KR20230073991A - Retardation-layer-equipped polarizing plate and image display device using same - Google Patents

Abstract

Provided is a thin phase retardation layer attached polarizing plate having excellent high temperature durability. According to an embodiment of the present invention, the rectangular retardation layer attached polarizing plate comprises: a polarizing plate including a polarizer with equal to or more than 11 wt% of a boric acid content; and a retardation layer, which is an alignment solidification layer of a liquid crystal compound. The long side direction of the retardation layer attached polarizing plate and the slow axis direction of the retardation layer are orthogonal.

Description

Polarizing plate with retardation layer and image display device using the same

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

In recent years, image display devices typified by liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices and inorganic EL display devices) are rapidly spreading. A polarizing plate and a retardation plate are typically used for the image display device. In practical terms, a polarizing plate with a retardation layer in which a polarizing plate and a retardation plate are integrated is widely used (for example, Patent Document 1). As the demand for reduction in thickness of the image display device becomes stronger, the demand for reduction in thickness is also increasing for the polarizing plate with the retardation layer. For the purpose of thinning the polarizing plate with the retardation layer, the thinning of the retardation film is progressing. In addition, in order to evaluate the durability of the retardation film, the manufactured retardation film is subjected to various reliability tests. In the case of a thin retardation film, deterioration by a reliability test (eg, heating reliability test) may be a problem.

Japanese Patent Publication No. 3325560

The present invention has been made to solve the above conventional problems, and its main object is to provide a thin polarizing plate with a retardation layer having excellent high-temperature durability.

A polarizing plate with a retardation layer according to an embodiment of the present invention is a rectangular polarizing plate with a retardation layer including a polarizing plate containing a polarizer having a boric acid content of 11% by weight or more and a retardation layer that is an orientation-hardened layer of a liquid crystal compound. The direction of the long side of the polarizing plate with the retardation layer and the direction of the slow axis of the retardation layer are orthogonal.

In one embodiment, the in-plane retardation Re (550) of the retardation layer is 100 nm to 190 nm, and also satisfies Re (450) / Re (550) < 1, and the slow axis of the retardation layer and the absorption axis of the polarizer The angle θ formed by this is 40° to 50°.

In one embodiment, an angle formed between an absorption axis of the polarizer and a long side direction of the polarizing plate with a retardation layer is 125° to 145°.

In one embodiment, the dimensional shrinkage of the polarizing plate with a retardation layer in a short side direction is 0.25 mm or more.

In one embodiment, the ratio of the length of the long side to the length of the short side of the polarizing plate with the retardation layer is 1.1 to 3.0.

In one embodiment, the retardation layer has a circular polarization function or an elliptically polarization function.

In one embodiment, the total thickness of the polarizing plate with the retardation layer is 60 μm or less.

In another aspect of an embodiment of the present invention, an image display device is provided. This image display device is equipped with the said polarizing plate with a retardation layer.

In one embodiment, the image display device is an organic electroluminescent display device or an inorganic electroluminescent display device.

ADVANTAGE OF THE INVENTION According to embodiment of this invention, the thin polarizing plate with a retardation layer which has excellent high-temperature durability can be provided.

1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention.

EMBODIMENT OF THE INVENTION Hereinafter, although embodiment of this invention is described, this invention is not limited to these embodiment.

(Definition of Terms and Symbols)

Definitions of terms and symbols in this specification are as follows.

(1) Refractive index (nx, ny, nz)

'nx' is the refractive index in the direction in which the in-plane refractive index is maximized (ie, the slow axis direction), 'ny' is the refractive index in the direction orthogonal to the slow axis within the plane (ie, the fast axis direction), and 'nz' is is the refractive index in the thickness direction.

(2) In-plane phase difference (Re)

'Re(λ)' is an in-plane retardation measured with light having a wavelength of λ nm at 23°C. For example, 'Re(550)' is an in-plane retardation measured with light having a wavelength of 550 nm at 23°C. Re(λ) can be obtained by the formula: Re(λ)=(nx-ny)×d when the thickness of the layer (film) is set to d(nm).

(3) Phase difference in thickness direction (Rth)

'Rth(λ)' is the phase difference in the thickness direction measured with light having a wavelength of λ nm at 23°C. For example, 'Rth (550)' is the phase difference in the thickness direction measured with light having a wavelength of 550 nm at 23°C. Rth(λ) can be obtained by the formula: Rth(λ)=(nx-nz)×d when the thickness of the layer (film) is d (nm).

(4) Nz factor

The Nz coefficient can be obtained by Nz=Rth/Re.

(5) Angle

When an angle is referred to herein, the angle includes both clockwise and counterclockwise directions with respect to the reference direction. Thus, for example, '45°' means ±45°.

A. Overall configuration of polarizing plate with retardation layer

1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention. The polarizing plate 100 with a retardation layer in the illustrated example includes the polarizing plate 10, the retardation layer 20, and the pressure-sensitive adhesive layer 30 in this order from the viewing side. The polarizing plate 10 typically includes a polarizer 11 and a protective layer 12 disposed on the viewing side of the polarizer 11 . Depending on the purpose, another protective layer (not shown) may be provided on the side opposite to the visible side of the polarizer 11 (the surface on which the protective layer 12 of the polarizer 11 is not laminated). The retardation layer 20 is an orientation-fixed layer of liquid crystal compounds (hereinafter sometimes simply referred to as a liquid-crystal orientation-fixed layer), and typically has a circular polarization function or an elliptically polarization function. The polarizing plate with a retardation layer is provided with the pressure-sensitive adhesive layer 30 as an outermost layer, and can be attached to an image display device (substantially, an image display cell). Practically, it is preferable that a release liner is temporarily attached to the surface of the pressure-sensitive adhesive layer 30 until the polarizing plate is put into use. By temporarily attaching the peeling liner, the pressure-sensitive adhesive layer can be appropriately protected, and roll-forming of the polarizing plate with the retardation layer is enabled.

The polarizing plate with a retardation layer of the embodiment of the present invention has a rectangular shape and has a short side and a long side. The ratio of the length of the long side to the length of the short side of the polarizing plate with the retardation layer (long side length/short side length) is, for example, a value exceeding 1, preferably 1.1 to 3.0, more preferably 1.3 to 2.7, and still more. Preferably it is 1.5-2.5. When the ratio of the length of the long side and the length of the short side of the polarizing plate with a retardation layer is within the above range, the deterioration of the polarizing plate with a retardation layer in the heating reliability test can be suppressed and a polarizing plate with a retardation layer having excellent high-temperature durability can be provided.

