JP2003337225A - Optical retardation plate and circularly polarizing plate - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an optical retardation plate and a circularly polarizing plate which can easily and stably be manufactured. <P>SOLUTION: The optical retardation plate formed by laminating a first optically anisotropic layer with π retardation composed of a homogeneously aligned rod-shaped liquid crystalline compound and a second optically anisotropic layer with π/2 retardation, is characterized by making the rod-shaped liquid crystalline compound in the first optically anisotropic layer aligned in a direction practically orthogonal to a rubbing axis with a liquid crystal alignment layer. Also, the circularly polarizing plate has the optical retardation plate on which further a polarizing film is equipped. <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 retardation plate effective as a λ / 4 plate used for a reflection type liquid crystal display device, a pickup for writing an optical disc, or an antireflection film, and a circular polarizing plate using the same. And the manufacturing methods thereof. In particular, the present invention relates to a retardation plate having an elongated transparent support and an optically anisotropic layer having a multilayer structure of rod-shaped liquid crystals formed by coating on the support, and a polarizing plate and a roll-to-roll method using the retardation plate. TECHNICAL FIELD The present invention relates to a circularly polarizing plate that can be laminated and manufactured, and a manufacturing method thereof.

[0002]

2. Description of the Related Art The .lambda. / 4 plate has numerous uses and is already in actual use. However, even if it is called a λ / 4 plate, most of them achieve λ / 4 at a certain specific wavelength. JP-A-10-68816 and JP-A-10-90521 disclose a retardation plate obtained by laminating two polymer films having optical anisotropy. The retardation plate described in JP-A-10-68816 is a quarter-wave plate in which the phase difference of birefringent light is ¼ wavelength and a half-wave plate in which the phase difference of birefringent light is ½ wavelength. The wave plate and the wave plate are attached in a state where their optical axes intersect. The retardation plate described in JP-A-10-90521 has a retardation value of 160 to 320 n.
At least two retardation plates of m are laminated so that their slow axes are at angles that are neither parallel nor orthogonal to each other. The retardation film described in any of the publications is specifically composed of a laminate of two polymer films. Both publications explain that this makes it possible to achieve λ / 4 in a wide wavelength range. However, in the production of the retardation film described in JP-A-10-68816 and JP-A-10-90521, in order to adjust the optical orientation (optical axis or slow axis) of two polymer films, two It is necessary to cut various kinds of polymer films at a predetermined angle and bond the obtained chips. If the phase difference plate is manufactured by laminating chips, the processing is complicated, quality deterioration easily occurs due to axial misalignment, yield decreases, cost increases, and deterioration due to contamination easily occurs. Further, it is difficult to strictly control the retardation value of the polymer film. On the other hand, a method for providing a broadband λ / 4 plate more simply by providing at least two optically anisotropic layers containing a liquid crystal compound is disclosed in Japanese Patent Laid-Open No. 2001-4837.
No. 2001-21720, No. 2000-
No. 206331 is disclosed. Particularly, the method of Japanese Patent Laid-Open No. 2001-4837 in which the same liquid crystal molecules can be used is attractive from the viewpoint of manufacturing cost.

[0003]

By the way, when laminating optically anisotropic layers containing a liquid crystalline compound to produce a retardation plate, it is important to control the orientation of the liquid crystalline compound.
For example, the rod-shaped liquid crystalline compound can form an optically anisotropic layer by horizontally aligning it with respect to the substrate. When a layer containing a rod-shaped liquid crystalline compound is formed on a rubbing-treated liquid crystal alignment film, the rod-shaped liquid crystalline compound is normally horizontally aligned with its long axis aligned with the rubbing direction. However, as a result of diligent study by the present inventor
When a normal liquid crystal alignment film in which liquid crystal molecules are aligned in a direction coinciding with the rubbing axis is used when forming the liquid crystal molecular layer disclosed in JP-A-01-4837, the accuracy of liquid crystal alignment is reduced. Turned out to be. Further, it was found that many optical defects occur depending on the kind of rod-shaped liquid crystal compound or the composition of the liquid crystal composition.

The present invention has been made in view of the above problems, and it functions as a retardation plate in a wide band (visible light wavelength range), can be thinned, and can be manufactured easily and stably. An object is to provide a retardation plate. Another object of the present invention is to provide a circularly polarizing plate that functions as a circularly polarizing plate in a wide band (visible light wavelength range), can be thinned, and can be manufactured easily and stably. Further, the present invention provides a retardation plate and a circularly polarizing plate which function well in a wide band (visible light wavelength region) and can be thinned, by stably controlling the alignment of liquid crystal compound molecules. An object is to provide a method for manufacturing a retardation plate and a circularly polarizing plate that can be easily and stably manufactured. Another object of the present invention is to provide a novel liquid crystal alignment control technology for rod-shaped liquid crystals.

[0005]

Means for Solving the Problems The inventors of the present invention have made earnest studies on a retardation plate composed of a laminate of a λ / 4 liquid crystal layer and a λ / 2 liquid crystal layer, and as a result, formed a λ / 2 liquid crystal layer. Therefore, it is necessary to horizontally align the rod-shaped liquid crystal compound with a large azimuth angle with respect to the longitudinal direction of the transparent support. However, when a liquid crystal alignment film for aligning liquid crystal molecules along the rubbing axis is used, It was found that the alignment control force of the liquid crystal alignment film does not stabilize the alignment of liquid crystal molecules. Further, it is necessary that the rod-shaped liquid crystals of the λ / 2 liquid crystal layer and the λ / 4 liquid crystal layer are horizontally aligned with high accuracy. However, the liquid crystal molecules are inclined and aligned in various directions near the free interface, so that the latter optical It was found that there were defects. Based on these findings, further intensive studies have been conducted, and the present invention has been completed.

Means for solving the above problems are as follows. (1) A long transparent support, and a rod-like liquid crystal compound horizontally aligned above the transparent support and having a measurement wavelength of 550 n
A first optical anisotropic layer having a phase difference of substantially π at m, and a second optical layer containing a horizontally aligned rod-like liquid crystal compound and having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm. A retardation plate including an anisotropic layer and a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the first optically anisotropic layer. The angle between the in-plane slow axis of the first optically anisotropic layer and the longitudinal direction of the transparent support is substantially 75 °, and the in-plane of the second optically anisotropic layer is The angle between the slow axis and the longitudinal direction of the transparent support is substantially 15 °, and the in-plane slow axis of the second optically anisotropic layer and the first optically anisotropic layer Horizontal orientation of the rod-like liquid crystalline compound contained in the first optically anisotropic layer, which has an angle of substantially 60 ° with the in-plane slow axis. A retardation plate whose azimuth angle is substantially perpendicular to the rubbing axis of the first liquid crystal alignment film. (2) A long transparent support, a rod-like liquid crystal compound horizontally aligned above the long transparent support, and a measurement wavelength of 550 n
A first optical anisotropic layer having a phase difference of substantially π at m, and a second optical layer containing a horizontally aligned rod-like liquid crystal compound and having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm. An anisotropic layer, a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the first optically anisotropic layer, and the second optical anisotropic film A retardation plate including a second liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the organic layer, wherein the in-plane of the first optically anisotropic layer is provided. Has an angle of substantially 75 ° with the longitudinal direction of the transparent support, and the in-plane slow axis of the second optically anisotropic layer and the longitudinal direction of the transparent support are The angle is substantially 15 °, the in-plane slow axis of the second optically anisotropic layer and the first optically anisotropic layer. Has an angle of substantially 60 ° with the in-plane slow axis, and the angle between the rubbing axis of the first liquid crystal alignment film and the longitudinal direction of the transparent support is substantially −15.
And the angle between the rubbing axis of the second liquid crystal alignment film and the longitudinal direction of the transparent support is substantially 15 °.
Is a retarder.

(3) The first liquid crystal alignment film is represented by at least one repeating unit represented by any one of the following general formulas (I) to (III) and the following general formula (IV). (1) which contains at least one copolymerized polymer containing at least one repeating unit.
Alternatively, the retardation plate according to (2).

[0008]

[Chemical 1]

In the formula, R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M represents a proton, an alkali metal ion or an ammonium ion; L ⁰ and L ¹ are each independently —O—, —S—, —CO—, —NR ⁴ —, —SO ₂
-, An alkylene group, an alkenylene group, an arylene group and a divalent linking group selected from the group consisting of them; R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁰ represents Represents a substituted or unsubstituted hydrocarbon group having 10 to 100 carbon atoms and containing at least two aromatic rings or aromatic heterocycles; Cy represents a condensed aromatic hydrocarbon group or a condensed aromatic heterocyclic group; Represents; Q represents a polymerizable group; m, n ¹ , n ² and p represent mol% of each repeating unit, m is 10 to 99 mol%, and n ¹
And n ² are each 1 to 90 mol%, and p is 0.1 to
It is 20 mol%.

(4) The first optically anisotropic layer contains at least one horizontal alignment promoter composed of a compound represented by the following general formula (V), and has a polar angle direction of the rod-shaped liquid crystal compound. The retardation plate according to any one of (1) to (3) above, wherein the orientation angle is substantially less than 10 °. Formula ^{(V) (Hb-L 2} -) n B 1 In formula (V), Hb is an aliphatic substituted oligosiloxanoxy of carbon atoms is an aliphatic group or a number of carbon atoms of 6 to 40 6 to 40 Represents a xy group; L ² is —O—, —S—, —C
^{O -, - NR 5 -,} - SO 2 -, an alkylene group, an alkenylene group, a divalent linking group selected from arylene groups and combinations thereof; R ⁵ is a hydrogen atom or a carbon atoms 1 ~ 6 alkyl group; n is 2-12
B ¹ represents an n-valent group containing at least three cyclic structures.

(5) The rod-shaped liquid crystal compound contained in the first optical anisotropic layer or the second optical anisotropic layer is at least one of rod-shaped liquid crystal compounds represented by the following general formula (VI). The retardation plate according to any one of (1) to (4) above. Formula ^{(VI) Q 11 -L 11 -Cy} 11 -L 12 - (Cy 12 -L 13) n -Cy
¹³ -L ¹⁴ -Q ^{12 In the} formula, Q ¹¹ and Q ¹² each independently represent a polymerizable group; L ¹¹ and L ¹⁴ each independently represent a divalent linking group; L ¹² and L ¹³ each independently Represents a single bond or a divalent linking group; Cy ¹¹ , Cy ¹² and Cy ¹³ each independently represent a divalent cyclic group; and n represents 0, 1 or 2.

(6) A first liquid crystal alignment film having a rubbing axis whose angle to the longitudinal direction of the transparent support is substantially −15 ° is formed above the elongated transparent support. 1. The step of forming a liquid crystal alignment film, wherein a layer containing a rod-shaped liquid crystal compound is formed on the first liquid crystal alignment film, and the rod-shaped liquid crystal compound is substantially aligned with the rubbing axis of the first liquid crystal alignment film. Which are horizontally aligned with azimuth angles that are orthogonal to each other and have a phase difference of substantially π at a measurement wavelength of 550 nm
And a rubbing shaft having an angle of substantially 15 ° with the longitudinal direction of the transparent support above the transparent support. A second liquid crystal alignment film forming step of forming a second liquid crystal alignment film having the same; forming a layer containing a rod-shaped liquid crystal compound on the second liquid crystal alignment film; A second optically anisotropic layer in which the liquid crystal alignment film of No. 2 is horizontally aligned at an azimuth angle substantially parallel to the rubbing axis to form a second optically anisotropic layer having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm. The method for producing a retardation plate, which comprises the step of forming an optically anisotropic layer. (7) The first liquid crystal alignment film forming step and the first
The method for producing a retardation plate according to (6), wherein after the step of forming the optically anisotropic layer, the step of forming the second liquid crystal alignment film and the step of forming the second optically anisotropic layer are performed. (8) The second liquid crystal alignment film forming step and the second
The method for producing a retardation plate according to (7), wherein after the step of forming the optically anisotropic layer, the step of forming the first liquid crystal alignment film and the step of forming the first optically anisotropic layer are performed.

(9) Substantially -1 with an arbitrary in-plane axis a1
A step of forming a first liquid crystal alignment film having a rubbing axis in a direction forming 5 °; forming a layer containing a rod-shaped liquid crystal compound on the first liquid crystal alignment film; It is substantially orthogonal to the rubbing axis of the first liquid crystal alignment film and substantially 7 with respect to the in-plane axis a1.
A first optically anisotropic layer forming step of forming a first optically anisotropic layer having a phase difference of substantially π at a measurement wavelength of 550 nm by horizontally orienting in the direction of 5 °, and an arbitrary in-plane axis a2
A second step of forming a second liquid crystal alignment film having a rubbing axis whose angle is substantially 15 °, and forming a layer containing a rod-like liquid crystalline compound on the second liquid crystal alignment film. At the same time, the rod-shaped liquid crystal compound is horizontally aligned in a direction substantially parallel to the rubbing axis of the second liquid crystal alignment film, and the phase difference at a measurement wavelength of 550 nm is substantially π.
The second optically anisotropic layer forming step of forming a second optically anisotropic layer of / 2 and the first optically anisotropic layer and the second optically anisotropic layer are respectively performed. In-plane axes a1 and a
And 2 are substantially parallel to each other and the latitudinal axis of the first optically anisotropic layer and the latitudinal axis of the second optically anisotropic layer are substantially 60 °. A method of manufacturing a retardation plate including. In the production method of (9), the first and second optically anisotropic layers may be laminated after being peeled from the respective liquid crystal alignment films, or may be laminated without being peeled. .
Further, the first optically anisotropic layer forming step or the second optically anisotropic layer forming step may also serve as the laminating step.

