JP2024082163A - Polarizing plate with phase difference layer and image display device - Google Patents

Abstract

The present invention provides a polarizing plate with a retardation layer that has excellent anti-reflection properties and is capable of suppressing corrosion of metal members when applied to an organic EL display device. [Solution] A retardation layer-attached polarizing plate having at least a polarizer-containing polarizing plate, a first retardation layer, and a second retardation layer in this order, and further having a third retardation layer, the first retardation layer and the second retardation layer exhibit a refractive index characteristic of nx>ny≧nz, the third retardation layer exhibits a refractive index characteristic of nz>nx=ny, the first retardation layer has an Re(550) of 200 nm to 300 nm, the second retardation layer has an Re(550) of 120 nm to 170 nm, the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is 5° to 25°, the angle between the slow axis of the second retardation layer and the absorption axis of the polarizer is 65° to 85°, and at least one of the first retardation layer, the second retardation layer, and the third retardation layer is made of a resin film. [Selected Figure] Figure 1A

Description

The present invention relates to a polarizing plate with a retardation layer and an image display device.

In recent years, with the spread of thin displays, image display devices (organic EL display devices) equipped with organic EL panels have been proposed. Since organic EL panels have a highly reflective metal layer, they are prone to problems such as reflection of external light and reflection of the background. It is known that these problems can be prevented by providing a circular polarizer on the viewing side. A typical circular polarizer is one in which a retardation layer functioning as a λ/4 plate is laminated so that its slow axis forms an angle of about 45° with respect to the absorption axis of the polarizer. In addition, from the viewpoint of obtaining anti-reflection properties over a wide band and a wide viewing angle, circular polarizers have been proposed that further include a retardation layer functioning as a λ/2 plate and/or a retardation layer exhibiting a refractive index characteristic of nz>nx=ny (for example, Patent Documents 1 and 2).

Patent No. 6786640 Patent No. 5822006

When a polarizing plate with a retardation layer is applied to an organic EL display device, for example, under high temperature and high humidity conditions, the metal components (e.g., electrodes, sensors, wiring, metal layers) of the organic EL display device may corrode. The main object of the present invention is to provide a polarizing plate with a retardation layer that has excellent anti-reflection properties and can suppress corrosion of metal components when applied to an organic EL display device.

[1] A retardation layer-attached polarizing plate according to an embodiment of the present invention has a polarizing plate including a polarizer, a first retardation layer, and a second retardation layer, at least in this order, and further has a third retardation layer, the first retardation layer and the second retardation layer have a refractive index characteristic of nx>ny≧nz, the third retardation layer has a refractive index characteristic of nz>nx=ny, the first retardation layer has an Re(550) of 200 nm to 300 nm, the second retardation layer has an Re(550) of 120 nm to 170 nm, the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is 5° to 25°, the angle between the slow axis of the second retardation layer and the absorption axis of the polarizer is 65° to 85°, and at least one of the first retardation layer, the second retardation layer, and the third retardation layer is composed of a resin film.
[2] In the above [1], the third retardation layer may be composed of a resin film.
[3] In the above [1] or [2], the polarizing plate may include the polarizer and a protective layer arranged only on the side of the polarizer opposite to the side on which the first retardation layer is arranged.
[4] In any one of the above [1] to [3], the third retardation layer may have an Rth(550) of −10 nm to −150 nm.
[5] In any one of [1] to [4] above, the retardation layer-attached polarizing plate may have the polarizing plate, the third retardation layer, the first retardation layer, and the second retardation layer, at least in this order.
[6] In the above [5], the third retardation layer may have an Rth(550) of −20 nm to −150 nm.
[7] In any one of [1] to [4] above, the retardation layer-attached polarizing plate may have the polarizing plate, the first retardation layer, the third retardation layer, and the second retardation layer, at least in this order.
[8] In the above [7], the third retardation layer may have an Rth(550) of −20 nm to −150 nm.
[9] In any one of [1] to [4] above, the retardation layer-attached polarizing plate may have the polarizing plate, the first retardation layer, the second retardation layer, and the third retardation layer, at least in this order.
[10] In the above [9], the third retardation layer may have an Rth(550) of −20 nm to −150 nm.
[11] In any one of the above [1] to [10], the retardation layer-attached polarizing plate may be used in an organic EL display device.
[12] An image display device according to an embodiment of the present invention includes the retardation layer-attached polarizing plate according to any one of [1] to [11] above.

According to an embodiment of the present invention, a polarizing plate with a retardation layer is provided that has excellent anti-reflection properties and can suppress corrosion of metal members when applied to an organic EL display device.

1 is a schematic cross-sectional view showing an outline of a configuration of a retardation layer-attached polarizing plate in one embodiment of the present invention. 1 is a schematic cross-sectional view showing an outline of a configuration of a retardation layer-attached polarizing plate in one embodiment of the present invention. 1 is a schematic cross-sectional view showing an outline of a configuration of a retardation layer-attached polarizing plate in one embodiment of the present invention. 1 is a schematic cross-sectional view showing a general configuration of an organic EL display device according to one embodiment of the present invention.

The following describes embodiments of the present invention with reference to the drawings, but the present invention is not limited to these embodiments. In order to make the description clearer, the drawings may show the width, thickness, shape, etc. of each part more diagrammatically than the embodiments, but these are merely examples and do not limit the interpretation of the present invention. In this specification, (meth)acrylic refers to acrylic and/or methacrylic. In addition, in this specification, the term "to" indicating a numerical range includes the upper and lower numerical limits.

(Definition of terms and symbols)
The definitions of terms and symbols used in this specification are as follows.
(1) Refractive index (nx, ny, nz)
"nx" is the refractive index in the direction in which the in-plane refractive index is maximum (i.e., the slow axis direction), "ny" is the refractive index in the direction perpendicular to the slow axis in the plane (i.e., the fast axis direction), and "nz" is the refractive index in the thickness direction.
(2) In-plane retardation (Re)
"Re(λ)" is the in-plane retardation measured with light having a wavelength of λ nm at 23° C. For example, "Re(550)" is the in-plane retardation measured with light having a wavelength of 550 nm at 23° C. Re(λ) is calculated by the formula: Re(λ)=(nx−ny)×d, where d (nm) is the thickness of the layer (film).
(3) Retardation in the thickness direction (Rth)
"Rth(λ)" is the retardation in the thickness direction measured with light having a wavelength of λ nm at 23° C. For example, "Rth(550)" is the retardation in the thickness direction measured with light having a wavelength of 550 nm at 23° C. Rth(λ) is calculated by the formula: Rth(λ)=(nx-nz)×d, where d (nm) is the thickness of the layer (film).
(4) Nz Coefficient The Nz coefficient is calculated by Nz=Rth/Re.
(5) Angle When referring to an angle in this specification, the angle includes both clockwise and counterclockwise angles with respect to a reference direction. Thus, for example, "45°" means 45° clockwise and 45° counterclockwise.

A. Retardation Layer-Attached Polarizing Plate The retardation layer-attached polarizing plate according to an embodiment of the present invention has a polarizing plate including a polarizer, a first retardation layer, and a second retardation layer, at least in this order, and further has a third retardation layer. The first retardation layer and the second retardation layer have a refractive index characteristic of nx>ny≧nz; the third retardation layer has a refractive index characteristic of nz>nx=ny; the first retardation layer has an Re(550) of 200 nm to 300 nm; the second retardation layer has an Re(550) of 120 nm to 170 nm; the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is 5° to 25°; the angle between the slow axis of the second retardation layer and the absorption axis of the polarizer is 65° to 85°; at least one of the first retardation layer, the second retardation layer, and the third retardation layer is composed of a resin film. A polarizing plate with a retardation layer having such a configuration can effectively suppress corrosion of metal components caused by iodine and the like in the polarizer, and therefore, when used in an organic EL display device, can exhibit excellent anti-reflection properties and contribute to improving the durability of the organic EL display device.

