JP7417623B2 - Optical laminates, polarizing plates, and image display devices - Google Patents

Description

The present invention relates to an optical laminate, a polarizing plate, and an image display device.

Conventionally, polarizing plates having an optical laminate including an optically anisotropic layer and a polarizer have been used for liquid crystal display devices and organic electroluminescence (hereinafter also abbreviated as "EL") for the purpose of optical compensation and antireflection. Used in display devices, etc.
In recent years, optical laminates (e.g., broadband λ/4 wavelength plate) that can respond to light rays of all wavelengths and give the same effect to white light, which is a composite wave in which visible light rays are mixed, have been developed. ) is being developed, and in particular, due to the demand for thinner devices to which polarizing plates are applied, optical laminates included in polarizing plates are also required to be thinner.
In response to such demands, for example, Patent Documents 1 and 2 propose the use of a polymerizable liquid crystal compound with reverse wavelength dispersion as a polymerizable compound used particularly for forming an optically anisotropic layer. .

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

The present inventors studied an optical laminate having an optically anisotropic layer obtained by polymerizing a polymerizable liquid crystal composition containing the compound (polymerizable liquid crystal compound) described in Patent Documents 1 and 2. However, it was confirmed that the durability against ammonia, which is a basic nucleophile, is extremely weak. Hereinafter, durability against ammonia will be simply referred to as "durability."
It is known that ammonia is generated from certain types of members, so it is necessary to improve the durability. In particular, the present inventors have focused on organic EL display devices ranging from a type in which a film on which a touch sensor is formed is attached externally to an organic EL element (out-cell type), to a type in which a touch sensor is formed directly on an organic EL element (out-cell type). It was revealed that when changing to an on-cell type, problems with the durability of the optically anisotropic layer become apparent.

An object of the present invention is to provide an optical laminate with excellent durability.
Another object of the present invention is to provide a polarizing plate and an image display device.

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

(1) having an optically anisotropic layer and a barrier layer in this order,
The optically anisotropic layer is a layer formed using an optically anisotropic layer forming composition containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion,
An optical laminate, wherein the barrier layer is a layer formed from a barrier layer forming composition containing a polyfunctional (meth)acrylamide monomer.
(2) The optical laminate according to (1), wherein the barrier layer is formed from a composition containing a polyfunctional (meth)acrylamide compound having a (meth)acrylic equivalent of 100 or less.
(3) The optical laminate according to (1) or (2), wherein the barrier layer has a thickness of 0.1 to 10 μm.
(4) The optical laminate according to any one of (1) to (3), wherein the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is a compound represented by formula (II) described below.
(5) Re(450), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 450 nm; and Re(550), which is the in-plane retardation value of the optically anisotropic layer measured at a wavelength of 550 nm. ) and Re(650), which is the in-plane retardation value measured at a wavelength of 650 nm, of the optically anisotropic layer satisfy the relationship Re(450)≦Re(550)≦Re(650), ( The optical laminate according to any one of 1) to (4).
(6) The optical laminate according to any one of (1) to (5), further comprising one or more liquid crystal hardened layers between the optically anisotropic layer and the barrier layer.
(7) The optical laminate according to any one of (1) to (6), and a polarizer, wherein the polarizer, the optically anisotropic layer included in the optical laminate, and the optical laminate A polarizing plate comprising, in this order, a barrier layer comprising:
(8) The optically anisotropic layer is a λ/4 wavelength plate, and the angle between the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45°±10°. ) polarizing plate.
(9) An image display device comprising the optical laminate according to any one of (1) to (6) or the polarizing plate according to (7) or (8).
(10) The image display device according to (9), which is a liquid crystal display device.
(11) The image display device according to (9), which is an organic electroluminescence display device.
(12) From the viewing side, it has a polarizing plate and an image display panel in this order,
The polarizing plate is the polarizing plate described in (8),
The polarizing plate is provided with the barrier layer side of the polarizing plate facing the image display panel side,
The image display panel is an organic electroluminescent panel including an organic electroluminescent element,
An image display device including a silicon nitride layer between the organic electroluminescent element and the barrier layer.
(13) The image display device according to (12), wherein a layer existing between the polarizing plate and the silicon nitride layer has a thickness of less than 40 μm.

According to the present invention, an optical laminate having excellent durability can be provided.
Further, according to the present invention, a polarizing plate and an image display device can be provided.

1 is a schematic cross-sectional view showing an example of an embodiment of an optical laminate of the present invention. 1 is a schematic cross-sectional view showing an example of an embodiment of an optical laminate of the present invention. 1 is a schematic cross-sectional view showing an example of an embodiment of an optical laminate of the present invention. FIG. 1 is a schematic cross-sectional view showing an example of an embodiment of a polarizing plate of the present invention. 1 is a schematic cross-sectional view showing an example of an embodiment of an image display device of the present invention.

The present invention will be explained in detail below.
Although the description of the constituent elements described below may be made based on typical embodiments of the present invention, the present invention is not limited to such embodiments.
Note that in this specification, a numerical range expressed using "~" means a range that includes the numerical values written before and after "~" as the lower limit and upper limit.
Moreover, in this specification, each component may use one type of substance corresponding to each component, or may use two or more types in combination. Here, when two or more types of substances are used together for each component, the content of the component refers to the total content of the substances used in combination, unless otherwise specified.
In addition, in this specification, the bonding direction of the divalent group (for example, -O-CO-) expressed is not particularly limited unless the bonding position is specified, and for example, the following formula ( When D ₁ in II) is -CO-O-, if the position bonded to the G ₁ side is *1 and the position bonded to the Ar side is *2, then D ₁ is *1- It may be CO-O-*2 or *1-O-CO-*2.
In addition, in this specification, "(meth)acrylate" is a generic term for "acrylate" and "methacrylate,""(meth)acrylic" is a generic term for "acrylic" and "methacrylic," and "(meth)acrylate" is a generic term for "acrylic" and "methacrylic." ) "acryloyl" is a generic term for "acryloyl" and "methacryloyl".
In addition, in this specification, "orthogonal" and "parallel" regarding angles mean a strict angle range of ±10°, and "same" and "different" regarding angles mean a difference of less than 5°. It can be judged based on whether or not it is.
Furthermore, in this specification, "visible light" refers to 380 to 780 nm.
Further, in this specification, unless there is a special note regarding the measurement wavelength, the measurement wavelength is 550 nm.

In this specification, "slow axis" means the direction in which the refractive index is maximum within the plane. Note that when referring to the slow axis of the optically anisotropic layer, the slow axis of the entire optically anisotropic layer is intended.

In this 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 AxoScan OPMF-1 (manufactured by Optoscience) using light at the measurement wavelength.
Specifically, by inputting the average refractive index ((nx+ny+nz)/3) and film thickness (d (μm)) in AxoScan OPMF-1,
Slow axis direction (°)
Re(λ)=R0(λ)
Rth(λ)=((nx+ny)/2-nz)×d
is calculated.
Note that R0(λ) is displayed as a numerical value calculated by AxoScan OPMF-1, but it means Re(λ).

<Optical laminate>
The optical laminate of the present invention has an optically anisotropic layer and a barrier layer in this order.
Further, the optically anisotropic layer is a layer formed from an optically anisotropic layer-forming composition containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion (hereinafter also simply referred to as "specific liquid crystal compound"). .
Further, the barrier layer is a layer formed from a barrier layer forming composition containing a polyfunctional (meth)acrylamide monomer.

The optical laminate of the present invention having a predetermined optically anisotropic layer and a predetermined barrier layer has excellent durability (ammonia durability).
Although this is not clear in detail, the present inventors speculate as follows.

Polymerizable liquid crystal compounds exhibiting reverse wavelength dispersion are susceptible to decomposition by water and nucleophilic species such as ammonia, and this problem tends to be particularly pronounced when ammonia, which is a basic compound, is present.
Specifically, the present inventors found that when an optically anisotropic layer prepared using a specific liquid crystal compound is exposed to ammonia gas, the structure derived from the specific liquid crystal compound contained in the optically anisotropic layer is decomposed. It is known that this phenomenon occurs rapidly, and that the variation in in-plane retardation value becomes large and that the reverse wavelength dispersion property decreases. The reason for this is presumed to be due to the following phenomenon.
That is, one way to make a specific liquid crystal compound have reverse wavelength dispersion is to give it electron-withdrawing properties. On the other hand, it is presumed that such molecular design increases the positive polarization of the carbon atoms constituting the specific liquid crystal compound, making it more susceptible to attack by nucleophilic species (ammonia).

Therefore, in the present invention, by blocking the infiltration of ammonia into the optically anisotropic layer with a predetermined barrier layer, the decomposition reaction of the structure derived from the specific liquid crystal compound is suppressed, and an improvement effect is obtained. Conceivable.

FIGS. 1, 2, and 3 are schematic cross-sectional views showing an example of the optical laminate of the present invention.
Here, the optical laminate 10 shown in FIG. 1 is an optical laminate having a layered structure including a support 11, an alignment film 12, a positive A plate 13, and a barrier layer 14 in this order.
Further, the optical laminate 20 shown in FIG. 2 is an optical laminate having a layered structure including a support 11, a positive C plate 15, and a barrier layer 14 in this order.
Further, the optical laminate 30 shown in FIG. 3 is an optical laminate having a layer structure including a support 11, an alignment film 12, a positive A plate 13, a vertically aligned normal wavelength dispersion liquid crystal hardening layer 16, and a barrier layer 14 in this order. It is the body.

