TW202016579A - Polarizing plate with phase difference layer and image display device using the same which is thin, excellent in handleability, and excellent in optical characteristics - Google Patents

Abstract

An object of the present invention is to provide a polarizing plate with a phase difference layer which is thin, excellent in handleability, and excellent in optical characteristics. The solution is a polarizing plate with phase difference of the present invention, which is provided with a polarizing plate and a phase difference layer, and the polarizing plate includes a polarizing film and a protective layer arranged on at least one side of the polarizing film. The polarizing film is composed of a dichroic substance-containing polyvinyl alcohol-based resin film, and the thickness of which is 8 [mu]m or less, the orthogonal absorbance per 1 [mu]m thickness at a wavelength of 210 nm is 1.00 or less. The phase difference layer is a positioned cured layer of a liquid crystal compound.

Description

Polarizing plate with phase difference layer and image display device using the same

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

Background of the invention In recent years, image display devices including liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices) have rapidly become popular. The image display device uses polarizing plates and retardation plates on behalf of the upper system. In practical applications, a polarizing plate with a phase difference layer integrated with a polarizing plate and a phase difference plate is widely used (for example, Patent Document 1). Recently, as the demand for thinner image display devices has increased, The demand for thinner polarizers has also increased. In addition, in recent years, the demand for curved image display devices and/or flexible or bendable image display devices has increased, while polarizing plates and polarizing plates with retardation layers are required to be thinner and further Softening. For the purpose of thinning the polarizing plate with the retardation layer, the protective layer and the retardation film of the polarizing film having a large influence on the thickness are being thinned. However, if the protective layer and the retardation film are thinned, the influence of the shrinkage of the polarizing film will be relatively large, which causes problems such as warpage of the image display device and reduced operability of the polarizing plate with the retardation layer.

In order to solve the above problems, even the polarizing film needs to be thinned. However, if the thickness of the polarizing film is simply reduced, the optical characteristics will be reduced. More specifically, one or both of the degree of polarization and the transmissivity of the monomer having a trade-off relationship are reduced to an unacceptable level in practical applications. As a result, the optical characteristics of the polarizing plate with the retardation layer become insufficient.

Prior technical literature Patent Literature Patent Document 1: Japanese Patent No. 3325560

Summary of the invention Problems to be solved by invention The present invention was made to solve the conventional problems, and its main object is to provide a polarizing plate with a retardation layer that is thin, excellent in handleability, and excellent in optical characteristics.

Solution to Problem The polarizing plate with a phase difference layer of the present invention has a polarizing plate and a phase difference layer, and the polarizing plate includes a polarizing film and a protective layer located on at least one side of the polarizing film. The polarizing film is composed of a dichroic substance-containing polyvinyl alcohol-based resin film, and its thickness is 8 μm or less, and the orthogonal absorbance per 1 μm thickness at a wavelength of 210 nm is 1.00 or less. This retardation layer is an oriented cured layer of a liquid crystal compound. In one embodiment, the unit weight of the polarizing plate with a retardation layer is 6.5 mg/cm ² or less. In one embodiment, the total thickness of the polarizing plate with a retardation layer is 60 μm or less. In one embodiment, the retardation layer is a single layer of the alignment-cured layer of the liquid crystal compound, Re (550) of the retardation layer is 100 nm to 190 nm, and the slow axis of the retardation layer and the absorption axis of the polarizing film The angle formed is 40°~50°. In one embodiment, the phase difference layer has a laminated structure of an alignment hardening layer of the first liquid crystal compound and an alignment hardening layer of the second liquid crystal compound; Re(550) of the alignment hardening layer of the first liquid crystal compound is 200 nm to 300 nm , And the angle formed by the slow axis and the absorption axis of the polarizing film is 10°~20°; the Re(550) of the alignment cured layer of the second liquid crystal compound is 100nm~190nm, and the slow axis and the polarizing film The angle formed by the absorption axis is 70°~80°. In one embodiment, the ratio of the orthogonal absorbance A ₄₇₀ at a wavelength of ₄₇₀ nm to the orthogonal absorbance A ₆₀₀ at a wavelength of 600 nm (A ₄₇₀ /A ₆₀₀ ) 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 iodine concentration of the polarizing film is 3.0% by weight or more. 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 shows a relationship of nz>nx=ny. In one embodiment, the polarizing plate with a retardation layer further has a conductive layer or an isotropic base material with a conductive layer outside the retardation layer. The invention further provides a polarizing plate with a retardation layer, which has a polarizing plate and a retardation layer, and the polarizing plate includes a polarizing film and a protective layer on at least one side of the polarizing film; the retardation layer is a liquid crystal compound Orientation curing layer; the polarizing film is composed of iodine-containing polyvinyl alcohol-based resin film, and the thickness is 8 μm or less; the orthogonal absorbance per 1 μm thickness of the polarizing film at a wavelength of 210 nm is 1.00 or less, the polarizing film is at a wavelength The ratio of the orthogonal absorbance A ₄₇₀ at ₄₇₀ nm to the orthogonal absorbance A ₆₀₀ at a wavelength of 600 nm (A ₄₇₀ /A ₆₀₀ ) is 0.7 to 2.00, and the orthogonal b value of the polarizing film is greater than -10 and below +10. According to another aspect of the present invention, an image display device is provided. The image display device includes the polarizing plate with a phase difference layer. In one embodiment, the image display device is an organic electroluminescence display device or an inorganic electroluminescence display device.

Invention effect According to the present invention, a thin polarized film with excellent optical properties can be obtained by combining the following methods: adding a halide (typically potassium iodide) to a polyvinyl alcohol (PVA) resin, including air-assisted extension and Two-stage extension in water, and drying and shrinking by heating roller. By using the polarizing film, it is possible to realize a thin polarizing plate with a retardation layer which is excellent in handleability and excellent in optical characteristics.

Forms for carrying out the invention The embodiments of the present invention are described below, but the present invention is not limited by these embodiments.

(Definition of terms and symbols) The definitions of terms and symbols in this manual are as follows. (1) Refractive index (nx, ny, nz) "Nx" is the refractive index in the direction in which the in-plane refractive index becomes maximum (that is, the direction of the slow axis), "ny" is the refractive index in the direction orthogonal to the slow axis (that is, the direction of the fast axis) in the plane, and " "nz" is the refractive index in the thickness direction. (2) In-plane phase difference (Re) "Re(λ)" is the in-plane phase difference measured with light of wavelength λnm at 23°C. For example, "Re(550)" is the in-plane phase difference measured at 23°C with light having a wavelength of 550 nm. Re(λ) can be obtained by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (thin film) is d (nm). (3) Phase difference in thickness direction (Rth) "Rth(λ)" is the phase difference in the thickness direction measured at 23°C with light having a wavelength of λnm. For example, "Rth(550)" is the phase difference in the thickness direction measured at 23°C with light having a wavelength of 550 nm. Rth(λ) can be obtained by the formula: Rth(λ)=(nx-nz)×d when the thickness of the layer (thin film) is d (nm). (4) Nz coefficient The Nz coefficient can be obtained by Nz=Rth/Re. (5) Angle When an angle is mentioned in this specification, the angle includes both clockwise and counterclockwise relative to the reference direction. Therefore, for example, "45°" means ±45°.

A. Overall composition of polarizing plate with retardation layer 1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. The polarizing plate with a retardation layer 100 of this embodiment includes a polarizing plate 10 and a retardation layer 20. The polarizing plate 10 includes a polarizing film 11, a first protective layer 12 disposed on one side of the polarizing film 11, and a second protective layer 13 disposed on the other side of the polarizing film 11. One of the first protective layer 12 and the second protective layer 13 may be omitted according to the purpose. For example, when the phase difference layer 20 can function as a protective layer of 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 resin film containing a dichroic substance. The thickness of the polarizing film is 8 μm or less, and the orthogonal absorbance (hereinafter referred to as unit absorbance) per thickness of 1 μm at a wavelength of 210 nm is 1.00 or less.

As shown in FIG. 2, in another embodiment of the polarizing plate 101 with a phase difference layer, another phase difference layer 50 and/or a conductive layer or an isotropic base material 60 with a conductive layer may be provided. The other retardation layer 50 and the isotropic base material 60 of the conductive layer or the conductive layer can be provided on the outer side of the retardation layer 20 (the side opposite to the polarizing plate 10). Another phase difference layer represents that the upper refractive index characteristic shows the relationship of nz>nx=ny. The other retardation layer 50 and the isotropic base material 60 of the conductive layer or the conductive layer are representatively arranged sequentially from the phase difference layer 20 side. The other retardation layer 50 and the conductive layer or the isotropic base material 60 with the conductive layer represent any layer that can be provided as needed, and either or both can be omitted. For convenience, the phase difference layer 20 may be referred to as a first phase difference layer, and the other phase difference layer 50 may be referred to as a second phase difference layer. In addition, when a conductive layer or an isotropic substrate with a conductive layer is to be provided, the polarizing plate with a retardation layer can be applied to incorporate a touch sensor between the image display unit (such as an organic EL unit) and the polarizing plate. The so-called internal touch panel type input display device.

In the embodiment of the present invention, the first retardation layer 20 is a cured layer of the liquid crystal compound. The first retardation layer 20 may be a single layer of the directional curing layer shown in FIGS. 1 and 2, or may have a laminated structure of the first directional curing layer 21 and the second directional curing layer 22 shown in FIG. 3.

The above-mentioned embodiments may be combined as appropriate, and the constituent elements of the above-mentioned embodiments may be added with changes obvious in the industry. For example, the second retardation layer 50 and/or the conductive layer or the isotropic substrate 60 with the conductive layer may be provided on the polarizing plate 102 with a retardation layer in FIG. 3. For another example, the configuration of providing the isotropic base material 60 with a conductive layer on the outer side of the second retardation layer 50 may be replaced with an optically equivalent configuration (for example, a laminate of the second retardation layer and the conductive layer) .

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

The polarizing plate with a retardation layer of the present invention may be in the form of a sheet or a strip. In this specification, the term “strip-shaped” means an elongated shape having a sufficiently long length relative to the width, and includes, for example, an elongated shape with a length of 10 times or more relative to the width, and preferably 20 times or more. . The long polarizing plate with retardation layer can be rolled into a roll shape.

In practical use, an adhesive layer (not shown) can be provided on the opposite side of the phase difference layer from the polarizing plate, and the polarizing plate with the phase difference layer can be attached to the image display unit. Also, the surface of the adhesive layer should be temporarily attached to the release film before the polarizing plate with the retardation layer is used. By temporarily adhering the release film, a roll can be formed while protecting the adhesive layer.

The total thickness of the polarizing plate with a retardation layer is preferably 60 μm or less, and preferably 55 μm or less, more preferably 50 μm or less, and particularly preferably 40 μm or less. The lower limit of the total thickness may be 28 μm, for example. According to the embodiment of the present invention, the polarizing plate with the extremely thin retardation layer as described above can be realized. The polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. The polarizing plate with retardation layer is particularly suitable for curved image display devices and/or flexible or bent image display devices. In addition, the total thickness of the polarizing plate with a retardation layer means all the layers of the polarizing plate with a retardation layer after deducting the adhesive layer used to make the polarizing plate and the panel or glass and the like adhered to the outside by the adhesive Total thickness (that is, the total thickness of the polarizing plate with a retardation layer does not include the adhesive layer for attaching the polarizing plate with a retardation layer to the adjacent members such as the image display unit and the release film that can temporarily adhere to the surface The thickness).