A-1. Overall configuration of a polarizing plate with a retardation layer Fig. 1A is a schematic cross-sectional view showing an outline of a polarizing plate with a retardation layer in one embodiment of the present invention. The polarizing plate with a retardation layer 100A has a polarizing plate 10, a third retardation layer 40, a first retardation layer 20, and a second retardation layer 30 in this order.
1B is a schematic cross-sectional view showing a schematic configuration of a retardation layer-attached polarizing plate according to another embodiment of the present invention. The retardation layer-attached polarizing plate 100B has a polarizing plate 10, a first retardation layer 20, a third retardation layer 40, and a second retardation layer 30 in this order.
1C is a schematic cross-sectional view showing a schematic configuration of a retardation layer-attached polarizing plate in yet another embodiment of the present invention. The retardation layer-attached polarizing plate 100C has a polarizing plate 10, a first retardation layer 20, a second retardation layer 30, and a third retardation layer 40 in this order.
In the retardation layer-attached polarizing plates 100A, 100B, and 100C (hereinafter, sometimes collectively referred to as "retardation layer-attached polarizing plates 100"), at least one of the first retardation layer 20, the second retardation layer 30, and the third retardation layer 40 is made of a resin film. For example, from the viewpoint of thinning, one or two of the first retardation layer 20, the second retardation layer 30, and the third retardation layer 40, preferably only one of them, is made of a resin film, and the other retardation layers are made of an oriented solidified layer of a liquid crystal compound.
In one embodiment, the retardation layer adjacent to the polarizing plate is made of a resin film.When the retardation layer adjacent to the polarizing plate is made of an orientation solidified layer of a liquid crystal compound, the polarizer may deteriorate (e.g., fade) due to the influence of the liquid crystal compound, polymerization initiator, etc. contained in the layer, but by disposing the retardation layer made of a resin film adjacent to the polarizing plate, such deterioration of the polarizer can be prevented.

The polarizing plate 10 includes a polarizer 12 and further includes a protective layer 14 arranged on the side of the polarizer 12 opposite to the side on which the first retardation layer 20 is arranged. In the illustrated example, no protective layer is arranged between the polarizer 12 and the adjacent retardation layer, and the first retardation layer 20 or the third retardation layer 40 is arranged adjacent to the polarizer 12. Omitting the protective layer in this way can contribute to making the retardation layer-attached polarizing plate 100 thinner. The retardation layer-attached polarizing plate 100 is preferably used in an organic EL display device, and is arranged so that the polarizer 12 is on the viewing side rather than the first retardation layer 20 in the organic EL display device.

The retardation layer-attached polarizing plate 100 further has an adhesive layer 50 as the outermost layer on the side opposite to the polarizing plate 10. The retardation layer-attached polarizing plate 100 can be attached to an optical member such as an organic EL panel by the adhesive layer 50. Although not shown, in practice, a release liner is attached to the surface of the adhesive layer 50. The release liner can be temporarily attached until the retardation layer-attached polarizing plate is used. By using the release liner, for example, the adhesive layer 50 can be protected and the retardation layer-attached polarizing plate 100 can be formed into a roll.

The retardation layer-attached polarizing plate 100 may further have other functional layers not shown. The type, characteristics, number, combination, arrangement, etc. of the other functional layers that the retardation layer-attached polarizing plate may have may be appropriately set according to the purpose. For example, the retardation layer-attached polarizing plate may further have a conductive layer or a conductive layer-attached isotropic substrate. A retardation layer-attached polarizing plate having a conductive layer or a conductive layer-attached isotropic substrate is applied to, for example, a so-called inner touch panel type input display device in which a touch sensor is incorporated inside an image display panel. As another example, the retardation layer-attached polarizing plate may further have other retardation layers. The optical characteristics (e.g., refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement, etc. of the other retardation layers may be appropriately set according to the purpose. As a specific example, the viewing side of the polarizer may be provided with other retardation layers (typically, a layer that imparts (elliptical) polarizing function, a layer that imparts ultra-high retardation) that improve visibility when viewed through polarized sunglasses. By providing such a layer, excellent visibility can be achieved even when the display screen is viewed through polarized lenses such as polarized sunglasses, and the device can be suitably applied to image display devices that can be used outdoors.

The members constituting the retardation layer-attached polarizing plate 100 are typically laminated via any suitable adhesive layer. Specific examples of the adhesive layer include an adhesive layer and a pressure-sensitive adhesive layer. Although not shown, the protective layer 14 is attached to the polarizer 12, for example, via an adhesive layer (preferably using an active energy ray-curable adhesive). For example, the polarizing plate 10 and each retardation layer are laminated via an adhesive layer (preferably using an active energy ray-curable adhesive) or via a pressure-sensitive adhesive layer (preferably using an acrylic pressure-sensitive adhesive). The thickness of the adhesive layer is, for example, 0.1 μm or more, preferably 0.3 μm to 5 μm, and more preferably 0.5 μm to 3 μm. The thickness of the pressure-sensitive adhesive layer is, for example, 3 μm or more, preferably 5 μm to 100 μm, and more preferably 10 μm to 50 μm.

The total thickness (including the thickness of the adhesive layer) of the laminated portion from the polarizing plate 10 to the adhesive layer 50 is, for example, 150 μm or less, preferably 100 μm or less, and for example, 40 μm or more, preferably 50 μm or more. The thickness of the laminated portion from the polarizing plate 10 to the furthest retardation layer (the total thickness excluding the adhesive layer 50) is, for example, 130 μm or less, preferably 70 μm or less, and for example, 20 μm or more, preferably 40 μm or more. In general, the retardation layer made of a liquid crystal alignment solidification layer is thinner than the retardation layer made of a resin film. In addition, the third retardation layer made of a resin film tends to be thinner than the first retardation layer and the second retardation layer made of a resin film. Therefore, according to an embodiment in which the first retardation layer and the second retardation layer are composed of a liquid crystal alignment solidified layer, and the third retardation layer is composed of a resin film, a very thin retardation layer-attached polarizing plate can be obtained in which the thickness of the laminated portion from the polarizing plate 10 to the furthest retardation layer is, for example, 80 μm or less, preferably 70 μm or less, and more preferably 60 μm or less, and, for example, 20 μm or more, preferably 30 μm or more.

The retardation layer-attached polarizing plate 100 may be in the form of a sheet or a long sheet. In this specification, "long sheet" means a long and narrow shape whose length is sufficiently longer than its width, and includes, for example, a long and narrow shape whose length is 10 times or more, preferably 20 times or more, larger than its width. A long laminate can be wound into a roll.

A-2. Polarizing Plate The polarizing plate 10 includes a polarizer 12, and preferably further includes a protective layer 14 on the side of the polarizer 12 opposite to the side on which the first retardation layer 20 is disposed. If necessary, the polarizing plate 10 may include a protective layer on the side of the polarizer 12 on which the first retardation layer 20 is disposed.

A-2-1. Polarizer The polarizer 12 is typically a resin film containing a dichroic material (e.g., iodine). Examples of the resin film include hydrophilic polymer films such as polyvinyl alcohol (PVA)-based films, partially formalized PVA-based films, and partially saponified ethylene-vinyl acetate copolymer-based films.

The thickness of the polarizer is, for example, 18 μm or less, preferably 15 μm or less, more preferably 12 μm or less, and even more preferably 8 μm or less. The thickness of the polarizer is preferably 1 μm or more.

The polarizer preferably exhibits absorption dichroism at any wavelength between 380 nm and 780 nm. The single transmittance of the polarizer is, for example, 40.0% to 46.0%, preferably 41.0% to 45.0%, and more preferably 41.5% to 44.5%. The degree of polarization of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, and even more preferably 99.9% or more.

The polarizer may be produced by any suitable method. Specifically, the polarizer may be produced from a single-layer resin film, or may be produced using a laminate including a substrate.

A typical method for producing a polarizer from the above-mentioned single-layer resin film includes subjecting the resin film to a dyeing process using a dichroic substance such as iodine or a dichroic dye, and a stretching process. As the resin film, for example, a hydrophilic polymer film such as a polyvinyl alcohol (PVA)-based film, a partially formalized PVA-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film is used. The method may further include an insolubilization process, a swelling process, a crosslinking process, etc. Such a manufacturing method is well known and commonly used in the industry, so a detailed description will be omitted.

