JP6999059B2 - Polarizing plate with retardation layer and image display device using it - Google Patents

Description

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

In recent years, image display devices represented by liquid crystal displays and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly become widespread. A polarizing plate and a retardation plate are typically used in an image display device. Practically, a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1), and recently, there is a strong demand for thinner image display devices. As a result, there is an increasing demand for thinner polarizing plates with a retardation layer. Further, in recent years, there has been an increasing demand for a curved image display device and / or a bendable or bendable image display device, and further thinning and further flexibility are required for a polarizing plate and a polarizing plate with a retardation layer. ing. For the purpose of reducing the thickness of the polarizing plate with a retardation layer, the protective layer of the polarizing film and the retardation film, which greatly contribute to the thickness, are being thinned. However, when the protective layer and the retardation film are made thinner, the influence of the shrinkage of the polarizing film becomes relatively large, which causes problems such as warpage of the image display device and deterioration of operability of the polarizing plate with the retardation layer.

In order to solve the above problems, it is necessary to reduce the thickness of the polarizing film as well. However, if the thickness of the polarizing film is simply reduced, the optical characteristics are deteriorated. More specifically, one or both of the degree of polarization and the single transmittance, which are in a trade-off relationship, are reduced to a practically unacceptable degree. As a result, the optical characteristics of the polarizing plate with a retardation layer are also insufficient.

Japanese Patent No. 3325560

The present invention has been made to solve the above-mentioned conventional problems, and a main object thereof is to provide a polarizing plate with a retardation layer which is thin, has excellent handleability, and has excellent optical characteristics. ..

The polarizing plate with a retardation layer of the present invention has a polarizing plate including a polarizing film and a protective layer on at least one side of the polarizing film, and a retardation layer. The polarizing film is made of a polyvinyl alcohol-based resin film containing a dichroic substance, has a thickness of 8 μm or less, and has a ratio of an orthogonal absorbance A ₅₅₀ at a wavelength of 550 nm to an orthogonal absorbance A ₂₁₀ at a wavelength of 210 nm (A ₅₅₀ /). A ₂₁₀ ) is 1.4 to 3.5. The Re (550) of the retardation layer is 100 nm to 190 nm, and Re (450) / Re (550) is 0.8 or more and less than 1, the slow axis of the retardation layer and the absorption axis of the polarizing film. The angle between the two is 40 ° to 50 °.
In one embodiment, the protective layer is composed of a base material having an elastic modulus of 3000 MPa or more.
In one embodiment, from a resin film having a total thickness of the polarizing plate with a retardation layer of 90 μm or less, a specular hue of 3.5 or less, and a protective layer having an elastic modulus of 3000 MPa or more. It is composed.
In one embodiment, the protective layer is composed of a triacetyl cellulose-based resin film.
In one embodiment, the polarizing plate includes the polarizing film and the protective layer arranged only on one side of the polarizing film, and the retardation layer is the polarizing film via the pressure-sensitive adhesive layer. It is pasted on.
In one embodiment, the retardation layer is made of a polycarbonate resin film.
In one embodiment, the retardation layer is made of a polycarbonate resin film having a thickness of 40 μm or less.
In one embodiment, the ratio (A ₄₇₀ / A ₆₀₀ ) of the orthogonal absorbance A ₄₇₀ at a wavelength of 470 nm and the orthogonal absorbance A ₆₀₀ at a wavelength of 600 nm of the polarizing film is 0.7 to 2.00.
In one embodiment, the orthogonal b value of the polarizing film is greater than -10 and less than +10.
In one embodiment, the single transmittance of the polarizing film is 42.5% or more.
In one embodiment, the polarizing plate with a retardation layer further has another retardation layer outside the retardation layer, and the refractive index characteristic of the other retardation layer is nz> nx = ny. Show the relationship.
In one embodiment, the polarizing plate with a retardation layer further has a conductive layer or an isotropic substrate with a conductive layer on the outside of the retardation layer.
In one embodiment, the polarizing plate with a retardation layer has a long shape, the polarizing film has an absorption axis in the long direction, and the retardation layer has an absorption axis of 40 ° to more in the long direction. A diagonally stretched film having a slow axis in a direction forming an angle of 50 °. In one embodiment, the polarizing plate with a retardation layer is wound in a roll shape.
According to another aspect of the present invention, an image display device is provided. This image display device includes the above-mentioned polarizing plate with a retardation layer.
In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.

According to the present invention, addition of a halide (typically potassium iodide) to a polyvinyl alcohol (PVA) -based resin, two-stage stretching including air auxiliary stretching and water stretching, and drying and shrinkage by a heating roll. By adopting the above in combination, it is possible to obtain a polarizing film having extremely excellent optical characteristics while being thin. By using such a polarizing film, it is possible to realize a polarizing plate with a retardation layer, which is thin, has excellent handleability, and has excellent optical characteristics.

It is schematic cross-sectional view of the polarizing plate with a retardation layer by one Embodiment of this invention. It is schematic cross-sectional view of the polarizing plate with a retardation layer by another embodiment of this invention. It is a schematic diagram which shows an example of the drying shrinkage treatment using the heating roll in the manufacturing method of the polarizing film used for the polarizing plate with a retardation layer of this invention.

Hereinafter, embodiments of the present invention will be described, but the present invention is not limited to these embodiments.

(Definition of terms and symbols)
Definitions of terms and symbols herein are as follows.
(1) Refractive index (nx, ny, nz)
"Nx" is the refractive index in the direction in which the refractive index in the plane is maximized (that is, the slow-phase axis direction), and "ny" is the direction orthogonal to the slow-phase axis in the plane (that is, the phase-advancing axis direction). Is the refractive index of, and "nz" is the refractive index in the thickness direction.
(2) In-plane phase difference (Re)
“Re (λ)” is an in-plane phase difference measured with light having a wavelength of λ nm at 23 ° C. For example, "Re (550)" is an in-plane phase difference measured with light having a wavelength of 550 nm at 23 ° C. Re (λ) is obtained by the formula: Re (λ) = (nx−ny) × d, where d (nm) is the thickness of the layer (film).
(3) Phase difference in the thickness direction (Rth)
“Rth (λ)” is a phase difference in the thickness direction measured with light having a wavelength of λ nm at 23 ° C. For example, "Rth (550)" is a phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23 ° C. Rth (λ) is obtained 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 obtained by Nz = Rth / Re.
(5) Angle When referring to an angle herein, the angle includes both clockwise and counterclockwise with respect to the reference direction. Therefore, for example, "45 °" means ± 45 °.

A. Overall Configuration of Polarizing Plate with Difference Layer FIG. 1 is a schematic cross-sectional view of the polarizing plate with a retardation layer according to one embodiment of the present invention. The polarizing plate 100 with a retardation layer of the present embodiment has a polarizing plate 10 and a retardation layer 20. The polarizing plate 10 includes a polarizing film 11, a first protective layer 12 arranged on one side of the polarizing film 11, and a second protective layer 13 arranged on the other side of the polarizing film 11. .. Depending on the purpose, one of the first protective layer 12 and the second protective layer 13 may be omitted. For example, if the retardation layer 20 can also function as a protective layer for the polarizing film 11, the second protective layer 13 may be omitted. In the embodiment of the present invention, the polarizing film is composed of a polyvinyl alcohol-based resin film containing a dichroic substance. The thickness of the polarizing film is 8 μm or less, and the ratio of the orthogonal absorbance A ₅₅₀ at a wavelength of 550 nm to the orthogonal absorbance A ₂₁₀ at a wavelength of 210 nm (A ₅₅₀ / A ₂₁₀ ) is 1.4 to 3.5.

As shown in FIG. 2, in the polarizing plate 101 with a retardation layer according to another embodiment, another retardation layer 50 and / or a conductive layer or an isotropic base material 60 with a conductive layer may be provided. Another retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically provided on the outside of the retardation layer 20 (opposite to the polarizing plate 10). The other retardation layer typically shows a relationship in which the refractive index characteristics are nz> nx = ny. Another retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically provided in this order from the retardation layer 20 side. The other retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer are typically arbitrary layers provided as needed, and one or both of them may be omitted. For convenience, the retardation layer 20 may be referred to as a first retardation layer, and another retardation layer 50 may be referred to as a second retardation layer. When a conductive layer or an isotropic substrate with a conductive layer is provided, the polarizing plate with a retardation layer is a so-called inner in which a touch sensor is incorporated between an image display cell (for example, an organic EL cell) and the polarizing plate. It can be applied to a touch panel type input display device.

In the embodiment of the present invention, Re (550) of the first retardation layer 20 is 100 nm to 190 nm, and Re (450) / Re (550) is 0.8 or more and less than 1. Further, the angle formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizing film 11 is 40 ° to 50 °.

The above embodiments may be combined as appropriate, and the components of the above embodiments may be modified in a manner obvious in the art. For example, the configuration in which the isotropic base material 60 with a conductive layer is provided on the outside of the second retardation layer 50 is replaced with an optically equivalent configuration (for example, a laminate of the second retardation layer and the conductive layer). It is also good.

The polarizing plate with a retardation layer according to the embodiment of the present invention may further include another retardation layer. The optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, and the like of the other retardation layer can be appropriately set according to the purpose.

The polarizing plate with a retardation layer of the present invention may be single-wafered or elongated. As used herein, the term "long" means an elongated shape having a length sufficiently long with respect to the width, and for example, an elongated shape having a length of 10 times or more, preferably 20 times or more with respect to the width. include. The long polarizing plate with a retardation layer can be wound in a roll shape. When the polarizing plate with a retardation layer is elongated, the polarizing plate and the retardation layer are also elongated. In this case, the polarizing film preferably has an absorption axis in the longitudinal direction. The first retardation layer is preferably a diagonally stretched film having a slow axis in a direction forming an angle of 40 ° to 50 ° with respect to the elongated direction. If the polarizing film and the first retardation layer have such a configuration, a polarizing plate with a retardation layer can be manufactured by roll-to-roll.

Practically, an adhesive layer (not shown) is provided on the side opposite to the polarizing plate of the retardation layer, and the polarizing plate with the retardation layer can be attached to the image display cell. Further, it is preferable that a release film is temporarily attached to the surface of the pressure-sensitive adhesive layer until a polarizing plate with a retardation layer is used. Temporary attachment of the release film protects the pressure-sensitive adhesive layer and enables roll formation.

The specular hue (√ (a ^{* 2} + b ^{* 2} )) of the polarizing plate with a retardation layer is preferably 3.5 or less, and more preferably 3.0 or less. If the specular hue is within the above range, undesired coloring and the like are suppressed, and as a result, a polarizing plate with a retardation layer having excellent reflection characteristics can be obtained.

The total thickness of the polarizing plate with a retardation layer is preferably 140 μm or less, more preferably 120 μm or less, still more preferably 100 μm or less, still more preferably 90 μm or less, still more preferably 85 μm or less. be. The lower limit of the total thickness can be, for example, 30 μm. According to the embodiment of the present invention, it is possible to realize such an extremely thin polarizing plate with a retardation layer. Such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Such a polarizing plate with a retardation layer may be particularly preferably applied to a curved image display device and / or a bendable or bendable image display device. The total thickness of the polarizing plate with a retardation layer constitutes the polarizing plate with a retardation layer, excluding the pressure-sensitive adhesive layer for bringing the polarizing plate with a retardation layer into close contact with an external adherend such as a panel or glass. The total thickness of all layers (that is, the total thickness of the polarizing plate with a retardation layer is provisionally applied to the pressure-sensitive adhesive layer for attaching the polarizing plate with a retardation layer to an adjacent member such as an image display cell and its surface. Does not include the thickness of the release film that can be worn).

Hereinafter, the components of the polarizing plate with a retardation layer will be described in more detail.