The unit weight of the polarizing plate with a retardation layer according to an embodiment of the present invention is, for example, 6.5 mg/cm ² or less, preferably 2.0 mg/cm ² to 6.0 mg/cm ² , and preferably 3.0 mg/cm ² to 5.5 mg/ cm ² , more preferably from 3.5 mg/cm ² to 5.0 mg/cm ² . When the display panel is thin, the panel may be slightly deformed due to the weight of the polarizing plate with a retardation layer, which may cause display defects, but a polarizing plate with a retardation layer having a unit weight of 6.5 mg/cm ² or less is used , The panel can be prevented from being deformed. In addition, the polarizing plate with the retardation layer having the above unit weight has good handleability even after being thinned, and can exhibit extremely excellent flexibility and bending durability.

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

B. Polarizing plate B-1. Polarizing film The polarizing film 11 has a thickness of 8 μm or less as described above, and a unit absorbance at a wavelength of 210 nm of 1.00 or less. Compared with a general thin polarizing film, the polarizing film used in the present invention has a very small unit absorbance at a wavelength of 210 nm. This means that the content ratio of iodide ions in the polarizing film that does not form a complex with PVA (absorption in the ultraviolet region near 210 nm) is very small. In the polarizing film, iodine can be roughly divided into iodine ions having absorption in the ultraviolet region and PVA-iodine complex having absorption in the visible light. Among them, those that contribute to the polarization characteristics of the polarizing film are PVA-iodine complexes. Since the amount of iodine that can be contained in the polarizing film is limited, the reduction of iodide ion will increase the PVA-iodine complex. That is, in a thin polarizing film having a thickness of 8 μm or less, the optical characteristics can be improved by reducing iodide ions. This tendency is particularly noticeable in polarizing films having a thin thickness and a high iodine concentration in the film. The unit absorbance at a wavelength of 210 nm is preferably 0.80 or less, and preferably 0.60 or less. The lower limit of the unit absorbance at a wavelength of 210 nm may be 0.20, for example. Absorbance units based orthogonal transmittance of the polarizing plate as measured at the time of obtaining the degree of polarization to be described later as a reference Tc calculated by the following formula orthogonal absorbance A _210, A ₂₁₀ and the absorbance by the thickness orthogonal to thereby seek Get. In addition, the unit absorbance of the polarizing plate substantially corresponds to the unit absorbance of the polarizing film. Orthogonal absorbance = log10 (100/Tc) One of the characteristics of the present invention is to use a thin polarizing film having the above-mentioned characteristics. In addition, the polarizing film is related to having the unit absorbance as described above, so 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 preferably 1.4 Above, and above 1.8 is better, above 2.0 is better, above 2.2 is even better. The upper limit of the ratio (A ₅₅₀ /A ₂₁₀ ) may be 3.5, for example. This means that the content ratio of iodide ions in the polarizing film decreases, and the content ratio of PVA-I ₅ ^- complex compound having absorption near 600 nm increases.

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

The polarizing film should show absorption dichroism at any wavelength from 380nm to 780nm. The single transmittance of the polarizing film is preferably 49.0% or less, and more preferably 48.0% or less. On the other hand, the single transmittance is preferably 41.5% or more, and preferably 42.0% or more, and more preferably 42.5% or more. The polarization degree of the polarizing film is preferably 99.990% or more, and preferably 99.998% or less. The above-mentioned monomer transmittance is representatively a Y value obtained by using an ultraviolet visible light spectrophotometer to measure and correct the optical performance. The above-mentioned polarization degree is representatively 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 the optical performance. Polarization (%)={(Tp-Tc)/(Tp+Tc)} ^1/2 ×100

In one embodiment, the transmittance of a thin polarizing film with a thickness of 8 μm or less represents a layered body of a polarizing film (refractive index on the surface: 1.53) and a protective film (refractive index: 1.50) as the measurement object, and uses ultraviolet visible spectrophotometry To measure. Depending on the refractive index of the surface of the polarizing film and/or the refractive index of the surface of the protective film in contact with the air interface, the reflectance of each layer at the interface will change, and as a result, the measured value of the transmittance may change. Therefore, for example, when a protective film with a refractive index other than 1.50 is used, the measured value of the transmittance can be corrected according to the refractive index of the surface of the protective film in contact with the air interface. Specifically, the correction value C of the transmittance is represented by the following formula using polarized light reflectance R ₁ (transmission axis reflectance) parallel to the transmission axis of 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) where R ₀ is the transmission axis reflectance when using a protective film with a refractive index of 1.50, n ₁ is the refractive index of the protective film used, and T ₁ is the transmission of the polarizing film rate. For example, when using a substrate with a surface refractive index of 1.53 (cycloolefin-based film, hard-coated film, etc.) as the protective film, the correction amount C is about 0.2%. At this time, by adding 0.2% to the measured transmittance, the polarizing film with a surface refractive index of 1.53 can be converted into the transmittance when a protective film with a surface refractive index of 1.50 is used. In addition, after calculation according to the above formula, the amount of change in the correction value C after changing the transmittance T _{1 of the} polarizing film by 2% is 0.03% or less, so the influence of the transmittance of the polarizing film on the value of the correction value C is limited. In addition, when the protective film has absorption other than surface reflection, appropriate correction can be performed according to the absorption amount.

It is desirable that, in the orthogonal polarizing absorbance at a wavelength of 470nm A ₄₇₀ and the absorbance at a wavelength of orthogonal 600nm A ₆₀₀ ratio of (A ₄₇₀ / A ₆₀₀₎ of 0.7 or more, and 0.75 or more is desirable, more suitably from Above 0.80, especially above 0.85. The ratio (A ₄₇₀ /A ₆₀₀ ) is preferably 2.00 or less, and preferably 1.33 or less. As long as the ratio (A ₄₇₀ /A ₆₀₀ ) is within the above range, the content ratio of PVA-I ₃ ^- complex compound having absorption around 480 nm can be maintained without greatly reducing it. As a result, good polarization performance can be achieved in all visible light regions. Under the premise that the amount of iodine of the thin polarizing film is limited, it is difficult to control both the above unit absorbance and ratio (A ₄₇₀ /A ₆₀₀ ) within the desired range by the prior art, but the polarizing film used in the present invention can be Wait for both to be controlled within the desired range.

In addition, 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 preferably +5 or less. Orthogonal b value means the hue when the polarizing film (the polarizing plate with retardation layer is finally arranged) is in the orthogonal state, the greater the absolute value of this value, the orthogonal hue (black display of the image display device) ) Looks more toned. For example, when the orthogonal b value is -10 or lower, the black display will look blue, and the display performance will be reduced. That is, according to the embodiment of the present invention, a polarizing plate with a retardation layer can be produced, which can achieve excellent hue during black display. In addition, the orthogonal b value can be measured using a spectrophotometer represented by V-7100.

The iodine concentration of the polarizing film is preferably 3% by weight or more, and preferably 4% by weight or more, and more preferably 6% by weight or more. The upper limit of the iodine concentration may be, for example, 12% by weight. As long as the iodine concentration is within the above range, the effect of reducing the above unit absorbance is significant. In other words, the above effect is more noticeable in the thin polarizing film whose iodine concentration becomes higher as described above.

Any and appropriate polarizing films can be used for the polarizing film. Representatively, the polarizing film can be produced by using a laminate of two or more layers.

Specific examples of the polarizing film obtained using the laminate include a polarizing film obtained by using a laminate of a resin substrate and a PVA-based resin layer formed on the resin substrate by coating. A polarizing film obtained by using a laminate of a resin base material and a PVA-based resin layer formed on the resin base material can be produced, for example, by applying a PVA-based resin solution to the resin base material, and It is dried to form a PVA-based resin layer on the resin substrate to obtain a laminate of the resin substrate and the PVA-based resin layer; and the laminate is stretched and dyed to form a polarizing film of the PVA-based resin layer. In the present embodiment, stretching typically includes immersing the laminate in a boric acid aqueous solution and stretching. If necessary, the stretching may further include stretching the laminate in air at a high temperature (for example, 95° C. or higher) before stretching in the boric acid aqueous solution. The resulting resin substrate/polarizing film laminate can be used directly (that is, the resin substrate can also be used as the protective layer of the polarizing film), or the resin substrate can be peeled from the resin substrate/polarizing film laminate and peeled off therefrom The surface is laminated with an arbitrary and appropriate protective layer according to the purpose for later use. The details of the manufacturing method of the polarizing film are described in, for example, Japanese Patent Laid-Open No. 2012-73580. In this specification, the entire contents of this gazette are used as a reference.

The manufacturing method of the polarizing film typically includes the following steps: forming a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of the elongated thermoplastic resin substrate to form a laminate; and, for the above The laminate is sequentially subjected to aerial auxiliary stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment. The drying shrinkage treatment heats the laminate while being transported in the longitudinal direction, thereby shrinking it by 2% in the width direction the above. Thereby, it is possible to provide a polarizing film having excellent optical characteristics, the thickness of which is 8 μm or less, and the unit absorbance at a wavelength of 210 nm is 1.00 or less. That is, by introducing auxiliary extension, even when PVA is coated on the thermoplastic resin, the crystallinity of PVA can be improved, and high optical characteristics can be achieved. At the same time, increasing the orientation of PVA in advance can prevent problems such as reduced orientation or dissolution of PVA when immersed in water in the subsequent dyeing step or extension step, and high optical characteristics can be achieved. In addition, when the PVA-based resin layer is immersed in a liquid, it is possible to suppress the disorder of the orientation of the polyvinyl alcohol molecule and the decrease in the orientation compared to the case where the PVA-based resin layer does not contain a halide. Therefore, it is possible to improve the optical characteristics of the polarizing film produced by the treatment step performed by immersing the laminate in a liquid such as dyeing treatment and water extension treatment. In addition, the shrinkage of the laminate in the width direction through the drying shrinkage treatment can improve the optical characteristics.

B-2. Protective layer The first protective layer 12 and the second protective layer 13 are each formed of any suitable thin film that can be used as a protective layer of a polarizing film. Specific examples of the material of the main component of the film include cellulose resins such as triethyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, and polyacetyl Transparent resins such as imine-based, polyether-based, poly-based, polystyrene-based, polynorbornene-based, polyolefin-based, (meth)acrylic, and acetate-based. In addition, thermosetting resins such as (meth)acrylic system, urethane system, (meth)acrylate urethane system, epoxy system, and polysiloxane system, ultraviolet curing resin, etc. may also be mentioned. Other examples include glassy polymers such as siloxane-based polymers. Moreover, the polymer film described in Japanese Patent Laid-Open No. 2001-343529 (WO01/37007) can also be used. As the material of the film, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted amide 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, for example Examples thereof include resin compositions having an alternating copolymer composed of isobutylene and N-methylmaleimide and an acrylonitrile-styrene copolymer. The polymer film may be, for example, an extruded product of the above resin composition.