(10) The retardation plate according to any one of (1) to (5) and below the transparent support, the polarization axis is substantially orthogonal to the longitudinal direction of the transparent support. A circularly polarizing plate including a polarizing film. (11) A first optically anisotropic layer containing a horizontally aligned rod-shaped liquid crystalline compound and having a phase difference of substantially π at a measurement wavelength of 550 nm, and a horizontally aligned rod-shaped liquid crystalline compound at a measurement wavelength of 550 nm. A second optically anisotropic layer having a retardation of substantially π / 2;
A circularly polarizing plate comprising a polarizing film and a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the optically anisotropic layer of The angle between the in-plane slow axis of the optically anisotropic layer and the absorption axis of the polarizing film is substantially 75 °, and the in-plane slow axis of the second optically anisotropic layer and the polarized light are The angle with the absorption axis of the membrane is substantially 1
5 °, and the angle between the in-plane slow axis of the second optically anisotropic layer and the in-plane slow axis of the first optically anisotropic layer is substantially 60 °, A circularly polarizing plate in which an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound included in the first optically anisotropic layer is substantially perpendicular to a rubbing axis of the first liquid crystal alignment film. (12) A first optically anisotropic layer containing a horizontally aligned rod-shaped liquid crystalline compound and having a phase difference of substantially π at a measurement wavelength of 550 nm, and a horizontally aligned rod-shaped liquid crystalline compound at a measurement wavelength of 550 nm. A second optically anisotropic layer having a retardation of substantially π / 2;
A first liquid crystal alignment film having a rubbing axis that determines the azimuth angle of horizontal alignment of the rod-shaped liquid crystalline compound in the optically anisotropic layer, and the rod-shaped liquid crystalline compound in the second optically anisotropic layer. A second with a rubbing axis that determines the azimuth of the horizontal orientation of the
And a polarizing film, wherein the in-plane slow axis of the first optically anisotropic layer and the absorption axis of the polarizing film have an angle of substantially 75 °. And the angle between the in-plane slow axis of the second optically anisotropic layer and the absorption axis of the polarizing film is substantially 15 °, and the in-plane of the second optically anisotropic layer is Has an angle of substantially 60 ° with the in-plane slow axis of the first optically anisotropic layer, and the rubbing axis of the first liquid crystal alignment film and the absorption of the polarizing film. The angle with the axis is substantially −15 °, and the angle between the rubbing axis of the second liquid crystal alignment film and the absorption axis of the polarizing film is substantially 1.
A circularly polarizing plate having an angle of 5 °. (13) A first liquid crystal forming, above a long transparent support, a first liquid crystal alignment film having a rubbing axis whose angle to the longitudinal direction of the transparent support is substantially −15 °. An alignment film forming step, forming a layer containing a rod-shaped liquid crystal compound on the first liquid crystal alignment film, and making the rod-shaped liquid crystal compound substantially orthogonal to the rubbing axis of the first liquid crystal alignment film. Horizontally oriented at an azimuth angle of
a first optically anisotropic layer forming step of forming a first optically anisotropic layer having a phase difference of substantially π in nm; and a longitudinal direction of the transparent support above the transparent support. A second liquid crystal alignment film forming step of forming a second liquid crystal alignment film having a rubbing axis whose angle is substantially 15 °, and a layer containing a rod-shaped liquid crystal compound on the second liquid crystal alignment film. And the rod-shaped liquid crystal compound is horizontally aligned at an azimuth angle substantially parallel to the rubbing axis of the second liquid crystal alignment film, and the phase difference at a measurement wavelength of 550 nm is substantially π / 2. Second forming the second optically anisotropic layer
Of the optically anisotropic layer forming step, and below the transparent support,
A polarizing film forming step of forming a polarizing film having a polarizing axis in a direction substantially perpendicular to the longitudinal direction of the transparent support by substantially matching the longitudinal direction of the transparent support with the absorption axis. Manufacturing method of circularly polarizing plate. (14) After the first liquid crystal alignment film forming step and the first optical anisotropic layer forming step, the second liquid crystal aligning film forming step and the second optical anisotropic layer forming step are performed. The method for producing a circularly polarizing plate according to (13). (15) After the second liquid crystal alignment film forming step and the second optical anisotropic layer forming step, the first liquid crystal aligning film forming step and the first optical anisotropic layer forming step are performed. The method for producing a circularly polarizing plate according to (13).

(16) Substantially with an arbitrary in-plane axis a1
A step of forming a first liquid crystal alignment film having a rubbing axis in a direction forming an angle of 15 °, a layer containing a rod-shaped liquid crystal compound is formed on the first liquid crystal alignment film, and the rod-shaped liquid crystal compound is added to the layer. The first liquid crystal alignment film is horizontally aligned in a direction substantially orthogonal to the rubbing axis and substantially 75 ° with respect to the in-plane axis a1, and a phase difference at a measurement wavelength of 550 nm is substantially π. The angle between the step of forming a certain first optically anisotropic layer and an arbitrary in-plane axis a2 is substantially 1.
Forming a second liquid crystal alignment film having a rubbing axis of 5 °; forming a layer containing a rod-shaped liquid crystal compound on the second liquid crystal alignment film; A step of horizontally aligning the second liquid crystal alignment film in a direction substantially parallel to the rubbing axis to form a second optically anisotropic layer having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm; The first optically anisotropic layer and the second optically anisotropic layer have in-plane axes a1 and a2 substantially parallel to each other and a slow axis of the first optically anisotropic layer. Laminating the second optically anisotropic layer with an angle of 60 ° with respect to the slow axis, and laminating the polarizing film having a polarization axis in a direction substantially perpendicular to the in-plane axes a1 and a2. A method of manufacturing a circularly polarizing plate including a step of forming.

In the present specification, "substantially 15 °",
"Substantially -15 °", "Substantially 75 °", "Substantially 60 °", "Substantially parallel" and "Substantially orthogonal"
Means that the angle is strictly within ± 5 °. The error from the strict angle is preferably less than 4 °, more preferably less than 3 °. Further, in the present specification, the “slow axis” means the direction in which the refractive index becomes maximum, and the “rubbing axis” means the direction of rubbing treatment. Further, in the present specification, "above the transparent support"
And "below the transparent support" merely indicates the direction with the transparent support as the center, and should not be construed as limiting the mode in which the retardation plate and the circularly polarizing plate of the present invention are used. I won't.

[0017]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below.
The retardation plate of the present invention contains a transparent support and a horizontally aligned rod-shaped liquid crystal compound above the support, and has a measurement wavelength of 55.
It includes a first optically anisotropic layer having a phase difference of substantially π at 0 nm and a horizontally aligned rod-like liquid crystal compound, and has a phase difference of substantially π / 2 at a measurement wavelength of 550 nm.
The second optically anisotropic layer is a laminated structure. Further, the circularly polarizing plate of the present invention has a structure in which a polarizing film is provided below the transparent support of the retardation plate of the present invention. In the retardation plate and the circularly polarizing plate of the present invention, the stacking order of the first optically anisotropic layer and the second optically anisotropic layer is not particularly limited, and which is closer to the transparent support. It may be.

Each of the first and second optically anisotropic layers has only to achieve a phase difference of substantially π or π / 2 at a specific wavelength. However, it is preferable that the phase difference π or π / 2 is achieved at 550 nm which is a wavelength approximately in the middle of the visible region. Specific wavelength (λ)
To achieve the phase difference π at
The retardation value of the optically anisotropic layer measured in 1. may be adjusted to λ / 2. In order to achieve the phase difference π / 2 at the specific wavelength (λ), the retardation value of the optically anisotropic layer measured at the specific wavelength (λ) may be adjusted to λ / 4. That is, the first optically anisotropic layer has a retardation value of 240 to 240 measured at a wavelength of 550 nm.
290 nm is preferable, and 250 to 280 nm
Is more preferable. The second optically anisotropic layer has a retardation value of 1 measured at a wavelength of 550 nm.
It is preferably 10 to 145 nm, and 120 to 14
More preferably, it is 0 nm.

The retardation value means an in-plane retardation value with respect to light incident in the direction normal to the optically anisotropic layer. Specifically, it is a value defined by the following formula. Retardation value (Re) = (nx−ny) × d, where nx and ny are main in-plane refractive indices of the optically anisotropic layer or the birefringent film, and d is the optically anisotropic layer or It is the thickness (nm) of the birefringence film. Japanese Patent Laid-Open No. 10-68816 describes a Poincare sphere for achieving circularly polarized light.

FIG. 1 is a schematic diagram showing the basic construction of the retardation plate of the present invention. As shown in FIG. 1, in addition to the elongated transparent support (S) and the first optically anisotropic layer (A), the basic retardation plate has a second optically anisotropic layer ( B). The retardation of the first optically anisotropic layer (A) is substantially π.
And the retardation of the second optically anisotropic layer (B) is substantially π / 2. The angle (α) between the longitudinal direction (s) of the transparent support (S) and the in-plane slow axis (a) of the first optically anisotropic layer (A) is 75 °. The rubbing axis (ra) and the slow axis (a) of the liquid crystal alignment film of the first optically anisotropic layer (A) are orthogonal to each other. The angle (β) between the in-plane slow axis (b) of the second optically anisotropic layer (B) and the longitudinal direction (s) of the transparent support (S) is 15 °. The rubbing axis (rb) and the slow axis (b) of the liquid crystal alignment film of the second optically anisotropic layer (B) are aligned with each other. The angle (γ between the in-plane slow axis (b) of the second optically anisotropic layer (B) and the in-plane slow axis (a) of the first optically anisotropic layer (A). ) Is 60 °. The first optically anisotropic layer (A) and the second optically anisotropic layer (B) shown in FIG. 1 are rod-shaped liquid crystalline molecules (c1 and c2), respectively.
including. The rod-shaped liquid crystal molecules (c1 and c2) are horizontally aligned. Rod-like liquid crystalline molecules (c1 and c
The major axis direction of 2) corresponds to the in-plane slow axis (a and b) of the optically anisotropic layer (A and B).

FIG. 2 is a schematic view showing a typical constitution of the circularly polarizing plate of the present invention. The circularly polarizing plate shown in FIG. 2 is further polarized in addition to the transparent support (S), the first optically anisotropic layer (A) and the second optically anisotropic layer (B) shown in FIG. It has a membrane (P). As in FIG. 1, the angle (α) between the longitudinal direction (s) of the transparent support (S) and the in-plane slow axis (a) of the first optically anisotropic layer (A) was 75 °. Yes, the in-plane slow axis (f) of the second optically anisotropic layer (B) and the transparent support (S)
The angle (β) with respect to the longitudinal direction (s) is 15 °, and the in-plane slow axis (b) of the second optically anisotropic layer (B) and the first optically anisotropic layer The angle (γ) with the in-plane slow axis (a) of (A) is 60 °. Further, the polarization axis (p) of the polarizing film (P) and the longitudinal direction (s) of the transparent support (S) are orthogonal to each other. The first optically anisotropic layer (A) and the second optically anisotropic layer (B) shown in FIG. 2 also contain rod-like liquid crystalline molecules (c1 and c2), respectively. The rod-shaped liquid crystal molecules (c1 and c2) are horizontally aligned. The long axis direction of the rod-like liquid crystal molecules (c1 and c2) corresponds to the in-plane slow axis (a and b) of the optically anisotropic layer (A and B).

Materials used for manufacturing the retardation plate of the present invention and manufacturing examples thereof will be described in detail below.
In the following description, for convenience, a method of manufacturing a retardation plate having a structure in which first and second optically anisotropic layers are sequentially laminated on a transparent support will be described. The order of laminating the optically anisotropic layers may be reversed.

In the retardation plate of the present invention, first, above the transparent support, the first liquid crystal alignment which determines the azimuth angle of the horizontal alignment of the rod-shaped liquid crystalline compound contained in the first optically anisotropic layer is provided. Form a film. In the present invention, the rod-like liquid crystalline compound in the first optically anisotropic layer is added to the transparent support in the longitudinal direction.
In order to perform horizontal alignment in a direction of substantially 75 °, a rubbing-treated liquid crystal alignment film is used, and the rod-shaped liquid crystal compound is horizontally aligned in a direction substantially orthogonal to the rubbing axis of the liquid crystal alignment film. It is characterized by When the optical axis of the rod-shaped liquid crystalline compound is oriented at an angle larger than 45 ° with respect to the long axis direction of the transparent support, the liquid crystal is such that the optical axes of the rod-shaped liquid crystalline molecules are aligned in the direction orthogonal to the rubbing direction. Stable alignment can be achieved by using an alignment film (hereinafter referred to as an orthogonal liquid crystal alignment film).

For example, the surface of a long transparent support is coated with a solution of a polymer as a material for an orthogonal liquid crystal alignment film, which will be described later, and dried to form a film, which is then rubbed to obtain an orthogonal liquid crystal. An alignment film can be formed. The rubbing treatment can be carried out by rubbing the surface of the film with paper or cloth in a certain direction several times. In the present invention, the rubbing treatment can be performed in a direction in which the angle with the longitudinal direction of the transparent support is substantially -15 °. That is, the angle between the rubbing axis and the longitudinal direction of the transparent support is substantially -1.
The rubbing treatment can be performed so that the angle becomes 5 °. On the formed orthogonal liquid crystal alignment film, a coating liquid containing a rod-shaped liquid crystalline compound is applied to orient the rod-shaped liquid crystalline compound,
The liquid crystal molecules are aligned in a direction forming 90 ° with respect to the rubbing axis of the orthogonal liquid crystal alignment film. That is, the rod-shaped liquid crystal compound is 75 ° with respect to the longitudinal direction of the transparent support.
It is possible to form the first optically anisotropic layer which is oriented in the direction of and has a phase difference of π.