B. Polarizing plate B-1. Polarizing film As described above, the polarizing film 11 has a thickness of 8 μm or less, and the ratio (A ₅₅₀ / A ₂₁₀ ) of the orthogonal absorbance A ₅₅₀ at a wavelength of 550 nm to the orthogonal absorbance A ₂₁₀ at a wavelength of 210 nm is 1.4 to 3. It is 5. The polarizing film used in the present invention has a very large ratio (A ₅₅₀ / A ₂₁₀ ) as compared with a normal thin polarizing film, and in one embodiment, the ratio (A ₄₇₀ / A ₆₀₀ ) is also very large. This is because the content ratio of iodine ions (having absorption in the ultraviolet region near 210 nm) that do not form a complex with PVA in the polarizing film is very small, and the content ratio of PVA-iodine complex (having absorption in the visible region). Means that is very large. More specifically, the polarizing film has a very large content ratio of PVA-I ₅ ^- complex having absorption near 600 nm, and a large content ratio of PVA-I ₃ ^- complex having absorption near 480 nm. It is maintained without decreasing. Here, since the thickness of the polarizing film means the length of the optical path length, if the thickness of the polarizing film is simply reduced, the optical path length is shortened and the polarizing performance is also deteriorated. Since the amount of iodine that can be contained in the polarizing film is limited, it is essential to efficiently utilize the iodine contained in the polarizing film in order to achieve both high polarization performance and thinning of the polarizing film. In other words, by reducing iodine ions that have absorption in the ultraviolet and do not contribute to polarization performance, and by improving the ratio of PVA-iodine complexes that have absorption in the visible region, both high polarization performance and thinning of the polarizing film can be achieved. Will be possible. In other words, by increasing the ratio (A ₅₅₀ / A ₂₁₀ ), it is possible to achieve thinness and high optical characteristics. Furthermore, by maintaining the ratio (A ₄₇₀ / A ₆₀₀ ) above a predetermined value, good polarization performance can be realized over the entire visible light range. Given the limited amount of iodine in thin polarizing films, it has been difficult to increase both the ratio (A ₅₅₀ / A ₂₁₀ ) and the ratio (A ₄₇₀ / A ₆₀₀ ) with conventional techniques. The polarizing film used in the above can increase both of these. The ratio (A ₅₅₀ / A ₂₁₀ ) is preferably 1.8 or more, more preferably 2.0 or more, and even more preferably 2.2 or more. The upper limit of the ratio (A ₅₅₀ / A ₂₁₀ ) can be, for example, 3.5. Further, the ratio (A ₄₇₀ / A ₆₀₀ ) is typically 0.7 or more, preferably 0.75 or more, more preferably 0.80 or more, still more preferably 0.85 or more. be. The upper limit of the ratio (A ₄₇₀ / A ₆₀₀ ) is, for example, 2.00, preferably 1.33. The orthogonal absorbance is determined by the following formula based on the orthogonal transmittance Tc measured when determining the degree of polarization described later.
Orthogonal absorbance = log10 (100 / Tc)
It is one of the features of the present invention to use a thin polarizing film having such characteristics.

The thickness of the polarizing film is preferably 1 μm to 8 μm, more preferably 1 μm to 7 μm, further preferably 2 μm to 5 μm, particularly preferably 2 μm to 4 μm, and particularly preferably 2 μm to 3 μm.

The polarizing film preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm. The simple substance transmittance of the polarizing film is preferably 46.0% or less, more preferably 45.0% or less. On the other hand, the single transmittance is preferably 41.5% or more, more preferably 42.0% or more, and further preferably 42.5% or more. The degree of polarization of the polarizing film is preferably 99.990% or more, and preferably 99.998% or less. The single transmittance is typically a Y value measured with an ultraviolet-visible spectrophotometer and corrected for luminosity factor. The degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured by using an ultraviolet-visible spectrophotometer and corrected for luminosity factor.
Degree of polarization (%) = {(Tp-Tc) / (Tp + Tc)} ^1/2 × 100

In one embodiment, the transmittance of a thin polarizing film having a thickness of 8 μm or less is typically a lamination of a polarizing film (refractive index on the surface: 1.53) and a protective film (refractive index: 1.50). It is measured using an ultraviolet-visible spectrophotometer with the body as the measurement target. Depending on the refractive index of the surface of the polarizing film and / or the refractive index of the surface in contact with the air interface of the protective film, the reflectance at the interface of each layer may change, and as a result, the measured value of the transmittance may change. .. Therefore, for example, when a protective film having a refractive index of not 1.50 is used, the measured value of the transmittance may be corrected according to the refractive index of the surface of the protective film in contact with the air interface. Specifically, the transmittance correction value C is expressed by the following equation using the reflectance _R1 (transmittance axis reflectance) of the polarized light parallel to the transmission axis at the interface between the protective film and the air layer.
C = R ₁ -R ₀
R ₀ = ((1.50-1) ² / (1.50 + 1) ² ) × (T _1/100 )
R ₁ = ((n 1-1) ² / (n _{1 +1} ) ² ) × (T _1/100 )
Here, R ₀ is the transmittance of the transmission axis when a protective film having a refractive index of 1.50 is used, n ₁ is the refractive index of the protective film used, and T ₁ is the transmittance of the polarizing film. Is. For example, when a base material having a surface refractive index of 1.53 (a cycloolefin-based film, a film with a hard coat layer, etc.) is used as a protective film, the correction amount C is about 0.2%. In this case, by adding 0.2% to the transmittance obtained by the measurement, the transmittance when a polarizing film having a surface refractive index of 1.53 is used and a protective film having a refractive index of 1.50 is used. It can be converted into a rate. According to the calculation based on the above equation, the amount of change in the correction value C when the transmittance T ₁ of the polarizing film is changed by 2% is 0.03% or less, and the transmittance of the polarizing film is the correction value C. The effect on the value of is limited. Further, when the protective film has absorption other than surface reflection, appropriate correction can be performed according to the absorption amount.

Further, the orthogonal b value of the polarizing film is, for example, greater than -10, preferably -7 or more, and more preferably -5 or more. The orthogonal b value is preferably +10 or less, and more preferably +5 or less. The orthogonal b value indicates the hue when the polarizing film (eventually, the polarizing plate with a retardation layer) is arranged in an orthogonal state, and the larger the absolute value of this numerical value, the more the orthogonal hue (black in the image display device). Display) means that it looks tinted. For example, when the orthogonal b value is as low as −10 or less, the black display appears to be colored blue, and the display performance is deteriorated. That is, according to the embodiment of the present invention, it is possible to obtain a polarizing plate with a retardation layer that can realize an excellent hue when displaying black. The orthogonal b value can be measured by a spectrophotometer typified by V-7100.

As the polarizing film, any suitable polarizing film may be adopted. The polarizing film can be typically made by using a laminated body having two or more layers.

Specific examples of the polarizing film obtained by using the laminated body include a polarizing film obtained by using a laminated body of a resin base material and a PVA-based resin layer coated and formed on the resin base material. The polarizing film obtained by using the laminate of the resin base material and the PVA-based resin layer coated and formed on the resin base material is, for example, a resin base material obtained by applying a PVA-based resin solution to the resin base material and drying it. A PVA-based resin layer is formed on the PVA-based resin layer to obtain a laminate of a resin base material and a PVA-based resin layer; the laminate is stretched and dyed to obtain a PVA-based resin layer as a polarizing film; obtain. In the present embodiment, stretching typically includes immersing the laminate in an aqueous boric acid solution for stretching. Further, stretching may further comprise, if necessary, stretching the laminate in the air at a high temperature (eg, 95 ° C. or higher) prior to stretching in boric acid aqueous solution. The obtained laminated body of the resin base material / polarizing film may be used as it is (that is, the resin base material may be used as the protective layer of the polarizing film), and the resin base material is peeled off from the laminated body of the resin base material / polarizing film. Then, an arbitrary appropriate protective layer according to the purpose may be laminated on the peeled surface and used. Details of the method for producing such a polarizing film are described in, for example, Japanese Patent Application Laid-Open No. 2012-73580. The entire description of the publication is incorporated herein by reference.

Typically, a method for producing a polarizing film is to form a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin base material to form a laminate. Further, the laminated body is subjected to an aerial auxiliary stretching treatment, a dyeing treatment, an underwater stretching treatment, and a drying shrinkage treatment in which the laminate is shrunk by 2% or more in the width direction by heating while being conveyed in the longitudinal direction. including. This can provide a polarizing film having excellent optical properties, having a thickness of 8 μm or less and a ratio (A ₅₅₀ / A ₂₁₀ ) of 1.4 to 3.5. That is, by introducing the auxiliary stretching, even when PVA is applied on the thermoplastic resin, the crystallinity of PVA can be enhanced and high optical characteristics can be achieved. At the same time, by increasing the orientation of PVA in advance, it is possible to prevent problems such as deterioration of PVA orientation and dissolution when immersed in water in a subsequent dyeing step or stretching step, and high optical characteristics. Will be possible to achieve. Further, when the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecule and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical characteristics of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as a dyeing treatment and a stretching treatment in water. Further, the optical characteristics can be improved by shrinking the laminated body in the width direction by the drying shrinkage treatment.

B-2. Protective Layer The first protective layer 12 and the second protective layer 13 are each formed of any suitable film that can be used as a protective layer for a polarizing film. Specific examples of the material that is the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and polysulfone-based. , Polyester-based, polycarbonate-based, polyolefin-based, (meth) acrylic-based, acetate-based transparent resins and the like. Further, thermosetting resins such as (meth) acrylic, urethane, (meth) acrylic urethane, epoxy, and silicone, or ultraviolet curable resins can also be mentioned. In addition to this, for example, glassy polymers such as siloxane-based polymers can also be mentioned. Further, the polymer film described in JP-A-2001-343529 (WO01 / 37007) can also be used. As the material of this film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain. Can be used, and examples thereof include a resin composition having an alternating copolymer composed of isobutene and N-methylmaleimide and an acrylonitrile / styrene copolymer. The polymer film can be, for example, an extruded product of the above resin composition. In one embodiment, the protective layer (particularly, the protective layer on the visual side) contains a TAC resin. By using a TAC resin film as the protective layer, bending durability can be improved.

As will be described later, the polarizing plate with a retardation layer of the present invention is typically arranged on the visible side of an image display device, and the first protective layer 12 is typically arranged on the visible side thereof. Therefore, the first protective layer 12 may be subjected to surface treatment such as hard coat treatment, antireflection treatment, anti-sticking treatment, and anti-glare treatment, if necessary. Further / or, if necessary, the first protective layer 12 is provided with a process for improving visibility when visually recognizing through polarized sunglasses (typically, a (elliptical) circular polarization function is imparted. (To give an ultra-high phase difference) may be applied. By performing such processing, excellent visibility can be realized even when the display screen is visually recognized through a polarizing lens such as polarized sunglasses. Therefore, the polarizing plate with a retardation layer can be suitably applied to an image display device that can be used outdoors.

The thickness of the first protective layer is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, and even more preferably 10 μm to 35 μm. When the surface treatment is applied, the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.

The second protective layer 13 is preferably optically isotropic in one embodiment. As used herein, "optically isotropic" means that the in-plane retardation Re (550) is 0 nm to 10 nm and the thickness direction retardation Rth (550) is -10 nm to +10 nm. say. The second protective layer 13 may, in one embodiment, be a retardation layer having any suitable retardation value. In this case, the in-plane retardation Re (550) of the retardation layer is, for example, 110 nm to 150 nm. The thickness of the second protective layer is preferably 5 μm to 80 μm, more preferably 10 μm to 40 μm, and even more preferably 10 μm to 30 μm. From the viewpoint of thinning and weight reduction, preferably, the second protective layer may be omitted.

B-3. Method for manufacturing a polarizing film The polarizing film is, for example, a polyvinyl alcohol-based resin layer (PVA-based resin layer) containing a halide and a polyvinyl alcohol-based resin (PVA-based resin) on one side of a long thermoplastic resin base material. To form a laminate, and to shrink the laminate by 2% or more in the width direction by heating it while transporting it in the longitudinal direction, including an aerial auxiliary stretching treatment, a dyeing treatment, and an underwater stretching treatment. It can be produced by a method including shrinking treatment and applying in this order. The content of the halide in the PVA-based resin layer is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin. The drying shrinkage treatment is preferably performed using a heating roll, and the temperature of the heating roll is preferably 60 ° C to 120 ° C. The shrinkage ratio in the width direction of the laminated body by the dry shrinkage treatment is preferably 2% or more. According to such a manufacturing method, the polarizing film described in the above section B-1 can be obtained. In particular, by preparing a laminate containing a PVA-based resin layer containing a halide, stretching the laminate to multi-step stretching including aerial auxiliary stretching and underwater stretching, and heating the stretched laminate with a heating roll. , It is possible to obtain a polarizing film having excellent optical properties (typically, a single transmittance and a ratio (A ₅₅₀ / A ₂₁₀ )).

