JP2003315555A - Stacked retardation plate and image displaying device using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a stacked retardation plate that, when applied to a liquid crystal display device, exhibits excellent viewing angle characteristics and further realizes thickness reduction. <P>SOLUTION: A stacked retardation plate is formed by stacking together: an optically anisotropic layer (A) composed of a polymer and exhibiting an in-plane phase difference of 20 to 300 nm and the ratio of a thickness direction phase difference to the in-plane phase difference of 1.0 or larger; and an optically anisotropic layer (B) composed of a non-liquid-crystalline polymer such as a polyimide exhibiting an in-plane phase difference of 3 nm or larger and the ratio of a thickness direction phase difference to the in-plane phase difference of 1.0 or larger. This kind of stacked retardation plate exhibits such excellent optical characteristics that the in-plane phase difference (Re) is 10 nm or larger and the difference between a thickness direction phase difference and the in-plane phase difference is 50 nm or larger. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminated retardation plate and various image display devices using the same.

[0002]

2. Description of the Related Art Conventionally, in various image display devices, a retardation plate having a controlled refractive index has been required in order to realize excellent display quality in all directions. It is selected according to the display method of the display device. Especially, VA (Vertically Aligned) type, OCB (Optic
In a liquid crystal display device of an ally Compensated Bend type or the like, the refractive index (nx,
ny, nz) is “nx>ny> nz”, that is, a retardation plate exhibiting optically negative biaxiality is required. As a retardation plate satisfying “nx>ny> nz” in this way, for example, nx> ny = nz by free-end uniaxial stretching.
The laminated retardation plate obtained by laminating the two stretched polymer films described above in such a manner that the slow axis directions in the plane are orthogonal to each other, or by stretching the polymer film by tenter transverse stretching or biaxial stretching, "nx> A single-layer retardation film in which ny> nz is controlled is known.

However, the former laminated retardation plate has an advantage that the range of retardation values obtained by combining the stretched films is widened, but on the other hand, one is a thick type and the film is further thickened by lamination. It had the drawback of becoming On the other hand, the latter single-layer retardation plate has an advantage of having an optical characteristic of “nx>ny> nz” even though it is a single layer, but on the other hand, it is a thick type and the obtained range of retardation values is It has the drawback of being narrow. Therefore, it is necessary to further stack another retardation film to widen the range of retardation values. Further, using this single-layer retardation plate, in order to obtain a retardation value whose retardation value in the thickness direction is significantly larger than the in-plane retardation value, similar to the former laminated retardation plate,
It is necessary to laminate another retardation film. As a result, there is a drawback that the thickness is further increased.

Also disclosed is a method for producing a thin single-layer retardation film satisfying "nx>ny>nz" by using a non-liquid crystal polymer such as polyimide (for example, Patent Document 1). Refer to 1). However, in such a single-layer polyimide retardation film, if the retardation in the thickness direction is set to a large value, coloring may be observed and the display quality may be deteriorated, for unknown reasons.

[0005]

[Patent Document 1] Japanese Patent Laid-Open No. 2000-190385

[0006]

Therefore, the present invention is a laminated type retardation plate exhibiting excellent viewing angle characteristics and high contrast when used in a liquid crystal display device and having a large thickness retardation value. In addition, the present invention is to provide a laminated retardation plate in which coloring is prevented and which can be thinned.

[0007]

In order to achieve the above object, the laminated retardation plate of the present invention is a laminated retardation plate including at least two optical anisotropic layers, and at least a polymer optical layer. Anisotropic layer (A), polyamide, polyimide,
An optical anisotropic layer (B) made of at least one non-liquid crystalline polymer selected from the group consisting of polyester, polyaryletherketone, polyetherketone, polyamideimide and polyesterimide, and a surface represented by the following mathematical formula The in-plane retardation (Re) is 10 nm or more, and the thickness direction retardation (Rth) represented by the following formula and the in-plane retardation (R
The difference (Rth-Re) from e) is 50 nm or more. Re = (nx-ny) * d Rth = (nx-nz) * d In the above formula, nx, ny and nz respectively represent the refractive indices in the X-axis, Y-axis and Z-axis directions of the laminated retardation plate. , The X-axis is an axial direction showing the maximum refractive index in the plane of the laminated retardation plate, the Y-axis is an axial direction perpendicular to the X-axis in the plane, Z
The axis is a thickness direction perpendicular to the X axis and the Y axis, and
d indicates the thickness of the laminated retardation plate.

The inventors of the present invention thus laminate the optical anisotropic layer (A) made of the polymer and the optical anisotropic layer (B) made of the non-liquid crystalline polymer such as polyimide,
The in-plane retardation (Re) is 10 nm or more, and the difference between the thickness direction retardation (Rth) and the in-plane retardation (Re) (Rth-Re) 5
Exhibits excellent optical characteristics of 0 nm or more, and
It has been found that a laminated retardation plate having a reduced thickness can be obtained. Furthermore, with such a laminated retardation plate, it is possible to prevent the problem of coloring that is caused by realizing a large retardation in the thickness direction with a polyimide film alone as in the conventional case. Therefore, according to the laminated retardation plate of the present invention, for example, when applied to various image display devices such as liquid crystal display devices, not only can excellent display characteristics such as wide viewing angle characteristics be realized, but also the device itself It is very useful because it can be made thin.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION As described above, the laminated retardation plate of the present invention has at least the optical anisotropic layer (A) made of a polymer.
And an optically anisotropic layer (B) made of at least one non-liquid crystalline polymer selected from the group consisting of polyamide, polyimide, polyester, polyaryletherketone, polyetherketone, polyamideimide and polyesterimide, The in-plane retardation (Re) is 10 nm or more, and the difference (Rth-Re) between the thickness direction retardation (Rth) and the in-plane retardation (Re) is 50 nm or more.

In the laminated retardation plate of the present invention, by laminating the optical anisotropic layers (A) and (B), the refractive index in the X axis, Y axis and Z axis as a whole is "nx>n".
y> nz ”and the Re value is 10
nm or more, the difference between Rth and Re (Rth-Re)
Is 50 nm or more.
In a liquid crystal display device of a display mode such as a mode or OCB mode, birefringence of a liquid crystal cell can be sufficiently compensated, and an excellent effect of widening a viewing angle can be obtained. If the Re value is less than 10 nm or the Rth-Re is less than 50 nm, there is a problem that the above-described viewing angle expansion effect cannot be obtained.

The Re value is preferably in the range of 10 to 500 nm, more preferably 20 to 300 nm.
Is the range. The value of (Rth-Re) is 5
It is preferably in the range of 0 to 1,000 nm, more preferably in the range of 50 to 900 nm, and particularly preferably in the range of 50 to 800 nm.

The Rth is 60 nm or more, preferably in the range of 60 to 1500 nm, more preferably in the range of 60 to 1400 nm, and particularly preferably 6
It is in the range of 0 to 1300 nm. Further, Rth / Re of the laminated retardation plate of the present invention is 1 or more.

In the present invention, the optically anisotropic layer (A)
By combining with the optical anisotropic layer (B),
There is no particular limitation as long as the conditions of Re and (Rth-Re) as described above can be satisfied as a whole. For example, the in-plane retardation [Re (A)] shown in the following formula is 20 to 300 nm, and Thickness direction retardation [Rth (A)] and the in-plane retardation [Rth (A)]
The ratio [Rth (A) / Re (A)] with e (A)] is preferably 1.0 or more. This is because when the ratio [Rth (A) / Re (A)] between the thickness direction retardation and the in-plane retardation is less than 1.0, for example, when used in a liquid crystal display device, There is a problem that the retardation value cannot be sufficiently compensated and the viewing angle becomes narrow, and the in-plane retardation is less than 20 nm or 30.
This is because if it is larger than 0 nm, the viewing angle becomes narrow. The Rth (A) / Re (A) is more preferably 1.2 or more, and particularly preferably 1.2 to 40. Re (A) = (nx (A) -ny (A)). D (A) Rth (A) = (nx (A) -nz (A)). D (A) In the above formula, nx (A) , Ny (A) and nz (A) are
The respective refractive indices in the X-axis, Y-axis and Z-axis directions of the optically anisotropic layer (A) are shown, and the X-axis is the axis showing the maximum refractive index in the plane of the optically anisotropic layer (A). Direction, the Y axis is an axial direction perpendicular to the X axis in the plane, the Z axis is a thickness direction perpendicular to the X axis and the Y axis, and d (A) is The thickness of the optically anisotropic layer (A) is shown (the same applies hereinafter).

On the other hand, the refractive index of the optically anisotropic layer (B) is not particularly limited as long as it is an optically anisotropic layer made of a non-liquid crystal polymer as described above. For example, the X axis, the Y axis, and the Z axis.
The refractive index on the axis may satisfy the relationship of “nx (B)> ny (B)> nz (B)”, or “nx (B) ≈ny (B)> nz”.
(B) ”may be satisfied. In the above formula, nx (B), n
y (B) and nz (B) are each the above-mentioned optical anisotropic layer (B).
In the X-axis, Y-axis and Z-axis direction, the X-axis is the axial direction showing the maximum refractive index in the plane of the optically anisotropic layer (B), the Y-axis is the In the plane, the axis direction is perpendicular to the X axis, and the Z axis indicates the thickness direction perpendicular to the X axis and the Y axis (the same applies hereinafter).

The optical anisotropic layer (B) is "nx (B)>ny".
(B)> nz (B) ”, the in-plane retardation [Re (B)] shown by the following formula is 3 nm or more, and the thickness direction retardation [Rth (B)] shown by the following formula Ratio [Rth] with internal phase difference [Re (B)]
(B) / Re (B)] is preferably 1.0 or more. The ratio [Rth (B) / Re (B)] between the thickness direction retardation and the in-plane retardation is 1.
If it is less than 0, for example, when used in a liquid crystal display device, the retardation value in the thickness direction cannot be sufficiently compensated, and there is a problem that the viewing angle becomes narrow. In addition, the optical anisotropic layer (B) has “nx (B) ≈ny (B)>
nz (B) ”, that is, the in-plane phase difference [Re
(B)] is approximately 0 nm, for example, by setting the in-plane retardation [Re (A)] of the optically anisotropic layer (A) in the above range, Re in the laminated retardation plate of the present invention can be improved. And (Rth-R
The condition of e) can also be satisfied. The Re (B) is more preferably 3 to 800 nm, and particularly preferably 5
To 500 nm, and the Rth (B) / Re (B) is more preferably 1.2 or more, and particularly preferably 1.2 to 160. In the formula below, d (B) represents the thickness of the optically anisotropic layer (B) (the same applies hereinafter). Re (B) = (nx (B) -ny (B)) * d (B) Rth (B) = (nx (B) -nz (B)) * d (B)

Optically anisotropic layer (A) and optically anisotropic layer (B)
As a specific example of the combination with, for example, in-plane retardation [R
e (A)] is 20 to 300 nm, and its thickness direction retardation
Ratio [Rth (A)] to the in-plane phase difference [Re (A)] [Rth (A) / Re
(A)] is 1.0 or more and the optically anisotropic layer (A), in-plane retardation [Re (B)] is 3 nm or more, thickness direction retardation [Rth (B)]
And an optically anisotropic layer (B) having a ratio [Rth (B) / Re (B)] of 1.0 or more to the in-plane retardation [Re (B)].

The total thickness of the laminated retardation plate of the present invention is usually 1 mm or less, which is sufficiently thinner than the conventional laminated retardation plate as described above. Preferably 1 to 500 μm
And particularly preferably in the range of 5 to 300 μm. For example, as described above, "a conventional laminated retardation plate in which two stretched polymer films with nx> ny = nz are laminated so that the in-plane slow axis directions are orthogonal to each other"
In comparison with the above, according to the laminated retardation plate of the present invention, the thickness can be reduced to, for example, about ½.

The thickness of the optically anisotropic layer (A) is, for example, 1 to 800 μm, preferably 5 to 500 μm.
m, more preferably 10 to 400 μm, and particularly preferably 50 to 400 μm. The thickness of the optically anisotropic layer (B) is, for example, 1 to 50 μm, preferably 2 to 30 μm, and particularly preferably 1 to 20 μm.
Is. As described above, since the thickness of the optical anisotropic layer (B) can be made sufficiently thin, the total thickness of the laminated retardation plate of the present invention is also thin, and the optical anisotropic layer (A) is laminated to improve the optical characteristics. Will also be excellent.

The material for forming the optically anisotropic layer (A) is not particularly limited, but for example, a polymer showing positive birefringence is preferable. This is because the in-plane retardation and the thickness direction retardation of the optically anisotropic layer (A) can be increased by selecting such a polymer. In addition,
In the present invention, the “polymer exhibiting positive birefringence” means
When a film is stretched, it refers to a polymer that exhibits the property of maximizing refraction in the stretching direction. The optically anisotropic layer (A) formed from the polymer may be a stretched film or an unstretched film. Good (same below).