FIG. 4 shows a schematic sectional view showing an example of an embodiment of a polarizing plate of the invention, and FIG. 5 shows a schematic sectional view showing an example of an embodiment of an image display device of the invention.
Here, the polarizing plate 40 shown in FIG. 4 includes a polarizer protective film 41, a polarizer 42, a support 11, an alignment film 12, a positive A plate 13, a vertically aligned normal wavelength dispersion liquid crystal cured layer 16, and a barrier layer. 14 in this order.
The image display device 50 shown in FIG. 5 also includes a polarizer protective film 41, a polarizer 42, a support 11, an alignment film 12, a positive A plate 13, a vertically aligned normal wavelength dispersion liquid crystal cured layer 16, and a barrier layer. 14, an image display device having a layered structure including a silicon nitride layer 53, a touch sensor 52, and an organic electroluminescent element 51 in this order.

In FIGS. 1, 3, 4, and 5, the positive A plate corresponds to the optically anisotropic layer included in the optical laminate of the present invention.
Moreover, in FIG. 2, the positive C plate corresponds to the optically anisotropic layer included in the optical laminate of the present invention.
Further, in FIGS. 1 to 5, an adhesive layer, an easy-to-adhesion layer, etc., which are not shown, may be included if necessary.
The optical laminate of the present invention includes at least an optically anisotropic layer and a barrier layer.
Each layer and component of the optical laminate of the present invention will be explained in detail below.

(barrier layer)
The barrier layer is formed from a barrier layer forming composition containing a polyfunctional (meth)acrylamide monomer.
The composition for forming a barrier layer may contain a polymerization initiator, other monomers, additives, etc., as necessary.

In general, (meth)acrylamide monomers and polymers formed from them are used for various purposes by taking advantage of their high hydrophilicity.
Although highly hydrophobic resin materials (e.g., olefin polymers, etc.) have been considered suitable as a barrier for highly polar molecules such as ammonia, the present inventors found that polyfunctional (meth)acrylamide It has been found that by forming a barrier layer using a composition for forming a barrier layer containing a monomer, an optical laminate having excellent barrier ability against highly polar molecules such as ammonia can be obtained.

The number of functional groups in the polyfunctional (meth)acrylamide monomer is preferably 2 or more functional, more preferably 3 or more, and still more preferably 3 to 4 functional.

In the present invention, for better durability, the polyfunctional (meth)acrylamide monomer is preferably a (meth)acrylate compound having a (meth)acrylic equivalent of 150 or less; is more preferably a (meth)acrylate compound having a value of 100 or less. The lower limit of the (meth)acrylic equivalent is not particularly limited, but is often 80 or more.
In addition, (meth)acrylic equivalent means the molecular weight per (meth)acryloyl group. That is, the (meth)acrylic equivalent is the molecular weight divided by the number of (meth)acryloyl groups.

Although the molecular weight of the polyfunctional (meth)acrylamide monomer is not particularly limited, it is preferably 1000 or less, more preferably 600 or less, since the effects of the present invention are more excellent. The lower limit is not particularly limited, but is preferably 200 or more.

The polyfunctional (meth)acrylamide monomer can be obtained from, for example, a polyvalent amine compound (eg, diethylenetriamine, triethylenetetramine, etc.), polyethyleneimine, etc., and (meth)acrylic acid. It can also be obtained as (meth)acrylamide obtained from various compounds containing a plurality of primary or secondary amino groups and (meth)acrylic acid.
Specific examples of polyfunctional (meth)acrylamide monomers include N,N',N''-triacryloyldiethylenetriamine, N,N',N''-triacryloyl-3,3'-diaminodipropylamine, N,N' ,N″,N′″-tetraacryloyltriethylenetetramine, N,N′,N″,N′″,N″″-pentaacryloyltetraethylenepentamine, N,N′-{[(2-acrylamide-2 -[(3-acrylamidopropoxy)methyl]propane-1,3,-diyl)bis(oxy)]bis(propane-1,3-diyl)}diacrylamide, N,N'-diacryloyl-4,7, 10-trioxa-1,13-tridecanediamine is mentioned. These may be used alone or in combination.

The content of the polyfunctional (meth)acrylamide monomer in the composition for forming a barrier layer is not particularly limited, but is preferably 50% by mass or more, and 75% by mass or more based on the solid content in the composition for forming a barrier layer. The content is more preferably 90% by mass or more. The upper limit of the content of the polyfunctional (meth)acrylamide monomer relative to the solid content in the composition is not particularly limited, but may be 100% by mass.

Other monomers may be added to the composition for forming a barrier layer, if necessary. Other monomers may be copolymerizable with the above-mentioned polyfunctional (meth)acrylamide monomer. Other copolymerizable monomers include known (meth)acrylate compounds and monofunctional (meth)acrylamide monomers.

The composition for forming a barrier layer may contain a polymerization initiator. In particular, when hardening the barrier layer with light or heat, it is preferable to add a photopolymerization initiator or a thermal polymerization initiator. It is preferable to use a radical polymerization initiator as the polymerization initiator because the reaction between the monomers can proceed sufficiently and desired durability can be imparted. Known radical polymerization initiators can be used. The content of the polymerization initiator in the composition for forming a barrier layer is not particularly limited, but is preferably 0.1 to 15% by mass, and preferably 0.3 to 5% by mass, based on the solid content in the composition for forming a barrier layer. 0% by mass is more preferred.

The composition for forming a barrier layer may contain a solvent.
Solvents include water and organic solvents. Examples of the organic solvent include various solvents exemplified as organic solvents that may be included in the polymerizable liquid crystal composition described below. The solvents may be used alone or in combination.

The composition for forming a barrier layer may contain components other than those mentioned above.
Other ingredients include surfactants (including so-called leveling agents). By adding a surfactant, the occurrence of surface defects such as unevenness and repellency is suppressed, and a high-quality optical laminate with excellent appearance can be obtained.

The method for forming a barrier layer using the composition for forming a barrier layer is not particularly limited, but as a preferred embodiment, the composition for forming a barrier layer is applied onto a predetermined base material (for example, an optically anisotropic layer described below). A method of forming a coating film and subjecting the coating film to a curing treatment can be mentioned.

The above coating can be performed by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, and a die coating method).

Known methods can be used for curing the coating film, and energy ray irradiation, light irradiation treatment, or heat treatment is preferred, and light irradiation treatment is particularly preferred.
It is preferable to use ultraviolet light during the light irradiation treatment.
The conditions for the light irradiation treatment are not particularly limited, but are preferably from 10 mJ/cm ² to 50 J/cm ² , more preferably from 20 mJ/cm ² to 5 J/cm ² .
Furthermore, in order to promote the polymerization reaction, light irradiation treatment may be performed under heating conditions.

The thickness of the barrier layer is preferably 0.1 μm or more, more preferably 0.2 μm or more. The upper limit is not particularly limited, but from the viewpoint of ensuring flexibility of the optical laminate, it is preferably 10 μm or less, more preferably 8 μm or less.

In addition, as another preferred embodiment, the composition for forming a barrier layer is applied onto a temporary support for transfer to form a coating film, the coating film is subjected to a curing treatment, and then the transfer target ( For example, a method of transferring a barrier layer formed on an optically anisotropic layer (described later) and removing a temporary support for transfer, a method of forming a barrier layer on a predetermined base material (support or temporary support for transfer), Examples include a method in which a composition is applied to form a coating film, the coating film is subjected to a curing treatment, and then an optically anisotropic layer-forming composition described below is applied and cured.

(Optically anisotropic layer)
The optically anisotropic layer is a layer formed using an optically anisotropic layer forming composition (hereinafter also referred to as "polymerizable liquid crystal composition") containing a specific liquid crystal compound.
The specific liquid crystal compound is a polymerizable liquid crystal compound and is a compound that exhibits "reverse wavelength dispersion."
Here, in this specification, a compound exhibiting "reverse wavelength dispersion" refers to an in-plane retardation (Re) value at a specific wavelength (visible light range) of an optically anisotropic layer prepared using the compound. When measured, the Re value is the same or becomes higher as the measurement wavelength becomes larger.

One of the preferred embodiments of the specific liquid crystal compound is a compound represented by the following formula (II).
L ₁ -G ₁ -D ₁ -Ar-D ₂ -G ₂ -L ₂ ...(II)
In the above formula (II), D ₁ and D ₂ each independently represent a single bond, -O-, -CO-, -CO-O-, -C(=S)O-, -CR ¹ R ² - , -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O- CO-CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -O-CO-, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O- It represents CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, or -CO-NR ¹ -.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms. When a plurality of each of R ¹ , R ² , R ³ and R ⁴ exists, each of 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 are each independently a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, a group formed by connecting a plurality of the above alicyclic hydrocarbon groups, an aromatic hydrocarbon group, or , represents a group formed by connecting a plurality of the above aromatic hydrocarbon groups, and one or more of -CH ₂ - constituting the above alicyclic hydrocarbon group is substituted with -O-, -S- or -NH- may have been done.
The group formed by connecting a plurality of alicyclic hydrocarbon groups mentioned above means a group formed by connecting divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms with each other through a single bond. Moreover, the group formed by connecting a plurality of aromatic hydrocarbon groups mentioned above means a group formed by connecting aromatic hydrocarbon groups to each other through a single bond.
L ₁ and L ₂ each independently represent a monovalent organic group, and at least one of L ₁ and L ₂ represents a monovalent group having a polymerizable group.
Ar represents any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7). Note that in the following formulas (Ar-1) to (Ar-7), * represents the bonding position with D ₁ or D ₂ .