B-3-1. Preparation of Laminate As a method for preparing a laminate of a thermoplastic resin base material and a PVA-based resin layer, any appropriate method can be adopted. Preferably, a coating liquid containing a halide and a PVA-based resin is applied to the surface of the thermoplastic resin base material and dried to form a PVA-based resin layer on the thermoplastic resin base material. As described above, the content of the halide in the PVA-based resin layer is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.

Any appropriate method can be adopted as the coating method of the coating liquid. For example, a roll coating method, a spin coating method, a wire bar coating method, a dip coating method, a die coating method, a curtain coating method, a spray coating method, a knife coating method (comma coating method, etc.) and the like can be mentioned. The coating / drying temperature of the coating liquid is preferably 50 ° C. or higher.

The thickness of the PVA-based resin layer is preferably 3 μm to 40 μm, more preferably 3 μm to 20 μm.

Before forming the PVA-based resin layer, the thermoplastic resin base material may be surface-treated (for example, corona treatment or the like), or the easy-adhesive layer may be formed on the thermoplastic resin base material. By performing such a treatment, the adhesion between the thermoplastic resin base material and the PVA-based resin layer can be improved.

B-3-1-1. Thermoplastic resin base material The thickness of the thermoplastic resin base material is preferably 20 μm to 300 μm, more preferably 50 μm to 200 μm. If it is less than 20 μm, it may be difficult to form a PVA-based resin layer. If it exceeds 300 μm, for example, in the underwater stretching treatment described later, it may take a long time for the thermoplastic resin base material to absorb water, and an excessive load may be required for stretching.

The thermoplastic resin base material preferably has a water absorption rate of 0.2% or more, more preferably 0.3% or more. The thermoplastic resin base material absorbs water, and the water can act as a plasticizer to plasticize. As a result, the drawing stress can be significantly reduced, and the drawing can be performed at a high magnification. On the other hand, the water absorption rate of the thermoplastic resin base material is preferably 3.0% or less, more preferably 1.0% or less. By using such a thermoplastic resin base material, it is possible to prevent problems such as deterioration of the appearance of the obtained polarizing film due to a significant decrease in the dimensional stability of the thermoplastic resin base material during production. Further, it is possible to prevent the base material from breaking during stretching in water and the PVA-based resin layer from being peeled off from the thermoplastic resin base material. The water absorption rate of the thermoplastic resin base material can be adjusted, for example, by introducing a modifying group into the constituent material. The water absorption rate is a value obtained according to JIS K 7209.

The glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 120 ° C. or lower. By using such a thermoplastic resin base material, it is possible to sufficiently secure the stretchability of the laminated body while suppressing the crystallization of the PVA-based resin layer. Further, considering that the thermoplastic resin base material is plasticized with water and well stretched in water, the temperature is more preferably 100 ° C. or lower, more preferably 90 ° C. or lower. On the other hand, the glass transition temperature of the thermoplastic resin base material is preferably 60 ° C. or higher. By using such a thermoplastic resin base material, the thermoplastic resin base material is deformed (for example, unevenness, tarmi, wrinkles, etc.) when the coating liquid containing the PVA-based resin is applied and dried. It is possible to satisfactorily produce a laminated body by preventing the above-mentioned problems. Further, the PVA-based resin layer can be well stretched at a suitable temperature (for example, about 60 ° C.). The glass transition temperature of the thermoplastic resin base material can be adjusted, for example, by heating with a crystallization material that introduces a modifying group into the constituent material. The glass transition temperature (Tg) is a value obtained according to JIS K 7121.

As the constituent material of the thermoplastic resin base material, any suitable thermoplastic resin can be adopted. Examples of the thermoplastic resin include ester resins such as polyethylene terephthalate resins, cycloolefin resins such as norbornene resins, olefin resins such as polypropylene, polyamide resins, polycarbonate resins, and copolymer resins thereof. Can be mentioned. Among these, norbornene-based resin and amorphous polyethylene terephthalate-based resin are preferable.

In one embodiment, an amorphous (non-crystallized) polyethylene terephthalate resin is preferably used. Among them, an amorphous (difficult to crystallize) polyethylene terephthalate resin is particularly preferably used. Specific examples of the amorphous polyethylene terephthalate resin include a copolymer further containing isophthalic acid and / or a cyclohexanedicarboxylic acid as a dicarboxylic acid, and a copolymer further containing cyclohexanedimethanol or diethylene glycol as a glycol.

In a preferred embodiment, the thermoplastic resin substrate is composed of a polyethylene terephthalate resin having an isophthalic acid unit. This is because such a thermoplastic resin base material is extremely excellent in stretchability and can suppress crystallization during stretching. It is considered that this is because the introduction of the isophthalic acid unit gives a large bending to the main chain. The polyethylene terephthalate resin has a terephthalic acid unit and an ethylene glycol unit. The content ratio of the isophthalic acid unit is preferably 0.1 mol% or more, more preferably 1.0 mol% or more, based on the total of all repeating units. This is because a thermoplastic resin base material having extremely excellent stretchability can be obtained. On the other hand, the content ratio of the isophthalic acid unit is preferably 20 mol% or less, more preferably 10 mol% or less, based on the total of all repeating units. By setting such a content ratio, the crystallinity can be satisfactorily increased in the drying shrinkage treatment described later.

The thermoplastic resin base material may be stretched in advance (before forming the PVA-based resin layer). In one embodiment, the elongated thermoplastic resin substrate is laterally stretched. The lateral direction is preferably a direction orthogonal to the stretching direction of the laminate described later. In addition, in this specification, "orthogonal" includes a case where it is substantially orthogonal. Here, "substantially orthogonal" includes the case of 90 ° ± 5.0 °, preferably 90 ° ± 3.0 °, and more preferably 90 ° ± 1.0 °.

The stretching temperature of the thermoplastic resin base material is preferably Tg −10 ° C. to Tg + 50 ° C. with respect to the glass transition temperature (Tg). The draw ratio of the thermoplastic resin base material is preferably 1.5 to 3.0 times.

Any suitable method can be adopted as the method for stretching the thermoplastic resin base material. Specifically, it may be fixed-end stretching or free-end stretching. The stretching method may be a dry method or a wet method. The stretching of the thermoplastic resin base material may be carried out in one step or in multiple steps. When performed in multiple stages, the above-mentioned draw ratio is the product of the draw ratios of each stage.

B-3-1-2. Coating liquid The coating liquid contains a halide and a PVA-based resin as described above. The coating liquid is typically a solution in which the halide and the PVA-based resin are dissolved in a solvent. Examples of the solvent include water, dimethyl sulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, polyhydric alcohols such as trimethylolpropane, and amines such as ethylenediamine and diethylenetriamine. These can be used alone or in combination of two or more. Among these, water is preferable. The PVA-based resin concentration of the solution is preferably 3 parts by weight to 20 parts by weight with respect to 100 parts by weight of the solvent. With such a resin concentration, it is possible to form a uniform coating film in close contact with the thermoplastic resin base material. The content of the halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin.

Additives may be added to the coating liquid. Examples of the additive include a plasticizer, a surfactant and the like. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. Examples of the surfactant include nonionic surfactants. These can be used for the purpose of further improving the uniformity, dyeability, and stretchability of the obtained PVA-based resin layer.

As the PVA-based resin, any suitable resin can be adopted. For example, polyvinyl alcohol and ethylene-vinyl alcohol copolymers can be mentioned. Polyvinyl alcohol is obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer is obtained by saponifying the ethylene-vinyl acetate copolymer. The saponification degree of the PVA-based resin is usually 85 mol% to 100 mol%, preferably 95.0 mol% to 99.95 mol%, and more preferably 99.0 mol% to 99.93 mol%. .. The degree of saponification can be determined according to JIS K 6726-1994. By using a PVA-based resin having such a saponification degree, a polarizing film having excellent durability can be obtained. If the degree of saponification is too high, gelation may occur.

The average degree of polymerization of the PVA-based resin can be appropriately selected depending on the intended purpose. The average degree of polymerization is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. The average degree of polymerization can be determined according to JIS K 6726-1994.

As the halide, any suitable halide can be adopted. For example, iodide and sodium chloride can be mentioned. Iodides include, for example, potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferable.

The amount of the halide in the coating liquid is preferably 5 parts by weight to 20 parts by weight with respect to 100 parts by weight of the PVA-based resin, and more preferably 10 parts by weight to 15 parts by weight with respect to 100 parts by weight of the PVA-based resin. It is a department. If the amount of the halide exceeds 20 parts by weight with respect to 100 parts by weight of the PVA-based resin, the halide may bleed out and the finally obtained polarizing film may become cloudy.

Generally, the stretching of the PVA-based resin layer increases the orientation of the polyvinyl alcohol molecules in the PVA-based resin. However, when the stretched PVA-based resin layer is immersed in a liquid containing water, the polyvinyl alcohol molecules become more oriented. The orientation may be disturbed and the orientation may decrease. In particular, when the laminate of the thermoplastic resin base material and the PVA-based resin layer is stretched in boric acid water, the laminate is stretched in boric acid water at a relatively high temperature in order to stabilize the stretching of the thermoplastic resin base material. In the case of stretching, the tendency of the degree of orientation to decrease is remarkable. For example, while stretching a PVA film alone in boric acid water is generally performed at 60 ° C., stretching of a laminate of A-PET (thermoplastic resin base material) and a PVA-based resin layer is performed. It is carried out at a high temperature of about 70 ° C., and in this case, the orientation of PVA at the initial stage of stretching may decrease before it is increased by stretching in water. On the other hand, by preparing a laminate of a PVA-based resin layer containing a halide and a thermoplastic resin base material, and stretching the laminate in air at a high temperature (auxiliary stretching) before stretching it in boric acid water. , Crystallization of the PVA-based resin in the PVA-based resin layer of the laminated body after the auxiliary stretching can be promoted. As a result, when the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecule and the decrease in the orientation can be suppressed as compared with the case where the PVA-based resin layer does not contain a halide. This makes it possible to improve the optical characteristics of the polarizing film obtained through a treatment step of immersing the laminate in a liquid, such as a dyeing treatment and a stretching treatment in water.

B-3-2. Aerial auxiliary stretching treatment In particular, in order to obtain high optical properties, a two-stage stretching method that combines dry stretching (auxiliary stretching) and boric acid water stretching is selected. By introducing auxiliary stretching as in the case of two-stage stretching, it is possible to stretch while suppressing the crystallization of the thermoplastic resin base material, and excessive crystallization of the thermoplastic resin base material in the subsequent stretching in boric acid water. This solves the problem that the stretchability is lowered, and the laminated body can be stretched at a higher magnification. Furthermore, when the PVA-based resin is applied on the thermoplastic resin base material, it is compared with the case where the PVA-based resin is applied on a normal metal drum in order to suppress the influence of the glass transition temperature of the thermoplastic resin base material. Therefore, it is necessary to lower the coating temperature, and as a result, the crystallization of the PVA-based resin becomes relatively low, which may cause a problem that sufficient optical characteristics cannot be obtained. On the other hand, by introducing auxiliary stretching, it is possible to improve the crystallinity of the PVA-based resin even when the PVA-based resin is applied on the thermoplastic resin, and it is possible to achieve high optical characteristics. Become. At the same time, by increasing the orientation of the PVA-based resin in advance, it is possible to prevent problems such as deterioration and dissolution of the orientation of the PVA-based resin when immersed in water in a subsequent dyeing step or stretching step. , It becomes possible to achieve high optical characteristics.

The stretching method of the aerial auxiliary stretching may be fixed-end stretching (for example, a method of stretching using a tenter stretching machine) or free-end stretching (for example, a method of uniaxial stretching through a laminate between rolls having different peripheral speeds). Although good, free-end stretching can be positively adopted in order to obtain high optical properties. In one embodiment, the aerial stretching treatment includes a heating roll stretching step of stretching the laminate by the difference in peripheral speed between the heating rolls while transporting the laminated body in the longitudinal direction thereof. The aerial stretching treatment typically includes a zone stretching step and a heating roll stretching step. The order of the zone stretching step and the heating roll stretching step is not limited, and the zone stretching step may be performed first, or the heating roll stretching step may be performed first. The zone stretching step may be omitted. In one embodiment, the zone stretching step and the heating roll stretching step are performed in this order. Further, in another embodiment, in the tenter stretching machine, the film is stretched by grasping the end portion of the film and widening the distance between the tenters in the flow direction (the widening of the distance between the tenters is the stretching ratio). At this time, the distance of the tenter in the width direction (perpendicular to the flow direction) is set to approach arbitrarily. Preferably, it can be set to be closer to the free end stretch with respect to the stretch ratio in the flow direction. In the case of free end stretching, it is calculated by shrinkage rate in the width direction = (1 / stretching ratio) ^1/2 .

