Dichroic Organic Dye]
A polarizing plate SHC-215U manufactured by Polatechno Co., Ltd., in which a polyvinyl alcohol film was dyed with a dichroic organic dye, was prepared.
Next, the support S1 side of the surface protective layer H1 and the polarizing plate SHC-215U were attached to each other 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 for forming a photoalignment layer E1 was prepared with the following composition, dissolved for 1 hour with stirring, and filtered through a 0.45 μm filter.
―――――――――――――――――――――――――――――――――
Composition for forming a photo-aligned layer 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 with the following composition, dissolved by heating at 80 ° C. for 2 hours with stirring, and filtered through a 0.45 μm filter. The molar content of the radically polymerizable group is 1.98 mmol / g.
―――――――――――――――――――――――――――――――――
Composition for forming an anisotropic layer of light absorption P1
―――――――――――――――――――――――――――――――――
-The following dichroic dye D1 2.6 parts by mass-The following dichroic dye D2 2.6 parts by mass-The following dichroic dye D3 2.2 parts by mass-The following liquid crystal compound M1 100.0 parts by mass-polymerization initiator IRGACURE369 (manufactured by BASF) 5.0 parts by mass, BYK361N (manufactured by Big Chemie Japan) 0.9 parts by mass, cyclopentanone 925.0 parts by mass ―――――――――――――――― ―――――――――――――――――

Dichro dye D1

Dichroic pigment D2

Dichroic pigment D3

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

(Compound A)

(Compound B)

<Formation of light absorption anisotropic layer P1>
The composition E1 for forming a photoalignment layer was applied onto a cellulose triacetate film TJ40 (manufactured by Fujifilm: thickness 40 μm) and dried at 60 ° C. for 2 minutes. Then, the obtained coating film was irradiated with linearly polarized ultraviolet rays (100 mJ / cm ² ) using a polarized ultraviolet exposure apparatus to prepare a photoalignment layer E1.
The composition P1 for forming a light absorption anisotropic layer was applied onto the obtained photo-alignment layer E1 with a wire bar. Next, the obtained coating film was heated at 120 ° C. for 60 seconds and cooled to room temperature.
Then, the light absorption anisotropic layer P1 having a thickness of 1.7 μm was formed by irradiating with ultraviolet rays having 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 in the smectic B phase.

<Formation of protective layer B1>
Dipentaerythritol hexaacrylate (Aronix M-403, manufactured by Toa Synthetic Co., Ltd.) (50 parts by mass) and acrylate resin (Evecryl 4858, manufactured by Daicel UCB Co., Ltd.) (50 mass) on the formed light absorption anisotropic layer P1. Part) and 2- [4- (methylthio) benzoyl] -2- (4-morpholinyl) propane (IRGACURE907, manufactured by BASF) (3 parts by mass) dissolved in isopropanol (250 parts by mass). (Composition for forming a protective layer) was applied by a bar coating method, and heated and dried in a drying oven at 50 ° C. for 1 minute.
^{The obtained coating film is 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 Denki Co., Ltd.). A protective layer B1 (3 μm) was formed on the absorption anisotropic layer P1 to prepare a polarizing film 3B containing the light absorption anisotropic layer P1.

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

[Preparation of Polarizer 4 using dichroic organic dye and polymerizable liquid crystal]
<Formation of photo-aligned layer PA1>
The coating liquid PA1 for forming an alignment layer, which will be described later, was continuously coated 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 warm 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 obtain a photoalignment layer. PA1 was formed to obtain a TAC film with a photoalignment layer PA1.
The film thickness of the photoalignment layer PA1 was 0.3 μm.

―――――――――――――――――――――――――――――――――
Coating liquid PA1 for forming an alignment layer
―――――――――――――――――――――――――――――――――
The following polymer PA-1 100.00 parts by mass The following acid generator PAG-1 5.00 parts by mass The following acid generator CPI-110TF 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>
The following composition for forming a light absorption anisotropic layer P2 was continuously applied on the obtained photo-alignment layer PA1 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.
Then, a light absorption anisotropic layer P2 was produced on the light alignment layer PA1 by irradiating with an LED (light emitting diode) lamp (center wavelength 365 nm) for ^{2 seconds under an illuminance of 200 mW / cm 2.} The molar content of the radically polymerizable group is 1.17 mmol / g.
The film thickness of the light absorption anisotropic layer P2 was 1.5 μm.