As the polymer, since a stretched film can be mentioned as a form of the optically anisotropic layer (A) as described above, for example, a thermoplastic polymer which is easily stretched is preferable. Examples of the thermoplastic polymer include polyolefin (polyethylene, polypropylene, etc.), polynorbornene-based polymer, polyester, polyvinyl chloride, polyacrylonitrile, polysulfone,
Polyarylate, polyvinyl alcohol, polymethacrylic acid ester, polyacrylic acid ester, cellulose ester and copolymers thereof can be used. These polymers may be used alone, for example,
You may use 2 or more types together. In addition, JP 2001-3
The polymer film described in Japanese Patent No. 43529 (WO01 / 37007) can also be used as the optically anisotropic layer (A). Examples of the polymer material include a thermoplastic resin having a substituted or unsubstituted imide group in its side chain and a resin composition containing a thermoplastic resin having a substituted or unsubstituted phenyl group and a cyano group in its side chain. Examples of the resin composition that can be used include an alternating copolymer of isobutene and N-methylenemaleimide and an acrylonitrile / styrene copolymer. The polymer film may be, for example, an extruded product of the resin composition. Moreover, it is preferable that it is excellent in transparency.

Materials for forming the optically anisotropic layer (B) are polyamide, polyimide, polyester, polyaryl ether ketone, polyether ketone, polyamide imide, polyester imide, etc., which are excellent in heat resistance, chemical resistance and transparency. Is a non-liquid crystal polymer. Unlike a liquid crystal material, such a non-liquid crystal material has nx> nz and ny>, depending on its own property, regardless of the orientation of the substrate.
A film having an optical uniaxial property, nz, is formed. Therefore, for example, the substrate used when forming the anisotropic layer (B) is not limited to the oriented substrate, and for example, a non-oriented substrate can be used as it is.

These polymers may be used alone, or as a mixture of two or more kinds having different functional groups such as a mixture of polyaryletherketone and polyamide. May be. Among these polymers, polyimide is particularly preferable because it has high transparency, high orientation, and high stretchability.

The molecular weight of the polymer is not particularly limited, but for example, the weight average molecular weight (Mw) is from 1,000 to.
It is preferably in the range of 1,000,000, and more preferably in the range of 2,000 to 500,000. The weight average molecular weight can be measured by a gel permeation chromatograph (GPC) method using polyethylene oxide as a standard sample and DMF (N, N-dimethylformamide) as a solvent.

As the polyimide, for example, a polyimide having a high in-plane orientation and soluble in an organic solvent is preferable.
Specifically, for example, it includes a condensation polymerization product of 9,9-bis (aminoaryl) fluorene and an aromatic tetracarboxylic dianhydride disclosed in Japanese Patent Publication No. 2000-511296 and has the following formula ( Polymers containing one or more repeating units shown in 1) can be used.

[0025]

[Chemical 1] In the formula (1), R ^{3 to} R ⁶ are each a hydrogen atom, a halogen atom, a phenyl group, a phenyl group substituted with ₁ to 4 halogen atoms or a C ₁ to ₁₀ alkyl group, and a C ₁ to ₁₀ alkyl group. It is at least one kind of substituent independently selected from the group consisting of Preferably, R ^{3 to} R ⁶ are halogen, a phenyl group, 1 to 4 halogen atoms or C ₁ to
₁₀ alkyl-substituted phenyl and C ₁ ~ _10,
It is at least one type of substituent independently selected from the group consisting of alkyl groups.

[0026] In the formula (1), Z represents, C ₆ ~ ₂₀
A tetravalent aromatic group of, preferably a pyromellitic group,
A polycyclic aromatic group, a derivative of a polycyclic aromatic group, or a group represented by the following formula (2).

[0027]

[Chemical 2] In the formula (2), Z ′ is, for example, a covalent bond, C (R ⁷ ) ₂
Group, CO group, O atom, S atom, SO ₂ group, Si (C ₂ H ₅ ) ₂
Group or NR ⁸ group, and when there are plural groups, they are the same or different. W represents an integer of 1 to 10. R ⁷ is independently hydrogen or C
(R ⁹⁾ _3. R ⁸ is hydrogen, having 1 to about 20 carbon atoms
Of an alkyl or C ₆ ~ ₂₀ aryl group, and when there are plural, it may be the same or different. R ⁹ is
Each is independently hydrogen, fluorine, or chlorine.

Examples of the polycyclic aromatic group include a tetravalent group derived from naphthalene, fluorene, benzofluorene or anthracene. Examples of the substituted derivative of the polycyclic aromatic group include C ₁
~ ₁₀ alkyl groups, their fluorinated derivatives, and F and C
The polycyclic aromatic group may be substituted with at least one group selected from the group consisting of halogen such as l.

In addition to this, for example, Table 8-5118
Homopolymers whose repeating units are represented by the following general formula (3) or (4) and polyimides whose repeating units are represented by the following general formula (5) are described in JP-A No. The polyimide of the following formula (5) is a preferred form of the homopolymer of the following formula (3).

[0030]

[Chemical 3]

[Chemical 4]

[Chemical 5]

In the above general formulas (3) to (5), G and G ′ are, for example, a covalent bond, a CH ₂ group, a C (CH ₃ ) ₂ group, a C
(CF ₃ ) ₂ group, C (CX ₃ ) ₂ group (where X is halogen), CO group, O atom, S atom, SO ₂ group, Si (C
H ₂ CH ₃ ) ₂ group, and from the group consisting of N (CH ₃ ) group,
Each represents a group independently selected, and may be the same or different.

In the above formulas (3) and (5), L is a position
It is a substituent, and d and e represent the number of substitutions. L is
For example, halogen, C_1-3Alkyl group, C_1-3Halogenated
An alkyl group, a phenyl group, or a substituted phenyl group
In the case of a plurality, each is the same or different.
Examples of the substituted phenyl group include halogen and C
_1-3An alkyl group, and C_1-3From a halogenated alkyl group
Have at least one substituent selected from the group consisting of
A substituted phenyl group. Also, with the halogen
Are, for example, fluorine, chlorine, bromine or iodine.
You can d is an integer from 0 to 2 and e is 0
It is an integer from 1 to 3.

In the above formulas (3) to (5), Q represents a substituent and f represents the number of substitutions. Q is, for example, selected from the group consisting of hydrogen, halogen, an alkyl group, a substituted alkyl group, a nitro group, a cyano group, a thioalkyl group, an alkoxy group, an aryl group, a substituted aryl group, an alkyl ester group, and a substituted alkyl ester group. And a plurality of Qs, they are the same or different. Examples of the halogen include fluorine, chlorine, bromine and iodine. Examples of the substituted alkyl group include halogenated alkyl groups. Examples of the substituted aryl group include, for example,
Examples thereof include halogenated aryl groups. f is an integer from 0 to 4, g and h are integers from 0 to 3 and 1 to 3, respectively. Also, g and h are 1
It is preferably larger.

In the above formula (4), R ¹⁰ and R ¹¹ are each independently selected from the group consisting of hydrogen, halogen, phenyl group, substituted phenyl group, alkyl group and substituted alkyl group. Among them, R ¹⁰ and R ¹¹
It is preferable that each is independently a halogenated alkyl group.

In the above formula (5), M ¹ and M ² are the same or different and are, for example, halogen, C _1-3 alkyl group, C _1-3 halogenated alkyl group, phenyl group or substituted. It is a phenyl group. Examples of the halogen include fluorine, chlorine, bromine and iodine.
Examples of the substituted phenyl group include a substituted phenyl group having at least one kind of substituent selected from the group consisting of halogen, C _1-3 alkyl group, and C _1-3 halogenated alkyl group. .

Specific examples of the polyimide represented by the above formula (3) include those represented by the following formula (6).

[Chemical 6]

Further, examples of the polyimide include a copolymer obtained by appropriately copolymerizing an acid dianhydride or a diamine other than the skeleton (repeating unit) as described above.

Examples of the acid dianhydride include aromatic tetracarboxylic acid dianhydride. Examples of the aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride, benzophenone tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, heterocyclic aromatic tetracarboxylic dianhydride, 2, 2'-substituted biphenyltetracarboxylic dianhydride and the like can be mentioned.

Examples of the pyromellitic dianhydride include, for example, pyromellitic dianhydride, 3,6-diphenylpyromellitic dianhydride, 3,6-bis (trifluoromethyl) pyromellitic dianhydride, and 3,6-bis (trifluoromethyl) pyromellitic dianhydride. Examples thereof include 6-dibromopyromellitic dianhydride and 3,6-dichloropyromellitic dianhydride. Examples of the benzophenone tetracarboxylic acid dianhydride include 3,3 ′, 4,4′-benzophenone tetracarboxylic acid dianhydride, 2,3,3 ′, 4′-benzophenone tetracarboxylic acid dianhydride, and 2,2 ', 3,3'-benzophenone tetracarboxylic acid dianhydride and the like. Examples of the naphthalene tetracarboxylic acid dianhydride include 2,
3,6,7-naphthalene-tetracarboxylic dianhydride, 1,
2,5,6-naphthalene-tetracarboxylic dianhydride, 2,
6-dichloro-naphthalene-1,4,5,8-tetracarboxylic dianhydride and the like. Examples of the heterocyclic aromatic tetracarboxylic dianhydride include thiophene-2,
3,4,5-tetracarboxylic dianhydride, pyrazine-2,3,
5,6-tetracarboxylic dianhydride, pyridine-2,3,5,
Examples thereof include 6-tetracarboxylic dianhydride. 2,
Examples of the 2′-substituted biphenyltetracarboxylic dianhydride include 2,2′-dibromo-4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, 2,2′-dichloro-4,
4 ', 5,5'-biphenyltetracarboxylic dianhydride, 2,
Examples thereof include 2'-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride.

Other examples of the aromatic tetracarboxylic dianhydride include 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride and bis (2,3-dicarboxyphenyl) methane. Dianhydride, bis (2,5,6-trifluoro-
3,4-dicarboxyphenyl) methane dianhydride, 2,2-
Bis (3,4-dicarboxyphenyl) -1,1,1,3,3,3
-Hexafluoropropane dianhydride, 4,4 '-(3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride, bis (3,4-dicarboxyphenyl) ether dianhydride, 4, 4'-oxydiphthalic dianhydride, bis (3,4-dicarboxyphenyl) sulfonic acid dianhydride (3,3 ', 4,
4'-diphenylsulfone tetracarboxylic acid dianhydride),
4,4 ′-[4,4′-isopropylidene-di (p-phenyleneoxy)] bis (phthalic anhydride), N, N- (3,4-dicarboxyphenyl) -N-methylamine dianhydride Things, screws (3,4-
Examples include dicarboxyphenyl) diethylsilane dianhydride.

Of these, as the aromatic tetracarboxylic dianhydride, 2,2′-substituted biphenyltetracarboxylic dianhydride is preferable, and more preferable is 2,2′-substituted biphenyltetracarboxylic dianhydride.
2′-bis (trihalomethyl) -4,4 ′, 5,5′-biphenyltetracarboxylic dianhydride, and more preferably
It is 2,2'-bis (trifluoromethyl) -4,4 ', 5,5'-biphenyltetracarboxylic dianhydride.

Examples of the diamines include aromatic diamines, and specific examples thereof include benzenediamine, diaminobenzophenone, naphthalenediamine, heterocyclic aromatic diamines, and other aromatic diamines.

As the benzenediamine, for example,
o-, m- and p-phenylenediamine, 2,4-diaminotoluene, 1,4-diamino-2-methoxybenzene,
And diamines selected from the group consisting of benzenediamines such as 1,4-diamino-2-phenylbenzene and 1,3-diamino-4-chlorobenzene. Examples of the diaminobenzophenone include 2,2′-diaminobenzophenone and 3,3′-diaminobenzophenone. As the naphthalenediamine,
Examples thereof include 1,8-diaminonaphthalene and 1,5-diaminonaphthalene. Examples of the heterocyclic aromatic diamine include 2,6-diaminopyridine and 2,4-
Examples include diaminopyridine and 2,4-diamino-S-triazine.

In addition to these, as the aromatic diamine, 4,4'-diaminobiphenyl, 4,4'-diaminodiphenylmethane, 4,4 '-(9-fluorenylidene)-
Dianiline, 2,2'-bis (trifluoromethyl) -4,4 '
-Diaminobiphenyl, 3,3'-dichloro-4,4'-diaminodiphenylmethane, 2,2'-dichloro-4,4'-diaminobiphenyl, 2,2 ', 5,5'-tetrachlorobenzidine, 2, 2-bis (4-aminophenoxyphenyl) propane, 2,2-bis (4-aminophenyl) propane, 2,2-
Bis (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 4,4'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 1,3-bis
(3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene, 4,4'-bis (4-aminophenoxy) biphenyl, 4, 4'-bis (3-aminophenoxy) biphenyl, 2,2-bis [4- (4-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1 , 1,3,3,3-hexafluoropropane, 4,
4'-diaminodiphenyl thioether, 4,4'-diaminodiphenyl sulfone and the like can be mentioned.

Examples of the polyetherketone which is a material for forming the birefringent layer (a) include, for example, JP-A-2001-2001.
Examples thereof include polyaryl ether ketones represented by the following general formula (7) described in Japanese Patent No. 49110.

[0046]

[Chemical 7] In the above formula (7), X represents a substituent and q represents the number of substitutions. X is, for example, a halogen atom, a lower alkyl group, a halogenated alkyl group, a lower alkoxy group, or a halogenated alkoxy group, and when X is plural,
Each is the same or different.