The aerial auxiliary stretching may be performed in one step or in multiple steps. When performed in multiple stages, the draw ratio is the product of the draw ratios in each stage. The stretching direction in the aerial auxiliary stretching is preferably substantially the same as the stretching direction in the underwater stretching.

The draw ratio in the aerial auxiliary stretching is preferably 2.0 to 3.5 times. The maximum draw ratio when the aerial auxiliary stretching and the underwater stretching are combined is preferably 5.0 times or more, more preferably 5.5 times or more, still more preferably 6.0 times with respect to the original length of the laminated body. That is all. In the present specification, the "maximum draw ratio" means the draw ratio immediately before the laminate breaks, and separately confirms the draw ratio at which the laminate breaks, and means a value 0.2 lower than that value.

The stretching temperature of the aerial auxiliary stretching can be set to an arbitrary appropriate value depending on the forming material of the thermoplastic resin base material, the stretching method, and the like. The stretching temperature is preferably the glass transition temperature (Tg) or higher of the thermoplastic resin base material, more preferably the glass transition temperature (Tg) of the thermoplastic resin base material (Tg) + 10 ° C. or higher, and particularly preferably Tg + 15 ° C. or higher. On the other hand, the upper limit of the stretching temperature is preferably 170 ° C. By stretching at such a temperature, it is possible to suppress the rapid progress of crystallization of the PVA-based resin and suppress defects due to the crystallization (for example, hindering the orientation of the PVA-based resin layer due to stretching). can. The crystallization index of the PVA-based resin after the auxiliary stretching in the air is preferably 1.3 to 1.8, and more preferably 1.4 to 1.7. The crystallization index of the PVA-based resin can be measured by the ATR method using a Fourier transform infrared spectrophotometer. Specifically, the measurement is carried out using the polarized light as the measurement light, and the crystallization index is calculated according to the following formula using the intensities of 1141 cm ^-1 and 1440 cm ^-1 of the obtained spectra.
_{Crystallization} index = (IC / _IR )
However,
IC: _Intensity of 1141 cm ^{-1 when measured by incident measurement light IR: Intensity of 1440 cm -1} _when ^measured by incident measurement light.

B-3-3. Insolubilization treatment If necessary, an insolubilization treatment is performed after the aerial auxiliary stretching treatment and before the underwater stretching treatment or the dyeing treatment. The insolubilization treatment is typically performed by immersing a PVA-based resin layer in a boric acid aqueous solution. By performing the insolubilization treatment, it is possible to impart water resistance to the PVA-based resin layer and prevent the orientation of PVA from deteriorating when immersed in water. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight with respect to 100 parts by weight of water. The liquid temperature of the insolubilizing bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C.

B-3-4. Dyeing treatment The dyeing treatment is typically performed by dyeing the PVA-based resin layer with a dichroic substance (typically iodine). Specifically, it is carried out by adsorbing iodine on the PVA-based resin layer. Examples of the adsorption method include a method of immersing a PVA-based resin layer (laminate) in a dyeing solution containing iodine, a method of applying the dyeing solution to the PVA-based resin layer, and a method of applying the dyeing solution to the PVA-based resin layer. Examples include a method of spraying. A method of immersing the laminate in a dyeing solution (dyeing bath) is preferable. This is because iodine can be adsorbed well.

The stain solution is preferably an aqueous iodine solution. The blending amount of iodine is preferably 0.05 part by weight to 0.5 part by weight with respect to 100 parts by weight of water. In order to increase the solubility of iodine in water, it is preferable to add iodide to the aqueous iodine solution. Examples of iodide include potassium iodide, lithium iodide, sodium iodide, zinc iodide, aluminum iodide, lead iodide, copper iodide, barium iodide, calcium iodide, tin iodide, and titanium iodide. And so on. Among these, potassium iodide is preferable. The blending amount of the iodide is preferably 0.1 part by weight to 10 parts by weight, and more preferably 0.3 part by weight to 5 parts by weight with respect to 100 parts by weight of water. The liquid temperature at the time of dyeing the dyeing liquid is preferably 20 ° C. to 50 ° C. in order to suppress the dissolution of the PVA-based resin. When the PVA-based resin layer is immersed in the dyeing solution, the immersion time is preferably 5 seconds to 5 minutes, more preferably 30 seconds to 90 seconds in order to secure the transmittance of the PVA-based resin layer.

The dyeing conditions (concentration, liquid temperature, immersion time) can be set so that the single transmittance and the ratio (A ₅₅₀ / A ₂₁₀ ) of the finally obtained polarizing film become desired values. As such a dyeing condition, an iodine aqueous solution is preferably used as the dyeing solution, and the ratio of the iodine and potassium iodide contents in the iodine aqueous solution is set to 1: 5 to 1:20. The ratio of the iodine and potassium iodide contents in the iodine aqueous solution is preferably 1: 5 to 1:10. As a result, a polarizing film having the above optical characteristics can be obtained.

When the dyeing treatment is continuously performed after the treatment of immersing the laminate in the treatment bath containing boric acid (typically, the insolubilization treatment), the boric acid contained in the treatment bath is mixed in the dyeing bath. The boric acid concentration in the dyeing bath may change over time, resulting in unstable dyeability. In order to suppress the destabilization of dyeability as described above, the upper limit of the boric acid concentration in the dyeing bath is preferably 4 parts by weight, more preferably 2 parts by weight, based on 100 parts by weight of water. It will be adjusted. On the other hand, the lower limit of the boric acid concentration in the dyeing bath is preferably 0.1 part by weight, more preferably 0.2 part by weight, still more preferably 0.5 part by weight with respect to 100 parts by weight of water. Is. In one embodiment, the dyeing process is performed using a dyeing bath containing boric acid in advance. Thereby, the rate of change in the boric acid concentration when the boric acid in the treatment bath is mixed in the dyeing bath can be reduced. The amount of boric acid previously blended in the dyeing bath (that is, the content of boric acid not derived from the above-mentioned treatment bath) is preferably 0.1 part by weight to 2 parts by weight with respect to 100 parts by weight of water. , More preferably 0.5 parts by weight to 1.5 parts by weight.

B-3-5. Cross-linking treatment If necessary, carry out a cross-linking treatment after the dyeing treatment and before the underwater stretching treatment. The cross-linking treatment is typically performed by immersing a PVA-based resin layer in an aqueous boric acid solution. By performing the cross-linking treatment, water resistance can be imparted to the PVA-based resin layer, and the orientation of PVA can be prevented from being lowered when immersed in high-temperature water by subsequent stretching in water. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 5 parts by weight with respect to 100 parts by weight of water. Further, when the cross-linking treatment is performed after the dyeing treatment, it is preferable to further add iodide. By blending iodide, the elution of iodine adsorbed on the PVA-based resin layer can be suppressed. The blending amount of iodide is preferably 1 part by weight to 5 parts by weight with respect to 100 parts by weight of water. Specific examples of iodide are as described above. The liquid temperature of the cross-linked bath (boric acid aqueous solution) is preferably 20 ° C to 50 ° C.

B-3-6. Underwater stretching treatment The underwater stretching treatment is performed by immersing the laminate in a stretching bath. According to the underwater stretching treatment, the thermoplastic resin base material or the PVA-based resin layer can be stretched at a temperature lower than the glass transition temperature (typically, about 80 ° C.), and the PVA-based resin layer is crystallized. It is possible to stretch at a high magnification while suppressing the above. As a result, a polarizing film having excellent optical characteristics can be manufactured.

Any suitable method can be adopted as the stretching method of the laminated body. Specifically, it may be fixed-end stretching or free-end stretching (for example, a method of uniaxial stretching through a laminate between rolls having different peripheral speeds). Preferably, free-end stretching is selected. The stretching of the laminate may be carried out in one step or in multiple steps. In the case of performing in multiple stages, the draw ratio (maximum draw ratio) of the laminated body described later is the product of the draw ratios of each stage.

The underwater stretching is preferably carried out by immersing the laminate in a boric acid aqueous solution (boric acid water stretching). By using the boric acid aqueous solution as the stretching bath, it is possible to impart rigidity to withstand the tension applied during stretching and water resistance that does not dissolve in water to the PVA-based resin layer. Specifically, boric acid can generate a tetrahydroxyboric acid anion in an aqueous solution and crosslink with a PVA-based resin by hydrogen bonding. As a result, the PVA-based resin layer can be imparted with rigidity and water resistance, can be stretched satisfactorily, and a polarizing film having excellent optical characteristics can be produced.

The boric acid aqueous solution is preferably obtained by dissolving boric acid and / or borate in water as a solvent. The boric acid concentration is preferably 1 part by weight to 10 parts by weight, more preferably 2.5 parts by weight to 6 parts by weight, and particularly preferably 3 parts by weight to 5 parts by weight with respect to 100 parts by weight of water. Is. By setting the boric acid concentration to 1 part by weight or more, the dissolution of the PVA-based resin layer can be effectively suppressed, and a polarizing film having higher characteristics can be produced. In addition to boric acid or borate, an aqueous solution obtained by dissolving a boron compound such as borax, glyoxal, glutaraldehyde or the like in a solvent can also be used.

Preferably, the iodide is added to the stretching bath (boric acid aqueous solution). By blending iodide, the elution of iodine adsorbed on the PVA-based resin layer can be suppressed. Specific examples of iodide are as described above. The concentration of iodide is preferably 0.05 parts by weight to 15 parts by weight, and more preferably 0.5 parts by weight to 8 parts by weight with respect to 100 parts by weight of water.

The stretching temperature (liquid temperature of the stretching bath) is preferably 40 ° C. to 85 ° C., more preferably 60 ° C. to 75 ° C. At such a temperature, the PVA-based resin layer can be stretched at a high magnification while suppressing dissolution. Specifically, as described above, the glass transition temperature (Tg) of the thermoplastic resin base material is preferably 60 ° C. or higher in relation to the formation of the PVA-based resin layer. In this case, if the stretching temperature is lower than 40 ° C., there is a possibility that the thermoplastic resin base material cannot be stretched satisfactorily even if the plasticization of the thermoplastic resin base material by water is taken into consideration. On the other hand, the higher the temperature of the stretching bath, the higher the solubility of the PVA-based resin layer, and there is a possibility that excellent optical characteristics cannot be obtained. The immersion time of the laminate in the stretching bath is preferably 15 seconds to 5 minutes.

The stretching ratio by stretching in water is preferably 1.5 times or more, more preferably 3.0 times or more. The total draw ratio of the laminated body is preferably 5.0 times or more, more preferably 5.5 times or more, with respect to the original length of the laminated body. By achieving such a high draw ratio, it is possible to manufacture a polarizing film having extremely excellent optical characteristics. Such a high draw ratio can be achieved by adopting an underwater stretching method (boric acid underwater stretching).

B-3-7. Dry shrinkage treatment The dry shrinkage treatment may be performed by heating the entire zone by heating the zone, or by heating the transport roll (using a so-called heating roll) (heating roll drying method). Preferably both are used. By drying using a heating roll, it is possible to efficiently suppress the heating curl of the laminated body and produce a polarizing film having an excellent appearance. Specifically, by drying the laminated body along the heating roll, the crystallization of the thermoplastic resin base material can be efficiently promoted and the crystallinity can be increased, which is relatively low. Even at the drying temperature, the crystallinity of the thermoplastic resin substrate can be satisfactorily increased. As a result, the rigidity of the thermoplastic resin base material is increased, and the PVA-based resin layer is in a state of being able to withstand shrinkage due to drying, and curling is suppressed. Further, by using the heating roll, the laminated body can be dried while being maintained in a flat state, so that not only curling but also wrinkles can be suppressed. At this time, the laminated body can be improved in optical characteristics by shrinking in the width direction by a drying shrinkage treatment. This is because the orientation of PVA and the PVA / iodine complex can be effectively enhanced. The shrinkage ratio in the width direction of the laminate by the dry shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%. By using the heating roll, the laminated body can be continuously contracted in the width direction while being conveyed, and high productivity can be realized.