―――――――――――――――――――――――――――――――――
Composition for forming an anisotropic layer of light absorption P2
―――――――――――――――――――――――――――――――――
-The following bicolor dye D-4 0.25 parts by mass-The following bicolor dye D-5 0.36 parts by mass-The following bicolor dye D-6 0.59 parts by mass-The following polymer liquid crystal compound P- 1 2.21 parts by mass ・ The following low molecular weight liquid crystal compound M-1 1.36 parts by mass ・ Polymerization initiator IRGACUREOXE-02 (manufactured by BASF) 0.150 parts by mass ・ The following surfactant F-1 0.026 mass Parts ・ Cyclopentanone 46.00 parts by mass ・ tetrahydrofuran 46.00 parts by mass ・ benzyl alcohol 3.00 parts by mass ――――――――――――――――――――――――― ――――――――

Dichro dye D-4

Dichro dye D-5

Dichro dye D-6

Polymer liquid crystal compound P-1

Low molecular weight liquid crystal compound M-1

Surfactant F-1

<Formation of hardened layer K1>
The following cured layer forming composition K1 was continuously applied with a wire bar on the obtained light absorption anisotropic layer P2 to form a coating film.
Next, the coating film was dried at room temperature, and then ^{irradiated for 15 seconds under an irradiation condition of an illuminance of 28 mW / cm 2} using a high-pressure mercury lamp to prepare a cured layer K1 on the light absorption anisotropic layer P2.
The film thickness of the cured layer K1 was 0.05 μm.
―――――――――――――――――――――――――――――――――
Composition for forming a hardened layer K1
―――――――――――――――――――――――――――――――――
-Mixture of the following rod-shaped liquid crystal compound L1 2.61 parts by mass-The following modified trimethylolpropane triacrylate 0.11 parts by mass-The following photopolymerization initiator I-1 0.05 parts by mass-The following surfactant F-3 0. 21 parts by mass, methyl isobutyl ketone 297 parts by mass ―――――――――――――――――――――――――――――――――

Mixture L1 of rod-shaped liquid crystal compound (The numerical value in the following formula represents mass%, and R represents a group bonded with an oxygen atom.)

Modified trimethylolpropane triacrylate

Photopolymerization Initiator I-1

Surfactant F-3

<Formation of oxygen blocking layer B2>
The following composition for forming an oxygen blocking layer B2 was continuously applied on the cured layer K1 with a wire bar. Then, it was dried with warm air at 100 ° C. for 2 minutes to form an oxygen blocking layer B2 having a thickness of 1.0 μm on the cured layer K1 to prepare a polarizing film 4B containing a light absorption anisotropic layer P2.
The luminous efficiency correction single transmittance of the polarizer was 43%.
―――――――――――――――――――――――――――――――――
Oxygen blocking layer forming composition B2
―――――――――――――――――――――――――――――――――
-The following modified polyvinyl alcohol 3.80 parts by mass-Initiator Irg2959 0.20 parts by mass-70 parts by mass of water-30 parts by mass of methanol ―――――――――――――――――――― ―――――――――――――

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. Then, only TJ40 was peeled off to prepare 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 Achillate Film 1]
The following composition was put into a mixing tank and stirred to prepare a cellulose acetate solution to be used as a core layer cellulose acylate dope.
─────────────────────────────────
Core layer Cellulose acylate dope ─────────────────────────────────
100 parts by mass of cellulose acetate having an acetyl substitution degree of 2.88 ・ 12 parts by mass of the polyester compound B described in Examples of JP-A-2015-227955 ・ 2 parts by mass of the following compound G ・ Methylene chloride (first solvent) 430 Parts by mass / methanol (second solvent) 64 parts by mass ─────────────────────────────────

Compound G

The following matting solution was added to 90 parts by mass of the above core layer cellulose acylate dope to prepare a cellulose acetate solution to be used as the outer layer cellulose acylate dope.
─────────────────────────────────
Matte 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 acid Rate Dope 1 part by mass ─────────────────────────────────

After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope with 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 on both sides thereof. And three layers were simultaneously cast on a drum at 20 ° C. from the casting port (band casting machine). The film was peeled off from the drum with a solvent content of about 20% by mass, both ends of the film in the width direction were fixed with tenter clips, and the film was dried while being stretched laterally at a stretching ratio of 1.1 times. Then, the obtained film was conveyed between the rolls of the heat treatment apparatus to be further dried to prepare a cellulose acylate film 1 having a thickness of 20 μm. The Re (550) of the obtained cellulose acylate film 1 was 0 nm.