In the embodiment of the present invention, the direction of the long side of the polarizing plate 100 with the retardation layer and the direction of the slow axis of the retardation layer 20 are orthogonal. In a polarizing plate with a retardation layer, dimensional shrinkage of the polarizing plate with a retardation layer may occur under the conditions used in the heating reliability test. This dimensional shrinkage tends to be larger in the short side direction, and the retardation layer may also shrink more in the short side direction along with the shrinkage. When the direction of the long side of the polarizing plate 100 with the retardation layer is orthogonal to the direction of the slow axis of the retardation layer 20, the retardation layer contracts in the direction of the slow axis, and the phase difference can be reduced. In addition, when the retardation layer is a liquid crystal alignment solidified layer, the orientation of the liquid crystal compound is increased by heating, and the retardation may increase. Therefore, the increase in the phase difference due to the increased orientation of the liquid crystal compound and the decrease in the phase difference due to the contraction in the slow axis direction of the retardation layer can be balanced. As a result, it is possible to provide a polarizing plate with a retardation layer that suppresses deterioration by the heating reliability test and has excellent high-temperature durability. In this specification, 'orthogonal' includes not only the case of being completely orthogonal, but also the case where the angle between the direction of the long side of the polarizing plate with the retardation layer and the direction of the slow axis of the retardation layer is substantially orthogonal, for example, 85° to 95°.

The angle between the absorption axis of the polarizer 11 and the longitudinal direction of the polarizing plate 100 with the retardation layer is preferably 125° to 145°, more preferably 130° to 140°, still more preferably 132°. ~ 138°, particularly preferably about 135°. When the angle formed between the absorption axis of the polarizer 11 and the long side direction of the polarizing plate 100 with a retardation layer is within the above range, it is possible to further suppress deterioration by the heating reliability test and to provide a polarizing plate with a retardation layer having excellent high-temperature durability. can

As described above, the retardation layer 20 is a liquid crystal alignment solidified layer. The retardation layer 20 may be a single layer or may have a laminated structure of a first liquid crystal orientation fixed layer and a second liquid crystal orientation fixed layer.

The polarizing plate with a retardation layer may further be provided with a retardation layer and/or a conductive layer different from the retardation layer 20 or an isotropic substrate with a conductive layer (none of which is shown). Another retardation layer is typically provided between the retardation layer 20 and the pressure-sensitive adhesive layer 30 (that is, on the outside of the retardation layer 20). The other retardation layer typically exhibits a relationship of nz>nx=ny in refractive index characteristics. A conductive layer or an isotropic substrate with a conductive layer is typically provided between the retardation layer 20 and the pressure-sensitive adhesive layer 30 . Other retardation layers and a conductive layer or an isotropic substrate with a conductive layer are typically provided in this order from the retardation layer 20 side. The other retardation layer and the conductive layer or the isotropic base material with a conductive layer are arbitrary layers provided as needed, and any one or both of them may be omitted. When a conductive layer or an isotropic base material with a conductive layer is provided, the polarizing plate with a retardation layer is applied to a so-called inner touch panel type input display device in which a touch sensor is built in between an image display cell (eg, an organic EL cell) and a polarizing plate. can

Optical characteristics (eg, refractive index characteristics, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, placement position, etc. of other retardation layers may be appropriately set according to the purpose.

The total thickness of the polarizing plate with the retardation layer is preferably 100 μm or less, more preferably 60 μm or less, still more preferably 55 μm or less, even more preferably 50 μm or less, and particularly preferably 40 μm or less. below The total thickness may be, for example, 28 μm or more. According to the embodiment of the present invention, such an extremely thin polarizing plate with a retardation layer can be realized. In addition, such a polarizing plate with a retardation layer can have extremely excellent flexibility and bending durability. Therefore, such a polarizing plate with a retardation layer can be particularly suitably applied to a curved image display device and/or a bendable or foldable image display device. In addition, the total thickness of the polarizing plate with a retardation layer refers to the total thickness of the polarizing plate, the retardation layer (when other retardation layers are present, the retardation layer and the other retardation layer), and the adhesive layer or pressure-sensitive adhesive layer for laminating them (that is, , The total thickness of the polarizing plate with a retardation layer does not include the thickness of the conductive layer or the isotropic substrate with a conductive layer, and the pressure-sensitive adhesive layer 30 and the release liner that can be temporarily attached to the surface thereof).

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

B. Polarizer

B-1. polarizer

The polarizer is typically composed of a polyvinyl alcohol (PVA)-based resin film containing a dichroic substance. The thickness of the polarizer is preferably 1 μm to 8 μm, more preferably 1 μm to 7 μm, still more preferably 2 μm to 5 μm. If the thickness of the polarizer is in such a range, it can greatly contribute to the thickness reduction of the polarizing plate with the retardation layer. Moreover, the effect of this invention is remarkable in the thin polarizing plate with a retardation layer using such a polarizer.

The boric acid content of the polarizer is 11% by weight or more, preferably 11% by weight to 25% by weight, more preferably 12% by weight to 25% by weight. When the boric acid content of the polarizer is within such a range, deterioration in the heating reliability test can be suppressed, and a polarizing plate with a phase difference layer having excellent high-temperature durability can be provided. In addition, the appearance durability at the time of heating can be improved while favorably maintaining the ease of adjustment of curling at the time of bonding and favorably suppressing curling at the time of heating. Boric acid content is computable as the amount of boric acid contained in the polarizer per unit weight using a following formula from the neutralization method, for example.

The iodine content of the polarizer is preferably 2% by weight or more, more preferably 2% by weight to 10% by weight. If the iodine content of the polarizer is in such a range, the synergistic effect with the boric acid content described above keeps the ease of curling adjustment at the time of bonding well, and the appearance at the time of heating while suppressing the curl at the time of heating favorably Durability can be improved. In this specification, 'iodine content' means the amount of all iodine contained in a polarizer (PVA-type resin film). More specifically, in the polarizer, iodine exists in the form of iodine ions (I ^- ), iodine molecules (I ₂ ), polyiodine ions (I ₃ ^- , I ₅ ^- ), etc. The iodine content in the present specification is, It means the amount of iodine including all of these forms. The iodine content can be calculated by, for example, a calibration curve method of fluorescence X-ray analysis. Further, polyiodine ions exist in a state in which a PVA-iodine complex is formed in the polarizer. By forming such a complex, absorption dichroism can be expressed in the wavelength range of visible light. Specifically, the complex of PVA and triiodide ion (PVA·I ₃ ^- ) It has an absorption peak around 470 nm, and the complex of PVA and 5-iodide ions (PVA·I ₅ ^- ) It has an absorption peak around 600 nm. As a result, polyiodine ions can absorb light in a wide range of visible light depending on their form. On the other hand, iodine ion (I ^- ) has an absorption peak around 230 nm and is not substantially involved in absorption of visible light. Therefore, polyiodine ions present in a complex state with PVA may be mainly involved in the absorption performance of the polarizer.