FIG. 3 is a schematic view showing an example of the drying shrinkage treatment. In the drying shrinkage treatment, the laminate 200 is dried while being transported by the transport rolls R1 to R6 heated to a predetermined temperature and the guide rolls G1 to G4. In the illustrated example, the transport rolls R1 to R6 are arranged so as to alternately and continuously heat the surface of the PVA resin layer and the surface of the thermoplastic resin base material. For example, one surface of the laminate 200 (for example, thermoplasticity) is arranged. The transport rolls R1 to R6 may be arranged so as to continuously heat only the resin substrate surface).

The drying conditions can be controlled by adjusting the heating temperature of the transport roll (temperature of the heating roll), the number of heating rolls, the contact time with the heating roll, and the like. The temperature of the heating roll is preferably 60 ° C. to 120 ° C., more preferably 65 ° C. to 100 ° C., and particularly preferably 70 ° C. to 80 ° C. The crystallinity of the thermoplastic resin can be satisfactorily increased, curling can be satisfactorily suppressed, and an optical laminate having extremely excellent durability can be produced. The temperature of the heating roll can be measured with a contact thermometer. In the illustrated example, six transport rolls are provided, but there is no particular limitation as long as there are a plurality of transport rolls. The number of transport rolls is usually 2 to 40, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roll is preferably 1 second to 300 seconds, more preferably 1 to 20 seconds, and further preferably 1 to 10 seconds.

The heating roll may be provided in a heating furnace (for example, an oven) or in a normal production line (in a room temperature environment). Preferably, it is provided in a heating furnace provided with an air blowing means. By using both drying with a heating roll and hot air drying together, a steep temperature change between the heating rolls can be suppressed, and shrinkage in the width direction can be easily controlled. The temperature of hot air drying is preferably 30 ° C to 100 ° C. The hot air drying time is preferably 1 second to 300 seconds. The wind speed of the hot air is preferably about 10 m / s to 30 m / s. The wind speed is the wind speed in the heating furnace and can be measured by a mini-vane type digital anemometer.

B-3-8. Other Treatments Preferably, a washing treatment is performed after the underwater stretching treatment and before the drying shrinkage treatment. The cleaning treatment is typically performed by immersing a PVA-based resin layer in an aqueous potassium iodide solution.

C. First Phase Difference Layer The first phase difference layer 20 may have any suitable optical and / or mechanical properties depending on the intended purpose. The first retardation layer 20 typically has a slow phase axis. In one embodiment, the angle θ formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizing film 11 is 40 ° to 50 °, preferably 42 ° to 48 °, as described above. It is more preferably about 45 °. If the angle θ is in such a range, by using a λ / 4 plate as the first retardation layer as described later, very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics). A polarizing plate with a retardation layer can be obtained.

The first retardation layer preferably shows a relationship in which the refractive index characteristics are nx> ny ≧ nz. The first retardation layer is typically provided to impart antireflection properties to the polarizing plate and can function as a λ / 4 plate in one embodiment. In this case, the in-plane retardation Re (550) of the first retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, and even more preferably 130 nm to 160 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, ny <nz may be satisfied as long as the effect of the present invention is not impaired.

The Nz coefficient of the first retardation layer is preferably 0.9 to 3, more preferably 0.9 to 2.5, still more preferably 0.9 to 1.5, and particularly preferably 0.9 to 1. It is 3. By satisfying such a relationship, a very excellent reflected hue can be achieved when the obtained polarizing plate with a retardation layer is used in an image display device.

The first retardation layer may exhibit a reverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, and a positive wavelength dispersion characteristic in which the retardation value decreases according to the wavelength of the measurement light. It may be shown, and may show a flat wavelength dispersion characteristic in which the phase difference value hardly changes with the wavelength of the measured light. In one embodiment, the first retardation layer exhibits reverse dispersion wavelength characteristics. In this case, Re (450) / Re (550) of the retardation layer is preferably 0.8 or more and less than 1, and more preferably 0.8 or more and 0.95 or less. With such a configuration, very excellent antireflection characteristics can be realized.

The absolute value of the photoelastic coefficient of the first retardation layer is preferably 2 × 10 ^-11 m ² / N or less, more preferably 2.0 × 10 ^-13 m ² / N to 1.5 × 10 ^-11 . It contains m ² / N, more preferably 1.0 × ^10-12 m ² / N to 1.2 × 10 ^-11 m ² / N. When the absolute value of the photoelastic coefficient is in such a range, the phase difference change is unlikely to occur when the shrinkage stress during heating occurs. As a result, thermal unevenness of the obtained image display device can be satisfactorily prevented.

The first retardation layer is typically composed of a stretched film of a resin film. In one embodiment, the thickness of the first retardation layer is preferably 70 μm or less, more preferably 45 μm to 60 μm. When the thickness of the first retardation layer is within such a range, it is possible to satisfactorily adjust the curl at the time of bonding while satisfactorily suppressing the curl at the time of heating. Further, as will be described later, in the embodiment in which the first retardation layer is made of a polycarbonate resin film, the thickness of the first retardation layer is preferably 40 μm or less, more preferably 10 μm to 40 μm. Yes, more preferably 20 μm to 30 μm. By forming the first retardation layer with a polycarbonate-based resin film having such a thickness, it is possible to contribute to the improvement of bending durability and the reflected hue while suppressing the generation of curl.

The first retardation layer 20 may be made of any suitable resin film that can satisfy the above characteristics. Typical examples of such resins include polycarbonate resins, polyester carbonate resins, polyester resins, polyvinyl acetal resins, polyarylate resins, cyclic olefin resins, cellulose resins, polyvinyl alcohol resins, and polyamide resins. , Polyethylene resin, polyether resin, polystyrene resin, acrylic resin and the like. These resins may be used alone or in combination (eg, blending, copolymerization). When the first retardation layer is composed of a resin film exhibiting a reverse dispersion wavelength characteristic, a polycarbonate-based resin or a polyester carbonate-based resin (hereinafter, may be simply referred to as a polycarbonate-based resin) can be preferably 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 has a structural unit derived from a fluorene-based dihydroxy compound, a structural unit derived from an isosorbide-based dihydroxy compound, an alicyclic diol, an alicyclic dimethanol, di, tri or polyethylene glycol, and an alkylene. Includes structural units derived from at least one dihydroxy compound selected from the group consisting of glycols or spiroglycols. Preferably, the polycarbonate-based resin is 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 di, tri or polyethylene glycol. Containing structural units derived from; more preferably structural units derived from fluorene dihydroxy compounds, structural units derived from isosorbide dihydroxy compounds, and structural units derived from di, tri or polyethylene glycol. .. The polycarbonate-based resin may contain structural units derived from other dihydroxy compounds, if necessary. Details of the polycarbonate-based resin that can be suitably used for the present invention are, for example, JP-A-2014-10291, JP-A-2014-226666, JP-A-2015-21816, JP-A-2015-21217. , 2015-21218, and the description is incorporated herein by reference.

The glass transition temperature of the polycarbonate resin is preferably 110 ° C. or higher and 150 ° C. or lower, more preferably 120 ° C. or higher and 140 ° C. or lower. If the glass transition temperature is excessively low, the heat resistance tends to deteriorate, dimensional changes may occur after film molding, and the image quality of the obtained organic EL panel may be deteriorated. If the glass transition temperature is excessively high, the molding stability during film molding may be deteriorated, and the transparency of the film may be impaired. The glass transition temperature is determined according to JIS K 7121 (1987).

The molecular weight of the polycarbonate resin can be expressed by the reducing viscosity. The reduced viscosity is measured by using methylene chloride as a solvent, precisely adjusting the polycarbonate concentration to 0.6 g / dL, and using a Ubbelohde viscous tube at a temperature of 20.0 ° C. ± 0.1 ° C. The lower limit of the reduction viscosity is usually preferably 0.30 dL / g, more preferably 0.35 dL / g or more. The upper limit of the reduction viscosity is usually preferably 1.20 dL / g, more preferably 1.00 dL / g, and further preferably 0.80 dL / g. If the reduced viscosity is smaller than the lower limit, there may be a problem that the mechanical strength of the molded product is reduced. On the other hand, if the reduced viscosity is larger than the upper limit value, the fluidity at the time of molding is lowered, and there may be a problem that the productivity and the moldability are lowered.

A commercially available film may be used as the polycarbonate resin film. Specific examples of commercially available products include Teijin's product name "Pure Ace WR-S", "Pure Ace WR-W", "Pure Ace WR-M", and Nitto Denko's product name "NRF". Will be.

The first retardation layer 20 is obtained, for example, by stretching a film formed of the polycarbonate-based resin. As a method for forming a film from a polycarbonate-based resin, any appropriate molding processing method can be adopted. Specific examples include a compression molding method, a transfer molding method, an injection molding method, an extrusion molding method, a blow molding method, a powder molding method, an FRP molding method, a cast coating method (for example, a casting method), a calendar molding method, and a hot press. The law etc. can be mentioned. Extrusion molding method or cast coating method is preferable. This is because the smoothness of the obtained film can be enhanced and good optical uniformity can be obtained. The molding conditions can be appropriately set according to the composition and type of the resin used, the characteristics desired for the retardation layer, and the like. As described above, since many film products of the polycarbonate resin are commercially available, the commercially available film may be subjected to the stretching treatment as it is.

The thickness of the resin film (unstretched film) can be set to an arbitrary appropriate value according to a desired thickness of the first retardation layer, desired optical characteristics, stretching conditions described later, and the like. It is preferably 50 μm to 300 μm.

Any suitable stretching method and stretching conditions (for example, stretching temperature, stretching ratio, stretching direction) can be adopted for the stretching. Specifically, various stretching methods such as free-end stretching, fixed-end stretching, free-end contraction, and fixed-end contraction can be used alone or simultaneously or sequentially. As for the stretching direction, it can be performed in various directions and dimensions such as a length direction, a width direction, a thickness direction, and an oblique direction. The stretching temperature is preferably Tg-30 ° C to Tg + 60 ° C, more preferably Tg-10 ° C to Tg + 50 ° C with respect to the glass transition temperature (Tg) of the resin film.

By appropriately selecting the stretching method and stretching conditions, a retardation film having the desired optical characteristics (for example, refractive index characteristics, in-plane retardation, Nz coefficient) can be obtained.

In one embodiment, the retardation film is made by uniaxially stretching or fixed end uniaxially stretching the resin film. Specific examples of the fixed-end uniaxial stretching include a method of stretching the resin film in the width direction (lateral direction) while running the resin film in the longitudinal direction. The draw ratio is preferably 1.1 to 3.5 times.

In another embodiment, the retardation film can be made by continuously obliquely stretching a long resin film in the direction of the above angle θ with respect to the longitudinal direction. By adopting diagonal stretching, a long stretched film having an orientation angle of an angle θ with respect to the longitudinal direction of the film (a slow axis in the direction of the angle θ) can be obtained, for example, when laminated with a polarizing film. Roll-to-roll is possible, and the manufacturing process can be simplified. The angle θ may be an angle formed by the absorption axis of the polarizing film and the slow axis of the retardation layer in the polarizing plate with a retardation layer. As described above, the angle θ is preferably 40 ° to 50 °, more preferably 42 ° to 48 °, and even more preferably about 45 °.

Examples of the stretching machine used for diagonal stretching include a tenter type stretching machine capable of applying a feeding force, a pulling force, or a pulling force at different speeds in the lateral and / or vertical directions. The tenter type stretching machine includes a horizontal uniaxial stretching machine, a simultaneous biaxial stretching machine, and the like, but any suitable stretching machine can be used as long as the long resin film can be continuously and diagonally stretched.

By appropriately controlling the left and right velocities in the stretching machine, a retardation layer having the desired in-plane phase difference and having a slow phase axis in the desired direction (substantially long). A phase difference film) can be obtained.

The stretching temperature of the film may change depending on the in-plane retardation value and thickness desired for the retardation layer, the type of resin used, the thickness of the film used, the stretching ratio, and the like. Specifically, the stretching temperature is preferably Tg-30 ° C to Tg + 30 ° C, more preferably Tg-15 ° C to Tg + 15 ° C, and most preferably Tg-10 ° C to Tg + 10 ° C. By stretching at such a temperature, a first retardation layer having appropriate characteristics in the present invention can be obtained. Tg is the glass transition temperature of the constituent material of the film.

D. Second Phase Difference Layer The second phase difference layer may be a so-called positive C plate having a refractive index characteristic of nz> nz = ny as described above. By using the positive C plate as the second retardation layer, it is possible to satisfactorily prevent reflection in the oblique direction, and it is possible to widen the viewing angle of the antireflection function. In this case, the retardation Rth (550) in the thickness direction of the second retardation layer is preferably −50 nm to −300 nm, more preferably −70 nm to −250 nm, still more preferably −90 nm to −200 nm, and particularly preferably. It is -100 nm to -180 nm. Here, "nx = ny" includes not only the case where nx and ny are exactly equal to each other, but also the case where nx and ny are substantially equal to each other. That is, the in-plane retardation Re (550) of the second retardation layer can be less than 10 nm.

The second retardation layer with a refractive index characteristic of nz> nx = ny can be formed of any suitable material. The second retardation layer preferably consists of a film containing a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) that can be homeotropically oriented may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compound and the method for forming the retardation layer described in [0020] to [0028] of JP-A-2002-333642. In this case, the thickness of the second retardation layer 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.

E. Conductive layer or isotropic base material with conductive layer The conductive layer is an arbitrary suitable base material by any suitable film forming method (for example, vacuum deposition method, sputtering method, CVD method, ion plating method, spray method, etc.). It can be formed by forming a metal oxide film on top of it. Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium-tin composite oxide, tin-antimon composite oxide, zinc-aluminum composite oxide, and indium-zinc composite oxide. Of these, indium-tin composite oxide (ITO) is preferable.

When the conductive layer contains a metal oxide, the thickness of the conductive layer is preferably 50 nm or less, more preferably 35 nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.

Even if the conductive layer is transferred from the base material to the first retardation layer (or the second retardation layer if present) and the conductive layer alone is used as a constituent layer of the polarizing plate with the retardation layer. Often, it may be laminated on the first retardation layer (or the second retardation layer if present) as a laminate with the substrate (base material with a conductive layer). Preferably, the substrate is optically isotropic, and therefore the conductive layer can be used as an isotropic substrate with a conductive layer in a polarizing plate with a retardation layer.

As the optically isotropic base material (isotropic base material), any suitable isotropic base material can be adopted. As the material constituting the isotropic base material, for example, a material having a resin having no conjugate system such as a norbornene resin or an olefin resin as a main skeleton, or an acrylic resin having a cyclic structure such as a lactone ring or a glutarimide ring. Examples include the material contained in the main chain. When such a material is used, when an isotropic base material is formed, the expression of the phase difference due to the orientation of the molecular chains can be suppressed to be small. The thickness of the isotropic substrate is preferably 50 μm or less, more preferably 35 μm or less. The lower limit of the thickness of the isotropic substrate is, for example, 20 μm.

The conductive layer and / or the conductive layer of the isotropic substrate with the conductive layer can be patterned, if necessary. By patterning, a conductive portion and an insulating portion can be formed. As a result, electrodes can be formed. The electrode can function as a touch sensor electrode that senses contact with the touch panel. As the patterning method, any suitable method may be adopted. Specific examples of the patterning method include a wet etching method and a screen printing method.

F. Image display device The polarizing plate with a retardation layer according to the above items A to E can be applied to an image display device. Therefore, the present invention includes an image display device using such a polarizing plate with a retardation layer. Typical examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (for example, an organic EL display device and an inorganic EL display device). The image display device according to the embodiment of the present invention includes the polarizing plate with a retardation layer according to the above items A to E on the visual recognition side thereof. The polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display cell side (for example, a liquid crystal cell, an organic EL cell, an inorganic EL cell) (so that the polarizing film is on the visual recognition side). In one embodiment, the image display device has a curved shape (substantially a curved display screen) and / or is bendable or bendable. In such an image display device, the effect of the polarizing plate with a retardation layer of the present invention becomes remarkable.

Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not limited to these Examples. The measurement method of each characteristic is as follows. Unless otherwise specified, "parts" and "%" in Examples and Comparative Examples are based on weight.
(1) Thickness The thickness of 10 μm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). Thicknesses exceeding 10 μm were measured using a digital micrometer (manufactured by Anritsu, product name “KC-351C”).
(2) Single-unit transmittance and orthogonal absorbance For the polarizing plates (protective film / polarizing film) of the examples and comparative examples, the single-unit transmittance Ts measured using an ultraviolet-visible spectrophotometer (V-7100 manufactured by Nippon Spectroscopy), parallel. The transmittance Tp and the orthogonal transmittance Tc were defined as Ts, Tp and Tc of the polarizing film, respectively. These Ts, Tp and Tc are Y values measured by the JIS Z8701 two-degree visual field (C light source) and corrected for luminosity factor. The refractive index of the protective film was 1.50, and the refractive index of the surface of the polarizing film opposite to the protective film was 1.53.
Further, using the Tc measured at each wavelength, the orthogonal absorbance was determined by the following formula.
Orthogonal absorbance = log10 (100 / Tc)
The orthogonal absorbance A ₂₁₀ was obtained from the orthogonal transmittance Tc ₂₁₀ having a measurement wavelength of 210 nm, and the orthogonal absorbance A ₅₅₀ was obtained from the orthogonal transmittance Tc ₅₅₀ having a measurement wavelength of 550 nm, respectively, using UV-3150 manufactured by Shimadzu Corporation. Further, the orthogonal absorbance A ₄₇₀ was obtained from the orthogonal transmittance Tc ₄₇₀ having a measurement wavelength of 470 nm, and the orthogonal absorbance A ₆₀₀ was obtained from the orthogonal transmittance Tc ₆₀₀ having a measurement wavelength of 600 nm, respectively, using V-7100 manufactured by JASCO Corporation.
For A ₄₇₀ and A ₆₀₀ , the same measurement can be performed with LPF-200 manufactured by Otsuka Electronics Co., Ltd.
(3) Orthogonal b value The polarizing plate used in the Examples and Comparative Examples was measured using an ultraviolet-visible spectrophotometer (manufactured by JASCO Corporation, product name "V7100"), and the hue in the cross Nicol state was determined. .. The lower the orthogonal b value (negative value and larger absolute value), the more the hue is blue rather than neutral.
(4) Warpage The polarizing plates with retardation layers obtained in Examples and Comparative Examples were cut out to a size of 110 mm × 60 mm. At this time, the polarizing film was cut out so that the absorption axis direction was the long side direction. The cut-out polarizing plate with a retardation layer was bonded to a glass plate having a size of 120 mm × 70 mm and a thickness of 0.2 mm via an adhesive to prepare a test sample. The test sample was put into a heating oven maintained at 85 ° C. for 24 hours, and the amount of warpage after taking out was measured. When the test sample was allowed to stand on a flat surface with the glass plate facing down, the height of the highest portion from the flat surface was defined as the amount of warpage.
(5) Bending durability The polarizing plates with a retardation layer obtained in Examples and Comparative Examples were cut out to a size of 50 mm × 100 mm. At this time, the polarizing film was cut out so that the absorption axis direction was the short side direction. Using a folding resistance tester with a constant temperature and humidity chamber (CL09 type-D01 manufactured by YUASA), the cut polarizing plate with a retardation layer was subjected to a bending test under the condition of 20 ° C. and 50% RH. Specifically, the polarizing plate with a retardation layer is repeatedly bent in a direction parallel to the absorption axis direction so that the retardation layer side is on the outside, and cracks, peeling, film breakage, etc. that cause display defects occur. The number of bends until the occurrence was measured and evaluated according to the following criteria (bend diameter: 2 mmφ).
<Evaluation criteria>
Less than 10,000 times: Defective 10,000 times or more and less than 30,000 times: Good 30,000 times or more: Excellent (6) Front reflectance The polarizing plate with a retardation layer obtained in Examples and Comparative Examples has no ultraviolet absorbing function. Reflective plate using acrylic adhesive (manufactured by Toray Film Co., Ltd., trade name "DMS-X42"; reflectance 86%, reflective hue without polarizing plate a ^* =-0.22, b ^* = 0.32) A measurement sample was prepared by pasting on the top. At this time, the polarizing plate with the retardation layer was bonded so that the retardation layer side faced the reflector. The measurement sample is measured by the SCE method using a spectrocolorimeter (CM-2600d manufactured by Konica Minolta), and the values of a ^* and b ^* are substituted into √ (a ^{* 2} + b ^{* 2} ). , The specular hue was calculated.
(7) Elastic modulus The film to be measured is formed into a tensile test dumbbell with a parallel portion width of 10 mm and a length of 40 mm based on JIS K6734: 2000, and a tensile test is performed according to JIS K7161: 1994 to determine the tensile elastic modulus. I asked. Here, the length direction usually coincides with the stretching direction of the polarizing film.

[Example 1]
1. 1. Preparation of Polarizing Film As the thermoplastic resin base material, an amorphous isophthal copolymer polyethylene terephthalate film (thickness: 100 μm) having a long shape, a water absorption of 0.75%, and a Tg of about 75 ° C. was used. One side of the resin base material was corona-treated.
100 weight of PVA-based resin in which polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetacetyl-modified PVA (manufactured by Nippon Synthetic Chemical Industry Co., Ltd., trade name "Gosefimer Z410") are mixed at a ratio of 9: 1. 13 parts by weight of potassium iodide was added to the portion and dissolved in water to prepare a PVA aqueous solution (coating liquid).
The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60 ° C. to form a PVA-based resin layer having a thickness of 8 μm, and a laminate was prepared.
The obtained laminate was stretched 2.4 times in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds in an oven at 130 ° C. (aerial auxiliary stretching treatment).
Next, the laminate was immersed in an insolubilizing bath at a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 4 parts by weight of boric acid with 100 parts by weight of water) for 30 seconds (insolubilization treatment).
Next, the finally obtained polarizing film was placed in a dyeing bath having a liquid temperature of 30 ° C. (an aqueous iodine solution obtained by mixing iodine and potassium iodide in a weight ratio of 1: 7 with respect to 100 parts by weight of water). Immersion was carried out for 60 seconds while adjusting the concentration so that the simple substance transmittance (Ts) and the ratio (A ₅₅₀ / A ₂₁₀ ) became desired values (dyeing treatment).
Then, it was immersed in a cross-linked bath having a liquid temperature of 40 ° C. (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) for 30 seconds. (Crossing treatment).
Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4.0% by weight) having a liquid temperature of 70 ° C., the total draw ratio is 5.5 in the longitudinal direction (longitudinal direction) between rolls having different peripheral speeds. Uniaxial stretching was performed so as to be doubled (underwater stretching treatment).
Then, the laminate was immersed in a washing bath having a liquid temperature of 20 ° C. (an aqueous solution obtained by blending 4 parts by weight of potassium iodide with 100 parts by weight of water) (cleaning treatment).
Then, while drying in an oven kept at 90 ° C., it was brought into contact with a heating roll made of SUS whose surface temperature was kept at 75 ° C. for about 2 seconds (dry shrinkage treatment). The shrinkage rate in the width direction of the laminated body by the dry shrinkage treatment was 2.5%.
In this way, a polarizing film having a thickness of 3.4 μm was formed on the resin substrate.

2. 2. Fabrication of Polarizing Plate A cycloolefin-based film (thickness: 28 μm, elasticity) with a hard coat layer (refractive index 1.53) as a protective layer on the surface of the polarizing film obtained above (the surface opposite to the resin substrate). Rate: 2100 MPa) was bonded via an ultraviolet curable adhesive. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 μm, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive. Then, after slitting both ends, the resin base material was peeled off to obtain a long polarizing plate (width: 1300 mm) having a structure of a protective layer / adhesive layer / polarizing film. The simple substance transmittance of the polarizing plate (substantially, the polarizing film) was 43.5%, and the degree of polarization was 99.97%. Further, A ₅₅₀ / A ₂₁₀ was 2.77, A ₄₇₀ / A ₆₀₀ was 0.76, and the orthogonal b value was -3.6.

3. 3. Preparation of retardation film constituting the retardation layer 3-1. Polymerization of polyester carbonate-based resin Polymerization was carried out using a batch polymerization apparatus consisting of two vertical reactors equipped with a stirring blade and a reflux condenser controlled at 100 ° C. Bis [9- (2-phenoxycarbonylethyl) fluoren-9-yl] methane 29.60 parts by mass (0.046 mol), isosorbide (ISB) 29.21 parts by mass (0.200 mol), spiroglycol (SPG) 42 .28 parts by mass (0.139 mol), 63.77 parts by mass (0.298 mol) of diphenyl carbonate (DPC) and calcium acetate monohydrate 1.19 x 10 ^-2 parts by mass (6.78 x 10- ⁾ as a catalyst. ⁵ mol) was charged. After substituting nitrogen under reduced pressure in the reactor, heating was performed with a heat medium, and stirring was started when the internal temperature reached 100 ° C. The internal temperature was brought to 220 ° C. 40 minutes after the start of the temperature rise, and the depressurization was started at the same time as controlling to maintain this temperature, and the temperature was 13.3 kPa 90 minutes after reaching 220 ° C. The phenol vapor produced by the polymerization reaction was guided to a reflux condenser at 100 ° C., the monomer component contained in a small amount in the phenol vapor was returned to the reactor, and the non-condensed phenol vapor was guided to a condenser at 45 ° C. for recovery. Nitrogen was introduced into the first reactor and the pressure was once restored to atmospheric pressure, and then the oligomerized reaction solution in the first reactor was transferred to the second reactor. Then, the temperature rise and depressurization in the second reactor were started, and the internal temperature was 240 ° C. and the pressure was 0.2 kPa in 50 minutes. Then, the polymerization was allowed to proceed until the stirring power became a predetermined value. When the predetermined power was reached, nitrogen was introduced into the reactor to repressurize, the produced polyester carbonate-based resin was extruded into water, and the strands were cut to obtain pellets.

3-2. Preparation of retardation film After vacuum-drying the obtained polyester carbonate resin (pellet) at 80 ° C for 5 hours, a single-screw extruder (manufactured by Toshiba Machine Co., Ltd., cylinder set temperature: 250 ° C), T-die (width 200 mm) , Set temperature: 250 ° C.), chill roll (set temperature: 120 to 130 ° C.), and a film-forming device equipped with a winder was used to prepare a long resin film having a thickness of 130 μm. The obtained long resin film was stretched while adjusting so that a predetermined retardation was obtained, to obtain a retardation film having a thickness of 48 μm. The stretching conditions were a stretching temperature of 143 ° C. and a stretching ratio of 2.8 times in the width direction. The Re (550) of the obtained retardation film was 141 nm, the Re (450) / Re (550) was 0.86, and the Nz coefficient was 1.12.

4. Fabrication of polarizing plate with retardation layer 2. On the surface of the polarizing film of the polarizing plate obtained in 3. above. The retardation film obtained in 1 above was bonded via an acrylic pressure-sensitive adhesive (thickness 5 μm). At this time, the absorption axis of the polarizing film and the slow axis of the retardation film were bonded so as to form an angle of 45 °. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 85 μm. The obtained polarizing plate with a retardation layer was subjected to the evaluations (4) to (5) above. The results are shown in Table 1.

[Example 2-1]
1. 1. Preparation of polarizing film The thickness of the polarizing film obtained by changing the coating thickness of the PVA aqueous solution (coating solution) to 13 μm was set to 4.6 μm, and the transmittance of the polarizing film was adjusted by adjusting the concentration of the dyeing bath. A polarizing film was formed on the resin substrate in the same manner as in Example 1 except that Ts) was set to 43.0%.

2. 2. Fabrication of polarizing plate 1. A polarizing plate having a protective layer / adhesive layer / polarizing film configuration was produced in the same manner as in Example 1 except that the polarizing film obtained in 1 was used. The simple substance transmittance of the polarizing plate (substantially, the polarizing film) was 43.0%, and the degree of polarization was 99.995%. Further, A ₅₅₀ / A ₂₁₀ was 1.65, A ₄₇₀ / A ₆₀₀ was 0.87, and the orthogonal b value was -3.0.

3. 3. Preparation of Phase Difference Film A long polyester carbonate resin film having a thickness of 130 μm obtained in the same manner as in Example 1 was stretched in the width direction while adjusting so that a predetermined phase difference could be obtained, and the thickness was about 48 μm. A phase difference film was obtained. The Re (550) of the obtained retardation film was 144 nm.

4. Fabrication of a polarizing plate with a retardation layer In the same manner as in Example 1, the above 2. On the surface of the polarizing film of the polarizing plate obtained in 3. above. By laminating the retardation films obtained in 1 above, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing element / pressure-sensitive adhesive layer / retardation layer was produced. The total thickness of the obtained polarizing plate with a retardation layer was 87 μm. The obtained polarizing plate with a retardation layer was subjected to the evaluations (4) to (6) above. The results are shown in Table 1.

[Example 2-2]
1. 1. Preparation of polarizing film Polarizing on the resin substrate in the same manner as in Example 2-1 except that the concentration of the dyeing bath was adjusted so that the simple substance transmittance (Ts) of the polarizing film was 44.0%. A membrane was formed.

2. 2. Fabrication of polarizing plate 1. A polarizing plate having a protective layer / adhesive layer / polarizing film configuration was produced in the same manner as in Example 1 except that the polarizing film obtained in 1 was used. The simple substance transmittance of the polarizing plate (substantially, the polarizing film) was 44.0%, and the degree of polarization was 99.96%. Further, A ₅₅₀ / A ₂₁₀ was 1.48, A ₄₇₀ / A ₆₀₀ was 0.87, and the orthogonal b value was -5.0.

3. 3. Fabrication of a polarizing plate with a retardation layer In the same manner as in Example 1, the above 2. The retardation film obtained in the same manner as in Example 2-1 is bonded to the surface of the polarizing film of the polarizing plate obtained in 1 above, and has a structure of a protective layer / adhesive layer / polarizing element / pressure-sensitive adhesive layer / retardation layer. A polarizing plate with a retardation layer was produced. The total thickness of the obtained polarizing plate with a retardation layer was 87 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 3-1]
1. 1. Preparation of Polarizing Film A polarizing film having a thickness of 4.6 μm was formed on the resin substrate in the same manner as in Example 2-1.

2. 2. Fabrication of polarizing plate 1. It was carried out except that the polarizing film obtained in the above was used and a triacetyl cellulose (TAC) film with a hard coat layer (hard coat layer thickness 7 μm, TAC thickness 25 μm, elastic modulus: 3600 MPa) was used as a protective layer. A polarizing plate having a protective layer / adhesive layer / polarizing film configuration was produced in the same manner as in Example 1.

3. 3. Preparation of retardation film constituting the retardation layer The polyester carbonate resin (pellets) obtained in the same manner as in Example 1 except that 0.7 parts by mass of PMMA was melt-kneaded was vacuum-dried at 80 ° C. for 5 hours. After that, it is equipped with a single-screw extruder (manufactured by Toshiba Machinery Co., Ltd., cylinder set temperature: 250 ° C), T-die (width 200 mm, set temperature: 250 ° C), chill roll (set temperature: 120-130 ° C), and winder. A long resin film having a thickness of 105 μm was produced by using the film forming apparatus. The obtained long resin film was stretched 2.8 times in the width direction at 138 ° C. while adjusting so as to obtain a predetermined retardation, to obtain a retardation film having a thickness of 38 μm. The Re (550) of the obtained retardation film was 144 nm, and the Re (450) / Re (550) was 0.86.

4. Fabrication of polarizing plate with retardation layer 2. On the surface of the polarizing film of the polarizing plate obtained in 3. above. The retardation film obtained in 1 above was bonded via an acrylic pressure-sensitive adhesive (thickness 5 μm). At this time, the absorption axis of the polarizing film and the slow axis of the retardation film were bonded so as to form an angle of 45 °. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 81 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 3-2]
A long polyester carbonate resin film having a thickness of 105 μm obtained in the same manner as in Example 3-1 was stretched in the width direction while adjusting so as to obtain a predetermined phase difference, and a retardation film having a thickness of 38 μm was obtained. Obtained. The Re (550) of the obtained retardation film was 140 nm.
A polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer in the same manner as in Example 3-1 except that the retardation film is used as the retardation layer. Got The total thickness of the obtained polarizing plate with a retardation layer was 81 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 3-3]
A long polyester carbonate resin film having a thickness of 105 μm obtained in the same manner as in Example 3-1 was stretched in the width direction while adjusting so as to obtain a predetermined phase difference, and a retardation film having a thickness of 38 μm was obtained. Obtained. The Re (550) of the obtained retardation film was 149 nm.
A polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer in the same manner as in Example 3-1 except that the retardation film is used as the retardation layer. Got The total thickness of the obtained polarizing plate with a retardation layer was 81 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 4-1]
1. 1. Preparation of Polarizing Film A polarizing film having a thickness of 4.6 μm was formed on the resin substrate in the same manner as in Example 2-2.

2. 2. Fabrication of polarizing plate 1. A polarizing plate having a protective layer / adhesive layer / polarizing film configuration was produced in the same manner as in Example 3-1 except that the polarizing film obtained in 1 was used.

3. 3. Preparation of polarizing plate with retardation layer The retardation film prepared in the same manner as in Example 3-1 was obtained from the above 2. It was bonded to the surface of the polarizing film of the polarizing plate obtained in the same manner as in Example 3-1. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 81 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 4-2]
1. 1. Preparation of Polarizing Film A polarizing film having a thickness of 4.6 μm was formed on the resin substrate in the same manner as in Example 2-2.

2. 2. Fabrication of polarizing plate 1. A polarizing plate having a protective layer / adhesive layer / polarizing film configuration was produced in the same manner as in Example 3-1 except that the polarizing film obtained in 1 was used.

3. 3. Preparation of polarizing plate with retardation layer The retardation film prepared in the same manner as in Example 3-2 was obtained from the above 2. It was bonded to the surface of the polarizing film of the polarizing plate obtained in the same manner as in Example 3-1. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 81 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Example 5]
The polycarbonate resin film obtained in the same manner as in Example 1 was obliquely stretched by a method according to Example 2 of JP-A-2014-194483 to obtain a retardation film having a thickness of 58 μm. The Re (550) of the obtained retardation film is 144 nm, Re (450) / Re (550) is 0.86, the Nz coefficient is 1.21, and the orientation angle (direction of the slow phase axis). Was 45 ° with respect to the long direction. This retardation film and the polarizing plate of Example 2-2 are laminated by roll-to-roll via an acrylic pressure-sensitive adhesive (thickness 5 μm) to form a protective layer / adhesive layer / polarizing film / pressure-sensitive adhesive layer / retardation layer. A polarizing plate with a retardation layer having a configuration was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 97 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Comparative Example 1]
1. 1. Preparation of Polarizer A polyvinyl alcohol-based resin film having an average degree of polymerization of 2,400, a degree of saponification of 99.9 mol%, and a thickness of 30 μm was prepared. The polyvinyl alcohol film was immersed in a swelling bath (water bath) at 20 ° C. for 30 seconds between rolls having different peripheral speed ratios and stretched 2.4 times in the transport direction while swelling (swelling step). Dyeing by immersing in a dyeing bath at 30 ° C. (an aqueous solution having an iodine concentration of 0.03% by weight and a potassium iodide concentration of 0.3% by weight) so that the single transmittance after final stretching becomes a desired value. While using the original polyvinyl alcohol film (polyvinyl alcohol film not stretched at all in the transport direction) as a reference, the film was stretched 3.7 times in the transport direction (dyeing step). The immersion time at this time was about 60 seconds. Next, the original polyvinyl alcohol film was placed while immersing the dyed polyvinyl alcohol film in a cross-linked bath at 40 ° C. (an aqueous solution having a boric acid concentration of 3.0% by weight and a potassium iodide concentration of 3.0% by weight). It was stretched up to 4.2 times in the transport direction as a reference (crosslinking step). Further, the obtained polyvinyl alcohol film is immersed in a stretching bath at 64 ° C. (an aqueous solution having a boric acid concentration of 4.0% by weight and a potassium iodide concentration of 5.0% by weight) for 50 seconds to obtain the original polyvinyl alcohol. After stretching up to 6.0 times in the transport direction with reference to the alcohol film (stretching step), it was immersed in a washing bath at 20 ° C. (an aqueous solution having a potassium iodide concentration of 3.0% by weight) for 5 seconds (washing). Process). The washed polyvinyl alcohol film was dried at 30 ° C. for 2 minutes to prepare a stator (thickness 12 μm).