In the above formula (Ar-1), Q ¹ represents N or CH, Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ is a hydrogen atom or represents an alkyl group having 1 to 6 carbon atoms, and Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms, which may have a substituent, or an aromatic heterocyclic group having 3 to 12 carbon atoms; represent.
Examples of the alkyl group having 1 to 6 carbon atoms represented by R ⁷ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n-pentyl group. and n-hexyl group.
Examples of the aromatic hydrocarbon group having 6 to 12 carbon atoms represented by Y ¹ include a phenyl group, a 2,6-diethylphenyl group, and an aryl group such as a naphthyl group.
Examples of the aromatic heterocyclic group having 3 to 12 carbon atoms represented by Y ¹ include heteroaryl groups such as thienyl group, thiazolyl group, furyl group, and pyridyl group.
Further, examples of the substituent that Y ¹ may have include an alkyl group, an alkoxy group, and a halogen atom.
As the alkyl group, an alkyl group having 1 to 18 carbon atoms is preferable, 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) t-butyl group, and cyclohexyl group), more preferably an alkyl group having 1 to 4 carbon atoms, and particularly preferably a methyl group or an ethyl group. 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. An alkoxy group having 1 to 4 carbon atoms is more preferred, and a methoxy group or an ethoxy group is particularly preferred.
Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, of which a fluorine atom or a chlorine atom is preferred.

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

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

In the above formula (Ar-2), X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.
In addition ^, the nonmetallic atom of Groups 14 to 16 ^represented by represents. ], a carbon atom to which a hydrogen atom or a substituent is bonded [=C-(R ^C1 ) ₂ , R ^C1 represents a hydrogen atom or a substituent. ].
Specific examples of the substituent include an alkyl group, an alkoxy group, an alkyl-substituted alkoxy group, a cyclic alkyl group, an aryl group (e.g., a phenyl group, a naphthyl group, etc.), a cyano group, an amino group, a nitro group, and an alkyl group. Examples include carbonyl group, sulfo group, and hydroxyl group.

In addition, in the above formula (Ar-3), D ⁴ and D ⁵ are each independently a single bond, -CO-, -O-, -S-, -C(=S)-, -CR ^1a R ^2a -, -CR ^3a =CR ^4a -, -NR ^5a -, or a divalent linking group consisting of a combination of two or more thereof, and R ^1a to R ^5a each independently represent a hydrogen atom, Represents a fluorine atom or an alkyl group having 1 to 4 carbon atoms.
Here, examples of the divalent linking group include -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 each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms.

In the above formula (Ar-3), SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms. One or more of -CH ₂ - constituting a linear or branched alkylene group is substituted 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 methylene group, ethylene group, propylene group, butylene group, pentylene group, hexylene group, methylhexylene group, and A butylene group is preferred.

Furthermore, 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 preferably linear. The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 20, even more preferably 1 to 10. Further, the aryl group may be monocyclic or polycyclic, but monocyclic is preferable. The number of carbon atoms in the aryl group is preferably 6 to 25, more preferably 6 to 10. Further, the heteroaryl group may be monocyclic or polycyclic. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3. The heteroatom constituting the heteroaryl group is preferably a nitrogen atom, a sulfur atom, or an oxygen atom. The heteroaryl group preferably has 6 to 18 carbon atoms, more preferably 6 to 12 carbon atoms. Furthermore, the alkyl group, aryl group, and heteroaryl group may be unsubstituted or may have a substituent. Examples of the substituent include the same substituents that Y ¹ in the above formula (Ar-1) may have.

Furthermore, 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.
Furthermore, in the above formulas (Ar-4) to (Ar-7), Ay represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms which may have a substituent, or an aromatic hydrocarbon ring and an aromatic Represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of heterocycles.
Here, the aromatic rings in Ax and Ay may have a substituent, or Ax and Ay may be bonded to each other 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 [0095] of Patent Document 1 (International Publication No. 2014/010325).
Further, examples of the alkyl group having 1 to 6 carbon atoms represented by Q ³ include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, tert-butyl group, n -pentyl group and n-hexyl group, and examples of the substituent include the same substituents as the substituent that Y ¹ in the above formula (Ar-1) may have.

Regarding the definition and preferred range of each substituent of the polymerizable liquid crystal compound represented by the above formula (II), D ¹ , D ² , G ¹ , G regarding compound (A) described in JP-A No. 2012-021068 ² , L ¹ , L ² , R ⁴ , R ⁵ , R ⁶ , R ⁷ , X ¹ , Y ¹ , Q ¹ , Q ² , the descriptions are respectively D ₁ , D ₂ , G ₁ , G ₂ , L ₁ , Reference can be made to L ₂ , R ¹ , R ² , R ³ , R ⁴ , Q ¹ , Y ¹ , Z ¹ , and Z ² and is represented by the general formula (I) described in JP-A No. 2008-107767. ^The description of ^{A 1} _, A ₂ , and , Ay, and Q ¹ can be referred to for Ax, Ay, and Q ³ , respectively. Regarding Z ³ , reference can be made to the description of Q ¹ regarding compound (A) described in JP-A-2012-21068.

In particular, the organic groups represented by L ₁ and L ₂ are preferably groups represented by -D ₃ -G ₃ -Sp-P ₃ , respectively.
_D3 has the same meaning as _D1 .
_G3 is a single bond, a divalent aromatic ring group or heterocyclic group having 6 to 12 carbon atoms, a group formed by connecting a plurality of the above aromatic ring groups or heterocyclic groups, or a divalent aromatic ring group having 5 to 8 carbon atoms. Represents an alicyclic hydrocarbon group or a group formed by connecting a plurality of the above alicyclic hydrocarbon groups, and the methylene group contained in the above alicyclic hydrocarbon group is -O-, -S- or - It may be substituted with NR ⁷ -, where R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
The group formed by connecting a plurality of the above aromatic ring groups or heterocyclic groups means a group formed by connecting divalent aromatic ring groups or heterocyclic groups having 6 to 12 carbon atoms with each other through a single bond. Furthermore, the group formed by connecting a plurality of alicyclic hydrocarbon groups mentioned above means a group formed by connecting divalent alicyclic hydrocarbon groups having 5 to 8 carbon atoms with each other through a single bond.
As _G3 , a group in which two cyclohexane rings are bonded via a single bond is also preferable.
Sp is a single bond, -(CH ₂ ) _n -, -(CH ₂ ) _n -O-, -(CH ₂ -O-) _n -, -(CH ₂ CH ₂ -O-) _m , -O- (CH ₂ ) _n -, -O-(CH ₂ ) _n -O-, -O-(CH ₂ -O-) _n -, -O-(CH ₂ CH ₂ -O-) _m , -C(= O)-O-(CH ₂ ) _n -, -C(=O)-O-(CH ₂ ) _n -O-, -C(=O)-O-(CH ₂ -O-) _n -, - C(=O)-O-(CH ₂ CH ₂ -O-) _m , -C(=O)-N(R ⁸ )-(CH ₂ ) _n -, -C(=O)-N(R ⁸ )-(CH ₂ ) _n -O-, -C(=O)-N(R ⁸ )-(CH ₂ -O-) _n -, -C(=O)-N(R ⁸ )-(CH ₂ A spacer represented by CH ₂ -O-) _m or -(CH ₂ ) _n -O-(C=O)-(CH ₂ ) _n -C(=O)-O-(CH ₂ ) _{n -} represents a group. 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. Furthermore, the hydrogen atom of -CH ₂ - in each of the above groups may be substituted with a methyl group.
_P3 represents a polymerizable group.

Although the polymerizable group is not particularly limited, a polymerizable group capable of radical polymerization or cationic polymerization is 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 acryloyl groups generally have a high polymerization rate, and acryloyl groups are preferred from the viewpoint of improving productivity, but methacryloyl groups can also be used as polymerizable groups for highly birefringent liquid crystals.
Examples of the cationic polymerizable group include known cationic polymerizable groups, such as an alicyclic ether group, a cyclic acetal group, a cyclic lactone group, a cyclic thioether group, a spiro-orthoester group, and a vinyloxy group. Among these, an alicyclic ether group or a vinyloxy group is preferred, and an epoxy group, an oxetanyl group, or a vinyloxy group is more preferred.
Examples of particularly preferred polymerizable groups include the following.

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

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

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

II-2-8

II-2-9

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

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

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

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

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 compounds may be used alone or in combination of two or more.
The solid content refers to components other than the solvent in the polymerizable liquid crystal composition, and is calculated as the solid content even if the composition 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 liquid crystal orientation.
Note that the polymerizable rod-like compound may or may not have liquid crystallinity.