The thickness of the orthogonal liquid crystal alignment film is 0.01 to.
The thickness is preferably 5 μm, more preferably 0.05 to 1 μm. In addition, after forming a first liquid crystal alignment film (orthogonal liquid crystal alignment film) on the temporary support and further orienting the liquid crystal compound of the first optically anisotropic layer, the first liquid crystal layer is transparently supported. It may be transferred onto the body. The liquid crystal compound fixed in the alignment state can maintain the alignment state without the liquid crystal alignment film.

The first liquid crystal alignment film is an orthogonal liquid crystal alignment in which the rod-shaped liquid crystal compound in the first optically anisotropic layer is horizontally aligned and aligned in a direction substantially orthogonal to the rubbing axis. It is a film. The orthogonal liquid crystal alignment film is described in Japanese Patent Application No. 2000-246279 and 2000.
No. 174829, No. 2001-64626 and No. 2001-97169, the materials are described and can be applied to the present invention. Among them, an orthogonal liquid crystal alignment film composed of a copolymer containing a repeating unit represented by the following general formula (I) and (II) or (III) and a repeating unit represented by the following general formula (IV) is preferable.

[0027]

[Chemical 2]

In the formula, R ^{1 to} R ³ each independently represent a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms; M represents a proton, an alkali metal ion or an ammonium ion; L ⁰ and L ¹ are each independently —O—, —S—, —CO—, —NR ⁴ —, —SO ₂
-, An alkylene group, an alkenylene group, an arylene group and a divalent linking group selected from the group consisting of them; R ⁴ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; R ⁰ represents Represents a substituted or unsubstituted hydrocarbon group having 10 to 100 carbon atoms and containing at least two aromatic rings or aromatic heterocycles; Cy represents a condensed aromatic hydrocarbon group or a condensed aromatic heterocyclic group; Represents; Q represents a polymerizable group; m, n ¹ , n ² and p represent mol% of each repeating unit, m is 10 to 99 mol%, and n ¹
And n ² are each 1 to 90 mol%, and p is 0.1 to
It is 20 mol%.

The general formulas (I) to (III) will be described in detail below. In the above formula (I), R ¹ represents a hydrogen atom, a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ¹ is a hydrogen atom or has 1 carbon atom
Is preferably an alkyl group of 6 to 6, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom or a methyl group. R ¹
Is a hydrogen atom, it is an acrylic acid copolymer, and R ¹
When is methyl, it is a methacrylic acid copolymer. In the above formula (I), M represents a proton, an alkali metal (eg, Na, K) ion, or an ammonium ion. Ammonium ions are organic groups (eg methyl groups)
May be substituted (first-class to fourth-class). Examples of ammonium ions are ⁺ NH ₄ , ⁺ NH ₃ CH ₃ , ⁺ NH
^{_{2 (CH 3) 2, +}} NH (CH 3) 3 and ⁺ N (CH _{3) 4} are included.

Since COOM in the above formula (I) is a hydrophilic group, the acrylic acid-based copolymer exhibits water solubility. Therefore, the liquid crystal alignment film can be formed using the aqueous solvent. In the formula (I), m is a mol% of the repeating unit and represents 10 to 99 mol%. m is preferably 10 to 95 mol%, and more preferably 25 to 90 mol%.

In the above formula (II), R ² is a hydrogen atom,
It represents a halogen atom or an alkyl group having 1 to 6 carbon atoms. R ² is preferably a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, more preferably a hydrogen atom, a methyl group or an ethyl group, and most preferably a hydrogen atom or a methyl group. The general formula (I
In I), L ⁰ is —O—, —S—, —CO—, —NR
⁴ -, - SO ₂ -, an alkylene group, an alkenylene group, an arylene group and a divalent linking group selected from the group consisting of, among ^{others, -CO-L 2 - (-} CO-
There attached to the backbone, -L ² - is -O -, - CO -, - NR 4
Represents a divalent linking group selected from the group consisting of-, an alkylene group, and a combination thereof. L
⁰ is -CO-O-, -CO-NH-, -CO-
O-alkylene group-, -CO-O-alkylene group-O-
Alternatively, it is preferably -CO-O-alkylene group -CO-O-, and particularly preferably -CO-O- or -CO-NH-. The alkylene group may have a branched or cyclic structure. The alkylene group has preferably 1 to 30 carbon atoms, more preferably 1 to 15 carbon atoms, and most preferably 1 to 12 carbon atoms.

In the above formula (II), R ⁰ represents a substituted or unsubstituted hydrocarbon group having 10 to 100 carbon atoms and containing at least two aromatic rings or aromatic heterocycles. The ring or the aromatic heterocycle may have a substituent. The aromatic ring or aromatic heterocycle is preferably an aromatic ring, and is preferably an aromatic ring having 6 to 18 ring-constituting carbon atoms. Examples of the aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and a naphthacene ring. Examples of the aromatic heterocycle include a pyridine ring and a pyrimidine ring. A benzene ring or a naphthalene ring is preferable, and a benzene ring is most preferable. The substituent that the aromatic ring or aromatic heterocycle may have includes a halogen atom, carboxyl, cyano, nitro, carbamoyl, sulfamoyl, alkyl group, cycloalkyl group, alkoxy group, alkylthio group, acyl group. , An acyloxy group, an alkyl-substituted carbamoyl group, an alkyl-substituted sulfamoyl group, an amide group, a sulfonamide group and an alkylsulfonyl group.

In the above formula (II), the groups connecting the plurality of aromatic rings are each independently an ethynylene group, a single bond, -CO-, -O-CO-, -CO-O-,
-Alkylene group -O-, -CO-NH-, -O-CO-
O -, - NHSO ₂ - or -NH-CO-O-a. At least one is preferably a single bond or an ethynylene group. In the formula (II), n ¹ is the mol% of the repeating unit and represents 1 to 90 mol%. n ¹ is preferably 5 to 80 mol%, more preferably 10 to 70 mol%. Below, the example of the repeating unit which has a hydrocarbon containing two, three, or four aromatic rings or aromatic heterocycles in the side chain is shown.

[0034]

[Chemical 3]

[0035]

[Chemical 4]

[0036]

[Chemical 5]

[0037]

[Chemical 6]

[0038]

[Chemical 7]

[0039]

[Chemical 8]

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Chemical 11]

[0043]

[Chemical 12]

[0044]

[Chemical 13]

[0045]

[Chemical 14]

[0046]

[Chemical 15]

[0047]

[Chemical 16]

[0048]

[Chemical 17]

[0049]

[Chemical 18]

[0050]

[Chemical 19]

[0051]

[Chemical 20]

[0052]

[Chemical 21]

[0053]

[Chemical formula 22]

[0054]

[Chemical formula 23]

[0055]

[Chemical formula 24]

[0056]

[Chemical 25]

[0057]

[Chemical formula 26]

[0058]

[Chemical 27]

[0059]

[Chemical 28]

[0060]

[Chemical 29]

[0061]

[Chemical 30]

[0062]

[Chemical 31]

The following is an example of an acrylic acid type copolymer containing a repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in the side chain. AA is a repeating unit derived from acrylic acid, and MA
Is a repeating unit derived from methacrylic acid. The proportion of repeating units is mol%.

[0064] _{PA301 :-( AA) 60 - (VI} -1) 40 - PA302 :-( AA) 70 - (VI-2) 30 - PA303 :-( AA) 60 - (VI-5) 40 - PA304: _{- (AA) 65 - (VI} -9) 55 - PA305 :-( AA) 70 - (VI-11) 30 - PA306 :-( AA) 80 - (VI-15) 20 - PA307 :-( AA) 70 _{- (VI-15) 30 -} PA308 :-( AA) 60 - (VI-15) 40 - PA309 :-( AA) 70 - (VI-16) 30 - PA310 :-( AA) 60 - (VI-16 _{) 40 - PA311 :-( AA) 50} - (VI-16) 50 - PA312 :-( AA) 70 - (VI-18) 30 - PA313 :-( AA) 60 - (VI-18) 40 - PA314: _{- (AA) 50 - (VI} -18) 50 - PA315 :-( AA) 60 - (VI-23) 40 - PA316: _{- (AA) 60 - (VI} -25) 40 - PA317 :-( AA) 60 - (VI-32) 40 - PA318 :-( AA) 60 - (VI-35) 40 - PA319 :-( AA) 60 _{- (VI-37) 40 -} PA320 :-( AA) 60 - (VI-45) 40 - PA321 :-( AA) 60 - (VI-55) 40 -

[0065] _{PA322 :-( MA) 60 - (VI} -1) 40 - PA323 :-( MA) 70 - (VI-2) 30 - PA324 :-( MA) 60 - (VI-5) 40 - PA325: _{- (MA) 65 - (VI} -9) 35 - PA326 :-( MA) 70 - (VI-11) 30 - PA327 :-( MA) 80 - (VI-15) 20 - PA328 :-( MA) 70 _{- (VI-15) 30 -} PA329 :-( MA) 60 - (VI-15) 40 - PA330 :-( MA) 70 - (VI-16) 30 - PA331 :-( MA) 60 - (VI-16 _{) 40 - PA332 :-( MA) 50} - (VI-16) 50 - PA333 :-( MA) 70 - (VI-18) 30 - PA334 :-( MA) 60 - (VI-18) 40 - PA335: _{- (MA) 50 - (VI} -18) 50 - PA336 :-( MA) 60 - (VI-23) 40 - PA337: _{- (MA) 60 - (VI} -25) 40 - PA338 :-( MA) 60 - (VI-32) 40 - PA339 :-( MA) 60 - (VI-35) 40 - PA340 :-( MA) 60 _{- (VI-37) 40 -} PA341 :-( MA) 60 - (VI-45) 40 - PA342 :-( MA) 60 - (VI-55) 40 -

The repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles in its side chain preferably has a tolan structure. less than,
An example of a repeating unit having a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles containing a tolan structure in a side chain is shown.

[0067]

[Chemical 32]

[0068]

[Chemical 33]

[0069]

[Chemical 34]

[0070]

[Chemical 35]

[0071]

[Chemical 36]

[0072]

[Chemical 37]

[0073]

[Chemical 38]

[0074]

[Chemical Formula 39]

[0075]

[Chemical 40]

[0076]

[Chemical 41]

[0077]

[Chemical 42]

[0078]

[Chemical 43]

[0079]

[Chemical 44]

[0080]

[Chemical formula 45]

[0081]

[Chemical formula 46]

[0082]

[Chemical 47]

[0083]

[Chemical 48]

[0084]

[Chemical 49]

[0085]

[Chemical 50]

[0086]

[Chemical 51]

[0087]

[Chemical 52]

The following is an example of an acrylic acid-based copolymer containing a repeating unit having a side chain of a hydrocarbon group containing two, three or four aromatic rings or aromatic heterocycles containing a tolan structure. . AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. EA and ClA are repeating units represented by the following formula (M is the same definition as M in formula (I)). The proportion of repeating units is mol%.

[0089]

[Chemical 53]

[0090] _{PA401 :-( AA) 60 - (VI} -101) 40 - PA402 :-( AA) 70 - (VI-101) 30 - PA403 :-( AA) 60 - (VI-102) 40 - PA404: _{- (AA) 65 - (VI} -107) 35 - PA405 :-( AA) 70 - (VI-111) 30 - PA406 :-( AA) 80 - (VI-114) 20 - PA407 :-( AA) 70 _{- (VI-120) 30 -} PA408 :-( AA) 60 - (VI-123) 40 - PA409 :-( AA) 70 - (VI-125) 30 - PA410 :-( AA) 60 - (VI-125 _{) 40 - PA411 :-( AA) 50} - (VI-125) 50 - PA412 :-( AA) 70 - (VI-126) 30 - PA413 :-( AA) 60 - (VI-128) 40 - PA414: _{- (AA) 50 - (VI} -132) 50 - PA415 :-( A _{) 70 - (VI-133)} 30 - PA416 :-( AA) 60 - (VI-133) 40 - PA417 :-( AA) 70 - (VI-138) 30 - PA418 :-( AA) 60 - (VI _{-138) 40 - PA419 :-( AA)} 60 - (VI-139) 40 - PA420 :-( AA) 60 - (VI-141) 40 - PA421 :-( AA) 60 - (VI-143) 40 -

[0091] _{PA422 :-( MA) 60 - (VI} -101) 40 - PA423 :-( MA) 70 - (VI-101) 30 - PA424 :-( MA) 60 - (VI-102) 40 - PA425: _{- (MA) 65 - (VI} -107) 35 - PA426 :-( MA) 70 - (VI-111) 30 - PA427 :-( MA) 80 - (VI-114) 20 - PA428 :-( MA) 70 _{- (VI-120) 30 -} PA429 :-( MA) 60 - (VI-123) 40 - PA430 :-( MA) 70 - (VI-125) 30 - PA431 :-( MA) 60 - (VI-125 _{) 40 - PA432 :-( MA) 50} - (VI-125) 50 - PA433 :-( MA) 70 - (VI-126) 30 - PA434 :-( MA) 60 - (VI-128) 40 - PA435: _{- (MA) 50 - (VI} -132) 50 - PA436 :-( M _{) 70 - (VI-133)} 30 - PA437 :-( MA) 60 - (VI-133) 40 - PA438 :-( MA) 70 - (VI-138) 30 - PA439 :-( MA) 60 - (VI _{-138) 40 - PA440 :-( MA)} 60 - (VI-139) 40 - PA441 :-( MA) 60 - (VI-141) 40 - PA442 :-( MA) 60 - (VI-142) 40 - _{PA451 :-( ClA) 60 - (VI} -145) 40 - PA452 :-( EA) 60 - (VI-146) 40 - PA453 :-( ClA) 60 - (VI-147) 40 - PA454 :-( EA ) _60- (VI-148) _40-

In the above formula (III), Cy represents an aliphatic ring group, an aromatic group or a heterocyclic group. The aliphatic ring of the aliphatic ring group is preferably a 5-membered to 7-membered ring,
A 6-membered ring is more preferable, and a 6-membered ring is the most preferable. Examples of the aliphatic ring include a cyclohexane ring, a cyclohexene ring and a bicyclo [2.2.1] hept-2-ene ring. Another aliphatic ring, aromatic ring or heterocyclic ring may be condensed with the aliphatic ring. Examples of the aromatic ring of the aromatic group include a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, a pyrene ring and a naphthacene ring. The well-meaning aromatic ring may be condensed with an aliphatic ring or a heterocycle. The heterocycle of the heterocyclic group is preferably a 5-membered to 7-membered ring, more preferably a 5-membered ring or a 6-membered ring. The heterocycle preferably has aromaticity. The aromatic heterocycle is generally unsaturated and preferably has the most double bonds. Examples of the heterocycle include furan ring, thiophene ring, pyrrole ring, oxazole ring, isoxazole ring, isothiazole ring, imidazole ring, pyrazole ring, furazan ring, pyran ring, pyridine ring, pyridazine ring, pyrimidine ring and pyrazine. Includes rings. Another heterocycle, an aliphatic ring or an aromatic ring may be condensed with the heterocycle.