Examples of the halogen atom include a fluorine atom, a bromine atom, a chlorine atom and an iodine atom, and among these, a fluorine atom is preferable. Examples of the lower alkyl group, for example, preferably a lower alkyl group having a straight-chain or branched C ₁ ~ _6, more preferably a straight-chain or branched alkyl group of C ₁ ~ _4. Specifically, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, and
A tert-butyl group is preferable, and a methyl group and an ethyl group are particularly preferable. Examples of the halogenated alkyl group include halides of the lower alkyl groups such as trifluoromethyl group. Examples of the lower alkoxy group, for example, preferably a straight chain or branched chain alkoxy group of C ₁ ~ _6, more preferably a straight chain or branched chain alkoxy group of C ₁ ~ _4. Specifically, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group,
Butoxy group, isobutoxy group, sec-butoxy group, and tert-butoxy group are more preferable, and methoxy group and ethoxy group are particularly preferable. Examples of the halogenated alkoxy group include halides of the lower alkoxy groups such as trifluoromethoxy group.

In the above formula (7), q is an integer from 0 to 4. In the above formula (7), it is preferable that q = 0 and that the carbonyl group bonded to both ends of the benzene ring and the oxygen atom of the ether are in the para position relative to each other.

In the above formula (7), R ¹ is a group represented by the following formula (8), and m is an integer of 0 or 1.

[0050]

[Chemical 8] In the formula (8), X ′ represents a substituent, and is the same as X in the formula (7), for example. In the formula (8), when a plurality of X's are present, they are the same or different. q'represents the number of substitutions of X ', is an integer from 0 to 4, and q' = 0 is preferable. Further, p is an integer of 0 or 1.

In the above formula (8), R ² represents a divalent aromatic group. Examples of the divalent aromatic group include o-,
Examples thereof include a m- or p-phenylene group, or a divalent group derived from naphthalene, biphenyl, anthracene, o-, m- or p-terphenyl, phenanthrene, dibenzofuran, biphenyl ether, or biphenyl sulfone. . In these divalent aromatic groups, hydrogen directly bonded to the aromatic may be replaced with a halogen atom, a lower alkyl group or a lower alkoxy group. Among these, R ² is preferably an aromatic group selected from the group consisting of the following formulas (9) to (15).

[0052]

[Chemical 9]

In the above formula (7), R ¹ is preferably a group represented by the following formula (16), and in the following formula (16), R ² and p have the same meanings as the above formula (8). .

[0054]

[Chemical 10]

Further, in the above formula (7), n represents the degree of polymerization, for example, in the range of 2 to 5000, and preferably,
It is in the range of 5 to 500. Further, the polymerization may be composed of repeating units having the same structure or may be composed of repeating units having different structures. In the latter case, the repeating unit may be polymerized by block polymerization or random polymerization.

Further, at the terminal of the polyaryletherketone represented by the above formula (7), it is preferable that the p-tetrafluorobenzylene group side is fluorine and the oxyalkylene group side is hydrogen atom. The ether ketone can be represented by, for example, the following general formula (17). In the formula below, n represents the same degree of polymerization as in formula (7).

[0057]

[Chemical 11]

Specific examples of the polyaryletherketone represented by the above formula (7) include the following formulas (18) to (2).
1) and the like, and in each of the following formulas,
n represents the same degree of polymerization as in the above formula (7).

[0059]

[Chemical 12]

[Chemical 13]

[Chemical 14]

[Chemical 15]

In addition to these, the birefringent layer (a)
Examples of the above-mentioned polyamide or polyester which is a forming material include polyamides and polyesters described in JP-A-10-508048, and their repeating units are represented by the following general formula (22). You can

[0061]

[Chemical 16] In the formula (22), Y is O or NH. Also,
E is, for example, a covalent bond, a C ₂ alkylene group, a halogenated C ₂ alkylene group, a CH ₂ group, a C (CX ₃ ) ₂ group (here,
X is halogen or hydrogen. ), A CO group, an O atom,
It is at least one group selected from the group consisting of S atom, SO ₂ group, Si (R) ₂ group, and N (R) group, and they may be the same or different. In the above E,
R is at least one kind of a C _1-3 alkyl group and a C _1-3 halogenated alkyl group, and is in the meta position or the para position with respect to the carbonyl functional group or the Y group.

In the above (22), A and A'are
It is a substituent, and t and z represent the respective substitution numbers. Also, p is an integer from 0 to 3, and q is 1
Is an integer from 0 to 3, and r is an integer from 0 to 3.

The A is, for example, hydrogen, halogen, C
_1-3 alkyl group, C _1-3 halogenated alkyl group, alkoxy group represented by OR (where R is as defined above), aryl group, substituted aryl group by halogenation, C _1-9 alkoxycarbonyl group, C _1-9 alkylcarbonyloxy group, C _1-12 aryloxycarbonyl group, C _1-12 arylcarbonyloxy group and substituted derivatives thereof, C _1-12 arylcarbamoyl group, and C
_1-12 selected from the group consisting of an arylcarbonylamino group and a substituted derivative thereof, and when there are a plurality of groups, they are the same or different. A'is, for example, halogen,
It is selected from the group consisting of a C _1-3 alkyl group, a C _1-3 halogenated alkyl group, a phenyl group and a substituted phenyl group, and when there are a plurality of groups, they are the same or different. Examples of the substituent on the phenyl ring of the substituted phenyl group include halogen, C _1-3 alkyl group, C _1-3 halogenated alkyl group and combinations thereof. The t
Is an integer from 0 to 4 and z is an integer from 0 to 3.

Among the repeating units of the polyamide or polyester represented by the above formula (22), those represented by the following general formula (23) are preferable.

[0065]

[Chemical 17] In the formula (23), A, A ′, and Y are each represented by the formula (2).
2) and v is an integer of 0 to 3, preferably 0 to 2. x and y are 0 or 1 respectively, but are never 0 at the same time.

Next, the laminated retardation plate of the present invention can be manufactured, for example, as follows.

First, the optical anisotropic layer (A) is prepared.
This optical anisotropic layer (A) has an in-plane retardation [R
e (A)] is 20 to 300 nm, and the thickness direction retardation [Rth
The ratio [Rth (A) / Re (A)] between (A)] and the in-plane retardation [Re (A)] may be 1.0 or more. The film made of such a polymer may be an unstretched film or a stretched film as described above. As the stretched film,
For example, it can be obtained by stretching a polymer film formed by extrusion molding or casting film formation. The stretched film may be a uniaxially stretched film or a biaxially stretched film.

The stretching method is also not particularly limited, and for example,
Conventionally known stretching methods such as uniaxial stretching such as roll method longitudinal stretching and biaxial stretching such as tenter transverse stretching can be used. The roll method longitudinal stretching may be, for example, either a method using a heating roll or a method using an atmosphere under heating conditions, or these may be used in combination. In addition, examples of the biaxial stretching include simultaneous biaxial stretching by an all tenter method and sequential biaxial stretching by a roll tenter method. The stretching ratio is not particularly limited and can be appropriately determined depending on, for example, the stretching method and the forming material. As properties of the optically anisotropic layer (A), those having excellent surface smoothness, uniform birefringence, transparency and heat resistance are preferable.

The thickness of the polymer film before stretching is usually 10 to 800 μm, preferably 10 to 700.
μm. The thickness of the stretched polymer film, that is, the optical anisotropic layer (A) is as described above.

On the other hand, in the optically anisotropic layer (B), the in-plane retardation [Re (B)] is 3 nm or more, and the ratio [Rth (B) / It is not particularly limited as long as Re (B)] is 1.0 or more, but for example, it can be prepared as follows.

The optically anisotropic layer (B) is formed, for example, by coating the non-liquid crystalline polymer on a substrate to form a coating film,
It can be formed on the substrate by solidifying the non-liquid crystalline polymer in the coating film. Due to the nature of the non-liquid crystal polymer such as polyimide, nx> nz, ny> nz (nx
≈ny> nz). Therefore, it is possible to form an optically anisotropic layer that exhibits optical uniaxiality, that is, a phase difference only in the thickness direction. The optical anisotropic layer (B)
May be used by peeling it from the base material, or may be used in a state of being formed on the base material.

At this time, it is preferable to use the optically anisotropic layer (A) as the substrate. If this non-liquid crystalline polymer is directly coated on the optically anisotropic layer (A) as a substrate, the optically anisotropic layers (A) and (B) are laminated with a pressure-sensitive adhesive or an adhesive. This is because the number of stacked layers can be reduced and further thinning can be achieved, since this is unnecessary.

Further, as described above, since the non-liquid crystal polymer has the property of exhibiting optical uniaxiality, it is not necessary to utilize the orientation of the substrate. Therefore, both an oriented substrate and a non-oriented substrate can be used as the base material. Further, for example, it may be one that causes a phase difference due to birefringence, or one that does not cause a phase difference due to birefringence. Examples of the transparent substrate that causes a phase difference due to the birefringence include a stretched film and the like, and a substrate having a controlled refractive index in the thickness direction can also be used. The control of the refractive index, for example, by bonding a polymer film with a heat-shrinkable film,
Further, it can be carried out by a method of heating and stretching.

The method for applying the non-liquid crystalline polymer onto the substrate is not particularly limited, but for example, the method for heating and melting the non-liquid crystalline polymer as described above or the above-mentioned non-liquid crystalline polymer may be used. Examples include a method of applying a polymer solution in which a liquid crystal polymer is dissolved in a solvent. Among them, the method of applying the polymer solution is preferable because it is excellent in workability.

The polymer concentration in the polymer solution is not particularly limited, but for example, since the viscosity is such that coating is easy, for example, 5 to 50 parts by weight of the non-liquid crystalline polymer is used per 100 parts by weight of the solvent. It is preferably present, and more preferably 10 to 40 parts by weight.

The solvent of the polymer solution is not particularly limited as long as it can dissolve the forming material such as the non-liquid crystalline polymer, and can be appropriately determined according to the type of the forming material. As specific examples, for example, halogenated hydrocarbons such as chloroform, dichloromethane, carbon tetrachloride, dichloroethane, tetrachloroethane, trichloroethylene, tetrachloroethylene, chlorobenzene, orthodichlorobenzene; phenols, phenols such as rosechlorophenol; benzene, toluene, Aromatic hydrocarbons such as xylene, methoxybenzene, and 1,2-dimethoxybenzene; ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, 2-pyrrolidone, and N-methyl-2-pyrrolidone; Ester solvents such as ethyl acetate and butyl acetate; t-butyl alcohol, glycerin, ethylene glycol, triethylene glycol, ethylene glycol monomethyl ether, diethylene glycol Alcohol solvents such as dimethyl ether, propylene glycol, dipropylene glycol, 2-methyl-2,4-pentanediol; amide solvents such as dimethylformamide and dimethylacetamide; nitrile solvents such as acetonitrile and butyronitrile; Ethereal solvents such as diethyl ether, dibutyl ether, tetrahydrofuran;
Alternatively, carbon disulfide, ethyl cellosolve, butyl cellosolve and the like can be mentioned. These solvents may be used alone or in combination of two or more.

The polymer solution may be further mixed with various additives such as stabilizers, plasticizers and metals, if necessary.

Further, the polymer solution may contain, for example, another different resin as long as the orientation and the like of the forming material are not significantly deteriorated. Examples of the other resin include various general-purpose resins, engineering plastics,
Examples thereof include thermoplastic resins and thermosetting resins.

Examples of the general-purpose resin include polyethylene (PE), polypropylene (PP), polystyrene (PS), polymethylmethacrylate (PMMA), A
Examples include BS resin and AS resin. Examples of the engineering plastic include polyacetate (POM), polycarbonate (PC), polyamide (PA: nylon), polyethylene terephthalate (PET), and polybutylene terephthalate (PB).
T) and the like. Examples of the thermoplastic resin include polyphenylene sulfide (PPS), polyether sulfone (PES), polyketone (PK), polyimide (PI), polycyclohexanedimethanol terephthalate (PCT), polyarylate (PAR), and liquid crystal polymer. (LCP) and the like. Examples of the thermosetting resin include epoxy resin and phenol novolac resin.

Thus, when the other resin or the like is blended in the polymer solution, the blending amount is, for example, 0 to 50% by mass relative to the polymer material,
Preferably, it is 0 to 30% by mass.

Examples of the coating method of the polymer solution include a spin coating method, a roll coating method, a flow coating method, a printing method, a dip coating method, a casting film forming method, a bar coating method and a gravure printing method. To be Further, in coating, a polymer layer superposing method can be adopted as necessary.

The non-liquid crystal polymer forming the coating film can be solidified, for example, by drying the coating film. The drying method is not particularly limited, and examples thereof include natural drying and heat drying. The conditions can also be appropriately determined depending on, for example, the type of the non-liquid crystalline polymer, the type of the solvent, etc., but the temperature is usually 40 ° C. to 300 ° C., preferably 50 ° C.
To 250 ° C, more preferably 60 ° C to 200 ° C
Is. The coating film may be dried at a constant temperature or may be increased or decreased in stages. The drying time is not particularly limited, but is usually 10 seconds to 30 minutes, preferably 30 seconds to 25 minutes, and more preferably 1 minute to 20 minutes or less.