From the viewpoint of compatibility with the above-mentioned specific liquid crystal compound, the above-mentioned polymerizable rod-like compound is a compound having a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group (hereinafter referred to as "alkylcyclohexane ring"). (also abbreviated as “containing compound”) is preferable.
Here, "a cyclohexane ring in which one hydrogen atom is substituted with a linear alkyl group" means, for example, as shown in the following formula (2), when it has two cyclohexane rings, the terminal side of the molecule refers to a cyclohexane ring in which one hydrogen atom of the cyclohexane ring 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), and among them, from the viewpoint of imparting wet heat durability to the optically anisotropic layer, a (meth)acryloyl group is used. It is preferable that it is a compound represented by the following formula (3).

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

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

When the polymerizable liquid crystal composition contains the polymerizable rod-like compound, the content of the polymerizable rod-like compound is preferably 1 to 30% by mass based on the total mass of the specific liquid crystal compound and the 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 "other polymerizable liquid crystal compound") other than the above-mentioned specific liquid crystal compound and polymerizable rod-like compound.
Here, the polymerizable group that the other polymerizable liquid crystal compound has is not particularly limited, and examples thereof include a (meth)acryloyl group, a vinyl group, a styryl group, and an allyl group. Among these, a (meth)acryloyl group is preferred.

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

Examples of such other polymerizable liquid crystal compounds include compounds represented by formula (M1) and compounds represented by formula (M2) described in paragraphs 0030 to 0033 of JP-A No. 2014-077068, Further, examples include compounds represented by formula (M3), and more specifically, specific examples described in paragraphs 0046 to 0055 of the same publication.
The other polymerizable liquid crystal compounds may be used alone or in combination of two or more.

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

The polymerizable liquid crystal composition preferably contains a non-liquid crystalline polyfunctional polymerizable compound from the viewpoint of further improving the durability of the formed polarizing plate having an optically anisotropic layer.
This is because the increased density of crosslinking points suppresses the movement of the compound (estimated to be a liquid crystal decomposition product) that becomes a catalyst for the hydrolysis reaction, resulting in a slowing down of the hydrolysis reaction, during which time water flows to the edge of the hydrolysis reaction. It is estimated that this is due to the progress of diffusion of

The non-liquid crystalline polyfunctional polymerizable compound is preferably a compound with a low acrylic equivalent from the viewpoint of the orientation of the above-mentioned specific liquid crystal compound.
Specifically, a compound having a (meth)acrylic equivalent of 120 or less is preferred, a compound having a (meth)acrylic equivalent of 100 or less is more preferred, and a compound having a (meth)acrylic equivalent of 90 or less is even more preferred.

Examples of non-liquid crystalline polyfunctional polymerizable compounds include esters of polyhydric alcohols and (meth)acrylic acid, vinylbenzene and derivatives thereof, vinyl sulfone, acrylamide, and methacrylamide.
Here, specific examples of the ester of polyhydric alcohol and (meth)acrylic acid include ethylene glycol di(meth)acrylate, 1,4-cyclohexane diacrylate, pentaerythritol tetra(meth)acrylate, and pentaerythritol tetra(meth)acrylate. Erythritol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate Examples include acrylate, 1,2,3-cyclohexanetetramethacrylate, polyurethane polyacrylate, and polyester polyacrylate.
Further, specific examples of vinylbenzene and derivatives thereof include 1,4-divinylbenzene, 4-vinylbenzoic acid-2-acryloylethyl ester, and 1,4-divinylcyclohexanone.
Further, specific examples of the vinyl sulfone include divinyl sulfone.
Further, specific examples of acrylamide include methylene bisacrylamide and the like.

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

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

From the viewpoint of improving the durability of the optically anisotropic layer, the polymerization initiator is preferably an oxime type 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, with a chlorine atom being preferred.
In the above formula (III), the divalent aromatic group represented by Ar ³ includes, for example, an aromatic hydrocarbon ring such as a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthroline ring; a furan ring, Examples include divalent groups 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), the divalent organic group having 1 to 12 carbon atoms represented by L ⁶ includes, for example, a linear or branched alkylene group having 1 to 12 carbon atoms. Examples include methylene, ethylene, and propylene groups.
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 is preferable, such as a group represented by the following formula (3a) and a group represented by the following formula (3b). .

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

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, and 1 to 10 parts by mass, based on 100 parts by mass of the specific liquid crystal compound contained in the polymerizable liquid crystal composition. ~5 parts by mass is more preferred.

The polymerizable liquid crystal composition may contain an alignment control agent, if necessary.
Examples of the alignment control agent include low-molecular alignment control agents and polymeric alignment control agents. Examples of low-molecular alignment control agents include paragraphs 0009 to 0083 of JP-A No. 2002-020363, paragraphs 0111 to 0120 of JP-A No. 2006-106662, and paragraphs 0021 to 0021 of JP-A No. 2012-211306. 0029, the contents of which are incorporated herein. In addition, as for the polymer orientation control agent, for example, the descriptions in paragraphs 0021 to 0057 of JP-A No. 2004-198511 and paragraphs 0121 to 0167 of JP-A No. 2006-106662 can be referred to, the contents of which are incorporated herein by reference. Incorporated into the specification.
The amount of the alignment control agent used is preferably 0.01 to 10% by mass, more preferably 0.05 to 5% by mass, based on the total solid content of the polymerizable liquid crystal composition. By using an alignment control agent, for example, a homogeneous alignment state in which the alignment is 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 in forming an optically anisotropic layer.
Examples of organic solvents include ketones (e.g., acetone, 2-butanone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, and cyclopentanone), ethers (e.g., dioxane, and tetrahydrofuran), and aliphatic hydrocarbons. (e.g., hexane), alicyclic hydrocarbons (e.g., cyclohexane), aromatic hydrocarbons (e.g., toluene, xylene, and trimethylbenzene), halogenated carbons (e.g., dichloromethane, dichloroethane, dichlorobenzene, and chlorotoluene), esters (e.g., methyl acetate, ethyl acetate, and butyl acetate), water, alcohols (e.g., ethanol, isopropanol, butanol, and cyclohexanol), cellosolves (e.g., methyl cellosolve, and ethyl cellosolve), cellosolve acetates, sulfoxides (e.g., dimethyl sulfoxide), amides (e.g., dimethylformamide, and dimethylacetamide), and these may be used alone or in combination. may be used together.

The polymerizable liquid crystal composition may contain components other than the above-mentioned components, such as a liquid crystal compound other than the above-mentioned specific liquid crystal compound, a surfactant, a tilt angle control agent, an alignment aid, a plasticizer, and Examples include crosslinking agents.

The optically anisotropic layer is formed using the polymerizable liquid crystal composition described above.
The method for producing the optically anisotropic layer is not particularly limited, but for example, it can be formed on a predetermined substrate (for example, a polarizer described below, a support described below or an alignment layer provided thereon, or a barrier layer described above). , a method in which a polymerizable liquid crystal composition is applied to form a coating film, the coating film is subjected to alignment treatment to bring the specific liquid crystal compound into a predetermined alignment state, and then a curing treatment is performed on the coating film. It will be done.

The above coating can be performed by a known method (for example, a wire bar coating method, an extrusion coating method, a direct gravure coating method, a reverse gravure coating method, a die coating method, etc.).

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

The curing treatment (irradiation with active energy rays (light irradiation treatment) and/or heat treatment) on the coating film can also be called a fixing treatment for fixing the orientation of the specific liquid crystal compound.
Among these, it is preferable to carry out light irradiation treatment. In polymerization by light irradiation, it is preferable to use ultraviolet rays.
The irradiation amount is preferably 10 mJ/cm ² to 50 J/cm ² , more preferably 20 mJ/cm ² to 5 J/cm ² , even more preferably 30 mJ/cm ² to 3 J/cm ² , particularly 50 to 1000 mJ/cm ² preferable.
Furthermore, in order to promote the polymerization reaction, light irradiation treatment may be performed under heating conditions.
Note that, as described above, the optically anisotropic layer can be formed on the support described below, on the polarizer described below, and on the barrier layer described above.

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) because the display quality in the viewing angle direction of an image display device having an optical laminate is improved.
Re(450)≦Re(550)≦Re(650)...(IV)
Here, in the above formula (IV), Re (450) represents the in-plane retardation of the optically anisotropic film at a wavelength of 450 nm, and Re (550) represents the in-plane retardation of the optically anisotropic film at a wavelength of 550 nm. Re(650) represents the in-plane retardation of the optically anisotropic film at a wavelength of 650 nm.

Preferably, the optically anisotropic layer is a positive A plate.
In addition, in this specification, a positive A plate is defined as follows. A positive A plate (positive A plate) has a refractive index of nx in the slow axis direction (the direction in which the in-plane refractive index is maximum) in the film plane, and is perpendicular to the in-plane slow axis in the plane. When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relationship of formula (A1) is satisfied. Note that the positive A plate has a positive Rth value.
Formula (A1) nx>ny≒nz
Note that the above "≒" includes not only the case where both are completely the same, but also the case where both are substantially the same. "Substantially the same" means, for example, that "ny≒nz" also applies when (ny-nz) x 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 aligning a rod-shaped polymerizable liquid crystal compound. For details of the method for producing the positive A plate, for example, the descriptions in JP-A No. 2008-225281 and JP-A No. 2008-026730 can be referred to.