The polarizer preferably exhibits absorption dichroism at any wavelength of 380 nm to 780 nm. The single transmittance (Ts) of the polarizer is preferably 40% to 48%, more preferably 41% to 46%. The polarization degree (P) of the polarizer is preferably 97.0% or more, more preferably 99.0% or more, still more preferably 99.9% or more. The single transmittance is typically a Y value measured using an ultraviolet/visible ray spectrophotometer and corrected for visibility. The degree of polarization can be obtained by the following formula based on the parallel transmittance (Tp) and the orthogonal transmittance (Tc) obtained by measuring, typically, using an ultraviolet/visible ray spectrophotometer and correcting visibility.

Polarization degree (%) = {(Tp-Tc)/(Tp+Tc)} ^1/2 × 100

A polarizer can typically be produced using a laminate of two or more layers. As a specific example of the light polarizer obtained using a laminated body, the polarizer obtained using the laminated body of the resin base material and the PVA system resin layer applied and formed on the said resin base material is mentioned. A polarizer obtained by using a laminate of a resin substrate and a PVA-based resin layer coated and formed on the resin substrate, for example, by applying a PVA-based resin solution to the resin substrate and drying it to form a PVA-based resin layer on the resin substrate, and obtaining a laminate of the PVA-based resin layer; It can be produced by extending|stretching and dyeing the said laminated body, and using a PVA system resin layer as a polarizer. Stretching typically involves immersing the layered product in an aqueous solution of boric acid, followed by stretching. Further, if necessary, the stretching may further include air stretching the laminate at a high temperature (eg, 95° C. or higher) prior to stretching in a boric acid aqueous solution. The obtained laminate of the resin substrate/polarizer may be used as it is (that is, the resin substrate may be used as a protective layer for the polarizer), and the resin substrate is peeled from the laminate of the resin substrate/polarizer, and the peel surface is used for the purpose. Any suitable protective layer according to the above may be laminated and used. The details of the manufacturing method of such a polarizer are described, for example in Unexamined-Japanese-Patent No. 2012-73580 and Unexamined-Japanese-Patent No. 6470455. These publications are incorporated herein by reference in their entirety.

A method for producing a polarizer typically includes forming a polyvinyl alcohol-based resin layer containing a halide and a polyvinyl alcohol-based resin on one side of a long thermoplastic resin substrate to form a laminate, and air-assisted to the laminate. It includes carrying out stretching treatment, dyeing treatment, underwater stretching treatment, and drying shrinkage treatment for shrinking by 2% or more in the width direction by heating while conveying in the longitudinal direction in this order. Accordingly, a polarizer having a very thin shape, excellent optical properties, and suppressed variation in optical properties can be provided. That is, by introducing auxiliary stretching, it becomes possible to increase the crystallinity of PVA even when applying PVA on a thermoplastic resin, and it becomes possible to achieve high optical properties. In addition, at the same time, by increasing the orientation of PVA in advance, it is possible to prevent problems such as deterioration in orientation and dissolution of PVA when immersed in water in a subsequent dyeing step or stretching step, and it is possible to achieve high optical properties. . Further, in the case where the PVA-based resin layer is immersed in a liquid, the disorder of the orientation of the polyvinyl alcohol molecules and the decrease in orientation can be suppressed compared to the case where the PVA-based resin layer does not contain a halide. Thereby, the optical characteristics of the polarizer obtained through the processing process performed by immersing a layered product in liquid, such as a dyeing process and an underwater extension process, can be improved. Further, optical properties can be improved by shrinking the laminate in the width direction by dry shrinkage treatment.

B-2. protective layer

The protective layer 12 is formed of any appropriate film that can be used as a protective layer for a polarizer. Specific examples of the material serving as the main component of the film include cellulose-based resins such as triacetyl cellulose (TAC), polyester-based, polyvinyl alcohol-based, polycarbonate-based, polyamide-based, polyimide-based, polyethersulfone-based, and transparent resins such as polysulfone, polystyrene, polynorbornene, polyolefin, (meth)acrylic, and acetate resins. Further, thermosetting resins such as (meth)acrylic, urethane-based, (meth)acrylurethane-based, epoxy-based, and silicone-based resins or ultraviolet curable resins may be used. In addition, glassy type polymers, such as a siloxane type polymer, are also mentioned, for example. Moreover, the polymer film of Unexamined-Japanese-Patent No. 2001-343529 (WO01/37007) can also be used. As the material for this film, a resin composition containing, for example, a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain can be used. For example, isobutene and N- A resin composition containing an alternating copolymer composed of methyl maleimide and an acrylonitrile/styrene copolymer is exemplified. The polymer film may be, for example, an extrusion molding of the resin composition.

As will be described later, the polarizing plate with the retardation layer is typically disposed on the viewing side of the image display device, and the protective layer 12 is typically disposed on the visual viewing side. Therefore, surface treatment such as hard coat treatment, antireflection treatment, antisticking treatment, and antiglare treatment may be applied to the protective layer 12 as necessary.

The thickness of the protective layer is preferably 10 μm to 50 μm, more preferably 10 μm to 30 μm. In addition, when the surface treatment is applied, the thickness of the outer protective layer is the thickness including the thickness of the surface treatment layer.

C. phase difference layer

As described above, the retardation layer 20, which is a liquid crystal alignment hardening layer, typically has a circular polarization function or an elliptically polarization function. The refractive index characteristic of the retardation layer typically shows a relationship of nx>ny=nz. The retardation layer is typically provided to impart antireflection properties to the polarizing plate, and can function as a λ/4 plate when the retardation layer is a single layer. In this case, the in-plane retardation Re (550) of the retardation layer is preferably 100 nm to 190 nm, more preferably 110 nm to 170 nm, still more preferably 130 nm to 160 nm. In addition, 'ny=nz' here includes not only the case where ny and nz are completely equal, but also the case where they are substantially equal. Therefore, there may be cases where ny>nz or ny<nz is satisfied within a range that does not impair the effects of the present invention. The retardation layer is preferably an alignment-fixed layer of a liquid crystal compound having a circular polarization function or an elliptically polarization function.

When the retardation layer 20 is composed of a single layer, its thickness is preferably 0.5 μm to 7 μm, more preferably 1 μm to 5 μm. By using a liquid crystal compound, an in-plane retardation equivalent to that of a resin film can be achieved with a significantly thinner thickness than that of the resin film.

The Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3. By satisfying such a relationship, when the obtained polarizing plate with a retardation layer is used for an image display device, an extremely excellent reflected color can be achieved.

The retardation layer may exhibit reverse dispersion wavelength characteristics in which the retardation value increases with the wavelength of the measurement light, or may exhibit positive wavelength dispersion characteristics in which the retardation value decreases with the wavelength of the measurement light. A flat wavelength dispersion characteristic that hardly changes even with the wavelength may be exhibited. In one embodiment, the retardation layer exhibits reverse dispersion wavelength characteristics. In this case, Re(450)/Re(550) of the retardation layer is preferably less than 1, more preferably 0.8 or more and less than 1, still more preferably 0.8 or more and 0.95 or less. With such a configuration, extremely excellent antireflection properties can be realized. In addition, in the case of a liquid crystal alignment hardened layer exhibiting reverse dispersion wavelength characteristics, the increase in the retardation value by the heating test may be greater. According to the embodiment of the present invention, even if the retardation layer is a liquid crystal orientation solidified layer exhibiting reverse dispersion wavelength characteristics, a polarizing plate with a retardation layer having excellent high-temperature durability can be provided.

The angle θ between the slow axis of the retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40° to 50°, more preferably 42° to 48°, still more preferably about 45°. is ° If the angle θ is within this range, a polarizing plate with a retardation layer having very excellent circular polarization characteristics (as a result, very excellent antireflection characteristics) can be obtained by using the λ/4 plate as the retardation layer as described above. .

In another embodiment, the retardation layer 20 may have a laminated structure of a first liquid crystal alignment fixed layer and a second liquid crystal alignment fixed layer. In this case, either of the 1st liquid-crystal alignment hardened layer and the 2nd liquid-crystal alignment hardened layer can function as a lambda/4 board, and the other can function as a lambda/2 board. Accordingly, the thickness of the first liquid crystal alignment fixed layer and the second liquid crystal alignment fixed layer can be adjusted so as to obtain a desired in-plane retardation of the λ/4 plate or the λ/2 plate. For example, when the first liquid crystal alignment fixed layer functions as a lambda / 2 plate and the second liquid crystal alignment fixed layer functions as a lambda / 4 plate, the thickness of the first liquid crystal alignment fixed layer is, for example, 2.0 μm to 3.0 μm, The thickness of the 2nd liquid-crystal orientation hardening layer is 1.0 micrometer - 2.0 micrometer, for example. In this case, the in-plane retardation Re (550) of the first liquid crystal alignment fixed layer is preferably 200 nm to 300 nm, more preferably 230 nm to 290 nm, still more preferably 250 nm to 280 nm. The in-plane retardation Re (550) of the second liquid crystal alignment hardened layer is as described above with respect to the single layer.

The angle between the slow axis of the first liquid crystal alignment solidified layer and the absorption axis of the polarizer is preferably 10° to 20°, more preferably 12° to 18°, still more preferably about 15°. The angle formed by the slow axis of the second liquid crystal alignment solidified layer and the absorption axis of the polarizer is preferably 70° to 80°, more preferably 72° to 78°, still more preferably about 75°. With such a configuration, it is possible to obtain characteristics close to ideal reverse wavelength dispersion characteristics, and as a result, extremely excellent antireflection characteristics can be realized.

As described above, the retardation layer 20 is preferably an alignment hardening layer of a liquid crystal compound. By using a liquid crystal compound, the difference between nx and ny of the retardation layer obtained can be significantly increased compared to non-liquid crystal materials, so that the thickness of the retardation layer for obtaining a desired in-plane retardation can be significantly reduced. As a result, further thinning of the polarizing plate with a retardation layer can be realized. In this specification, the 'liquid crystal alignment solidified layer' refers to a layer in which a liquid crystal compound is aligned in a predetermined direction within the layer and the alignment state is fixed. In addition, the 'alignment hardened layer' is a concept including an alignment hardened layer obtained by curing a liquid crystal monomer as will be described later.

The retardation layer, which is an alignment-fixed layer of a liquid crystal compound, may be formed using a composition containing a polymerizable liquid crystal compound. In this specification, the polymerizable liquid crystal compound contained in the composition refers to a compound having a polymerizable group and having liquid crystallinity. A polymerizable group means a group involved in a polymerization reaction, and is preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group capable of participating in a polymerization reaction by an active radical or an acid generated from a photopolymerization initiator.

Expression of liquid crystal may be either thermotropic or lyotropic. In addition, as a structure of a liquid crystal phase, a nematic liquid crystal or a smectic liquid crystal may be used. From the viewpoint of ease of manufacture, the liquid crystal is preferably a thermotropic nematic liquid crystal.

In one embodiment, the retardation layer which is a single layer is formed using a composition containing a liquid crystal compound represented by the following formula (1).

L ¹ -SP ¹ -A ¹ -D ³ -G ¹ -D ¹ -Ar-D ² -G ² -D ⁴ -A ² -SP ² -L ² (1)

L ¹ and L ² each independently represent a monovalent organic group, and at least one of L ¹ and L ² represents a polymerizable group. Any appropriate group is included as the monovalent organic group. As a polymerizable group represented by at least one of L ¹ and L ² , a radical polymerizable group (group capable of radical polymerization) is exemplified. As the radical polymerizable group, any suitable radical polymerizable group can be used. Preferably, it is an acryloyl group or a methacryloyl group. Polymerization rate is fast and an acryloyl group is preferable from a viewpoint of productivity improvement. A methacryloyl group can similarly be used as a polymerizable group of a highly birefringent liquid crystal.

SP ¹ and SP ² , respectively A divalent linking group in which one or more of -CH ₂ - independently constituting a single bond, a linear or branched chain alkylene group, or a linear or branched chain alkylene group having 1 to 14 carbon atoms is substituted with -O-. indicates As a C1-C14 linear or branched alkylene group, Preferably, a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group are mentioned.

A ¹ and A ² each independently represent an alicyclic hydrocarbon group or an aromatic ring substituent. A ¹ and A ² are preferably a C6 or more aromatic ring substituent or a C6 or more cycloalkylene ring.

D ¹ , D ² , D ³ and D ⁴ each independently represent a single bond or a divalent linking group. Specifically, D ¹ , D ² , D ³ and D ⁴ are single bonds, -O-CO-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, - CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ - or -CO-NR ¹ -. However, at least one of D ¹ , D ² , D ³ and D ⁴ represents -O-CO-. Especially, it is preferable that D ³ is -O-CO-, and D ³ and D ⁴ are -O-CO-. it is more preferable D ¹ and D ² are preferably single bonds. R ¹ , R ² , R ³ and R ⁴ each independently represent a hydrogen atom, a fluorine atom or an alkyl group having 1 to 4 carbon atoms.