[Formation of photo-alignment layer 1]
Next, referring to the description of Example 3 of JP2012-155308A, a coating liquid 1 for a photoalignment layer was prepared and coated on a cellulose acylate film 1 with a wire bar. Then, the obtained cellulose acylate film 1 was dried with warm air at 60 ° C. for 60 seconds to prepare a coating film 1 having a thickness of 300 nm.

Subsequently, the composition A1 for forming a positive A plate having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Composition of composition A1 for forming a positive A plate ――――――――――――――――――――――――――――――――――
-The following polymerizable liquid crystal compound X-1 16.00 parts by mass-The following specific liquid crystal compound L-1 42.00 parts by mass-The following specific liquid crystal compound L-2 42.00 parts by mass-The following polymerization initiator S-1 0. 50 parts by mass, the following polymerizable compound B-1 2,000 parts by mass, the leveling agent (the following compound T-1) 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 in the atmosphere using an ultra-high pressure mercury lamp. At this time, a wire grid polarizer (ProFlux PPL02 manufactured by Moxtek, Inc.) was set so as to be parallel to the surface of the coating film 1 and exposed, and photoalignment treatment was performed to obtain a photoalignment layer 1.
^{At this time, the illuminance of the ultraviolet rays was set to 10 mJ / cm 2 in the} UV-A region (ultraviolet A wave, integration of wavelengths of 320 to 380 nm).

[Preparation of Optical Film 1 Containing Positive A Plate A1]
Next, the composition A1 for forming a positive A plate was applied onto the photoalignment layer 1 using a bar coater. The obtained coating film is heat-aged at a film surface temperature of 100 ° C. for 20 seconds, cooled to 90 ° C., and then exposed to ultraviolet rays of ^{300 mJ / cm 2 using an air-cooled metal halide lamp (manufactured by Eye Graphics Co., Ltd.) under air.} A positive A plate A1 (corresponding to an optically anisotropic layer) was formed by immobilizing the nematic orientation state, and an optical film 1 containing the positive A plate A1 was produced.

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

[Preparation of Optically Anisotropic Film 1 in which Positive C Plate Films are Laminated]
Next, the surface of the optical film 1 on the positive A plate A1 side was corona-treated, and then the following composition C-1 was applied. The coating film formed on the temporary support for formation is heated to 60 ° C. under a heating atmosphere, and ultraviolet irradiation (300 mJ / cm ² ) is performed at 70 ° C. at an oxygen concentration of 100 ppm under a nitrogen purge to orient the liquid crystal 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 crystal compound (M-1) 83 parts by mass-The following rod-shaped liquid crystal compound (M-2) 15 parts by mass-The following rod-shaped liquid crystal compound (M-3) 2 parts by mass-The following urethane monomer (EBECRYL1290,
(Manufactured by Daicel Ornex) 3.3 parts by mass ・ The following polymerization initiator (IrgacureOXE01,
(Manufactured by BASF) 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 crystal compound (M-1)

Rod-shaped liquid crystal compound (M-2)

Rod-shaped liquid crystal compound (M-3)

Urethane monomer

Polymerization initiator

Fluorine-based polymer (M-4)

Fluorine-based polymer (M-5)

Onium salt compound S01

[Preparation of laminated body 1]
After the cellulose acylate film 1 side of the optically anisotropic film 1 produced above is corona-treated, it is attached to the PVA polarizer side of the polarizing element 1 with the surface protective layer H1 produced above and the above PVA adhesive. The laminated body 1 of Production Example 1 was used. At this time, the angle formed by the absorption axis of the polarizing element included in the polarizing element 1 with the surface protective layer H1 and the slow axis of the positive A plate A1 contained in the optically anisotropic film 1 is 45 °. Combined (the same applies below).

[Production Example 2]
In the same manner as in Production Example 1, the cellulose acylate film 1 side of the optically anisotropic film 1 and the polarizer protective film side of the polarizing element 2 with the surface protective layer H1 produced above are corona-treated, respectively, and then the above. The laminate 2 of Production Example 2 was obtained by pasting with the PVA adhesive of.