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

Further, the optically anisotropic layer may be a positive C plate.
In addition, in this specification, a positive C plate is defined as follows. A positive C plate (positive C plate) has a refractive index of nx in the slow axis direction (the direction in which the in-plane refractive index is maximum) in the film plane, and is orthogonal to the in-plane slow axis in the plane. When the refractive index in the direction is ny and the refractive index in the thickness direction is nz, the relationship of formula (A2) is satisfied. Note that the positive C plate has a negative Rth value.
Formula (A2) nx≒ny<nz
Note that the above "≒" includes not only the case where both are completely the same, but also the case where both are substantially the same. "Substantially the same" means, for example, that "nx≒ny" also applies when (nx-ny) x 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 aligning a rod-shaped polymerizable liquid crystal compound. For details of the method for producing the positive C plate, for example, the descriptions in JP 2017-187732, JP 2016-53709, and JP 2015-200861 can be referred to.

(Liquid crystal hardening layer)
The optical laminate of the present invention further includes one or more liquid crystals between the optically anisotropic layer and the barrier layer, since the display quality in the viewing angle direction of an image display device having the optical laminate is improved. It is preferable to have a hardened layer.
As the liquid crystal hardening layer, for example, when the optically anisotropic layer is a positive A plate, the above-mentioned positive C plate is preferably mentioned, and when the optically anisotropic layer is a positive C plate, the above-mentioned positive C plate is preferably mentioned. A positive A plate is preferably mentioned.

(Support)
The optical laminate of the present invention may have a support for supporting the optical laminate.
The support is preferably transparent, and specifically preferably has a light transmittance of 80% or more.
The support may have optical anisotropy or may be optically isotropic.

As the support, a polymer film is preferred from the viewpoint of making the optical laminate flexible.
Materials for the polymer film include cellulose polymers; (meth)acrylic polymers having acrylic acid ester polymers such as polymethyl methacrylate and lactone ring-containing polymers; thermoplastic norbornene polymers; polycarbonate polymers; polyethylene terephthalate, and , polyester polymers such as polyethylene naphthalate; styrene polymers such as polystyrene and acrylonitrile-styrene copolymer (AS resin); polyolefin polymers such as polyethylene, polypropylene, and ethylene-propylene copolymer; Vinyl polymers; amide polymers such as nylon and aromatic polyamides; imide polymers; sulfone polymers; polyether sulfone polymers; polyether ether ketone polymers; polyphenylene sulfide polymers; vinylidene chloride polymers; vinyl alcohol Examples include vinyl butyral-based polymers; arylate-based polymers; polyoxymethylene-based polymers; epoxy-based polymers; and polymers obtained by mixing these polymers.
Further, the polarizer described later 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, from the viewpoint of imparting self-reliance and flexibility to the optical laminate.
The support may be adjacent to the optically anisotropic layer (or adjacent via an alignment film, which will be described later), or may be adjacent to the barrier layer.

(alignment film)
When the optical laminate of the present invention has any of the above-mentioned supports on the surface of the optically anisotropic layer opposite to the barrier layer, the optical laminate has an alignment film between the support and the optically anisotropic layer. is preferable. Note that the above-mentioned support may also serve as an alignment film.

In order to form a positive A plate, which is one embodiment of an optically anisotropic layer, a technique is used to align the molecules of a specific liquid crystal compound in a desired state. A common technique is to orient a compound in a desired direction.
As the alignment film, a rubbed film of a layer containing an organic compound such as a polymer, an obliquely evaporated film of an inorganic compound, a film having microgrooves, or ω-tricosanoic acid, dioctadecylmethylammonium chloride, or methyl stearate. Examples include films in which LB (Langmuir-Blodgett) films are accumulated using the Langmuir-Blodgett method using organic compounds such as LB.
Further, examples of the alignment film include a photo-alignment film that exhibits an alignment function when irradiated with light.

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

As the alignment film, it is also preferable to use a so-called photo-alignment film (photo-alignment layer), which is an alignment layer obtained by irradiating a photo-alignable material with polarized or non-polarized light.
It is preferable to impart an alignment regulating force to the photo-alignment film by a step of irradiating polarized light from a vertical or oblique direction, or a step of irradiating non-polarized light from an oblique direction.
By using a photo-alignment film, it is possible to horizontally align a specific liquid crystal compound with excellent symmetry. Therefore, a positive A plate formed using a photo-alignment film is particularly useful for optical compensation in liquid crystal display devices that do not require a pre-tilt angle of the driving liquid crystal, such as IPS (In-Place-Switching) mode liquid crystal display devices. It is useful for a λ/4 wavelength plate used in a circularly polarizing plate that requires uniform circular polarization conversion no matter what direction it is viewed from.

Examples of the photo-alignment material used in the photo-alignment film include JP-A Nos. 2006-285197, 2007-076839, 2007-138138, 2007-094071, and 2007- Azo compounds described in JP 121721, JP 2007-140465, JP 2007-156439, JP 2007-133184, JP 2009-109831, JP 3883848, JP 4151746 , aromatic ester compounds described in JP-A No. 2002-229039, maleimide and/or alkenyl-substituted nadimide compounds having photo-alignable units described in JP-A Nos. 2002-265541 and 2002-317013, patents No. 4205195, photocrosslinkable silane derivatives described in Japanese Patent No. 4205198, photocrosslinkable polyimides, polyamides, or esters described in Japanese Patent No. 2003-520878, Japanese Patent No. 2004-529220, and Japanese Patent No. 4162850, Described in JP 9-118717, JP 10-506420, JP 2003-505561, WO 2010/150748, JP 2013-177561, JP 2014-12823 photodimerizable compounds, in particular cinnamate compounds, chalcone compounds and coumarin compounds.
Particularly preferred examples include azo compounds, photocrosslinkable polyimides, polyamides, polyesters, cinnamate compounds, and chalcone compounds.

The thickness of the photo-alignment film is not particularly limited, but it is preferably 0.01 to 10 μm, from the viewpoint of alleviating surface irregularities that may exist on the support and forming an optically anisotropic layer with a uniform thickness. The thickness is more preferably 0.01 to 1 μm, and even more preferably 0.01 to 0.5 μm.

(Other layers)
The optical laminate of the present invention may include, as other layers, an adhesive layer, an easy-to-adhesion layer, and a layer having optical anisotropy that is different from the above-mentioned optically anisotropic layer. For example, the layer having optical anisotropy can be composed of any material such as a polymer film, a liquid crystal hardened layer, an inorganic layer, etc., but from the viewpoint of making the optical laminate thinner and achieving both flexibility and toughness, the liquid crystal hardened layer It is preferable that
For such a liquid crystal hardening layer, a liquid crystal composition containing a polymerizable rod-like liquid crystal compound or a discotic liquid crystal compound having normal dispersion or flat dispersion is oriented and fixed in the same manner as the optically anisotropic layer described above. things can be applied. The alignment state, optical properties, strength, etc. of these liquid crystal cured layers can be appropriately designed so that desired properties can be imparted to the optical laminate of the present invention. One preferred embodiment is an optical laminate (for example, the optical laminate shown in FIG. 3) including an optically anisotropic layer/vertically aligned normal wavelength dispersion liquid crystal cured layer/barrier layer.

<Polarizing plate>
The optical laminate of the present invention can constitute a highly functional polarizing plate by laminating it with a polarizer.
The polarizing plate of the present invention has the above-described optical laminate of the present invention and a polarizer, and the polarizer, the optically anisotropic layer of the optical laminate, and the barrier layer of the optical laminate are arranged in this order. Included is a polarizing plate.

(polarizer)
The polarizer is a so-called linear polarizer that has the function of converting light into specific linearly polarized light. The polarizer is not particularly limited, but an absorption type polarizer can be used.
The type of polarizer is not particularly limited, and examples include polarizers whose main component is commonly used polyvinyl alcohol resin. For example, it is produced by adsorbing iodine or a dichroic dye to a polyvinyl alcohol resin and stretching the resin. Containing polyvinyl alcohol resin as a main component means that the content of polyvinyl alcohol resin is 50% by mass or more based on the total mass of the polarizer.
The polyvinyl alcohol resin is a resin containing the repeating unit -CH ₂ -CHOH-, and includes, for example, polyvinyl alcohol and ethylene-vinyl alcohol copolymer.

In addition, liquid crystal compounds and dichroic azo dyes as described in WO 2017/195833 and JP 2017-83843 (for example, in the light-absorbing anisotropic film described in WO 2017/195833) A coated polarizer produced by coating using a dichroic azo dye used is also preferred. In addition, a polyene polarizer, a reflective polarizer, a wire grid polarizer, etc. may be used.

The thickness of the polarizer is not particularly limited, but is preferably 5 to 20 μm, more preferably 3 to 15 μm, and even more preferably 2 to 13 μm. By reducing the thickness of the polarizer, a lighter and thinner display device can be obtained when mounted on a display device. Furthermore, if the display device is flexible or has a curved surface, a thin polarizing plate can be more preferably applied.

