JP2023073123A - Polarizer with phase difference layer and image display device with the same - Google Patents

Abstract

To provide a polarizer with a phase difference layer with an excellent durability to high temperatures.SOLUTION: A polarizer 100 with a phase difference layer includes a polarizer 10 including a polarizer 11 with a thickness of at least 7 μm; a first phase difference layer 20 as an orientation solidification layer of a liquid crystal compound; and a second phase difference layer 30 made of a resin film containing a polymer with a negative double refraction.SELECTED DRAWING: Figure 1

Description

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

2. Description of the Related Art 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) have rapidly spread. Polarizing plates and retardation plates are typically used in image display devices. Practically, a polarizing plate with a retardation layer, in which a polarizing plate and a retardation plate are integrated, is widely used (for example, Patent Document 1). As the demand for thinner image display devices increases, the demand for thinner polarizing plates with retardation layers also increases. For the purpose of thinning the polarizing plate with a retardation layer, thinning of the retardation plate is progressing, and a retardation plate manufactured using a liquid crystal material is used. A thin retardation plate tends to undergo a large dimensional shrinkage of the polarizing plate under high-temperature conditions, and the retardation may change. Further, in a retardation layer formed using a liquid crystal material, the effect of dimensional shrinkage becomes greater, and as a result, the reflection hue may change more.

Japanese Patent No. 3325560

The present invention has been made to solve the above-mentioned conventional problems, and its main purpose is to provide a polarizing plate with a retardation layer that suppresses the in-plane unevenness of the reflection hue and has excellent high-temperature durability. .

A polarizing plate with a retardation layer according to an embodiment of the present invention includes a polarizing plate including a polarizer having a thickness of 7 μm or more, a first retardation layer which is an alignment fixed layer of a liquid crystal compound, and a polymer exhibiting negative birefringence. and a second retardation layer composed of a resin film containing
In one embodiment, the second retardation layer is adjacent to the first retardation layer.
In one embodiment, the second retardation layer is a positive C plate.
In one embodiment, the thickness of the second retardation layer is 1 μm to 30 μm.
In one embodiment, the polymer exhibiting negative birefringence is at least one selected from the group consisting of acrylic resins, styrene resins, and maleimide resins.
In one embodiment, the in-plane retardation of the first retardation layer is 100 nm<Re(550)<160 nm, Re(450)/Re(550)<1, and Re(650 )/Re(550)>1.
In one embodiment, the angle between the slow axis of the first retardation layer and the absorption axis of the polarizer is 40° to 50°.
In one embodiment, the first phase layer has a laminated structure of a fixed alignment layer A of a liquid crystal compound and a fixed alignment layer B of a liquid crystal compound, and the fixed alignment layer A functions as a λ/2 plate. , the orientation fixed layer B functions as a λ/4 plate.
In one embodiment, the angle formed by the slow axis of the liquid crystal compound alignment fixed layer A and the absorption axis of the polarizer is 70° to 80°, and the liquid crystal compound alignment fixed layer B has a slow axis. The angle between the phase axis and the absorption axis of the polarizer is 10° to 20°.
An image display device is provided in another aspect of the present invention. This image display device includes the retardation layer-attached polarizing plate.

According to the embodiment of the present invention, it is possible to provide a polarizing plate with a retardation layer that suppresses in-plane unevenness in reflection hue and has excellent high-temperature durability. According to the embodiment of the present invention, even in a polarizing plate with a retardation layer including a retardation layer that is a liquid crystal alignment fixed layer, the retardation change of the polarizing plate is suppressed in a high-temperature environment. Therefore, a change in reflection hue can also be suppressed. As a result, it is possible to provide a polarizing plate with a retardation layer that suppresses in-plane unevenness of the reflection hue and has excellent high-temperature durability.

1 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to one embodiment of the present invention; FIG. FIG. 4 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the invention;

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

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

A. Overall Configuration of Retardation Layer-Equipped Polarizing Plate FIG. 1 is a schematic cross-sectional view of a retardation layer-attached polarizing plate according to one embodiment of the present invention. A polarizing plate 100 with a retardation layer in the illustrated example has a polarizing plate 10, a first retardation layer 20, and a second retardation layer 30 in this order from the viewing side. The polarizing plate 10 typically includes a polarizer 11 and protective layers 12 and 13 arranged on both sides of the polarizer 11 . Protective layer 13 may be omitted. Each member constituting the retardation layer-attached polarizing plate can be laminated via any appropriate adhesive layer (not shown). Specific examples of the adhesive layer include an adhesive layer and an adhesive layer. The first retardation layer 20 is an alignment fixed layer of a liquid crystal compound (hereinafter sometimes simply referred to as a liquid crystal alignment fixed layer). The second retardation layer 30 is composed of a resin film containing a polymer exhibiting negative birefringence. In the illustrated example, the first retardation layer 20 is a single layer. By having the first retardation layer 20, which is a liquid crystal alignment fixed layer, and the second retardation layer 30 composed of a resin film containing a polymer exhibiting negative birefringence, in-plane unevenness in the reflection hue is reduced. It is possible to provide a retardation layer-attached polarizing plate having suppressed and excellent high-temperature durability. The first retardation layer, which is a liquid crystal alignment fixed layer, is susceptible to contraction of the polarizing plate in a high-temperature environment, and the retardation may change. Therefore, the reflected hue of the retardation layer-attached polarizing plate may change, and in-plane unevenness of the reflected hue may occur. By having the second retardation layer composed of a resin film containing a polymer exhibiting negative birefringence, the influence of dimensional shrinkage of the polarizing plate on the first retardation layer can be mitigated. As a result, the change in retardation of the first retardation layer can be suppressed. In addition, since the second retardation layer is composed of a resin film containing a polymer exhibiting negative birefringence, the retardation change due to dimensional shrinkage of the polarizing plate in a high-temperature environment can be reduced. Therefore, the retardation change in the retardation layer-attached polarizing plate in a high-temperature environment can be suppressed, and the in-plane reflected hue unevenness can be further suppressed. Preferably, the first retardation layer 20 and the second retardation layer 30 are adjacent. By adjoining the first retardation layer, which is a liquid crystal alignment fixed layer, and the second retardation layer composed of a resin film, the in-plane unevenness of the reflection hue is further suppressed, and excellent high-temperature durability. can provide a polarizing plate with a retardation layer. In this specification, "adjacent" includes not only direct adjacency but also adjacency via an arbitrary adhesive layer. As used herein, the term "liquid crystal alignment fixed layer" refers to a layer in which a liquid crystal compound is aligned in a predetermined direction and the alignment state is fixed. In addition, the "alignment fixed layer" is a concept including an alignment cured layer obtained by curing a liquid crystal monomer as described later.

In the illustrated example, the second retardation layer 30 is laminated on the surface of the first retardation layer 20 not in contact with the polarizing plate 10, but the second retardation layer 30 is formed between the polarizing plate 10 and the first It may be arranged between the phase difference 20 .