[Production Example 3]
In the same manner as in Production Example 1, the cellulose acylate film 1 side of the optically anisotropic film 1 and the protective layer B1 side of the polarizer of the polarizer 3 with the surface protective layer H1 prepared above are each corona-treated. , Attached with the above UV adhesive to obtain the laminate 2 of Production Example 3.

[Production Example 4]
In the same manner as in Production Example 1, after corona-treating the cellulose acylate film 1 side of the optically anisotropic film 1 and the alignment layer PA1 side of the polarizer of the polarizing element 4 with the surface protective layer H1 produced above, respectively. , The laminate 4 of Production Example 4 was obtained by pasting with the above UV adhesive.

[Production Example 5]
As a surface protective layer H2, the low-reflection surface film CV-LC5 (FUJIFILM, moisture permeability 1g ^/ m 2 · day or more) were 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 above adhesive sheet. Then, only TJ40 was peeled off to prepare a polarizer 4 with a surface protective layer H2.
In the same manner as in Production Example 1, the cellulose acylate film 1 side of the optically anisotropic film 1 and the alignment layer layer PA1 side of the polarizer of the polarizer 4 with the surface protective layer H2 prepared above were corona-treated, respectively. After that, it was attached with the above UV adhesive to obtain a laminate 5 of Production Example 5.

[Production Examples 6 to 29]
Production Examples 1 to 4 except that the positive A plate forming composition shown in Table 4 below was used instead of the positive A plate forming composition A1 and the polarizer 1 was changed to the polarizer shown in Table 4 below. Laminates 6 to 29 were prepared according to the same procedure as in the above.
The compositions of the 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 a positive A plate)
In the positive A plate forming composition A1, 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. Except for the above, the positive A plate forming composition A2 was prepared in the same manner as the positive A plate forming composition A1.

(Preparation of composition A3 for forming a positive A plate)
In the positive A plate forming composition A1, 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. Except for the above, the positive A plate forming composition A3 was prepared in the same manner as the positive A plate forming composition A1.

Specific liquid crystal compound L-9

(Preparation of composition A4 for forming a positive A plate)
A composition A4 for forming a positive A plate having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Composition of composition A4 for forming a positive A plate ――――――――――――――――――――――――――――――――――
-The following specified liquid crystal compound L-17 70.00 parts by mass-The following specified liquid crystal compound L-5 30.00 parts by mass-Polymerization initiator OXE-03 (manufactured by BASF Japan) 4.00 parts by mass-Adeca Arclus NCI- 831 (manufactured by Adeca) 5.00 parts by mass, leveling agent (compound T-1) 0.10 parts by mass, antioxidant BHT (manufactured by Tokyo Kasei Kogyo Co., Ltd.) 0.90 parts by mass, methyl ethyl ketone (solvent) 60. 00 parts by mass, cyclopentanone (solvent) 240.00 parts by mass ――――――――――――――――――――――――――――――――――

Liquid crystal compound L-17

(Preparation of composition A5 for forming a positive A plate)
Similar to the positive A plate forming composition A4, except that 100 parts by mass of the following specified liquid crystal compound L-7 was used in place of the specific liquid crystal compounds L-17 and L-5 in the positive A plate forming composition A4. The composition A5 for forming a positive A plate was prepared by the method of.

(Preparation of composition A6 for forming a positive A plate)
Similar to the positive A plate forming composition A4, except that 100 parts by mass of the following specified liquid crystal compound L-8 was used in place of the specific liquid crystal compounds L-17 and L-5 in the positive A plate forming composition A4. The composition A6 for forming a positive A plate was prepared by the method of.

(Preparation of Composition A7 for Forming Positive A Plate)
Similar to the positive A plate forming composition A4, except that 100 parts by mass of the following specified liquid crystal compound L-10 was used in place of the specific liquid crystal compounds L-17 and L-5 in the positive A plate forming composition A4. A7, a composition for forming a positive A plate, was prepared by the above method.

Specific liquid crystal compound L-10

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

Specific liquid crystal compound L-11

(Preparation of Composition A9 for Forming Positive A Plate)
Similar to the positive A plate forming composition A4, except that 100 parts by mass of the following specified liquid crystal compound L-12 was used in place of the specific liquid crystal compounds L-17 and L-5 in the positive A plate forming composition A4. The composition A9 for forming a positive A plate was prepared by the method of.