A polarizer obtained by using a laminate including the above-mentioned substrate can be produced, for example, by using a laminate of a resin substrate and a resin film or resin layer (typically, a PVA-based resin layer). Specifically, a PVA-based resin solution is applied to a resin substrate, and dried to form a PVA-based resin layer on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; and the laminate is stretched and dyed to make the PVA-based resin layer into a polarizer. In this embodiment, preferably, a PVA-based resin layer containing a halide and a PVA-based resin is formed on one side of the resin substrate. The stretching typically includes immersing the laminate in an aqueous boric acid solution and stretching it. Furthermore, the stretching may further include, as necessary, stretching the laminate in the air at a high temperature (e.g., 95°C or higher) before stretching in the aqueous boric acid solution. In addition, in this embodiment, preferably, the laminate is subjected to a drying shrinkage treatment in which the laminate is heated while being transported in the longitudinal direction to shrink the laminate by 2% or more in the width direction. Typically, the manufacturing method of the present embodiment includes subjecting the laminate to an air-assisted stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in this order. By introducing the auxiliary stretching, even when PVA is applied onto a thermoplastic resin, it is possible to increase the crystallinity of PVA, and high optical properties can be achieved. In addition, by simultaneously increasing the orientation of PVA in advance, problems such as a decrease in the orientation of PVA and dissolution can be prevented when immersed in water in the subsequent dyeing and stretching steps, and high optical properties can be achieved. Furthermore, when the PVA-based resin layer is immersed in a liquid, the orientation disorder and the decrease in the orientation of PVA molecules can be suppressed compared to when the PVA-based resin layer does not contain a halide, and high optical properties can be achieved. Furthermore, by shrinking the laminate in the width direction by the drying shrinkage treatment, high optical properties can be achieved. A polarizing plate can be obtained by laminating a protective layer on the peeled surface obtained by peeling the resin substrate from the obtained resin substrate/polarizer laminate, or on the surface opposite to the peeled surface. Details of the manufacturing method of such a polarizer are described, for example, in JP 2012-73580 A and Japanese Patent No. 6470455. The entire disclosures of these publications are incorporated herein by reference.

A-2-2. Protective layer The protective layer 14 may be formed of any suitable resin film that can be used as a protective layer for a polarizer, for example. Specific examples of the resin that is the main component of the resin film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based resins, polyvinyl alcohol-based resins, polycarbonate-based resins, polyamide-based resins, polyimide-based resins, polyethersulfone-based resins, polysulfone-based resins, polystyrene-based resins, cycloolefin-based resins such as polynorbornene, polyolefin-based resins, (meth)acrylic resins, and acetate-based resins.

The polarizing plate with a retardation layer 100 is typically placed on the viewing side of an image display device, and the protective layer 14 is placed on the viewing side. Therefore, the protective layer 14 may be subjected to surface treatments such as hard coat (HC) treatment, anti-reflection treatment, anti-sticking treatment, and anti-glare treatment, as necessary.

The thickness of the protective layer is, for example, 5 μm to 80 μm, preferably 10 μm to 50 μm, and more preferably 15 μm to 35 μm. Note that if the above-mentioned surface treatment has been applied, the thickness of the protective layer includes the thickness of the surface treatment layer.

A-3. First Retardation Layer The first retardation layer 20 has a refractive index characteristic of nx>ny≧nz. In one embodiment, the first retardation layer can function as a λ/2 plate. The in-plane retardation Re(550) of the first retardation layer is, for example, 200 nm to 300 nm, preferably 220 nm to 290 nm, and more preferably 230 nm to 280 nm. Here, "ny=nz" includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, there may be cases where ny<nz within a range that does not impair the effects of the present invention.

The Nz coefficient of the first retardation layer is preferably 0.9 to 3, more preferably 0.9 to 2.5, even more preferably 0.9 to 1.5, and particularly preferably 0.9 to 1.3. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used in an image display device, an extremely excellent reflection hue can be achieved.

The first retardation layer is arranged so that its slow axis forms an angle of, for example, 5° to 25°, preferably 10° to 20°, and more preferably about 15° with the absorption axis of the polarizer 12. With this configuration, a polarizing plate with a retardation layer having very good circular polarization properties (and, as a result, very good antireflection properties) can be obtained.

The first retardation layer may exhibit an inverse dispersion wavelength characteristic in which the retardation value increases with the wavelength of the measurement light, may exhibit a positive wavelength dispersion characteristic in which the retardation value decreases with the wavelength of the measurement light, or may exhibit a flat wavelength dispersion characteristic in which the retardation value hardly changes with the wavelength of the measurement light. In one embodiment, the first retardation layer exhibits an inverse dispersion wavelength characteristic. In this case, Re(450)/Re(550) of the retardation layer is, for example, 0.8 or more and less than 1, and preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent anti-reflection properties can be realized.

In one embodiment, the first retardation layer contains a resin having an absolute value of a photoelastic coefficient of preferably 2×10 ⁻¹¹ m ² /N or less, more preferably 2.0×10 ⁻¹³ m ² /N to 1.5× ^{10 −11} m ² /N, and even more preferably 1.0×10 ⁻¹² m ² /N to 1.2× ^{10 −11} m ² /N. If the absolute value of the photoelastic coefficient is in such a range, a change in retardation is unlikely to occur when shrinkage stress occurs during heating. As a result, the thermal unevenness of the obtained image display device can be well prevented.

The first retardation layer is formed of any suitable material that can satisfy the above characteristics. The first retardation layer is composed of, for example, a resin film or an oriented solidified layer of a liquid crystal compound.

Examples of resins contained in the resin film include polycarbonate-based resins, polyester carbonate-based resins, polyester-based resins, polyvinyl acetal-based resins, polyarylate-based resins, cycloolefin-based resins, cellulose-based resins, polyvinyl alcohol-based resins, polyamide-based resins, polyimide-based resins, polyether-based resins, polystyrene-based resins, acrylic-based resins, and the like. These resins may be used alone or in combination (e.g., blended or copolymerized). When the first retardation layer exhibits reverse dispersion wavelength characteristics, a resin film containing a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter sometimes simply referred to as a polycarbonate-based resin) may be suitably used. When the first retardation layer exhibits flat wavelength dispersion characteristics, a resin film containing a cycloolefin-based resin may be suitably used.

As the polycarbonate-based resin, any suitable polycarbonate-based resin can be used as long as the effects of the present invention can be obtained. For example, the polycarbonate-based resin contains a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from at least one dihydroxy compound selected from the group consisting of alicyclic diol, alicyclic dimethanol, di-, tri- or polyethylene glycol, and alkylene glycol or spiro glycol. Preferably, the polycarbonate-based resin contains a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, a structural unit derived from an alicyclic dimethanol and/or a structural unit derived from a di-, tri- or polyethylene glycol; more preferably, it contains a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, and a structural unit derived from a di-, tri- or polyethylene glycol. The polycarbonate-based resin may contain a structural unit derived from another dihydroxy compound as necessary. Details of polycarbonate-based resins that can be suitably used in the first retardation layer are described, for example, in JP-A-2014-10291, JP-A-2014-26266, JP-A-2015-212816, JP-A-2015-212817, and JP-A-2015-212818, and the descriptions in these publications are incorporated herein by reference.

The above-mentioned cycloolefin resin is a general term for resins polymerized using cycloolefins as polymerization units, and examples thereof include the resins described in JP-A-1-240517, JP-A-3-14882, and JP-A-3-122137. Specific examples include ring-opening (co)polymers of cycloolefins, addition polymers of cycloolefins, copolymers of cycloolefins with ethylene, propylene, and other α-olefins (typically random copolymers), as well as graft modified products of these modified with unsaturated carboxylic acids or derivatives thereof, and hydrogenated products thereof. Specific examples of cycloolefins include norbornene monomers. Examples of norbornene-based monomers include norbornene and its alkyl and/or alkylidene substituted derivatives, such as 5-methyl-2-norbornene, 5-dimethyl-2-norbornene, 5-ethyl-2-norbornene, 5-butyl-2-norbornene, 5-ethylidene-2-norbornene, and polar group substituted derivatives thereof, such as halogen; dicyclopentadiene, 2,3-dihydrodicyclopentadiene, and the like; dimethano Octahydronaphthalene, its alkyl and/or alkylidene substituted derivatives, and polar group substituted derivatives such as halogen, for example, 6-methyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-ethylidene-1,4:5,8-dimethano-1,4,4a,5,6,7,8 ,8a-octahydronaphthalene, 6-chloro-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-cyano-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-pyridyl-1,4:5,8-dimethano-1,4,4a,5,6,7,8,8a-octahydronaphthalene, 6-methoxycarbonyl-1,4:5,8-dimethano -1,4,4a,5,6,7,8,8a-octahydronaphthalene, etc.; trimers and tetramers of cyclopentadiene, such as 4,9:5,8-dimethano-3a,4,4a,5,8,8a,9,9a-octahydro-1H-benzoindene, 4,11:5,10:6,9-trimethano-3a,4,4a,5,5a,6,9,9a,10,10a,11,11a-dodecahydro-1H-cyclopentaanthracene, etc.

Other cycloolefins capable of ring-opening polymerization can be used in combination as long as the object of the present invention is not impaired. Specific examples of such cycloolefins include compounds having one reactive double bond, such as cyclopentene, cyclooctene, and 5,6-dihydrodicyclopentadiene.

The number average molecular weight (Mn) of the cycloolefin resin, as measured by gel permeation chromatography (GPC) using a toluene solvent, is preferably 25,000 to 200,000, more preferably 30,000 to 100,000, and even more preferably 40,000 to 80,000. If the number average molecular weight is within the above range, a resin film having excellent mechanical strength, solubility, formability, and castability can be obtained.