In the polarizing plate, the relationship between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is not particularly limited and can be appropriately set depending on the desired function.
When applying the polarizing plate to antireflection applications, the optically anisotropic layer is a λ/4 wavelength plate, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45 ± 10°. (35-55°) is preferred.
In addition, when the polarizing plate is applied to optical compensation for oblique viewing angles of IPS (In-Plane-Switching) liquid crystal, the optically anisotropic layer is a multilayer of a positive A plate and a positive C plate of a λ/4 wavelength plate. structure, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is in the range of 0 ± 10° (-10 to 10°) or in the range of 90 ± 10° (80 to 100°). °) is preferred.

(Polarizer protective film)
The polarizing plate may have a polarizer protective film on the surface of the polarizer.
The polarizer protective film may be disposed only on one surface of the polarizer (on the surface opposite to the optically anisotropic layer side), or may be disposed on both surfaces of the polarizer. The support that constitutes the optical laminate may also serve as a polarizing plate protective film.
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.
As the hard coat layer, a known layer can be used, and for example, a layer obtained by polymerizing and curing a known polyfunctional monomer may be used. Further, a coating having antiglare, antifouling, and antireflection properties may be used.
Further, as the transparent support, a known transparent support can be used. For example, the material for forming the transparent support is a cellulose-based polymer (hereinafter referred to as "cellulose acylate") typified by triacetyl cellulose. ), thermoplastic norbornene resins (Zeonex and Zeonor manufactured by Nippon Zeon Co., Ltd., Arton manufactured by JSR Corporation), acrylic resins, polyester resins, and polystyrene resins.
The thickness of the polarizer protective film is not particularly limited, but from the viewpoint of reducing the thickness of the polarizing plate, it is preferably 40 μm or less, more preferably 25 μm or less, even more preferably 10 μm or less, and particularly preferably 5 μm or less. Although the lower limit is not particularly limited, it is often 1 μm or more.

In order to ensure adhesion between each layer, an adhesive layer or adhesive layer may be placed between each layer. Furthermore, a transparent support may be placed between each layer.
The polarizing plate has another optical laminate of the present invention or another optically anisotropic layer other than the optical laminate of the present invention on the side opposite to the side having the optical laminate of the present invention. You can leave it there.

<Image display device>
The above polarizing plate can be preferably used in image display devices, such as liquid crystal display devices, organic electroluminescent display devices, micro LED display devices, electronic paper, and the like.
The image display device of the present invention is an image display device having the above-described optical laminate of the present invention or the polarizing plate of the present invention, and may be a liquid crystal display device or an organic electroluminescence display device, for example. Good too.

(Liquid crystal display device)
The liquid crystal display device of the present invention is an example of an image display device, and includes the polarizing plate of the present invention described above and a liquid crystal cell.
In addition, in the present invention, it is preferable to use the polarizer in the polarizing plate of the present invention as the front side polarizer among the polarizers provided on both sides of the liquid crystal cell. It is also more preferable to use the polarizer in the polarizing plate of the present invention.

In a preferred embodiment, the optical laminate of the present invention included in the polarizing plate can be placed closer to the liquid crystal cell than the polarizer. In this case, the barrier layer included in the optical laminate can be placed closer to the liquid crystal cell than the optically anisotropic layer described above. In this arrangement, deterioration sources such as trace amounts of ammonia molecules that may be generated from the liquid crystal cell and its constituent members, touch sensors, adhesives, etc. that may be provided between the liquid crystal cell and the optically anisotropic layer are removed from the optically anisotropic layer. It is possible to prevent the water from penetrating and impart desirable durability. In this embodiment, the optically anisotropic layer functions as an optical compensation function.

The liquid crystal cell used in the liquid crystal display device is preferably in VA (Vertical Alignment) mode, OCB (Optical Compensated Bend) mode, IPS (In-Place-Switching) mode, or TN (Twisted Nematic) mode. , but not limited to these. The optically anisotropic layer can have optical properties suitable for improving or controlling the viewing angle characteristics in accordance with each of these modes.

In another preferred embodiment, the optical laminate of the present invention included in the polarizing plate can be placed outside the polarizer when viewed from the liquid crystal cell. In this case, the barrier layer included in the optical laminate can be placed on a side farther from the liquid crystal cell than the optically anisotropic layer described above. This arrangement prevents polar molecules such as ammonia generated from the external environment on the front side and from the backlight etc. on the rear side from reaching the optically anisotropic layer, providing desirable durability. can do.

In this case, the optically anisotropic layer is, for example, a λ/4 wavelength plate, so that if it is placed on the front side, it can improve the visibility obstruction caused by wearing polarized sunglasses, and if it is placed on the rear side, it can recycle polarized light. It is possible to provide an effect of enhancing the brightness improvement effect caused by or an effect of improving color unevenness caused by the backlight member. Furthermore, by using a λ/2 wavelength plate, it is possible to provide a function of preventing reflections on windows and automobile windshields.

(Organic electroluminescent display device)
As a preferred embodiment of the organic electroluminescent display device of the present invention, the polarizing plate of the present invention and the image display panel are arranged in this order from the viewing side, that is, the polarizer and the optical laminate of the present invention. and an organic EL display panel in this order. In this case, in the polarizing plate of the present invention, the optically anisotropic layer is a λ/4 wavelength plate, and the angle between the transmission axis of the polarizer and the slow axis of the optically anisotropic layer is 45±10°. It is preferable to use a polarizing plate having an angle of 35° to 55°, and the barrier layer included in the polarizing plate is preferably disposed on the organic EL display panel side. With this arrangement, especially when the organic EL panel has a silicon nitride layer between the organic electroluminescent layer and the optical laminate, ammonia that may be generated from the silicon nitride layer is transferred to the optically anisotropic layer. The desired durability can be achieved by preventing infiltration by the barrier layer.
That is, the polarizing plate of the present invention can be used as a so-called antireflection film.

An organic EL display panel is a display panel constructed using organic EL elements in which an organic light emitting layer (organic electroluminescence layer) is sandwiched between electrodes (between a cathode and an anode). The structure of the organic EL display panel is not particularly limited, and a known structure may be employed.

In the organic electroluminescent display device of the present invention, it is one of the preferred embodiments that an adhesive layer is present between the polarizing plate and the silicon nitride layer, but it is also possible to have other layers such as metal mesh electrodes. You can also do it.
The thickness of the layer existing between the circularly polarizing plate and the silicon nitride layer is preferably less than 40 μm, and more preferably from 1 to 30 μm, since the effects of the present invention are noticeable.

In another preferred embodiment, the optical laminate of the present invention can be placed on the viewing side of the polarizer of a circularly polarizing plate placed on the viewing side of the organic EL panel. The effects of the optical laminate of the present invention obtained in this case and the gain as a display device obtained are the same as those when disposed on the front side of a liquid crystal display device.

The present invention will be explained in more detail below based on Examples. The materials, usage amounts, proportions, processing details, processing procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the Examples shown below.

<Preparation example 1>
(Preparation of support)
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 with a degree of acetyl substitution of 2.88 ・12 parts by mass of polyester compound B described in the 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

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

After filtering the core layer cellulose acylate dope and the outer layer cellulose acylate dope through a filter paper with an average pore size of 34 μm and a sintered metal filter with an average pore size of 10 μm, the core layer cellulose acylate dope and the outer layer cellulose acylate dope are placed on both sides of the core layer cellulose acylate dope. Three layers of the above were simultaneously cast from a casting port onto a drum at 20°C (band casting machine). The film was peeled off from the drum when the solvent content was approximately 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 in the transverse direction. Thereafter, the obtained film was further dried by conveying it between rolls of a heat treatment apparatus, thereby producing a cellulose acylate film 1 having a thickness of 20 μm. The Re(550) of the obtained cellulose acylate film 1 was 0 nm.

(Preparation of photo alignment film)
Next, referring to the description in Example 3 of JP-A No. 2012-155308, a photo-alignment film coating liquid 1 was prepared and applied to the cellulose acylate film 1 using a wire bar. Thereafter, the obtained cellulose acylate film 1 was dried with warm air at 60° C. for 60 seconds to produce a coating film 1 with a thickness of 300 nm.

(Preparation of optically anisotropic layer)
Subsequently, a composition A1 for forming a positive A plate having the following composition was prepared.
――――――――――――――――――――――――――――――――
Composition of composition A1 for forming positive A plate――――――――――――――――――――――――――――
- 16.00 parts by mass of the following polymerizable liquid crystal compound X-1 - 42.00 parts by mass of the following specific liquid crystal compound L-1 - 42.00 parts by mass of the following specific liquid crystal compound L-2 - 0. 50 parts by mass・Polymerizable compound B-1 below 2.00 parts by mass・Leveling agent (compound T-1 below) 0.20 parts by mass・Methyl ethyl ketone (solvent) 230.00 parts by mass・Cyclopentanone (solvent) 70. 00 parts by mass――――――――――――――――――――――――――――

Polymerizable liquid crystal compound X-1

Specific liquid crystal compound L-1

Specific liquid crystal compound L-2

Compound T-1

The numerical value described for each repeating unit in compound T-1 represents the content (mass%) of each repeating unit with respect to all repeating units.

Polymerization initiator S-1

Polymerizable compound B-1

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

Next, the composition A1 for forming a positive A plate was applied onto the photo-alignment film 1 using a bar coater. The obtained coating film was heated and aged for 20 seconds at a film surface temperature of 100°C, 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. was irradiated to fix the nematic orientation state, thereby forming a positive A plate A1 (corresponding to an optically anisotropic layer), and producing an optical film L including the positive A plate A1.