The polarizing plate with a retardation layer of the present invention will be disposed on the viewing side of the image display device as described later, and the first protective layer 12 will be disposed on the viewing side. Therefore, the first protective layer 12 may be subjected to surface treatments such as hard coating treatment, anti-reflection treatment, anti-adhesion treatment, and anti-glare treatment, if necessary. And/or, the first protective layer 12 may be provided with a process that can improve the visibility when viewing through polarized sunglasses (typically, to impart (elliptical) circular polarizing function and impart ultrahigh phase difference) as required. By performing the processing described above, even if the displayed image is visually recognized through polarized lenses such as polarized sunglasses, excellent visibility can still be achieved. Therefore, the polarizing plate with a retardation layer can also be suitably used for image display devices that can be used outdoors.

The thickness of the first protective layer is preferably 5 μm to 80 μm, and preferably 10 μm to 40 μm, and more preferably 10 μm to 30 μm. In addition, when surface treatment is performed, the thickness of the outer protective layer includes the thickness of the surface treatment layer.

In one embodiment, the second protective layer 13 is preferably optically isotropic. In this specification, "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. In one embodiment, the second protective layer 13 is a phase difference layer having an arbitrary and appropriate phase difference value. At this time, 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, and preferably 10 μm to 40 μm, and more preferably 10 μm to 30 μm. From the viewpoint of thinning and weight reduction, it is desirable that the second protective layer can be omitted.

B-3. Manufacturing method of polarizing film The polarizing film can be obtained by, for example, a manufacturing method including: forming a polyvinyl alcohol-based resin layer (PVA-based resin layer) on one side of a long thermoplastic resin substrate to form a laminate, the polyvinyl alcohol-based resin layer containing Halides and polyvinyl alcohol-based resins (PVA-based resins); and, the air-assisted extension treatment, dyeing treatment, underwater extension treatment, and drying shrinkage treatment are sequentially performed on the laminate, the drying shrinkage treatment conveys the accumulation along the long side direction The body is heated and contracted by more than 2% in the width direction. The halide content in the PVA-based resin layer is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin. Drying shrinkage treatment should be processed by heating roller, and the temperature of heating roller should be 60℃~120℃. The shrinkage rate in the width direction of the laminate after drying shrinkage treatment is preferably 2% or more. According to the above manufacturing method, the polarizing film described in the above item B-1 can be produced. In particular, a polarizing film having excellent optical characteristics (typically, single-piece transmittance and unit polarization at a wavelength of 210 nm) can be produced by: after manufacturing a laminate including a halide-containing PVA-based resin layer , The multi-layer stretching including the aerial auxiliary stretching and the underwater stretching is performed on the stretching of the above-mentioned laminate, and then the stretched laminate is heated by a heating roller.

B-3-1. Making a laminate As a method for producing a laminate of a thermoplastic resin base material and a PVA-based resin layer, any suitable method can be adopted. It is preferable to apply a coating solution containing a halide and a PVA-based resin to the surface of the thermoplastic resin substrate and dry it, thereby forming a PVA-based resin layer on the thermoplastic resin substrate. As described above, the halide content in the PVA-based resin layer is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin.

The method for applying the coating liquid can be any appropriate method. 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 doctor blade coating method (comma coating method, etc.), etc. are mentioned. The coating and 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, and more preferably 3 μm to 20 μm.

Before forming the PVA-based resin layer, the thermoplastic resin substrate may be subjected to surface treatment (for example, corona treatment, etc.), or an easy adhesion layer may be formed on the thermoplastic resin substrate. By performing the treatment, the adhesion between the thermoplastic resin base material and the PVA-based resin layer can be improved.

B-3-1-1. Thermoplastic resin substrate The thickness of the thermoplastic resin substrate 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 is greater than 300 μm, for example, the thermoplastic resin substrate may take a long time to absorb water during the water-extending treatment described below, and may cause an excessive load on the elongation.

The water absorption rate of the thermoplastic resin substrate is preferably 0.2% or more, and more preferably 0.3% or more. The thermoplastic resin substrate absorbs water, and water can play the role of a plasticizer for plasticization. As a result, the extension stress can be greatly reduced and the extension can be performed at a high rate. On the other hand, the water absorption rate of the thermoplastic resin substrate is preferably 3.0% or less, and more preferably 1.0% or less. By using such a thermoplastic resin base material, it is possible to prevent the dimensional stability of the thermoplastic resin base material from being significantly reduced during manufacturing, which may cause defects such as deterioration of the appearance of the polarizing film produced. It can prevent the base material from breaking when extending in water, or the PVA-based resin layer peeling off from the thermoplastic resin base material. In addition, the water absorption rate of the thermoplastic resin base material can be adjusted by, for example, introducing a modified group into the constituent material. The water absorption rate is a value determined in accordance with 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, the crystallization of the PVA-based resin layer can be suppressed, and the extensibility of the laminate can be sufficiently ensured. In addition, in consideration of plasticizing the thermoplastic resin base material with water and allowing good water extension, it is preferably 100°C or lower, more preferably 90°C or lower. On the other hand, the glass transition temperature of the thermoplastic resin substrate is preferably 60°C or higher. By using such a thermoplastic resin base material, it is possible to prevent defects such as deformation of the thermoplastic resin base material (e.g., unevenness, sag, wrinkle, etc.) when coating and drying the coating solution containing the PVA-based resin, As a result, the laminate is produced satisfactorily. In addition, the PVA-based resin layer can be stretched well at an appropriate temperature (for example, about 60°C). In addition, the glass transition temperature of the thermoplastic resin substrate can be adjusted by, for example, heating by using a crystallization material that can introduce a modified group into the constituent material. The glass transition temperature (Tg) is a value determined in accordance with JIS K 7121.

As the constituent material of the thermoplastic resin base material, any suitable thermoplastic resin can be used. Examples of thermoplastic resins 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, etc. Among these, norbornene-based resins and amorphous polyethylene terephthalate-based resins are more desirable.

In one embodiment, an amorphous (uncrystallized) polyethylene terephthalate resin is preferably used. Among them, the use of amorphous (difficult to crystallize) polyethylene terephthalate resins is particularly preferred. Specific examples of the amorphous polyethylene terephthalate-based resin include copolymers further containing isophthalic acid and/or cyclohexane dicarboxylic acid as the dicarboxylic acid, or cyclohexane dicarboxylic acid. Methanol or diethylene glycol is a copolymer of glycol.

In a preferred embodiment, the thermoplastic resin substrate is composed of a polyethylene terephthalate resin having isophthalic acid units. This is because the thermoplastic resin substrate has extremely excellent extensibility and can suppress crystallization during elongation. We speculate that it is caused by the introduction of isophthalic acid units to give the main chain a huge deflection. The polyethylene terephthalate-based resin has terephthalic acid units and ethylene glycol units. The content ratio of the isophthalic acid unit is preferably 0.1 mol% or more, and more preferably 1.0 mol% or more with respect to the total of all repeating units. This is because a thermoplastic resin substrate with extremely excellent elongation can be produced. On the other hand, the content ratio of the isophthalic acid unit is preferably 20 mol% or less, and more preferably 10 mol% or less with respect to the total of all repeating units. By setting the content ratio, the degree of crystallization can be favorably increased in the drying shrinkage treatment described later.

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

The extension temperature of the thermoplastic resin substrate relative to the glass transition temperature (Tg) is preferably Tg-10°C~Tg+50°C. The extension ratio of the thermoplastic resin substrate is preferably 1.5 times to 3.0 times.

As for the method of stretching the thermoplastic resin substrate, any suitable method can be adopted. Specifically, it may be a fixed end or a free end. The extension method can be dry or wet. The extension of the thermoplastic resin substrate can be performed in one stage or in multiple stages. When performing in multiple stages, the above-mentioned stretching magnification is the product of the stretching magnifications in each stage.

B-3-1-2. Coating liquid The coating liquid system contains the halide and the PVA resin as described above. The coating liquid represents a solution obtained by dissolving the halide and the PVA resin in a solvent. Examples of the solvent include polyhydric alcohols such as water, dimethylsulfoxide, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, various glycols, and trimethylolpropane. Diamines, diethylenetriamine and other amines. These can be used alone or in combination of two or more. Among these, water is better. The concentration of the PVA resin in the solution is preferably 3 to 20 parts by weight relative to 100 parts by weight of the solvent. As long as it is the resin concentration, a uniform coating film adhered to the thermoplastic resin substrate can be formed. The content of the halide in the coating liquid is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin.

Additives can also be incorporated in the coating solution. Examples of additives include plasticizers and surfactants. Examples of the plasticizer include polyhydric alcohols such as ethylene glycol and glycerin. The surfactant may, for example, be a nonionic surfactant. These can be used to further improve the uniformity, dyeability, and extensibility of the resulting PVA-based resin layer.

Any appropriate resin can be used for the PVA-based resin. Examples thereof include polyvinyl alcohol and ethylene-vinyl alcohol copolymer. Polyvinyl alcohol can be obtained by saponifying polyvinyl acetate. The ethylene-vinyl alcohol copolymer can be obtained by saponifying the ethylene-vinyl acetate copolymer. The saponification degree of the PVA 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 obtained in accordance with JIS K 6726-1994. By using the saponification degree PVA-based resin, a polarizing film excellent in durability can be obtained. When the degree of saponification is too high, there is a risk of gelation.

The average degree of polymerization of the PVA-based resin can be appropriately selected according to the purpose. The average polymerization degree is usually 1000 to 10000, preferably 1200 to 4500, and more preferably 1500 to 4300. In addition, the average degree of polymerization can be obtained in accordance with JIS K 6726-1994.

As the halide, any suitable halide can be used. Examples include iodide and sodium chloride. Examples of the iodide include potassium iodide, sodium iodide, and lithium iodide. Among these, potassium iodide is preferred.

The amount of halide in the coating liquid is preferably 5 to 20 parts by weight relative to 100 parts by weight of the PVA-based resin, and more preferably 10 to 15 parts by weight relative to 100 parts by weight of the PVA-based resin. If the amount of halide is more than 20 parts by weight with respect to 100 parts by weight of the PVA-based resin, the halide may overflow and the polarizing film finally made may become cloudy.

Generally speaking, when the PVA resin layer is stretched, the orientation of the polyvinyl alcohol molecules in the PVA resin layer becomes higher, but if the stretched PVA resin layer is immersed in a liquid containing water, there will be polyethylene The orientation of alcohol molecules is disordered and the orientation is reduced. In particular, when the laminate of the thermoplastic resin substrate and the PVA-based resin layer is extended in boric acid water, the above orientation is extended when the laminate is extended at a relatively high temperature in boric acid water to stabilize the extension of the thermoplastic resin substrate. The tendency to decrease the degree is significant. For example, the extension of the PVA film monomer in boric acid water is generally carried out at 60°C, whereas the extension of the laminate of A-PET (thermoplastic resin substrate) and PVA-based resin layer is at 70°C The temperature before and after, ie, at a higher temperature, at this time, the orientation of the PVA at the initial stage of extension will decrease before it rises due to extension in water. In this regard, after producing a laminate of a halide-containing PVA-based resin layer and a thermoplastic resin substrate, the laminate is subjected to high-temperature elongation (auxiliary elongation) in air before being extended in boric acid water, thereby facilitating the auxiliary elongation Crystallization of the PVA-based resin in the PVA-based resin layer of the laminate. As a result, when the PVA-based resin layer is immersed in the liquid, the orientation disorder and the decrease in the orientation of the polyvinyl alcohol molecule can be suppressed more than when the PVA-based resin layer contains no halide. Therefore, it is possible to improve the optical characteristics of the polarizing film produced by the treatment step performed by immersing the laminate in a liquid such as dyeing treatment and water extension treatment.