When the cycloolefin resin is obtained by hydrogenating a ring-opening polymer of a norbornene monomer, the hydrogenation rate is preferably 90% or more, more preferably 95% or more, and even more preferably 99% or more. Within such a range, the resin has excellent resistance to heat deterioration, resistance to light deterioration, etc.

Various products of the above cycloolefin resin are commercially available. Specific examples include Zeonex and Zeonor manufactured by Zeon Corporation, Arton manufactured by JSR Corporation, Topas manufactured by TICONA, and APEL manufactured by Mitsui Chemicals.

The first retardation layer can be obtained, for example, by stretching the unstretched resin film. In the stretching, any appropriate stretching method and stretching conditions (for example, stretching temperature, stretching ratio, stretching direction) can be adopted. Specifically, various stretching methods such as free end stretching, fixed end stretching, free end shrinkage, fixed end shrinkage, etc. can be used alone, simultaneously, or sequentially. Regarding the stretching direction, it can be performed in various directions and dimensions such as the length direction, width direction, thickness direction, and oblique direction. The stretching temperature is preferably Tg-30°C to Tg+60°C relative to the glass transition temperature (Tg) of the resin film, and more preferably Tg-10°C to Tg+50°C.

By appropriately selecting the above-mentioned stretching method and stretching conditions, it is possible to obtain a resin film having the above-mentioned desired optical properties (e.g., refractive index properties, in-plane retardation, Nz coefficient).

In one embodiment, the first phase difference layer is produced by uniaxially stretching or fixed-end uniaxially stretching the unstretched resin film. A specific example of fixed-end uniaxial stretching is a method in which the resin film is stretched in the width direction (lateral direction) while running in the longitudinal direction. The stretching ratio is preferably 1.1 to 3.5 times.

The thickness of the first retardation layer, which is a stretched resin film, is, for example, 10 μm to 100 μm, preferably 10 μm to 70 μm, more preferably 10 μm to 60 μm, and even more preferably 20 μm to 50 μm.

The above-mentioned liquid crystal compound alignment solidified layer is a layer in which the liquid crystal compound is aligned in a predetermined direction within the layer and the alignment state is fixed. The "alignment solidified layer" is a concept that includes an alignment solidified layer obtained by hardening a liquid crystal monomer as described below. In the first retardation layer, typically, rod-shaped liquid crystal compounds are aligned in the slow axis direction of the first retardation layer (homogeneous alignment). Examples of rod-shaped liquid crystal compounds include liquid crystal polymers and liquid crystal monomers. The liquid crystal compound is preferably polymerizable. If the liquid crystal compound is polymerizable, the alignment state of the liquid crystal compound can be fixed by aligning the liquid crystal compound and then polymerizing it.

The alignment solidified layer of the liquid crystal compound (liquid crystal alignment solidified layer) can be formed by performing an alignment treatment on the surface of a predetermined substrate, applying a coating liquid containing a liquid crystal compound to the surface to align the liquid crystal compound in a direction corresponding to the alignment treatment, and fixing the alignment state. Any appropriate alignment treatment can be adopted as the alignment treatment. Specific examples include mechanical alignment treatment, physical alignment treatment, and chemical alignment treatment. Specific examples of mechanical alignment treatment include rubbing treatment and stretching treatment. Specific examples of physical alignment treatment include magnetic field alignment treatment and electric field alignment treatment. Specific examples of chemical alignment treatment include oblique deposition method and photoalignment treatment. Any appropriate conditions can be adopted as the treatment conditions for various alignment treatments depending on the purpose.

The alignment of liquid crystal compounds is achieved by treating them at a temperature that exhibits a liquid crystal phase according to the type of liquid crystal compound. By carrying out such temperature treatment, the liquid crystal compounds take on a liquid crystal state, and the liquid crystal compounds are aligned according to the alignment treatment direction of the substrate surface.

In one embodiment, the alignment state is fixed by cooling the liquid crystal compound aligned as described above. If the liquid crystal compound is polymerizable or crosslinkable, the alignment state is fixed by subjecting the liquid crystal compound aligned as described above to a polymerization treatment or crosslinking treatment.

As the liquid crystal compound, any suitable liquid crystal polymer and/or liquid crystal monomer can be used. The liquid crystal polymer and the liquid crystal monomer can be used alone or in combination. Specific examples of liquid crystal compounds and methods for producing a liquid crystal alignment solidified layer are described, for example, in JP 2006-163343 A, JP 2006-178389 A, and WO 2018/123551 A. The descriptions in these publications are incorporated herein by reference.

The thickness of the first retardation layer, which is a liquid crystal alignment solidification layer, is, for example, 1 μm to 10 μm, preferably 1 μm to 8 μm, more preferably 1 μm to 6 μm, and even more preferably 1 μm to 4 μm.

A-4. Second phase difference layer The second phase difference layer 30 has a refractive index characteristic of nx>ny≧nz. In one embodiment, the second phase difference layer can function as a λ/4 plate. The in-plane retardation Re(550) of the second phase difference layer is, for example, 120 nm to 170 nm, preferably 130 nm to 160 nm, and more preferably 140 nm to 150 nm. Here, "ny=nz" includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, there may be cases where ny<nz within a range that does not impair the effects of the present invention.

The Nz coefficient of the second retardation layer is preferably 0.9 to 3, more preferably 0.9 to 2.5, even more preferably 0.9 to 1.5, and particularly preferably 0.9 to 1.3. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used in an image display device, an extremely excellent reflection hue can be achieved.

The second retardation layer is arranged so that its slow axis forms an angle of, for example, 65° to 85°, preferably 70° to 80°, and more preferably about 75° with the absorption axis of the polarizer 12. The angle between the slow axis of the second retardation layer and the slow axis of the first retardation layer is, for example, 50° to 70°, preferably 55° to 65°, and more preferably about 60°. With this configuration, a polarizing plate with a retardation layer having very good circular polarization properties (and, as a result, very good antireflection properties) can be obtained.

The second retardation layer may exhibit an inverse dispersion wavelength characteristic in which the retardation value increases with the wavelength of the measurement light, may exhibit a positive wavelength dispersion characteristic in which the retardation value decreases with the wavelength of the measurement light, or may exhibit a flat wavelength dispersion characteristic in which the retardation value hardly changes with the wavelength of the measurement light. In one embodiment, the second retardation layer exhibits an inverse dispersion wavelength characteristic. In this case, Re(450)/Re(550) of the retardation layer is, for example, 0.8 or more and less than 1, and preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent anti-reflection properties can be realized.

In one embodiment, the second retardation layer contains a resin having an absolute value of a photoelastic coefficient of preferably 2×10 ⁻¹¹ m ² /N or less, more preferably 2.0×10 ⁻¹³ m ² /N to 1.5× ^{10 −11} m ² /N, and even more preferably 1.0×10 ⁻¹² m ² /N to 1.2× ^{10 −11} m ² /N. If the absolute value of the photoelastic coefficient is in such a range, a change in retardation is unlikely to occur when shrinkage stress occurs during heating. As a result, the thermal unevenness of the obtained image display device can be well prevented.

The second retardation layer is formed of any suitable material that can satisfy the above characteristics. The second retardation layer is composed of, for example, a resin film or an oriented solidified layer of a liquid crystal compound.

The resin contained in the resin film may be the same as the resin contained in the resin film constituting the first phase difference layer. The second phase difference layer may be obtained, for example, by stretching the unstretched resin film. As described for the first phase difference layer, any appropriate stretching method and stretching conditions (e.g., stretching temperature, stretching ratio, stretching direction) may be adopted for stretching. By appropriately selecting the stretching method and stretching conditions, a resin film having the desired optical properties (e.g., refractive index properties, in-plane retardation, Nz coefficient) can be obtained.

The thickness of the second retardation layer, which is a stretched resin film, is, for example, 10 μm to 100 μm, preferably 10 μm to 70 μm, more preferably 10 μm to 60 μm, and even more preferably 20 μm to 50 μm.

As the liquid crystal compound contained in the alignment and solidification layer of the liquid crystal compound, any suitable liquid crystal polymer and/or liquid crystal monomer can be used. Specifically, the same liquid crystal compound as the liquid crystal compound contained in the liquid crystal alignment and solidification layer constituting the first retardation layer can be exemplified, and the method of preparation thereof is as described above.

The thickness of the second retardation layer, which is a liquid crystal alignment solidification layer, is, for example, 1 μm to 10 μm, preferably 1 μm to 8 μm, more preferably 1 μm to 6 μm, and even more preferably 1 μm to 4 μm.