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 aligned.

(Formation of positive C plate film 1)
The surface of the positive A plate A1 formed above was subjected to corona treatment, and the following positive C plate forming composition C1 was applied to the corona treated surface and aged with warm air at 70° C. for 90 seconds.
Next, a positive C plate C1 was prepared in which the alignment of the liquid crystal compound was fixed by UV irradiation (300 mJ/cm ² ) at 40° C. under a nitrogen purge with an oxygen concentration of 0.1%, and the support/alignment film/positive A An optical film M including plate A1 (optically anisotropic layer)/positive C plate C1 in this order was produced. The thickness of the positive C plate C1 was 0.4 μm. The positive C plate C1 corresponds to another layer having optical anisotropy in the present invention.

――――――――――――――――――――――――――――――――
(Composition C-1)
――――――――――――――――――――――――――――――――
・83 parts by mass of the following rod-like liquid crystal compound M-1 with normal wavelength dispersion ・15 parts by mass of the rod-like liquid crystal compound M-2 with normal wavelength dispersion below ・2 parts by mass of the rod-like liquid crystal compound M-3 with normal wavelength dispersion below Compound B1 4.5 parts by mass・The following polymerization initiator (IrgacureOXE01,
(manufactured by BASF) 5 parts by weight Viscoat #360 (manufactured by Osaka Organic Chemical Industry Co., Ltd.) 8 parts by weight 0.3 parts by weight of the following surfactant T-2 0.5 parts by weight of the following surfactant T-3 The following onium compound S01 2.0 parts by mass・Acetone 229.6 parts by mass・Propylene glycol monomethyl ether acetate 42.0 parts by mass・Methanol 8.4 parts by mass―――――――――――――――― ――――――――――――――――――

Normal wavelength dispersion rod-shaped liquid crystal compound M-1

Normal wavelength dispersion rod-like liquid crystal compound M-2

Normal wavelength dispersion rod-shaped liquid crystal compound M-3

Compound B1

Polymerization initiator

Surfactant T-2 [Mw: 15k. In the formula, the numerical value written for each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units. ]

Surfactant T-3 [Weight average molecular weight: 11,200 (The numerical value written for each repeating unit represents the content (mass%) of each repeating unit with respect to all repeating units.)]

Onium salt compound S01

(Preparation of barrier layer)
A barrier layer forming composition B1 having the following composition was prepared.
――――――――――――――――――――――――――――――――
Composition B1 for forming barrier layer
――――――――――――――――――――――――――――――――
- 14.35 parts by mass of the following polyfunctional (meth)acrylamide compound BM-1 - 0.57 parts by mass of the following polymerization initiator S-2 - 0.07 parts by mass of the above surfactant T-3 - Methanol (solvent) 85. 00 parts by mass――――――――――――――――――――――――――――

Polyfunctional (meth)acrylamide compound BM-1
(Number of functional groups: 3, molecular weight: 265, acrylic equivalent: 88)

Polymerization initiator S-2

The surface of the optical film M produced above on the positive C plate C1 side was subjected to corona treatment, and the barrier layer forming composition B1 was coated thereon using a wire bar coater. It was left standing for a minute. Thereafter, the obtained coating film was cured using a high-pressure mercury lamp of 150 mW/cm ² to form a barrier layer B1 to form a cellulose acylate film 1 (support)/photo alignment film 1/positive A plate. An optical laminate 1 was obtained in which A1 (optically anisotropic layer)/positive C plate C1/barrier layer B1 were laminated in this order. The thickness of the barrier layer was 1.0 μm.

<Preparation examples 2 to 4>
In Production Examples 2 and 3, polyfunctional (meth)acrylamide compound BM-2 and polyfunctional (meth)acrylamide compound BM-3 were used instead of polyfunctional (meth)acrylamide compound BM-1, respectively. An optical laminate in which cellulose acylate film 1 (support)/photo alignment film 1/positive A plate A1 (optically anisotropic layer)/positive C plate C1/barrier layer B1 is laminated in the same manner as in Example 1. 2 and 3 were obtained.
In addition, as Production Example 4, cellulose acylate film 1 (support)/photo alignment film 1/positive An optical laminate 4 was obtained in which A plate A1 (optically anisotropic layer)/positive C plate C1/barrier layer B1 were laminated in this order.

Polyfunctional (meth)acrylamide compound BM-2
(Number of functional groups: 4, molecular weight: 362, acrylic equivalent: 91)

Polyfunctional (meth)acrylamide compound BM-3
(Number of functional groups: 3, molecular weight: 293, acrylic equivalent: 98)

<Preparation example 5>
As Production Example 5, cellulose acylate film 1 (supported Optical laminates 2 and 3 were obtained in which the following layers were laminated in this order: photo-alignment film 1/positive A plate A1 (optically anisotropic layer)/positive C plate C1/barrier layer B1.

Polyfunctional (meth)acrylamide compound BM-4
(Number of functional groups: 4, molecular weight: 509, acrylic equivalent: 127)

<Preparation example 6>
Cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A1 (optically anisotropic layer) / positive C plate was prepared in the same manner as in Production Example 1 except that barrier layer B1 was not formed. An optical laminate 6 was obtained in which the layers were stacked in the order of C1.

<Preparation of polarizing plate>
The surface of the obtained optical laminates 1 to 5 on the support side and the side of the polyvinyl alcohol polarizer with a polarizing plate protective film on only one side, on which the polarizing plate protective film is not provided, are bonded with a sheet-like adhesive (Soken Co., Ltd.). Polarizing plate protective film / polarizer / cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A1 (optically anisotropic layer) / positive C Polarizing plates (Examples 1 to 5) were obtained in which the plate C1/barrier layer B1 was laminated in this order.
In addition, a polarizing plate (Comparative Example 1) was obtained in the same manner as above except that optical laminate 6 was used instead of optical laminate 1.

<Durability evaluation>
The polarizer protective film sides of the polarizing plates of Examples 1 to 5 and Comparative Example 1 cut out into 40 mm squares were pasted on a glass plate using an adhesive film, and a screw cap bottle containing a methanol solution of 2 mol% ammonia was prepared. exposure to ammonia for 16 hours. The exposed surface was placed on the screw cap bottle so that the optical laminate side (ie, barrier layer B1) was the exposed surface.
After exposure, the in-plane retardation Re (450) and Re (550) values of the exposed polarizing plate at wavelengths of 450 nm and 550 nm were measured using Axo Scan (0PMF-1, manufactured by Axometrics).
When H = Re (550), H before ammonia exposure is H0, H after ammonia exposure is H1, ΔH (%) = | H1 - H0 | / H0 × 100 is used as an index, and evaluated as follows. did. The results are shown in Table 3 below.
AA: ΔH is less than 2% A: ΔH is 2% or more and less than 5% B: ΔH is 5% or more and less than 10% C: ΔH is 10% or more

As can be seen from the evaluation results shown in Table 3, the optical laminate and polarizing plate of the present invention exhibit excellent durability even under conditions of exposure to deterioration-causing substances such as ammonia. Therefore, it is clear that it exhibits excellent durability even when incorporated into various image display devices.
Further, from a comparison between Example 1 and Example 5, durability is better when the barrier layer is formed from a composition containing a polyfunctional (meth)acrylamide compound having an acrylic equivalent of 100 or less. I understand.

<Preparation example 7>
Among the components of the positive A plate forming composition A1 used to form the optically anisotropic layer, polymerizable liquid crystal compound X-1, specific liquid crystal compound L-1, and specific liquid crystal compound L-2 (100 parts by mass in total) Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A2 (corresponding to the optically anisotropic layer).
Cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A2 (optically anisotropic An optical laminate 7 was obtained in which the following layers were laminated in this order: positive C plate C1/barrier layer B1.

<Preparation example 8>
Among the components of the positive A plate forming composition A1 used to form the optically anisotropic layer, polymerizable liquid crystal compound X-1, specific liquid crystal compound L-1, and specific liquid crystal compound L-2 (100 parts by mass in total) Instead, 100 parts by mass of the polymerizable liquid crystal compound shown below was used to form a positive A plate A3 (corresponding to the optically anisotropic layer).
Cellulose acylate film 1 (support)/photo alignment film 1/positive A plate A3 (optically anisotropic) was prepared in the same manner as in Production Example 1 except that positive A plate A3 was used instead of positive A plate A1 An optical laminate 8 was obtained in which the following layers were laminated in this order: positive C plate C1/barrier layer B1.

<Preparation example 9>
Cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A2 (optically anisotropic layer) / positive C plate was prepared in the same manner as in Production Example 7 except that barrier layer B1 was not formed. An optical laminate 9 was obtained in which layers were stacked in the order of C1.

<Preparation example 10>
Cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A3 (optically anisotropic layer) / positive C plate was prepared in the same manner as in Production Example 8, except that barrier layer B1 was not formed. An optical laminate 10 was obtained in which the layers were stacked in the order of C1.