B-3-2. Air-assisted extension processing In particular, in order to obtain high optical characteristics, a method of combining two-stage extension of dry extension (auxiliary extension) and boric acid underwater extension is selected. Such as the two-stage extension method, by introducing auxiliary extension, it can be extended while suppressing the crystallization of the thermoplastic resin substrate, solving the problem of the decrease in the extensibility caused by the excessive crystallization of the thermoplastic resin substrate in the subsequent boric acid water extension The problem is that the laminate can be extended at a higher magnification. In addition, when coating the PVA-based resin on the thermoplastic resin substrate, in order to suppress the influence of the glass transition temperature of the thermoplastic resin substrate, the coating temperature must be made higher than when the PVA-based resin is coated on a general metal drum If it is lower, as a result, the crystallization of the PVA-based resin becomes relatively low and sufficient optical characteristics cannot be obtained. In this regard, by introducing auxiliary extension, even when the PVA-based resin is coated on the thermoplastic resin, the crystallinity of the PVA-based resin can be improved, and high optical characteristics can be achieved. At the same time, the orientation of the PVA-based resin is improved in advance to prevent problems such as reduced orientation and dissolution of the PVA-based resin when immersed in water in the subsequent dyeing step and extension step, and high optical characteristics can be achieved.

The extension method of air-assisted extension can be fixed-end extension (such as the method of using a tenter stretching machine) or free-end extension (such as the method of uniaxially extending the laminate through rollers with different peripheral speeds) However, in order to obtain high optical characteristics, the free end extension can be actively used. In one embodiment, the aerial stretching process includes a heating roller stretching step, which is to transport the above-mentioned layered body along its longitudinal direction and at the same time extend using the circumferential speed difference between the heating rollers. The air stretching process typically includes a zone stretching step and a heating roller stretching step. In addition, the order of the region stretching step and the heating roller stretching step is not limited, and the region stretching step may be performed first, or the heating roller stretching step may be performed first. The region extension step can also be omitted. In one embodiment, the region extending step and the heating roller extending step are performed in sequence. Furthermore, in another embodiment, the film end is held in a tenter stretching machine, and the distance between the tenter machines is expanded in the flow direction to extend (the increase in the distance between the tenter machines is the stretching ratio). At this time, the distance of the tenter in the width direction (the direction perpendicular to the flow direction) is set to be arbitrarily close. Preferably, it can be set to an extension magnification with respect to the flow direction to use free-end extension for approach. When the free end is extended, it is calculated as the shrinkage ratio in the width direction = (1/extension ratio) ^1/2 .

The air-assisted extension can be performed in one stage or in multiple stages. When carried out in multiple stages, the stretching magnification is the product of the stretching magnifications in each stage. The extension direction of the air-assisted extension should be approximately the same as the extension direction of the underwater extension.

The extension magnification of air-assisted extension should be 2.0 to 3.5 times. The maximum extension magnification when combining air-assisted extension and underwater extension is preferably 5.0 times or more relative to the original length of the laminate, preferably 5.5 times or more, and more preferably 6.0 times or more. The "maximum elongation ratio" in this specification means the elongation ratio before the laminate is to be broken, and it is a value that is 0.2 lower than its value after confirming the elongation ratio of the laminate to break.

The extension temperature of the air-assisted extension can be set to an arbitrary and appropriate value according to the forming material of the thermoplastic resin base material, the extension method, and the like. The elongation temperature is preferably higher than the glass transition temperature (Tg) of the thermoplastic resin substrate, and more preferably the glass transition temperature (Tg) of the thermoplastic resin substrate + 10°C or higher, and particularly preferably Tg + 15°C or higher. On the other hand, the upper limit of the extension temperature is preferably 170°C. By stretching at the above-mentioned temperature, the rapid progress of crystallization of the PVA-based resin can be suppressed, and thus the defects caused by the crystallization can be suppressed (for example, the orientation of the PVA-based resin layer is hindered by stretching). The crystallization index of the PVA resin after air-assisted extension is preferably 1.3 to 1.8, and more preferably 1.4 to 1.7. The crystallization index of PVA resin can be measured by ATR method using Fourier transform infrared spectrophotometer. Specifically, the measurement was carried out using polarized light as the measurement light, and using the intensities of 1141 cm ^-1 and 1440 cm ^-1 of the obtained spectrum, the crystallization index was calculated according to the following formula. 1141cm ^-1 intensity incident measurement light and the time of measurement, I _R:: crystallinity index = (I _C / I _R) However, I _C 1440cm ^-1 when the intensity of the incident measurement light and measured.

B-3-3. Insoluble treatment If necessary, the insolubilization treatment may be performed after the air-assisted extension treatment and before the water extension treatment or dyeing treatment. The above-mentioned insolubilization treatment represents that the PVA-based resin layer is immersed in a boric acid aqueous solution. By performing the insolubilization treatment, the PVA-based resin layer can be given water resistance, and the orientation of the PVA can be prevented from decreasing when immersed in water. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 4 parts by weight relative to 100 parts by weight of water. The liquid temperature of the insoluble bath (boric acid aqueous solution) is preferably 20°C to 50°C.

B-3-4. Dyeing treatment The above-mentioned dyeing treatment is performed by dyeing the PVA-based resin layer with a dichroic substance (typically iodine). Specifically, it is performed by adsorbing iodine to the PVA-based resin layer. Examples of the adsorption method include a method of immersing the 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 spraying the dyeing solution to the PVA Method on the resin layer. The method of immersing the laminate in a dyeing liquid (dyeing bath) is preferable. This is because it can adsorb iodine well.

The above dyeing solution is preferably an aqueous iodine solution. The blending amount of iodine is preferably 0.05 to 0.5 parts by weight relative to 100 parts by weight of water. In order to improve the solubility of iodine in water, it is appropriate to mix iodide in the iodine aqueous solution. Examples of the 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. Among these, potassium iodide is preferred. The blending amount of the iodide is preferably 0.1 to 10 parts by weight, and more preferably 0.3 to 5 parts by weight relative to 100 parts by weight of water. In order to suppress the dissolution of the PVA-based resin, the temperature of the dyeing liquid during dyeing is preferably 20°C to 50°C. When immersing the PVA-based resin layer in the dyeing solution, in order to ensure the transmittance of the PVA-based resin layer, the immersion time is preferably 5 seconds to 5 minutes, and more preferably 30 seconds to 90 seconds.

The dyeing conditions (concentration, liquid temperature, immersion time) can be set in such a manner that the monomer transmittance of the polarizing film finally obtained and the unit absorbance at a wavelength of 210 nm become desired values. The dyeing condition is preferably to use an iodine aqueous solution as the dyeing solution, and set the content ratio of iodine and potassium iodide in the iodine aqueous solution to be 1:5 to 1:20. The content ratio of iodine and potassium iodide in the iodine aqueous solution is preferably 1:5~1:10. Thereby, a polarizing film having optical characteristics as described above can be produced.

When the layered body is immersed in a treatment bath containing boric acid (typically insoluble treatment) and then dyeing is carried out, the boric acid contained in the treatment bath will be mixed into the dyeing bath and the concentration of boric acid in the dyeing bath will vary with the As time changes, as a result, the dyeability becomes unstable. In order to suppress the above-mentioned destabilization of the dyeing property, the upper limit of the boric acid concentration of the dyeing bath is adjusted to 4 parts by weight relative to 100 parts by weight of water, more preferably to 2 parts by weight. On the other hand, the lower limit of the boric acid concentration of the dyeing bath is preferably 0.1 part by weight, more preferably 0.2 part by weight, and still more preferably 0.5 part by weight with respect to 100 parts by weight of water. In one embodiment, a dyeing bath in which boric acid has been blended in advance is used for dyeing treatment. In this way, the ratio of the change in boric acid concentration when the boric acid in the treatment bath is mixed into the dyeing bath can be reduced. The amount of boric acid blended into the dyeing bath in advance (that is, the content of boric acid not derived from the above treatment bath) is preferably 0.1 to 2 parts by weight, more preferably 0.5 parts by weight relative to 100 parts by weight of water ~1.5 parts by weight.

B-3-5. Cross-linking treatment If necessary, the cross-linking treatment may be performed after the dyeing treatment and before the extension treatment in water. The above-mentioned cross-linking treatment can be performed by immersing the PVA-based resin layer in an aqueous solution of boric acid. By performing the cross-linking treatment, the PVA-based resin layer can be provided with water resistance, and the orientation of the PVA can be prevented from decreasing when immersed in high-temperature water during subsequent water stretching. The concentration of the boric acid aqueous solution is preferably 1 part by weight to 5 parts by weight relative to 100 parts by weight of water. In addition, when the cross-linking treatment is performed after the above-mentioned dyeing treatment, it is preferable to further blend iodide. By blending iodide, the elution of iodine that has been 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 relative to 100 parts by weight of water. Specific examples of iodide are as described above. The liquid temperature of the cross-linking bath (boric acid aqueous solution) is preferably 20°C to 50°C.

B-3-6. Extended water treatment The underwater stretching treatment is performed by immersing the laminate in the stretching bath. By water stretching, it can be stretched at a temperature lower than the glass transition temperature of the thermoplastic resin substrate or PVA-based resin layer (typically around 80°C), while suppressing crystallization of the PVA-based resin layer Perform high magnification extension. As a result, a polarizing film having excellent optical characteristics can be produced.

The method of extending the laminate can be any suitable method. Specifically, it may be a fixed-end extension or a free-end extension (for example, a method of uniaxially extending a laminate between rollers having different peripheral speeds). Preferably, the free end extension is selected. The extension of the laminate can be performed in one stage or in multiple stages. When performing in multiple stages, the stretching magnification (maximum stretching magnification) of the laminate to be described later is the product of the stretching magnification in each stage.

The extension in water is preferably carried out by immersing the laminate in an aqueous solution of boric acid (boric acid extension in water). By using an aqueous solution of boric acid as an extension bath, the PVA-based resin layer can be given rigidity to withstand tension during extension and water resistance insoluble in water. Specifically, boric acid generates tetrahydroxyboric acid anions in the aqueous solution and can be cross-linked with the PVA-based resin by hydrogen bonding. As a result, it is possible to impart rigidity and water resistance to the PVA-based resin layer and perform good stretching, thereby producing a polarizing film having excellent optical characteristics.

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

It is suitable to blend iodide in the above extension bath (boric acid aqueous solution). By blending iodide, the elution of iodine that has been adsorbed on the PVA-based resin layer can be suppressed. Specific examples of the iodide are mentioned above. The concentration of iodide relative to 100 parts by weight of water is preferably 0.05 to 15 parts by weight, more preferably 0.5 to 8 parts by weight.