Specific liquid crystal compound L-12

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

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.
―――――――――――――――――――――――――――――――――
Composition of composition A11 for forming a positive A plate ――――――――――――――――――――――――――――――――――
-The following specific liquid crystal compound L-14 35.00 parts by mass-The above polymerizable liquid crystal compound X-1 15.00 parts by mass-The following polymerizable liquid crystal compound X-2 35.00 parts by mass-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, Adeca Arckles NCI-831 (manufactured by Adeca) 4.00 parts by mass, the above acid anhydride K-1 4. 00 parts by mass, leveling agent (compound T-1) 0.10 parts by mass, antioxidant BHT (manufactured by Tokyo Kasei Kogyo 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 a positive A plate)
A composition A12 for forming a positive A plate having the following composition was prepared.
―――――――――――――――――――――――――――――――――
Composition of composition A12 for forming a 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, the polymerization initiator S-1 0.50 parts by mass, the acid anhydride K-1 4.00 parts by mass, the polymerizable compound B-1 2.00 parts by mass, the leveling agent (the 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

<Preparation of silicon nitride layer>
The glass EAGLE-XG manufactured by Corning Inc. was used as a glass substrate A (thickness: 1.1 mm). The glass substrate A was set in the substrate holder in the vacuum chamber of the CVD apparatus, and the vacuum chamber was closed. Next, the inside of the vacuum chamber was exhausted, and when the pressure reached 0.1 Pa, the raw material gas was introduced. The flow rate of silane gas was 100 cc / min, the flow rate of ammonia gas was 300 cc / min, and the flow rate of hydrogen gas was 1000 cc / min.
When the pressure in the vacuum chamber stabilizes at 100 Pa, a plasma excitation power of 2000 W is supplied to the electrodes from a high frequency power supply of 13.5 MHz to form a gas barrier film containing silicon nitride as a main component on the surface of the glass substrate. A glass substrate with a silicon nitride layer was used.
The film thickness of the gas barrier film was 50 nm. The film thickness was controlled by an experiment conducted in advance. Further, during the film formation, the substrate temperature was adjusted to 70 ° C. or lower by the temperature adjusting means built in the substrate holder.
800 in the ATR (total reflection type infrared absorption method) mode of FT-IR using an infrared spectroscope (a device in which ATR-PRO410-S is attached to FT-IR6100 manufactured by JASCO Corporation) for the produced gas barrier film. The peak intensity of the Si—N bond located at ~ 900 cm ^-1 and the peak intensity of the NH bond located at ^{3300 to 3400 cm -1 were measured.} From this measurement result, NH / SiN, which is the intensity ratio between the peak intensity of the Si—N bond and the peak intensity of the NH bond, was calculated. As a result, NH / Si—N was 0.11.
Incidentally, 100MyuPET film under the same conditions (moisture permeability: ^3g / m 2 · day) to form a film of silicon nitride layer on the water vapor permeability measuring apparatus (. MOCON, INC manufactured AQUATRAN2 (registered trademark)) with 40 As a result of measuring the moisture permeability in an atmosphere of 90% RH at ° C, it was less than ^{0.9 × 10 -1} g / m ^{2 · day.} That is, the moisture permeation of only the silicon nitride layer 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, a value measured by pasting a black glue (containing carbon black) having a high absorption rate and not reflecting at all on the support side of the surface protective layers H1 and H2 was defined as the surface reflectance.
Instead of the organic EL display device, a reflective substrate was prepared by attaching aluminum foil to a PET film having a thickness of 100 μm using an adhesive sheet N1. Laminates 1 to 29 were attached onto the reflective substrate using the adhesive sheet N2, the reflectance (total reflection) was measured, and the value obtained by subtracting the surface reflectance was taken as the effective reflectance. This effective reflectance serves as an index of the antireflection function of the circularly polarizing plate composed of the polarizer layer and the optically anisotropic layer.
For the total reflectance, a spectrocolorimeter (manufactured by Konica Minolta) was used, and the Y value of the display system in the observation condition 10 ° field of view and the observation light source D65 was taken as the total reflectance.