<Preparation of polarizing plate>
The surface of the obtained optical laminate 7 on the support side and the side of the polyvinyl alcohol polarizer with a polarizing plate protective film on only one side, on which the polarizing plate protective film is not provided, were glued together using a sheet-like adhesive (Soken Kagaku Co., Ltd.). Polarizing plate protective film / polarizer / cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A2 (optically anisotropic layer) / positive C plate C1. A polarizing plate (Example 6) in which barrier layer B1 was laminated in the following order was obtained.
Similarly, the surface of the obtained optical laminate 8 on the support side and the side of the polyvinyl alcohol polarizer having a polarizing plate protective film on only one side, on which the polarizing plate protective film is not provided, are bonded with a sheet-like adhesive ( Polarizing plate protective film / polarizer / cellulose acylate film 1 (support) / photo alignment film 1 / positive A plate A3 (optically anisotropic layer) / positive A polarizing plate (Example 7) was obtained in which C plate C1/barrier layer B1 was laminated in this order.
Further, a polarizing plate (Comparative Example 2) was obtained in the same manner as above except that the optical laminate 9 was used instead of the optical laminate 7.
Similarly, a polarizing plate (Comparative Example 3) was obtained in the same manner as above except that the optical laminate 10 was used instead of the optical laminate 8.

<Durability evaluation>
The polarizer protective film side of the polarizing plates of Examples 6 to 7 and Comparative Examples 2 to 3 cut into 40 mm squares was pasted on a glass plate using an adhesive film, and screws were filled with a methanol solution of 2 mol% ammonia. Ammonia was exposed for 36 hours by placing it on the mouth bottle. The exposed surface was placed on the screw cap bottle so that the optical laminate side (ie, barrier layer B1) was the exposed surface.
After exposure, the in-plane retardation Re (450) and Re (550) values of the exposed polarizing plate at wavelengths of 450 nm and 550 nm were measured using Axo Scan (0PMF-1, manufactured by Axometrics).
When H = Re (550), H before ammonia exposure is H0, H after ammonia exposure is H1, ΔH (%) = | H1 - H0 | / H0 × 100 is used as an index, and evaluated as follows. did. The results are shown in Table 4 below.
AA: ΔH is less than 2% A: ΔH is 2% or more and less than 5% B: ΔH is 5% or more and less than 10% C: ΔH is 10% or more

As can be seen from the evaluation results shown in Table 4, it was found that even if the type of polymerizable liquid crystal compound used to form the optically anisotropic layer was changed, the same results as the evaluation results shown in Table 3 could be obtained.

<Production of organic EL display device>
Disassemble the SAMSUNG GALAXY S5 equipped with an organic EL display panel (organic EL display element), peel off the touch panel with circularly polarizing plate from the organic EL display device, and then peel off the circularly polarizing plate from the touch panel to remove the organic EL display panel, A touch panel and a circularly polarizing plate were each isolated. Next, a silicon nitride layer (thickness: 50 nm) was provided on the surface of the isolated touch panel by sputtering, and then the organic EL display panel was bonded again. The organic EL display device was produced by laminating the film on the touch panel so that it was on the side.
In another embodiment, a FlexPai manufactured by Royole equipped with an organic EL display panel (organic EL display element) was disassembled, and the circularly polarizing plate was peeled off from the organic EL display device. Next, the polarizing plate of the example produced above was laminated to the isolated organic EL display panel (the outermost surface was a silicon nitride layer) so that the barrier layer side became the panel side, to produce an organic EL display device. .

For the manufactured organic EL display device, by using the polarizing plate of the example including the optical laminate of the positive A plate A1, the positive C plate C1, and the barrier layer, an antireflection effect was exhibited when observed from the front and from an oblique direction. It was confirmed that

10, 20, 30 Optical laminate 11 Support 12 Alignment film 13 Positive A plate (optically anisotropic layer)
14 Barrier layer 15 Positive C plate (optically anisotropic layer)
16 Vertically aligned normal wavelength dispersion liquid crystal cured layer 40 Polarizing plate 41 Polarizer protective film 42 Polarizer 50 Image display device 51 Organic electroluminescent element 52 Touch sensor 53 Silicon nitride layer

Claims (13)

having an optically anisotropic layer and a barrier layer in this order,
Further comprising one or more liquid crystal hardening layers between the optically anisotropic layer and the barrier layer,
The optically anisotropic layer is a layer formed using an optically anisotropic layer forming composition containing a polymerizable liquid crystal compound exhibiting reverse wavelength dispersion,
The optical laminate, wherein the barrier layer is a layer formed from a barrier layer forming composition that contains a polyfunctional (meth)acrylamide monomer and does not contain a polymerization inhibitor. The optical laminate according to claim 1, wherein the barrier layer is formed from a composition containing a polyfunctional (meth)acrylamide compound having a (meth)acrylic equivalent of 100 or less. The optical laminate according to claim 1 or 2, wherein the barrier layer has a thickness of 0.1 to 10 μm. The optical laminate according to any one of claims 1 to 3, wherein the polymerizable liquid crystal compound exhibiting reverse wavelength dispersion is a compound represented by the following formula (II).
L ₁ -G ₁ -D ₁ -Ar-D ₂ -G ₂ -L ₂ ...(II)
Here, in the formula (II),
D ₁ and D ₂ each independently represent a single bond, -O-, -CO-, -CO-O-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² - CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² - , -CR ¹ R ² -CR ³ R ⁴ -O-CO-, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, - Represents NR ¹ -CR ² R ³ - or -CO-NR ¹ -.
R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom, or an alkyl group having 1 to 4 carbon atoms. When a plurality of each of R ¹ , R ² , R ³ and R ⁴ exists, each of 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 are each independently a divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms, a group formed by connecting a plurality of the above alicyclic hydrocarbon groups, an aromatic hydrocarbon group, or , represents a group formed by connecting a plurality of the above aromatic hydrocarbon groups, and one or more of -CH ₂ - constituting the above alicyclic hydrocarbon group is substituted with -O-, -S- or -NH- may have been done.
L ₁ and L ₂ each independently represent a monovalent organic group, and at least one of L ₁ and L ₂ represents a monovalent group having a polymerizable group.
Ar represents any aromatic ring selected from the group consisting of groups represented by formulas (Ar-1) to (Ar-7).
In the formulas (Ar-1) to (Ar-7),
* represents the bonding position with D ₁ or D ₂ .
Q ¹ represents N or CH.
Q ² represents -S-, -O-, or -N(R ⁷ )-, and R ⁷ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.
Y ¹ represents an aromatic hydrocarbon group having 6 to 12 carbon atoms or an aromatic heterocyclic group having 3 to 12 carbon atoms, which may have a substituent.
Z ¹ , Z ² and Z ³ each independently represent 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, or Represents 6 to 20 monovalent aromatic hydrocarbon groups, halogen atoms, cyano groups, nitro groups, -OR ⁸ , -NR ⁹ R ¹⁰ , or -SR ¹¹ , and R ⁸ to R ¹¹ are each independently , represents 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-, and R ¹² is a hydrogen atom or Represents a substituent.
X represents a hydrogen atom or a nonmetallic atom of Groups 14 to 16 to which a substituent may be bonded.
D ⁴ and D ⁵ are each independently a single bond, or -CO-, -O-, -S-, -C(=S)-, -CR ^1a R ^2a -, -CR ^3a =CR ^4a - , -NR ^5a -, or a combination of two or more of these, and R ^1a to R ^5a each independently represent a hydrogen atom, a fluorine atom, or a carbon atom having 1 to 4 carbon atoms. Represents an alkyl group.
SP ¹ and SP ² each independently represent a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched alkylene group having 1 to 12 carbon atoms; One or more constituent -CH ₂ - represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)-, or -CO-, and Q is Represents a substituent.
L ³ and L ⁴ each independently represent a monovalent organic group.
Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of 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 rings in Ax and Ay may have a substituent, or Ax and Ay may be bonded to each other to form a ring.
Q ³ represents 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; 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 in-plane retardation measured at a wavelength of 650 nm of the optically anisotropic layer, satisfies the relationship Re(450)≦Re(550)≦Re(650). 4. The optical laminate according to any one of 4. The optical laminate according to claim 1, further comprising an alignment film on a surface of the optically anisotropic layer opposite to the barrier layer. An optical laminate comprising the optical laminate according to any one of claims 1 to 6 and a polarizer, the polarizer, an optically anisotropic layer included in the optical laminate, and a barrier layer included in the optical laminate. and a polarizing plate, which are included in this order. The polarized light according to claim 7, wherein the optically anisotropic layer is a λ/4 wavelength plate, and the angle between the slow axis of the optically anisotropic layer and the absorption axis of the polarizer is 45°±10°. Board. An image display device comprising the optical laminate according to any one of claims 1 to 6 or the polarizing plate according to claim 7 or 8. The image display device according to claim 9, which is a liquid crystal display device. The image display device according to claim 9, which is an organic electroluminescent display device. From the viewing side, it includes a polarizing plate and an image display panel in this order,
The polarizing plate is the polarizing plate according to claim 8,
The polarizing plate is provided with the barrier layer side of the polarizing plate facing the image display panel side,
The image display panel is an organic electroluminescent panel including an organic electroluminescent element,
An image display device including a silicon nitride layer between the organic electroluminescent element and the barrier layer. The image display device according to claim 12, wherein a layer existing between the polarizing plate and the silicon nitride layer has a thickness of less than 40 μm.