The extension temperature (the liquid temperature of the extension bath) is preferably 40°C to 85°C, and more preferably 60°C to 75°C. As long as the temperature is reached, the PVA-based resin layer can be suppressed from dissolving, and at the same time, it can be stretched at a high rate. Specifically, as described above, considering the relationship with the formation of the PVA-based resin layer, the glass transition temperature (Tg) of the thermoplastic resin substrate is preferably 60° C. or higher. At this time, if the stretching temperature is lower than 40°C, even if the thermoplastic resin base material is considered to be plasticized with water, it may not be stretched well. On the other hand, the higher the temperature of the stretching bath, the higher the solubility of the PVA-based resin layer, and it may be impossible to obtain excellent optical characteristics. The immersion time of the laminate in the extension bath is preferably 15 seconds to 5 minutes.

The stretching magnification for stretching in water is preferably 1.5 times or more, preferably 3.0 times or more. The total elongation ratio of the laminate is preferably 5.0 times or more relative to the original length of the laminate, and more preferably 5.5 times or more. By achieving the above-mentioned high extension magnification, a polarizing film with extremely excellent optical characteristics can be manufactured. The high extension ratio can be achieved by using an underwater extension method (boric acid underwater extension).

B-3-7. Dry shrinkage treatment The above-mentioned drying shrinkage treatment can be carried out by heating the area by heating the entire area, or by heating the conveying roller (so-called using a heating roller) (heating roller drying method). It is preferable to use both. By using a heating roller to dry, the heating curl of the laminate can be effectively suppressed, and a polarizing film excellent in appearance can be manufactured. Specifically, by drying the laminate along the heating roller, the crystallization of the above thermoplastic resin substrate can be efficiently promoted to increase the degree of crystallization, even at a relatively low drying temperature, It can still increase the crystallinity of the thermoplastic resin substrate well. As a result, the rigidity of the thermoplastic resin base material is increased to be able to withstand the shrinkage of the PVA-based resin layer due to drying, so that curling is suppressed. In addition, by using a heating roller, the laminate can be dried while maintaining the flat state. Therefore, not only the generation of curl but also the generation of wrinkles can be suppressed. At this time, the laminate can be shrunk in the width direction by drying shrinkage treatment to improve the optical characteristics. It is because it can effectively improve the orientation of PVA and PVA/iodine complex. The shrinkage rate in the width direction of the laminate after drying shrinkage treatment is preferably 1% to 10%, more preferably 2% to 8%, and particularly preferably 4% to 6%. By using a heating roller, the laminate can be transported while continuously shrinking in the width direction, and high productivity can be achieved.

FIG. 4 is a schematic diagram showing an example of drying shrinkage treatment. In the drying shrinkage treatment, the transport rollers R1 to R6 and guide rollers G1 to G4 that have been heated to a predetermined temperature are used to transport the laminate 200 while drying. In the illustrated example, the conveying rollers R1 to R6 are arranged such that the surface of the PVA resin layer and the surface of the thermoplastic resin substrate can be alternately and continuously heated, but, for example, the conveying rollers R1 to R6 can be arranged to continuously heat only the laminate 200 One side (for example, thermoplastic resin substrate side).

The drying conditions can be controlled by adjusting the heating temperature of the conveyor roller (temperature of the heating roller), the number of heating rollers, and the contact time with the heating roller. The temperature of the heating roller is preferably 60°C to 120°C, more preferably 65°C to 100°C, and particularly preferably 70°C to 80°C. It is possible to increase the crystallinity of the thermoplastic resin well and suppress curl well, and to manufacture an optical laminate having extremely excellent durability. In addition, the temperature of the heating roller can be measured with a contact thermometer. There are six conveying rollers in the illustrated example, but there are no particular restrictions as long as there are a large number of conveying rollers. There are usually 2 to 40 conveying rollers, preferably 4 to 30. The contact time (total contact time) between the laminate and the heating roller is preferably 1 second to 300 seconds, preferably 1 to 20 seconds, and more preferably 1 to 10 seconds.

The heating roller may be installed in a heating furnace (for example, an oven), or may be installed in a general manufacturing line (room temperature environment). It should be installed in the heating furnace with air supply mechanism. By using the heating roller for drying and hot air drying, the rapid temperature change between the heating rollers can be suppressed, and the shrinkage in the width direction can be easily controlled. The temperature of hot air drying should be 30℃~100℃. Moreover, the hot air drying time should be 1 second to 300 seconds. The wind speed of hot air should be about 10m/s~30m/s. In addition, the wind speed is the wind speed in the heating furnace, which can be measured with a mini fan-type digital anemometer.

B-3-8. Other processing It is advisable to perform washing treatment after extension treatment in water and before drying shrinkage treatment. The above-mentioned cleaning treatment can be performed by immersing the PVA-based resin layer in an aqueous potassium iodide solution.

C. The first phase difference layer The first retardation layer 20 is the orientation-cured layer of the above-mentioned liquid crystal compound. By using a liquid crystal compound, the difference between nx and ny of the obtained retardation layer can be made much larger than that of the non-liquid crystal material, so the thickness of the retardation layer required to obtain the desired in-plane retardation can be greatly reduced many. As a result, the polarizing plate with the retardation layer can be further thinned and lightened. The "oriented cured layer" in this specification refers to a layer in which the liquid crystal mixture is oriented in a predetermined direction within the layer, and the orientation state has been fixed. In addition, the concept of "orientation cured layer" includes an orientation hardened layer obtained by curing liquid crystal monomers as described later. In the present embodiment, it means that the rod-shaped liquid crystal compounds are aligned in the state of being aligned along the slow axis direction of the first retardation layer (orientation along the plane).

Examples of the liquid crystal compound include liquid crystal compounds in which the liquid crystal phase is a nematic phase (nematic liquid crystal). As the liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. The display mechanism of the liquid crystallinity of the liquid crystal compound may be lyotropic or thermally induced. The liquid crystal polymer and the liquid crystal monomer may be used alone or in combination.

When the liquid crystal compound is a liquid crystal monomer, the liquid crystal monomer is preferably a polymerizable monomer and a crosslinkable monomer. This is because the orientation state of the liquid crystal monomer can be fixed by polymerizing or crosslinking (ie, curing) the liquid crystal monomer. After the liquid crystal monomers are aligned, for example, as long as the liquid crystal monomers are polymerized or cross-linked with each other, the alignment state can be fixed thereby. Here, the polymer is formed by polymerization, and the three-dimensional network structure is formed by crosslinking, but these are non-liquid crystals. Therefore, for example, the first phase difference layer formed will not be transformed into a liquid crystal phase, a glass phase, or a crystal phase due to a temperature change unique to the liquid crystal compound. As a result, the first retardation layer becomes a retardation layer that is extremely stable without being affected by temperature changes.

The temperature range in which the liquid crystal monomer exhibits liquid crystallinity varies depending on its type. Specifically, the temperature range is preferably 40°C to 120°C, more preferably 50°C to 100°C, and most preferably 60°C to 90°C.

Any suitable liquid crystal monomer can be used for the liquid crystal monomer. For example, the polymerizable mesogen compounds described in Japanese Patent Table 2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, GB2280445, etc. can be used. Specific examples of the polymerizable mesogen compound include, for example, the trade name LC242 of BASF, the trade name E7 of Merck, and the trade name LC-Sillicon-CC3767 of Wacker-Chem. The liquid crystal monomer is preferably a nematic liquid crystal monomer.

The alignment cured layer of the liquid crystal compound can be formed by performing an alignment treatment on the surface of a predetermined substrate, and applying a coating liquid containing a liquid crystal compound on the surface to make the liquid crystal compound correspond to the direction of the above alignment treatment Orientation, and then fix the orientation state. In one embodiment, the substrate is any suitable resin film, and the directional curing layer formed on the substrate can be transferred to the surface of the polarizing plate 10. In another embodiment, the base material may be the second protective layer 13. In this case, the transfer step is omitted, and after the formation of the orientation curing layer (first phase difference layer), the roll-to-roll method can be used for layer stacking, thereby improving productivity.

The above-mentioned directional processing can adopt any appropriate directional processing. Specific examples include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of mechanical orientation treatment include friction treatment and extension treatment. Specific examples of physical orientation processing include magnetic field orientation processing and electric field orientation processing. Specific examples of the chemical orientation treatment include oblique vapor deposition method and light orientation treatment. The processing conditions of various directional treatments can adopt any appropriate conditions according to the purpose.

The orientation of the liquid crystal compound can be performed at a temperature at which the liquid crystal phase can be developed according to the type of the liquid crystal compound. By performing the temperature treatment, the liquid crystal compound will become a liquid crystal state, and the liquid crystal compound will be oriented according to the orientation treatment direction of the substrate surface.

In one embodiment, the alignment state is fixed by cooling the liquid crystal compound that has been aligned in the above manner. When the liquid crystal compound is a polymerizable monomer or a crosslinkable monomer, the alignment state is fixed by performing polymerization treatment or crosslinking treatment on the liquid crystal compound that has been aligned in the above manner.

Specific examples of the liquid crystal compound and the method for forming the alignment-cured layer are described in Japanese Patent Application Laid-Open No. 2006-163343. In this specification, the description of this publication is used as a reference.

、杯芳烴等之環狀母核配置於分子中心，且直鏈的烷基、烷氧基、取代苄醯氧基等作為其側鏈呈放射狀取代者。盤狀液晶之代表例可舉：C.Destrade等人之研究報告，Mol.Cryst.Liq.Cryst.第71期第111頁(1981年)所記載之苯衍生物、聯伸三苯衍生物、參茚并苯衍生物、酞青素衍生物；B.Kohne等人之研究報告，Angew.Chem.第96期第70頁(1984年)所記載之環己烷衍生物；以及J.M.Lehn等人之研究報告，J.Chem.Soc.Chem.Commun.第1794頁(1985年)、J.Zhang等人之研究報告，J.Am.Chem.Soc.第116期第2655頁(1994年)所記載之氮雜冠醚系或苯乙炔系的大環。盤狀液晶化合物的更多具體例可舉例如日本專利特開2006-133652號公報、日本專利特開2007-108732號公報、日本專利特開2010-244038號公報所記載之化合物。本說明書中係援用上述文獻及公報之記載作為參考。Another example of the alignment-cured layer may be a form in which the discotic liquid crystal compound is aligned in any state of vertical alignment, mixed alignment, and oblique alignment. The discotic liquid crystal compound is typically oriented so that the disc surface of the discotic liquid crystal compound is substantially perpendicular to the film surface of the first retardation layer. The so-called discotic liquid crystal compound is substantially vertical means that the average value of the angle formed by the film surface and the disc surface of the discotic liquid crystal compound is preferably 70°~90°, and more preferably 80°~90°, 85°~90 ° Better. The so-called discotic liquid crystal compound generally refers to a liquid crystal compound having a discotic molecular structure, the discotic molecular structure is like benzene, 1,3,5-tri

, Calixarene and other cyclic mother cores are arranged in the molecular center, and straight-chain alkyl groups, alkoxy groups, substituted benzyloxy groups, etc., as their side chains are radially substituted. Representative examples of discotic liquid crystals include the research report of C. Destrade et al., Mol. Cryst. Liq. Cryst. No. 71, page 111 (1981). Indene benzene derivatives, phthalocyanine derivatives; B. Kohne et al. research report, Angew. Chem. 96th page 70 (1984) described cyclohexane derivatives; and JMLehn et al. Report, J. Chem. Soc. Chem. Commun. page 1794 (1985), J. Zhang et al. research report, J. Am. Chem. Soc. No. 116 page 2655 (1994) Macrocyclic of azacrown ether system or phenylacetylene system. More specific examples of the discotic liquid crystal compound include compounds described in Japanese Patent Laid-Open No. 2006-133652, Japanese Patent Laid-Open No. 2007-108732, and Japanese Patent Laid-Open No. 2010-244038. In this specification, the descriptions of the above documents and gazettes are used as references.