FIG. 2 is a schematic cross-sectional view of a polarizing plate with a retardation layer according to another embodiment of the invention. The polarizing plate 101 with a retardation layer in the illustrated example is composed of a polarizing plate 10, a first retardation layer 20 which is a liquid crystal alignment fixed layer, and a resin film containing a polymer exhibiting negative birefringence. It has a retardation layer 30 in this order from the viewing side. In the illustrated example, the first retardation layer 20 has a laminated structure of a liquid crystal alignment fixed layer A21 and a liquid crystal alignment fixed layer B22. Provided is a polarizing plate with a retardation layer that suppresses in-plane unevenness in reflected hue and has excellent high-temperature durability even when a liquid crystal alignment fixed layer having a laminated structure is used as the first retardation layer 20. can do. In the illustrated example, the liquid crystal alignment fixed layer B22 and the second retardation layer 30 are arranged adjacent to each other, but the second retardation layer 30 is arranged between the polarizing plate 10 and the liquid crystal alignment fixed layer A21. may have been

In one embodiment, the retardation layer-attached polarizing plates 100 and 101 have an adhesive layer as the outermost layer (for example, the surface of the second retardation layer 30 in the illustrated example on which the first retardation layer 20 is not laminated). , 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 until the polarizing plate is used. By temporarily attaching the release liner, the pressure-sensitive adhesive layer can be appropriately protected.

The retardation layer-attached polarizing plate may further include a retardation layer (not shown) other than the first retardation layer 20 and the second retardation layer 30 . Another retardation layer is an arbitrary layer provided as needed, and may be omitted. The optical properties (for example, refractive index properties, in-plane retardation, Nz coefficient, photoelastic coefficient), thickness, arrangement position, etc. of the separate retardation layer can be appropriately set according to the purpose.

In the retardation layer-attached polarizing plate, the ratio of the thickness of the polarizer to the thickness of the first retardation layer is, for example, the thickness of the polarizer/thickness of the first retardation layer is 0.5 to 7, It is preferably 1-6, more preferably 2-5. According to the embodiment of the present invention, even in such a polarizing plate with a retardation layer, a change in retardation due to dimensional shrinkage in a high-temperature environment can be suppressed, and a change in reflection hue can also be suppressed.

The total thickness of the retardation layer-attached polarizing plate is preferably 40 μm to 120 μm, more preferably 40 μm to 110 μm, still more preferably 50 μm to 100 μm. A polarizing plate with a retardation layer including a polarizing plate having a certain thickness can have such a thickness. Such a polarizing plate with a retardation layer tends to be greatly affected by dimensional shrinkage of the polarizing plate in a high-temperature environment. According to the embodiment of the present invention, even in a polarizing plate with a retardation layer having the thickness described above, a change in retardation due to dimensional shrinkage in a high-temperature environment can be suppressed, and a change in reflection hue can also be suppressed. In addition, the total thickness of the polarizing plate with a retardation layer means the polarizing plate, the retardation layer (when another retardation layer is present, the retardation layer and another retardation layer), and the thickness for laminating these. It refers to the total thickness of the adhesive layers (that is, the total thickness of the retardation layer-attached polarizing plate does not include the thickness of the pressure-sensitive adhesive layer provided as the outermost layer and the thickness of the release liner that can be temporarily adhered to the surface thereof).

The constituent elements of the retardation layer-attached polarizing plate will be described in more detail below.

B. Polarizing plate B-1. Polarizer A polarizer is typically composed of a polyvinyl alcohol (PVA) resin film containing a dichroic substance. The thickness of the polarizer is, as described above, 7 μm or more, for example 8 μm or more, for example 10 μm or more, for example 12 μm or more, or for example 15 μm or more. When the thickness of the polarizer is large, the dimensional shrinkage of the retardation layer-attached polarizing plate tends to increase, and the retardation change may become more pronounced. In the embodiment of the present invention, even when a polarizer having the above thickness is used, it is excellent in high-temperature durability, and retardation change due to dimensional shrinkage can be suppressed. As a result, in-plane reflective hue unevenness of the polarizing plate with a retardation layer can be suppressed. The thickness of the polarizer is, for example, 30 μm or less.

The boric acid content of the polarizer is preferably 20 wt % or less, more preferably 5 wt % to 20 wt %, still more preferably 10 wt % to 18 wt %. If the boric acid content of the polarizer is within such a range, it is possible to provide a polarizing plate with a retardation layer having excellent high-temperature durability. If the boric acid content is less than 5% by weight, the polarizer may become polyene and the durability may decrease. According to the embodiment of the present invention, even when placed in a high-temperature environment, a change in retardation due to dimensional shrinkage of the polarizing plate can be suppressed, and a change in reflected hue can also be suppressed. As a result, a polarizing plate with a retardation layer having excellent reflection hue can be provided. The boric acid content of the polarizer can be adjusted, for example, by adjusting the boric acid content in the aqueous solutions used in the following steps. The boric acid content can be calculated as the amount of boric acid contained in the polarizer per unit weight, for example, using the following formula from the neutralization method.

The iodine content of the polarizer is preferably 2% by weight or more, more preferably 2% to 10% by weight. If the iodine content of the polarizer is within such a range, the synergistic effect with the above-mentioned boric acid content can maintain the ease of curl adjustment during bonding and prevent curl during heating. It is possible to improve the appearance durability during heating while satisfactorily suppressing the As used herein, "iodine content" means the total amount of iodine contained in the polarizer (PVA-based resin film). More specifically, iodine exists in the form of iodine ions (I ⁻ ), iodine molecules (I ₂ ), polyiodine ions (I ₃ ⁻ , I ₅ ⁻ ) and the like in the polarizer. The iodine content means the amount of iodine including all these forms. The iodine content can be calculated, for example, by a calibration curve method of fluorescent X-ray analysis. The polyiodine ions are present in the polarizer in the form of a PVA-iodine complex. Absorption dichroism can be expressed in the visible light wavelength range by forming such a complex. Specifically, the complex of PVA and triiodide ion (PVA·I ₃ ⁻ ) has an absorption peak near 470 nm, and the complex of PVA and pentaiodide ion (PVA·I ₅ ⁻ ) has an absorption peak near 600 nm. has an absorption peak at As a result, polyiodine ions can absorb light in a wide range of visible light, depending on their morphology. On the other hand, iodine ions (I ⁻ ) have an absorption peak near 230 nm and are not substantially involved in the absorption of visible light. Therefore, polyiodine ions present in a complex with PVA may be primarily responsible for 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 degree of polarization 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 spectrophotometer and subjected to visibility correction. The degree of polarization is typically obtained by the following formula based on the parallel transmittance Tp and the orthogonal transmittance Tc measured using an ultraviolet-visible spectrophotometer and subjected to visibility correction.
Degree of polarization (%) = {(Tp-Tc)/(Tp+Tc)} ^1/2 × 100

A polarizer can be manufactured by any suitable method. For example, any appropriate resin film such as a polyvinyl alcohol (PVA) resin film is subjected to various treatments such as swelling treatment, stretching treatment, dyeing treatment with a dichroic substance such as iodine, cross-linking treatment, washing treatment, and drying treatment. It can be manufactured by applying.