G ¹ and G ² each independently represent a single bond or an alicyclic hydrocarbon group. Specifically, G ¹ and G ² may represent an unsubstituted or substituted divalent alicyclic hydrocarbon group having 5 to 8 carbon atoms. In addition, one or more of -CH ₂ - constituting the alicyclic hydrocarbon group may be substituted with -O-, -S- or -NH-. G ¹ and G ² are, Preferably it represents a single bond.

Ar represents an aromatic hydrocarbon ring or an aromatic heterocyclic ring. Ar represents an aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-6), for example. In addition, in the following formulas (Ar-1) to (Ar-6), *1 represents a bonding position with D ¹ , and *2 represents a bonding position with D ² indicates the binding position.

In formula (Ar-1), Q ¹ represents N or CH, and Q ² is -S-, -O-, or -N(R ⁵ )-. R ⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

In formulas (Ar-1) to (Ar-6), Z ¹ , Z ² and Z ³ are each independently a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and a monovalent alicyclic hydrocarbon group having 3 to 20 carbon atoms. group, a monovalent aromatic hydrocarbon group having 6 to 20 carbon atoms, a halogen atom, a cyano group, a nitro group, -NR ⁶ R ⁷ or -SR ⁸ . R ^{6 to} R ⁸ each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and Z ¹ and Z ² may combine with each other to form a ring. The ring may be any of an alicyclic ring, a heterocyclic ring, and an aromatic ring, and is preferably an aromatic ring. The ring formed may be substituted by a substituent.

In formulas (Ar-2) and (Ar-3), each of A ³ and A ⁴ independently represents a group selected from the group consisting of -O-, -N(R ⁹ )-, -S-, and -CO-. and R ⁹ represents a hydrogen atom or a substituent. Examples of the substituent represented by R ⁹ include the same substituents that Y ¹ in the formula (Ar-1) may have.

In the formula (Ar-2), X represents a hydrogen atom or a non-metal atom of groups 14 to 16 having an unsubstituted or substituent. Examples of the group 14 to group 16 nonmetal atoms represented by X include an oxygen atom, a sulfur atom, an unsubstituted or substituted nitrogen atom, and an unsubstituted or substituted carbon atom. Examples of the substituent include the same substituents that Y ¹ in the formula (Ar-1) may have.

In formula (Ar-3), D ⁵ and D ⁶ are each independently a single bond, -O-CO-, -C(=S)O-, -CR ¹ R ² -, -CR ¹ R ² -CR ³ R ⁴ -, -O-CR ¹ R ² -, -CR ¹ R ² -O-CR ³ R ⁴ -, -CO-O-CR ¹ R ² -, -O-CO-CR ¹ R ² -, -CR ¹ R ² -O-CO-CR ³ R ⁴ -, -CR ¹ R ² -CO-O-CR ³ R ⁴ -, -NR ¹ -CR ² R ³ -, or -CO-NR ¹ -. R ¹ , R ² , R ³ and R ⁴ are as described above.

In formula (Ar-3), SP ³ and SP ⁴ is Each independently, one or more of -CH ₂ - constituting a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear or branched chain alkylene group having 1 to 12 carbon atoms represents a divalent linking group substituted with -O-, -S-, -NH-, -N(Q)- or -CO-, and Q represents a polymerizable group.

In Formula (Ar-3), L ³ and L ⁴ each independently represent a monovalent organic group, and at least one of L ³ and L ⁴ and L ¹ and L ² in Formula (1) represent a polymerizable group.

In the formulas (Ar-4) to (Ar-6), Ax represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of aromatic hydrocarbon rings and aromatic heterocycles. In the formulas (Ar-4) to (Ar-6), Ax preferably has an aromatic heterocycle, more preferably has a benzothiazole ring. In the formulas (Ar-4) to (Ar-6), Ay is at least one selected from the group consisting of a hydrogen atom, an unsubstituted or optionally substituted alkyl group having 1 to 6 carbon atoms, an aromatic hydrocarbon ring, and an aromatic heterocyclic ring. represents an organic group having 2 to 30 carbon atoms and having an aromatic ring of In formulas (Ar-4) to (Ar-6), Ay preferably represents a hydrogen atom.

In formulas (Ar-4) to (Ar-6), Q ³ represents a hydrogen atom or an unsubstituted or optionally substituted alkyl group having 1 to 6 carbon atoms. In formulas (Ar-4) to (Ar-6), Q ³ preferably represents a hydrogen atom.

Among such Ar, preferably, a group (atomic group) represented by the formula (Ar-4) or the formula (Ar-6) is exemplified.

The specific example of the liquid crystal compound represented by Formula (1) is disclosed in International Publication No. 2018/123551. The description of the publication is incorporated herein by reference. These compounds may be used alone or in combination of two or more.

A composition containing a liquid crystal compound preferably contains a polymerization initiator. As the polymerization initiator, any appropriate polymerization agent is used. Preferably, it is a photopolymerization initiator capable of initiating a polymerization reaction by irradiation with ultraviolet rays. Examples of the photopolymerization initiator include α-carbonyl compounds (described in the specifications of US Patent Nos. 2367661 and 2367670), acyloin ethers (described in the specification of US Patent No. 2448828), and α-hydrocarbon substituted aromatic acyloin compounds. (described in the specification of US Patent No. 2722512), a polynuclear quinone compound (described in the specification of US Patent No. 3046127 and US Patent No. 2951758), a combination of triarylimidazole dimer and p-aminophenyl ketone (US Patent No. 3549367 description), an oxadiazole compound (described in the specification of U.S. Patent No. 4212970), and an acylphosphine oxide compound (Japanese Patent Publication No. 63-40799, Japanese Patent Publication No. 5-29234, Japanese Unexamined Patent Publication No. Hei 10- 95788 and Japanese Unexamined Patent Publication No. 10-29997). The description of the publication is incorporated herein by reference. The polymerization initiator may be used alone or in combination of two or more.

It is preferable that the composition containing a liquid crystal compound contains a solvent from a viewpoint of workability|operativity of forming a retardation layer. Any suitable solvent can be used as the solvent, and an organic solvent is preferably used.

The composition containing the liquid crystal compound further contains any suitable other component. For example, antioxidants such as phenolic antioxidants, liquid crystal compounds other than the above, leveling agents, surfactants, tilt angle control agents, alignment aids, plasticizers, and crosslinking agents.