A-5. Third retardation layer The third retardation layer 40 is a so-called positive C plate whose refractive index characteristics show the relationship nz>nx=ny. By using a positive C plate, it is possible to prevent reflection in an oblique direction very well, and it is possible to widen the viewing angle of the anti-reflection function. Here, "nx=ny" includes not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re(550) of the third retardation layer can be less than 10 nm.

The thickness direction retardation Rth(550) of the third retardation layer is, for example, −10 nm to −150 nm, and is appropriately set depending on the configuration of the retardation layer-attached polarizing plate, the use of the image display device, and the like.
For example, when the third retardation layer is disposed between the polarizing plate and the first retardation layer, the Rth(550) of the third retardation layer is preferably −20 nm to −150 nm, more preferably −40 nm to −140 nm, and even more preferably −60 nm to −130 nm. In one embodiment, the Rth(550) of the third retardation layer disposed between the polarizing plate and the first retardation layer is −80 nm to −140 nm.
For example, when the third retardation layer is disposed between the first retardation layer and the second retardation layer, the Rth(550) of the third retardation layer is preferably −20 nm to −150 nm, more preferably −40 nm to −140 nm, and even more preferably −60 nm to −130 nm. In one embodiment, the Rth(550) of the third retardation layer disposed between the first retardation layer and the second retardation layer is −80 nm to −140 nm.
For example, when the third retardation layer is disposed on the opposite side of the second retardation layer to the side where the first retardation layer is disposed, the Rth(550) of the third retardation layer is preferably −20 nm to −150 nm, more preferably −40 nm to −120 nm, and even more preferably −50 nm to −110 nm. In one embodiment, the Rth(550) of the third retardation layer disposed on the opposite side of the second retardation layer to the side where the first retardation layer is disposed is −40 nm to −80 nm.

The third phase difference layer preferably has a puncture elastic modulus of 50 g/mm or more, more preferably 52 g/mm or more, and even more preferably 55 g/mm or more. The puncture elastic modulus of the third phase difference layer is, for example, 200 g/mm or less. When the puncture elastic modulus of the third phase difference layer is within the above range, the dimensional change of the adjacent phase difference layer (for example, the expansion, contraction, etc. of the first phase difference layer and/or the second phase difference layer composed of a stretched film of a resin film) can be suitably suppressed. In this specification, the puncture elastic modulus refers to the value obtained by dividing the force (g) just before the phase difference film breaks (or tears) when a needle (puncture tool) is pierced perpendicularly to the main surface of the phase difference film (for example, the third phase difference layer) by the strain (mm) at that time. As the needle, one with a tip diameter of 1 mmφ and 0.5R can be used. The needle piercing speed can be 0.33 cm/sec. The puncture modulus can be measured by sandwiching the retardation film between two plates with a circular hole having a diameter of 15 mm or less (for example, a diameter of 11 mm) through which a needle can pass. The puncture modulus can be measured in an environment at a temperature of 23°C. For example, the puncture modulus can be measured for five retardation films, and the average value can be used as the puncture modulus of the retardation film. Commercially available devices can be used to measure the puncture modulus. Examples of commercially available devices include a handy compression tester "KES-G5 Needle Penetration Force Measurement Specification" manufactured by Kato Tech Co., Ltd. and a small tabletop tester "EZ Test" manufactured by Shimadzu Corporation.

The third phase difference layer is formed of any suitable material. In one embodiment, the third phase difference layer is composed of an oriented solidified layer of a liquid crystal compound. In another embodiment, the third phase difference layer is composed of a resin film. When the first phase difference layer composed of a resin film is arranged adjacent to the polarizing plate, the first phase difference layer also undergoes dimensional changes following the dimensional changes of the polarizer, which may result in color unevenness in the reflected hue. However, when the third phase difference layer composed of a resin film is arranged adjacent to the polarizing plate, such color unevenness in the reflected hue can be suppressed.

Resin materials that form the third retardation layer are typically made of resin materials with negative birefringence. Resins with negative birefringence are resins that exhibit a maximum refractive index in the direction perpendicular to the stretching direction when uniaxially stretched. Examples of resins with negative birefringence include resins in which a chemical bond or functional group with large polarization anisotropy, such as an aromatic ring or a carbonyl group, is introduced into the side chain. Specific examples of resins with negative birefringence include acrylic resins, styrene resins, maleimide resins, modified polyolefin resins, and fumaric acid ester resins. The above resin materials can be used alone or in combination of two or more.

The acrylic resin can be obtained, for example, by addition polymerization of an acrylate monomer. Examples of acrylic resins include polymethyl methacrylate (PMMA), polybutyl methacrylate, and polycyclohexyl methacrylate.

The styrene-based resin can be obtained, for example, by addition polymerization of a styrene-based monomer. Examples of the styrene-based monomer include styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, p-nitrostyrene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, 2,5-dichlorostyrene, and p-t-butylstyrene.

The maleimide resin can be obtained, for example, by addition polymerization of a maleimide monomer. Examples of the maleimide monomer include N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2-ethylphenyl)maleimide, N-(2-propylphenyl)maleimide, N-(2-isopropylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-dipropylphenyl)maleimide, N-(2,6-diisopropylphenyl)maleimide, N-(2-methyl-6-ethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-(2,6-dichlorophenyl)maleimide, N-(2-bromophenyl)maleimide, N-(2,6-dibromophenyl)maleimide, N-(2-biphenyl)maleimide, and N-(2-cyanophenyl)maleimide. Maleimide monomers can be obtained, for example, from Tokyo Chemical Industry Co., Ltd.

In the above addition polymerization, the birefringence properties of the resulting resin can be controlled by substituting the side chains after polymerization, or by carrying out maleimidization or grafting reactions.

The resin having negative birefringence may be copolymerized with other monomers. By copolymerizing other monomers, brittleness, moldability, and heat resistance can be improved. Examples of such other monomers include olefins such as ethylene, propylene, 1-butene, 1,3-butadiene, 2-methyl-1-butene, 2-methyl-1-pentene, and 1-hexene; acrylonitrile; (meth)acrylates such as methyl acrylate and methyl methacrylate; maleic anhydride; and vinyl esters such as vinyl acetate.

When the resin having negative birefringence is a copolymer of the styrene monomer and the other monomer, the blending ratio of the styrene monomer is preferably 50 mol% to 80 mol%. When the resin having negative birefringence is a copolymer of the maleimide monomer and the other monomer, the blending ratio of the maleimide monomer is preferably 2 mol% to 50 mol%. By blending in such a range, a resin film having excellent toughness and moldability can be obtained.

As the resin having the negative birefringence, preferably used are styrene-maleic anhydride copolymer, styrene-acrylonitrile copolymer, styrene-(meth)acrylate copolymer, styrene-maleimide copolymer, vinyl ester-maleimide copolymer, olefin-maleimide copolymer, etc. These can be used alone or in combination of two or more. These resins exhibit high negative birefringence and can have excellent heat resistance. These resins can be obtained, for example, from Nova Chemical Japan, Arakawa Chemical Industries, Ltd., etc.

As the resin having negative birefringence, a polymer having a repeating unit represented by the following general formula (I) is preferably used. Such a polymer exhibits even higher negative birefringence and can have excellent heat resistance and mechanical strength. Such a polymer can be obtained, for example, by using an N-phenyl-substituted maleimide in which a phenyl group having a substituent at least at the ortho position is introduced as the N-substituent of the maleimide monomer as the starting material.

In the above general formula (I), R ₁ to R ₅ each independently represent hydrogen, a halogen atom, a carboxylic acid, a carboxylate, a hydroxyl group, a nitro group, or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms (provided that R ₁ and R ₅ are not simultaneously hydrogen atoms), R ₆ and R ₇ represent hydrogen or a linear or branched alkyl or alkoxy group having 1 to 8 carbon atoms, and n represents an integer of 2 or greater.

Resins having negative birefringence are not limited to the above, and for example, resins having negative birefringence described in JP-T-2008-544304 and JP-T-2008-544317 can be used.

The resin film forming the third retardation layer may further contain any suitable additive, if necessary. Specific examples of additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, UV absorbers, flame retardants, colorants, antistatic agents, compatibilizers, crosslinking agents, thickeners, etc. The type and content of the additives may be appropriately set depending on the purpose. The content of the additives in the resin film is, for example, about 3% to 10% by weight.