B-2. Protective Layers Protective layers 12, 13 are formed of any suitable film that can be used as a protective layer for a polarizer. Specific examples of materials that are the main component of the film include cellulose resins such as triacetyl cellulose (TAC), polyesters, polyvinyl alcohols, polycarbonates, polyamides, polyimides, polyethersulfones, and polysulfones. , polystyrene-based, polynorbornene-based, polyolefin-based, (meth)acrylic-based, and acetate-based transparent resins. Thermosetting resins such as (meth)acrylic, urethane, (meth)acrylic urethane, epoxy, and silicone, or ultraviolet curable resins may also be used. In addition, for example, a glassy polymer such as a siloxane-based polymer can also be used. Further, polymer films described in JP-A-2001-343529 (WO01/37007) can also be used. Materials for this film include, for example, a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in a side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and nitrile group in a side chain. can be used, for example, a resin composition comprising an alternating copolymer of isobutene and N-methylmaleimide and an acrylonitrile/styrene copolymer. The polymer film can be, for example, an extrudate of the resin composition.

The polarizing plate with a retardation layer is typically arranged on the viewing side of the image display device, and the protective layer 12 is typically arranged on the viewing side. Therefore, the protective layer 12 may be subjected to surface treatment such as hard coat treatment, anti-reflection treatment, anti-sticking treatment, and anti-glare treatment, if 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 performed, the thickness of the outer protective layer (protective layer 12) is the thickness including the thickness of the surface treatment layer.

C. First Retardation Layer The first retardation layer 20 is an alignment fixed layer of a liquid crystal compound. By using a liquid crystal compound, it is possible to realize an in-plane retardation equivalent to that of a resin film with a thickness much thinner than that of a resin film. Further, in the liquid crystal alignment fixed layer, the retardation change due to the dimensional shrinkage of the retardation layer-attached polarizing plate in a high-temperature environment may become more remarkable. In the embodiment of the present invention, even when the retardation layer, which is a fixed alignment layer of a liquid crystal compound, is employed, it is possible to provide a polarizing plate with a retardation layer that is excellent in high-temperature durability. The first retardation layer may be a single layer or a laminate of two or more layers. The first retardation layer is typically provided to impart antireflection properties to the polarizing plate.

C-1. Single Layer First Retardation Layer When the first retardation layer 20 is a single layer, the single layer first retardation layer can function as a λ/4 plate. The in-plane retardation Re(550) of the first retardation layer is preferably more than 100 nm and less than 160 nm, more preferably 110 nm to 155 nm, still more preferably 130 nm to less than 150 nm.

The Nz coefficient of the first retardation layer, which is a single 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 in an image display device, a very excellent reflection hue can be achieved.

The thickness of the first retardation layer is preferably 0.5 μm to 10 μm, more preferably 0.5 μm to 7 μm, still more preferably 1 μm to 5 μm.

The first retardation layer preferably exhibits reverse dispersion wavelength characteristics. In this case, Re(550)/Re(650) is preferably greater than 1, more preferably greater than 1 and 1.2 or less, still more preferably 1.01 to 1.15. In addition, Re(450)/Re(550) of the first retardation layer is preferably less than 1, more preferably less than 0.95, still more preferably less than 0.90. Re(450)/Re(550) is, for example, 0.8 or more. With such a configuration, very excellent antireflection properties can be achieved.

The angle between the slow axis of the first retardation layer 20 and the absorption axis of the polarizer 11 is preferably 40° to 50°, more preferably 42° to 48°, and more preferably about 45°. °. If the angle is in such a range, by using the retardation layer as a λ / 4 plate as described above, a retardation having very good circular polarization properties (as a result, very good antireflection properties) A layered polarizing plate can be obtained.

As described above, the first retardation layer 20 is an alignment fixed layer of a liquid crystal compound. By using a liquid crystal compound, the difference between nx and ny in the resulting retardation layer can be significantly increased compared to a non-liquid crystal material. can be significantly reduced. As a result, it is possible to further reduce the thickness of the retardation layer-attached polarizing plate.

The retardation layer, which is a fixed alignment layer of a liquid crystal compound, can be formed using a composition containing a polymerizable liquid crystal compound. The polymerizable liquid crystal compound contained in the composition as used herein refers to a compound having a polymerizable group and liquid crystallinity. A polymerizable group means a group involved in a polymerization reaction, preferably a photopolymerizable group. Here, the photopolymerizable group refers to a group that can participate in a polymerization reaction by an active radical generated from a photopolymerization initiator, an acid, or the like.

Liquid crystalline expression may be thermotropic or lyotropic. Further, the structure of the liquid crystal phase may be nematic liquid crystal or smectic liquid crystal. Thermotropic nematic liquid crystals are preferred from the standpoint of ease of production.

In one embodiment, the single-layer retardation 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. Monovalent organic groups include any suitable groups. Examples of the polymerizable group represented by at least one of L ¹ and L ² include radically polymerizable groups (groups capable of radical polymerization). Any appropriate radically polymerizable group can be used as the radically polymerizable group. An acryloyl group or a methacryloyl group is preferred. An acryloyl group is preferred because it has a high polymerization rate and improves productivity. A methacryloyl group can also be used as a polymerizable group for highly birefringent liquid crystals.

SP ¹ and SP ² each independently constitute a single bond, a linear or branched alkylene group, or a linear or branched alkylene group having 1 to 14 carbon atoms —CH ₂ represents a divalent linking group in which one or more of - are substituted with -O-; The linear or branched alkylene group having 1 to 14 carbon atoms preferably includes methylene group, ethylene group, propylene group, butylene group, pentylene group and hexylene group.

A ¹ and A ² each independently represent an alicyclic hydrocarbon group or an aromatic ring substituent. A ¹ and A ² are preferably aromatic ring substituents having 6 or more carbon atoms or cycloalkylene rings having 6 or more carbon atoms.

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 a single bond, —O—CO—, —C(=S)O—, —CR ¹ R ² —, —CR ¹ R ² —CR ^{3R 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 - represents However, at least one of D ¹ , D ² , D ³ and D ⁴ represents -O-CO-. Among them, D ³ is preferably -O-CO-, and D ³ and D ⁴ are more preferably -O-CO-. 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 —CH ₂ — constituting the alicyclic hydrocarbon group may be substituted with —O—, —S— or —NH—. G ¹ and G ² preferably represent a single bond.

Ar represents an aromatic hydrocarbon ring or an aromatic heterocycle. Ar represents, for example, an aromatic ring selected from the group consisting of groups represented by the following formulas (Ar-1) to (Ar-6). In the following formulas (Ar-1) to (Ar-6), *1 represents the bonding position with ^D1 , and *2 represents the bonding position with ^D2 .

In formula (Ar-1), Q ¹ represents N or CH, and Q ² represents -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 each independently represents a hydrogen atom, a monovalent aliphatic hydrocarbon group having 1 to 20 carbon atoms, and 3 carbon atoms. represents a monovalent alicyclic hydrocarbon group of up to 20, a monovalent aromatic hydrocarbon group of 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 an alicyclic, heterocyclic or aromatic ring, preferably an aromatic ring. The formed ring may be substituted with a substituent.

In formulas (Ar-2) and (Ar-3), A ³ and A ⁴ are each independently a group consisting of -O-, -N(R ⁹ )-, -S- and -CO- represents a group selected from the above, 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 above formula (Ar-1) may have.

In formula (Ar-2), X represents a hydrogen atom or an unsubstituted or substituted group 14 to group 16 nonmetallic atom. Examples of the group 14 to group 16 nonmetallic 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 above 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 represents -. R ¹ , R ² , R ³ and R ⁴ are as described above.

In formula (Ar-3), SP ³ and SP ⁴ are each independently a single bond, a linear or branched alkylene group having 1 to 12 carbon atoms, or a linear chain having 1 to 12 carbon atoms. divalent in which one or more —CH ₂ — constituting a branched or branched alkylene group is 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) above is represents a polymerizable group.

In formulas (Ar-4) to (Ar-6), Ax is 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 heterocyclic rings. represents In formulas (Ar-4) to (Ar-6), Ax preferably has an aromatic heterocyclic ring, more preferably a benzothiazole ring. In formulas (Ar-4) to (Ar-6), Ay is a hydrogen atom, an unsubstituted or optionally substituted alkyl group having 1 to 6 carbon atoms, or an aromatic hydrocarbon ring and aromatic represents an organic group having 2 to 30 carbon atoms and having at least one aromatic ring selected from the group consisting of heterocyclic rings. 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), ^Q3 preferably represents a hydrogen atom.

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

A 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. Any appropriate polymerization agent can be used as the polymerization initiator. A photopolymerization initiator capable of initiating a polymerization reaction by ultraviolet irradiation is preferred. Examples of photopolymerization initiators include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670), acyloin ethers (described in US Pat. No. 2,448,828), α-hydrocarbon substituted Aromatic acyloin compounds (described in US Pat. No. 2,722,512), polynuclear quinone compounds (described in US Pat. Nos. 3,046,127 and 2,951,758), combinations of triarylimidazole dimers and p-aminophenyl ketones ( US Pat. No. 3,549,367), oxadiazole compounds (US Pat. No. 4,212,970), and acylphosphine oxide compounds (JP-B-63-40799, JP-B-5-29234, JP-A-10-95788 and JP-A-10-29997). The description of the publication is incorporated herein by reference. Only one type of polymerization initiator may be used, or two or more types may be used in combination.

A composition containing a liquid crystal compound preferably contains a solvent from the viewpoint of workability for forming a retardation layer. Any suitable solvent can be used as the solvent, and organic solvents are preferably used.

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

The liquid crystal alignment fixed layer is formed by applying an alignment treatment to the surface of a predetermined base material, coating the surface with a composition (coating liquid) containing a liquid crystal compound, and aligning the liquid crystal compound in the direction corresponding to the alignment treatment. and fixing the orientation state. In one embodiment, the substrate is any appropriate resin film, and the liquid crystal alignment solidified layer formed on the substrate can be transferred to the surface of the polarizing plate.

Any appropriate alignment treatment may be employed as the alignment treatment. Specific examples include mechanical orientation treatment, physical orientation treatment, and chemical orientation treatment. Specific examples of mechanical orientation treatment include rubbing treatment and stretching treatment. Specific examples of physical orientation treatment include magnetic orientation treatment and electric field orientation treatment. Specific examples of chemical alignment treatment include oblique vapor deposition and photo-alignment treatment. Arbitrary appropriate conditions can be adopted as the processing conditions for various alignment treatments depending on the purpose.

Alignment of the liquid crystal compound is performed by treatment at a temperature at which a liquid crystal phase is exhibited depending on the type of liquid crystal compound. By performing such a temperature treatment, the liquid crystal compound assumes a liquid crystal state, and the liquid crystal compound is aligned in accordance with the orientation treatment direction of the base material surface.

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 orientation state is fixed by subjecting the liquid crystal compound oriented as described above to a polymerization treatment or a crosslinking treatment.

Details of the method for forming the alignment fixed layer are described in JP-A-2006-163343. The description of the publication is incorporated herein by reference.

C-2. First Retardation Layer Having Laminated Structure In one embodiment, the first retardation layer has a laminated structure of an alignment fixed layer A of a liquid crystal compound and an alignment fixed layer B of a liquid crystal compound. When the first retardation layer has a laminated structure, one of the liquid crystal alignment fixed layer A and the liquid crystal alignment fixed layer B can function as a λ/4 plate, and the other can function as a λ/2 plate. For example, when the liquid crystal alignment fixed layer A functions as a λ/2 plate and the liquid crystal alignment fixed layer B functions as a λ/4 plate, Re (550) of the liquid crystal alignment fixed layer A is preferably 200 nm to 300 nm. , more preferably 200 nm to 270 nm, still more preferably 210 nm to 260 nm, and particularly preferably 230 nm to 260 nm. Re(550) of the liquid crystal alignment layer B is preferably 100 nm to 200 nm, more preferably 100 nm to 170 nm, still more preferably 110 nm to 150 nm, and particularly preferably 110 nm to 130 nm.

The thickness of the A layer can be adjusted, for example, so as to obtain the desired in-plane retardation of the λ/2 plate. The thickness of the A layer is, for example, 2.0 μm to 4.0 μm. The thickness of the B layer can be adjusted, for example, so as to obtain the desired in-plane retardation of the λ/4 plate. The thickness of the B layer is, for example, 0.5 μm to 2.5 μm. In the present embodiment, the angle formed by the slow axis of the A layer and the absorption axis of the polarizer is preferably 10° to 20°, more preferably 12° to 18°, still more preferably 12°. ~16°. Further, the angle formed by the slow axis of the B layer and the absorption axis of the polarizer is preferably 70° to 80°, more preferably 72° to 78°, still more preferably 72° to 76°. be. When the first retardation layer has a laminated structure, each layer (e.g., A layer and B layer) may exhibit an inverse dispersion wavelength characteristic in which the retardation value increases according to the wavelength of the measurement light, A positive wavelength dispersion characteristic in which the phase difference value decreases according to the wavelength of the measurement light may be exhibited, or a flat wavelength dispersion characteristic in which the phase difference value hardly changes with the wavelength of the measurement light may be exhibited.

The retardation layer (at least one layer if it has a laminated structure) typically exhibits a relationship of nx>ny=nz in refractive index characteristics. Note that "ny=nz" includes not only the case where ny and nz are completely equal but also the case where they are substantially equal. Therefore, ny>nz or ny<nz may be satisfied within a range that does not impair the effects of the present invention. The Nz coefficient of the retardation layer is preferably 0.9 to 1.5, more preferably 0.9 to 1.3.

In this embodiment, examples of the liquid crystal compound used in the first retardation layer include a liquid crystal compound having a nematic liquid crystal phase (nematic liquid crystal). As such a liquid crystal compound, for example, a liquid crystal polymer or a liquid crystal monomer can be used. Either lyotropic or thermotropic mechanism may be used to develop the liquid crystallinity of the liquid crystal compound. The liquid crystal polymer and 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 alignment state of the liquid crystal monomer can be fixed by polymerizing or cross-linking (that is, curing) the liquid crystal monomer. After aligning the liquid crystal monomers, for example, the alignment state can be fixed by polymerizing or cross-linking the liquid crystal monomers. Here, a polymer is formed by polymerization and a three-dimensional network structure is formed by cross-linking, but these are non-liquid crystalline. Therefore, the formed retardation layer does not undergo a transition to a liquid crystal phase, a glass phase, or a crystal phase due to a change in temperature, which is peculiar to liquid crystalline compounds. As a result, the retardation layer becomes a highly stable retardation layer that is not affected by temperature changes.

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

Any appropriate liquid crystal monomer can be employed as the liquid crystal monomer. For example, polymerizable mesopolymers described in JP-T-2002-533742 (WO00/37585), EP358208 (US5211877), EP66137 (US4388453), WO93/22397, EP0261712, DE19504224, DE4408171, and GB2280445 Gen compounds and the like can be used. Specific examples of such polymerizable mesogenic compounds include LC242 (trade name) available from BASF, E7 (trade name) available from Merck, and LC-Sillicon-CC3767 (trade name) available from Wacker-Chem. A nematic liquid crystal monomer is preferable as the liquid crystal monomer. Specific examples of the liquid crystal compound and details of the method for forming the alignment fixed layer are as described above.

The liquid crystal alignment fixed layer A functions as a λ/2 plate and the liquid crystal alignment fixed layer B functions as a λ/4 plate. B may be a λ/4 plate. The angle between the slow axis of the liquid crystal alignment fixed layer A and the absorption axis of the polarizer is about 75°, and the angle between the slow axis of the liquid crystal alignment fixed layer B and the absorption axis of the polarizer is about 15°. may be

D. Second Retardation Layer The second retardation layer 30 is preferably composed of a resin film containing a polymer exhibiting negative birefringence. Here, the term "exhibiting negative birefringence" means that when a polymer is oriented by stretching or the like, the refractive index in the stretching direction becomes relatively small. In other words, it means that the refractive index in the direction orthogonal to the stretching direction is increased. By being composed of a resin film containing a polymer exhibiting negative birefringence, the second retardation layer can reduce the change in retardation due to dimensional shrinkage of the polarizing plate. Therefore, a change in retardation in the polarizing plate with a retardation layer in a high-temperature environment can be suppressed, and in-plane reflected hue unevenness can be suppressed.

The second retardation layer is preferably a so-called positive C plate whose refractive index characteristics exhibit a relationship of nz>nx=ny. By using a positive C plate as the second retardation layer, it is possible to satisfactorily prevent reflection in oblique directions and widen the viewing angle of the antireflection function. The thickness direction retardation Rth (550) of the second retardation layer is preferably −10 nm to −200 nm, more preferably −20 nm to −180 nm, still more preferably −30 nm to −160 nm, particularly preferably −40 nm to −140 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 second retardation layer can be less than 10 nm.

The thickness of the second retardation layer 30 can be set to any appropriate thickness. The thickness of the second retardation layer is preferably 1 μm to 30 μm, more preferably 2 μm to 20 μm, still more preferably 3 μm to 8 μm.

Polymers exhibiting negative birefringence include, for example, polymers in which chemical bonds or functional groups with large polarization anisotropy such as aromatic rings and/or carbonyl groups are introduced into side chains. Specific examples include acrylic resins, styrene resins, maleimide resins, and the like. Preferably, at least one polymer selected from the group consisting of acrylic resins, styrene resins, and maleimide resins can be used, and more preferably, styrene resins can be used. Only one type of polymer exhibiting negative birefringence may be used, or two or more types may be used in combination.

Acrylic resins can be obtained, for example, by addition polymerization of acrylate monomers. Examples of acrylic resins include polymethyl methacrylate (PMMA), polybutyl methacrylate, polycyclohexyl methacrylate, and the like.

Styrenic resins can be obtained, for example, by addition polymerization of styrenic monomers. Styrenic monomers include, for example, styrene, α-methylstyrene, o-methylstyrene, p-methylstyrene, p-chlorostyrene, p-nitrostyrene, p-aminostyrene, p-carboxystyrene, p-phenylstyrene, 2,5-dichlorostyrene, pt-butylstyrene and the like.

A maleimide-based resin can be obtained, for example, by addition-polymerizing a maleimide-based monomer. Maleimide-based monomers include, for example, N-ethylmaleimide, N-cyclohexylmaleimide, N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(2-ethylphenyl)maleimide, N-(2-propylphenyl ) maleimide, N-(2-isopropylphenyl)maleimide, N-(2,6-dimethylphenyl)maleimide, N-(2,6-dipropylphenyl)maleimide, N-(2,6-diisopropylphenyl)maleimide, N-(2-methyl-6-ethylphenyl)maleimide, N-(2-chlorophenyl)maleimide, N-(2,6-dichlorophenyl)maleimide, N-(2-bromophenyl)maleimide, N-(2,6 -dibromophenyl)maleimide, N-(2-biphenyl)maleimide, N-(2-cyanophenyl)maleimide and the like. Maleimide-based monomers can be obtained, for example, from Tokyo Kasei Kogyo Co., Ltd. and the like.

In the addition polymerization, the birefringence properties of the obtained resin can be controlled by substituting the side chains, maleimidation, grafting, or the like after the polymerization.

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

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

The polymer exhibiting negative birefringence is preferably a styrene-maleic anhydride copolymer, a styrene-acrylonitrile copolymer, a styrene-(meth)acrylate copolymer, a styrene-maleimide copolymer, a vinyl ester- Maleimide copolymers, olefin-maleimide copolymers, and the like are used. These can be used alone or in combination of two or more. These polymers can exhibit high negative birefringence and excellent heat resistance. These polymers can be obtained, for example, from Nova Chemical Japan, Arakawa Chemical Industries, Ltd., and the like.

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

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

The polymer exhibiting negative birefringence is not limited to those described above, and for example, a cyclic olefin copolymer disclosed in Japanese Unexamined Patent Application Publication No. 2005-350544 can also be used. Furthermore, compositions containing polymers and inorganic fine particles, as disclosed in JP-A-2005-156862, JP-A-2005-227427, etc., can also be preferably used. Further, these can be modified by copolymerization, branching, cross-linking, molecular terminal modification (or capping), stereoregular modification, and the like.

The resin composition forming the second retardation layer may further contain any appropriate additive as necessary. Specific examples of additives include plasticizers, heat stabilizers, light stabilizers, lubricants, antioxidants, ultraviolet absorbers, flame retardants, colorants, antistatic agents, compatibilizers, cross-linking agents, thickeners, etc. is mentioned. The type and content of the additive can be appropriately set according to the purpose. The content of the additive is typically about 3 to 10 parts by weight per 100 parts by weight of the total solid content of the resin composition. If the content of the additive is excessively high, the transparency of the polymer film may be impaired, or the additive may exude from the surface of the polymer film.

Any appropriate molding method can be adopted as a molding method for the second retardation layer. Examples thereof include compression molding, transfer molding, injection molding, extrusion molding, blow molding, powder molding, FRP molding, solvent casting, and the like. Among these, the extrusion molding method and the solvent casting method are preferably used. This is because a retardation film having high smoothness and good optical uniformity can be obtained. Specifically, in the extrusion molding method, the resin composition containing the above thermoplastic resin, plasticizer, additives, etc. is heated and melted, and this is extruded into a thin film on the surface of a casting roll using a T-die or the like, It is a method of forming a film by cooling. In the solvent casting method, a concentrated solution (dope) obtained by dissolving the above resin composition in a solvent is degassed and cast uniformly in a thin film on the surface of a metal endless belt or rotating drum, or a plastic substrate. , a method of forming a film by evaporating a solvent. The molding conditions can be appropriately set according to the composition and type of the resin to be used, the molding method, and the like.

E. Adhesive layer Any appropriate adhesive can be used as an adhesive that constitutes the adhesive layer (adhesive layer between the image display device) provided as the outermost layer. Examples of adhesives include rubber-based adhesives, acrylic-based adhesives, silicone-based adhesives, urethane-based adhesives, vinyl alkyl ether-based adhesives, polyvinyl alcohol-based adhesives, polyvinylpyrrolidone-based adhesives, polyacrylamide-based adhesives, A cellulose-based pressure-sensitive adhesive and the like are included. Among these pressure-sensitive adhesives, those having excellent optical transparency, appropriate wettability, cohesiveness, and adhesion properties, and excellent weather resistance and heat resistance are preferably used. Acrylic pressure-sensitive adhesives are preferably used as those exhibiting such characteristics.

F. Image Display Device The polarizing plate with a retardation layer according to the above items A to E can be applied to an image display device. Accordingly, embodiments of the present invention include image display devices using such retardation layer-attached polarizing plates. Typical examples of image display devices include liquid crystal display devices and electroluminescence (EL) display devices (eg, organic EL display devices and inorganic EL display devices). An image display device according to an embodiment of the present invention includes the retardation layer-attached polarizing plate according to the above items A to E on the viewing side thereof. The retardation layer-attached polarizing plate is laminated so that the retardation layer is on the image display cell (for example, liquid crystal cell, organic EL cell, inorganic EL cell) side (so that the polarizer is on the viewing side).

EXAMPLES The present invention will be specifically described below with reference to Examples, but the present invention is not limited to these Examples. The measurement method of each characteristic is as follows. "Parts" and "%" in Examples and Comparative Examples are by weight unless otherwise specified.

(1) Thickness A thickness of 10 μm or less was measured using an interferometric film thickness meter (manufactured by Otsuka Electronics Co., Ltd., product name “MCPD-3000”). A thickness exceeding 10 μm was measured using a digital micrometer (manufactured by Anritsu Co., Ltd., product name “KC-351C”).

(2) Uneven Reflection Hue The polarizing plates with retardation layers obtained in Examples and Comparative Examples were cut into a size of 60 mm long and 130 mm wide to obtain a sample. A portion of the sample measuring 30 mm long and 25 mm wide was defined as measuring position A, a portion measuring 30 mm long and 65 mm wide was defined as measuring position B, and a portion measuring 30 mm long and 105 mm wide was defined as measuring position C, respectively.
Then, the pressure-sensitive adhesive layer of the retardation layer-attached polarizing plate was laminated on a glass plate (80 mm×150 mm) having a thickness of 0.5 mm. After that, the polarizing plate with a retardation layer attached to the glass plate was placed under conditions of 80° C. for 500 hours. Hue a* value and hue b* value at measurement positions A, B and C were measured using a spectrophotometer (Konica Minolta, product name: CM-26d). Plot the hue a* value and hue b* value of each measurement position, compare the results of measurement position A and measurement position B, and the result of measurement position B and measurement position C, respectively, and find that the hue difference is large (plot The value of the one with the larger distance between the two was taken as the hue unevenness of each sample.

(3) Retardation Change The retardation layer-attached polarizing plates obtained in Examples and Comparative Examples were cut into pieces having a width of 15 mm and a length of 200 mm to obtain samples. Using a tensiometer (manufactured by MYCARBON, product name: Digital Luggage Scale), tension was applied in the longitudinal direction of the obtained sample. In-plane phase difference was measured using a phase difference measuring device (product name: KOBRA-WPR manufactured by Oji Keisokuki Co., Ltd.) at tension levels of 0 kg, 0.5 kg, 1 kg, 1.5 kg and 2 kg. The phase difference measured at each tension was plotted to calculate the slope, which was used as the change in phase difference.

[Production Example 1: Production of polarizing plate]
1. Preparation of polarizer A long roll of polyvinyl alcohol (PVA) resin film (manufactured by Kuraray, product name “PE3000”) with a thickness of 30 μm was uniaxially stretched in the longitudinal direction by a roll stretching machine so that it was 5.9 times longer in the longitudinal direction. A polarizer having a thickness of 12 μm was produced by simultaneously performing swelling, dyeing, cross-linking, and washing treatments while stretching, and finally performing a drying treatment.
Specifically, in the swelling treatment, the film was stretched 2.2 times while being treated with pure water at 20°C. Next, the dyeing treatment is performed in an aqueous solution at 30° C. in which the weight ratio of iodine and potassium iodide is 1:7 and the iodine concentration is adjusted so that the single transmittance of the resulting polarizer is 45.0%. while stretching to 1.4 times. Furthermore, a two-step cross-linking treatment was adopted for the cross-linking treatment, and in the first-step cross-linking treatment, the film was stretched 1.2 times while being treated in an aqueous solution of boric acid and potassium iodide at 40°C. The boric acid content of the aqueous solution for the first-stage cross-linking treatment was 5.0% by weight, and the potassium iodide content was 3.0% by weight. In the second-stage cross-linking treatment, the film was stretched 1.6 times while being treated in an aqueous solution of boric acid and potassium iodide at 65°C. The boric acid content of the aqueous solution for the second-stage cross-linking treatment was 3.7% by weight, and the potassium iodide content was 5.0% by weight. Further, the cleaning treatment was performed with an aqueous solution of potassium iodide at 20°C. The potassium iodide content of the aqueous solution for the cleaning treatment was 3.1% by weight. Finally, the drying treatment was performed at 70° C. for 5 minutes to obtain a polarizer.

2. Preparation of Polarizing Plate An HC-COP film was attached as a protective layer to the surface of the polarizer obtained above (the surface opposite to the resin substrate) via an ultraviolet curable adhesive. Specifically, the curable adhesive was applied so as to have a total thickness of 1.0 μm, and was bonded using a roll machine. After that, UV rays were applied from the protective layer side to cure the adhesive. The HC-COP film is a film in which a hard coat (HC) layer (thickness 2 μm) is formed on a cycloolefin (COP) film (manufactured by Zeon Corporation, product name “ZF12”, thickness 25 μm), and the COP film was placed on the polarizer side. Then, the resin substrate was peeled off to obtain a polarizing plate having a structure of protective layer (HC layer/COP film)/adhesive layer/polarizer.

[Production Example 2: Production of first retardation layer A (single first retardation layer)]
55 parts by weight of the compound represented by the following formula (I), 25 parts by weight of the compound represented by the following formula (II), and 20 parts by weight of the compound represented by the formula (III) were combined with 400 parts by weight of cyclopentanone (CPN). After adding to the part, it was dissolved by heating to 60° C. and stirring. After that, the solution of the above compound is returned to room temperature, and the solution of the above compound is added with 3 parts by weight of Irgacure 907 (manufactured by BASF Japan), 0.2 parts by weight of Megafac F-554 (manufactured by DIC), and p -0.1 parts by weight of methoxyphenol (MEHQ) was added and further stirred. The solution after stirring was transparent and uniform. The resulting solution was filtered through a 0.20 μm membrane filter to obtain a polymerizable composition.
Further, the 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 resulting coating film was rubbed with a commercially available rubbing device to form an alignment film.
Then, 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, ultraviolet light is irradiated for 30 seconds at an intensity of 30 mW / cm ² to form a first retardation layer (thickness 3 μm) was obtained. The in-plane retardation Re(550) of the first retardation layer was 130 nm. In addition, the Re(450)/Re(550) of the first retardation layer was 0.851, indicating reverse dispersion wavelength characteristics. The first retardation layer can function as a λ/4 plate.

[Production Example 3: Production of Second Retardation Layer]
An autoclave equipped with a stirrer, a cooling tube, a nitrogen inlet tube and a thermometer was charged with 48 parts by weight of hydroxypropyl methylcellulose (manufactured by Shin-Etsu Chemical, trade name: Metolose 60SH-50), 15601 parts by weight of distilled water, 8161 parts by weight of diisopropyl fumarate, 240 parts by weight of 3-ethyl-3-oxetanylmethyl acrylate and 45 parts by weight of t-butyl peroxypivalate, which is a polymerization initiator, were added, and after nitrogen bubbling was performed for 1 hour, the mixture was maintained at 49°C for 24 hours while stirring. By doing so, radical suspension polymerization was carried out. It was then cooled to room temperature and the suspension containing the polymer particles formed was centrifuged. The resulting polymer was washed twice with distilled water and twice with methanol, and then dried under reduced pressure. The obtained fumaric acid ester resin was dissolved in a toluene/methyl ethyl ketone mixed solution (toluene/methyl ethyl ketone 50% by weight/50% by weight) to obtain a 20% solution. Further, 5 parts by weight of tributyl trimellitate as a plasticizer was added to 100 parts by weight of the fumaric acid ester resin to prepare a dope. As the support film, a biaxially stretched film (thickness: 75 μm) of polyester (polyethylene-terephthalate/isophthalate copolymer) was used. The prepared dope was applied to the support film so that the film thickness after drying was 5 μm, and dried at 140°C. The coating film (positive C plate) after drying had Re(550)≈0 nm and Rth(550)=−75 nm.

ポリエチレンテレフタレート（ＰＥＴ）フィルム（厚み３８μｍ）表面を、ラビング布を用いてラビングし、配向処理を施した。配向処理の方向は、偏光板に貼り合わせる際に偏光子の吸収軸の方向に対して視認側から見て１５°方向となるようにした。この配向処理表面に、上記液晶塗工液をバーコーターにより塗工し、９０℃で２分間加熱乾燥することによって液晶化合物を配向させた。このようにして形成された液晶層に、メタルハライドランプを用いて１ｍＪ/ｃｍ^２の光を照射し、当該液晶層を硬化させることによって、ＰＥＴフィルム上に液晶配向固化層Ａを形成した。液晶配向固化層Ａの厚みは２．５μｍ、面内位相差Ｒｅ（５５０）は２７０ｎｍであった。さらに、液晶配向固化層Ａは、ｎｘ＞ｎｙ＝ｎｚの屈折率特性を示した。 [Production Example 4: Production of first retardation layer B (first retardation layer having a laminated structure)]
Polymerizable liquid crystal exhibiting a nematic liquid crystal phase (manufactured by BASF: trade name “Paliocolor LC242”, represented by the following formula) 10 g, and a photopolymerization initiator for the polymerizable liquid crystal compound (manufactured by BASF: trade name “Irgacure 907 ”) was dissolved in 40 g of toluene to prepare a liquid crystal composition (coating liquid).

The surface of a polyethylene terephthalate (PET) film (thickness: 38 μm) was rubbed with a rubbing cloth and subjected to orientation treatment. The direction of the orientation treatment was set to be 15° from the direction of the absorption axis of the polarizer when viewed from the viewing side when attached to the polarizing plate. The above liquid crystal coating solution was applied to the alignment-treated surface using a bar coater, and dried by heating at 90° C. for 2 minutes to align the liquid crystal compound. A metal halide lamp was used to irradiate the liquid crystal layer thus formed with light of 1 mJ/cm ² to cure the liquid crystal layer, thereby forming a liquid crystal alignment fixed layer A on the PET film. The liquid crystal alignment fixed layer A had a thickness of 2.5 μm and an in-plane retardation Re (550) of 270 nm. Furthermore, the liquid crystal alignment fixed layer A exhibited refractive index characteristics of nx>ny=nz.

In the same manner as above, except that the coating thickness was changed and that the alignment treatment direction was set to be 75° to the direction of the absorption axis of the polarizer when viewed from the viewing side, A liquid crystal alignment fixed layer B was formed. The liquid crystal alignment fixed layer B had a thickness of 1.5 μm and an in-plane retardation Re (550) of 140 nm. Furthermore, the liquid crystal alignment fixed layer B exhibited refractive index characteristics of nx>ny=nz.

[Example 1]
A protective layer (triacetyl cellulose (TAC) film, thickness: 20 μm) was attached to the polarizer of the polarizing plate obtained in Production Example 1 via an adhesive layer, and protective layer (HC layer/COP film)/adhesive A polarizing plate of layer/polarizer/adhesive layer/protective layer (TAC) was obtained.
Separately, the liquid crystal alignment fixed layer A and the liquid crystal alignment fixed layer B obtained in Production Example 4 were aligned so that the angle formed by the absorption axis of the polarizer and the slow axis of the alignment fixed layer A was 15°, and the absorption axis of the polarizer and the alignment The transfer (bonding) was performed in this order so that the angle between the solidified layer B and the slow axis was 75°. The oriented fixed layer A and the oriented fixed layer B were each laminated via an ultraviolet curable adhesive (having a thickness of 1 μm after curing).
Next, an ultraviolet curable adhesive (thickness after curing: 1 μm) is applied to the liquid crystal alignment fixed layer B, the second retardation layer obtained in Production Example 3 is laminated, and the liquid crystal alignment fixed layer A/adhesive layer is laminated. A laminate of /liquid crystal alignment fixed layer B/adhesive layer/second retardation layer was obtained.
Next, the TAC-side surface of the obtained polarizing plate and the liquid crystal alignment solid layer A of the laminate were laminated via an acrylic pressure-sensitive adhesive layer (thickness: 5 μm). Then, the substrate of the second retardation layer was peeled off. After that, an acrylic adhesive (thickness 26 μm) is applied to the release surface of the substrate of the second retardation layer, and the protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/protective layer ( TAC)/adhesive layer/first retardation layer (liquid crystal alignment fixed layer A/adhesive layer/liquid crystal alignment fixed layer B)/adhesive layer/second retardation layer/adhesive layer A polarizing plate with a retardation layer was obtained. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

(Comparative example 1)
A polarizing plate with a retardation layer was obtained in the same manner as in Example 1, except that the second retardation layer was not laminated. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

[Production Example 5: Production of positive C plate as liquid crystal alignment fixed 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 indicate mol % of monomer units, and are expressed as block polymer for convenience: weight average molecular weight 5000), nematic liquid crystal phase A polymerizable liquid crystal (manufactured by BASF: trade name Paliocolor LC242) 80 parts by weight and a photopolymerization initiator (manufactured by Ciba Specialty Chemicals: trade name Irgacure 907) 5 parts by weight are dissolved in 200 parts by weight of cyclopentanone to form a liquid crystal. A coating solution was prepared. Then, the coating solution was applied to the vertically aligned PET substrate using a bar coater, and dried by heating at 80° C. for 4 minutes to align the liquid crystal. By irradiating the liquid crystal layer with ultraviolet rays and curing the liquid crystal layer, a retardation layer (thickness: 3 μm) exhibiting a refractive index characteristic of nz>nx=ny was formed on the substrate.

(Comparative example 2)
A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the retardation layer obtained in Production Example 5 was used instead of the second retardation layer obtained in Production Example 3. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

[Example 2]
A protective layer (triacetyl cellulose (TAC) film, thickness: 20 μm) was attached to the polarizer of the polarizing plate obtained in Production Example 1 via an adhesive layer, and protective layer (HC layer/COP film)/adhesive A polarizing plate of layer/polarizer/adhesive layer/protective layer (TAC) was obtained.
Separately, the first retardation layer A obtained in Production Example 2 is formed into the polarizing plate so that the angle formed by the absorption axis of the polarizer and the slow axis of the first retardation layer A is 45°. It was laminated with a protective layer (TAC) of The first retardation layer and the protective layer (TAC) were laminated via an ultraviolet curable adhesive (having a thickness of 1 μm after curing).
Next, the TAC-side surface of the obtained polarizing plate and the first retardation layer were laminated via an acrylic pressure-sensitive adhesive layer (thickness: 5 μm). Then, the substrate of the second retardation layer was peeled off. After that, an acrylic adhesive (thickness 26 μm) is applied to the release surface of the substrate of the second retardation layer, and the protective layer (HC layer/COP film)/adhesive layer/polarizer/adhesive layer/protective layer ( TAC)/adhesive layer/first retardation layer/adhesive layer/second retardation layer/adhesive layer. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

(Comparative Example 3)
A polarizing plate with a retardation layer was obtained in the same manner as in Example 2, except that the second retardation layer was not laminated. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

(Comparative Example 4)
A polarizing plate with a retardation layer was obtained in the same manner as in Example 1 except that the retardation layer obtained in Production Example 5 was used instead of the second retardation layer obtained in Production Example 3. The obtained polarizing plate was subjected to the above evaluation. Table 1 shows the results.

[evaluation]
As is clear from Table 1, the retardation layer-attached polarizing plates of Examples of the present invention were excellent in high-temperature durability, and in-plane unevenness in reflection hue was suppressed.

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

REFERENCE SIGNS LIST 10 polarizing plate 11 polarizer 12 protective layer 13 protective layer 20 first retardation layer 30 second retardation layer 100 polarizing plate with retardation layer 101 polarizing plate with retardation layer

Claims (10)

A polarizing plate containing a polarizer having a thickness of 7 μm or more;
A first retardation layer which is an alignment fixed layer of a liquid crystal compound;
and a second retardation layer comprising a resin film containing a polymer exhibiting negative birefringence. 2. The retardation layer-attached polarizing plate according to claim 1, wherein said second retardation layer is adjacent to said first retardation layer. 3. The retardation layer-attached polarizing plate according to claim 1, wherein the second retardation layer is a positive C plate. 4. The polarizing plate with a retardation layer according to claim 1, wherein the second retardation layer has a thickness of 1 μm to 30 μm. The polarized light with retardation layer according to any one of claims 1 to 4, wherein the polymer exhibiting negative birefringence is at least one selected from the group consisting of acrylic resins, styrene resins, and maleimide resins. board. The in-plane retardation of the first retardation layer is 100 nm<Re(550)<160 nm, and
6. The polarizing plate with a retardation layer according to claim 1, which satisfies Re(450)/Re(550)<1 and Re(650)/Re(550)>1. 7. The retardation layer-attached polarizing plate according to claim 6, wherein the angle formed by the slow axis of the first retardation layer and the absorption axis of the polarizer is 40° to 50°. The first phase layer has a laminated structure of an alignment fixed layer A of a liquid crystal compound and an alignment fixed layer B of a liquid crystal compound,
6. The retardation layer-attached polarizing plate according to claim 1, wherein said fixed orientation layer A functions as a [lambda]/2 plate and said fixed orientation layer B functions as a [lambda]/4 plate. The angle formed by the slow axis of the fixed alignment layer A of the liquid crystal compound and the absorption axis of the polarizer is 70° to 80°, and the slow axis of the fixed alignment layer B of the liquid crystal compound and the polarizer 9. The polarizing plate with a retardation layer according to claim 8, wherein the angle formed with the absorption axis of is 10° to 20°. An image display device comprising the retardation layer-attached polarizing plate according to any one of claims 1 to 9.

Images