The liquid-crystal alignment hardening layer performs orientation treatment on the surface of a predetermined base material, applies a composition (coating solution) containing a liquid crystal compound to the surface, and aligns the liquid crystal compound in a direction corresponding to the orientation treatment, It can be formed by fixing the orientation state. In one embodiment, the substrate is any suitable resin film, and the liquid crystal alignment hardening layer formed on the substrate can be transferred to the surface of the polarizing plate.

As the orientation treatment, any appropriate orientation treatment may be employed. Specifically, a mechanical orientation treatment, a physical orientation treatment, and a chemical orientation treatment are mentioned. Specific examples of the mechanical orientation treatment include rubbing treatment and stretching treatment. Specific examples of the physical orientation treatment include magnetic field orientation treatment and electric field orientation treatment. Specific examples of the chemical orientation treatment include an oblique deposition method and an optical orientation treatment. Arbitrary appropriate conditions may be employed for the processing conditions of various alignment treatments depending on the purpose.

The alignment of the liquid crystal compound is performed by treating at a temperature at which a liquid crystal phase is exhibited depending on the type of the liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound assumes a liquid crystal state and aligns the liquid crystal compound according to the orientation treatment direction of the surface of the substrate.

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

The details of the formation method of an orientation hardening layer are described in Unexamined-Japanese-Patent No. 2006-163343. The description of the publication is incorporated herein by reference.

D. Other retardation layers

As described above, the other retardation layer may be a so-called positive C plate having a refractive index characteristic of nz>nx=ny. By using the positive C plate as the other retardation layer, the reflection in the oblique direction can be satisfactorily prevented, and the antireflection function can be widened to a wide viewing angle. In this case, the retardation Rth (550) of the other retardation layer in the thickness direction is preferably -50 nm to -300 nm, more preferably -70 nm to -250 nm, still more preferably -90 nm to -200 nm. nm, particularly preferably -100 nm to -180 nm. Here, 'nx=ny' includes not only the case where nx and ny are strictly equal, but also the case where nx and ny are substantially equal. That is, the in-plane retardation Re (550) of the other retardation layer may be less than 10 nm.

Another retardation layer having a refractive index characteristic of nz>nx=ny may be formed of any suitable material. The other retardation layer preferably includes a film containing a liquid crystal material fixed in a homeotropic orientation. The liquid crystal material (liquid crystal compound) capable of homeotropic alignment may be a liquid crystal monomer or a liquid crystal polymer. Specific examples of the liquid crystal compound and the method for forming the retardation layer include the liquid crystal compound described in [0020] to [0028] of Japanese Unexamined Patent Publication No. 2002-333642 and the method for forming the retardation layer. In this case, the thickness of the other retardation layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 8 μm, still more preferably 0.5 μm to 5 μm.

E. Adhesive layer

Arbitrary suitable adhesives can be used as the adhesive which comprises the adhesive layer 30. Examples of the adhesive include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinylalkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, and cellulose-based adhesives. Among these pressure-sensitive adhesives, those having excellent optical transparency, appropriate adhesive properties such as wettability, cohesiveness, and adhesiveness, and excellent weather resistance, heat resistance, and the like are preferably used. As one exhibiting such characteristics, an acrylic pressure-sensitive adhesive is preferably used.

F. 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 formation method (eg, vacuum deposition 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, more preferably 35 nm or less. The lower limit of the thickness of the conductive layer is preferably 10 nm.

The conductive layer is transferred from the substrate to the retardation layer (other retardation layers if present), and the conductive layer alone may be used as a component layer of the polarizing plate with the retardation layer, or the retardation layer as a laminate with the substrate (substrate with a conductive layer) (if present, another retardation layer). Preferably, the base material is optically isotropic, and therefore the conductive layer can be used for a polarizing plate with a retardation layer as an isotropic base material with a conductive layer.

As the optically isotropic substrate (isotropic substrate), any suitable isotropic substrate can be employed. As the material constituting the isotropic base material, for example, a material whose main skeleton is a resin without a conjugated system such as norbornene resin or olefin resin, and a cyclic structure such as lactone ring or glutarimide ring in the main chain of acrylic resin. Materials etc. are mentioned. When such a material is used, when an isotropic base material is formed, the occurrence of phase difference according to the orientation of molecular chains can be suppressed to a small level. 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 substrate is, for example, 20 µm.

The conductive layer and/or the conductive layer of the isotropic substrate with a conductive layer may be patterned as needed. A conductive portion and an insulating portion may be formed by patterning. As a result, electrodes can be formed. The electrodes may function as touch sensor electrodes that detect contact with the touch panel. As the patterning method, any suitable method can be employed. Specific examples of the patterning method include a wet etching method and a screen printing method.

G. Manufacturing method of polarizing plate with retardation layer

The polarizing plate with a retardation layer of the embodiment of the present invention can be manufactured by any suitable method. In one embodiment, a polarizing plate with a retardation layer is obtained by laminating a polarizing plate and a retardation layer cut into a rectangle having a designed size through an appropriate adhesive so that the direction of the long side of the rectangle and the direction of the slow axis of the retardation layer are orthogonal. can be manufactured When the polarizing plate and the retardation layer are stacked, they may be stacked such that an absorption axis of the polarizer and a slow axis of the retardation layer form a predetermined angle.

In one embodiment, a polarizing plate with a retardation layer is formed by laminating a large-sized (e.g., long) polarizing plate and a retardation layer with any suitable adhesive so that the absorption axis of the polarizer and the slow axis of the retardation layer are at a predetermined angle, Then, it can be manufactured by cutting into a rectangle of the designed size so that the long side direction of the resulting polarizing plate with a retardation layer and the slow axis of the retardation layer are orthogonal to each other.

H. Image display device

The polarizing plate with a retardation layer described in the above paragraphs A to F can be applied to an image display device. Therefore, the embodiment of the present invention includes an image display device using such a polarizing plate with a retardation layer. Representative examples of the image display device include a liquid crystal display device and an electroluminescence (EL) display device (eg, an organic EL display device and an inorganic EL display device). An image display device according to an embodiment of the present invention includes the polarizing plate with a retardation layer described in the above items A to F on its viewing side. Polarizing plates with a retardation layer are laminated so that the retardation layer is on the side of an image display cell (for example, a liquid crystal cell, an organic EL cell, or an inorganic EL cell) (so that the polarizer is on the viewing side). In one embodiment, the image display device has a curved shape (actually, a curved display screen) and/or is capable of being bent or folded.