The solvent of the polymer solution remaining in the optically anisotropic layer (B) may change the optical characteristics of the laminated retardation film with time in proportion to the amount of the solvent.
The residual amount is, for example, preferably 5% or less, more preferably 2% or less, and further preferably 0.2% or less.

Further, as the base material, by using a base material which contracts in one direction in the plane, an optical anisotropic layer (B) exhibiting optical biaxiality, that is, nx>ny> nz is obtained. It can also be prepared. Specifically,
For example, in the same manner as described above, the non-liquid crystalline polymer is directly applied onto the shrinkable substrate to form a coating film, and then the substrate is shrunk. When the base material contracts, the coating film on the base material also contracts in the in-plane direction with the contraction of the base material, so that the coating film further has a refraction difference in the plane, resulting in optical biaxiality ( (nx>ny> nz). Then, by solidifying the non-liquid crystalline polymer forming this coating film, the biaxial optically anisotropic layer (B) is formed.

It is preferable that the base material is stretched, for example, in any one direction in the plane in order to have shrinkability in one direction in the plane. In this way, by stretching in advance, a contracting force is generated in the direction opposite to the stretching direction. Utilizing the shrinkage difference in the plane of this substrate,
The in-plane refractive index difference is imparted to the non-liquid crystal polymer of the coating film. The thickness of the base material before stretching is not particularly limited, but is, for example, in the range of 10 to 200 μm, preferably in the range of 20 to 150 μm, and particularly preferably 3
It is in the range of 0 to 100 μm. And the draw ratio is not particularly limited.

The contraction of the base material can be performed, for example, by forming a coating film on the base material in the same manner as described above and then subjecting it to heat treatment. The condition of the heat treatment is not particularly limited and can be appropriately determined depending on, for example, the type of material of the base material, and for example, the heating temperature is 25
To 300 ° C., preferably 50 to 200 ° C., and particularly preferably 60 to 180 ° C. Although the degree of shrinkage is not particularly limited, for example, a shrinkage ratio of more than 0 and 10% or less can be mentioned, with the length of the base material before shrinkage being 100%.

On the other hand, by forming a coating film on a substrate and stretching the transparent substrate and the coating film together as described above, optical biaxiality, that is, nx>ny> nz is exhibited. The optically anisotropic layer (B) can also be formed on the substrate. According to this method, a laminate of the base material and the coating film,
By stretching together in one direction in the plane, the coating film further exhibits a difference in refraction in the plane and exhibits optical biaxiality (nx>ny> nz).

The method for stretching the laminate of the base material and the coating film is not particularly limited. For example, free-end longitudinal stretching in which the film is uniaxially stretched in the longitudinal direction, or the film is stretched in the width direction while the longitudinal direction of the film is fixed. Examples include fixed-end lateral stretching for uniaxial stretching and sequential or simultaneous biaxial stretching for stretching in both the longitudinal direction and the width direction.

The stretching of the laminate may be performed by, for example, pulling both the base material and the coating film together, but for example, only the base material is stretched for the following reason. It is preferable. When only the substrate is stretched, the coating film on the substrate is indirectly stretched by the tension generated in the substrate by this stretching. Then, since stretching the single layer body is usually uniform stretching rather than stretching the laminated body, if only the transparent substrate is uniformly stretched as described above, the base material is accompanied by the stretching. This is because the above coating film can also be stretched uniformly.

The stretching conditions are not particularly limited, and can be appropriately determined depending on, for example, the substrate and the type of the non-liquid crystalline polymer. The heating temperature during stretching can be appropriately determined depending on, for example, the types of the base material and the non-liquid crystalline polymer, their glass transition points (Tg), types of additives, and the like.
For example, it is 80 to 250 ° C., preferably 120 to 2
20 ° C., particularly preferably 140 to 200 ° C. Particularly, it is preferable that the temperature is near the Tg of the material of the base material or higher.

By laminating the optically anisotropic layer (A) and the optically anisotropic layer (B) obtained as described above with, for example, a pressure-sensitive adhesive or an adhesive, the laminated retardation plate of the present invention. Can be formed. Further, the optical anisotropic layer (B) formed on a base material (first base material) is adhered to the optical anisotropic layer (A) via an adhesive or the like, and then the first base The material may be peeled off.

The adhesive or pressure-sensitive adhesive is not particularly limited, and examples thereof include transparent pressure-sensitive adhesives and pressure-sensitive adhesives such as acrylic, silicone-based, polyester-based, polyurethane-based, polyether-based, and rubber-based adhesives. Conventionally known ones can be used. Among these, from the viewpoint of preventing changes in the optical properties of the laminated retarder, those that do not require a high temperature process at the time of curing or drying are preferable, and specifically, a long curing treatment or a drying time is required. Acrylic adhesives that do not are desirable.

Further, the present invention is not limited to such a bonding method,
For example, as described above, by using the optical anisotropic layer (A) as a base material for forming the optical anisotropic layer (B), and directly forming the optical anisotropic layer (B) thereon, The both may be directly laminated to form the laminated retardation plate of the present invention. With such a configuration, for example, since the pressure-sensitive adhesive layer and the adhesive layer are not necessary, the number of laminated layers can be reduced, and further thinning can be realized. In addition, the optical anisotropic layer (A)
As described above, the optically anisotropic layer (B) is directly laminated using the above as a base material, and this laminated body is further stretched in the same manner as described above,
The optical anisotropic layer (A) may be contracted, and the optical anisotropic layer (B) may be contracted by the contraction.

The laminated retardation plate of the present invention preferably further has a pressure-sensitive adhesive layer or an adhesive layer as the outermost layer. This facilitates adhesion between the laminated retardation plate of the present invention and other members such as other optical layers and liquid crystal cells, and can prevent peeling of the laminated retardation plate of the present invention. . The pressure-sensitive adhesive may be one outermost layer of the laminated retardation plate, or may be laminated on both outermost layers.

The material of the pressure-sensitive adhesive layer is not particularly limited, and conventionally known materials such as acrylic polymers can be used. Particularly, it prevents foaming and peeling due to moisture absorption, lowers optical characteristics due to difference in thermal expansion, and the like. From the viewpoint of preventing warpage of the liquid crystal cell when used in a liquid crystal cell, and further forming the liquid crystal display device having high quality and excellent durability, for example, it is preferable that the adhesive layer has a low moisture absorption rate and excellent heat resistance. . Further, it may be an adhesive layer containing fine particles and exhibiting light diffusion property. To form the pressure-sensitive adhesive layer on the surface of the laminated retardation plate, for example, a solution or a melt of various pressure-sensitive adhesive materials is directly added to a predetermined surface of the polarizing plate by a developing method such as casting or coating. And a method of forming a pressure-sensitive adhesive layer on a liner, which will be described later, and transferring it to a predetermined surface of the laminated retardation plate.

When the surface of the pressure-sensitive adhesive layer provided on the laminated retardation plate is exposed as described above, the surface is covered with a liner for the purpose of preventing contamination until the pressure-sensitive adhesive layer is put into practical use. It is preferable. This liner can be formed, for example, by a method of providing a suitable film such as a transparent film with one or more release coats using a release agent such as silicone type, long chain alkyl type, fluorine type, molybdenum sulfide, etc., if necessary.

The pressure-sensitive adhesive layer and the like may be, for example, a single layer body or a laminated body. As the laminate, for example,
It is also possible to use a laminate in which monolayers of different compositions and different types are combined. Further, when they are arranged on both sides of the laminated retardation plate, they may be the same pressure-sensitive adhesive layer, or may have different compositions or different types of pressure-sensitive adhesive layers.

The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on, for example, the construction of the polarizing plate, and is generally 1 to 500.
μm.

The pressure-sensitive adhesive forming the pressure-sensitive adhesive layer includes
For example, those having excellent optical transparency and exhibiting appropriate wettability, cohesiveness, and adhesive tackiness are preferable. As a concrete example, an acrylic polymer or a silicone polymer,
Examples thereof include adhesives prepared by appropriately using polymers such as polyester, polyurethane, polyether and synthetic rubber as base polymers.

The control of the adhesive property of the pressure-sensitive adhesive layer can be controlled by, for example, the composition and molecular weight of the base polymer forming the pressure-sensitive adhesive layer, the crosslinking method, the content ratio of the crosslinkable functional group, the mixing ratio of the crosslinking agent, and the like. This can be appropriately performed by a conventionally known method such as adjusting the degree of crosslinking or the molecular weight.

The laminated retardation plate of the present invention is, as described above,
They may be used alone or, if necessary, may be combined with other optical members to form a laminate for various optical applications. Specifically, it is useful as a member for optical compensation.
The other optical member is not particularly limited, and examples thereof include the polarizers shown below.

The laminated retardation plate of the present invention can be used as the optical film in a laminated polarizing plate containing an optical film and a polarizer, for example.

The structure of such a polarizing plate is not particularly limited as long as it has the laminated retardation plate of the present invention, but examples thereof include the following. The laminated polarizing plate is not limited to the following configuration as long as it has the laminated retardation plate of the invention and a polarizer, and may further include other optical members and the like. , Other configuration requirements may be omitted.

As an example of the laminated polarizing plate, for example,
The laminated retardation plate of the present invention, having a polarizer and two transparent protective layers, the transparent protective layer on both sides of the polarizer,
An example is a mode in which they are laminated via an adhesive layer, and the laminated retardation plate is further laminated to one transparent protective layer via an adhesive layer. In addition, the laminated retardation plate includes the optically anisotropic layer (A) and the optically anisotropic layer (B) as described above.
However, any surface may face the transparent protective layer.

The transparent protective layer may be laminated on both sides of the polarizer as described above, or may be laminated only on one of the surfaces. Moreover, when laminating | stacking on both surfaces, you may use the same type of transparent protective layer, or may use a different type of transparent protective layer, for example. The method for adhering each layer is not particularly limited, and a pressure-sensitive adhesive or an adhesive may be used as the adhesive layer, or if the layers can be directly laminated, the adhesive layer may not be interposed.

As another example of the laminated polarizing plate,
The laminated retardation plate of the present invention, having a polarizer and a transparent protective layer, a transparent protective layer is laminated on one surface of the polarizer via an adhesive layer, and an adhesive layer on the other surface of the polarizer. Thus, the laminated retardation plates are laminated.

Since the laminated retardation plate is a laminated body in which the optical anisotropic layer (A) and the optical anisotropic layer (B) are laminated with the adhesive layer in between, either surface faces the polarizer. However, for example, it is preferable that the laminated retardation plate is arranged so that the optical anisotropic layer (A) side faces the polarizer for the following reasons. With such a configuration, the optically anisotropic layer (A) of the laminated retardation plate can also be used as a transparent protective layer in the laminated polarizing plate. That is, instead of laminating the transparent protective layers on both surfaces of the polarizer, the transparent protective layer is laminated on one surface of the polarizer, and the optical anisotropic layer (A) faces the other surface. By stacking the laminated retardation plates, the optically anisotropic layer (A) also serves as the other transparent protective layer of the polarizer. Therefore, it is possible to obtain a polarizing plate having a further reduced thickness.

The polarizer is not particularly limited, and for example, various films may be dyed by adsorbing a dichroic substance such as iodine or a dichroic dye by a conventionally known method, followed by crosslinking, stretching and drying. What was prepared by doing so can be used. Among these, a film that transmits linearly polarized light when natural light is incident thereon is preferable, and a film having excellent light transmittance and polarization degree is preferable. Examples of various films for adsorbing the dichroic substance include polyvinyl alcohol (PV
A) type film, partially formalized PVA type film,
Ethylene / vinyl acetate copolymer partially saponified film,
Examples thereof include hydrophilic polymer films such as cellulosic films, and in addition to these, polyene oriented films such as PVA dehydrated products and polyvinyl chloride dehydrochlorinated products can also be used. Among these, PV is preferable.
It is an A-based film. The thickness of the polarizing film is usually in the range of 1 to 80 μm, but is not limited to this.

The protective layer is not particularly limited, and a conventionally known transparent film can be used. For example, those having excellent transparency, mechanical strength, thermal stability, moisture barrier property, isotropic property, etc. are preferable. . Specific examples of the material of such a transparent protective layer include a cellulose-based resin such as triacetyl cellulose, a polyester-based, a polycarbonate-based, a polyamide-based, a polyimide-based, a polyether sulfone-based,
Examples thereof include transparent resins such as polysulfone-based, polystyrene-based, polynorbornene-based, polyolefin-based, acrylic-based, and acetate-based resins. Further, the above-mentioned acrylic, urethane-based, acrylic urethane-based, epoxy-based, silicone-based, etc. thermosetting resins or ultraviolet-curing resins are also included. Among these, a TAC film having a surface saponified with an alkali or the like is preferable from the viewpoint of polarization characteristics and durability.

Further, the polymer film described in JP 2001-343529 A (WO 01/37007) may be mentioned. Examples of the polymer material include a resin composition containing a thermoplastic resin having a substituted or unsubstituted imide group in the side chain and a thermoplastic resin having a substituted or unsubstituted phenyl group and a nitrile group in the side chain. Can be used, and examples thereof include a resin composition having an alternating copolymer of isobutene and N-methylenemaleimide and an acrylonitrile / styrene copolymer. The polymer film may be, for example, an extruded product of the resin composition.