The aliphatic ring group, aromatic group and heterocyclic group may have a substituent. Examples of the substituent include an alkyl group (eg, methyl group, ethyl group, t-butyl group), substituted alkyl group (eg, chloromethyl group, hydroxymethyl group, trimethylammonio chloride group), alkoxy group (eg, , Methoxy group), halogen atom (F,
Cl, Br), carboxyl group, acyl group (eg formyl group), amino group, sulfo group, aryl group (eg phenyl group), aryloxy group (eg phenoxy group) and oxo group. In the formula (III), n ² represents a mol% of repeating units, and is 1 to 90.
Mol%. n ² is preferably 5 to 80 mol%, and more preferably 10 to 70 mol%.

Examples of the repeating unit represented by the formula (III) are shown below.

[0095]

[Chemical 54]

[0096]

[Chemical 55]

[0097]

[Chemical 56]

[0098]

[Chemical 57]

[0099]

[Chemical 58]

Examples of acrylic acid type copolymers containing the repeating unit represented by the formula (III) are shown below. AA is a repeating unit derived from acrylic acid, and MA is a repeating unit derived from methacrylic acid. The proportion of repeating units is mol%.

[0102] _{PA501 :-( AA) 70 - (III} -1) 30 - PA502 :-( AA) 60 - (III-1) 40 - PA503 :-( AA) 50 - (III-1) 50 - PA504: _{- (AA) 40 - (III} -1) 60 - PA505 :-( AA) 60 - (III-2) 40 - PA506 :-( AA) 60 - (III-3) 40 - PA507 :-( AA) 60 _{- (III-4) 40 -} PA508 :-( AA) 60 - (III-5) 40 - PA509 :-( AA) 40 - (III-6) 40 - PA510 :-( AA) 50 - (III-7 ) ₅₀ -PA511 :-( AA) _70- (III-8) _30-

[0102] _{PA512 :-( AA) 60 - (III} -9) 40 - PA513 :-( AA) 60 - (III-10) 40 - PA514 :-( AA) 60 - (III-11) 40 - PA515: _{- (AA) 50 - (III} -12) 50 - PA516 :-( AA) 50 - (III-13) 50 - PA517 :-( AA) 70 - (III-14) 30 - PA518 :-( AA) 50 _{- (III-15) 50 -} PA519 :-( AA) 60 - (III-16) 40 - PA520 :-( AA) 60 - (III-17) 40 - PA521 :-( AA) 60 - (III-18 _{) 40 - PA522 :-( AA) 60} - (III-19) 40 -

[0103] _{PA523 :-( AA) 75 - (III} -20) 25 - PA524 :-( AA) 60 - (III-20) 40 - PA525 :-( AA) 70 - (III-21) 30 - PA526: _{- (AA) 80 - (III} -22) 20 - PA527 :-( AA) 70 - (III-22) 30 - PA528 :-( AA) 60 - (III-22) 40 - PA529 :-( AA) 70 -(III-23) ₃₀ -PA530 :-( AA) _70- (III-24) ₃₀ -PA531 :-( AA) _80- (III-25) ₂₀ -PA532 :-( AA) _70- (III-25 _{) 30 - PA533 :-( AA) 60} - (III-25) 40 -

[0104] _{PA534 :-( AA) 60 - (III} -26) 40 - PA535 :-( AA) 70 - (III-27) 30 - PA536 :-( AA) 80 - (III-28) 20 - PA537: _{- (AA) 70 - (III} -29) 30 - PA538 :-( AA) 60 - (III-30) 40 - PA539 :-( AA) 70 - (III-31) 30 - PA540 :-( AA) 70 _{- (III-32) 30 -} PA541 :-( AA) 60 - (III-33) 40 - PA542 :-( AA) 70 - (III-34) 30 - PA543 :-( AA) 70 - (III-35 ) ₃₀ −

[0105] _{PA601 :-( MA) 70 - (III} -1) 30 - PA602 :-( MA) 60 - (III-1) 40 - PA603 :-( MA) 50 - (III-1) 50 - PA604: _{- (MA) 40 - (III} -1) 60 - PA605 :-( MA) 60 - (III-2) 40 - PA606 :-( MA) 60 - (III-3) 40 - PA607 :-( MA) 60 _{- (III-4) 40 -} PA608 :-( MA) 60 - (III-5) 40 - PA609 :-( MA) 40 - (III-6) 40 - PA610 :-( MA) 50 - (III-7 ) ₅₀ -PA611 :-( MA) _70- (III-8) _30-

[0106] _{PA612 :-( MA) 60 - (III} -9) 40 - PA613 :-( MA) 60 - (III-10) 40 - PA614 :-( MA) 60 - (III-11) 40 - PA615: _{- (MA) 50 - (III} -12) 50 - PA616 :-( MA) 50 - (III-13) 50 - PA617 :-( MA) 70 - (III-14) 30 - PA618 :-( MA) 50 _{- (III-15) 50 -} PA619 :-( MA) 60 - (III-16) 40 - PA620 :-( MA) 60 - (III-17) 40 - PA621 :-( MA) 60 - (III-18 _{) 40 - PA622 :-( MA) 60} - (III-19) 40 -

[0107] _{PA623 :-( MA) 75 - (III} -20) 25 - PA624 :-( MA) 60 - (III-20) 40 - PA625 :-( MA) 70 - (III-21) 30 - PA626: _{- (MA) 80 - (III} -22) 20 - PA627 :-( MA) 70 - (III-22) 30 - PA628 :-( MA) 60 - (III-22) 40 - PA629 :-( MA) 70 -(III-23) ₃₀ -PA630 :-( MA) _70- (III-24) ₃₀ -PA631 :-( MA) _80- (III-25) ₂₀ -PA632 :-( MA) _70- (III-25 _{) 30 - PA633 :-( MA) 60} - (III-25) 40 -

[0108] _{PA634 :-( MA) 60 - (III} -26) 40 - PA635 :-( MA) 70 - (III-27) 30 - PA636 :-( MA) 80 - (III-28) 20 - PA637: _{- (MA) 70 - (III} -29) 30 - PA638 :-( MA) 60 - (III-30) 40 - PA639 :-( MA) 70 - (III-31) 30 - PA640 :-( MA) 70 _{- (III-32) 30 -} PA641 :-( MA) 60 - (III-33) 40 - PA642 :-( MA) 70 - (III-34) 30 - PA643 :-( MA) 70 - (III-35 ) ₃₀ −

In the above formula (IV), R ³ represents a hydrogen atom or a methyl group. In the formula (IV), L
¹ is -NH-alkylene group -O-CO-, -alkylene group -O-CO-, -O-alkylene group -O-CO-,
-O-arylene group-O-alkylene group-O-CO-,
-O-arylene group-O-alkylene group-, -O-arylene group -O-, -NH-alkylene group -O-CO-,
It represents a linking group selected from the group consisting of -NH-alkylene group -O- and -NH-alkylene group-. -NH-alkylene group -O-CO-, -alkylene group -O-CO
-, -O-alkylene group -O-CO-, -O-arylene group -O-alkylene group -O-CO-, -O-arylene group -O- and -NH-alkylene group -O-CO- are preferable. , -NH-alkylene group -O-CO- is particularly preferred. The alkylene group may have a branched or cyclic structure. The number of carbon atoms in the alkylene group is 1 to 3
0 is preferable, 1-20 is more preferable, 1-15 is further preferable, 1-1
Most preferably, it is 2. The arylene group is preferably a phenylene group or a naphthylene group,
A phenylene group is more preferable, and a p-phenylene group is most preferable. The arylene group may have a substituent. Examples of the substituent of the arylene group are the same as the examples of the substituent of the arylene group described above.

In the above formula (IV), Q is a polymerizable group.
As described above, the polymerizable group is preferably the same group as the polymerizable group (Q) of the liquid crystal molecule. In particular,
Q is preferably an unsaturated polymerizable group, an epoxy group or an aziridinyl group, and more preferably an ethylenically unsaturated polymerizable group. In the formula (IV), p represents mol% of the repeating unit and p is 0.1 to 20 mol%. p is preferably 0.1 to 10 mol% and 3 to 5 mol%
Is more preferable. Below, the example of the repeating unit which has a polymeric group in a side chain is shown.

[0111]

[Chemical 59]

[0112]

[Chemical 60]

[0113]

[Chemical formula 61]

[0114]

[Chemical formula 62]

[0115]

[Chemical formula 63]

When a repeating unit having a polymerizable group in the side chain is introduced into the acrylic acid-based copolymer, the acrylic acid-based copolymer has a repeating unit having a polymerizable group in the side chain of 0.
The content is preferably 1 to 10 mol%, more preferably 3 to 5 mol%.

In addition to the above acrylic acid-based orthogonal liquid crystal alignment film, a polyvinyl alcohol-based liquid crystal alignment film disclosed in Japanese Patent Application No. 2000-246279 or a polyamic acid-based liquid crystal alignment film disclosed in Japanese Patent Application No. 2000-64626 is used. May be.

Next, a second liquid crystal alignment film is formed and a second optically anisotropic liquid crystal layer is formed on the second liquid crystal alignment film. If the second liquid crystal alignment film is a liquid crystal alignment film capable of horizontally aligning the rod-shaped liquid crystal compound in the second optically anisotropic layer, there are no particular restrictions on its material and its forming method. Absent. For example, a method of rubbing a film made of an organic compound (preferably a polymer), a method of obliquely depositing an inorganic compound, a method of forming a layer having microgrooves, or an organic compound (using a Langmuir-Blodgett method (LB film)) Example, ω-tricosanoic acid, dioctadecylmethylammonium chloride,
Liquid crystal alignment films made of various materials can be formed by various methods such as a method of accumulating methyl stearyl acid). Furthermore, a liquid crystal alignment film that has an alignment function by applying an electric field, a magnetic field, or light irradiation is also known.

As the second liquid crystal alignment film, a liquid crystal alignment film formed by rubbing a film made of a polymer is particularly preferable. The rubbing treatment is carried out by rubbing the surface of the polymer layer with paper or cloth in a certain direction several times. For example, after coating a polymer solution on the surface of the first optically anisotropic layer and drying it to form a film,
A second liquid crystal alignment film can be formed by performing rubbing treatment. In the present invention, the second liquid crystal alignment film can be formed by performing a rubbing treatment in a direction in which the angle with the longitudinal direction of the transparent support is substantially 15 °. That is, the rubbing treatment is performed so that the angle between the rubbing axis and the longitudinal direction of the transparent support is substantially 15 °,
A second liquid crystal alignment film can be formed. When a coating liquid containing a rod-shaped liquid crystalline compound is applied on the formed second liquid crystal orientation film orthogonal liquid crystal orientation film and the rod-shaped liquid crystal compound is oriented, the liquid crystal molecules are rubbed on the liquid crystal orientation film. Orient in a direction substantially parallel to the axis. That is, the rod-shaped liquid crystal compound can be oriented in a direction of 15 ° with respect to the longitudinal direction of the transparent support to form a second optically anisotropic layer having a phase difference of π / 2.