[Example]

Hereinafter, the present invention will be specifically described by examples, but the present invention is not limited by these examples. The measurement method of each characteristic is as follows. In addition, unless otherwise specified, 'parts' and '%' in Examples and Comparative Examples are based on weight.

(1) Thickness

The thickness of 10 µm or less was measured using an interference film thickness meter (manufactured by Otsuka Electronics, product name 'MCPD-3000'). The thickness exceeding 10 µm was measured using a digital micrometer (manufactured by Anritz Corporation, product name 'KC-351C').

(2) Phase difference change Δ

The adhesive layer of the polarizing plate with the retardation layer obtained in Examples and Comparative Examples was laminated by bonding to a glass plate (80 mm × 150 mm) having a thickness of 0.5 mm, and the phase difference value Re with a retardation measuring device (manufactured by Oji Instruments, product name: KOBRA) (550) (initial phase difference value) was measured. Next, the polarizing plate with the retardation layer was heated in an oven at 80°C for 100 hours. Next, the polarizing plate with a retardation layer was left to stand until room temperature, and similarly the retardation value of the polarizing plate with a retardation layer was measured to calculate a phase difference change value Δ (initial retardation value - retardation value after heating).

(3) Dimensional shrinkage

The pressure-sensitive adhesive layer of the polarizing plate with a retardation layer obtained in Examples and Comparative Examples was bonded to and laminated on a glass plate (80 mm × 150 mm) having a thickness of 0.5 mm. Then, the sample was heated in an oven at 80°C for 100 hours. Next, the polarizing plate with the retardation layer was left to stand at room temperature, and dimensional shrinkage on the short side side of the polarizing plate with the retardation layer was measured using an XY measuring instrument (manufactured by Mitutoyo Corporation, product name: Image measuring instrument QVA1517-PRO AEIM (SP)). measured. The part with the largest amount of shrinkage was taken as the amount of dimensional shrinkage of the polarizing plate with the retardation layer. In addition, the shrinkage rate was calculated from the measured dimensional shrinkage using the following formula.

Shrinkage rate in the short side direction = (shrinkage distance in the short side direction) / (short side length before heating test) × 100

[Example 1]

[Production Example 1: Production of Polarizing Plate]

1. Fabrication of polarizer

As the thermoplastic resin base material, an amorphous isophthalic copolymerized polyethylene terephthalate film (thickness: 100 μm) was used, which was long and had a water absorption of 0.75% and a Tg of about 75°C. Corona treatment was performed on one side of the resin substrate.

Polyvinyl alcohol (polymerization degree 4200, saponification degree 99.2 mol%) and acetoacetyl-modified PVA (manufactured by Nihon Kosei Chemical Industry Co., Ltd., trade name 'Gose Fimer Z410') were mixed in a ratio of 9:1 to 100 parts by weight of a PVA-based resin, potassium iodide Added 13 parts by weight was dissolved in water to prepare a PVA aqueous solution (coating liquid).

A PVA-based resin layer having a thickness of 13 μm was formed by applying the PVA aqueous solution to the corona-treated surface of the resin substrate and drying at 60° C., thereby producing a laminate.

The obtained layered product was uniaxially stretched at the free end by 2.4 times in the machine direction (longitudinal direction) between rolls having different circumferential speeds in a 130°C oven (air assisted stretching treatment).

Next, the laminate was immersed in an insolubilization bath (boric acid aqueous solution obtained by blending 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 (insolubilization treatment).

Next, in a dyeing bath (100 parts by weight of water, an iodine aqueous solution obtained by blending iodine and potassium iodide at a weight ratio of 1:7) with a liquid temperature of 30 ° C., the polarizer finally obtained has a single transmittance (Ts) of 43.0% or more It was immersed for 60 seconds while adjusting the concentration so as to be (dyeing treatment).

Next, it was immersed in a crosslinking bath (a boric acid aqueous solution obtained by blending 3 parts by weight of potassium iodide and 5 parts by weight of boric acid with respect to 100 parts by weight of water) at a liquid temperature of 40°C for 30 seconds (crosslinking treatment).

Thereafter, the laminate was immersed in an aqueous solution of boric acid at a liquid temperature of 70°C (boric acid concentration: 3.7% by weight, potassium iodide concentration: 5% by weight), while the total draw ratio was increased in the machine direction (longitudinal direction) between rolls having different circumferential speeds. Uniaxial stretching was performed so as to be 5.5 times (underwater stretching treatment).

Thereafter, the laminate was immersed in a washing bath (aqueous solution obtained by blending 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 drying in an oven maintained at 90°C, it was brought into contact with a SUS heating roll maintained at a surface temperature of 75°C for about 2 seconds (dry shrinkage treatment). The shrinkage rate in the width direction of the layered product by the drying shrinkage treatment was 5.2%.

In this way, a polarizer (boric acid content: 20% by weight) having a thickness of 5 μm was formed on the resin substrate.

2. Fabrication of polarizer

An HC-COP film was bonded as a protective layer to the surface of the polarizer obtained above (surface on the opposite side to the resin substrate) through an ultraviolet curing adhesive. Specifically, the coating was applied so that the total thickness of the curable adhesive was 1.0 μm, and bonding was performed using a roll machine. Thereafter, UV rays were irradiated from the protective layer side to cure the adhesive. In addition, the HC-COP film is a film in which a hard coat (HC) layer (thickness of 2 μm) is formed on a cycloolefin (COP) film (manufactured by Nippon Zeon, product name 'ZF12', thickness of 25 μm), and the COP film is a polarizer It was bonded so that it became a side. Then, the resin substrate was peeled off to obtain a polarizing plate having a configuration of protective layer (HC layer/COP film)/adhesive layer/polarizer.

[Production Example 2: Production of Phase Contrast Layer]

After adding 55 parts by weight of the compound represented by formula (I), 25 parts by weight of the compound represented by formula (II), and 20 parts by weight of the compound represented by formula (III) to 400 parts by weight of cyclopentanone (CPN), 60 ° C. It was heated and stirred to dissolve. Then, the solution of the above compound was returned to room temperature, and 3 parts by weight of Irgacure 907 (manufactured by BASF Japan) and Megapack F-554 (manufactured by DIC) were added to the solution of the above compound. 0.2 part by weight and 0.1 part by weight of p-methoxyphenol (MEHQ) were added and further stirred. The solution after stirring was clear and uniform. The resulting solution was filtered through a 0.20 µm membrane filter to obtain a polymerizable composition.

In addition, a polyimide solution for alignment film was applied to a glass substrate having a thickness of 0.7 mm by spin coating, dried at 100°C for 10 minutes, and then baked at 200°C for 60 minutes to obtain a coating film. The obtained coating film was rubbed with a commercially available rubbing device to form an alignment film.