In one embodiment, as shown in FIGS. 1 and 2, the first retardation layer 20 is a single layer of an orientation-cured layer of liquid crystal compound. When the first retardation layer 20 is composed of a single layer of the alignment-cured layer of the liquid crystal compound, its thickness is preferably 0.5 μm to 7 μm, and more preferably 1 μm to 5 μm. By using a liquid crystal compound, it is possible to achieve an in-plane retardation equivalent to that of a resin film by a thickness much thinner than that of a resin film.

The first phase difference layer represents that the upper refractive index characteristic exhibits the relationship of nx>ny=nz. The first phase difference layer is typically provided to impart anti-reflection properties to the polarizing plate, and when the first phase difference layer is a single layer of a directional curing layer, it can function as a λ/4 plate. At this time, the in-plane retardation Re(550) of the first retardation layer is preferably 100 nm to 190 nm, preferably 110 nm to 170 nm, and more preferably 130 nm to 160 nm. In addition, here "ny=nz" is not only the case where ny and nz are exactly the same, but also includes the case where they are substantially the same. Therefore, ny>nz or ny<nz may be achieved without impairing the effect of the present invention.

The Nz coefficient of the first retardation layer is preferably 0.9 to 1.5, and more preferably 0.9 to 1.3. By satisfying the above relationship, when the obtained polarizing plate with a phase difference layer is used in an image display device, a very excellent reflection hue can be achieved.

The first phase difference layer can exhibit the inverse dispersion wavelength characteristic that the phase difference value increases with the wavelength of the measurement light, and can also exhibit the positive wavelength dispersion characteristic that the phase difference value decreases with the wavelength of the measurement light, and can exhibit almost no phase difference value. A flat wavelength dispersion characteristic that changes with the wavelength of the measurement light. In one embodiment, the first retardation layer exhibits inverse dispersion wavelength characteristics. At this time, Re(450)/Re(550) of the retardation layer is preferably 0.8 or more and less than 1, more preferably 0.8 or more and 0.95 or less. With the above configuration, very excellent anti-reflection characteristics can be achieved.

The angle θ formed by the slow axis of the first retardation layer 20 and the absorption axis of the polarizing film 11 is preferably 40° to 50°, and preferably 42° to 48°, and more preferably about 45°. As long as the angle θ is within the above range, as described above, by using the first retardation layer as the λ/4 plate, a retardation-attached layer having very excellent circular polarization characteristics (resulting in very excellent antireflection characteristics) can be produced Polarizer.

In another embodiment, as shown in FIG. 3, the first retardation layer 20 has a layered structure of a first orientation-cured layer 21 and a second orientation-cured layer 22. At this time, either the first oriented cured layer 21 or the second oriented cured layer 22 can function as a λ/4 plate, and the other can function as a λ/2 plate. Therefore, the thicknesses of the first orientated cured layer 21 and the second orientated cured layer 22 can be adjusted to obtain a desired in-plane retardation of the λ/4 plate or the λ/2 plate. For example, when the first oriented cured layer 21 functions as a λ/2 plate and the second oriented cured layer 22 functions as a λ/4 plate, the thickness of the first oriented cured layer 21 is, for example, 2.0 μm to 3.0 μm, and the second The thickness of the directional curing layer 22 is, for example, 1.0 μm to 2.0 μm. At this time, the in-plane retardation Re(550) of the first directional cured layer is preferably 200 nm to 300 nm, and preferably 230 nm to 290 nm, and more preferably 250 nm to 280 nm. The in-plane retardation Re(550) of the second directional cured layer is as described above for the directional cured layer of a single layer. The angle formed by the slow axis of the first directional curing layer and the absorption axis of the polarizing film is preferably 10° to 20°, and preferably 12° to 18°, and more preferably about 15°. The angle formed by the slow axis of the second directional cured layer and the absorption axis of the polarizing film is preferably 70° to 80°, and preferably 72° to 78°, and more preferably about 75°. As long as it is the above-mentioned configuration, characteristics close to the ideal reverse wavelength dispersion characteristics can be obtained, and as a result, very excellent anti-reflection characteristics can be realized. Regarding the liquid crystal compound constituting the first orientated cured layer and the second orientated cured layer, the formation method of the first orientated cured layer and the second oriented cured layer, optical characteristics, etc., the single-layer oriented cured layer is as described above.

D. 2nd phase difference layer As described above, the second retardation layer can be a so-called positive C-plate (Positive C-plate) in which the refractive index characteristic exhibits the relationship nz>nx=ny. Using the positive C plate as the second retardation layer can prevent oblique reflections well, and can widen the angle of view of the anti-reflection function. At this time, the thickness direction retardation Rth(550) of the second retardation layer is preferably -50 nm to -300 nm, and preferably -70 nm to -250 nm, more preferably -90 nm to -200 nm, and particularly preferably -100 nm~ -180nm. Here, "nx=ny" includes not only the case where nx and ny are exactly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the second retardation layer may be less than 10 nm.

The second retardation layer having a refractive index characteristic of nz>nx=ny can be formed of any appropriate material. The second retardation layer is preferably composed of a thin film containing a liquid crystal material fixed in a vertical orientation. The liquid crystal material (liquid crystal compound) that can be oriented vertically can be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the method for forming the liquid crystal compound and the retardation layer include the liquid crystal compound and the method for forming the retardation layer described in paragraphs [0020] to [0028] in Japanese Patent Laid-Open No. 2002-333642. At this time, the thickness of the second retardation layer is preferably 0.5 μm to 10 μm, and preferably 0.5 μm to 8 μm, and more preferably 0.5 μm to 5 μm.

E. Conductive layer or isotropic substrate with conductive layer The conductive layer can be formed by forming a metal oxide film on any suitable substrate by any suitable film forming method (for example, vacuum evaporation method, sputtering method, CVD method, ion plating method, spray method, etc.). Examples of the metal oxide include indium oxide, tin oxide, zinc oxide, indium tin composite oxide, tin antimony composite oxide, zinc aluminum composite oxide, and indium zinc composite oxide. Among them, indium tin composite oxide (ITO) is preferred.

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

The conductive layer can be transferred to the first retardation layer (or the second retardation layer if there is a second retardation layer) from the above-mentioned base material, and the conductive layer alone is used as the constituent layer of the polarizing plate with retardation layer, also The first phase difference layer (or the second phase difference layer if there is a second phase difference layer) may be layered on the first phase difference layer in the form of a laminate of a conductive layer and a substrate (a substrate with a conductive layer). Preferably, the above substrate is optically isotropic, so the conductive layer can be used as an isotropic substrate with a conductive layer for a polarizing plate with a retardation layer.

As the optically isotropic substrate (isotropic substrate), any suitable isotropic substrate can be used. Examples of the material constituting the isotropic base material include materials having no conjugated resin as the main skeleton, such as norbornene-based resins or olefin-based resins, and having a lactone ring or glutarylene in the main chain of the acrylic resin. Materials such as imine rings and other cyclic structures. If the material is used, the phase difference exhibited along with the molecular chain orientation when forming the isotropic substrate can be suppressed to be small. The thickness of the isotropic substrate is preferably 50 μm or less, and more preferably 35 μm or less. The lower limit of the thickness of the isotropic base material is, for example, 20 μm.

The conductive layer of the conductive layer and/or the isotropic substrate with the conductive layer may be patterned according to need. By patterning, the conduction part and the insulation part can be formed. As a result, an electrode can be formed. The electrodes can function as touch sensing electrodes for sensing contact with the touch panel. Any appropriate method can be adopted as the patterning method. 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 phase difference layer described in the above items A to E can be applied to an image display device. Therefore, the present invention includes an image display device using the polarizing plate with the retardation layer. Representative examples of image display devices include liquid crystal display devices and electroluminescence (EL) display devices (for example, organic EL display devices and inorganic EL display devices). An image display device according to an embodiment of the present invention includes a polarizing plate with a phase difference layer described in the above items A to E on the viewing side. The polarizing plate with a retardation layer is laminated so that the retardation layer is on the image display unit (eg, liquid crystal unit, organic EL unit, inorganic EL unit) side (so that the polarizing film is on the viewing side). In one embodiment, the image display device has a curved shape (essentially a curved display screen), and/or can be flexed or bent. In the image display device, the effect of the polarizing plate with a retardation layer of the present invention is more remarkable. Examples

Hereinafter, the present invention will be specifically described with examples, but the present invention is not limited by these examples. The measuring method of each characteristic is as follows. In addition, as long as there is no special note, "parts" and "%" in the examples and comparative examples are based on weight. (1) 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”). The thickness greater than 10 μm is measured using a digital micrometer (manufactured by Anritsu Corporation, product name “KC-351C”). (2) Monomer transmittance, unit absorbance and orthogonal absorbance The polarizing plates (protective film/polarizing film) of Examples and Comparative Examples were measured using an ultraviolet visible light spectrophotometer (V-7100 manufactured by Japan Spectroscopy Corporation), and The measured single transmittance Ts, parallel transmittance Tp, and orthogonal transmittance Tc are taken as Ts, Tp, and Tc of the polarizing film, respectively. These Ts, Tp, and Tc are Y values obtained by measuring the 2 degree field of view (C light source) of JIS Z8701 and correcting the visual performance. In addition, the refractive index of the protective film is 1.50, and the refractive index of the surface of the polarizing film on the side opposite to the protective film is 1.53. Using UV-3150 manufactured by Shimadzu Corporation, from the orthogonal transmittance Tc ₂₁₀ measured at a measurement wavelength of 210 nm, the orthogonal absorbance A _{210 was} obtained by the following formula, and divided by the thickness as the unit absorbance. In addition, using V-7100 manufactured by Nippon Spectroscopy Co., Ltd., the orthogonal absorbance A _{470 was} obtained from the orthogonal transmittance Tc _{470 at} the measurement wavelength of 470 nm, and the orthogonal absorbance A _{600 was} obtained from the orthogonal transmittance Tc _{600 at} the measurement wavelength of 600 nm. Orthogonal absorbance = log10 (100/Tc) In addition, for A ₄₇₀ and A ₆₀₀ , LPF-200 manufactured by Otsuka Electronics Co., Ltd. can be used for equivalent measurement. (3) Iodine concentration For the polarizing films obtained in Examples and Comparative Examples, the fluorescent X-ray intensity was measured using a fluorescent X-ray analyzer (manufactured by Rigaku Corporation, trade name "ZSX-PRIMUS II", measuring diameter: ψ10mm) (kcps). From the obtained fluorescent X-ray intensity and thickness, the iodine concentration (% by weight) was determined according to the following formula. (Iodine concentration)=20.5×(Fluorescence X-ray intensity)/(Thickness of film) In addition, the coefficient when calculating the concentration will vary depending on the measuring device, but the coefficient can be obtained using an appropriate calibration curve. In the present example, a plurality of samples with arbitrary values of KI (I: K=1: 1 (mole ratio)) added to the PVA were prepared and measured to obtain the calibration curve. (4) Orthogonal b value The polarizing plates used in the examples and comparative examples were measured using an ultraviolet visible light spectrophotometer (manufactured by Nippon Spectroscopy Co., Ltd., product name "V7100"), and the hue in the orthogonal polarized state was obtained. It shows that the lower the orthogonal b value (negative value and larger absolute value) of the polarizing plate, the hue will be blue rather than neutral. (5) Warpage The polarizing plate with a retardation layer prepared in Examples and Comparative Examples was cut to a size of 110 mm × 60 mm. At this time, the absorption axis direction of the polarizing film is cut into the long-side direction. The polarizing plate with a retardation layer cut out was pasted on a glass plate of 120 mm×70 mm size and 0.2 mm thickness through 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 was measured after taking out. After placing the glass plate under the test sample on a flat surface, the height from the highest part of the flat surface is taken as the amount of warpage. (6) Unit weight The polarizing plate with a retardation layer prepared in Examples and Comparative Examples was cut to a predetermined size, and the weight (mg) was divided by the area (cm ² ) to calculate the phase difference layer The weight per unit area of the polarizing plate (unit weight). (7) Bending resistance The polarizing plate with a retardation layer prepared in Examples and Comparative Examples was cut to a size of 50 mm×100 mm. At this time, the absorption axis direction of the polarizing film is cut into the short-side direction. Using a folding endurance testing machine (made by YUASA, CL09 type-D01) with a constant temperature and humidity box, the polarizing plate with a retardation layer cut out was subjected to a bending test under the condition of 20°C and 50%RH. Specifically, the polarizing plate with a retardation layer is bent outwards with the retardation layer side in the direction parallel to the absorption axis direction, and measured until cracks, peeling, or film breakage that may cause display defects occur. The number of bending times was evaluated according to the following criteria (bending diameter: 2 mmφ). >Evaluation criteria> Less than 10,000 times: bad 10,000 times or more and less than 30,000 times: good 30,000 times or more: excellent

[Example 1] 1. Make polarizing film For the thermoplastic resin substrate, an elongated amorphous isophthalic acid copolymerized polyethylene terephthalate film (thickness: 100 μm) having a water absorption rate of 0.75% and a Tg of about 75°C is used. Corona treatment was applied to one side of the resin substrate. In the PVA series made by mixing polyvinyl alcohol (degree of polymerization 4200, degree of saponification 99.2 mol%) and acetylacetonyl modified PVA (manufactured by Japan Synthetic Chemical Industry Co., Ltd., trade name "GOHSEFIMER Z410") at 9:1 13 parts by weight of potassium iodide was added to 100 parts by weight of the resin, and the obtained was dissolved in water to prepare a PVA aqueous solution (coating solution). The PVA aqueous solution was applied to the corona-treated surface of the resin base material and dried at 60° C., thereby forming a PVA-based resin layer with a thickness of 13 μm to produce a laminate. The obtained laminate was uniaxially stretched in the longitudinal direction (longitudinal direction) by 2.4 times in the longitudinal direction (longitudinal direction) between rollers with different peripheral speeds in an oven at 130°C (air assisted stretching treatment). Next, the laminate was immersed in an insoluble bath (a boric acid aqueous solution obtained by mixing 4 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (insoluble treatment). Next, adjust the concentration of the dyeing bath (aqueous iodine solution obtained by mixing iodine and potassium iodide at a weight ratio of 1:7 with respect to 100 parts by weight of water) at a liquid temperature of 30° C. to adjust the concentration of the polarizer film finally prepared. The volume transmittance (Ts) and the unit absorbance at a wavelength of 210 nm become desired values and are simultaneously immersed in them for 60 seconds (dyeing treatment). Next, it was immersed in a crosslinking bath (a boric acid aqueous solution obtained by mixing 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C (crosslinking treatment ). Then, while immersing the laminate in a boric acid aqueous solution (boric acid concentration 4.0% by weight) at a liquid temperature of 70°C, uniaxial stretching was performed in the longitudinal direction (longitudinal direction) between rolls with different peripheral speeds to increase the total stretching ratio Up to 5.5 times (extended treatment in water). Thereafter, the laminate was immersed in a washing bath (aqueous solution obtained by mixing 4 parts by weight of potassium iodide with respect to 100 parts by weight of water) at a liquid temperature of 20° C. (washing treatment). Thereafter, while being dried in an oven at 90°C, the SUS-made heating roller whose contact surface temperature was kept at 75°C was kept for about 2 seconds (drying shrinkage treatment). The shrinkage rate in the width direction of the laminate after drying shrinkage treatment was 2%. Through the above procedure, a polarizing film with a thickness of 4.6 μm was formed on the resin substrate.

2. Fabricating a polarizing plate on the surface of the polarizing film (the surface opposite to the resin substrate) prepared above, an acrylic film (surface refractive index 1.50, 40 μm) is bonded as a protective layer through an ultraviolet curing adhesive. Specifically, the total thickness of the adhesive applied to the curing type is 1.0 μm, and the lamination is performed using a rolling machine. Thereafter, UV light is irradiated from the protective layer side to harden the adhesive. Next, after cutting off both ends, the resin substrate was peeled off to obtain a long polarizing plate (width: 1300 mm) having a protective layer/polarizing film. The polarizing plate (essentially a polarizing film) has a single transmittance of 43.5%, a unit absorbance at a wavelength of 210 nm of 0.91, A ₄₇₀ /A ₆₀₀ of 0.87, and an orthogonal b value of -3.00.

使用擦拭布擦拭聚對苯二甲酸乙二酯(PET)薄膜(厚度38μm)表面，施行定向處理。定向處理之方向係設為貼合至偏光板時由視辨側觀看時相對於偏光膜之吸收軸方向呈15°方向。利用棒塗機將上述液晶塗敷液塗敷至該定向處理表面，並於90℃下進行2分鐘加熱乾燥，藉此使液晶化合物定向。使用金屬鹵素燈以1mJ/cm² 的光照射依上述方式形成的液晶層，使該液晶層硬化，藉此於PET薄膜上形成液晶定向固化層A。液晶定向固化層A的厚度為2.5μm，面內相位差Re(550)為270nm。並且，液晶定向固化層A具有nx＞ny＝nz之折射率分布。 變更塗敷厚度，並將定向處理方向設為由視辨側觀看時相對於偏光膜之吸收軸方向呈75°方向，除此之外依與上述相同方式於PET薄膜上形成液晶定向固化層B。液晶定向固化層B的厚度為1.5μm，面內相位差Re(550)為140nm。並且，液晶定向固化層B具有nx＞ny＝nz之折射率分布。3. Production of a polymerizable liquid crystal (made by BASF Corporation: trade name "Paliocolor LC242", represented by the following formula) 10 g of the first orientated cured layer and the second orientated cured layer that constitute the retardation layer will show a nematic liquid crystal phase. 3 g of the photopolymerization initiator (manufactured by BASF: trade name "IRGACURE 907") of this polymerizable liquid crystal compound was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid). [Chemical Formula 1]

The surface of the polyethylene terephthalate (PET) film (thickness 38 μm) was wiped with a wiping cloth and subjected to orientation treatment. The direction of the orientation process is set to a 15° direction with respect to the absorption axis direction of the polarizing film when viewed from the viewing side when attached to the polarizing plate. The liquid crystal coating liquid was applied to the alignment treatment surface using a bar coater, and heated and dried at 90°C for 2 minutes, thereby aligning the liquid crystal compound. The liquid crystal layer formed in the above-described manner was irradiated with a metal halogen lamp at a light of 1 mJ/cm ² to harden the liquid crystal layer, thereby forming a liquid crystal alignment cured layer A on the PET film. The thickness of the liquid crystal alignment cured layer A was 2.5 μm, and the in-plane retardation Re(550) was 270 nm. In addition, the liquid crystal alignment cured layer A has a refractive index distribution of nx>ny=nz. Change the coating thickness and set the orientation processing direction to 75° with respect to the absorption axis direction of the polarizing film when viewed from the viewing side, except that the liquid crystal orientation curing layer B is formed on the PET film in the same manner as above . The thickness of the liquid crystal alignment cured layer B was 1.5 μm, and the in-plane retardation Re(550) was 140 nm. In addition, the liquid crystal alignment cured layer B has a refractive index distribution of nx>ny=nz.

4. Manufacture of polarizing plate with retardation layer On the surface of the polarizing film of the polarizing plate prepared in 2. above, the liquid crystal alignment cured layer A and the liquid crystal alignment cured layer B prepared in 3. are sequentially transferred. At this time, the transfer is performed in such a way that the angle formed by the absorption axis of the polarizing film and the slow axis of the orientation curing layer A is 15° and the angle formed by the absorption axis of the polarizing film and the slow axis of the orientation curing layer B is 75° ( fit). In addition, the respective transfer (lamination) is performed through the ultraviolet curing adhesive (thickness 1.0 μm) used in 2. above. In the above manner, a polarizing plate with a retardation layer composed of a protective layer/adhesive layer/polarizing film/adhesive layer/retardation layer (first oriented cured layer/adhesive layer/second oriented cured layer) was prepared. The total thickness of the obtained polarizing plate with retardation layer was 52 μm. The obtained polarizing plate with a retardation layer was subjected to the above evaluations (5) to (7). The amount of warpage was 1.8 mm.

[Example 2] A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that an acrylic film with a thickness of 20 μm was used as the protective layer. The total thickness of the obtained polarizing plate with retardation layer was 32 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The amount of warpage is 1.5 mm.

[Example 3] A polarizing plate with a retardation layer was produced in the same manner as in Example 1, except that a 25 μm thick triacetyl cellulose (TAC) film was used as the protective layer. The total thickness of the obtained polarizing plate with retardation layer was 37 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The amount of warpage was 1.3 mm.

[Comparative Example 1] 1. Make 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 with different peripheral speed ratios to swell, and at the same time, it was extended 2.4 times in the conveying direction (swelling step), and then at 30°C In the dyeing bath (aqueous solution with iodine concentration of 0.03% by weight and potassium iodide concentration of 0.3% by weight), the original polyvinyl alcohol film is immersed and dyed in such a way that the monomer transmittance after final elongation becomes the desired value. The polyvinyl alcohol film which is completely unstretched in the conveying direction) is extended by 3.7 times in the conveying direction (dyeing step). At this time, the immersion time is about 60 seconds. Next, the dyed polyvinyl alcohol film is immersed in a crosslinking bath (aqueous solution with a boric acid concentration of 3.0% by weight and a potassium iodide concentration of 3.0% by weight) at 40°C, while moving in the conveying direction based on the original polyvinyl alcohol film Extend to 4.2 times (crosslinking step). Then, the resulting polyvinyl alcohol film was immersed in an extension bath (aqueous solution with a boric acid concentration of 4.0% by weight and a potassium iodide concentration of 5.0% by weight) at 64°C for 50 seconds, and extended in the conveying direction based on the original polyvinyl alcohol film to After 6.0 times (extending step), it was immersed in a washing bath (aqueous solution with a potassium iodide concentration of 3.0% by weight) at 20°C for 5 seconds (washing step). The washed polyvinyl alcohol film was dried at 30°C for 2 minutes to prepare a polarizer (thickness 12 μm).