The type of polymer used in the second liquid crystal alignment film is determined according to the alignment (particularly the average tilt angle) of the rod-like liquid crystal compound used in the second optically anisotropic layer. In order to align the liquid crystal compound horizontally (average tilt angle: 0 to 50 °), a polymer that does not lower the surface energy of the liquid crystal alignment film (normal polymer for liquid crystal alignment film) is used.
Specific types of polymers are described in various literatures on liquid crystal cells or optical compensation sheets. The thickness of the liquid crystal alignment film is preferably 0.01 to 5 μm, more preferably 0.05 to 1 μm. In addition, after forming the second liquid crystal alignment film on the temporary support and aligning the liquid crystal compound of the second optically anisotropic layer to form the second optically anisotropic layer, the second optical anisotropic layer is formed. The anisotropic layer may be transferred to the transparent support (or on the first optically anisotropic layer). The liquid crystal compound fixed in the alignment state can maintain the alignment state without the liquid crystal alignment film. In order to laminate the first optically anisotropic layer and the second optically anisotropic layer, in the longitudinal direction of the support (or the temporary support) when the first optically anisotropic layer is formed. When the parallel in-plane axis is a1 and the in-plane axis parallel to the longitudinal direction of the temporary support (or the transparent support) when the second optically anisotropic layer is formed is a2,
The respective in-plane axes a1 and a2 are substantially parallel to each other, and the angle between the slow axis of the first optically anisotropic layer and the slow axis of the second optically anisotropic layer is substantially 60. The first optically anisotropic layer and the second optically anisotropic layer are laminated at 0 °.

The second liquid crystal alignment film is not necessary as long as the rod-shaped liquid crystal compound in the second optically anisotropic layer is stably aligned at a desired angle. Further, for the purpose of improving the adhesion between the liquid crystal compound and the transparent support, a liquid crystal alignment film that forms a chemical bond with liquid crystal molecules at the interface (Japanese Patent Laid-Open No. 9-1).
No. 52509), and when the liquid crystal alignment film is used for the purpose of improving the adhesiveness, the rubbing treatment does not have to be performed.

The first optically anisotropic layer and the second optically anisotropic layer contain at least one rod-like liquid crystal compound, but contain a liquid crystal alignment promoter in addition to them. It is particularly preferable to contain a liquid crystal aligning agent represented by the following general formula (V). Formula ^{(V) (Hb-L 2} -) n B 1 In formula (V), Hb is an aliphatic substituted oligosiloxanoxy of carbon atoms is an aliphatic group or a number of carbon atoms of 6 to 40 6 to 40 Represents a xy group. Hb has 6 to 4 carbon atoms
It is preferably an aliphatic group having 0 to 6 carbon atoms.
40 fluorine-substituted aliphatic groups or 6 to 40 carbon atoms
More preferably an aliphatic group having a branch of
Most preferably, it is a fluorine-substituted alkyl group having 6 to 40 carbon atoms or a branched alkyl group having 6 to 40 carbon atoms.

The aliphatic group is preferably a chain aliphatic group rather than a cyclic aliphatic group. The chain aliphatic group may have a branch. The number of carbon atoms in the aliphatic group is preferably 7 to 35, more preferably 8 to 30, and 9 to
It is more preferably 25, and most preferably 10-20. Aliphatic groups include alkyl groups, substituted alkyl groups, alkenyl groups, substituted alkenyl groups, alkynyl groups and substituted alkynyl groups. An alkyl group,
A substituted alkyl group, an alkenyl group and a substituted alkenyl group are preferable, and an alkyl group and a substituted alkyl group are more preferable. Examples of the substituent of the aliphatic group include a halogen atom,
Hydroxyl group, cyano group, nitro group, alkoxy group,
Substituted alkoxy group (eg, oligoalkoxy group), alkenyloxy group (eg, vinyloxy), acyl group (eg, acryloyl, methacryloyl), acyloxy group (eg, acryloyloxy, benzoyloxy), sulfamoyl group, aliphatic substituted sulfamoyl group And an epoxyalkyl group (eg, epoxyethyl).
As the substituent, a halogen atom is preferable, and a fluorine atom is more preferable. In the fluorine-substituted aliphatic group, the ratio of the fluorine atom replacing the hydrogen atom of the aliphatic group is 5
It is preferably 0 to 100%, more preferably 60 to 100%, further preferably 70 to 100%, further preferably 80 to 100%, and 85 to 100%. Is most preferred.

The aliphatic substituted oligosiloxanoxy group preferably has 7 to 35 carbon atoms, and 8 to 3 carbon atoms.
It is more preferably 0, further preferably 9 to 25, and most preferably 10 to 20.
The aliphatic substituted oligosiloxanoxy group is represented by the following formula. R ^1- (Si (R ² ) ₂ -O) _q -In the formula, R ¹ represents a hydrogen atom, hydroxyl or an aliphatic group; R ² represents a hydrogen atom, an aliphatic group or an alkoxy group; and q Represents an integer of 1 to 12.
The aliphatic group represented by R ¹ and R ² is preferably a chain aliphatic group rather than a cyclic aliphatic group. The chain aliphatic group may have a branch. The number of carbon atoms in an aliphatic group is
1 to 12 is preferable, 1 to 8 is more preferable, 1 to 6 is further preferable, 1 to
4 is particularly preferable. The aliphatic group represented by R ¹ and R ² includes an alkyl group, a substituted alkyl group,
Included are alkenyl groups, substituted alkenyl groups, alkynyl groups and substituted alkynyl groups. An alkyl group, a substituted alkyl group, an alkenyl group and a substituted alkenyl group are preferable, and an alkyl group and a substituted alkyl group are more preferable. The aliphatic group represented by R ¹ and R ² may have a substituent, and examples of the substituent include a halogen atom, a hydroxyl group, a cyano group, a nitro group, an alkoxy group and a substituted alkoxy group. Group (eg, oligoalkoxy group), alkenyloxy group (eg, vinyloxy), acyl group (eg, acryloyl, methacryloyl), acyloxy group (eg, acryloyloxy, benzoyloxy), sulfamoyl group, aliphatic-substituted sulfamoyl group and epoxy Alkyl groups (eg, epoxyethyl) are included.

The alkoxy group represented by R ² may have a cyclic structure or a branch. The alkoxy group preferably has 1 to 12 carbon atoms, more preferably has 1 to 8 carbon atoms, further preferably has 1 to 6 carbon atoms, and further preferably has 1 to 4 carbon atoms. Below, the example of Hb is shown.

[0126] _{Hb1: n-C 16 H 33} - Hb2: n-C 20 H 41 - Hb3: n-C 6 H 13 -CH (n-C 4 H 9) -CH 2 -
_{CH 2 - Hb4: n-C} 12 H 25 - Hb5: n-C 18 H 37 - Hb6: n-C 14 H 29 - Hb7: n-C 15 H 31 - Hb8: n-C 10 H 21 - Hb9: _{n-C 10 H 21 -CH (} n-C 4 H 9) -CH 2 -
_{CH 2 - Hb10: n-C} 8 F 17 -

Hb11: n-C₈H₁₇− Hb12: CH (CH₃)₂-{C₃H₆-CH (C
H₃)}₃-C₂H_Four− Hb13: CH (CH₃)₂-{C₃H₆-CH (C
H₃)}₂-C₃H₆-C (CH ₃) = CH-CH₂− Hb14: n-C₈H₁₇-CH (n-C₆H₁₃) -CH₂
-CH₂− Hb15: n-C₆H₁₃-CH (C₂H_Five) -CH₂-CH
₂− Hb16: n-C₈F₁₇-CH (n-C_FourF₉) -CH₂− Hb17: n-C₈F₁₇-CF (n-C₆F₁₃) -CF₂
-CF₂− Hb18: n-C₃F₇-CF (CF₃) -CF₂− Hb19: Si (CH₃)₃-{Si (CH₃)₂-O}₆
-O- Hb20: Si (OC₃H₇) (C₁₆F₃₃) (C₂H_Four-S
O₂-NH-C₈F₁₇) -O-

In the above formula (V), L ² represents a single bond or a divalent linking group. The divalent linking group is -alkylene group-, -fluorine-substituted alkylene group-, -O-,-
S -, - CO -, - NR -, - SO 2 - and is preferably a group selected from the group consisting of. R is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. L ^1A is -alkylene group-, -O-,
-S -, - CO -, - NR -, - SO 2 - and more preferably a divalent linking group selected from the group consisting of. R is preferably a hydrogen atom or an alkyl group having 1 to 20 carbon atoms, more preferably a hydrogen atom or an alkyl group having 1 to 15 carbon atoms, and having 1 hydrogen atom or 1 carbon atoms.
Most preferably, it is an alkyl group of ~ 12. The alkylene group or the fluorine-substituted alkylene group preferably has 1 to 40 carbon atoms, more preferably 1 to 30 carbon atoms, further preferably 1 to 20 carbon atoms, and 1 to 15 carbon atoms. Further preferably, 1 to 1
Most preferably, it is 2. An example of L ² is shown below. The left side binds to Hb and the right side binds to B ¹ .

L10: Single bond L11: —O— L12: —O—CO— L13: —CO—C ₄ H ₈ —O— L14: —O—C ₂ H ₄ —O—C ₂ H ₄ —O— L15: -S- L16: -N (n -C 12 H 25) - L17: -SO 2 -N (n-C 3 H 7) -CH 2 CH 2 -O
- L18: -O- {CF (CF 3) -CF 2 -O} 3 -CF
(CF ₃₎ -

In the above formula (V), n represents an integer of 2-12. n is preferably an integer of 2-9, more preferably an integer of 2-6, even more preferably 2, 3 or 4, and even more preferably 3 or 4. Most preferred.

In the above formula (V), B ¹ is an n-valent group having an excluded volume effect and containing at least three cyclic structures. B ¹ is preferably an n-valent group represented by the following formula (Va). Formula ^{(V-a) (-Cy 1} -L 3 -) n Cy 2 In Formula (V-a), Cy ¹ represents a divalent cyclic group. Cy ¹ preferably represents a divalent aromatic hydrocarbon group or a divalent heterocyclic group, more preferably a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group means an arylene group and a substituted arylene group. Examples of the arylene group, phenylene group, indenylene group, naphthylene group, fluorenylene group, phenanthrenylene group,
An anthrylene group and a pyrenylene group are included. Phenylene groups and naphthylene groups are preferred. Examples of the substituent of the substituted arylene group include an aliphatic group, an aromatic hydrocarbon group, a heterocyclic group, a halogen atom, an alkoxy group (for example, a methoxy group, an ethoxy group, a methoxyethoxy group), an aryloxy group (for example, Phenoxy group), arylazo group (eg phenylazo group), alkylthio group (eg methylthio group, ethylthio group, propylthio group), alkylamino group (eg methylamino group, propylamino group), acyl group (eg acetyl group) , Propanoyl group, octanoyl group, benzoyl group), acyloxy group (for example, acetoxy group, pivaloyloxy group, benzoyloxy group), hydroxyl group, mercapto group, amino group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group and ureido group. Is included. When another aromatic hydrocarbon ring is bonded to the divalent aromatic hydrocarbon group through a single bond, a vinylene bond or an ethynylene bond as a substituent, a specific liquid crystal alignment promoting function is obtained as described above. To be Furthermore, Hb-L ² - the equivalent to radicals may have as substituents.

The divalent heterocyclic group represented by Cy ¹ is 5
Having a 6-, or 7-membered heterocycle.
A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is the most preferable. As the hetero atom forming the hetero ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is generally an unsaturated heterocycle. Unsaturated heterocycles having the most double bonds are more preferred. Examples of heterocycles include
Furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, pyrazoline ring, pyrazolidine ring, triazole ring , A furazan ring, a tetrazole ring, a pyran ring, a thiyne ring, a pyridine ring, a piperidine ring, an oxazine ring, a morpholine ring, a thiazine ring, a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring and a triazine ring.

The heterocycle may be condensed with another heterocycle, an aliphatic ring or an aromatic hydrocarbon ring. Examples of the condensed heterocycle include benzofuran ring, isobenzofuran ring, benzothiophene ring, indole ring, indoline ring, isoindole ring, benzoxazole ring, benzothiazole ring,
Indazole ring, benzimidazole ring, chromene ring,
Chroman ring, isochroman ring, quinoline ring, isoquinoline ring, cinnoline ring, phthalazine ring, quinazoline ring, quinoxaline ring, dibenzofuran ring, carbazole ring, xanthene ring, acridine ring, phenanthridine ring, phenanthroline ring, phenazine ring, phenoxazine ring , Thianthrene ring, indolizine ring, quinolidine ring, quinuclidine ring, naphthyridine ring, purine ring and pteridine ring. The divalent heterocyclic group may have a substituent. Examples of the substituent are the same as the examples of the substituent of the substituted arylene group. A divalent heterocyclic group is a heteroatom (for example,
It may be bonded to L ³ or (when L ³ is a single bond) a cyclic group (Cy ² ) at the center of the molecule at the nitrogen atom of the piperidine ring). Further, the heteroatom to be bonded may form an onium salt (eg, oxonium salt, sulfonium salt, ammonium salt).

The cyclic structure of Cy ¹ and Cy ² described later is
You may form the planar structure as a whole. When the annular structure forms a planar structure (that is, a disc-shaped structure) as a whole, a specific liquid crystal alignment promoting function is obtained as described above. The following is an example of Cy ¹ . When a plurality of groups corresponding to Hb-L ² — are bonded to a divalent aromatic hydrocarbon group or a divalent heterocyclic group, any one of them is Hb-L ² — defined by the above formula. The rest is a substituent of a divalent aromatic hydrocarbon group or a divalent heterocyclic group.