The protective layer preferably has no color, for example. Specifically, the retardation value (Rth) in the film thickness direction represented by the following formula is -90 nm to +7.
It is preferably in the range of 5 nm, more preferably −
80 nm to +60 nm, particularly preferably -70 n
The range is from m to +45 nm. The phase difference value is -90n
Within the range of m to +75 nm, the coloring (optical coloring) of the polarizing plate due to the protective film can be sufficiently eliminated.
In the formula below, nx, ny, and nz are the same as those described above, and d represents the film thickness thereof. Rth = [[(nx + ny) / 2] -nz] · d

Further, the transparent protective layer may further have an optical compensation function. As such a transparent protective layer having an optical compensation function, for example, for the purpose of preventing coloring or the like, or enlarging the viewing angle for good visual recognition, which is caused by a change in the viewing angle based on the phase difference in the liquid crystal cell. Known ones can be used. Specific examples include various stretched films obtained by uniaxially or biaxially stretching the transparent resin described above, oriented films such as liquid crystal polymers, and laminates in which an orientation layer such as liquid crystal polymers is arranged on a transparent substrate. To be Among these, because it is possible to achieve a wide viewing angle with good visibility,
An alignment film of the liquid crystal polymer is preferable, and in particular, an optical compensation retardation plate in which an optical compensation layer composed of a tilted alignment layer of a discotic or nematic liquid crystal polymer is supported by the above-mentioned triacetyl cellulose film is preferable. . Examples of such an optical compensation retardation plate include commercially available products such as "WV film" manufactured by Fuji Photo Film Co., Ltd. Incidentally, the optical compensation retardation plate,
It may be one in which optical properties such as retardation are controlled by laminating two or more film supports such as the above retardation film and triacetyl cellulose film.

The thickness of the transparent protective layer is not particularly limited and can be appropriately determined depending on, for example, the phase difference and the protective strength, but is usually 500 μm or less, and preferably 5 to 3
00 μl, more preferably 5 to 150 μm

The transparent protective layer is a conventionally known method such as a method of coating the polarizing film with the various transparent resins or a method of laminating the polarizing film with the transparent resin film or the optical compensation retardation plate. Can be appropriately formed by the above method, or a commercially available product can be used.

Further, the transparent protective layer may be further subjected to, for example, a hard coat treatment, an antireflection treatment, a treatment for preventing sticking or diffusion, an antiglare treatment or the like. The hard coat treatment is, for the purpose of preventing scratches on the surface of the polarizing plate, for example, a treatment of forming a cured film excellent in hardness and slipperiness, which is composed of a curable resin, on the surface of the transparent protective layer. Is. As the curable resin, for example, a silicone-based, urethane-based, acrylic-based, or epoxy-based UV-curable resin can be used, and the treatment can be performed by a conventionally known method. The prevention of sticking is intended to prevent adhesion with an adjacent layer. The antireflection treatment aims at preventing reflection of external light on the surface of the polarizing plate, and can be performed by forming a conventionally known antireflection layer or the like.

The antiglare treatment is intended to prevent visual interference of light transmitted through the polarizing plate due to reflection of external light on the surface of the polarizing plate. For example, the transparent protective layer can be formed by a conventionally known method. This can be performed by forming a fine uneven structure on the surface. Examples of the method for forming such a concavo-convex structure include a surface roughening method such as a sandblast method and embossing, and a method of forming the transparent protective layer by blending transparent fine particles with the transparent resin as described above. To be

Examples of the transparent fine particles include silica, alumina, titania, zirconia, tin oxide, indium oxide, cadmium oxide and antimony oxide. In addition to these, inorganic fine particles having conductivity, cross-linking or It is also possible to use organic fine particles composed of uncrosslinked polymer particles or the like. The average particle size of the transparent fine particles is not particularly limited, but is, for example, 0.5 to 20 μm.
The range is m. The blending ratio of the transparent fine particles is
Although not particularly limited, in general, the transparent resin 1 as described above is used.
The range is preferably 2 to 70 parts by mass, more preferably 5 to 50 parts by mass, per 100 parts by mass.

The antiglare layer containing the transparent fine particles may be used as, for example, the transparent protective layer itself, or may be formed as a coating layer on the surface of the transparent protective layer. Further, the anti-glare layer may also serve as a diffusion layer (visual compensation function or the like) for diffusing the light transmitted through the polarizing plate and expanding the viewing angle.

The antireflection layer, the antisticking layer, the diffusion layer, the antiglare layer and the like are polarized separately from the transparent protective layer, for example, as an optical layer composed of a sheet provided with these layers. It may be laminated on a plate.

The method for laminating the respective constituents (optically anisotropic layer (A), optically anisotropic layer (B), laminated retardation plate, polarizer, transparent protective layer, etc.) is not particularly limited, and is conventionally known. It can be done by a method. In general, the same adhesives and adhesives as described above can be used, and the type thereof can be appropriately determined depending on the material of each of the constituents. Examples of the adhesive include acrylic type, vinyl alcohol type, silicone type,
Examples thereof include polyester-based, polyurethane-based, polyether-based polymer adhesives, and rubber-based adhesives. The above-mentioned pressure-sensitive adhesives and adhesives are difficult to peel off even under the influence of humidity and heat, and have excellent light transmittance and polarization degree.
Specifically, when the polarizer is a PVA-based film, a PVA-based adhesive is preferable from the viewpoint of, for example, the stability of the adhesive treatment. These adhesives or pressure-sensitive adhesives may be directly applied to the surface of the polarizer or the transparent protective layer, or a layer such as a tape or sheet composed of the adhesive or pressure-sensitive adhesive may be arranged on the surface. You may. In addition, for example, when prepared as an aqueous solution, other additives and a catalyst such as an acid may be added as necessary. When the adhesive is applied, for example, other additives or a catalyst such as an acid may be added to the adhesive aqueous solution. The thickness of such an adhesive layer is not particularly limited, but is, for example, 1 nm to
It is 500 nm, preferably 10 nm to 300 nm, and more preferably 20 nm to 100 nm. The method is not particularly limited, and, for example, a conventionally known method using an adhesive such as an acrylic polymer or a vinyl alcohol polymer can be adopted. Further, since it is possible to form a polarizing plate excellent in light transmittance and degree of polarization, which is unlikely to be peeled off even by humidity or heat, an adhesive containing a water-soluble crosslinking agent of a PVA-based polymer such as glutaraldehyde, melamine and oxalic acid is further formed. preferable. These adhesives can be used, for example, by applying an aqueous solution thereof to the surface of each constituent and drying it. In the aqueous solution, for example, if necessary,
Other additives and catalysts such as acids can also be added. Among these, a PVA-based adhesive is preferable as the adhesive because it has excellent adhesiveness to the PVA film.

Further, the laminated retardation plate of the present invention is, in addition to the above-mentioned polarizer, further various conventionally known optical members such as various other retardation plates, a diffusion control film and a brightness enhancement film. It can also be used in combination. Examples of the retardation plate include a uniaxially stretched or biaxially stretched polymer film, a Z-axis oriented treatment film, and a coating film of a liquid crystalline polymer. Examples of the diffusion control film include, for example, films utilizing diffusion, scattering, and refraction, and these include, for example, control of viewing angle,
It can be used for controlling glare and scattered light related to resolution. As the brightness enhancement film, for example,
Selective reflection of cholesteric liquid crystal and quarter wave plate (λ / 4
Plate) and a scattering film utilizing anisotropic scattering depending on the polarization direction. Further, the optical film can be combined with, for example, a wire grid type polarizer.

In practical use, the laminated polarizing plate may further include other optical layers in addition to the laminated retardation plate and the polarizer of the present invention. Examples of the optical layer include conventionally known various optical layers used for forming a liquid crystal display device, such as a polarizing plate, a reflector, a semi-transmissive reflector, and a brightness enhancement film as shown below. These optical layers are
One type may be used, two or more types may be used in combination, one layer may be used, or two or more layers may be laminated. The laminated polarizing plate further including such an optical layer is preferably used as, for example, an integrated polarizing plate having an optical compensation function, and is suitable for use in various image display devices such as being arranged on the surface of a liquid crystal cell. ing.

The integrated polarizing plate will be described below.

First, an example of the reflective polarizing plate or the semi-transmissive reflective polarizing plate will be described. The reflection type polarizing plate is further laminated with a reflection plate on the laminated polarizing plate of the present invention, and the semi-transmissive reflection type polarizing plate is further laminated with a semi-transmission reflection plate on the laminated polarizing plate of the present invention.

The reflective polarizing plate is usually disposed on the back side of a liquid crystal cell and is used in a liquid crystal display device (reflective liquid crystal display device) of the type that reflects incident light from the viewing side (display side) for display. Can be used. Such a reflective polarizing plate has an advantage that a liquid crystal display device can be thinned, for example, since a light source such as a backlight can be omitted.

The reflection type polarizing plate can be produced by a conventionally known method such as a method of forming a reflecting plate made of metal or the like on one surface of the polarizing plate showing the elastic modulus.
Specifically, for example, one surface (exposed surface) of the transparent protective layer in the polarizing plate is matted if necessary, and a metal foil or a vapor deposition film made of a reflective metal such as aluminum is provided on the surface as a reflection plate. And a reflective polarizing plate formed as above.

Further, as described above, a reflecting plate reflecting the fine concavo-convex structure is formed on the transparent protective layer having the fine concavo-convex structure on the surface by incorporating fine particles into various transparent resins.
A reflective polarizing plate and the like are also included. A reflector whose surface has a fine concavo-convex structure has the advantage that diffused incident light is diffused to prevent directivity and glare and prevent uneven brightness. Such a reflector is, for example, on the uneven surface of the transparent protective layer, a vacuum deposition method, an ion plating method, a vapor deposition method such as a sputtering method, a plating method, or the like, by a conventionally known method, directly by the metal foil or It can be formed as a metal vapor deposition film.

Further, instead of the method of directly forming the reflection plate on the transparent protection layer of the polarizing plate as described above, a reflection sheet having a reflection layer provided on a suitable film such as the transparent protection film as the reflection plate. Etc. may be used. Since the reflective layer in the reflective plate is usually composed of a metal, for example, prevention of a decrease in reflectance due to oxidation, and thus a long-lasting initial reflectance, from the viewpoint of avoiding the separate formation of a transparent protective layer, and the like, It is preferable that the form of use is such that the reflective surface of the reflective layer is covered with the film, the polarizing plate, or the like.

On the other hand, the semi-transmissive polarizing plate has a semi-transmissive reflecting plate in place of the reflecting plate in the reflective polarizing plate. Examples of the semi-transmissive reflector include a half mirror that reflects light through a reflective layer and transmits light.

The semi-transmissive polarizing plate is usually provided on the back side of the liquid crystal cell and reflects incident light from the viewing side (display side) when the liquid crystal display device is used in a relatively bright atmosphere. To display the image, and in a relatively dark atmosphere,
It can be used for a liquid crystal display device of a type that displays an image using a built-in light source such as a backlight built in the back side of a semi-transmissive polarizing plate. That is, the semi-transmissive polarizing plate can save energy for using a light source such as a backlight in a bright atmosphere, while it can be used in a relatively dark atmosphere by using the built-in light source. It is useful for the formation of etc.

Next, an example of a polarizing plate in which a brightness enhancement film is further laminated on the laminated polarizing plate will be described.

The brightness enhancement film is not particularly limited, and transmits linearly polarized light having a predetermined polarization axis, such as a dielectric multilayer thin film or a multilayer laminate of thin films having different refractive index anisotropies. Then, other light or the like that exhibits a characteristic of being reflected can be used. An example of such a brightness enhancement film is the product name “D-BEF” manufactured by 3M Company. In addition, a cholesteric liquid crystal layer, particularly an oriented film of a cholesteric liquid crystal polymer, or one in which the oriented liquid crystal layer is supported on a film substrate can be used. These reflect the circularly polarized light on one of the left and right and transmit the other light. For example, the product name "PCF350" manufactured by Nitto Denko Corporation and the product name "Tran manufactured by Merck
smax ”and the like.

The various laminated polarizing plates described above are, for example,
It may be an optical member in which another optical layer is laminated.

The optical member in which two or more optical layers are thus laminated can be formed, for example, by a method of sequentially laminating separately in the manufacturing process of a liquid crystal display device or the like.
When used as an optical member laminated in advance, there are advantages that, for example, the quality stability and the assembly workability are excellent, and the manufacturing efficiency of liquid crystal display devices and the like can be improved. In addition, for stacking,
Similar to the above, various adhesive means such as an adhesive layer can be used.