2. 2. Preparation of polarizing plate As an adhesive, a polyvinyl alcohol resin containing an acetoacetyl group (average polymerization degree of 1,200, saponification degree of 98.5 mol%, acetoacetylation degree of 5 mol%) and methylol melamine are used. The contained aqueous solution was used. Using this adhesive so that the thickness of the adhesive layer is 0.1 μm, a triacetyl cellulose (TAC) film with a hard coat layer (hard coat layer thickness of 7 μm) is applied to one surface of the polarizing element obtained above. A TAC film having a thickness of 25 μm and an elasticity of 3600 MPa was bonded to the other surface of the polarizing element with a roll bonding machine, and then heat-dried in an oven (temperature: 60 ° C., time: 5 minutes). ), To produce a polarizing plate having a structure of protective layer 1 (thickness 32 μm) / adhesive layer / polarizing element / adhesive layer / protective layer 2.

3. 3. Fabrication of polarizing plate with retardation layer 2. A retardation film was attached to the surface of the protective layer 2 of the polarizing plate obtained in the above manner in the same manner as in Example 1, and the protective layer 1 / adhesive layer / polarizing element / adhesive layer / protective layer 2 / adhesive layer / position. A polarizing plate with a retardation layer having a configuration of a retardation layer was produced. The total thickness of the obtained polarizing plate with a retardation layer was 122 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1.

[Comparative Example 2]
1. 1. Preparation of Polarizer A splitter (thickness 12 μm) was prepared in the same manner as in Comparative Example 1.

2. 2. Preparation of Polarizing Plate A polarizing plate having a structure of a protective layer 1 (thickness 32 μm) / adhesive layer / polarizing element / adhesive layer / protective layer 2 (thickness 25 μm) was prepared in the same manner as in Comparative Example 1.

ポリエチレンテレフタレート（ＰＥＴ）フィルム（厚み３８μｍ）表面を、ラビング布を用いてラビングし、配向処理を施した。配向処理の方向は、偏光板に貼り合わせる際に偏光子の吸収軸の方向に対して視認側から見て１５°方向となるようにした。この配向処理表面に、上記液晶塗工液をバーコーターにより塗工し、９０℃で２分間加熱乾燥することによって液晶化合物を配向させた。このようにして形成された液晶層に、メタルハライドランプを用いて１ｍＪ/ｃｍ^２の光を照射し、当該液晶層を硬化させることによって、ＰＥＴフィルム上に液晶配向固化層Ａを形成した。液晶配向固化層Ａの厚みは２．５μｍ、面内位相差Ｒｅ（５５０）は２７０ｎｍであった。さらに、液晶配向固化層Ａは、ｎｘ＞ｎｙ＝ｎｚの屈折率分布を有していた。
塗工厚みを変更したこと、および、配向処理方向を偏光子の吸収軸の方向に対して視認側から見て７５°方向となるようにしたこと以外は上記と同様にして、ＰＥＴフィルム上に液晶配向固化層Ｂを形成した。液晶配向固化層Ｂの厚みは１．５μｍ、面内位相差Ｒｅ（５５０）は１４０ｎｍであった。さらに、液晶配向固化層Ｂは、ｎｘ＞ｎｙ＝ｎｚの屈折率分布を有していた。また、液晶配向固化層ＡおよびＢのＲｅ（４５０）／Ｒｅ（５５０）は１．１１であった。 3. 3. Preparation of First Oriented Solidified Layer and Second Aligned Solidified Layer Constituting the Phase Difference Layer With 10 g of polymerizable liquid crystal (manufactured by BASF: trade name "Pariocolor LC242", represented by the following formula) showing a nematic liquid crystal phase. , 3 g of a photopolymerization initiator (manufactured by BASF: trade name "Irgacure 907") for the polymerizable liquid crystal compound was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid).

The surface of a polyethylene terephthalate (PET) film (thickness 38 μm) was rubbed with a rubbing cloth and subjected to an orientation treatment. The direction of the alignment treatment was set to be 15 ° when viewed from the visual recognition side with respect to the direction of the absorption axis of the polarizing element when the polarizing plate was attached. The liquid crystal coating liquid was applied to the alignment-treated surface with a bar coater, and the liquid crystal compound was oriented 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 cured to form a liquid crystal oriented solidified layer A on the PET film. The thickness of the liquid crystal oriented solidified layer A was 2.5 μm, and the in-plane retardation Re (550) was 270 nm. Further, the liquid crystal oriented solidified layer A had a refractive index distribution of nx> ny = nz.
On the PET film in the same manner as above, except that the coating thickness was changed and the orientation processing direction was set to be 75 ° when viewed from the visual side with respect to the direction of the absorber's absorption axis. The liquid crystal oriented solidified layer B was formed. The thickness of the liquid crystal oriented solidified layer B was 1.5 μm, and the in-plane retardation Re (550) was 140 nm. Further, the liquid crystal oriented solidified layer B had a refractive index distribution of nx> ny = nz. The Re (450) / Re (550) of the liquid crystal oriented solidified layers A and B was 1.11.

4. Fabrication of polarizing plate with retardation layer 2. On the surface of the polarizing plate obtained in step 2 on the protective layer 2 side, the above 3. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B obtained in 1 above were transferred in this order. At this time, the angle between the absorption axis of the stator and the slow axis of the oriented solidification layer A is 15 °, and the angle between the absorption axis of the splitter and the slow axis of the oriented solidification layer B is 75 °. Transferred (bonded). Each transfer (bonding) was performed via an ultraviolet curable adhesive (thickness 1 μm). In this way, it has a structure of protective layer 1 / adhesive layer / polarizing element / adhesive layer / protective layer 2 / adhesive layer / retardation layer (first oriented solidified layer / adhesive layer / second oriented solidified layer). A polarizing plate with a retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 75 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Comparative Example 3]
1. 1. Preparation of Polarizing Film A polarizing film having a thickness of 4.6 μm was formed on the resin substrate in the same manner as in Example 2-1.

2. 2. Fabrication of Polarizing Plate An acrylic film (surface refractive index 1.50, 20 μm) is applied as a protective layer on the surface of the polarizing film obtained above (the surface opposite to the resin substrate), and an ultraviolet curable adhesive is applied. It was pasted together through. Specifically, the curable adhesive was coated so as to have a total thickness of 1.0 μm, and bonded using a roll machine. Then, UV light was irradiated from the protective layer side to cure the adhesive. Then, after slitting both ends, the resin base material was peeled off to obtain a long polarizing plate (width: 1300 mm) having a structure of a protective layer / adhesive layer / polarizing film.

3. 3. Preparation of polarizing plate with retardation layer In the same manner as in Comparative Example 2, the above 2. The liquid crystal oriented solidified layer A and the liquid crystal oriented solidified layer B obtained in the same manner as in Comparative Example 2 were transferred to the surface of the polarizing film of the polarizing plate obtained in the above order in this order. In this way, a polarizing plate with a retardation layer having a structure of a protective layer / adhesive layer / polarizing film / adhesive layer / retardation layer (first alignment solidification layer / adhesion layer / second alignment solidification layer) is obtained. rice field. The total thickness of the obtained polarizing plate with a retardation layer was 32 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 2-1. The results are shown in Table 1.

[Comparative Example 4]
No potassium iodide was added to the PVA aqueous solution (coating liquid), the thickness of the polarizing film obtained by changing the PVA aqueous solution (coating liquid) was 3.3 μm, and no heating roll was used in the drying shrinkage treatment. The polarizing film and the polarizing plate are the same as in Example 1 except that the shrinkage rate in the width direction is 0.1% or less and the single transmittance of the polarizing film is adjusted by adjusting the concentration of the dyeing bath. Was produced. The simple substance transmittance of the polarizing plate (substantially, the polarizing film) was 43.4%, and A ₅₅₀ / A ₂₁₀ was 0.75. A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that this polarizing plate was used.

[evaluation]
As is clear from comparing Example 1 with Comparative Examples 1, 2 and 4, the polarizing film produced by a predetermined method is thin but exhibits excellent optical properties. By using such a polarizing film, a polarizing plate with a retardation layer is thin, has excellent optical characteristics, and warpage after a heating test is remarkably suppressed (as a result, excellent in handleability). Can be found to be obtained. Further, it can be seen that an excellent reflected hue can be obtained by using it in combination with a retardation layer composed of a polycarbonate-based resin (including polyester carbonate-based resin) film. In addition, the polycarbonate resin is thinned to 40 μm or less, the total thickness of the polarizing plate with a retardation layer is 85 μm or less, and a substrate having an elastic modulus of 3000 MPa or more, preferably a TAC film, is used as the protective layer. Bending characteristics can be further improved. On the other hand, the polarizing plate with a retardation layer of Comparative Example 3 is thin, has excellent optical characteristics, and although warpage after the heating test is remarkably suppressed, it has a large reflected hue and has display characteristics. I wasn't satisfied with it.

The polarizing plate with a retardation layer of the present invention is suitably used as a circular polarizing plate for a liquid crystal display device, an organic EL display device, and an inorganic EL display device.

10 polarizing plate 11 polarizing film 12 first protective layer 13 second protective layer 20 retardation layer 100 polarizing plate with retardation layer 101 polarizing plate with retardation layer

Claims (14)

It has a polarizing film, a polarizing plate including a protective layer on at least one side of the polarizing film, and a retardation layer.
The polarizing film is made of a polyvinyl alcohol-based resin film containing iodine , has a thickness of 8 μm or less, and has a ratio of orthogonal absorbance A ₅₅₀ at a wavelength of 550 nm to orthogonal absorbance A ₂₁₀ at a wavelength of 210 nm (A ₅₅₀ / A ₂₁₀ ). Is 1.4 to 3.5, and the single transmittance is 42.5% to 46.0%.
The Re (550) of the retardation layer is 100 nm to 190 nm, and Re (450) / Re (550) is 0.8 or more and less than 1.
The angle formed by the slow axis of the retardation layer and the absorption axis of the polarizing film is 40 ° to 50 °.
Polarizing plate with retardation layer. The polarizing plate with a retardation layer according to claim 1, wherein the protective layer is made of a triacetyl cellulose-based resin film. The polarizing plate includes the polarizing film and the protective layer arranged only on one side of the polarizing film.
The polarizing plate with a retardation layer according to claim 1 or 2, wherein the retardation layer is bonded to the polarizing film via an adhesive layer. The polarizing plate with a retardation layer according to any one of claims 1 to 3, wherein the retardation layer is made of a polycarbonate resin film. The invention according to any one of claims 1 to 4, wherein the ratio (A ₄₇₀ / A ₆₀₀ ) of the orthogonal absorbance A ₄₇₀ at a wavelength of 470 nm to the orthogonal absorbance A ₆₀₀ at a wavelength of 600 nm of the polarizing film is 0.7 to 2.00. Polarizing plate with a retardation layer. The polarizing plate with a retardation layer according to any one of claims 1 to 5, wherein the orthogonal b value of the polarizing film is greater than -10 and equal to or less than +10. The polarizing plate with a retardation layer according to any one of claims 1 to 6, wherein the polarizing film has a simple substance transmittance of 43.5% to 45.0%. The position according to any one of claims 1 to 7, wherein another retardation layer is further provided outside the retardation layer, and the refractive index characteristics of the other retardation layer indicate the relationship of nz> nz = ny. Polarizing plate with phase difference layer. The polarizing plate with a retardation layer according to any one of claims 1 to 8, further comprising a conductive layer or an isotropic substrate with a conductive layer on the outside of the retardation layer. The polarizing plate with a retardation layer according to any one of claims 1 to 9, wherein the total thickness is 100 μm or less. It is long and long
The polarizing film has an absorption axis in the long direction and has an absorption axis.
The retardation layer is a diagonally stretched film having a slow phase axis in a direction forming an angle of 40 ° to 50 ° with respect to the elongated direction.
The polarizing plate with a retardation layer according to any one of claims 1 to 10. The polarizing plate with a retardation layer according to claim 11, which is wound in a roll shape. An image display device comprising the polarizing plate with a retardation layer according to any one of claims 1 to 10. The image display device according to claim 13, which is an organic electroluminescence display device or an inorganic electroluminescence display device.

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