Next, the polymerizable composition obtained above was applied to the substrate (substantially the alignment film) by spin coating and dried at 100°C for 2 minutes. After cooling the obtained coating film to room temperature, using a high-pressure mercury lamp, 30 mW / cm 2 Ultraviolet rays were irradiated at a high intensity for 30 seconds to obtain a retardation layer that is an orientation-hardened layer of a liquid crystal compound. The in-plane retardation Re (550) of the retardation layer was 130 nm. In addition, Re(450)/Re(550) of the retardation layer was 0.851, indicating reverse dispersion wavelength characteristics. The retardation layer can function as a λ/4 plate.

[Manufacture Example 3: Production of Another Phase Contrast Layer]

20 parts by weight of a side chain type liquid crystal polymer represented by the following chemical formula (numbers 65 and 35 in the formula represent mole% of monomer units, and block polymers for convenience: weight average molecular weight: 5000), polymerizable liquid crystals showing a nematic liquid crystal phase 80 parts by weight (manufactured by BASF: trade name PaliocolorLC242) and 5 parts by weight of a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: trade name Irgacure 907) were dissolved in 200 parts by weight of cyclopentanone to prepare a liquid crystal coating liquid. And after coating the said coating liquid with the bar coater on the PET base material which performed the vertical alignment process, the liquid crystal was orientated by heat-drying at 80 degreeC for 4 minute(s). By irradiating the liquid crystal layer with ultraviolet rays and curing the liquid crystal layer, a second retardation layer (thickness of 3 μm) exhibiting a refractive index characteristic of nz>nx=ny was formed on the substrate.

The retardation layer obtained in Production Example 2 and the other retardation layer obtained in Production Example 3 were transferred in this order to the polarizer surface of the polarizing plate obtained in Production Example 1. At this time, transfer (bonding) was performed so that the angle between the absorption axis of the polarizer and the slow axis of the retardation layer obtained in Production Example 2 was 45°. In addition, each transfer (bonding) was performed through the ultraviolet curable adhesive (thickness 1.0 micrometer) used in manufacture example 1. In this way, a laminate having a configuration of protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/phase contrast layer/adhesive layer/other phase contrast layers was produced. Next, the laminate was cut into a rectangle with a long side of 130 mm and a short side of 66 mm so that the direction of the long side of the polarizing plate with the retardation layer and the slow axis of the retardation layer were orthogonal to each other.

Subsequently, an adhesive layer (thickness: 5 μm) is provided on the surface of the other phase contrast layer, and protective layer (HC layer/COP film)/adhesive layer/polarizer/protective layer (triacetyl cellulose film)/adhesive layer/phase contrast layer/adhesive layer / A polarizing plate with a retardation layer having a structure of another retardation layer / pressure-sensitive adhesive layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 100 μm. The obtained polarizing plate with a retardation layer was used for evaluation of the above (2) and (3). The results are shown in Table 1.

[Examples 2-4]

A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that in the production step of the polarizer, the concentration of the boric acid aqueous solution used in the crosslinking treatment step was changed and the polarizer having the boric acid content shown in Table 1 was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

(Comparative Example 1)

A polarizing plate with a retardation layer was produced in the same manner as in Example 1 except that in the production step of the polarizer, the concentration of the boric acid aqueous solution used in the crosslinking treatment step was changed and the polarizer having the boric acid content shown in Table 1 was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

(Comparative Example 2)

In the same manner as in Example 1, a laminate having a configuration of protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer (retardation layer / adhesive layer / other retardation layer) was produced. Next, the laminate was cut into a rectangle with a long side of 130 mm and a short side of 66 mm so that the direction of the long side of the polarizing plate with the retardation layer and the slow axis of the retardation layer were parallel.

Subsequently, an adhesive layer (thickness: 15 μm) is provided on the surface of the other retardation layer, and the configuration of the protective layer (HC layer / COP film) / adhesive layer / polarizer / adhesive layer / retardation layer / adhesive layer / other retardation layer / adhesive layer A polarizing plate with a retardation layer was obtained. The total thickness of the obtained polarizing plate with a retardation layer was 39.5 µm. The obtained polarizing plate with a retardation layer was used for evaluation of the above (2) and (3). The results are shown in Table 1.

(Comparative Examples 3 to 6)

A polarizing plate with a retardation layer was produced in the same manner as in Comparative Example 2 except that the concentration of the boric acid aqueous solution used in the crosslinking treatment step was changed in the polarizer production step and the polarizer having the boric acid content shown in Table 1 was obtained. The obtained polarizing plate with a retardation layer was subjected to the same evaluation as in Example 1. The results are shown in Table 1.

[Table 1]

[evaluation]

As is clear from Table 1, the polarizing plate with the retardation layer of the examples of the present invention was suppressed from decreasing the retardation even when subjected to a heating test, and had excellent high-temperature durability.

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

10: polarizer
11: polarizer
12: protective layer
20: phase difference layer
30: adhesive layer
100: polarizing plate with retardation layer

Claims (9)

A rectangular polarizing plate with a retardation layer comprising a polarizing plate containing a polarizer having a boric acid content of 11% by weight or more and a retardation layer that is an orientation-hardened layer of a liquid crystal compound,
A polarizing plate with a retardation layer, wherein a direction of a long side of the polarizing plate with a retardation layer and a direction of a slow axis of the retardation layer are orthogonal. According to claim 1,
The in-plane retardation Re (550) of the retardation layer is 100 nm to 190 nm, and also satisfies Re (450) / Re (550) < 1, and the angle between the slow axis of the retardation layer and the absorption axis of the polarizer (θ ) is 40 ° to 50 °, a polarizing plate with a retardation layer. According to claim 1,
A polarizing plate with a retardation layer, wherein an angle between an absorption axis of the polarizer and a long side direction of the polarizing plate with a retardation layer is 125° to 145°. According to claim 1,
A polarizing plate with a retardation layer, wherein the polarizing plate with a retardation layer has dimensional shrinkage in a direction of a short side of 0.25 mm or more. According to claim 1,
A polarizing plate with a retardation layer, wherein the ratio of the length of the long side to the length of the short side of the polarizing plate with the retardation layer is 1.1 to 3.0. According to claim 1,
A polarizing plate with a retardation layer, wherein the retardation layer has a circular polarization function or an elliptically polarization function. According to claim 1,
A polarizing plate with a retardation layer having a total thickness of 60 μm or less. An image display device comprising the polarizing plate with a retardation layer according to claim 1. According to claim 8,
An image display device that is an organic electroluminescent display device or an inorganic electroluminescent display device.

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