<Evaluation of wet heat durability>
The positive C plate side of the laminates 1 to 29 is bonded to the silicon nitride layer on the glass substrate with the silicon nitride layer using the adhesive layer N2, and the humidity and heat durability is 85 ° C., 85% relative humidity, and 60 hours. I did a test.
The layer existing between the circularly polarizing plate and the silicon nitride layer was only an adhesive layer, the thickness was 35 μm or less, and the moisture permeability was 100 g / m ² · day or more.
The effective reflectance of the laminated bodies 1 to 29 after the durability evaluation was evaluated in the same manner as described above, and the difference in the effective reflectance before and after the 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 larger than 0.2% and 0.5% or less B: Reflectance difference is larger 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 base material A was used, and the laminate 1 of Production Example 1 was bonded together using the adhesive layer N2. In the same manner as above, the difference in effective reflectance before and after moist heat durability was evaluated according to the above criteria and used as reference data.

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

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

<Manufacturing of organic EL display device>
The FlexPai manufactured by Royole Co., Ltd. mounted on the 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 bonded 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 attached. Made.

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

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

From the visual side, an organic electroluminescence display device including at least a circularly polarizing plate, an adhesive layer, a silicon nitride layer, a pair of electrodes, and an organic electroluminescence display element having an organic light emitting layer sandwiched between them in this order. And
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 by using a composition containing a polymerizable liquid crystal compound.
An organic electroluminescence display device in which the thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer is 35 μm or less.
The organic electroluminescence display device according to claim 1, wherein the polarizer is formed by using a composition containing the dichroic organic dye and a polymerizable liquid crystal compound.
Moisture permeability of the layer is 100 g / m 2 · day or more existing between the silicon nitride layer and the circularly polarizing plate, an organic electroluminescent display device according to claim 1 or 2.
The organic electroluminescence according to any one of claims 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 the following formula (II). Luminescence display device.
* -D 1 -Ar-D 2- * ... (II)
In the formula (II),
D 1 and D 2 are independently single-bonded, -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 -, - It represents NR 1- CR 2 R 3- or -CO-NR 1- .
R 1 , R 2 , R 3 and R 4 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 bonding position with D 1 or D 2.
Q 1 is represents N or CH.
Q 2 is, -S -, - O-, or, -N (R 7) - represents, 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 independently have 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, and a carbon number of carbon atoms. 6 to 20 monovalent aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR 8 , -NR 9 R 10 , or -SR 11 are represented, and R 8 to R 11 are independent of each other. , A hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z 1 and Z 2 may be bonded to 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-, where R 12 is a hydrogen atom or Represents a substituent.
X represents a non-metal atom of Group 14-16 to which a hydrogen atom or a substituent may be bonded.
D 4 and D 5 are independently single-bonded or -CO-, -O-, -S- , -C (= S)-, -CR 1a R 2a-, -CR 3a = CR 4a- , -NR 5a- , or a divalent linking group consisting of two or more of these, and R 1a to R 5a are independently hydrogen atoms, fluorine atoms, or carbon atoms 1 to 4, respectively. Represents an alkyl group.
SP 1 and SP 2 independently have 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-, where Q represents a divalent linking group. 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 an aromatic hydrocarbon ring and an aromatic heterocycle.
Ay has a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or at least one aromatic ring selected from the group consisting of an aromatic hydrocarbon ring and an aromatic heterocycle. , Represents an organic group having 2 to 30 carbon atoms.
The aromatic ring in Ax and Ay may have a substituent, or Ax and Ay may be bonded to form a ring.
Q 3 are a hydrogen atom or an alkyl group having 1 to 6 carbon atoms which may have a substituent.
Re (450), which is an in-plane retardation value measured at a wavelength of 450 nm of the optically anisotropic layer, and Re (550), which is an in-plane retardation value measured at a wavelength of 550 nm of the optically anisotropic layer, Claims 1 to 1, wherein Re (650), which is a value of in-plane retardation measured at a wavelength of 650 nm of the optically anisotropic layer, satisfies the relationship of Re (450) ≤ Re (550) ≤ Re (650). 4. The organic electroluminescence display device according to any one of 4.
The organic electroluminescence display device according to any one of claims 1 to 5, wherein the optically anisotropic layer is a positive A plate.
The organic electroluminescence display device according to any one of claims 1 to 6, wherein the optically anisotropic layer is a λ / 4 plate.
The organic electroluminescence display device according to any one of claims 1 to 7, wherein the angle formed by the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45 ° ± 10 °.
Claims 1 to 8 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 mass of the composition. The organic electroluminescent display device according to any one of the above items.
Has a surface protective layer on the viewing side of the circularly polarizing plate, the moisture permeability of the surface protective layer is is 1g / m 2 · day or more, the organic electroluminescent display according to any one of claims 1 to 9 apparatus.