[0135]

[Chemical 64]

[0136]

[Chemical 65]

[0137]

[Chemical formula 66]

[0138]

[Chemical formula 67]

[0139]

[Chemical 68]

[0140]

[Chemical 69]

[0141]

[Chemical 70]

In the formula (Va), L³Is a single bond
Or -alkylene group-, -alkenylene group-, -alkyn
Nylene group-,-O-,-S-,-CO-,-NR-,-
SO ₂-And selected from the group consisting of combinations thereof
Is a divalent linking group. R is a hydrogen atom or a carbon atom
It represents an alkyl group having a child number of 1 to 30. L³Is -O-,
-S-, -CO-, -NR-, -SO₂-And those
A divalent linking group selected from the group consisting of
Preferably. R has 1 hydrogen atom or carbon atom
It is preferably an alkyl group of 20 to 20, and a hydrogen atom or
Or an alkyl group having 1 to 15 carbon atoms.
Especially preferred, having 1 to 12 hydrogen atoms or carbon atoms
Most preferably, it is an alkyl group. Above alkylene
The number of carbon atoms in the group is preferably 1 to 40, and 1
It is more preferable that it is -30, and it is 1-20
Is more preferable, and 1 to 15 is even more preferable.
Most preferably, it is 1 to 12. Al above
The number of carbon atoms of the kenylene group or alkynylene group is 2 to
It is preferably 40, more preferably 2 to 30
It is preferably 2 to 20, more preferably 2 to 20.
It is still more preferable that it is 15, and it is 2-12
Is most preferred. Below, L³For example: On the left
Cy¹To the right side Cy²Bind to.

L20: Single bond L21: —S— L22: —NH— L23: —NH—SO ₂ —NH— L24: —NH—CO—NH— L25: —SO ₂ — L26: —O—NH— L27 : -C≡C- L28: -CH = CH- S- L29: -CH 2 -O- L30: -N (CH 3) - L31: -CO-O-

In the above formula (Va), n is 2 to 12
Represents any integer. n is preferably an integer of 2-9, more preferably an integer of 2-6, even more preferably 2, 3 or 4, and even more preferably 3 or 4. Most preferred. In the above formula (Va), Cy ² is an n-valent cyclic group. Cy ² is preferably an n-valent aromatic hydrocarbon group or an n-valent heterocyclic group. Examples of the aromatic hydrocarbon ring of the aromatic hydrocarbon group represented by Cy ² include a benzene ring,
Indene ring, naphthalene ring, fluorene ring, phenanthrene ring, anthracene ring and pyrene ring are included. A benzene ring and a naphthalene ring are preferable, and a benzene ring is particularly preferable. The aromatic hydrocarbon group represented by Cy ² may have a substituent. Examples of substituents are aliphatic groups,
Aromatic hydrocarbon group, heterocyclic group, halogen atom, alkoxy group (eg, methoxy group, ethoxy group, methoxyethoxy group), aryloxy group (eg, phenoxy group), arylazo group (eg, phenylazo group), alkylthio group (For example, a methylthio group, an ethylthio group,
Propylthio group), alkylamino group (eg, methylamino group, propylamino group), arylamino group (eg, phenylamino group), acyl group (eg, acetyl group, propanoyl group, octanoyl group, benzoyl group), acyloxy group (Eg, acetoxy group, pivaloyloxy group, benzoyloxy group), hydroxyl group, mercapto group, amino group, carboxyl group, sulfo group, carbamoyl group, sulfamoyl group and ureido group.

The heterocyclic group represented by Cy ² preferably has a 5-membered, 6-membered or 7-membered heterocyclic ring. A 5-membered ring or a 6-membered ring is more preferable, and a 6-membered ring is the most preferable.
As the hetero atom forming the hetero ring, a nitrogen atom, an oxygen atom and a sulfur atom are preferable. The heterocycle is preferably an aromatic heterocycle. The aromatic heterocycle is
Generally, it is an unsaturated heterocycle. Unsaturated heterocycles having the most double bonds are more preferred. Examples of the heterocycle, furan ring, thiophene ring, pyrrole ring, pyrroline ring, pyrrolidine ring, oxazole ring, isoxazole ring, thiazole ring, isothiazole ring, imidazole ring, imidazoline ring, imidazolidine ring, pyrazole ring, Pyrazoline ring, pyrazolidine ring, triazole ring, furazan ring, tetrazole ring, pyran ring, thiyne ring, pyridine ring, piperidine ring, oxazine ring, morpholine ring, thiazine ring,
It includes a pyridazine ring, a pyrimidine ring, a pyrazine ring, a piperazine ring and a triazine ring. A triazine ring is preferable, and a 1,3,5-triazine ring is particularly preferable. Another heterocycle, an aliphatic ring or an aromatic hydrocarbon ring may be condensed with the heterocycle. However, monocyclic heterocycles are preferred. An example of Cy ² is shown below.

[0146]

[Chemical 71]

[0147]

[Chemical 72]

[0148]

[Chemical formula 73]

[0149]

[Chemical 74]

The liquid crystal alignment accelerator is a compound in which the above-mentioned hydrophobic group (Hb), linking group (L ² ) and group (B ¹ ) having an excluded volume effect are combined. There is no particular limitation on these combinations. Hereinafter, examples of the liquid crystal alignment accelerator represented by the general formula (V) will be shown.

[0151]

[Chemical 75]

[0152]

[Chemical 76]

[0153]

[Chemical 77]

[0154]

[Chemical 78]

[0155]

[Chemical 79]

[0156]

[Chemical 80]

[0157]

[Chemical 81]

[0158]

[Chemical formula 82]

[0159]

[Chemical 83]

[0160]

[Chemical 84]

[0161]

[Chemical 85]

[0162]

[Chemical 86]

[0163]

[Chemical 87]

[0164]

[Chemical 88]

[0165]

[Chemical 89]

[0166]

[Chemical 90]

[0167]

[Chemical Formula 91]

[0168]

[Chemical Formula 92]

[0169]

[Chemical formula 93]

[0170]

[Chemical 94]

[0171]

[Chemical 95]

[0172]

[Chemical 96]

[0173]

[Chemical 97]

[0174]

[Chemical 98]

[0175]

[Chemical 99]

[0176]

[Chemical 100]

[0177]

[Chemical 101]

[0178]

[Chemical 102]

[0179]

[Chemical 103]

[0180]

[Chemical 104]

[0181]

[Chemical 105]

[0182]

[Chemical formula 106]

[0183]

[Chemical formula 107]

[0184]

[Chemical 108]

[0185]

[Chemical 109]

[0186]

[Chemical 110]

[0187]

[Chemical 111]

[0188]

[Chemical 112]

[0189]

[Chemical 113]

[0190]

[Chemical 114]

[0191]

[Chemical 115]

[0192]

[Chemical formula 116]

[0193]

[Chemical 117]

[0194]

[Chemical 118]

[0195]

[Chemical formula 119]

[0196]

[Chemical 120]

The first and second optically anisotropic layers of the present invention contain at least one rod-like liquid crystalline compound. In the first and second optically anisotropic layers, the rod-like liquid crystal compound molecules are preferably aligned substantially uniformly, and are fixed in a substantially uniformly aligned state. Is more preferable, and it is most preferable that liquid crystal molecules are fixed by a polymerization reaction. The alignment of the liquid crystal molecules is adjusted so that the angle between the in-plane slow axis of the optically anisotropic layer and the longitudinal direction of the transparent support is substantially 75 ° or 15 °. It is preferable that the liquid crystal molecules have horizontal alignment (homogeneous alignment). The term "substantial" in the present invention means ± 5 °, preferably ± 4 °. For example, substantially 75 ° means 75 ± 5 °. Examples of the rod-shaped liquid crystal compound include azomethines, azoxys, cyanobiphenyls, cyanophenyl esters, benzoic acid esters, cyclohexanecarboxylic acid phenyl esters, cyanophenylcyclohexanes, cyano-substituted phenylpyrimidines, and alkoxy-substituted phenylpyrimidines. , Phenyldioxane, tolan, and alkenylcyclohexylbenzonitrile are preferably used. In addition to the low molecular weight liquid crystalline compound as described above, a high molecular weight liquid crystalline compound can be used.

As the rod-like liquid crystal compound, Makromol. Ch
em., 190, 2255 (1989), Advanced Mater Ials
Volume 5, page 107 (1993), U.S. Pat. Nos. 4,683,327, 5,622,648, 5,770,107, International Publication WO95 / 22586, International Publication WO95 / 24455, International Publication WO97 / 00.
600 publication, international publication WO98 / 23580 publication,
International Publication WO98 / 52905, JP-A 1-27
2551, JP 6-16616, JP 7-11
The compounds described in JP-A-0469, JP-A-11-80081, and Japanese Patent Application No. 2001-64627 can be used. More preferably, the following general formula (V
It is a compound represented by I).

[0199] Formula ^{(VI) Q 11 -L 11 -Cy} 11 -L 12 - (Cy 12 -L 13) n -Cy
¹³ -L ¹⁴ -Q ^{12 In the} formula, Q ¹¹ and Q ¹² each independently represent a polymerizable group; L ¹¹ and L ¹⁴ each independently represent a divalent linking group; L ¹² and L ¹³ each independently Represents a single bond or a divalent linking group; Cy ¹¹ , Cy ¹² and Cy ¹³ each independently represent a divalent cyclic group; and n represents 0, 1 or 2.

In formula (VI), Q ¹¹ and Q ¹² each independently represent a polymerizable group. The polymerization reaction of the polymerizable group is preferably addition polymerization (including ring-opening polymerization) or condensation polymerization. In other words, the polymerizable group is preferably a functional group capable of addition polymerization reaction or condensation polymerization reaction.
Examples of the polymerizable group are shown below.

[0201]

[Chemical 121]

The polymerizable groups (Q ¹¹ and Q ¹² ) are preferably unsaturated polymerizable groups (Q-1 to Q-7), epoxy group (Q-8) or aziridinyl group (Q-9). , And more preferably an unsaturated polymerizable group, and most preferably an ethylenically unsaturated polymerizable group (Q-1 to Q-6).

L ¹¹ and L ¹⁴ each independently represent a divalent linking group. L ¹¹ and L ¹⁴ are each independently -O.
-, - S -, - CO -, - NR 12 -, a divalent chain group is preferably a divalent linking group selected from the group consisting of divalent cyclic groups, and combinations thereof. R ¹² represents an alkyl group having 1 to 7 carbon atoms or a hydrogen atom. R ¹² is preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, more preferably a methyl group, an ethyl group or a hydrogen atom, and most preferably a hydrogen atom. Examples of the divalent linking group composed of a combination are shown below. Here, the left side is connected to Q (Q ¹¹ or Q ¹² ) and the right side is connected to Cy (Cy ¹¹ or Cy ¹³ ).

L-1: —CO—O— divalent chain group —O— L-2: —CO—O— divalent chain group —O— divalent cyclic group —CO—O— L -3: -CO-O- divalent chain group -O- divalent cyclic group -O-CO- L-4: -CO-O- divalent chain group -O- divalent cyclic group -Divalent chain group-L-5: -CO-O-divalent chain group-O-divalent cyclic group-L-6: -CO-O-divalent chain group-O- Divalent cyclic group-divalent chain group-CO-O-L-7: -CO-O-divalent chain group-O-divalent cyclic group-O-CO-divalent chain group Group-

The divalent chain group contained in the divalent linking group represented by L ¹¹ and L ¹⁴ means an alkylene group, a substituted alkylene group, an alkenylene group, a substituted alkenylene group, an alkynylene group or a substituted alkynylene group. . An alkylene group, a substituted alkylene group, an alkenylene group and a substituted alkenylene group are preferable, and an alkylene group and an alkenylene group are more preferable. The alkylene group may have a branch. The number of carbon atoms of the alkylene group is 1 to
It is preferably 12, more preferably 2 to 10, and most preferably 3 to 8. The alkylene portion of the substituted alkylene group is the same as the above alkylene group. Examples of the substituent of the substituted alkylene group include a halogen atom. The alkenylene group may have a branch. The alkenylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and most preferably 2 to 4 carbon atoms. The alkenylene portion of the substituted alkenylene group is the same as the above alkenylene group. Examples of the substituent of the substituted alkenylene group include a halogen atom. The alkynylene group may have a branch. The alkynylene group has preferably 2 to 12 carbon atoms, more preferably 2 to 8 carbon atoms, and most preferably 2 to 4 carbon atoms. The alkynylene portion of the substituted alkynylene group is the same as the above alkynylene group. Examples of the substituent of the substituted alkynylene group include a halogen atom.

Definitions and examples of the divalent cyclic group contained in the divalent linking group represented by L ¹¹ and L ¹⁴ are the same as the definitions and examples of Cy ¹¹ , Cy ¹² and Cy ¹³ described later.

In the above formula (VI), L ¹² and L ¹³ each independently represent a single bond or a divalent linking group. L ¹² and L ¹³ are each independently -O-, -S-, -CO-,
It is preferably a divalent linking group or a single bond selected from the group consisting of —NR ¹² —, a divalent chain group, a divalent cyclic group and combinations thereof. R ¹² represents an alkyl group having 1 to 7 carbon atoms or a hydrogen atom, preferably an alkyl group having 1 to 4 carbon atoms or a hydrogen atom, and a methyl group, an ethyl group or a hydrogen atom. More preferably, it is most preferably a hydrogen atom. Regarding the divalent chain group and divalent cyclic group contained in the divalent linking group represented by L ¹² and L ¹³ , respectively, see L ¹¹
And L ¹⁴ are synonymous with the definition.

In the general formula (VI), n represents 0, 1 or 2. When n is 2, two L ³ may be the same or different, and two Cy ¹² may be the same or different. n is preferably 1 or 2, and more preferably 1.

In the above formula (VI), Cy ¹¹ , Cy ¹² and Cy ¹³ each independently represent a divalent cyclic group. The ring contained in the cyclic group is preferably a 5-membered ring, a 6-membered ring or a 7-membered ring, more preferably a 5-membered ring or a 6-membered ring, and most preferably a 6-membered ring.
The ring contained in the cyclic group may be a condensed ring. However, a monocycle is preferable to a condensed ring. The ring contained in the cyclic group may be an aromatic ring, an aliphatic ring or a heterocycle. Examples of the aromatic ring include a benzene ring and a naphthalene ring. Examples of the aliphatic ring include a cyclohexane ring. Examples of the heterocycle include a pyridine ring and a pyrimidine ring. The cyclic group having a benzene ring is preferably a 1,4-phenylene group. The naphthalene ring-containing cyclic group is preferably a naphthalene-1,5-diyl group or a naphthalene-2,6-diyl group. The cyclic group having a pyridine ring is preferably a pyridine-2,5-diyl group. The cyclic group having a pyrimidine ring is preferably a pyrimidine-2,5-diyl group. The cyclic group is particularly preferably a 1,4-phenylene group or a 1,4-cyclohexylene group. The cyclic group may have a substituent. Examples of the substituent include a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 5 carbon atoms,
A halogen-substituted alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, an alkylthio group having 1 to 5 carbon atoms, an acyl group having 1 to 5 carbon atoms, and a carbon atom number It includes an acyloxy group having 2 to 6 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a carbamoyl group, an alkyl-substituted carbamoyl group having 2 to 6 carbon atoms, and an amide group having 2 to 6 carbon atoms.

Examples of the polymerizable liquid crystal compound represented by the general formula (VI) are shown below.

[0211]

[Chemical formula 122]

[0212]

[Chemical 123]

[0213]

[Chemical formula 124]

[0214]

[Chemical 125]

[0215]

[Chemical formula 126]

[0216]

[Chemical 127]

[0217]

[Chemical 128]

[0218]

[Chemical formula 129]

[0219]

[Chemical 130]

[0220]

[Chemical 131]

[0221]

[Chemical 132]

[0222]

[Chemical 133]

[0223]

[Chemical 134]

[0224]

[Chemical 135]

[0225]

[Chemical 136]

[0226]

[Chemical 137]

For the first and second optically anisotropic layers, a coating liquid containing rod-shaped liquid crystal molecules and the following polymerizable initiator and other additives is added to the first and second liquid crystal alignment films, respectively. It can be formed by coating on top. An organic solvent is preferably used as the solvent used for preparing the coating liquid. Examples of organic solvents include amides (eg N, N-dimethylformamide), sulfoxides (eg dimethylsulfoxide), heterocyclic compounds (eg pyridine), hydrocarbons (eg benzene, hexane), alkyl halides (eg , Chloroform, dichloromethane), esters (eg, methyl acetate, butyl acetate),
Ketones (eg acetone, methyl ethyl ketone), ethers (eg tetrahydrofuran, 1,2-dimethoxyethane) are included. Alkyl halides and ketones are preferred. You may use together 2 or more types of organic solvents. The coating liquid is applied by a known method (for example, extrusion coating method, direct gravure coating method, reverse gravure coating method, die coating method).
Can be implemented by

The aligned liquid crystal molecules are fixed while maintaining the aligned state. The immobilization is preferably performed by a polymerization reaction of the polymerizable group (P) introduced into the liquid crystal molecule. The polymerization reaction includes a thermal polymerization reaction using a thermal polymerization initiator and a photopolymerization reaction using a photopolymerization initiator. Photopolymerization is preferred. Examples of the photopolymerization initiator include α-carbonyl compounds (described in US Pat. Nos. 2,367,661 and 2,367,670) and acyloin ethers (US Pat. No. 244).
8828 specification), α-hydrocarbon substituted aromatic acyloin compound (US Pat. No. 2,722,512 specification), polynuclear quinone compound (US Pat. No. 3,046,127),
No. 2951758), a combination of a triarylimidazole dimer and p-aminophenyl ketone (described in US Pat. No. 3,549,367), an acridine and a phenazine compound (JP-A-60-105).
667 publication, US Pat. No. 4,239,850 specifications)
And oxadiazole compounds (U.S. Pat.
No. 0 specification description) is included.

The amount of the photopolymerization initiator used is preferably 0.01 to 20% by weight of the solid content of the coating solution, and is 0.5.
It is more preferably about 5% by weight. Ultraviolet light is preferably used for the light irradiation for polymerizing the liquid crystal molecules. Irradiation energy is 20 mJ / cm ^{2 to} 50 J / c
m ² is preferable, and 100 to 800 mJ / cm ²
Is more preferable. Light irradiation may be carried out under heating conditions in order to accelerate the photopolymerization reaction.

The thickness of the first and second optically anisotropic layers is preferably 0.1 to 10 μm, and 0.5 to 10 μm.
More preferably, it is 5 μm.

The material of the transparent support is not particularly limited, and a glass plate or a polymer film can be used, but it is preferable to use a polymer film from the viewpoint of thinning and weight saving. In particular, it is preferable to use a polymer film having a small wavelength dispersion. Further, a transparent support having a small optical anisotropy is preferable. Here, that the support is transparent means that the light transmittance is 80% or more. Small wavelength dispersion means specifically Re40
The 0 / Re700 ratio is preferably less than 1.2. The small optical anisotropy specifically means that the in-plane retardation (Re) is preferably 20 nm or less, more preferably 10 nm or less. The long transparent support has a roll shape or a rectangular sheet shape. It is preferable that the first and second optically anisotropic layers are laminated using a roll-shaped transparent support and then cut into a required size.

Examples of polymers include cellulose esters,
Included are polycarbonates, polysulfones, polycycloolefins, polyether sulfones, polyacrylates and polymethacrylates. Cellulose esters are preferred, acetyl cellulose is more preferred, and triacetyl cellulose is most preferred. The polymer film is preferably formed by the solvent casting method. The thickness of the transparent support is preferably 20 to 500 μm, more preferably 50 to 200 μm. In order to improve the adhesion between the transparent support and the layer (adhesion layer, vertical liquid crystal alignment film or optically anisotropic layer) provided thereon, the transparent support is subjected to a surface treatment (eg glow discharge treatment, corona discharge treatment). , Ultraviolet (UV) treatment, flame treatment)
May be carried out. An adhesive layer (undercoat layer) may be provided on the transparent support.

For convenience of explanation, the mode of the retardation plate which makes the incident light a right-handed circularly polarized light is shown, but it goes without saying that a mode of making the left-handed circularly polarized light is included in the present invention. In the aspect of left circularly polarized light, the longitudinal direction of the long transparent support and the slow axis of the first optically anisotropic layer having a phase difference of π are −75 °,
The first and second optical anisotropic layers are laminated at an angle of −15 ° with the slow axis of the second optical anisotropic layer having a phase difference of π / 2. In the retardation plate of this aspect, the rubbing axis of the first liquid crystal alignment film is set to 1 with respect to the longitudinal direction of the transparent support.
It can be manufactured by setting the angle to 5 ° and setting the rubbing axis of the second liquid crystal alignment film to −15 °.

The retardation plate of the present invention is used as a λ / 4 plate in a reflective liquid crystal display device, a λ / 4 plate used as a pickup for writing on an optical disk, or a λ / plate used as an antireflection film. Particularly preferably, the four plates can be used. The λ / 4 plate is generally used as a circularly polarizing plate combined with a polarizing film. Therefore, when configured as a circularly polarizing plate that combines a retardation plate and a polarizing film,
It can be easily incorporated in a device such as a reflective liquid crystal display device. When the retardation plate of the present invention is used together with a polarizing film in a reflective liquid crystal display device, it is possible to reduce the bluish tint that occurs during black display. Further, the retardation plate of the present invention can be stored and transported in a roll state, and when laminated with a polarizing film, continuous processing can be performed by roll-to-roll, so that a circularly polarizing plate can be easily manufactured.

The circularly polarizing plate of the present invention comprises the retardation plate of the present invention and a polarizing film. The polarizing film is
The transparent support is laminated below the transparent support (on the side opposite to the first and second optically anisotropic layers) so that the longitudinal direction of the transparent support and the absorption axis are substantially aligned with each other. That is, the circularly polarizing plate of the present invention has a polarizing film having a polarizing axis in a direction substantially perpendicular to the longitudinal direction of the transparent support.

The polarizing film used in the present invention includes an iodine type polarizing film, a dye type polarizing film using a dichroic dye, and a polyene type polarizing film. The iodine type polarizing film and the dye type polarizing film are
Generally, it is manufactured using a polyvinyl alcohol film. The transmission axis of the polarizing film corresponds to the direction perpendicular to the stretching direction of the film. The polarizing film generally has protective films on both sides. However, in the present invention, the transparent support can function as a protective film on one side of the polarizing film. When a protective film is used separately from the transparent support, a cellulose ester film having high optical isotropy, particularly a triacetyl cellulose film is preferably used as the protective film.

The circularly polarizing plate of the present invention functions as a wide band λ / 4 plate. Here, the broadband λ / 4 plate is specifically a retardation value / wavelength value measured at wavelengths of 450 nm, 550 nm and 650 nm, which are all 0.
It means within the range of 2 to 0.3. The retardation value / wavelength value is preferably in the range of 0.21 to 0.29, more preferably in the range of 0.22 to 0.28, and in the range of 0.23 to 0.27. It is more preferably within the range, and most preferably within the range of 0.24 to 0.26.

[0238]

EXAMPLES The present invention will be described in more detail with reference to the following examples. The materials, reagents, ratios, operations and the like shown in the following examples can be appropriately changed without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. Example 1 Thickness 100 μm, width 500 mm, length 50
An optically isotropic roll-like triacetylcellulose film of 0 m was used as a transparent support. A diluting liquid of a liquid crystal alignment film (polymer having the following structural formula) was continuously applied to one surface of a transparent support to form an orthogonal liquid crystal alignment film of 0.5 μm in thickness. Then, rubbing treatment was continuously carried out in the direction of 16 ° on the right side with respect to the longitudinal direction of the transparent support.

Polymer for orthogonal liquid crystal alignment film (PA-13
2)

[Chemical 138]

On the liquid crystal alignment film, a coating solution having the following composition was continuously applied using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness of 1.6 μm.
The optically anisotropic layer (A) was formed. The optically anisotropic layer had a slow axis in the direction of 74 ° with respect to the longitudinal direction of the transparent support. The retardation value at 550 nm was 225 nm.

[0241]   Composition of coating liquid for optically anisotropic layer   The following rod-shaped liquid crystal compound (1) 14.5 mass%   The following sensitizer (1) 1.0% by mass   The following photopolymerization initiator (1) 3.0% by mass   The following horizontal alignment promoter (1) 1.0% by mass   Methyl ethyl ketone 80.5% by mass

Rod-shaped liquid crystal compound (1)

[Chemical 139]

Sensitizer (1)

[Chemical 140]

Photopolymerization initiator (1)

[Chemical 141]

Horizontal Alignment Promoter (1)

[Chemical 142]

Example 2 Thickness 100 μm, Width 500 m
An optically isotropic roll-shaped triacetylcellulose film having a length of m and a length of 500 m was used as a transparent support. A diluting solution of a liquid crystal alignment film (polymer having the following structural formula) was continuously applied to one surface of a transparent support to form a cross-linked liquid crystal alignment film having a thickness of 0.8 μm. Then, rubbing treatment was continuously carried out in the direction of 16 ° on the right side with respect to the longitudinal direction of the transparent support.

Polymer for orthogonal liquid crystal alignment film

[Chemical 143]

On the liquid crystal alignment film, a coating liquid having the following composition was continuously applied using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness of 1.6 μm.
The optically anisotropic layer (A) was formed. The optically anisotropic layer had a slow axis in the direction of 74 ° with respect to the longitudinal direction of the transparent support. The retardation value at 550 nm was 224 nm.

[0249]   Composition of coating liquid for optically anisotropic layer   The rod-shaped liquid crystal compound (1) 14.5% by mass   The above sensitizer (1) 1.0% by mass   The above photopolymerization initiator (1) 3.0% by mass   1.0% by mass of the above horizontal alignment promoter (1)   Methyl ethyl ketone 80.5% by mass

[Embodiment 3] Thickness 100 μm, width 500 m
An optically isotropic roll-shaped triacetyl cellulose film having a length of m and a length of 30 m was used as a transparent support. A diluting liquid of a liquid crystal alignment film (polymer having the following structural formula) was continuously applied to one surface of the transparent support to form a liquid crystal alignment film having a thickness of 0.5 μm. Then, the left hand 16 with respect to the longitudinal direction of the transparent support.
The rubbing treatment was continuously performed in the direction of °.

Polymer for liquid crystal alignment film

[Chemical 144]

On the liquid crystal alignment film, a coating liquid having the following composition was continuously applied using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness of 0.8.
An optically anisotropic layer (B) having a thickness of μm was formed. The optically anisotropic layer had a slow axis parallel to the rubbing direction, that is, in the direction of 16 ° with respect to the longitudinal direction of the transparent support. 5
The retardation value at 50 nm was 113 nm. Composition of coating liquid for optically anisotropic layer Rod-shaped liquid crystal compound (1) 13.0% by mass Sensitizer (1) 1.0% by mass Photopolymerization initiator (1) 3.0% by mass Horizontal alignment promoter (1) 1.0% by mass Methyl ethyl ketone 82.0% by mass

Example 4 The retardation plate produced in Example 1 was continuously coated with the diluent for the liquid crystal alignment film used in Example 3 on the optically anisotropic layer to form a liquid crystal alignment film. did. Next, in the liquid crystal alignment film, the right hand was 58 ° with respect to the slow axis of the optically anisotropic layer (A), and the left hand was 16 ° with respect to the longitudinal direction of the retardation plate prepared in Example 1. Was subjected to rubbing treatment. Then, the coating liquid of the liquid crystalline compound used in Example 3 was continuously applied on the liquid crystal alignment film using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness. An optically anisotropic layer (B) having a thickness of 0.8 μm was formed.