Any suitable manufacturing method can be used as a manufacturing method for the third retardation layer composed of the resin film. In one embodiment, the resin film containing the resin material can be used as the third retardation layer as it is after film formation (i.e., in an unstretched state). For example, when a film is formed by a solution film-forming method using a resin solution containing the resin material, stress occurs due to volume shrinkage when the resin solution is dried on the support, and the molecular chains of the polymer tend to be oriented in the in-plane direction. Therefore, when a resin material that has high birefringence expression and negative intrinsic birefringence is used, a coating film having large thickness direction birefringence can be formed on the support due to the shrinkage action during drying, and the coating film can be used as it is as a positive C plate.

The thickness of the third retardation layer, which is a resin film, is, for example, 1 μm to 40 μm, preferably 3 μm to 35 μm, and more preferably 5 μm to 30 μm.

A preferred example of the alignment and solidification layer of the liquid crystal compound constituting the third retardation layer is an alignment and solidification layer of a liquid crystal material fixed in homeotropic alignment. The liquid crystal material (liquid crystal compound) that can be homeotropically aligned may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method of forming the retardation layer include the liquid crystal compound and the method of forming the retardation layer described in [0020] to [0028] of JP-A-2002-333642.

The thickness of the third retardation layer, which is an alignment solidification layer of the liquid crystal compound, is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 8 μm, and even more preferably 0.5 μm to 5 μm.

A-6. Pressure-sensitive adhesive layer The pressure-sensitive adhesive layer 50 is provided as the outermost layer on the side opposite to the polarizing plate 10. As described above, the retardation layer-attached polarizing plate 100 can be attached to a member such as an organic EL panel via the pressure-sensitive adhesive layer 50.

The adhesive layer 50 may be made of any suitable adhesive. Specific examples include acrylic adhesives, rubber adhesives, silicone adhesives, polyester adhesives, urethane adhesives, epoxy adhesives, and polyether adhesives. By adjusting the type, number, combination, and compounding ratio of the monomers forming the base resin of the adhesive, as well as the compounding amount of the crosslinking agent, reaction temperature, reaction time, etc., an adhesive having the desired properties according to the purpose can be prepared. The base resin of the adhesive may be used alone or in combination of two or more types. An acrylic resin is preferably used as the base resin. Specifically, the adhesive layer is preferably made of an acrylic adhesive.

The adhesive layer can be formed by applying an adhesive composition containing a base resin, additives such as a crosslinking agent, and a solvent, and then drying the applied composition. For example, the adhesive layer can be formed by applying the adhesive composition directly to the adherend. Alternatively, the adhesive layer can be formed by applying the adhesive composition to a separately prepared substrate such as a base film, and then transferred to the adherend. Drying is typically performed by heating.

The thickness of the adhesive layer is, for example, 5 μm or more, preferably 10 μm or more, and, for example, 100 μm or less, preferably 80 μm or less.

A-7. Release Liner An example of the release liner is a flexible plastic film. Examples of the plastic film include a polyethylene terephthalate film, a polyethylene film, a polypropylene film, and a polyester film. The thickness of the release liner is, for example, 3 μm or more and, for example, 200 μm or less. The surface of the release liner is coated with a release agent. Specific examples of the release agent include a silicone-based release agent, a fluorine-based release agent, and a long-chain alkyl acrylate-based release agent.

B. Image display device The retardation layer-attached polarizing plate described in section A is typically applied to an image display device, preferably an image display device having a metal layer, more preferably an organic electroluminescence (organic EL) display device. Therefore, an image display device according to an embodiment of the present invention includes the retardation layer-attached polarizing plate. An organic EL display device according to an embodiment of the present invention typically includes an organic EL panel and the retardation layer-attached polarizing plate arranged on the viewing side of the organic EL panel.

The organic EL display device 200 illustrated in FIG. 2 has an organic EL panel 120 and a polarizing plate with a phase difference layer 100A arranged on the viewing side of the organic EL panel 120. The polarizing plate with a phase difference layer 100A is arranged so that the first phase difference layer 20 is closer to the organic EL panel 120 than the polarizer 12, and is attached to the organic EL panel 120 by an adhesive layer 50. The organic EL panel 120 includes metal members (e.g., electrodes, sensors, wiring, metal layers), but since the polarizing plate with a phase difference layer 100A has excellent anti-reflection properties, it can effectively prevent reflections caused by the metal members.

The present invention will be described in detail below with reference to examples, but the present invention is not limited to these examples. Various measurement methods are as follows. Furthermore, unless otherwise specified, "parts" and "%" in the examples and comparative examples are by weight.

1. Thickness Thicknesses of 1 μm or less were measured using a scanning electron microscope (manufactured by JEOL Ltd., product name "JSM-7100F"), and thicknesses of more than 1 μm were measured using a digital micrometer (manufactured by Anritsu Corporation, product name "KC-351C").
2. In-plane retardation Re(λ) and thickness direction retardation Rth(λ)
The in-plane retardation at each wavelength at 23° C. was measured using a Mueller matrix polarimeter (manufactured by Axometrics, product name "Axoscan").
3. Refractive Index The average refractive index was measured using an Abbe refractometer manufactured by Atago Co., Ltd., and the refractive indexes nx, ny, and nz were calculated from the above retardation value.
4. Single transmittance and degree of polarization The single transmittance Ts, parallel transmittance Tp, and crossed transmittance Tc of the polarizing plate were measured using a spectrophotometer (Otsuka Electronics Co., Ltd., "LPF-200"). These Ts, Tp, and Tc are Y values measured using a 2-degree visual field (C light source) according to JIS Z8701 and corrected for visibility. From the obtained Tp and Tc, the degree of polarization of the polarizing plate (polarizer) was calculated using the following formula.
Degree of polarization (%)={(Tp−Tc)/(Tp+Tc)} ^1/2 ×100

[Production Example 1: Preparation of Polarizing Plate A]
(Preparation of Polarizer)
As a thermoplastic resin substrate, a long amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 μm) having a Tg of about 75° C. was used, and one side of the resin substrate was subjected to a corona treatment.
A PVA aqueous solution (coating solution) was prepared by adding 13 parts by weight of potassium iodide to 100 parts by weight of a PVA-based resin prepared by mixing polyvinyl alcohol (polymerization degree 4,200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Mitsubishi Chemical Corporation, product name "GOHSENEX Z410") in a ratio of 9:1, and dissolving the resultant in water.
The above PVA aqueous solution was applied to the corona-treated surface of a resin substrate and dried at 60° C. to form a PVA-based resin layer having a thickness of 13 μm, thereby producing a laminate.
The obtained laminate was uniaxially stretched 2.4 times in the longitudinal direction (machine direction) in an oven at 130° C. (auxiliary in-air stretching treatment).
Next, the laminate was immersed in an insolubilizing bath (a boric acid aqueous solution obtained by mixing 4 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (insolubilizing treatment).
Next, the film was immersed in a dye bath (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1:7 with 100 parts by weight of water) having a liquid temperature of 30° C. for 60 seconds while adjusting the concentration so that the single transmittance (Ts) of the finally obtained polarizer would have a desired value (dyeing treatment).
Next, the plate was immersed in a crosslinking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with 100 parts by weight of water) at a liquid temperature of 40° C. for 30 seconds (crosslinking treatment).
Thereafter, the laminate was immersed in an aqueous boric acid solution (boric acid concentration: 4 wt %, potassium iodide concentration: 5 wt %) at a liquid temperature of 70° C., and uniaxially stretched in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds to a total stretch ratio of 5.5 times (underwater stretching treatment).
Thereafter, the laminate was immersed in a cleaning bath (an aqueous solution obtained by mixing 4 parts by weight of potassium iodide with 100 parts by weight of water) at a liquid temperature of 20° C. (cleaning treatment).
Thereafter, the film was dried in an oven maintained at about 90° C., while being brought into contact with a SUS heated roll whose surface temperature was maintained at about 75° C. (drying shrinkage treatment).
In this manner, a polarizer having a thickness of 5 μm was formed on the resin substrate.

(Preparation of Polarizing Plate A)
A HC-TAC film was attached as a protective layer to the surface of the obtained polarizer (the surface opposite to the resin substrate) via an ultraviolet-curing adhesive. Specifically, the ultraviolet-curing adhesive was applied to a thickness of 1.0 μm, and the two were attached using a rolling machine. Then, UV rays were irradiated from the protective layer side to cure the adhesive. The HC-TAC film was a film in which a hard coat (HC) layer (thickness 7 μm) was formed on a triacetyl cellulose (TAC) film (thickness 25 μm), and the two were attached so that the TAC film was on the polarizer side. Next, the resin substrate was peeled off and removed to obtain a polarizing plate A having a configuration of [polarizer/HC-attached TAC protective layer]. The single transmittance of the polarizing plate A was 43%, and the polarization degree was 99.9%.