It is preferable that the above-mentioned various polarizing plates further have a pressure-sensitive adhesive layer or an adhesive layer because they can be easily laminated on other members such as a liquid crystal cell. It can be arranged on one side or both sides of the polarizing plate. The material of the adhesive layer is not particularly limited,
A conventionally known material such as an acrylic polymer can be used. Particularly, a liquid crystal display device that prevents foaming and peeling due to moisture absorption, prevents deterioration of optical characteristics due to thermal expansion difference and the like, and prevents warpage of liquid crystal cells, and thus high quality and excellent durability. From the standpoint of formability, it is preferable that the pressure-sensitive adhesive layer has a low moisture absorption rate and excellent heat resistance. Further, it may be an adhesive layer containing fine particles and exhibiting light diffusion property. The pressure-sensitive adhesive layer is formed on the surface of the polarizing plate by, for example, adding a solution or a melt of various pressure-sensitive adhesive materials directly to a predetermined surface of the polarizing plate by a spreading method such as casting or coating. Or a method of forming a pressure-sensitive adhesive layer on a separator described later and transferring it to a predetermined surface of the polarizing plate, or the like.
In addition, such a layer may be formed on any surface of the polarizing plate, for example, may be formed on an exposed surface of the retardation plate in the polarizing plate.

When the surface of the pressure-sensitive adhesive layer provided on the polarizing plate is exposed as described above, the surface may be covered with a separator for the purpose of preventing contamination until the pressure-sensitive adhesive layer is put into practical use. preferable. This separator is
It can be formed by a method of providing one or more release coats with a release agent such as silicone-based, long-chain alkyl-based, fluorine-based or molybdenum sulfide on a suitable film such as the transparent protective film, if necessary.

The pressure-sensitive adhesive layer and the like may be, for example, a single layer body or a laminated body. As the laminate, for example,
It is also possible to use a laminate in which monolayers of different compositions and different types are combined. Further, when they are arranged on both sides of the polarizing plate, they may be, for example, the same pressure-sensitive adhesive layer, or may have different compositions or different types of pressure-sensitive adhesive layers.

The thickness of the pressure-sensitive adhesive layer can be appropriately determined depending on, for example, the constitution of the polarizing plate, and is generally 1 to 500.
μm.

As the pressure-sensitive adhesive forming the pressure-sensitive adhesive layer,
For example, those having excellent optical transparency and exhibiting appropriate wettability, cohesiveness, and adhesive tackiness are preferable. As a concrete example, an acrylic polymer or a silicone polymer,
Examples thereof include adhesives prepared by appropriately using polymers such as polyester, polyurethane, polyether and synthetic rubber as base polymers.

The adhesive property of the pressure-sensitive adhesive layer can be controlled by, for example, the composition and molecular weight of the base polymer forming the pressure-sensitive adhesive layer, the crosslinking method, the content ratio of the crosslinkable functional group, the mixing ratio of the crosslinking agent, and the like. This can be appropriately performed by a conventionally known method such as adjusting the degree of crosslinking or the molecular weight.

Each layer such as a laminated retardation plate and a polarizing plate of the present invention, a polarizing film forming various optical members (various polarizing plates in which optical layers are laminated), a transparent protective layer, an optical layer, an adhesive layer and the like. May be one having an ultraviolet absorbing ability by being appropriately treated with an ultraviolet absorber such as a salicylate compound, a benzophenone compound, a benzotriazole compound, a cyanoacrylate compound, a nickel complex salt compound.

The laminated retardation plate of the present invention and the laminated polarizing plate provided with the same are preferably used for forming various devices such as a liquid crystal display device as described above. For example, the laminated retardation film of the present invention is used. A plate or the laminated polarizing plate is arranged on one side or both sides of a liquid crystal cell to form a liquid crystal panel, which is a reflective type or a semi-transmissive type.
Alternatively, it can be used in a liquid crystal display device such as a transmissive / reflective type.

The type of the liquid crystal cell forming the liquid crystal display device can be arbitrarily selected. For example, an active matrix drive type represented by a thin film transistor type, a simple matrix represented by a twist nematic type or a super twist nematic type. Various types of liquid crystal cells such as a driving type can be used. Among these, the optical film and polarizing plate of the present invention are particularly preferably VA (vertical alignment; Vertical A
ligned) cell has very good optical compensation, so VA
It is very useful as a viewing angle compensation film for a mode liquid crystal display device.

Further, the liquid crystal cell usually has a structure in which liquid crystal is injected into a gap between opposed liquid crystal cell substrates, and the liquid crystal cell substrate is not particularly limited, and, for example, a glass substrate or a plastic substrate is used. Can be used. The material of the plastic substrate is not particularly limited, and conventionally known materials can be used.

When polarizing plates and optical members are provided on both surfaces of the liquid crystal cell, the laminated retardation plate or laminated polarizing plate of the present invention may be arranged on at least one surface, and they may be of the same kind. , May be different. Further, when forming the liquid crystal display device, for example, one or two or more layers of appropriate components such as a prism array sheet, a lens array sheet, a light diffusing plate and a backlight can be arranged at appropriate positions.

Further, the liquid crystal display device of the present invention includes a liquid crystal panel, and is not particularly limited except that the liquid crystal panel of the present invention is used as the liquid crystal panel. When a light source is included, it is not particularly limited, but for example, a flat light source that emits polarized light is preferable because light energy can be effectively used.

As an example of the liquid crystal panel of the present invention, for example, a liquid crystal cell, a laminated retardation film of the present invention, a polarizer and a transparent protective layer are provided, and the laminated retardation plate is provided on one surface of the liquid crystal cell. The polarizer and the transparent protective layer are laminated in this order on the other surface of the laminated retardation plate. The liquid crystal cell has a structure in which liquid crystal is held between two liquid crystal cell substrates. Further, the laminated retardation plate has the optical anisotropic layer (A) and the optical anisotropic layer (B) as described above.
Of the above, and any surface may face the polarizer.

The liquid crystal display device of the present invention comprises, for example, a diffusion plate, a diffusion plate, and the like on the viewing side optical film (laminated polarizing plate).
An antiglare layer, an antireflection film, a protective layer or a protective plate may be arranged, or a compensating retardation plate or the like may be appropriately arranged between the liquid crystal cell and the polarizing plate in the liquid crystal panel.

The laminated retardation plate of the present invention and the laminated polarizing plate provided with the same are not limited to the liquid crystal display device as described above. For example, organic electroluminescence (E
L) It can also be used for self-luminous display devices such as displays, PDPs, FEDs and the like. When used in a self-luminous flat display, for example, by setting the in-plane retardation value Δnd of the laminated retardation plate or the laminated polarizing plate of the present invention to λ / 4,
Since circularly polarized light can be obtained, it can be used as an antireflection filter.

An electroluminescence (EL) display device including the laminated retardation plate of the present invention and the laminated polarizing plate will be described below. The EL display device of the present invention only needs to have the laminated retardation plate of the present invention or the laminated polarizing plate including the same, and may be either an organic EL or an inorganic EL.

In recent years, also in EL display devices, it has been proposed to use an optical film such as a polarizer or a polarizing plate together with a λ / 4 plate to prevent reflection from the electrode in the black state. The laminated retardation plate and the laminated polarizing plate of the present invention are particularly effective when the EL layer emits linearly polarized light, circularly polarized light or elliptically polarized light, or emits natural light in the front direction. Also, it is very useful when the outgoing light in the oblique direction is partially polarized.

First, a general organic EL display device will be described. The organic EL display device generally has a light emitting body (organic EL light emitting body) in which a transparent electrode, an organic light emitting layer, and a metal electrode are laminated in this order on a transparent substrate. The organic light emitting layer is a laminate of various organic thin films, for example, a laminate of a hole injection layer made of a triphenylamine derivative or the like and a light emitting layer made of a fluorescent organic solid such as anthracene, or the like. Various combinations such as a laminated body of a light emitting layer and an electron injection layer made of a perylene derivative, a laminated body of the hole injection layer, a light emitting layer and an electron injection layer can be mentioned.

Then, such an organic EL display device is
By applying a voltage to the anode and the cathode, holes and electrons are injected into the organic light emitting layer, and energy generated by recombination of the holes and electrons excites and excites the fluorescent substance. The fluorescent substance thus emitted emits light when it returns to the ground state. The mechanism of the recombination of holes and electrons is the same as that of a general diode, and the current and the emission intensity show a strong non-linearity with rectification with respect to the applied voltage.

In the organic EL display device, at least one of the electrodes needs to be transparent in order to extract light emitted from the organic light emitting layer. Therefore, a transparent conductor such as indium tin oxide (ITO) is usually used. The transparent electrode formed in 1) is used as an anode. On the other hand, in order to facilitate electron injection and increase luminous efficiency, it is important to use a substance having a small work function for the cathode. Usually, Mg-Ag or Al is used.
-A metal electrode such as Li is used.

In the organic EL display device having such a structure, it is preferable that the organic light emitting layer is formed of an extremely thin film having a thickness of, for example, about 10 nm. This is because light is almost completely transmitted through the organic light emitting layer as well as the transparent electrode. As a result, at the time of non-light emission, the light that enters from the surface of the transparent substrate, passes through the transparent electrode and the organic light emitting layer, and is reflected by the metal electrode again exits to the surface side of the transparent substrate. Therefore, when viewed from the outside, the display surface of the organic EL display device looks like a mirror surface.

The organic EL display device of the present invention includes, for example, an organic EL display including the organic EL light emitter having a transparent electrode on the front surface side of the organic light emitting layer and a metal electrode on the back surface side of the organic light emitting layer. In the device, on the surface of the transparent electrode,
The laminated retardation plate of the present invention and the laminated polarizing plate are preferably arranged, and further, a λ / 4 plate is preferably arranged between the polarizing plate and the EL element. As described above, by arranging the laminated retardation plate and the laminated polarizing plate of the present invention, the organic EL display device exhibits the effect of suppressing the reflection of the outside world and improving the visibility. Further, it is preferable that a retardation plate is further arranged between the transparent electrode and the optical film.

The retardation plate and the polarizing plate are, for example,
Since it has a function of polarizing the light incident from the outside and reflected by the metal electrode, there is an effect that the mirror effect of the metal electrode is not visually recognized from the outside by the polarization action.
In particular, a quarter wave plate is used as the retardation plate, and the angle formed by the polarization directions of the polarizing plate and the retardation plate is π / 4.
The mirror surface of the metal electrode can be completely shielded by adjusting. That is, of the external light that enters the organic EL display device, only the linearly polarized light component is transmitted by the polarizing plate. This linearly polarized light is generally elliptically polarized light by the retardation plate, and in particular, when the retardation plate is a quarter wavelength plate and the angle is π / 4, it becomes circularly polarized light.

This circularly polarized light is transmitted through, for example, the transparent substrate, the transparent electrode, and the organic thin film, is reflected by the metal electrode, is transmitted again through the organic thin film, the transparent electrode, and the transparent substrate, and is again transmitted by the retardation plate. It becomes linearly polarized light. Since this linearly polarized light is orthogonal to the polarization direction of the polarizing plate, it cannot pass through the polarizing plate, and as a result, the mirror surface of the metal electrode can be completely shielded as described above. .

[0159]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to the following examples. The optical properties and thickness were measured by the following methods.

(Measurement of Phase Difference Value) Phase difference meter based on the parallel Nicol rotation method (KOBRA-, trade name, manufactured by Oji Scientific Instruments)
21 ADH) (measurement wavelength 610n
m).

(Measurement of film thickness) The film thickness was measured using a digital micrometer K-351C model manufactured by Anritsu.

Example A-1 A norbornene film having a thickness of 100 μm was transversely stretched with a tenter at 175 ° C. The stretching ratio is 1.4 times the length before stretching in the stretching direction. This gives a thickness of 69μ
An optically anisotropic layer A having m, Re (A) = 67 nm and Rth (A) = 136 nm was obtained. On the other hand, 2,2'-bis (3,4-dicarboxdiphenyl) hexafluoropropane) and 2,
A polyimide (weight average molecular weight 59,000) synthesized from 2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl was dissolved in cyclohexanone to prepare a 15% by weight polyimide solution. After coating this polyimide solution on a biaxially stretched stretched PET film,
The coated film was dried (temperature 150 ° C .; time 5 minutes), and an optically anisotropic layer (B) having a thickness of 3 μm was formed on the stretched PET film. The optical characteristics of this optically anisotropic layer (B) are Re (B) = 3 nm, Rth (B) = 110 nm, Rth (B) / Re
(B) = 32.7. Then, the optically anisotropic layer (B) and the optically anisotropic layer (A) on the stretched PET film are
After bonding with an acrylic adhesive with a thickness of 15 μm,
The stretched PET film was peeled off to obtain a laminated retardation plate.

Example A-2 A 70 μm thick polyester film was longitudinally stretched at 160 ° C. The stretching ratio, in the stretching direction, with respect to the length before stretching,
As 1.1 times. This gives a thickness of 64 μm and Re (A) =
65 nm, Rth (A) = 70 nm, Rth (A) / Re (A) = 1.1
An optically anisotropic layer (A) was obtained. Next, a polyimide solution prepared in the same manner as in Example A-1 was directly applied onto this optically anisotropic layer (A), and the applied film was dried (temperature 150 ° C .; time 5 minutes). ), The optical anisotropic layer (B) was formed on the optical anisotropic layer (A) to manufacture a laminated retardation plate. The optical anisotropic layer (B) has a thickness of 5 μm, and its optical characteristics are Re (B) = 5 nm, Rth (B) = 180 nm, Rth (B) /
Re (B) = 36.0. The optical properties of the optically anisotropic layer (B) were measured after peeling from the optically anisotropic layer (A).