[Example 5] The retardation plate prepared in Example 2 was continuously coated with the diluent for the liquid crystal alignment film used in Example 3 on the optically anisotropic layer to form a liquid crystal alignment film. did. Then, in the liquid crystal alignment film, the right hand was 58 ° with respect to the slow axis of the optically anisotropic layer (A), and the left hand was 16 ° with respect to the longitudinal direction of the retardation plate prepared in Example 2. Was subjected to rubbing treatment. Then, the coating liquid of the liquid crystalline compound used in Example 3 was continuously applied on the liquid crystal alignment film using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness. An optically anisotropic layer (B) having a thickness of 0.8 μm was formed.

[Comparative Example 1] A liquid crystal alignment film was formed using the same diluent as in Example 3. Then, rubbing treatment was continuously carried out in the direction of 74 ° to the left with respect to the longitudinal direction of the transparent support. On the liquid crystal alignment film, a coating solution having the same composition as in Example 3 was continuously applied using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness of 1.6 μm. An optically anisotropic layer (A) was formed. The optically anisotropic layer had a slow axis in the direction of 74 ° with respect to the longitudinal direction of the transparent support. The retardation value at 550 nm was 225 nm. In the retarder,
The diluent for the liquid crystal alignment film used in Example 3 was continuously applied on the optically anisotropic layer (A) to form a liquid crystal alignment film. Next, the liquid crystal alignment film is subjected to rubbing treatment so that the right hand is 58 ° with respect to the slow axis of the optically anisotropic layer (A) and the left hand is 16 ° with respect to the longitudinal direction of the retardation plate. did.
Then, the coating liquid of the liquid crystalline compound used in Example 3 was continuously applied on the liquid crystal alignment film using a bar coater, dried, and heated (alignment ripening), and further irradiated with ultraviolet rays to a thickness. An optically anisotropic layer (B) having a thickness of 0.8 μm was formed. The retardation value of the optically anisotropic layer (B) is 11
The crossing angle between the two anisotropic layers was 3 ° and was 58 °.

[Comparative Example 2] A retardation plate was formed in the same manner as in Example 4, except that the horizontal alignment promoter was omitted from the optically anisotropic layers (A) and (B). then,
The retardation value of the optically anisotropic layer (A) was 1 although the crossing angle between the two anisotropic layers was adjusted to 58 °.
At 80 nm, the retardation value of the optically anisotropic layer (B) was 73 nm, and it did not have optical performance as a λ / 4 plate.

Example 6: Evaluation of retardation plate Example 4
5 and Comparative Examples 1 and 2, a polarizing plate including a polarizing film and a protective film was used so that the polarization axis of the polarizing film and the longitudinal direction of the retardation plate were 90 °, that is, roll to A circularly polarizing plate was produced by laminating with a roll. Light from the polarizing film side of the obtained circularly polarizing plate (measurement wavelength is 450 nm,
550 nm and 650 nm) and the phase difference (retardation value: Re) of the light that passed through was measured. The results are shown in the table below

[0258]

[Table 1]

As shown in the table, it can be seen that the retardation plates manufactured in Examples 4 and 5 exhibit a phase difference of π / 2 particularly in the short wavelength region. In the retardation plates manufactured in Comparative Examples 1 and 2, the alignment state of liquid crystal was poor, and many alignment defects were observed.
It can be seen that the phase difference is also small in all wavelength ranges.

[0260]

According to the present inventor, there is provided a retardation plate which functions as a retardation plate in a wide band (visible light wavelength range), can be thinned, and can be manufactured easily and stably. be able to. Further, according to the present invention, it is an object of the present invention to provide a circularly polarizing plate that functions as a circularly polarizing plate in a wide band (visible light wavelength range), can be thinned, and can be easily and stably manufactured. To do. Further, the present invention provides a retardation plate and a circularly polarizing plate which function well in a wide band (visible light wavelength region) and can be thinned, by stably controlling the alignment of liquid crystal compound molecules. It is possible to provide a method of manufacturing a retardation plate and a circularly polarizing plate that can be manufactured easily and stably.

[Brief description of drawings]

FIG. 1 is a schematic diagram showing a basic configuration of a retardation plate of the present invention.

FIG. 2 is a schematic view showing a typical constitution of the circularly polarizing plate of the present invention.

[Explanation of symbols]

S Long transparent support s Longitudinal direction of transparent support A first optically anisotropic layer a In-plane slow axis of the first optically anisotropic layer B second optically anisotropic layer b In-plane slow axis of the second optically anisotropic layer d Rod-shaped liquid crystalline molecule P Polarizing film p Polarization axis of polarizing film angle between α a and s angle between β b and s γ angle between a and b ra The rubbing axis of the liquid crystal alignment film of the first optically anisotropic layer rb rubbing axis of the liquid crystal alignment film of the second optically anisotropic layer

   ─────────────────────────────────────────────────── ─── Continued front page    F-term (reference) 2H049 BA03 BA06 BA42 BB03 BC02                       BC22                 2H090 HA11 HB07Y HC05 HD14                       LA06 MA02 MA06 MB01                 2H091 FA07X FA07Z FA11X FA11Z                       FB02 GA06 KA10 LA18 LA30

Claims (7)

[Claims] 1. A long transparent support, a rod-like liquid crystal compound horizontally aligned above the long transparent support, and a measurement wavelength of 5
A first optically anisotropic layer having a retardation of substantially π at 50 nm and a horizontally aligned rod-like liquid crystal compound are included, and the retardation at a measurement wavelength of 550 nm is substantially π /
2 and a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the first optical anisotropic layer. A retardation plate including the first optical anisotropic layer, wherein an angle between the in-plane slow axis of the first optically anisotropic layer and the longitudinal direction of the transparent support is substantially 75 °, The angle between the in-plane slow axis of the anisotropic layer and the longitudinal direction of the transparent support is substantially 15 °, and the in-plane slow axis of the second optically anisotropic layer and the first optically anisotropic layer
And the angle with the in-plane slow axis of the optically anisotropic layer is substantially 60.
And the azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound contained in the first optically anisotropic layer is substantially orthogonal to the rubbing axis of the first liquid crystal alignment film. Phase difference plate. 2. A long transparent support, a rod-like liquid crystal compound horizontally aligned above the long transparent support, and a measuring wavelength of 5
A first optically anisotropic layer having a retardation of substantially π at 50 nm and a horizontally aligned rod-like liquid crystal compound are included, and the retardation at a measurement wavelength of 550 nm is substantially π /
A second optically anisotropic layer which is 2, and a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the first optically anisotropic layer, The second
A second liquid crystal alignment film having a rubbing axis that determines the azimuth angle of the horizontal alignment of the rod-shaped liquid crystalline compound in the optically anisotropic layer of the first optical anisotropy layer. The angle between the in-plane slow axis of the layer and the longitudinal direction of the transparent support is substantially 75 °, and the in-plane slow axis of the second optically anisotropic layer and the transparent support are The angle with the longitudinal direction is substantially 15 °, and the angle between the in-plane slow axis of the second optically anisotropic layer and the in-plane slow axis of the first optically anisotropic layer. Is substantially 60 °, the angle between the rubbing axis of the first liquid crystal alignment film and the longitudinal direction of the transparent support is substantially −15 °, and the second liquid crystal alignment film A retardation plate in which the angle between the rubbing axis and the longitudinal direction of the transparent support is substantially 15 °. 3. A step of forming a first liquid crystal alignment film having a rubbing axis having an angle of substantially −15 ° with the longitudinal direction of the transparent support above the elongated transparent support. ,
A layer containing a rod-shaped liquid crystal compound is formed on the first liquid crystal alignment film, and the rod-shaped liquid crystal compound is horizontally aligned at an azimuth angle substantially orthogonal to the rubbing axis of the first liquid crystal alignment film. And a step of forming a first optically anisotropic layer having a retardation of substantially π at a measurement wavelength of 550 nm, and an angle with the longitudinal direction of the transparent support is substantially above the transparent support. A step of forming a second liquid crystal alignment film having a rubbing axis of 15 °, a layer containing a rod-shaped liquid crystal compound is formed on the second liquid crystal alignment film, and the rod-shaped liquid crystal compound is added to the layer. The second liquid crystal alignment film is horizontally aligned at an azimuth angle substantially parallel to the rubbing axis, and the phase difference at a measurement wavelength of 550 nm is substantially π.
And a step of forming a second optically anisotropic layer having a thickness of / 2. 4. A step of forming a first liquid crystal alignment film having a rubbing axis in a direction substantially forming −15 ° with an arbitrary in-plane axis a1, and a rod-like liquid crystallinity on the first liquid crystal alignment film. A layer containing a compound is formed, and the rod-shaped liquid crystalline compound is formed in a direction substantially orthogonal to the rubbing axis of the first liquid crystal alignment film and substantially 75 ° to the in-plane axis a1. A step of horizontally aligning and forming a first optically anisotropic layer having a phase difference of substantially π at a measurement wavelength of 550 nm, and a rubbing axis whose angle with an arbitrary in-plane axis a2 is substantially 15 °. And a layer containing a rod-shaped liquid crystalline compound is formed on the second liquid crystal oriented film, and the rod-shaped liquid crystalline compound is added to the second liquid crystal oriented film. Orient it horizontally in a direction substantially parallel to the rubbing axis. A step of forming a second optically anisotropic layer having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm, and the first optically anisotropic layer and the second optically anisotropic layer. The respective in-plane axes a1 and a2 are substantially parallel, and the angle between the slow axis of the first optically anisotropic layer and the slow axis of the second optically anisotropic layer is substantially 6
A method of manufacturing a retardation plate, including a step of stacking at 0 °. 5. A horizontally oriented rod-shaped liquid crystal compound is included, and a phase difference at a measurement wavelength of 550 nm is substantially π.
And a second optically anisotropic layer containing a horizontally aligned rod-shaped liquid crystal compound and having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm, A circularly polarizing plate comprising a polarizing film and a first liquid crystal alignment film having a rubbing axis that determines an azimuth angle of horizontal alignment of the rod-shaped liquid crystal compound in the optically anisotropic layer of The angle between the in-plane slow axis of the optically anisotropic layer and the absorption axis of the polarizing film is substantially 75 °, and the in-plane slow axis of the second optically anisotropic layer and the polarized light are The angle with the absorption axis of the film is substantially 15 °, and the in-plane slow axis of the second optically anisotropic layer and the in-plane slow axis of the first optically anisotropic layer are Is substantially 60 °, and the azimuth angle of horizontal alignment of the rod-shaped liquid crystalline compound contained in the first optically anisotropic layer is the first liquid crystal alignment. Circularly polarizing plate which is substantially perpendicular to the rubbing axis. 6. A horizontally oriented rod-like liquid crystal compound is contained and a phase difference at a measurement wavelength of 550 nm is substantially π.
And a second optically anisotropic layer containing a horizontally aligned rod-shaped liquid crystal compound and having a phase difference of substantially π / 2 at a measurement wavelength of 550 nm, A first liquid crystal alignment film having a rubbing axis that determines the azimuth angle of horizontal alignment of the rod-shaped liquid crystalline compound in the optically anisotropic layer, and the rod-shaped liquid crystalline compound in the second optically anisotropic layer. Is a circularly polarizing plate including a second liquid crystal alignment film having a rubbing axis that determines the azimuth angle of the horizontal alignment of the liquid crystal, and a slow axis in the plane of the first optically anisotropic layer. The angle with the absorption axis of the polarizing film is substantially 75 °, and the second
The angle between the in-plane slow axis of the optically anisotropic layer and the absorption axis of the polarizing film is substantially 15 °, and the in-plane slow axis of the second optically anisotropic layer is The angle with the in-plane slow axis of the first optically anisotropic layer is substantially 60 °, and the angle between the rubbing axis of the first liquid crystal alignment film and the absorption axis of the polarizing film is substantially. Circularly polarizing plate having an optical axis of −15 ° and an angle between the rubbing axis of the second liquid crystal alignment film and the absorption axis of the polarizing film being substantially 15 °. 7. A step of forming a first liquid crystal alignment film having a rubbing axis whose angle to the longitudinal direction of the transparent support is substantially −15 ° above the elongated transparent support. ,
A layer containing a rod-shaped liquid crystal compound is formed on the first liquid crystal alignment film, and the rod-shaped liquid crystal compound is horizontally aligned at an azimuth angle substantially orthogonal to the rubbing axis of the first liquid crystal alignment film. And a step of forming a first optically anisotropic layer having a retardation of substantially π at a measurement wavelength of 550 nm, and an angle with the longitudinal direction of the transparent support is substantially above the transparent support. A step of forming a second liquid crystal alignment film having a rubbing axis of 15 °, a layer containing a rod-shaped liquid crystal compound is formed on the second liquid crystal alignment film, and the rod-shaped liquid crystal compound is added to the layer. The second liquid crystal alignment film is horizontally aligned at an azimuth angle substantially parallel to the rubbing axis, and the phase difference at a measurement wavelength of 550 nm is substantially π.
Of the second optically anisotropic layer which is / 2, and the longitudinal direction of the transparent support and the absorption axis are substantially aligned below the transparent support, and the transparent support of the transparent support is formed. And a step of forming a polarizing film having a polarization axis in a direction substantially perpendicular to the longitudinal direction.