2. Make polarizer The following aqueous solution is used for the agent system: a polyvinyl alcohol resin containing acetylacetoyl groups in a weight ratio of 3:1 (average degree of polymerization 1,200, degree of saponification 98.5 mol%, degree of acetylacetoylation 5 mol%) Those with methylol melamine. Using this adhesive agent, a 25 μm thick triacetyl cellulose (TAC) film with a thickness of 25 μm is bonded to one side of the polarizer prepared by the roller bonding machine, and the thickness is bonded to the other side of the polarizer After a TAC film of 25 μm, it was heated and dried in an oven (temperature 60° C., time 5 minutes) to produce a protective layer 1 (thickness 25 μm)/adhesive layer/polarizer/adhesive layer/protective layer 2 ( A polarizing plate with a thickness of 25 μm).

3. Manufacture of polarizing plate with retardation layer On the surface of the protective layer 2 of the polarizer plate prepared above, the liquid crystal alignment cured layer A and the liquid crystal alignment cured layer B were sequentially transferred in the same manner as in Example 1, to produce a protective layer 1/adhesive layer /Polarizer/adhesive layer/protective layer 2/adhesive layer/retardation layer (first oriented cured layer/adhesive layer/second oriented cured layer) polarizing plate with retardation layer. The total thickness of the obtained polarizing plate with retardation layer was 68 μm. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The amount of warpage was 4.2mm.

[Comparative Example 2] Without adding potassium iodide to the PVA aqueous solution (coating solution), the thickness of the polarizing film obtained after changing the PVA aqueous solution (coating solution) was 3.3 μm, and the shrinkage ratio in the width direction was 0.1 without using a heating roller in the drying shrinkage process % Or less, and adjusting the concentration of the dyeing bath to adjust the monomer transmittance of the polarizing film, except that the polarizing film and polarizing plate were produced in the same manner as in Example 1. The polarizing plate (essentially a polarizing film) had a single transmittance of 43.4% and a unit absorbance of 1.32 at a wavelength of 210 nm. Except for using the polarizing plate, a polarizing plate with a retardation layer was produced in the same manner as in Example 1.

[Comparative Example 3] 1. Make a polarizer A TAC film with a thickness of 25 μm was used as the protective layer, and otherwise a long polarizing plate (width: 1300 mm) having a protective layer/polarizing film configuration was produced in the same manner as in Example 1.

2. Production of retardation film constituting the retardation layer 2-1. For the polymerization of polyester carbonate-based resin, a batch consisting of 2 vertical reactors equipped with stirring blades and a reflux cooler controlled at 100°C is used. The secondary polymerization device performs polymerization. Feeding bis[9-(2-phenoxycarbonylethyl) stilb-9-yl]methane 29.60 parts by mass (0.046mol), isosorbide (ISB) 29.21 parts by mass (0.200mol), spiroglycerin (SPG) 42.28 parts by mass (0.139 mol), diphenyl carbonate (DPC) 63.77 parts by mass (0.298 mol) and calcium acetate monohydrate as a catalyst 1.19×10 ⁻² parts by mass (6.78×10 ⁻⁵ mol). After the reduced-pressure nitrogen was replaced in the reactor, it was heated with a heating medium, and stirring was started when the internal temperature reached 100°C. The internal temperature was brought to 220°C after 40 minutes from the start of the temperature increase, and the pressure was reduced while controlling the temperature so that it reached 13.3 kPa after 90 minutes from reaching 220°C. The phenol vapor produced by-product of the polymerization reaction was introduced into a reflux cooler at 100°C, some monomer components contained in the phenol vapor were returned to the reactor, and the uncondensed phenol vapor was introduced into a 45°C condenser for recovery. After introducing nitrogen into the first reactor and temporarily returning it to atmospheric pressure, the oligomerized reaction liquid in the first reactor was transferred to the second reactor. Next, the temperature rise and pressure reduction in the second reactor were started, and after 50 minutes, the internal temperature was 240° C. and the pressure was 0.2 kPa. Thereafter, the polymerization is performed until the predetermined stirring power is reached. At the time when the predetermined power is reached, nitrogen is introduced into the reactor to restore the pressure, and the resulting polyester carbonate-based resin is extruded into water to cut the bundle to obtain pellets.

2-2. Production of retardation film After the obtained polyester carbonate-based resin (pellet) was vacuum-dried at 80°C for 5 hours, a uniaxial extruder (manufactured by Toshiba Machinery Co., Ltd., cylinder set temperature: 250°C), T-die (wide 200mm, set temperature: 250°C), cooling roller (set temperature: 120~130°C) and film-forming device of the winder to produce a long resin film with a thickness of 135μm. The obtained long resin film was extended in the width direction at an extension temperature of 133° C. and an extension ratio of 2.8 times to obtain a retardation film with a thickness of 53 μm. Re(550) of the obtained retardation film was 141 nm, Re(450)/Re(550) was 0.82, and the Nz coefficient was 1.12.

3. Manufacture of polarizing plate with retardation layer The retardation film prepared in the above 2. is bonded to the surface of the polarizing film of the polarizing plate prepared in the above 1. through an acrylic adhesive (thickness 5 μm). At this time, the absorption axis of the polarizing film and the slow axis of the retardation film are bonded so as to form an angle of 45°. In the above manner, a polarizing plate with a retardation layer composed of a protective layer/adhesion layer/polarizing film/adhesive layer/retardation layer was prepared. The total thickness of the obtained polarizing plate with a retardation layer was 89 μm. The obtained polarizing plate with retardation layer was used for the evaluation of (6) and (7) above.

Table 1 shows the configuration and evaluation results of the polarizing plates with retardation layers obtained in Examples 1 to 3 and Comparative Examples 1 and 3. [Table 1]

[Evaluation] As is apparent from Table 1 and the comparison between Example 1 and Comparative Example 2, the polarizing plate with a retardation layer according to the example of the present invention is thin, warpage after the heating test is suppressed, and the optical characteristics are excellent. In addition, it can be seen that the weight per unit area of the polarizing plate with a retardation layer is equal to or less than a predetermined value, so that the bending resistance is improved.

Industrial availability The polarizing plate with a retardation layer of the present invention can be suitably used as a circular polarizing plate for liquid crystal display devices, organic EL display devices, and inorganic EL display devices.

10: polarizer 11: Polarizing film 12: The first protective layer 13: 2nd protective layer 20: Phase difference layer (1st phase difference layer) 21: The first directional curing layer 22: The second directional curing layer 50: Another phase difference layer (second phase difference layer) 60: conductive layer or isotropic substrate with conductive layer 100, 101, 102: polarizer with phase difference layer 200: laminate R1~R6: conveyor roller G1~G4: Guide roller

1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to an embodiment of the present invention. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the present invention. 3 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to still another embodiment of the present invention. 4 is a schematic diagram showing an example of a drying shrinkage treatment using a heating roller in the method of manufacturing a polarizing film used in a polarizing plate with a retardation layer of the present invention.

10: polarizer

11: Polarizing film

12: The first protective layer

13: 2nd protective layer

20: Phase difference layer (1st phase difference layer)

100: polarizing plate with retardation layer

Claims (14)

A polarizing plate with a phase difference layer has a polarizing plate and a phase difference layer, and the polarizing plate includes a polarizing film and a protective layer on at least one side of the polarizing film; The polarizing film is composed of a polyvinyl alcohol resin film containing a dichroic substance, and its thickness is 8 μm or less, and the orthogonal absorbance per 1 μm thickness at a wavelength of 210 nm is 1.00 or less; The retardation layer is an oriented cured layer of liquid crystal compound. For example, the polarizing plate with retardation layer of claim 1 has a unit weight of 6.5 mg/cm ² or less. For example, the polarizing plate with a retardation layer according to claim 1 has a total thickness of 60 μm or less. The polarizing plate with a retardation layer as claimed in claim 1, wherein the aforementioned retardation layer is a single layer of an orientation curing layer of liquid crystal compound, The Re(550) of the retardation layer is 100 nm to 190 nm, and The angle formed by the slow axis of the retardation layer and the absorption axis of the polarizing film is 40°-50°. The polarizing plate with a retardation layer as claimed in claim 1, wherein the aforementioned retardation layer has a laminated structure of an orientation curing layer of the first liquid crystal compound and an orientation curing layer of the second liquid crystal compound; Re (550) of the orientation curing layer of the first liquid crystal compound is 200 nm to 300 nm, and the angle formed by the slow axis and the absorption axis of the polarizing film is 10° to 20°; Re (550) of the alignment cured layer of the second liquid crystal compound is 100 nm to 190 nm, and the angle formed by the slow axis and the absorption axis of the polarizing film is 70° to 80°. The requested item is attached polarizing plate of the retardation layers 1, wherein the orthogonal polarizing film at a wavelength of 470nm absorbance A ₄₇₀ and the absorbance at a wavelength of orthogonal 600nm A ₆₀₀ ratio of (A ₄₇₀ / A ₆₀₀₎ of 0.7 to 2.00. The polarizing plate with a retardation layer according to claim 1, wherein the orthogonal b value of the polarizing film is greater than -10 and below +10. The polarizing plate with a retardation layer according to claim 1, wherein the iodine concentration of the polarizing film is 3.0% by weight or more. The polarizing plate with a retardation layer according to claim 1, wherein the single transmittance of the polarizing film is 42.5% or more. The polarizing plate with a retardation layer as claimed in claim 1, wherein there is another retardation layer outside the aforementioned retardation layer, and the refractive index characteristic of the other retardation layer shows a relationship of nz>nx=ny. The polarizing plate with a retardation layer according to claim 1, wherein the polarizing plate with a phase difference layer further has a conductive layer or an isotropic base material with a conductive layer. A polarizing plate with a retardation layer has a polarizing plate and a retardation layer, and the polarizing plate includes a polarizing film and a protective layer located on at least one side of the polarizing film; the retardation layer is an oriented cured layer of liquid crystal compound; The polarizing film is composed of a polyvinyl alcohol resin film containing iodine and has a thickness of 8 μm or less. The polarizing film has an orthogonal absorbance of 1.00 or less per thickness of 210 μm at a wavelength of 210 nm, and the polarizing film is orthogonal at a wavelength of 470 nm. The ratio of the absorbance A ₄₇₀ to the orthogonal absorbance A ₆₀₀ at a wavelength of 600 nm (A ₄₇₀ /A ₆₀₀ ) is 0.7 to 2.00, and the orthogonal b value of the polarizing film is greater than -10 and below +10. An image display device provided with a polarizing plate with a phase difference layer according to any one of claims 1 to 12. The image display device according to claim 13 is an organic electroluminescence display device or an inorganic electroluminescence display device.

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