Example A-3 A polyimide solution prepared in the same manner as in Example A-1 was applied to a triacetyl cellulose (TAC) film having a thickness of 80 μm and the temperature was adjusted to 18
Tenter transverse stretching was performed while drying at 0 ° C. for 5 minutes. The stretching ratio was 2.0 times before stretching in the stretching direction. By this stretching, the optically anisotropic layer (B) made of polyimide was formed on the stretched TAC film (optically anisotropic layer (A)), and a laminated retardation plate was obtained. The optically anisotropic layer (A) has a thickness of 67 μm, and its optical characteristics are Re (A) = 30 nm, Rth (A) = 55 nm, Rth (A) / Re
(A) = 1.8. In addition, the optical anisotropic layer (B)
Has a thickness of 5 μm and its optical characteristics are Re (B) =
40 nm, Rth (B) = 198 nm, and Rth (B) / Re (B) = 5.

(Example A-4) 4,4'-bis (3,4-)
Weight average molecular weight 60,000 synthesized from dicarboxyphenyl) -2,2-diphenylpropane dianhydride and 2,2'-dichloro-4,4-diaminobiphenyl
20% by weight of the above polyimide dissolved in cyclopentanone
A polyimide solution of was prepared. This polyimide solution,
It is applied to a TAC film with a thickness of 80 μm and the temperature is 180 °
While being dried for 5 minutes, the tenter transverse stretching was performed.
The stretching ratio was 1.1 times before stretching in the stretching direction. By this stretching, an optical anisotropic layer (B) made of polyimide is formed on the stretched TAC film (optical anisotropic layer (A)).
Was formed, and a laminated retardation plate was obtained. The optical anisotropic layer (A) has a thickness of 74 μm, and its optical characteristics are
Re (A) = 25 nm, Rth (A) = 50 nm, Rth (A) / Re (A) =
It was 2. The optical anisotropic layer (B) has a thickness of 6
μm, the optical characteristics are Re (B) = 38 nm, Rth
(B) = 220 nm and Rth (B) / Re (B) = 44.

Comparative Example A-1 A 100 μm thick norbornene film was subjected to tenter transverse stretching at 175 ° C. The stretching ratio was 1.8 times the length before stretching in the stretching direction. This gives a thickness of 88μ
m, Re (A) = 252 nm, Rth (A) = 252 nm, Rth (A) /
An optically anisotropic layer (A) with Re (A) = 1.0 was obtained. On the other hand, a norbornene film having a thickness of 100 μm is similarly used in the same manner as 1.5
Double stretched, thickness 95μm, Re (B) = 180nm, Rth
An optically anisotropic layer (B) having (B) = 181 nm and Rth (B) / Re (B) = 1.0 was obtained. Then, an acrylic pressure-sensitive adhesive having a thickness of 15 μm is applied to the optical anisotropic layer (A), and the in-plane slow axes of the optical anisotropic layer (A) and the optical anisotropic layer (B) are orthogonal to each other. I stuck them together so that Thus, a laminated retardation plate (nx>ny> nz) was manufactured.

Regarding the laminated retardation plates obtained in Examples A-1 to A-4 and Comparative Example 1, their thickness and in-plane retardation value (R
e) and the thickness direction retardation (Rth) were measured.
The results are shown in Table 1.

[0168]

[Table 1]

As shown in Table 1 above, the optically anisotropic layer (B)
In the laminated retardation plate of Comparative Example A-1 using the norbornene polymer as described above, a thickness of 183 μm was required to obtain the same optical characteristics as those in the example. On the other hand, according to the laminated retardation plate of each example using polyimide as the optically anisotropic layer (B), not only sufficient optical characteristics were obtained, but also the half of Comparative Example A-1 was obtained. We were able to achieve a thickness reduction of about 1.

Example B A laminated retardation plate of the present invention was produced, and using this, a laminated polarizing plate shown in FIGS. 1 to 8 was produced. In these figures, the same parts are designated by the same reference numerals.

Example B-1 In this example, a laminated polarizing plate 10 having the form shown in FIG. 1 was produced. First, a norbornene film having a thickness of 100 μm is 180 ° C.
Was longitudinally stretched. The stretching ratio is 1.2 times the length before stretching in the stretching direction. by this,
An optically anisotropic layer (A) 11a having a thickness of 90 μm was obtained. on the other hand,
Polyimide synthesized from 2,2'-bis (3,4-dicarboxdiphenyl) hexafluoropropane) and 2,2'-bis (trifluoromethyl) -4,4'-diaminobiphenyl (weight average molecular weight 59000) Was dissolved in cyclohexanone to prepare a 15% by weight polyimide solution. This polyimide solution is biaxially stretched and stretched P
After coating on the ET film, the coating film was dried (temperature 150 ° C .; time 5 minutes) to form an optically anisotropic layer (B) 11b having a thickness of 5 μm on the stretched PET film.
Then, the optically anisotropic layer (B) on the stretched PET film
11b and the optically anisotropic layer (A) 11a are formed to have a thickness of 15 μm.
After the adhesive was adhered via the acrylic pressure-sensitive adhesive 14, the stretched PET film was peeled off to obtain a laminated retardation plate 11 having a thickness of 110 μm.

Further, a polyvinyl alcohol (PVA) film having a thickness of 80 μm was stretched 5 times in an aqueous iodine solution and then dried to obtain a polarizing layer 13. Then, a TAC having a thickness of 80 μm is formed on one surface of the polarizing layer 13 through an acrylic pressure-sensitive adhesive layer 14 having a thickness of 15 μm.
A film 12 is adhered, and the laminated retardation plate 11 is adhered to the other surface so that the optical anisotropic layer (A) 11a is on the polarizing layer 13 side, and a wide viewing angle laminated polarizing plate having a thickness of 240 μm. Got 10.

Example B-2 In this example, a laminated polarizing plate 20 having the form shown in FIG. 2 was produced. In the same manner as in Example B-1 except that the laminated retardation plate 11 was adhered to the polarizing layer so that the optically anisotropic layer (B) 11b was on the polarizing layer 13 side, a wide viewing angle laminated body having a thickness of 240 μm was formed. Polarizer 20
Got

Example B-3 In this example, a laminated polarizing plate 30 having the form shown in FIG. 3 was produced. Thickness 70μ
m polyester film was stretched at 160 ° C in the stretching direction by tenter transverse stretching (stretching ratio 1.2
Times), and an optically anisotropic layer (A) 11a having a thickness of 59 μm was obtained.
Next, a polyimide solution prepared in the same manner as in Example 1 was applied onto the optically anisotropic layer (A) 11a and dried (temperature 180 ° C .; time 5 minutes) to give an optical layer having a thickness of 3 μm. An anisotropic layer (B) 11b was formed. As a result, a laminated retardation plate 31 having a thickness of 62 μm, which is a laminated body of the optical anisotropic layer (A) 11a and the optical anisotropic layer (B) 11b, was obtained. Next, through the acrylic pressure-sensitive adhesive layer 14 having a thickness of 15 μm,
The TAC film 12 having a thickness of 80 μm was adhered to one surface of the polarizing layer 13 similar to that in Example 1, and the laminated retardation layer was formed so that the optical anisotropic layer (A) 11 a was on the polarizing layer 13 side on the other surface. The plate 31 was adhered to obtain a wide viewing angle laminated polarizing plate 30 having a thickness of 192 μm.

Example B-4 In this example, a laminated polarizing plate 40 having the form shown in FIG. 4 was produced. A wide-viewing-angle lamination having a thickness of 192 μm was carried out in the same manner as in Example B-3 except that the laminated retardation plate 31 was adhered to the polarizing layer 13 so that the optically anisotropic layer (B) was on the polarizing layer 13 side. Polarizing plate 40
Got

Example B-5 In this example, a laminated polarizing plate 50 having the form shown in FIG. 5 was produced. The polyimide solution prepared in the same manner as in Example 1 was applied to a TAC film having a thickness of 80 μm, and while being dried at a temperature of 190 ° C. for 5 minutes, the tenter transverse stretching was performed so that the stretching ratio was 1.3 times. As a result, a laminated retardation plate 31 having a total thickness of 66 μm in which a polyimide film (optical anisotropic layer (B) 11 b) having a thickness of 6 μm is laminated on a stretched TAC film (optical anisotropic layer (A) 11 a) having a thickness of 60 μm Got Then, a TAC layer having a thickness of 80 μm was formed on one surface of the polarizing layer 13 similar to that of Example 1 through the PVA adhesive layer 15 having a thickness of 5 μm.
The laminated retardation plate 31 is adhered to the film 12 and the other surface so that the optical anisotropic layer (A) 11a is on the polarizing layer 13 side, and the wide viewing angle laminated polarizing plate 176 having a thickness of 183 μm.
Got

Example B-6 In this example, a laminated polarizing plate 60 having the form shown in FIG. 6 was produced. A wide viewing angle with a thickness of 176 μm was obtained in the same manner as in Example B-5 except that the laminated retardation plate 31 was adhered to the polarizing layer 13 so that the optically anisotropic layer (B) 11b was on the polarizing layer 13 side. The compounded laminated polarizing plate 60 was obtained.

Example B-7 In this example, a laminated polarizing plate 70 having the form shown in FIG. 7 was produced. The TAC film was transversely stretched with a tenter at 190 ° C. so that the stretching ratio was 1.4 times, to give an optical anisotropic layer (A) 1 having a thickness of 69 μm.
1a was obtained. Then, a TAC film 12 having a thickness of 80 μm was formed on one surface of the polarizing layer 13 similar to that of Example B-1, and the optical anisotropic layer (A) 11a was formed on the other surface of the polarizing layer 13.
Were bonded via PVA-based adhesive layers 15 having a thickness of 5 μm. Further, an optical anisotropic layer (B) 11b having a thickness of 5 μm obtained in the same manner as in Example B-1 was formed with a thickness of 15 μm.
After being laminated on the optically anisotropic layer (A) 11a via the acrylic adhesive 14 of m, the stretched PET film was peeled off to obtain a wide viewing angle laminated polarizing plate 70 having a thickness of 199 μm.

Example B-8 In this example, a laminated polarizing plate 80 having the form shown in FIG. 8 was produced. 4,4'-
Bis (3,4-dicarboxyphenyl) -2,2-diphenylpropane dianhydride and 2,2'-dichloro-
A polyimide having a weight average molecular weight of 65,000 synthesized from 4,4-diaminobiphenyl was dissolved in cyclopentanone to prepare a 20 wt% polyimide solution. This polyimide solution was applied to a TAC film having a thickness of 80 μm, and transversely stretched with a tenter while being dried at a temperature of 200 ° C. for 5 minutes. The stretching ratio was 1.5 times before stretching in the stretching direction. As a result, a thickness of 6 μm is formed on the stretched TAC film (optical anisotropic layer (A)) having a thickness of 54 μm.
The laminated retardation plate having a total thickness of 60 μm was formed by laminating the polyimide film (optically anisotropic layer (B)). Further, the laminated retardation plate was provided with a polyvinyl alcohol (PVA) -based pressure-sensitive adhesive layer 15 on one surface of the same polarizing layer as in Example B-1 such that the optically anisotropic layer (A) faced the same. The TAC film 12 having a thickness of 80 μm is bonded to the other surface of the polarizing layer with a PVA adhesive layer interposed therebetween.
Glued. Thereby, a wide viewing angle laminated polarizing plate having a thickness of 170 μm was obtained.

(Comparative Example B-1) Thickness 80 μm, Re
(A) 0.9 nm, Rth (A) 59 nm, Rth (A) / Re
The TAC film of (A) 66 was used as the optically anisotropic layer (A). On this, the same polyimide solution as in Example B-1 was applied and dried at 130 ° C. for 5 minutes to form an optical anisotropic layer (B) on the optical anisotropic layer (A). , Thickness 85μ
A laminated retardation plate showing m, nx≈ny> nz was produced.
Further, the laminated retardation plate was provided with a polyvinyl alcohol (PVA) -based pressure-sensitive adhesive layer having a thickness of 5 μm on one surface of the same polarizing layer as in Example B-1 so that the optically anisotropic layer (A) faced. And a PVA adhesive layer (thickness: 5 μm) on the other surface of the polarizing layer, and a thickness of 80 μm.
A μm TAC film was adhered. Thickness 1
A 70 μm wide viewing angle laminated polarizing plate was obtained.

(Comparative Example B-2) The same polyimide solution as in Example B-1 was coated on a polyester film, and 1
It was dried at 30 ° C. for 5 minutes, and then stretched 1.1 times at a temperature of 160 ° C. By removing the polyester film, an optically anisotropic layer (B) made of polyimide was obtained. This optically anisotropic layer (B) has a thickness of 6 μm and Re (B)
55nm, Rth (B) 240nm, Rth (B) / Re (B) 4.4
Met. Further, the optical anisotropic layer (A) was adhered to one surface of the same polarizing layer as in Example B-1 via a polyvinyl alcohol (PVA) -based pressure-sensitive adhesive layer having a thickness of 5 μm. A 80 μm-thick TAC film was adhered to the other surface via an acrylic pressure-sensitive adhesive (thickness 15 μm). Thereby, a wide viewing angle laminated polarizing plate containing no optically anisotropic layer (A) was obtained.