[Production Example 2A: Preparation of λ/2 Plate A (Liquid Crystal Alignment Solidified Layer)]
A liquid crystal composition (coating liquid) was prepared by dissolving 10 g of a polymerizable liquid crystal exhibiting a nematic liquid crystal phase (manufactured by BASF: product name "Paliocolor LC242", represented by the following formula) and 3 g of a photopolymerization initiator for the polymerizable liquid crystal compound (manufactured by BASF: product name "Irgacure 907") in 40 g of toluene.

The surface of a polyethylene terephthalate (PET) film (thickness 38 μm) was rubbed with a rubbing cloth and subjected to an orientation treatment. The orientation treatment direction was set to be 15° from the viewing side with respect to the direction of the absorption axis of the polarizer when it was laminated to the polarizing plate. The liquid crystal coating liquid was applied to this orientation treatment surface with a bar coater, and the liquid crystal compound was aligned by heating and drying at 90 ° C for 2 minutes. The liquid crystal layer thus formed was irradiated with light of 1 mJ / cm ² using a metal halide lamp, and the liquid crystal layer was hardened to form a liquid crystal alignment solidified layer (λ / 2 plate A) on the PET film. The thickness of the λ / 2 plate A was 2.5 μm, and the in-plane retardation Re (550) was 270 nm. Furthermore, the λ / 2 plate A showed a refractive index characteristic of nx > ny = nz.

[Production Example 2B: Production of λ/2 Plate B (Resin Film)]
A norbornene-based resin film (manufactured by JSR Corporation, product name "Arton R5000", thickness 80 μm) was uniaxially stretched 1.4 times at 135° C. The thickness of the obtained stretched film (λ/2 plate B) was 70 μm, and Re(550) was 270 nm. Furthermore, λ/2 plate B showed a refractive index characteristic of nx>ny=nz.

[Production Example 3A: Preparation of λ/4 Plate A (Liquid Crystal Alignment Solidified Layer)]
A liquid crystal alignment solidified layer (lambda/4 plate A) was formed on a PET film in the same manner as in Production Example 2B, except that the coating thickness was changed and the orientation treatment direction was set to a 75° direction relative to the absorption axis direction of the polarizer when viewed from the viewing side. The thickness of the lambda/4 plate A was 1.5 μm, and the in-plane retardation Re (550) was 140 nm. Furthermore, the lambda/4 plate A showed a refractive index characteristic of nx>ny=nz.

[Production Example 3B: Preparation of λ/4 Plate B (Resin Film)]
A stretched film of a resin film was obtained in the same manner as in Production Example 2B, except that a norbornene-based resin film having a thickness of 40 μm was used as the resin film raw material to be stretched. The thickness of the obtained stretched film (lambda / 4 plate B) was 35 μm, and Re (550) was 140 nm. Furthermore, the lambda / 4 plate B showed a refractive index characteristic of nx > ny = nz.

[Production Example 4A: Preparation of Positive C Plate A]
In an autoclave equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer, 48 parts by weight of hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical, trade name: Metolose 60SH-50), 15601 parts by weight of distilled water, 8161 parts by weight of diisopropyl fumarate, 240 parts by weight of 3-ethyl-3-oxetanylmethyl acrylate and 45 parts by weight of t-butyl peroxypivalate as a polymerization initiator were placed, and after nitrogen bubbling for 1 hour, the mixture was stirred and held at 49°C for 24 hours to carry out radical suspension polymerization. The mixture was then cooled to room temperature, and the suspension containing the generated polymer particles was centrifuged. The obtained polymer was washed twice with distilled water and twice with methanol, and then dried under reduced pressure. The obtained fumarate ester resin was dissolved in a toluene-methyl ethyl ketone mixed solution (toluene/methyl ethyl ketone, 50% by weight/50% by weight) to prepare a 20% solution. Furthermore, 5 parts by weight of tributyl trimellitate was added as a plasticizer to 100 parts by weight of the fumarate ester resin to prepare a dope. A biaxially stretched polyester (polyethylene-terephthalate/isophthalate copolymer) film (thickness 75 μm) was used as the support film. The prepared dope was applied to the support film so that the film thickness after drying was 8 μm, and dried at 140° C. This resulted in a resin film (positive C plate A) exhibiting a refractive index characteristic of nz>nx=ny. The thickness of the positive C plate A was 8 μm, the in-plane retardation Re(550) was ≒0 nm, and the thickness direction retardation Rth(550) was −40 nm.

[Production Example 4B: Preparation of Positive C Plate B]
A resin film (positive C plate B) exhibiting a refractive index characteristic of nz>nx=ny was obtained in the same manner as in Production Example 4A, except that the coating thickness of the resin solution was changed. The thickness of the positive C plate B was 17 μm, the in-plane retardation Re(550) was ≒0 nm, and the thickness direction retardation Rth(550) was −80 nm.

[Production Example 4C: Preparation of Positive C Plate C]
A resin film (positive C plate C) exhibiting a refractive index characteristic of nz>nx=ny was obtained in the same manner as in Production Example 4A, except that the coating thickness of the resin solution was changed. The thickness of the positive C plate C was 26 μm, the in-plane retardation Re(550) was ≒0 nm, and the thickness direction retardation Rth(550) was −120 nm.

[Production Example 4D: Preparation of Positive C Plate D]
A liquid crystal coating liquid was prepared by dissolving 20 parts by weight of a side-chain liquid crystal polymer represented by the following chemical formula (3) (the numbers 65 and 35 in the formula indicate the mole percent of the monomer unit, and are conveniently expressed as a block polymer: weight average molecular weight 5000), 80 parts by weight of a polymerizable liquid crystal exhibiting a nematic liquid crystal phase (manufactured by BASF: trade name Paliocolor LC242), and 5 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: trade name Irgacure 907) in 200 parts by weight of cyclopentanone. The coating liquid was then applied to a PET substrate that had been subjected to a vertical alignment treatment using a bar coater, and the liquid crystal was aligned by heating and drying at 80°C for 4 minutes. The liquid crystal layer was irradiated with ultraviolet light to harden the liquid crystal layer, thereby forming a liquid crystal alignment solidified layer (positive C plate D) exhibiting a refractive index characteristic of nz>nx=ny on the substrate. The positive C plate D had a thickness of 3 μm and a thickness direction retardation Rth(550) of −80 nm.

[Production Example 5: Preparation of Pressure-Sensitive Adhesive Layer A]
A monomer mixture containing 91.5 parts of butyl acrylate, 3 parts of acrylic acid, 0.5 parts of 4-hydroxybutyl acrylate and 5 parts of acryloylmorpholine was charged into a four-neck flask equipped with a stirring blade, a thermometer, a nitrogen gas inlet tube and a cooler. Furthermore, 0.1 parts of 2,2'-azobisisobutyronitrile as a polymerization initiator was charged together with 100 parts of ethyl acetate for 100 parts of this monomer mixture, and nitrogen gas was introduced while gently stirring to replace the atmosphere in the flask with nitrogen. The liquid temperature in the flask was kept at around 55°C and a polymerization reaction was carried out for 8 hours. Next, ethyl acetate was added to the obtained reaction liquid to adjust the solid concentration to 12% by weight, and a solution of an acrylic polymer having a weight average molecular weight (Mw) of 2.5 million was prepared.
An acrylic adhesive was prepared by blending 100 parts of the solid content of the obtained acrylic polymer solution with 0.3 parts of a peroxide-based crosslinking agent, benzoyl peroxide (product name: Niper BMT, manufactured by Nippon Oil & Fats Co., Ltd.), 0.2 parts of a trimethylolpropane/tolylene diisocyanate adduct (product name: Coronate L, manufactured by Tosoh Corporation), and 0.2 parts of a silane coupling agent (product name: KBM403, manufactured by Shin-Etsu Chemical Co., Ltd.).
The obtained acrylic adhesive was applied to the release surface of a 38 μm thick PET film (Mitsubishi Chemical Polyester Film Corporation, MRF38), which is a release liner with a silicone treatment applied to the release surface, and dried to form an adhesive layer A with a thickness of 20 μm.

[Example 1]
The positive C plate A was attached to the polarizer side of the polarizing plate A, and then the λ/2 plate A and the λ/4 plate A were transferred from the PET film onto the positive C plate A in this order. At this time, the transfer (attachment) was performed so that the slow axis of the λ/2 plate A and the slow axis of the λ/4 plate A were at 15° and 75° clockwise with respect to the absorption axis of the polarizer, respectively. The positive C plate, the λ/2 plate A, and the λ/4 plate A were attached via an ultraviolet-curing adhesive (thickness about 1 μm).
The above-mentioned adhesive layer A was bonded to the λ/4 plate A side of the obtained laminate together with the release liner to obtain a polarizing plate 1 with a retardation layer having a configuration of [polarizing plate A/positive C plate A/λ/2 plate A/λ/4 plate A/adhesive layer A/release liner].

[Examples 2 to 11, Comparative Examples 1 to 2]
A polarizing plate with a retardation layer was obtained in the same manner as in Example 1, except that each member was laminated to have the configuration shown in Table 1. The laminated retardation layer made of a resin film and the transfer of the retardation layer made of a liquid crystal alignment solidified layer from the substrate were performed via an ultraviolet-curable adhesive (thickness: about 1 μm). The transfer (lamination) was performed so that the slow axis of the λ/2 plate and the slow axis of the λ/4 plate were at 15° and 75° clockwise with respect to the absorption axis of the polarizer, respectively.

<Reflection hue evaluation>
An organic EL display device (manufactured by Samsung, product number "Galaxy A41") was disassembled to take out an organic EL panel. The release liner was peeled off from the retardation layer-attached polarizing plate obtained in the examples and comparative examples, and the exposed adhesive layer A was attached to this organic EL panel to prepare a measurement sample. Using a display measurement system (manufactured by Konica Minolta, "DMS505"), light was irradiated from the polarizing plate A side of the measurement sample, and the L ^* a ^* b ^* value (SCE method) was measured at an azimuth angle of 0° to 360° (in 15° increments) and a polar angle of 45°. Using the obtained L ^* a ^* b ^* value, the reflection hue ΔE00 was calculated according to the following formulas (1) to (7). The maximum value of ΔE00 obtained in each measurement is shown in Table 1. The smaller the value of ΔE00, the smaller the coloring due to reflection and the better the reflection hue.
(1) C ^* = √(a ^* ^2 + b ^* ^2)
(2) G = 0.5 x (1 - √((C ^* / 2) ^ 7 / ((C ^* / 2) ^ 7 + 25 ^ 7))
(3) a'=a ^* (1+G)
(4) C' = √(a'^2 + b ^* ^2)
(5) SL = 1 + 0.015 × (L ^* / 2 - 50) ^ 2 / √ (20 + (L ^* / 2 - 50) ^ 2)
(6) SC=1+0.045×C′/2
(7) ΔE00=√((L ^* /SL)^2+(C'/SC)^2)

<Metal corrosion evaluation>
A silver nanowire solution (manufactured by MERCK, nanowire size: diameter 115 nm, length 20 μm to 50 μm, isopropyl alcohol (IPA) solution with 0.5% solids) was applied to one side of a 50 μm polyethylene terephthalate (PET) film with a wire bar so that the wet film thickness was 15 μm, and dried in an oven at 100 ° C. for 5 minutes to form a silver nanowire coating film. Next, an overcoat solution (solids concentration: about 1%) containing 99 parts of methyl isobutyl ketone (MIBK), 1 part of pentaerythritol tetraacrylate (PETA), and 0.03 parts of a photopolymerization initiator (manufactured by BASF, product name "Irgacure 907") was applied to the surface of the silver nanowire coating film with a wire bar so that the wet film thickness was 10 μm, and dried in an oven at 100 ° C. for 5 minutes. The overcoat coating was then cured by irradiating it with active energy rays to produce a metal film having a structure of PET film/silver nanowire layer/overcoat layer (thickness 100 nm). This metal film was attached to a glass plate having a thickness of 0.5 mm using an adhesive (15 μm) to obtain a metal film/adhesive/glass plate laminate. The resistance value of the resulting laminate was measured using a non-contact resistance meter (manufactured by Napson, product name "EC-80"), and was found to be 50 Ω/□.

The release liner was peeled off from the retardation layer-attached polarizing plate obtained in the examples and comparative examples, and the laminate was attached to the overcoat layer surface of the metal film of the laminate via the exposed adhesive layer A to obtain a test sample. The resistance value of this test sample was measured with a non-contact resistance meter and was taken as the initial resistance value. Furthermore, the test sample was subjected to a reliability test (placed in an environment of 85°C and 85% RH for 7 hours, and then left in an environment of 23°C and 55% RH for 2 hours), and then the resistance value was measured in the same manner as above. The resistance value increase rate was calculated by the following formula. In addition, when the measured value (resistance value) exceeded the measurement limit (1000Ω/□) of the non-contact resistance meter, the measured value was assumed to be 1500Ω/□.
Resistance increase rate (%) = {(resistance after reliability test - initial resistance)/initial resistance} x 100
Furthermore, the evaluation was based on the following criteria:
Good: Resistance increase rate is less than 200%. Bad: Resistance increase rate is 200% or more.

As shown in Table 1, the retardation layer-attached polarizing plate of the embodiment in which at least one of the first retardation layer, the second retardation layer, and the third retardation layer is composed of a resin film has excellent anti-reflection properties and can suppress corrosion of metal members of an organic EL panel. In addition, the retardation layer-attached polarizing plates of Examples 1 to 9 in which the first retardation layer and the second retardation layer are composed of a liquid crystal alignment solidified layer and the third retardation layer is composed of a resin film have a thickness excluding the adhesive layer A of about 53 μm to about 71 μm, and are very thin. In addition, in a configuration in which a polarizer and a liquid crystal alignment solidified layer are adjacent to each other or a configuration in which two liquid crystal alignment solidified layers are adjacent to each other, components derived from the liquid crystal alignment solidified layer may migrate to the adjacent layer and change its optical properties, but such a problem can be prevented by arranging a retardation layer composed of a resin film between them. In addition, by arranging a retardation layer composed of a resin film between the adhesive layer and the liquid crystal alignment solidified layer, it is possible to prevent changes in the durability (adhesion) of the adhesive layer caused by the migration of components derived from the liquid crystal alignment solidified layer.

The polarizing plate with a retardation layer according to the embodiment of the present invention can be used, for example, in an image display device. Representative examples of the image display device include a liquid crystal display device, an organic EL display device, and an inorganic EL display device, and an organic EL display device is preferred.

REFERENCE SIGNS LIST 10 Polarizing plate 12 Polarizer 14 Protective layer 20 First retardation layer 30 Second retardation layer 40 Third retardation layer 50 Pressure-sensitive adhesive layer 100 Retardation layer-attached polarizing plate 200 Organic EL display device

Claims (12)

The polarizing plate includes a polarizer, a first retardation layer, and a second retardation layer, at least in this order.
Further, a third retardation layer is provided,
the first retardation layer and the second retardation layer have refractive index characteristics that satisfy the relationship of nx>ny≧nz,
The third retardation layer has a refractive index characteristic that exhibits a relationship of nz>nx=ny,
The first retardation layer has an Re(550) of 200 nm to 300 nm,
The second retardation layer has an Re(550) of 120 nm to 170 nm,
the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is 5° to 25°;
the angle between the slow axis of the second retardation layer and the absorption axis of the polarizer is 65° to 85°;
At least one of the first retardation layer, the second retardation layer, and the third retardation layer is made of a resin film.
Polarizing plate with retardation layer. The polarizing plate with a retardation layer according to claim 1, wherein the third retardation layer is made of a resin film. The polarizing plate with a retardation layer according to claim 1, wherein the polarizing plate includes the polarizer and a protective layer arranged only on the side of the polarizer opposite to the side on which the first retardation layer is arranged. The polarizing plate with a retardation layer according to claim 1, wherein the Rth(550) of the third retardation layer is -10 nm to -150 nm. The polarizing plate with a retardation layer according to claim 1, comprising at least the polarizing plate, the third retardation layer, the first retardation layer, and the second retardation layer, in this order. The polarizing plate with a retardation layer according to claim 5, wherein the Rth(550) of the third retardation layer is -20 nm to -150 nm. The polarizing plate with a retardation layer according to claim 1, comprising at least the polarizing plate, the first retardation layer, the third retardation layer, and the second retardation layer, in this order. The polarizing plate with a retardation layer according to claim 7, wherein the Rth(550) of the third retardation layer is -20 nm to -150 nm. The polarizing plate with a retardation layer according to claim 1, comprising at least the polarizing plate, the first retardation layer, the second retardation layer, and the third retardation layer, in this order. The polarizing plate with a retardation layer according to claim 9, wherein the Rth(550) of the third retardation layer is -20 nm to -150 nm. The polarizing plate with a retardation layer according to claim 1, which is used in an organic EL display device. An image display device comprising the retardation layer-attached polarizing plate according to claim 1 .

Images