(Comparative Example B-3) A TAC film having a thickness of 80 μm was transversely stretched at 190 ° C. by a factor of 1.4 to give a thickness of 58 μm, Re (A) 40 nm and Rt.
An optically anisotropic layer (A) having h (A) of 46 nm and Rth (A) / Re (A) 1.2 was obtained. On the other hand, the same polyimide solution as in Example B-1 was applied onto a polyester film, dried at 130 ° C. for 5 minutes, and subjected to 1.2 times the free end longitudinal stretching at 160 ° C. to give the polyester film. An optical anisotropic layer (B) made of polyimide was formed on the top. This optically anisotropic layer (B) has a thickness of 6 μm, Re (B) of 170 nm and Rth.
(B) 200 nm and Rth (B) / Re (B) 1.2. By laminating the optical anisotropic layer (A) and the optical anisotropic layer (B) so that they face each other with an acrylic adhesive having a thickness of 15 μm, the polyester film is removed to obtain a laminated retardation plate. Got This laminated retarder has a thickness of 6
4 μm, Re 210 nm, Rth 246 nm, Rt
h / Re was 1.2 and (Rth-Re) was 36 nm. The laminated retardation plate was adhered to one surface of the same polarizing layer as in Example B-1 so that the optically anisotropic layer (A) faced through a PVA-based pressure-sensitive adhesive layer having a thickness of 5 μm, and ,
On the other surface of the polarizing layer, a PVA-based adhesive layer (thickness 5 μm
m), a TAC film having a thickness of 80 μm was adhered. Thus, a wide viewing angle laminated polarizing plate having a thickness of 189 μm was obtained.

(Comparative Example B-4) A polarizing layer was obtained in the same manner as in Example B-1.

Examples B-1 to B-8 and Comparative Example B-1
To the optically anisotropic layer (A), the optically anisotropic layer (B), and the laminated retardation plate in the wide-viewing angle laminated polarizing plate obtained in Examples B to B-3, respectively, as described above, The thickness direction retardation and the like were measured. The results are shown in Table 2 below.

[0185]

[Table 2]

Examples B-1 to B-8, Comparative Examples B-1 to B
The viewing angle characteristics of the wide viewing angle laminated polarizing plate obtained in -3 and the polarizing plate obtained in Comparative Example B-4 were evaluated. Polarizing plates were arranged on both surfaces of a VA type liquid crystal cell so that their transmission axes were orthogonal to each other, to manufacture a liquid crystal display device. The wide viewing angle laminated polarizing plate of the example was arranged so that the laminated retardation plate was on the liquid crystal cell side. Then, the viewing angle at which Co (contrast) on the display screen of the liquid crystal display device was 10 or more was measured.

The contrast was calculated by the following method. A white image and a black image are displayed on the liquid crystal display device, and the product name Ez contrast 160D (manufactured by ELDIM) is used to display the front, top, bottom, left and right of the display screen at a diagonal angle of 45 ° -225.
The Y value, the x value, and the y value of the XYZ display system in the directions of ° and diagonal 135 ° -315 ° were measured. Then, the Y value (Y _w ) in the white image and the Y value (Y _B ) in the black image
From the above, the contrast “Y _w / Y _B ” at each viewing angle was calculated. On the other hand, as Comparative Example B-1, the contrast at the viewing angle was confirmed for a liquid crystal display device in which only the polarizing plate was mounted instead of the laminated polarizing plate. Table 3 below shows the range of the viewing angle at which the contrast is 10 or more. Further, the display screen of each of the liquid crystal display devices was visually observed to evaluate whether or not the laminated retardation plate was colored. The results are shown in Table 3 below.

(Table 3) Visual angle (°) Coloring Up / down Left / right Diagonal (45 ° -225 °) Diagonal (135 ° -315 °) Example B-1 ± 80 ± 80 ± 65 ± 65 None Example B-2 ± 80 ± 80 ± 65 ± 65 None Example B-3 ± 80 ± 80 ± 60 ± 60 None Example B-4 ± 80 ± 80 ± 60 ± 60 None Example B-5 ± 80 ± 80 ± 65 ± 65 None Example B-6 ± 80 ± 80 ± 65 ± 65 None Example B-7 ± 80 ± 80 ± 60 ± 60 None Comparative Example B-1 ± 80 ± 80 ± 40 ± 40 None Comparative Example B- 2 ± 80 ± 80 ± 55 ± 55 Yes Comparative Example B-3 ± 80 ± 80 ± 40 ± 40 Yes Comparative Example B-4 ± 80 ± 80 ± 35 ± 35 None

According to the laminated polarizing plate including the laminated retardation plate of the present invention as shown in Table 2 above, as shown in Table 3 above,
A liquid crystal display device having a wider viewing angle than that of each comparative example was obtained. In Comparative Example 1, the in-plane retardation (Re) is 10 because the in-plane retardation is not sufficiently compensated by the optically anisotropic layer (A).
and the (Rth-Re) of Comparative Example B-3 was less than 50 nm, the viewing angle characteristics in the diagonal direction were inferior, and coloring was also confirmed for Comparative Example B-3. In addition, Comparative Example B-2, which is composed only of the optical anisotropic layer (B) made of polyimide, does not show the excellent viewing angle characteristics in a diagonal direction as in Example, and the optical anisotropic layer (B) alone has a thickness of Coloring was also confirmed because the directional retardation was increased. From this, it can be said that the use of the wide viewing angle laminated polarizing plate according to the present invention makes it possible to provide a high-quality liquid crystal display device which is thinner than conventional ones and which is excellent in visibility.

[0190]

As described above, the laminated retardation film of the present invention has Re of 10 nm or more and (Rth-R
Since e) is 50 nm or more, when it is applied to various image display devices, it is excellent in wide viewing angle characteristics and can be made thin, which is very useful.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an example of a laminated polarizing plate in an example of the present invention.

FIG. 2 is a sectional view showing an example of a laminated polarizing plate in another example of the present invention.

FIG. 3 is a sectional view showing an example of a laminated polarizing plate in still another embodiment of the present invention.

FIG. 4 is a sectional view showing an example of a laminated polarizing plate in still another embodiment of the present invention.

FIG. 5 is a sectional view showing an example of a laminated polarizing plate in still another example of the present invention.

FIG. 6 is a sectional view showing an example of a laminated polarizing plate according to still another embodiment of the present invention.

FIG. 7 is a cross-sectional view showing an example of a laminated polarizing plate in still another example of the present invention.

FIG. 8 is a sectional view showing an example of a laminated polarizing plate in still another example of the present invention.

[Explanation of symbols]

10, 20, 30, 40, 50, 60, 70, 80 laminated polarizing plate 11 laminated retardation plate 11a optically anisotropic layer (A) 11b optically anisotropic layer (B) 12 transparent protective layer 13 polarizing layer 14 adhesive layer 15 Adhesive layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Takashi Yamaoka             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor Naru Murakami             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor Hiroyuki Yoshimi             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. (72) Inventor Masatake Hayashi             1-2 1-2 Shimohozumi, Ibaraki City, Osaka Prefecture Nitto             Electric Works Co., Ltd. F-term (reference) 2H049 BA06 BA42 BB03 BB44 BB45                       BB51 BC03 BC22                 2H091 FA08X FA08Z FA11X FA11Z                       FA12X FA12Z FA14Z FB02                       FD06 FD15 KA02 KA10 LA11                       LA19

Claims (13)

[Claims] 1. A laminated retardation plate including at least two optically anisotropic layers, which comprises a polymer optically anisotropic layer (A).
An optically anisotropic layer (B) made of at least one non-liquid crystalline polymer selected from the group consisting of polyamide, polyimide, polyester, polyaryletherketone, polyetherketone, polyamideimide and polyesterimide, Represented in-plane retardation (Re)
Is 10 nm or more, and the difference (Rth-Re) between the thickness direction retardation (Rth) represented by the following formula and the in-plane retardation (Re) is 50 nm or more. . Re = (nx-ny) * d Rth = (nx-nz) * d In the above formula, nx, ny and nz respectively represent the refractive indices in the X-axis, Y-axis and Z-axis directions of the laminated retardation plate. , The X-axis is an axial direction showing the maximum refractive index in the plane of the laminated retardation plate, the Y-axis is an axial direction perpendicular to the X-axis in the plane, Z
The axis is a thickness direction perpendicular to the X axis and the Y axis, and
d indicates the thickness of the laminated retardation plate. 2. The laminated retardation plate according to claim 1, wherein the material for forming the optically anisotropic layer (A) is a polymer exhibiting positive birefringence. 3. The laminated retardation plate according to claim 1, wherein the laminated retardation plate satisfies the following conditions. nx>ny> nz 4. The laminated retardation plate according to claim 1, wherein the optically anisotropic layer (B) satisfies the following conditions. nx (B) = ny (B)> nz (B) In the above formula, nx (B), ny (B) and nz (B) are
The respective refractive indices in the X-axis, Y-axis, and Z-axis directions of the optically anisotropic layer (B) are shown, and the X-axis is the axis showing the maximum refractive index in the plane of the optically anisotropic layer (B). Direction, the Y-axis is an axial direction perpendicular to the X-axis in the plane, and the Z-axis is a thickness direction perpendicular to the X-axis and the Y-axis. 5. The laminated retardation plate according to claim 1, wherein the optically anisotropic layer (B) satisfies the following conditions. nx (B)> ny (B)> nz (B) In the above formula, nx (B), ny (B) and nz (B) are
The respective refractive indices in the X-axis, Y-axis, and Z-axis directions of the optically anisotropic layer (B) are shown, and the X-axis is the axis showing the maximum refractive index in the plane of the optically anisotropic layer (B). Direction, the Y-axis is an axial direction perpendicular to the X-axis in the plane, and the Z-axis is a thickness direction perpendicular to the X-axis and the Y-axis. 6. The optical anisotropic layer (A) has an in-plane retardation [Re (A)] of 20 to 300 nm represented by the following formula, and a thickness direction retardation [Rth (A) represented by the following formula. ] And the in-plane phase difference [Re
The ratio [Rth (A) / Re (A)] with (A)] is 1.0 or more.
5. The laminated retardation plate according to any one of 5 above. Re (A) = (nx (A) -ny (A)) * d (A) Rth (A) = (nx (A) -nz (A)) * d (A) In the above formula, nx (A) , Ny (A) and nz (A) are
The respective refractive indexes in the X-axis, Y-axis, and Z-axis directions in the optically anisotropic layer (A) are the axial directions in which the maximum refractive index is in the plane of the optically anisotropic layer. ,
The Y axis is an axis direction perpendicular to the X axis in the plane, the Z axis is a thickness direction perpendicular to the X axis and the Y axis, and d (A) is the optical anisotropic direction. The thickness of the layer (A) is shown. 7. The optical anisotropic layer (A) has an in-plane retardation [Re (A)] of 20 to 300 nm represented by the following formula and a thickness direction retardation [Rth (A) represented by the following formula. ] And the in-plane phase difference [Re
(A)] ratio [Rth (A) / Re (A)] is 1.0 or more, and the optical anisotropic layer (B) has an in-plane retardation represented by the following mathematical formula.
[Reth (B)] 3 nm or more, the ratio [Rth (B) / Re of the thickness direction retardation [Rth (B)] and the in-plane retardation [Re (B)] represented by the following formula
(B)] The laminated retardation plate according to claim 5 or 6, which is 1.0 or more. Re (A) = (nx (A) -ny (A)). D (A) Rth (A) = (nx (A) -nz (A)). D (A) Re (B) = (nx ( B) -ny (B)) · d (B) Rth (B) = (nx (B) -nz (B)) · d (B) In the above formula, nx (A), ny (A) and nz ( A) is
The refractive indices in the X-axis, Y-axis and Z-axis directions of the optically anisotropic layer (A) are shown respectively, and nx (B), ny (B) and n
z (B) is X in the optically anisotropic layer (B).
Axis, Y-axis and Z-axis direction of the refractive index, the X-axis is the axial direction showing the maximum refractive index in the plane of the optically anisotropic layer, the Y-axis is in the plane of the X-axis Is the axial direction perpendicular to the axis, the Z axis is the thickness direction perpendicular to the X axis and the Y axis, and d (A) is the thickness of the optical anisotropic layer (A) and d (B ) Indicates the thickness of the optically anisotropic layer (B). 8. The laminated retardation plate according to claim 1, wherein the material forming the optically anisotropic layer (A) is a thermoplastic polymer. 9. The laminated retardation plate according to claim 8, wherein the optically anisotropic layer (A) is a stretched film. 10. The laminated retardation plate according to claim 1, further comprising an adhesive layer laminated on at least one outermost layer. 11. A liquid crystal panel comprising a liquid crystal cell and an optical member, wherein the optical member is arranged on at least one surface of the liquid crystal cell, wherein the optical member is a liquid crystal panel.
10. A liquid crystal panel which is the laminated retardation plate according to any one of items 10 to 10. 12. A liquid crystal display device including a liquid crystal panel, wherein the liquid crystal panel is the liquid crystal panel according to claim 11. 13. A self-luminous display device including the laminated retardation plate according to claim 1. Description: